PHOTODIODES - FROM

FUNDAMENTALS TO
APPLICATIONS

Edited by Ilgu Yun

Contents

Preface VII

Section 1 Fundamental Physics and Physical Design 1

Chapter 1 Two-Photon Absorption in Photodiodes 3

Toshiaki Kagawa

Chapter 2 Physical Design Fundamentals of High-Performance Avalanche

Heterophotodiodes with Separate Absorption and
Multiplication Regions 27
Viacheslav Kholodnov and Mikhail Nikitin

Section 2 Fabrication and Measurements 103

Chapter 3 Fabrication of Crystalline Silicon Solar Cell with Emitter

Diffusion, SiNx Surface Passivation and Screen Printing of
Electrode 105
S. M. Iftiquar, Youngwoo Lee, Minkyu Ju, Nagarajan Balaji, Suresh
Kumar Dhungel and Junsin Yi

Chapter 4 LWIR Photodiodes and Focal Plane Arrays Based on Novel

HgCdTe/CdZnTe/GaAs Heterostructures Grown by MBE
Technique 133
V. V. Vasiliev, V. S. Varavin, S. A. Dvoretsky, I. M. Marchishin, N. N.
Mikhailov, A. V. Predein, I. V. Sabinina, Yu. G. Sidorov, A. O.
Suslyakov and A. L. Aseev

Chapter 5 Photodiodes as Optical Radiation Measurement Standards 173

Ana Luz Muñoz Zurita, Joaquín Campos Acosta, Alejandro Ferrero
Turrión and Alicia Pons Aglio
VI Contents

Section 3 Device Applications 193

Chapter 6 Si-Based ZnO Ultraviolet Photodiodes 195

Lung-Chien Chen

Chapter 7 Infrared Photodiodes on II-VI and III-V Narrow-Gap

Semiconductors 215
Volodymyr Tetyorkin, Andriy Sukach and Andriy Tkachuk

Chapter 8 Al(Ga)InP-GaAs Photodiodes Tailored for Specific

Wavelength Range 261
Yong-gang Zhang and Yi Gu

Chapter 9 Single- and Multiple-Junction p-i-n Type Amorphous Silicon

Solar Cells with p-a-Si1-xCx:H and nc-Si:H Films 289
S. M. Iftiquar, Jeong Chul Lee, Jieun Lee, Juyeon Jang, Yeun-Jung
Lee and Junsin Yi

Section 4 Circuit Applications 313

Chapter 10 Noise Performance of Time-Domain CMOS Image Sensors 315

Fernando de S. Campos, José Alfredo C. Ulson, José Eduardo C.
Castanho and Paulo R. Aguiar

Chapter 11 Design of Multi Gb/s Monolithically Integrated Photodiodes

and Multi-Stage Transimpedance Amplifiers in Thin-Film SOI
CMOS Technology 331
Aryan Afzalian and Denis Flandre
Preface

This book represents recent progress and development of the photodiodes including the
fundamental reviews and the specific applications developed by the authors themselves.
The key idea of this book is that it allows authors to deal with a wide range of backgrounds
and recent research progresses in photodiode-related areas.
Most of the material in this book was developed for the researchers in the field of optical or
optoelectronic devices and circuits. A substantial proportion of the material is original and
has been prepared by the authors of each book chapter specifically for this book. With re‐
spect to the original collection of the book chapters, this book contains several improve‐
ments and several new problems and related solutions are also discussed in the area of fun‐
damental physics and characteristics, and the device and the circuit applications.
For editing this book, I have assumed that readers are well acquainted with the basic con‐
cepts of semiconductor physics fundamentals, especially with regard to: physical electron‐
ics; electronic materials; semiconductor processes; semiconductor device engineering; elec‐
tronic and optoelectronic circuits, etc.
The book is intended for at least three kinds of readers: a) graduate students of intermediate
and advanced courses in microelectronics or optoelectronics, who are presumed to be most‐
ly interested in photodiode-related applications; b) engineers in the area of optoelectronic
devices, who are especially interested in optical sources and optical detectors; c) professio‐
nal researchers of many areas of applications (not restricted to microelectronics or optoelec‐
tronics or photonics).
This book consists of 4 sections:
Section 1 contains the fundamental concepts of photon absorption in photodiodes. In addi‐
tion, the physical design scheme of the high-performance avalanche heterophotodiodes is
presented to guide the engineers how to design avalanche heterophotodiodes to optimize
their performances in specific applications.
Section 2 contains the fabrication of photodiode-based devices, such as solar cells, photodio‐
des, and focal plane arrays. Especially, the standards of optical radiation measurements us‐
ing photodiodes are also addressed.
Section 3 describes various types of photodiodes as device applications. It includes the ultra-
violet (UV) photodiodes, the infra-red (IR) photodiodes, compound semiconductor photodi‐
odes for specific wavelength, and wide bandgap solar cells.
VIII Preface

Section 4 presents the photodiode-related circuit applications. Here, the noise performance
of CMOS image sensor is investigated in time-domain analysis and the high-speed Optoe‐
lectronic Integrated Circuit (OEIC) fabricated by monolithic integration of photodiode and
amplifier is surveyed.
In presenting this book, I would like to express my thanks to the authors who participate in
writing for each book chapter and followed my construct comments, constructive criticism,
and useful suggestions. They include: Toshiaki Kagawa, Viacheslav Kholodnov, Mikhail Ni‐
kitin, Sergey Dvoretsky, S. M. Iftiquar, V.V. Vasiliev, Ana Luz Muñoz Zurita, Lung-Chien
Chen, Volodymyr Tetyorkin, Yong-Gang Zhang, Fernando de S. Campos, Iftiquar Sk, Aryan
Afzalian, and others.
I especially wish to express my sincere thanks to Ms. Romina Skomersic, Publishing Process
Manager in InTech-Open Access Publisher, for the valuable publishing suggestions. More‐
over, I wish to thank the InTech-Open Access Publisher for helping in the typing adjustment
and for revising the English text for each book chapter.
Finally, I would like to thank for my wife, Hyun Jung Cha, and my two adorable sons, Jiho
and Joonho Yun, for their sincere care and support during the whole summer of 2012.

Ilgu Yun
School of Electrical and Electronic Engineering,
Yonsei University
 Section 1

Fundamental Physics and Physical Design

 Chapter 1

Two-Photon Absorption in Photodiodes

Toshiaki Kagawa

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/50491

1. Introduction

Incident light with a photon energy ℏω induces two-photon absorption (TPA) when
Eg / 2ℏωEg , where Eg is the band gap of the photo-absorption layer of a photodiode (PD). Be‐
cause the absorption coefficient is small, photocurrent generated by TPA is too low to be
used in conventional optical signal receivers. However, the nonlinear dependence of the
photocurrent on the incident light intensity can be used for optical measurements and opti‐
cal signal processing. It has been used for autocorrelation in pulse shape measurements [1],
dispersion measurements [2,3] and optical clock recovery [4]. These applications exploit the
dependence of the generated photocurrent on the square of the instantaneous optical inten‐
sity. Measurement systems using TPA in a PD can detect rapidly varying optical phenom‐
ena without using high speed electronics.
This chapter reviews research on TPA and its applications at the optical fiber transmission‐
wavelength. Theory of TPA for semiconductors with diamond and zinc-blende crystal struc‐
tures is reviewed. In contrast to linear absorption for which the photon energy exceeds the
band gap, the TPA coefficient depends on the incident lightpolarization. The polarization
dependence is described by the nonlinear susceptibility tensor elements.
The polarization dependences of TPA induced by a single optical beam in GaAs- and Si-PDs
are compared to evaluate the effect of crystal symmetry. It is found that, in contrast to the
GaAs-PD, TPA in the Si-PD is isotropic for linearly polarized light at a wavelength of 1.55
μm. Photocurrents for circularly and elliptically polarized light are also measured. Ratios of
the nonlinear susceptibility tensor elements are deduced from these measurements. The dif‐
ferent isotropic properties of GaAs- and Si-PDs are discussed in terms of the crystal and
band structures.
Cross-TPA between two optical beams is also studied. The absorption coefficient of cross-
TPA strongly depends on the polarizations of the two optical beams. It is shown that the po‐
4 Photodiodes - From Fundamentals to Applications

larization dependence of cross-TPA is consistent with the nonlinear susceptibility tensor

elements obtained from the self-TPA analysis.

Cross-TPA can be applied to polarization measurements. Photocurrents generated in the Si-

PD by cross-TPA between asignal light under test and a reference light are used to detect the
polarization. The light under test is arbitrarily polarized and its Jones vector can be deter‐
mined by photocurrents generated by cross-TPA. This measurement method can detect the
instantaneous polarization when the reference light temporally overlaps with the light un‐
der test. Because the time division is limited only by the pulse width of the reference light, it
is possible to detect rapid variationsin the polarization. This method can measure not only
the linear polarization direction but also the elliptical polarization. Applications to measure‐
ment of the output optical pulse from an optical fiber with birefringence and a semiconduc‐
tor optical amplifier are demonstrated.

2. TPA in semiconductors with diamond and zinc-blende crystals

2.1. Polarization dependence

TPA is a third-order nonlinear optical process. Third order nonlinear polarization is induced
by the optical electric field according to

1
Pi (3)(ωi , ki ) = ε ∑ χ E (ω , k )E (ω , k )E (ω , k ) (1)
4 0 j,k,l ijkl j j j k k k l l l

whereε 0 is the permittivity of free space, χ is the third-order tensor, ω is the optical angular
frequency, k is the optical wavenumber vector, E is the optical electric field [5]. The suffixes
i, j, k, and l denote the orthogonal directions. The relationships between the optical angular
frequencies and the wavenumber vectors are determined by energy and momentum conser‐
vation, respectively.

Although the third-order nonlinear susceptibility tensor contains 34 elements, the number of
non-zero independent elements is limited by the crystal symmetry and the properties of the
incident light. It is apparent that relations χ xxxx = χ yyyy = χ zzzzand χ xxyy = χ xxzz = χ yyzz, etc. hold
for a cubic crystal. Elements like χ xxxyandχ xxyzwill be zero for crystals with 180° rotational
symmetry about a crystal axis. For degenerate TPA in which one or two parallel optical
beams with the same optical frequency propagate,ωi = − ωj = ωk = ωl and χ xyxy=χ xyyx hold.
There are thus only three independent elements, χ xxxx,χ xxyy , and χ xyyx, for degenerate TPA
in crystal classes of m3m (Si) and 4̄3m (GaAs) [5,6].

We consider cross- and self-TPA between two optical beams. The electric field is the sum of
the electric fields of thetwo incident optical beams.
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E = Ep ^p + Ee ^e (2)

where E p and E e are the electric field strengths and ^p and^e are the polarization unit vectors of
the two beams. For circular or elliptical polarization, ^p and ^e are complex to express the
phase difference between the electric field oscillations along two axes. The nonlinear polari‐
zation along the polarization vector ^p is given by

1
Pp (3) = ε (E 3 ∑ p * p * p p χ + 2Ep Ee 2 ∑ pi *ej * pk el χijkl ) (3)
4 0 p i, j,k ,l i j k l ijkl i, j,k ,l

wherep iand e i are elements of ^p and^e , andp i

*
and e i
*
are their complex conjugate, respec‐
tively. Because there are only three nonzero independent tensor elements, the nonlinear po‐
larization can be written as [7]

Pp (3) =
1
4 0 p{
ε E 3( | ^p ⋅ ^p | 2 ⋅ χxxyy + 2χxyyx + σχxxxx ∑
i
| pi | 4)
(4)
+ 2Ep Ee 2(χxxyy | ^p ⋅ ^e | 2 + χxyyx (1 + | ^p * ⋅ ^e | 2) + σχxxxx ∑ | pi | 2 | ei | 2)
i
}
where

χxxxx − χxxyy − 2χxyxy

σ= (5)
χxxxx

The first and second terms are polarization induced by the self- and cross-electric field
effects, respectively. Terms proportional to the inner product of ^p and ^e are invariant for
rotation of axes and are isotropic. In contrast, terms that are proportional to σ vary on the
rotation of the axes. Thus, σ shows the anisotropy of the third-order nonlinear optical
process.

Two optical beams propagate in the crystal under the effect of self- and cross-TPA.

d Ip
= − β pp I p 2 − β pe I p I e (6)
dz

where I p and I e are optical intensity densities of the two beams. The absorption coefficient is
proportional to the imaginary part of the nonlinear polarization given in Eq. (4).
6 Photodiodes - From Fundamentals to Applications

ω
β pp = (χ ″ xxyy | ^p ⋅ ^p | 2 + 2χ ″ xyyx + σ ″χ ″ xxxx ∑ | pi | 4) (7)
2n 2c 2ε0 i

and

ω
β pe = (χ ″ xxyy | ^p ⋅ ^e | 2 + χ ″ xyyx (1 + | ^p * ⋅ ^e | 2) + σ ″χ ″ xxxx ∑ | pi | 2 | ei | 2) (8)
n 2c 2ε0 i

where n is the refractive index, and c is the speed of light. χ ″ xxxx etc. are imaginary parts of
the nonlinear susceptibility tensor elements. σ ″is the anisotropy parameter for imaginary
parts of the nonlinear susceptibility tensor.

χ ″ xxxx − χ ″ xxyy − 2χ ″ xyyx

σ ″= (9)
χ ″ xxxx

2.2. Estimate of photocurrent induced by TPA in PDs

Commercially available PDs are usually designed to be used for photon energies greater
than the band gap of the photoabsorption layer. As the absorption coefficient is about 105
cm-1, absorption layer is several micrometers thick. On the other hand, the absorption coeffi‐
cient is much smaller for TPA. If we consider only self-TPA, Eq. (6) is solved as

I0
I p (z) = ≈ I (1 − β pp I 0z) (10)
β pp I 0 z + 1 0

where I 0 is the initial light intensity density. Using a typical value of 10-18 m2/V2 for the
imaginary parts of the nonlinear susceptibility tensor elements [7], the TPA coefficient is es‐
timated to be about 6 × 10−11 m/W. When the incident light density is 107 W/cm2, β pp I 0is esti‐
mated to be6 × 10−6μm-1. Because only a very small fraction of the incident light is absorbed
in PD with a photo-absorption layer that is several micrometers thick, the induced photocur‐
rent is proportional to the absorption coefficient β.

When optical pulses with an intensity density I 0 and pulse width T pare irradiated at a repe‐
tition rate of R, the induced photocurrent will be

q
J = ηβ pp I 02S d T p R (11)
ℏω

where η is the internal efficiency of the PD, d is the absorption layer thickness, and S is the
area of the incident beam. The photocurrent is estimated to be about 10-8 A assuming that
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the light intensity of 107 W/cm2 is illuminated on a spot with adiameter of 10 μm. We as‐
sume that the pulse width is 1 ps, the repetition rate is 100 MHz, absorption layer thickness
is 2 μm, and the internal efficiency is 1.

3. Experimental setup
Because the photocurrent of PD is proportional to the square of the instantaneous light pow‐
er density, it is necessary to concentrate the optical power into a narrow spatial region and a
short time period. Thus, a short pulsed light beam is more suitable for TPAmeasurements‐
than continuous wave light.
Figure 1 shows the experimental setup. A gain-switched laser diode (LD) generated optical
pulses with a wavelength of 1.55 μm, a pulse width of 50 ps and a repetition rate of 100
MHz. Light pulse from the gain-switched LD exhibit large wavelength chirping. The pulse
was compressed to about 10 ps by an optical fiber with positive wavelength dispersion. Its
peak power was then amplified using an Er-doped fiber amplifier (EDFA) to further com‐
press the pulse width through the nonlinear soliton effect in a normal-dispersion fiber. The
final pulse width was compressed toabout 1 ps.
To measure cross-TPA between two optical beams, a second gain switched LD with a wave‐
length of 1.55 μm was prepared. Noise due to interference between the two beams does not
affect the measurement because the optical frequency difference between the two beams is
greater than the bandwidth of the measurement system. Pulse with a repetition rate of
100MHz are completely synchronized with those of the first optical beam. The second opti‐
cal beam is also amplified by an EDFA.
Both the two beams were made linearly polarized by polarization controllers. After they
were launched into free space, they passed through polarizing beam splitters to ensure that
they were completely linearly polarized. Half-wave or quarter-wave plates were inserted if
it is necessary to control the polarization of the beams. The two beams were spatially over‐
lapped by a polarization-independent beam splitter and they were focused on a PD. It was
confirmed that the polarization did not change on reflection at the polarization-independent
beam splitter by monitoring the polarization before and after reflection. An optical power
meter was placed at the location of the PD and it was used to check if the optical power was
independent of the polarization.
When two optical beams are illuminated on a PD, photocurrents due to self-TPA and cross-
TPAare simultaneously generated. It is necessary to detect only the photocurrent generated
by the cross-TPA. Optical pulse streams were mechanically chopped at frequencies of 1.0
and 1.4 kHz. Electrical pulsesthat had been synchronized with mechanical choppers were
fed into a mixer circuit that generated a sumfrequency of 2.4 kHz. These generated electrical
pulses with the sum frequency were used as the reference signal for the lock-in amplifier.
Thus, the lock-in amplifier detected only the photocurrent generated by two-beam absorp‐
tion, that is, cross TPA.
8 Photodiodes - From Fundamentals to Applications

Figure 1. Measurement setup (LD: laser diode; NDF: normal dispersion fiber; ADF: abnormal dispersion fiber; PBS: po‐
larization beam splitter; PIBS: polarization independent beam splitter). The inset shows the rotation of the wave plate.
Light from the PBS is linearly polarized along the x axis,which is parallel tothe [1] axis of the PD.

4. Pulse width measurement by cross-TPA

Cross-TPA was used to measure the pulse width generated by the pulse compression proc‐
ess described in the previous section. After the compressed optical pulse was divided into
two branches by an optical fiber beam splitter, the timing between them was controlled by a
variable delay line. They were then irradiated on the Si-PD. The two beams were made or‐
thogonally linearly polarized to suppress noise due to interference. The photocurrent gener‐
ated by cross-TPA between the divided two optical beams is

∫
J (τ) = β h (t)h (t − τ)dt (12)

where h(t) is the pulse shape, and τ is the time delay between the two pulses. The pulse
width can be estimated by this self-correlation trace.
Figure 2 shows the self-correlation trace of the compressed optical pulse. The photocurrent
due to the cross-TPA is generated only when the two optical pulses temporally overlap on
the PD. It disappears when the time delay is larger than the pulse width. The self-correlation
trace has a full-width at half-maximum (FWHM) of 1.3 ps. The FWHM of the pulse is esti‐
mated to be about 0.9 ps assuming a Gaussian pulse shape.

5. Polarization dependence of self-TPA in Si- and GaAs-PDs

Measuring the photocurrent generated in PDs is the easiest way to study the polarization
dependence of self-TPA coefficient. Because the fraction of the incident photons that are ab‐
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sorbed is quite small, the generated photocurrent is directly proportional to the absorption
coefficientβ ppas shown by Eq. (10). The photocurrents generated in Si- and GaAs-PDs were
compared to discuss the polarization dependence of TPA in Si and GaAscrystals[8].

Figure 2. Self-correlation trace of the compressed pulse measured by TPA of Si-PD.

In the self-TPA measurement, only one optical beam is illuminated on a PD. The optical
beam with a pulse width of 0.9 ps in the measurement setup described in section 3was used
in the self-TPAmeasurement. The x- and y- axes are fixed in the laboratory frame. We con‐
sider the case when light that is linearly polarized alongthe x-axis is transformed by a half-
or quarter-wave plate. The principal axis of the wave plate is rotated at an angle of θ relative
to the x-axis. The polarization of the transformed light is expressedby

^p = ( )(
px
py
= )( )(
cosθ − sinθ 1 0 cosθ sinθ 1
sinθ cosθ 0 e iφ − sinθ cosθ 0
)( ) (13)

where ϕ=π and π/2 for half- and quarter-wave plates, respectively. The inset of Fig. 1 shows
the definition of the rotation angle. The principal axes of the quarter-wave plate are repre‐
sented by the X- and Y-axes. The phase of the polarization component along the Y-axis is
delayed by ϕ relative to that along the X-axis.
The anisotropy of self-TPA for linearly polarized light was measured for Si- and GaAs-PDs.
The crystal axis [001] is made parallel to the x-axis. The linear polarization is rotated by a
half-wave plate (i.e., ϕ=π in Eq. (13)). When the X-axis is tilted by an angle of θ relative to
the x-axis, the polarization direction of the output light from the half-wave plate is tilted by
10 Photodiodes - From Fundamentals to Applications

2θ. Thus, the polarization is parallel to the [001] and [011] directions when the rotation angle
of the half-wave plate is θ = 0 and 22.5° , respectively. Using Eq. (7), the anisotropy parame‐
ter σ" defined by Eq. (9) can be written as

β pp L 001 − β pp L 011
σ ″=2 (14)
β pp L 001

Figure 3. Photo currents generated when linearly polarized lightirradiated on (a) GaAs PD and (b) Si PD. The linear
polarization direction is rotated using a half-wave plate. The horizontal axis is the tilt angle of the half wave plate.The
solid lines in (a) and (b) show the values calculated using Eq. (15) with σ" = –0.45 and 0, respectively.

whereβ pp L 001 and β pp L 011 are the TPA coefficients for linearly polarized light polarized
along the [001] and [011] directions, respectively.This parameter can be experimentallydeter‐
mined by the ratio of photocurrents.

Figures 3(a) and (b) respectively show the photocurrents generated in GaAs- and Si-PD sas a
function of the rotation angle of the half-wave plate. For the GaAs-PD, the photocurrent var‐
ies with the polarization direction indicating that the TPA is anisotropic. The anisotropy pa‐
rameter σ'' is estimated to be –0.45. From Eqs. (7), (9) and (13), the dependence of the TPA
probability on the rotation angle θof the half-wave plate can be written as

1 ″
β pp L ∝ χ (4 − σ ″ + σ ″cos8θ) (15)
4 xxxx

The solid line in Fig. 3 (a) shows the value calculated using Eq. (15) and σ''= –0.45. In con‐
trast, the Si-PD exhibits negligibly small dependence on the polarization direction and the
TPA coefficient is almost isotropic; | σ ″ | is estimated to be less than 0.04.

Figure 4(a) and (b) respectively shows the dependence of the photocurrents generated in the
GaAs- and Si-PDs on the rotation angle of a quarter-wave plate (ϕ=π/2in Eq. (13)). The inci‐
dent light is linearly polarized along the [001] direction and circularly polarized at θ = 0 and
 Two-Photon Absorption in Photodiodes 11
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45° , respectively. The difference in the self-TPA coefficients for linear and circular polariza‐
tion isexpressed by the dichroism parameter

β pp L 001 − β pp C χ" xxxx + χ" xxyy − 2χ" xyyx

δ= = (16)
β pp L 001 2χ" xxxx

whereβ pp C is the TPA coefficient for circularly polarized light. This parameter is estimated to
be 0.1 and 0.39 from the measured photocurrents for linearly and circularly polarized light
in the GaAs- and Si-PD, respectively.

Figure 4. Photocurrent obtained when elliptically polarized light is incident on (a) GaAs and (b) Si PDs. Linearly polar‐
ized light along the [001] axis is transformed by a quarter-wave plate rotated at an angle of θ.The solid lines indicate
the results calculated using Eq. (17) and the parameters in Table 1.

The ratios χ '' xxyy / χ '' xxxx and χ '' xyyx / χ '' xxxx can be estimated from measured anisotropic
and dichroism parameters. Table 1 lists the obtained ratios for the nonlinear susceptibility
tensor elements for GaAs and Si.
From Eqs. (7), (9), (13) and (16), the dependence of the TPA coefficient on the quarter-wave
plate rotation angle θ is given by

1 ″
β pp ∝ χ (16 − σ ″ − 8δ + σ ″cos8θ + 8δcos4θ) (17)
16 xxxx

This self-TPA coefficient is maximized when

χ" xxyy 1
cos22θ = − (18)
χ" xxxx σ ″

The absorption coefficient for this elliptically polarized light is greater thanβ L 001 .
12 Photodiodes - From Fundamentals to Applications

The solid lines in Figs. 4(a) and (b) show the results calculated using Eq. (17) for GaAs and
Si, respectively. The photocurrent shown in Fig. 4(a) reaches a maximum at θ = 15° , which
indicates that Eq. (18) holds at this angle. The factor χ" xxyy / (σ ″χ" xxxx )in Eq. (18) is estimat‐
ed to be –0.75 for GaAs. This value is consistent with the values of σ ″andχ ″ xxyy / χ ″ xxxx in Ta‐
ble 1, indicating that thepolarization dependence of the GaAs-PD is consistent with the
analysis based on the nonlinear susceptibility.
On the other hand, the photocurrent generated in the Si-PD is maximized when the an‐
gle is 0 and the incident light is linearly polarized, which contrasts the situation for the
GaAs PD. Because the anisotropy parameter is small, Eq. (18) does not hold at any rota‐
tion angle θ.

6. Discussion of self-TPA polarization dependence

The polarization dependence of self-TPA is strongly dependent on the crystal symmetry and
the band structure. Hutchings and Wherettcalculated nonlinear susceptibility tensor ele‐
ments based on kp perturbation [9]. The ratios listed in Table 1 are consistent with their re‐
sults. Murayamaand Nakayama[10] have performed ab initio calculations.Their calculated
values for the ratiosχ" xxyy / χ" xxxx andχ" xyyx / χ" xxxx depend on the photon energy. The val‐
ues of ratios shown in Table 1 are very similar to those calculated for a photon energy of 1
eV. The small discrepancy between the photon energies is probably due to the parameters
used in the calculation.

GaAs Si

Anisotropy parameter σ" -0.45 | σ | < 0.04

″

Dichroism parameter δ 0.1 0.39

χ" xxyy / χ" xxxx 0.34 0.39

χ" xyyx / χ" xxxx 0.56 0.31

Table 1. Parameters obtained from the polarization dependence of the photocurrents of GaAs and Si PDs at a
wavelength of 1.55 μm.

It is very reasonable that GaAs and Si were observed to have quite different anisotropies be‐
cause of their different crystal symmetries and band structures. As GaAs has a direct transi‐
tion type band structure, an optical transition occurs at around the Γ point. The anisotropy
for GaAs is due to the allowed–allowed transition [7,9] (see Fig. 5(a)), which is the two-step
optical transition ofΓ15v → Γ15c → Γ1c . Γ15v, Γ1c, and Γ15care irreducible representations of the
point group T d(4̄3m) of the GaAs crystal for the highest valence band, the lowest conduction
band, and the higher conduction band at the Γ point, respectively [11]. The first transition
Γ15v → Γ15c occurs between p-like states, the second transition Γ15c → Γ1c occurs between p-like
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and s-like states. The polarization directions that induce the first and second transitions
must be different from each other. For example, transitions | pz (Γ15v ) → | px (Γ15c ) and
| px (Γ15c ) → | s(Γ1c ) are induced by dipole moments polarized along they- and x-axes, re‐
spectively. | pz (Γ15v ) , | px (Γ15c ) ,and | s(Γ1c ) are wave functions of each band [11]. This proc‐
ess does not contribute to χ xxxx andχ xxyy , but it contributes to χ ″ xyyx causing the anisotropy
″ ″

parameter σ’’ to be non-zero [7]. The matrix element of the optical dipole moment between
Γ15v and Γ 15c is non-zero because T d lacks space inversion symmetry.

On the other hand, Si has the indirect transition type band structure. Figure 5(b) schemati‐
cally shows the band structure and the irreducible representation of this space group [11,12].
A photon energy of 0.8 eV is too small to induce a direct TPA transition without phonon
absorption or emission at any point in the first Brillouin zone of Si. The final sate of the TPA
transition is Δ1, which has the minimum energy of the conduction band. Many complicated
transitionsequences that include optical and phonon transitions exist to reach the final point
Δ1 for electron.

When both optical transitions occur at Γ point, an electron is scattered to Δ1in the conduction
band. However, two step optical transitions in Si are quite different from that in GaAs. Si
crystal has a point group of O h(m3m) that has space inversion symmetry and the wavefunc‐
tion is an eigenstate of the parity at the Γ point. The matrix elements of the dipole moment
between the conduction bands of Γ 15, Γ2', and Γ12' vanish because they all have the same pari‐
ty. The only possible virtual final state of the two-step optical transition sequence in Γ point
is Γ1 in the higher conduction band. AsΓ1 has a much greater energy than Γ25' andΔ1, the tran‐
sition probability is thought quite small.

Figure 5. a) Schematic band structure and allowed–allowed transition in GaAs. (b) Schematic band structure of Si
14 Photodiodes - From Fundamentals to Applications

When a phonon process occurs after the first optical transition, the polarization effect of the
first optical transition on the intermediate state of TPA can be destroyed by the phonon
process. The anisotropy is thus considered to be reduced by this process.

7. Cross-TPA in Si-APD

As shown in the previous section, TPA in Si is isotropic. Thus, TPA in Si-PD is simpler than
that in GaAs-PD. In addition, a Si avalanche photodiode (APD) with the multiplication gain
is commercially available. Consequently, we concentrate on cross-TPA in Si-APD.

Cross-TPA depends on the relationship between the polarization vectors of the two beams.
We measure three cases: when both beams are linearly polarized, when one optical beam is
linearly polarized and the other is varied between linear, elliptical, and circular polarization
by a quarter-wave plate, and when one beam is circularly polarized and the other is varied
between linear, elliptical, and circular polarization [13].

Figure 6. Photocurrent due to cross- TPA between two linearly polarized beams. Solid line is the calculated results
using parameters in Table 1.

Figure 6 shows the photocurrent when both beams are linearly polarized. The horizon‐
tal axis of the figure is the rotation angle of the half- wave plate. The photocurrent was
 Two-Photon Absorption in Photodiodes 15
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normalized using the minimum photocurrent. The photocurrent is strongly dependent on

the orientation of the two linear polarization axes and has a maximum and minimum
values when the polarization axes of the two optical pulses are parallel and perpendicu‐
lar, respectively.

Equation (8) can be written as

1 ″ 1
β pe ∝ (χ xxyy + χ ″ xyyx ) cos4θ + (χ ″ xxyy + 3χ ″ xyyx ) (19)
2 2

The solid line in Fig.6 shows the result calculated using Eq. (19) and the parameters in Table 1.

The absorption coefficient hasa maximum and minimum when ^p and ^e are parallel and or‐
thogonal, respectively. The ratio of the maximum to minimum values is

^ ^e )
β pe (p // χ ″ xxyy
^ ^ =2 + ″ (20)
β pe (p ⊥ e ) χ xyyx

Using the parameters in Table 1 which were obtained from the self-TPA of Si, this ratio is
3.26. This value is consistent with the measured cross-TPA shown in Fig 6..

Figure 7. Photocurrent due to cross-TPA between linear polarized and elliptical polarized lights. Solid line is the calcu‐
lated results using parameters in Table 1.
16 Photodiodes - From Fundamentals to Applications

Figure 7 shows the photocurrent when one beam (^e ) was linearly polarized and the polari‐
zation of the other beam ( ^p ) was varied using a quarter-wave plate. The horizontal axis is
the rotation angle of the quarter-wave plate. The polarization of the second beam varied be‐
tween linear, elliptical, and circular in this case. The solid line shows the calculated value
using the parameters in Table 1. The photocurrent had maximum and minimum values
when the second beam was linearly and circularly polarized, respectively. The ratios are
theoretically written as

^ ^e )
β pe (p // 4 + 2χ ″ xxyy / χ ″ xyyx
^ = (21)
β pe (p ; circular) 3 + χ ″ xxyy / χ ″ xyyx

using Eq (8). This ratio is calculated to be 1.53 from the parameters in Table 1, and is consis‐
tent with the measurement.
Figure 8 shows the photocurrent when one beam was circularly polarized while the polari‐
zation of the other beam was varied using a quarter-wave plate between linear, elliptical,

and circular polarization. The unit vectors for circular polarization are σ ^ = 1 (x^ + i y
^ )and
+
2
^ = 1 (x^ − i y
σ ^ ). An arbitrary polarization vector ^p can be written as a linear combination of
−
2
these unit vectors.

^p = p σ
^ ^
+ + + p−σ − (22)

When^e = σ
^ , Eq (8) can be written as
−

β pe ∝ χ ″ xxyy | p+ | 2 + χ ″ xyyx (1 + | p− | 2). (23)

^ ⋅σ
We used the relations σ ^ = 1andσ
^ ⋅σ^ =σ
^ ⋅σ^ = 0. β is independent of ^p when
+ − + + − − pe

χ" xxyy = χ" xyyx because | p+ | 2 + | p− | 2 = 1.The photocurrent depends on the polarization, as
Fig. 8 shows, but this dependence is relatively small.
The dependence of the absorption coefficient on the rotation angle is

β pe ∝ (χ ″ xxyy − χ ″ xyyx )sin2θ + χ ″ xxyy + 3χ ″ xyyx (24)

The ratio of the maximum tominimum values is

^ =σ
β pe (p ^ )
+ 1 χ ″ xxyy
^ ^ = (1 + ″ ) (25)
β pe (p = σ −) 2 χ xyyx

It is estimated to be 1.13 using the parameters in Table 1.

 Two-Photon Absorption in Photodiodes 17
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Figure 8. Photocurrent due to cross TPA when one optical beam is circularly polarized.

The solid line in Fig. 8 is the calculated results using Eq. (24). When one optical beam is cir‐
cularly polarized, cross-TPA exhibits very weak dependences on the polarization of the oth‐
er optical beam because values of χ ″ xxyy and χ ″ xyyx are very close to each other: however, in
principle, they are not exactly equal for Si.
The calculated values shown by the solid lines in Figs. 6, 7, and 8 are obtained by nonlinear
susceptibility tensor elements that were deduced from the polarization dependence of self-
TPA. There is relatively good agreement with the measured cross-TPA. This demonstrates
that the polarization dependences of self- and cross-TPA of Si are consistent with theoretical
analysis based on the nonlinear susceptibility tensor.

8. Polarization measurement by cross-TPA

The polarization dependence of the cross-TPA in Si-APD can be used to measure the polari‐
zation. In this method, a Si-APD is irradiated by the arbitrarily polarized light to be meas‐
ured (signal light) and a linearly polarized referencebeam. The photocurrents generated by
cross-TPA between the signal light and the linearly polarized reference light are measured.
Polarization direction of the reference beam was varied in four ways. Polarization of the
arbitrarily polarized light can be determined from the four photocurrents of the APD [14].
Several applications require the ability to detect rapid variations in the polarization of an
optical signal. In all conventional polarization measurement methods, the temporal resolu‐
18 Photodiodes - From Fundamentals to Applications

tion is limited by the response speed of the PD and/or electrical devices employed. Measure‐
ments based on TPA can be employed to measure rapidly varying polarization without the
need to use high-speed electronics. Since the reference beam can be short pulses, the tempo‐
ral polarization of a short-time period can be measured using this method. The temporal
resolution is limited by only the pulse width of the reference light.

8.1. Principle of polarization measurement

The polarization of thelight to be measured can be generally described by the Jones vector

^p =
( ) ax
ay e iα
(26)

where a x and a y are respectively the amplitudes of the components in the x- and y-direc‐
tions, and α is their phase difference. These three parameters are generally functions of
time.The referencelight is linearly polarized and its Jones vector is given by

( )
^e = cosγ
sinγ
(27)

where γ expresses the polarization direction. The polarization of the reference lightis inde‐
pendent of time.

Let us consider four different polarization orientations of the linearly polarized reference
light beam, namely, γ 1 =0, γ 2 =π/2, γ 3 =π/4, and γ 4 =π/4.In the experiment, four photocur‐
rents due to the cross TPA between the signal light and these four linearly polarized referen‐
cebeams are measured by a lock-in amplifier. From Eq. (8), the cross-TPA probability, which
is proportional to the measured photocurrent, is given by

β1(γ = 0) ∝ ax 2(χ ″ xxyy + χ ″ xyyx ) + χ ″ xyyx (28)

β2(γ = π / 2) ∝ ay 2(χ ″ xxyy + χ ″ xyyx ) + χ ″ xyyx (29)

β3(γ = π / 4) ∝ ax ay cosα (χ ″ xxyy + χ ″ xyyx )

(30)
+(χ ″ xxyy + 3χ ″ xyyx ) / 2

β4(γ = − π / 4) ∝ − ax ay cosα (χ ″ xxyy + χ ″ xyyx )

(31)
+(χ ″ xxyy + 3χ ″ xyyx ) / 2

Thus, the parameters of the measured light are given by

 Two-Photon Absorption in Photodiodes 19
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x + 2 − β2 / β1
ax 2 = (32)
(x + 1)(1 + β2 / β1)

ay 2 = 1 − ax 2 (33)

(x + 3)(1 − β4 / β3)
cosα = (34)
2ax ay (x + 1)(1 + β4 / β3)

x ≡ χ ″ xxyy / χ ″ xyyx (35)

The polarization can be determined from the ratios of the photocurrent β 2 /β 1 and β 4 /β 3. x
is the ratio of the two independent non-diagonal elements of the third-order nonlinear sus‐
ceptibility tensor; it was estimated to be 1.3 using values in Table 1. However, it was found
that a x, a y, and αare quite insensitive to x.
Let us consider the case when the pulse width of the reference light is much shorter than
that of the light to be measured. The measured photocurrent produced by APD due to cross-
TPA samples the polarization of the light being measured during the reference light pulse. It
is thus possible to measure polarization as a function of time by varying the timing of the
short reference light pulse.
One problem with this measurement method is that the sign of sinα cannot be deter‐
mined as long as the reference light is linearly polarized. When it is important to deter‐
mine the sign ofsinα , it is necessary to compare the two photocurrents generated by cross-
TPA for right and left circularly polarized localized lights; let us define these absorption
coefficients as

β5(e^ =
1 1
2 i
()
) (36)

and

β6(e^ =
1 1
2 −i
)( ) (37)

respectively. The sign of sinα is positive when β 6 >β 5and vice versa.

8.2. Measurement of stationary polarization

Polarization measurements were performed using the same setup as that shown in Fig. 1.
The reference light is linearly polarized and its polarization direction γ was varied in four
ways by a half- wave plate. On the other hand, for the signal light, linear polarization was
20 Photodiodes - From Fundamentals to Applications

transferred to linear, elliptical, and circular polarization by a quarter wave plate. Because the
transferred polarization is theoretically given by Eq.(13) (ϕ=π/2), it is possible to compare
with the measured results.

Figure 9 shows the measured elements of the Jones vector of the light being measured. The
circles and triangles represent the measured points, while the soid lines represent the theo‐
retical curves given by Eq. (13). Figure 9(a) shows the amplitudes of a x and a y. The meas‐
ured values agree reasonably well with the theoretical ones. Figure 9(b), on the other hand,
shows the phase difference α. The measuredα is slightly greater than the theoretical value
for almost all values of θ. Small discrepancy between measured and theoretical phase differ‐
ence α is thought to be due to wavelength chirping of the measured light as will be dis‐
cussed insection 8.4.

Figure 9. Jones vector elements of light being measured with stationary polarization. (a) Amplitudes of the compo‐
nents in the x- and y-directions. (b) Phase difference betweenx- and y-directions. Circles and triangles are measured
values. Solid lines are the theoretical values.

The light to be measured is circularly polarized (ax = ay = 1 / 2, δ = π / 2) at θ = π/ 4, whereas,

the lightis linearly polarized along the x-axis (i.e., a x =1.0and, a y =0.0)at θ= 0 and π/2.

8.3. Measurement of time-dependent polarization

The instantaneous polarization when the two light pulses overlap was measured for the
cross-TPA. It is thus possible to measure the time-dependent polarization without using
high-speed electronics using this method. An optical pulse compressed to 0.9 ps was used
for the local oscillation ^e in this measurement. The time resolution is equal to the width of
this pulse. The timing of the short reference pulse was scanned over the signal light pulse to
trace the variation of the polarization ^p of the signal light pulse.

The polarization of the light being measured was varied with time using a polarization-
maintaining fiber. The output of the gain-switched LD was made linearly polarized and its
 Two-Photon Absorption in Photodiodes 21
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polarization direction was tilted at an angle of 45° relative to the fast and slow axes of the
fiber. The propagating optical pulse was separated by the birefringence of the polarization-
maintaining fiber since components polarized along the two axes have different the propa‐
gation velocities. Consequently, the polarization of the output optical pulse was made time-
dependent. A 20-m-long polarization-maintaining fiber imparted a propagation time
difference of about 30 ps between the two components.

Figure 10. Jones vector of the output pulse from a polarization maintaining fiber. (a) amplitude along the x- and y-
axes. (b) phase difference.

Figure 10 shows the Jones vector of the output pulse of a polarization maintaining fiber. The
x- and y-axes are parallel to the fastand slow axes, respectively. Figure 10(a) shows the
measured amplitudes a x and a y.They vary due to the different group velocities of the polar‐
ized light along two axes. The head and tail of output pulse are polarized along the fast and
slow axes, respectively. Figure 10(b) shows the measured phase difference α. It is deter‐
mined by the difference in the optical lengths for polarizations along the two axes. It varies
with time due wavelength chirping and nonlinear phase shift in the fiber.

8.4. Measurement of wavelength chirping

The measured phase difference α between the optical field oscillations along the x- and y-
axes is affected by the wavelength chirping. This effect is exploited to measure the wave‐
length chirping. We consider the case when the linearly polarized signal light is injected to a
wave plate whose principal axes are tilted relative the polarization directionof the incident
light. The transit times through the wave plate differ by ΔT for components along the two
major axes of the wave plate. For, a 7λ/4 wave plate

7
ΔT = ± (38)
4ν
22 Photodiodes - From Fundamentals to Applications

where ν is the optical frequency. The linearly polarized light is converted circularly polar‐
ized light because the phase shift between polarizations along the two principal axes is7π / 2
which is equivalent to − π / 2 .

Figure 11. Measurement of wavelength chirping of optical pulse from a gain switched LD. The left vertical axis is the
phase difference between polarization components along the two principal axes of the wave plate. The right vertical
axis is the estimated wavelength chirping gradient.

As the optical frequency is shifted by the wavelength chirping during the time period of ΔT,
the optical frequencies of components polarized along the two principal axes after the pulse
passes through the wave plate differ by

dν
Δν = ΔT (39)
dt

wheredν / dt is the wavelength chirping gradient. The output pulse propagates in free space
for a length of L reaching the PD. During the propagation time, polarization components
along the two principal axis of the wave plate have different oscillation frequencies. Thus,
the optical phase difference α between the two polarization components accumulates dur‐
ing the time period L/c, where c is the speed of light. The phase difference at the position
of PD is

π L
α= − ± 2πΔν (40)
2 c
 Two-Photon Absorption in Photodiodes 23
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The light is, therefore, converted into elliptically polarized light.

Because α can be measured from the TPA of the Si-APD, the wavelength chirping gradient
dν / dt can be determined. A 7λ/4 wave plate was used instead of a conventional λ/4 wave
plate to make the phase shift sufficiently large to detect.
Figure 11 shows the measured wavelength chirping of an optical pulse from a gain-switch‐
ed LD. The linearly polarization is tilted at 45° relative to the principal axis of the 7λ/4 wave
plate. The optical pulse passes through the wave plate and propagates in 40-cm of free space.
The chirping gradient | dν / dt | is shown by the left vertical axis in Fig. 11. The measured
value is consistent with the wavelength broadening observed by an optical spectrum ana‐
lyzer. The chirping gradient is large at the head of pulse due to the asymmetry pulse shape.

8.5. Measurement of dynamic birefringence of a semiconductor optical amplifier

Semiconductor optical amplifiers (SOAs) generally exhibit birefringence due to the real
and/or imaginary parts of the optical gain having different values for transverse electric (TE)
and the transverse magnetic (TM) polarizations. The real and imaginary parts of the SOA
gain are nonlinear for intense propagating light and induce dynamic birefringence [15,16].
Intense optical pulse affects the polarization of the pulse itself. Consequently, polarization of
the output pulse from a SOA varies with time.

Figure 12. Polarization of output pulse from an SOA when the polarization of the input pulse is tilted by 45 ° degree
against the x- and y-axes. The waveform of the output pulse is also shown. (a) The closed circles and triangles show
the measured polarization directions. The open circles show the measured output waveform. (b) The closed circles
show the measured absolute value of phase difference.

A linearly polarized signal light was injected into a SOA witha polarization direction tilted
at 45 ° against TE and TM modes. Time dependent Jones vector components of the output
pulse from the SOA are measured by the cross-TPA with a reference light pulse with a pulse
width of 0.9 ps. The results are shown in Figs. 12(a) and (b). The closed circles and triangles
24 Photodiodes - From Fundamentals to Applications

in Fig. 12(a) show the measured amplitudes a e 2 and a m 2, respectively. a e and a mare the
amplitudes of the Jones vectors for TE and TM polarization. The open circles and dashed
line show the measured output pulse shape. The polarization at the head of the pulse is al‐
most the same as that of the injected light pulse. However, the carrier density modulation in
the SOA rotates the polarization because the gains for the polarizations of the TE and TM
modes have different carrier density dependences. Figure 12(b) shows the measured phase
difference α. The phase difference varies dynamically due to self-phase modulation in the
SOA as a result of the carrier density modulation and spectrum hole burning.

9. Conclusions

Photocurrents generated by TPA in PDs were studied. The ratios of nonlinear susceptibility
tensor elements were deduced from the polarization dependence of self-TPA for Si- and
GaAs-PDs. The photocurrent was isotropic for linear polarization in the Si-PD. On the other
hand, TPA is anisotropic and the photocurrent depends on the linear polarization direction
in GaAs-PD. The photocurrents for elliptically and circularly polarized light can also be ana‐
lyzed by the imaginary parts of the nonlinear susceptibility.

The polarization dependence of cross-TPA was measured for a Si-APD. Three types of cross-
TPA that are linear-linear, linear-elliptic, and circular-elliptic polarizations were studied.
The measured results agree with theoretical values calculated by using parameters obtained
from the polarization dependence of self-TPA. These results demonstrate that both self- and
cross-TPA can be well described by analysis based on the nonlinear susceptibility tensor.

Cross-TPA was applied to polarization measurements. The Jones vector elements of anarbi‐
trarily polarized signal light can be determined from the four photocurrents generated by
cross-TPA between the signal light and the linearly polarized reference light. The time reso‐
lution is limited only by the pulse width of the reference light pulse. This measurement
method can thus be used to detect rapid polarization variation. It was demonstrated that the
polarization of a light pulse from a polarization-maintaining optical fiber and a SOA can be
measured by this method.

Author details

Toshiaki Kagawa*

Address all correspondence to: [email protected]

Shonan Institute of Technology, Japan

 Two-Photon Absorption in Photodiodes 25
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References

[1] Kikuchi, K. (1998). Highly sensitive interferometricautocorrelator using Si avalanche

photodiode as two-photon absorber. Electron. Lett., 34(1), 123-125.

[2] Wielandy, S., Fishteyn, M., Her, T., Kudelko, D., & Zhang, C. (2002). Real-time meas‐
urement of accumulated dispersion for automatic dispersion compensation. Electron.
Lett., 38(20), 1198-1199.

[3] Inui, T., Mori, K., Ohara, T., Tanaka, H., Komukai, T., & Morioka, T. (2004). 160
Gbit/s adaptive dispersion equaliser using asynchronous chirp monitor with bal‐
anced dispersion configuration. Electron Lett., 40(4), 256-257.

[4] Salem, R., Tudury, G. E., Horton, T. U., Carter, G. M., & Murphy, T. E. (2005). Polari‐
zation Insensitive Optical Clock Recovery at 80 Gb/s Using a Silicon Photodiode.
IEEE Photon. Technol. Lett., 17(9), 1968-1970.

[5] Butcher, P. N., & Cotter, D. (1990). The Elements of Nonlinear Optics. , Cambridge
Studies in Modern Optics: Cambridge University Press.

[6] Boyd, R. W. (2003). Nonlinear Optics:, Academic Press.

[7] Dvorak, M. D., Schroeder, W. A., Andersen, D. R., Amirl, A. L., & Wherett, B. S.
(1994). Measurement of the Anisotropy of Two-Photon Absorption Coefficients in
Zincblende Semiconductors. IEEE J. Quantum Electron., 30(2), 256-268.

[8] Kagawa, T. (2011). Polarization Dependence of Two-Photon Absorption in Si and

GaAs Photodiodes at a Wavelength of 1.55 μm. Jpn. J. Appl. Phys., 50, 122203.

[9] Hutchings, D. C., & Wherett, B. S. (1994). Theory of anisotropy of two-photon ab‐
sorption in zinc-blende semiconductors. Phys. Rev. B, 49(4), 2418-2426.

[10] Murayama, M., & Nakayama, T. (1995). Ab initio calculation of two-photon absorp‐
tion spectra in semiconductors. Phys. Rev.B, 52(7), 4986-4995.

[11] Yu, P. T., & Cardona, M. (2005). Fundamentals of Semiconductors, 3 rd ed.:Springer.

[12] Cardona, M., & Pollak, F. H. (1966). Energy-Band Structure of Germanium and Sili‐
con: The kp Method. Phys. Rev., 142(2), 530-543.

[13] Kagawa, T., & Ooami, S. (2007). Polarization dependence of two-photon absorption
in Si avalanche photodiode. Jpn. J. Appl. Phys., 46(2), 664-668.

[14] Kagawa, T. (2008). Measurement of Constant and Time-Dependent Polarizations Us‐

ing Two-Photon Absorption of Si Avalanche Photodiode. Jpn. J. Appl. Phys., 47(3),
1628-1631.

[15] Dorren, H. J. S., Lenstra, D., Liu, T., Hill, T., & Khoe, G. D. (2003). Nonlienar Polariza‐
tion Rotation in Semiconductor Optical Amplifiers: Theory and Application to All-
Optical Flip-Flop Memories. IEEE J. Quantum Electron., 30(1), 141-148.
26 Photodiodes - From Fundamentals to Applications

[16] Takahashi, Y., Neogi, A., & Kawaguchi, H. (1998). Polarization-Dependent Nonlinear

Gain in Semiconductor Lasers. IEEE J. Quantum Electron., 34(9), 1660-1672.

 Chapter 2

Physical Design Fundamentals of High-Performance

Avalanche Heterophotodiodes with Separate
Absorption and Multiplication Regions

Viacheslav Kholodnov and Mikhail Nikitin

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/50778

1. Introduction

Minimal value of dark current in reverse biased p − n junctions at avalanche breakdown is

determined by interband tunneling. For example, tunnel component of dark current be‐
comes dominant in reverse biased p − n junctions formed in a number semiconductor ma‐
terials with relatively wide gap Eg already at room temperature when bias V b is close to
avalanche breakdown voltage V BD (Sze, 1981), (Tsang, 1981). The above statement is ap‐
plicable, for example, to p − n junctions formed in semiconductor structures based on ter‐
nary alloy I n0.53Ga0.47 As which is one of the most important material for optical
communication technology in wavelength range λ up to 1.7 μm (Tsang, 1981), (Stillman,
1981), (Filachev et al, 2010), (Kim et al, 1981), (Forrest et al, 1983), (Tarof et al, 1990), (Ito
et al, 1981). Significant decreasing of tunnel current can be achieved in avalanche photo‐
diode (APD) formed on multilayer heterostructure (Fig. 1) with built-in p − n junction
when metallurgical boundary of p − n junction (x = 0) lies in wide-gap layer of heterostruc‐
ture (Tsang, 1981), (Stillman, 1981), (Filachev et al, 2010), (Kim et al, 1981), (Forrest et al,
1983), (Tarof et al, 1990), (Clark et al, 2007), (Hayat & Ramirez, 2012), (Filachev et al,
2011). Design and specification of heterostructure for creation high performance APD
must be such that in operation mode the following two conditions are satisfied. First,
space charge region (SCR) penetrates into narrow-gap light absorbing layer (absorber)
and second, due to decrease of electric field E (x) into depth from x = 0 (Fig. 1), process of
avalanche multiplication of charge carriers could only develop in wide-gap layer. This
concept is known as APD with separate absorption and multiplication regions (SAM-
28 Photodiodes - From Fundamentals to Applications

APD). Suppression of tunnel current is caused by the fact that higher value of E corre‐
sponds to wider gap Eg . Electric field in narrow-gap layer is not high enough to produce
high tunnel current in this layer. Dark current component due to thermal generation of
charge carriers in SCR (thermal generation current with density J G ) is proportional to in‐
trinsic concentration of charge carriers ni ∝ exp( − Eg / 2kB T ), here kB – Boltzmann constant,
T – temperature (Sze, 1981), (Stillman, 1981). Tunnel current density J T grows considera‐
bly stronger with narrowing Eg than ni and depends weakly on T (Stillman, 1981), (Bur‐
stein & Lundqvist, 1969). Therefore, component J T will prevail over J G in semiconductor
structures with reasonably narrow gap Eg even at room temperature. Another dark cur‐
rent component − diffusion-drift current caused by inflow of minority charge carriers into
SCR from quasi-neutral regions of heterostructure is proportional to ni2 × N −1 (Sze, 1981),
(Stillman, 1981) (where N is dopant concentration). To eliminate it one side of p − n junc‐
tion is doped heavily and narrow-gap layer is grown on wide-gap isotype heavily doped
+ +
substrate (Tsang, 1981). Thus heterostructure like as pwg − nwg − nng − nwg is the most opti‐
mal, where subscript ‹wg › means wide-gap and ‹ng › − narrow-gap, properly. To ensure
tunnel current’s density not exceeding preset value is important to know exactly allowa‐
ble variation intervals of dopants concentrations and thicknesses of heterostructure’s lay‐
ers. Thickness of narrow-gap layer W 2 is defined mainly by light absorption coefficient γ
and speed-of-response. But as it will be shown further tunnel current’s density depends
strongly on thickness of wide-gap layer W 1 and dopant concentrations in wide-gap N 1
and narrow-gap N 2 layers. Approach to optimize SAM-APD structure was proposed in
articles (Kim et al, 1981), (Forrest et al, 1983) (see also (Tsang, 1981)). Authors have devel‐
oped diagram for physical design of SAM-APD based on heterostructure including
I n0.53Ga0.47 As layer. However, diagram is not enough informative, even incorrect signifi‐
cantly, and cannot be reliably used for determining allowable variation intervals of heter‐
ostructure’s parameters. The matter is that diagram was developed under assumption
+
that when electric field E (x) (see Fig. 1b) at metallurgical boundary of pwg − nwg junction
E (0) ≡ E1 is higher than 4.5×105 V/cm then avalanche multiplication of charge carriers oc‐
+
curs in InP layer where pwg − nwg junction lies at any dopants concentrations and thick‐
nesses of heterostructure’s layers. However, electric field E1 = E1BD at which avalanche
breakdown of p − n junction occurs depends on both doping and thicknesses of layers
(Sze, 1981), (Tsang, 1981), (Osipov & Kholodnov, 1987), (Kholodnov, 1988), (Kholodnov,
1996-2), (Kholodnov, 1996-3), (Kholodnov, 1998), (Kholodnov & Kurochkin, 1998). As a
consequence, avalanche multiplication of charge carriers in considered heterostructure can
either does not occur at electric field value E1=4.5×105 V/cm or occurs in narrow-gap layer
(Osipov & Kholodnov, 1987), (Osipov &, Kholodnov, 1989). Value of electric field re‐
quired to initialize avalanche multiplication of charge carriers can even exceed E1BD (Sze,
1981), (Osipov & Kholodnov, 1987), (Kholodnov, 1996-2), (Kholodnov, 1996-3), (Kholod‐
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 29
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nov, 1998), (Kholodnov & Kurochkin, 1998) that has physical meaning in the case of tran‐
sient process only (Groves et al, 2005), (Kholodnov, 2009). Further, in development of
diagram was assumed that maximal allowable value of electric field in absorber at hetero-
interface with multiplication layer E2 (see Fig. 1b) is equal to 1.5×105 V/cm. But tunnel
current density J T in narrow-gap absorber I n0.53Ga0.47 As (Osipov & Kholodnov, 1989) is
much smaller at that value of electric field than density of thermal generation current J G
which in the best samples of InP − I n0.53Ga0.47 As − InP heterostructures (Tsang, 1981), (Tar‐
of et al, 1990), (Braer et al, 1990) can be up to 10-6 A/cm2. However, diagram does not take
into account the fact that tunnel current in wide-gap multiplication layer can be much
greater than in narrow-gap absorber (Osipov & Kholodnov, 1989). Therefore, total tunnel
current can exceed thermal generation current.

In present chapter is done systematic analysis of interband tunnel current in avalanche het‐
erophotodiode (AHPD) and its dependence on dopants concentrations N 1 in nwg wide-gap
and N 2 in nng narrow-gap layers of heterostructure and thicknesses W 1 and W 2, respectively
(Fig. 1) and fundamental parameters of semiconductor materials also. Performance limits of
AHPDs are analyzed (Kholodnov, 1996). Formula for quantum efficiency η of heterostruc‐
ture is derived taking into account multiple internal reflections from hetero-interfaces. Con‐
centration-thickness nomograms were developed to determine allowable variation intervals
of dopants concentrations and thicknesses of heterostructure layers in order to match preset
noise density and avalanche multiplication gain of photocurrent. It was found that maximal
possible AHPD’s speed-of-response depends on photocurrent’s gain due to avalanche mul‐
tiplication, as it is well known and permissible noise density for preset value of photocur‐
rent’s gain also. Detailed calculations for heterostructure InP − I n0.53Ga0.47 As − InP are
performed. The following values of fundamental parameters of InР (I, Fig. 1) and
I n0.53Ga0.47 As (II, Fig. 1) materials (Tsang, 1981), (Stillman, 1981), (Kim et al, 1981), (Forrest et
al, 1983), (Tarof et al, 1990), (Ito et al, 1981), (Braer et al, 1990), (Stillman et al, 1983), (Bur‐
khard et al, 1982), (Casey & Panish, 1978) are used in calculations: band-gaps E g 1= 1.35 eV
and E g 2= 0.73 eV; intrinsic charge carriers concentrations ni(1)=108 сm-3 and ni(2)=5.4×1011 сm-3;
relative dielectric constants ε1 = 12.4 and ε2=13.9; light absorption coefficient in I n0.53Ga0.47 As
γ =104 сm-1; specific effective masses m * = 2mc × mv / (mc + mv ) of light carriers m1= 0.06m0 and
m2= 0.045m0, where m0 – free electron mass. The chapter material is presented in analytical
form. For this purpose simple formulas for avalanche breakdown electric field E BD and volt‐
age V BD of p − n junction are derived taking into account finite thickness of layer. Analytical
expression for exponent in well-known Miller’s relation was obtained (Sze, 1981), (Tsang,
1981), (Miller, 1955) which describes dependence of charge carriers’ avalanche multiplica‐
tion factors on applied bias voltage V b. It is shown in final section that Geiger mode (Groves
et al, 2005) of APD operation can be described by elementary functions (Kholodnov, 2009).
30 Photodiodes - From Fundamentals to Applications

Figure 1. Energy diagram of heterostructure in operation mode (a) and electric field distribution in it (b). Ec and Ev −
energy of conduction band bottom and valence band top. Solid lines − N 2 = N 2(1), dashed − N 2 > N 2(1)

2. Formulation of the problem: Basic relations

+ +
Let’s consider pwg − nwg − nng − nwg heterostructure at reverse bias V b sufficient to initialize
avalanche multiplication of charge carries. This structure is basic for fabrication of AHPDs.
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 31
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From relations (Sze, 1981), (Tsang, 1981), (Filachev et al, 2011), (Grekhov & Serezhkin, 1980),
(Artsis & Kholodnov, 1984)

Ln Ln
% (-L , L ) =
Mn = M( - Lp ), M p = M( Ln ), M p n ò g( x) M( x)dx ò g( x)dx , (1)
- Lp - Lp

Ln éx ù
M( x) = Y ( x , - Lp ) (1 - m) , m( - Lp , Ln ) = ò a( x)Y ( x , -Wp )dx , Y ( x , x0 ) = exp ê ò (b - a)dx¢ú
êx ú
(2)
- Lp ë 0 û

can be determined, in principal, dependences of multiplication factors M in p − n structures

on V b, where M n and M p – multiplication factors of electrons and holes inflow into space
charge region (SCR); value of multiplication factor of charge carriers generated in SCR M̃
lies between M n and M р ; specific rate of charge carriers’ generation in SCR g = gd + g ph con‐
sists of dark gd and photogenerated g ph components; L p and L n – thicknesses of SCR in p
and n sides of structure; α(E ) and β(E )= K (E ) × α(E ) – impact ionization coefficients of elec‐
trons α(E ) and holes β(E ); Е(х) – electric field. Let’s denote by N 1 pt dopant concentration N 1
so that for N 1 < N 1 pt “punch-through” (depletion) of nwg layer occurs that means penetration
of non-equilibrium SCR into nng layer (Fig. 1). Optical radiation passing through wide-gap
window is absorbed in nng layer and generates electron-holes pairs in it. When N 1 < N 1 pt
then photo-holes appearing near nwg /nng heterojunction (х = W 1) are heated in electric field of
non-equilibrium SCR and, at moderate discontinuities in valence band top Ev at х = W 1, pho‐
to-holes penetrate into nwg layer (layer I) due to emission and tunneling. If W 1 is larger than
some value W 1min(N 1, N 2, W 2) (Osipov & Kholodnov, 1989), which is calculated below, then
avalanche multiplication of charge carriers occurs only in nwg layer, i.e. photo-holes fly
through whole region of multiplication. In this case photocurrent’s gain (Tsang, 1981), (Art‐
+
sis & Kholodnov, 1984) M ph =M р . Let pwg layer is doped so heavy that avalanche multiplica‐
tion of charge carriers in it can be neglected (Kholodnov, 1996-2), (Kholodnov & Kurochkin,
1998). Under these conditions thicknesses in relations (1) and (2) can be put L p = 0 and
L n = W 1, i.e.

M ph = Y (W1 ,0) / [1 - m(0, W1 )] (3)

It is remarkable that responsivity SI (λ) (where λ – is wavelength) of heterostructure increas‐

es dramatically once SCR reaches absorber nng (layer II on Fig. 1) and then depends weakly
on bias V b till avalanche breakdown voltage value V BD (Stillman, 1981). This effect is caused
by potential barrier for photo-holes on nwg /nng heterojunction and heating of photo-holes in
32 Photodiodes - From Fundamentals to Applications

electric field of non-equilibrium SCR. If losses due to recombination are negligible (Sze,
1981), (Tsang, 1981), (Stillman, 1981), (Forrest et al, 1983), (Stillman et al, 1983), (Ando et al,
1980), (Trommer, 1984), for example, at punch-through of absorber, then SI (λ) in operation
mode is determined by well-known expression (Sze, 1981), (Tsang, 1981), (Stillman, 1981),
(Filachev et al, 2011):

l
SI (l ) = h(l ) ´ ´ M ph (4)
1.24

where λ in μm and value of quantum efficiency η is considered below. Photocurrent gaining

and large drift velocity of charge carriers in SCR allow creating high-speed high-perform‐
ance photo-receivers with APDs as sensitive elements (Sze, 1981), (Tsang, 1981), (Filachev et
al, 2010), (Filachev et al, 2011), (Woul, 1980). Reason is high noise density of external elec‐
tronics circuit at high frequencies or large leakage currents that results in decrease in Noise
Equivalent Power (NEP) of photo-receiver with increase of М ph despite of growth APD’s
noise-to-signal ratio (Tsang, 1981), (Filachev et al, 2011), (Woul, 1980), (McIntyre, 1966). De‐
opt
crease in NEP takes place until М ph becomes higher then certain value М ph above which
noise of APD becomes dominant in photo-receiver (Sze, 1981), (Tsang, 1981), (Filachev et al,
2011), (Woul, 1980). Even at low leakage current and low noise density of external electron‐
ics circuit, avalanche multiplication of charge carriers may lead to degradation in NEP of
photo-receiver due to decreasing tendency of signal-to-noise ratio dependence on APD’s
М ph under certain conditions (Artsis & Kholodnov, 1984). Moreover, excess factor of avalan‐
che noise (Tsang, 1981), (Filachev et al, 2011), (Woul, 1980), (McIntyre, 1966) may decrease
with powering of avalanche process as, for example, in metal-dielectric-semiconductor ava‐
lanche structures, due to screening of electric field by free charge carriers (Kurochkin &
Kholodnov 1999), (Kurochkin & Kholodnov 1999-2). Using results obtained in (Artsis &
+ +
Kholodnov, 1984), (McIntyre, 1966), noise spectral density SN of pwg − nwg − nng − nwg hetero‐
structure which performance is limited by tunnel current can be written as:

2
2
SN = 2 ´ q ´ AS ´ M ph ´ å JT ,i (V )Fef ,i ( M ph ), (5)
i =1

where q – electron charge; АS – cross-section area of APD’s structure; F ef ,i (M ph ) – effective

noise factors (Artsis & Kholodnov, 1984) in wide-gap multiplication layer (i = 1) and in ab‐
sorber (i = 2); J T ,i (V ) – densities of primary tunnel currents in those layers, i.e. tunnel cur‐
rents which would exist in layers I and II in absence of multiplication of charge carriers due
to avalanche impact generation. Comparison of two different APDs in order to determine
which one is of better performance is reasonable only at same value of М ph . Expression (5)
shows, that for preset gain of photocurrent, noise density is determined by values of pri‐
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 33
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mary tunnel currents I T 1 = J T 1 × AS and I T 2 = J T 2 × AS (total primary tunnel current I T = I T 1+

I T 2). Distribution of electric field Е(х) that should be known to calculate parameters (4) and
(5) of AHPD is obtained from Poisson equation and in layers I and II is determined by ex‐
pressions:

æ qN1x ö
E( x) = çç E1 - ÷ ´ U _(l1 - x), (6)
è e0e1 ÷ø

é qN 2 ù
E( x) = ê E2 - ( x - W1 ) ú ´ U _(W1 + l2 - x), (7)
ëê e e
0 2 ûú

Where

æe qN1W1 ö
E2 = çç 1 E1 - ÷ ´ U _(l1 - W1 ), (8)
e
è 2 e0e 2 ÷ø

ei e0
li = E ´ U + (Wi - li ) + Wi ´ U _(li - Wi ), (9)
qN i i

U −(x) and U +(x) – asymmetric unit stepwise functions (Korn G. & Korn T., 2000), ε0 – dielectric
constant of vacuum, ε1 and ε2 – relative dielectric permittivity of nwg and nng layers (Fig. 1).

3. Avalanche multiplication factors of charge carriers in p-n structures

3.1. Preliminary remarks: Avalanche breakdown field

For successful development of semiconductor devices using effects of impact ionization and
avalanche multiplication of charge carriers is necessary to know dependences of avalanche
multiplication factors M (V ) of charge carriers in p − n structures on applied bias V b. We
need to know among them dependence of avalanche breakdown voltage V BD on parameters
of p − n structure and distribution of electric field E (x) related to V BD dependence. Usual
way to compute required dependencies is based on numerical processing of integral rela‐
tions (1) and (2) in each case. Impact ionization coefficients of electrons α(E ) and holes β(E )
depend drastically on electric field E . At the same time theoretical expressions for α(E ) and
β(E ) include usually some adjustable parameters. Therefore, to avoid large errors in calcu‐
lating of multiplication factors, in computation of (1) and (2) are commonly used experimen‐
tal dependences for α(E ) and β(E ). Avalanche breakdown voltage V BD is defined as applied
34 Photodiodes - From Fundamentals to Applications

bias voltage at which multiplication factor of charge carriers tends to infinity (Sze, 1981),
(Tsang, 1981), (Miller, 1955), (Grekhov & Serezhkin, 1980). Therefore, as seen from (2),
breakdown condition is reduced to integral equation with m = 1 where field distribution E (x)
is determined by solving Poisson equation. Bias voltage at which breakdown condition
V = V BD is satisfied can be calculated by method of successive approximations on computer.
Thus, this method of determining V BD and, hence, E (x) at V = V BD requires time-consuming
numerical calculations. The same applies to dependence M on V . Similar calculations were
performed for a number of semiconductor structures for certain thicknesses of diode’s base
by which is meant high-resistivity side of p + − n homojunction or narrow-gap region of het‐
erojunction (Kim et al, 1981), (Stillman et al, 1983), (Vanyushin et al, 2007). In addition to
great complexity, there are other drawbacks of this method of M (V ) and V BD determination
– difficulties in application and lack of illustrative presentation of working results. Availa‐
bility of analytical, more or less universal expressions would be very helpful to analyze dif‐
ferent characteristics of devices with avalanche multiplication of charge carriers, for
example, expression describing E (x), when we estimate tunnel currents in AHPDs. In this
section are presented required analytical dependences (Osipov & Kholodnov, 1987), (Kho‐
lodnov, 1988), (Kholodnov, 1996-3). For quick estimate of breakdown voltage in abrupt
p + − n homojunction or heterojunction is often used well-known Sze-Gibbons approximate
expression (Sze, 1981), (Sze & Gibbons, 1966):

VBD = AV ´ N -( s - 2)/ s , V, (10)

where

( )
3/ 2
s = 8, AV = 6 ´ 1013 ´ Eg / 1.1 , (11)

Gap Eg of semiconductor material forming diode’s base and dopant concentration N in it

are measured in eV and cm-3, properly. As follows from Poisson equation, voltage value giv‐
en by (10) corresponds to value of electric field at metallurgical boundary (x = 0, Fig. 2) of
p + − n junction:

E(0) = EBD = A ´ N 1/ s , (12)

where at s = 8

3/ 4
1.2 ´ q æ Eg ö
A= ´ç ÷ ´ 1010 , (13)
ee0 ç ee ÷
è 0ø
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 35
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ε0 and ε − dielectric constant of vacuum and relative dielectric permittivity of base material;
q − electron charge. Unless otherwise stated, in formulas (12) and (13) and below in sections
3.1-3.3 is used SI system of measurement units.

Figure 2. Schematic drawing of diode based on p + − n − n + heterostructure (a) and distribution of electric field in it at
avalanche breakdown voltage (b); 1 − N 1 = N 1(0), 2 − N 1 > N 1(0); N 1 − dopant concentration nwg in wide-gap layer I

Formulas (10) and (11) cannot be used for reliable estimates of V BD and E BD in semiconduc‐
tor structures with thin enough base. Indeed, dependence of V BD on N is due to two factors.
36 Photodiodes - From Fundamentals to Applications

First, as follows from Poisson equation, the larger N the steeper the field E (x) decreases into
the depth from x = 0 comparing to value E1 = E (0) (Fig. 1b). Second, value of electric field
E1 = E (0) at V = V BD falls with decreasing of N due to decreasing of | ∇ E | in SCR. Drop of
E (x) becomes more weaker with decreasing of N (Fig. 1b), therefore, at preset base’s thick‐
ness W , initiation of avalanche process will require fewer and fewer field intensity E1. At
sufficiently low concentration N , the lower the thicker W will be, variation of electric field
E (x) on the length of base is so insignificant that probability of impact ionization becomes
practically the same in any point of base. It means that breakdown voltage V BD and field
E BD are independent on N and at the same time are dependent on W , moreover, the thinner
W then, evidently, the higher E BD . So using of formulas (10) and (11) at any values of W ,
that done in many publications, contradicts with above conclusion. In next section 3.2 will
be shown that value of breakdown field of stepwise p + − n junction in a number of semicon‐
ductor structures can be estimated by following formula:

1/ s
é N ù
EBD ( N , W ) = EBD (0, W ) ´ ê1 + , (14)
% (W ) ú
N
ë û

where

1/( s -1)
æ ee ´ A ö
EBD (0, W ) = A ´ ç 0 ÷ , (15)
è s´q´W ø

s /( s -1)
% (W ) = æç ee 0 ´ A ö÷
N . (16)
è s´q´W ø

It seen from expression (14) that at N < Ñ (W ) electric field of avalanche breakdown E BD is
practically independent on dopant concentration N in diode’s base.

3.2. Avalanche breakdown field

+ +
Consider pwg − nwg − nng − nwg heterostructure (Fig. 2). Symbols nwg and nng indicate to un‐
equal, in general, doping of high-resistivity layers of structure. Denote as W 1, W 2 and N 1,
N 2 thicknesses of nwg and nng layers and dopant concentrations in them, properly. Case
W 2 = 0 corresponds to diode formed on homogeneous p + − n − n + structure. Let values N 1 and
W 1 such that upon applying avalanche breakdown voltage V BD to structure, SCR penetrates
into narrow-gap nng layer (Fig. 2). When W 1 and N 1, N 2 are small enough and W 2 is thick
enough then avalanche process develops in nng layer. In other words, with increasing bias
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 37
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V b applied to heterostructure, electric field E = E2 in narrow-gap layer on nwg /nng heterojunc‐

tion (Fig. 2) reaches avalanche breakdown field E2BD in this layer earlier than electric field E1
on metallurgical boundary (х = 0) of p + − n junction becomes equal to breakdown field E1BD
in wide-gap nwg layer. This is due to the fact that at small values of W 1 and N 1 variation of
field E (х) within wide-gap layer is insignificant and probability of impact ionization in nar‐
row-gap layer is much higher than in wide-gap. If, however, W 1 and N 1, N 2 are large
enough and W 2 thin enough, then avalanche process is developed in wide-gap nwg layer on‐
ly. For these values of thicknesses and concentrations electric field E1 reaches value E1BD
earlier than E2 – value E2BD . Because of significant decreasing of electric field E (х) in nwg
layer with increasing distance from х = 0, field E2 remains smaller E2BD despite the fact that
band-gap E g 1 in nwg layer is wider than band-gap E g 2 in nng layer. Distribution of electric
field E (x) in nwg and nng layers of considered heterostructure is obtained by solving Poisson
equation as defined by (6)-(9). When avalanche breakdown voltage V BD is applied to struc‐
ture, then either E1 = E1ВD (N 1, W 1) or E2 = E2ВD (N 2, W 2). In section 3.1 is noted that at low
enough concentrations N i avalanche breakdown fields EiBD (N i , W i ) should not depend on
N i and have definite value depending on W i , where i = 1, 2. To account for this effect, for‐
mula (12) should be modified so that when N → 0 then breakdown field E BD tends to some
non-zero value. It would seem that it is enough to add some independent on N constant to
right side of (12). It is easy to see that such modification of formula (12) leads to contradic‐
tion. To verify that let’s consider situation when avalanche multiplication of charge carriers
occurs in nwg layer, i.e. E1 is close to E1ВD and multiplication factor of holes Мр (1) is fixed.
Then, with increasing concentration N 1, field EI (W 1) (Fig. 2b) shall be monotonically falling
function of N 1. Indeed, with increasing N 1, field E1ВD and | ∇ EI (x) | are increasing also. In‐
creasing | ∇ EI | must be such that when x became larger some value x̄ then value EI (x) has
decreased (Fig. 2b). Otherwise, field E (x) would increase throughout SCR that reasonably
would lead to growth of Мр . This is evident from (1) and (2). On the other hand, adding con‐
stant to right side of expression (12) does not change ∂ E1BD / ∂ N 1 and therefore results in, as
follows from (6) and (9), non-monotonic dependence EI (W 1) on N 1. Equation (14) which can
be rewritten for each of nwg and nng layers as:

EiBD ( N i , Wi ) = Ai ´ [ N i + N% i (Wi )]1/ s (17)

does not lead to that and other contradictions, From (17) follows that:

s
% (W ) = éê EiBD (0, Wi ) ùú
N (18)
i i
êë Ai úû
38 Photodiodes - From Fundamentals to Applications

To determine dependences EiBD (0, W i ), let’s consider behavior of EI (W 1) when parameters

of heterostructure N 1, N 2 and W 2 are varying. From (6)-(9), (17) and (18) we find that when
value

s
æ e ´ A1 ö
D = N 2 + N% 2 (W2 ) - çç 1 ÷÷ ´ N% 1 (W1 ) > 0 (19)
è e 2 ´ A2 ø

then avalanche breakdown is controlled by nwg layer. It means that

qN 1 × W 1
EI (W 1) = E1ВD (N 1, W 1) − (20)
ε0ε1

If, however, Δ < 0 then avalanche breakdown is controlled by nwg /nng heterojunction, i.e.

ε2
EI (W 1) = E (N , W 2) (21)
ε1 2ВD 2

From (17)-(21) we obtain that

ì A1 % (1/ s) -1 q ´ W1
¶EI (WI ) ï ´ N1 - , at D > 0
N1 ® 0 =í s e 0 e1 (22)
¶N1 ï0
î , at D < 0

Formulas (15) and (16) follow from expressions (18), (19) and requirement (23)

ïì ¶E (W ) ïü ïì ¶E (W ) ïü
lim í I I N1 ® 0 ý = lim í I I N1 ® 0 ý (23)
î ¶N1
D®-0 ï
þï D®+0
îï ¶N1 þï

which means smoothness of field dependence E (x) in real heterostructures, where parame‐
ters are varying continuously. Particularly, in semiconductors for which relations (11) and
(13) are valid, breakdown field at metallurgical boundary of p + − n junction (or at heterojunc‐
tion boundary, in narrow-gap layer of heterojunction, including isotype) can be described
by formula

1/8
é N ù
EBD ( N , W ) = EBD (0, W ) ´ ê1 + (24)
% (W ) ú
N
ë û
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 39
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where

E BD (0, W ) = X ε3/7 × X g−6/7 × EВD

(InP )
(0, W ); Ñ (W ) = X ε−4/7 × X g−6/7 Ñ InP (W ) (25)

And values for InP semiconductor widely used for manufacturing of AHPDs (Tsang, 1981),
(Stillman, 1981), (Filachev et al, 2010), (Filachev et al, 2011) are as follows:

(InP )
EВD (0, W ) = 4.3 × 105 × W −1/7
, V / cm; Ñ InP (W ) = 3.4 × 1015 × W −8/7
, cm −3 (26)

X ε = 12.4 / ε, X g = 1.35 / Eg and gap Eg in diode’s base is measured in eV and its thickness W
– in μm, respectively.

3.3. Avalanche breakdown voltage

It follows from expressions (6)-(9) and (14)-(16) that breakdown voltage V BD for p + − n − n +
structure is given by expressions

2/ s
ee0 2 é N% (W ) ù -
s-2
é N % (W ) ù 2/ s -
s-2 % 1
N
VBD = A ´ ê1 + ú ´ N s º A ´ 1+
V ê ú ´N
s , if < (27)
2q ë N û ë N û N q

i.e. when diode’s base is not punch-through and

ìé N ù
1/ s
N ü N% 1
ï ï
VBD ( N , W ) = VBD (0, W ) ´ í ê1 + ú - ý , if > (28)
%
N (W ) û %
2 s ´ N (W ) ï N q
îï ë þ

i.e. when diode base is punch-through. In expression (28)

1
s-2
æ ee ´ A ö s -1 (29)
VBD (0, W ) = A ´ ç 0 ÷ ´ W s -1
è s´q ø

Value of parameter θ is defined from equation θ = s × (1 + θ)1/s and with good degree of accu‐
racy it equals to s s/(s−1). Because θ > > 1, therefore expression (27) practically coincides with
formula (10), i.e. V ВD of diode with thick base is independent on its thickness W . For diodes
with thin base formed on semiconductors with parameters satisfying relations (11) and (14),
namely when
40 Photodiodes - From Fundamentals to Applications

7 /8
æ 15 ö
% ( N ) = 9 ´ X -1/ 2 ´ X -3/ 4 ´ ç 3 ´ 10 ÷
W £W (30)
e g ç N ÷
è ø

breakdown voltage of diode depends on W and N as follows

VBD ( N , W ) = VBD (0, W ) ´

éæ N ö
1/8
N ù (31)
´ êç 1 + Xe4/7 ´ X g6/7 ´ W 8/7 ´ 15 ÷ - X 4/7
e ´ X 6/7
g ´ W 8/7
´ 18
ú
êè 2.65 ´ 10 ø 4.24 ´ 10 ú
ë û

where

VBD (0, W ) = 43.1 ´ Xe3/7 ´ X g-6/7 ´ W 6/7 (32)

In expressions (30)-(32) X ε = 12.4 / ε, X g = 1.35 / Eg and gap Eg in base, dopant concentration

in it N and thickness W is measured in eV, cm-3 and μm, respectively.
Avalanche breakdown voltage of double heterostructure discussed in Section 4 (Fig. 1) de‐
pends on relations between fundamental parameters of materials of nwg and nng layers, their
thicknesses and doping, and is determined, as follows from (6)-(9) and (14)-(16), by different
combinations (with slight modification) of expressions (27)-(29) for these layers of hetero‐
structure.

3.4. About correlation between impact ionization coefficients of electrons and holes

One of main goals of many experimental and theoretical studies of impact ionization phe‐
nomenon in semiconductors is to determine impact ionization coefficients of electrons α(E )
and holes β(E ) as functions of electric field E (Sze, 1981), (Tsang, 1985), (Grekhov & Serezh‐
kin, 1980), (Stillman & Wolf, 1977), (Dmitriev et al, 1987). Parameters of some semiconductor
devices, for example, APDs (Sze, 1981), (Filachev et al, 2011), (Artsis & Kholodnov, 1984),
(Stillman & Wolf, 1977) depend significantly on ratio K (E) = β(E) / α(E). Performance of APD
can be calculated on computer if α(E ) and β(E ) are known (Sze, 1981), (Tsang, 1985), (Fila‐
chev et al, 2011), (Grekhov & Serezhkin, 1980), (Stillman & Wolf, 1977), (Dmitriev et al,
1987). Dependences α(E ) and β(E ) are known, with greater or lesser degree of accuracy, for
a number of semiconductors (Sze, 1981), (Tsang, 1985), (Grekhov & Serezhkin, 1980), (Still‐
man & Wolf, 1977), (Dmitriev et al, 1987). However in works concerned determination of
impact ionization coefficients the problem of interrelation between α(E ) and β(E ) has never
been put. Even so, laws of conservation of energy and quasi-momentum in the act of impact
ionization are maintained mainly by electron-hole subsystem of semiconductor (Tsang,
1985), (Grekhov & Serezhkin, 1980), (Dmitriev et al, 1987). Therefore, there is a reason to hy‐
pothesize some correlation between α(E ) and β(E ), although perhaps not quite unique, for
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 41
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example, owing to big role of phonons in formation of distribution functions. It is shown in

this section that for number of semiconductors the following approximate relation is satis‐
fied (Kholodnov, 1988)

7
æ 10 5 ö a( E) - b( E) e3
Z( E , a( E), b( E)) º 9 ´ 10 2 ´ ç ´ = C( E) ´ Z0 » Z0 º 6 ,
ç E ÷÷ é a( E) ù Eg (33)
è ø ln ê
b( E ) ú
ë û

Where: ε – relative dielectric permittivity, and gap Eg , electric field E , α and β are measured
in eV, V/cm and 1/cm, properly.

To derive relation (33) let’s consider thin p + − n − n + structure in which thickness of high-re‐
sistivity base layer W satisfies to inequality

1- s
Aee 0
W < W0 = ´N s (34)
qs

where ε0 – dielectric constant of vacuum; ε – relative dielectric permittivity of base material;

q – electron charge; s and A – constants defining dependence of electric field E BD ≈ A × N 1/s
at metallurgical boundary (x = 0) of abrupt p + − n junction on dopant concentration N in base
for avalanche breakdown in thick p + − n − n + structure (Sections 3.1-3.3, (Sze, 1981), (Grekhov
& Serezhkin, 1980), (Sze & Gibbons, 1966)). When condition (34) is satisfied then avalanche
breakdown field can be written as

1
æ Aee0 ö s -1 (35)
EBD (W ) » A ´ ç ÷
è sqW ø

And, under these conditions, variation of electric field Е(x) along length of base W is so in‐
significant that probability of impact ionization is practically the same in any point of base
of considered structure. For many semiconductors including Ge, Si, GaAs, InP, GaP rela‐
tions given below are valid (Sze, 1981), (Kholodnov, 1988-2), (Kholodnov, 1996), (Sze & Gib‐
bons, 1966)

3/ 4
1.2q æ Eg ö
s = 8, A = ´ç ÷ ´ 1010 , (36)
ee0 ç 11q ÷
è ø

In this case as it follows from (34) and (35)

42 Photodiodes - From Fundamentals to Applications

7 /8
1 æ 3 ´ 1015 ö
W0 = ´ e ´ Eg3/ 4 ´ ç , (37)
4 ç N ÷÷
è ø

And avalanche breakdown electric field for thin p + − n − n + structure is defined by approxi‐
mate universal formula

3/7
æ E2 ö 106
g
EBD (W ) » ç ÷ ´ , (38)
ç e ÷ W 1/7
è ø

In expressions (37) and (38) and below in this Section 3.4 concentration is measured in cm-3,
energy – in eV, length – in μm, electric field – in V/cm. On the other hand condition of ava‐
lanche breakdown of p + − n − n + structure (Sections 2, 3.1 and (Sze, 1981), (Tsang, 1985), (Gre‐
khov & Serezhkin, 1980), (Stillman & Wolf, 1977))

{ }
W x

m(0, W ) = ∫ α(E (x)) × exp ∫ β(E (x )) − α(E(x )) d x

0 0
′ ′ ′
dx = 1, (39)

takes the form

é a( EBD ) ù
W ´ [a( EBD ) - b( EBD )] = ln ê ú, (40)
ë b( EBD ) û

That means the same probability of impact ionization in any point of diode’s base. And rela‐
tion (33) follows from expressions (38) and (40). Let’s estimate applicable electric field inter‐
val for this relation. Expression (38) will be valid when inequality (41) is satisfied both for
electrons and for holes

æW ö
EBD (W ) ´ W > çç ´ ER + Eion ÷÷ ´ 10 4 (41)
è lR ø

where λR , Еion , ЕR – mean free path for charge carriers scattered by optical phonons, thresh‐
old ionization energy of electrons or holes and energy of Raman phonon, respectively (Sze,
1981), (Tsang, 1985), (Grekhov & Serezhkin, 1980), (Stillman & Wolf, 1977), (Dmitriev, 1987).
Taking into account that for many semiconductors
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7 6
e 7 /6 E l R Eg
5 ´ 10 -3 ´ E » Wmin << ion l R << Wmax » 1014 ´ 7 3 , (42)
Eg ion ER ERe

From (38) and (41) we find desired interval of electric field:

ER Eg
104 × ≈ E BD (W max) ≈ Emin < E < Emax ≈ E BD (W min) ≈ 2 × 106 × . (43)
λR ε × 6 Eion

Interval of electric field (43) is most often realized in experimental studies (Sze, 1981),
(Tsang, 1985), (Grekhov & Serezhkin, 1980), (Stillman & Wolf, 1977), (Dmitriev, 1987). Ratio
W min / λR is usually not more than a few units. Therefore, when W < W min then
Eion
E BD ≈ × 104 and hence when E > Emax instead of (33) must be valid relation
W

Eion a( E) - b( E)
´ = c( E) » 1
E é a( E) ù (44)
ln ê ú
ë b( E) û

where Еion to be understood by largest in value threshold ionization energy of electrons and
holes. On basis of relations (33) (or its upgraded version, if parameters s and A differ from
values of (36)) and (44)) can be obtained although approximate but relatively simple and
universal analytical dependences of charge carriers multiplication factors and excess noise
factors (Tsang, 1985), (Stillman et al, 1983), (Artsis & Kholodnov, 1984), (Woul, 1980), (McIn‐
tyre 1966), (Stillman & Wolf, 1977) on voltage as well as analytical expressions for avalanche
breakdown voltage at different spatial distributions of dopant concentration in p − n struc‐
tures.

3.5. Miller’s relation for multiplication factors of charge carriers in p-n structures

Usual way to calculate dependences of avalanche multiplication factors of charge carriers M

(Section 2) in p − n structures on applied voltage V b is based on numerical processing of inte‐
gral relations (1) and (2) in each case. Distribution of specific rate of charge carriers’ genera‐
tion g(x) in space charge region (SCR), i.e. when − L p < x < L n (see inset in Fig. 3), is accepted
in this Section 3.5 as exponential (and as special case − uniform). It is valuable for practical
applications to have analytical, more or less universal, dependences M on V b. In article (Sze
& Gibbons, 1966) was proposed analytical expressions for avalanche breakdown voltage
V BD , i.e. applied voltage value at which M = ∞ , in asymmetric abrupt and linear p − n junc‐
tions. Expression for V BD (Sze & Gibbons, 1966) in the case of asymmetric abrupt p + − n junc‐
tion was generalized in (Osipov & Kholodnov, 1987) for the case of thin p + − n(p) − n +
44 Photodiodes - From Fundamentals to Applications

structure (like as p − i − n ) as discussed in Section 3.3. Using as model abrupt (stepwise) p − n

junction under assumption that K (E ) = β / α = const (Kholodnov, 1988-2) has been shown that
from (1), (2) and approximate relation (33), which is valid for number of semiconductors in‐
cluding Ge, Si, GaAs, InP, GaP , can be obtained analytical dependences of multiplication
factors of charge carriers on voltage.

Figure 3. Dependences of exponents in Miller’s relation for electron nn and holes np for "thick" abrupt р − n junction
on applied voltage V at different values K = β / α equal to 1, 2, 3, and 4
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 45
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Rewrite (33) in the form

α(E )
K (E ) − 1 5
= ×
εε0
(
lnK (E ) 6 6 × 108 × q
) ( ) ( )
3
×
1.1
Еg
6
×
E
105
7
(45)

In (45) and below in this Section 3.5 is accepted (unless otherwise specified) the following,
convenient for this study, system of symbols and units (Sze, 1981): gap Eg and threshold
ionization energy Еion in eV; electric field E in V/cm; bias V b in V; multiplication factors α
and β in cm-1, electron charge q in C; dielectric constant of vacuum ε0 in F/m; concentration
including shallow donors N D and acceptors N A in cm-3; concentration gradient a in cm-4;
width of SCR L р and L n in p and n layers and thicknesses of these layers (inset in Figure 3)
in μm, light absorption coefficient γ in cm -1. In this section, analytical dependences M (V ) in
p − n structures have been calculated under no K (E) = const condition. Such calculations are
K (E ) − 1
possible because ratio varies, typically, much slighter than E 7. In some cases it al‐
lnK (E )
lows using relation (45) to integrate analytically (in some cases – approximately) expressions
(1) and (2) and, thus, get analytical, more or less universal, relatively simple dependences
M (V ). The most typical cases are considered: abrupt (stepwise) and gradual (linear) p − n
junctions like as in model given in (Sze, 1987), (Sze & Gibbons, 1966) and thin p + − n(p) − n +
structure (like as p − i − n ) with stepwise doping profile as in model presented in (Osipov &
Kholodnov, 1987). For purposes of discussion and comparison of obtained results with nu‐
merical calculations and experimental data, multiplication factors will be written in tradi‐
tional common form

1 1 % = 1
Mn = , Mp = ,M , (46)
1 - vnn 1- v
np
1 - vn%

where v = V / V BD . This form was first proposed by Miller in 1955 (Miller, 1955) and then, de‐
spite lack of analytical expressions for exponents nn , np , ñ , has been widely used as "Miller’s
relation" (Sze, 1981), (Tsang, 1985), (Grekhov & Serezhkin, 1980), (Leguerre & Urgell, 1976),
(Bogdanov et al, 1986). It was found that values of these exponents depend on many factors
including, in general, voltage as well (Kholodnov, 1988-2), (Grekhov & Serezhkin, 1980), Fig.
3. Form of writing (46) clearly shows that M (V ) → ∞ when V →V BD .

3.5.1. Stepwise p − n junction

In this case from relations (1), (2) and (45) and Poisson equation (SI units)

ì qN A
ï , x<0
dE ï ee0
=í (47)
dx ï qN D
- , x>0
ï ee
î 0
46 Photodiodes - From Fundamentals to Applications

follow that

4 4
Mn = ( K0 - 1) / ( K0 - K0v ), M p = K0v ´ Mn (48)

V BD = 6 × 1013 × ( 1.1Е )
g
3/2
× N eff−3/4, N eff =
NA × ND
NA + ND
(49)

where K 0 – value K (х) when Е(х)=Е(0)=Е0, i.e. value of K at metallurgical boundary of p − n

junction (see inset in Fig. 3). Formula (49) for V BD at N D < < N Aor N A < < N D becomes well-
known Sze-Gibbons relation (Sze, 1981), (Sze & Gibbons, 1966). If charge carriers are gener‐
ated uniformly in SCR then computations lead to following expressions:

M% N ´ exp[x A ´ e( K0 - 1) + x D / g ] + N D ´ exp[x D ´ e(1 - K0 ) + x A / g ]

= A , (50)
Mn N A + ND

when

x A , D ( v) ´ ( N eff / N A , D ) ´ v 4 ´ ln K0 £ 1; (51)

-1
æ 1- v4
1- Keff ö
ç 8 v4 ´ ÷
% = ç1 - K
M
Keff -1
÷ ´ Mn , (52)
eff
ç ÷
ç ÷
è ø

when

N eff
v4 ´
N A ,D (53)
Keff >> 1,

e(x) – unity function (Zeldovich & Myshkis, 1972), K eff = K 0 + K 0−1. Expression (50) is ob‐
tained by expanding the function Y (x, − L p ) as a power series in

∫ (β − α)d x ,
−L
′

and expression (52) was derived by standard method of integrating fast-changing functions
(Zeldovich & Myshkis, 1972).
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3.5.2. Gradual (linear) p − n junction

In this case Poisson equation can be written as (SI units):

dE q´s
=- ´x (54)
dx ee0

where σ - slope of linear concentration profile

and therefore

5 4
Mn = ( K0 - 1) / ( K0 - K0v ), M p = K0v ´ Mn (55)

2/ 5 6/ 5 1/ 5
æ 3 ´ 10 20 ö æ Eg ö æ 17.7 ö
VBD = 60 ´ ç ÷÷ ´ç ÷ ´ç ÷ . (56)
ç ç 1.1 ÷
è s ø è ø è e ø

In derivation of relations (55) and (56) was used known expression for voltage distribution
on linear p − n junction (Sze, 1981) and was also taken into account that (Gradstein & Ryz‐
hyk, 1963)

y
( y - x)7 4096 15/ 2
ò x
dx =
6435
y (57)
0

Formula (56) differs from known formula Sze-Gibbons for avalanche breakdown voltage of
linear p − n junction (Sze, 1981), (Sze & Gibbons, 1966) by last multiplicand, which for typical
values of ε ≈ 10 (Sze, 1981), (Casey & Panish, 1978) is close to unity.

3.5.3. Thin p + − n( p) − n + structure ( p − i − n )

When thickness of high-resistivity region (base) of considered structure

W > W̃ =
6εε0
5q
× ( )
Еg
1.1
3/4
×
1010
N
3/4
7/8 ≈ 2 ε × Еg ×
3 × 1015
N
( ) 7/8
, (58)

where N – dopant concentration (for example, donor) in base, and when V b = V BD then SCR
does not extend to entire thickness of base ((Osipov & Kholodnov, 1987), Sections 3.1-3.3, in‐
set in Fig. 4). In this case, expressions (48)-(53) remain apparently valid. In opposite case,
base is depleted by free charge carriers when V b < V BD that gives in the result substantially
48 Photodiodes - From Fundamentals to Applications

other expressions for avalanche multiplication factors of charge carriers and avalanche

breakdown voltage. When W < W̃ then from relations (1), (2) and (45) and Poisson equation

dE qN
=- (59)
dx ee0

Figure 4. Dependences of analytical (solid lines) and numerical (dashed lines) (Leguerre & Urgell, 1976) limiting values
of exponent nB = lim n(V ) in Miller’s relation (46) on concentration of donor dopant N D in "thick" high-resistivity layer
V →V BD

of stepwise p + − n − n + structure, 1 − Si, 2 − Ge, 3 − GaAs, 4 − GaP. Values K (E), as in (Leguerre & Urgell, 1976), are
taken from (Sze & Gibbons, 1966). In inset − scheme of "thick" p + − n − n + structure
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 49
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we find that

Mn = ( K0 - 1) / ( K0 - K0v% ), M p = K0v% ´ Mn ,
8 8
(60)

where

(V + V1 )8 - (V - V1 )8
v% 8 = , (61)
V2 8

qNW 2
V1 = ´ 10 -6 , (62)
2ee0

4 6
æ 6ee0 ö æ 1.1 ö 1
V28 = ç ÷ ´ç ÷ ´ . (63)
ç 5 ´ 108 qW 2 ÷ ç E ÷ N
è ø è gø

In deriving expressions (60)-(63), multiplication of charge carriers in p + and n + layers and

voltage drop on them is considered negligible. This is justified because of significant de‐
creasing of electric field E (х) deep into high-doped layers of the structure (Sze, 1981), (Kho‐
lodnov 1996-1), (Kholodnov 1998), (Leguerre & Urgell, 1976). Admissibility of such neglect
is confirmed also by formula (49) when N A < < N D or when N D < < N A. Avalanche break‐
down voltage is determined by equation ṽ = 1 which has no exact analytical solution. How‐
ever, till W surpasses W̃ / 8, then value of field at x = W is much less than value of field at
x = 0. In this case, using smallness parameter

8
æ V ö
çç 1 - 2 ´ 1 ÷÷ << 1 (64)
è V2 ø

we find that in zeroth-order approximation with respect to this parameter

VBD = V2 - V1 . (65)

In the case of very thin base when

1 %
W £ W0 = W , (66)
8
50 Photodiodes - From Fundamentals to Applications

electric field varies so slightly along base that probability of impact ionization is practically
the same in any point of it ((Osipov & Kholodnov, 1987), (Kholodnov 1988-1), Sections 3.2
and 3.4). As a result

7 7
Mn = ( K - 1) / ( K - K v ), M p = K v ´ Mn , (67)

% = gW K v ´ exp( gW ) - 1
M ´ ´ Mn , (68)
gW + v7 ´ ln K exp( gW ) - 1

V BD = 7 ×
3
× (
3q
25 50εε0 ) × ( 1.1Е W ) × 10 ≈ 98 × ( W ×εЕ )
3 g
6
6 g
6/7
, (69)

where γ < 0, if structure is illuminated through p + region (front-side illuminated) and γ > 0 if
structure is illuminated through n + region (back-side illuminated).

3.6. Discussion of the results. Comparison with computed and experimental data

3.6.1. To formulas for avalanche breakdown electric field and voltage for abrupt p+ - n junction

In sections 3.1-3.3 were derived approximate universal formulas for avalanche breakdown
field E BD and voltage V BD for abrupt p + − n junction taking into account finite thickness of
high-resistivity layer W . Comparative values of breakdown field E BD (0, W ) for Si , Ge and
InP most often used for fabrication of APDs computed by formulas (25) and (26) and found
from numerical solution of breakdown integral equation m = 1, where m is defined by (2) are
shown on Fig. 5 (Sze, 1981), (Tsang, 1985), (Stillman, 1981), (Filachev et al, 2010), (Filachev et
al, 2011), (Groves et al, 2005), (Stillman et al, 1983), (Trommer, 1984), (Woul, 1980), (Leguerre
& Urgell, 1976), (Bogdanov et al, 1986), (Gasanov et al, 1988), (Brain, 1981), (Tager & Vald-
Perlov, 1968). It is seen that in the most practically interesting range W ≈ (0.2 ÷ 10) μm for all
(a) (c)
a.m. semiconductors analytical E BD (0, W ) and calculated E BD (0, W ) values of breakdown
(a) (с)
field differ by less than 20 %. Relatively drastic fall of ratio E BD (0, W )/E BD (0, W ) in compari‐
son to unity with decrease of W (for thin enough W ) is due to the fact that, as shown in Sec.
3.4, if

ε
W < W min ≈ 5 × 10−3 × 7/6
× Еion , μm, (70)
Еg

then formulas (25) and (26) are not true. To estimate breakdown field E BD (0, W ) at values
W defined by (70) can be used the following formula
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Eion
EBD (0, W ) = 10 4 ´ , V/cm (71)
W

(а)
Figure 5. Dependence of ratio between analytical value of breakdown field E BD (0, W ) obtained by formulas (25) and
(c) *
(26) and numerical value E BD (0, W ). Dashed curve − analytical value of effective avalanche breakdown field E BD (0, W )
= X ε−3/7 × X g6/7 × E BD (0, W ) ≡ EВD
(InP )
(0, W ). Curves 1 and 1' − Si, 2 − InP, 3 − Ge. Values α(E) and β(E) are taken: for curves
1 and 3 − from Table 1 of monograph (Grekhov & Serezhkin, 1980), for curve 1' − from (Kuzmin et al, 1975), for curve
2 − from (Cook et al, 1982)

If assume that in Si threshold energy of impact ionization Еion of holes is higher than elec‐
trons, and it equals to 5 eV (Sze, 1981), then from (70) we find for Si W min ≈ 0.1 μm. Estimates
based on data from studies (Sze, 1981), (Tsang, 1985), (Stillman et al, 1983), (Grekhov & Ser‐
ezhkin, 1980), (Stillman & Wolf, 1977) show that for Ge and InP value W min is 2-3 times
smaller.

Therefore curve 1 in Fig. 5 starts to fall significantly below unity at larger values W than
curves 2 and 3. Analytical and computed dependences E BD on N for InP used in high-per‐
formance APDs for wavelength range λ = (1 ÷ 1, 7) μm as wide-gap layers in double hetero‐
52 Photodiodes - From Fundamentals to Applications

structures (Fig. 1, 2) are shown on Fig. 6 (Tsang, 1985), (Stillman, 1981), (Filachev et al, 2010),
(Forrest et al, 1983), (Filachev et al, 2011), (Stillman et al, 1983), (Ando et al, 1980), (Trommer,
(a) (c)
1984). It is seen that E BD (N , W ) and E BD (N , W ) differ from each other by less than 10 %. In
(a)
Fig. 7 and 8 are shown universal dependences of breakdown voltage V BD on N and W cal‐
culated by formulas (11), (27)-(29). It is seen from Fig. 7 that Sze-Gibbons relations (10) and
(11) (Sze, 1981), (Sze & Gibbons, 1966) can be used to determine V BD when
N > N min ≈ 10 × Ñ (W ) only. Value of this minimal concentration, for example, for classic sem‐
iconductors Si , Ge , GaAs , GaP and InP at W = (1-2) μm equals to (1 ÷ 5) × 1016cm-3. As shown
on lower inset in Fig. 7, dependence V BD on N is in the strict sense non-monotonic. Such
kind of dependence V BD on N is due to the fact that for small enough N breakdown field
E BD is growing faster with increasing N than |∇ E | ∝ N in diode’s base. Maximum V BD is
reached, as it follows from (28), at

æ s ö
% (W )
N = N max = ç 2 s -1 - 1 ÷ ´ N (72)
ç ÷
è ø

and expressed as

é s ù
(max)
VBD = ê( s - 1) ´ 2 s -1 + 1ú ´ (2 s)-1 ´ VBD (0, W ) (73)
êë úû

(rel )
when s = 8, value N max ≈ 1.2 × Ñ , ΔV max ≈ 2.86 × 10−2 < < 1 and absolute value ΔV max can reach
(a)
tens Volts, and even more (see Fig. 7). The analytical dependences V BD (N , W ) (Fig. 7 and 8)
(c)
for a number of semiconductors are in good agreement with V BD (N , W ) computed on the
basis of integral equations (1) and (2) (Sze, 1981), (Tsang, 1985), (Stillman, 1981), (Stillman et
al, 1983), (Grekhov & Serezhkin, 1980), (Leguerre & Urgell, 1976). Note that results of com‐
(a) (c) (a) (c)
parison V BD (N , W ) with V BD (N , W ) and ЕBD (N , W ) with ЕBD (N , W ) depend on accuracy
of determination of impact ionization coefficients of electrons α(Е) and holes β(Е) which are
sharp functions of electric field Е . As a rule, different authors obtain different results (Sze,
1981), (Tsang, 1985), (Stillman, 1981), (Stillman et al, 1983), (Grekhov & Serezhkin, 1980),
(Sze & Gibbons, 1966), (Stillman & Wolf 1977), (Dmitriev et al, 1987), (Tager & Vald-Perlov,
1968), (McIntyre, 1972), (Cook et al, 1982) (see, for example, curves 1 and 1' in Fig. 5). In ad‐
dition, deducing of relations (1) and (2) is based on local relation between α and β (Sze,
1981), (Tsang, 1985), (Stillman, 1981), (Filachev et al, 2011), (Stillman et al, 1983), (Grekhov &
Serezhkin, 1980), (Sze & Gibbons, 1966), (Stillman & Wolf 1977), (Dmitriev et al, 1987), (Ta‐
ger & Vald-Perlov, 1968), (McIntyre, 1972), (Cook et al, 1982) which is not always valid
(McIntyre, 1972), (Gribnikov et al, 1981), (Okuto & Crowell, 1974), (McIntyre, 1999).
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Figure 6. Dependence of field E BD on N for InP : 1 − W = 0.5 μm, 2 − W = 2 μm, 3 − W = 8 μm. Solid lines – formulas
(24)-(26), dashed curves − numerical calculation. Values α(E) and β(E) are taken from (Cook et al, 1982). In inset is
shown dependence of effective concentration Ñ * = X ε4/7 × X g6/7 × Ñ ≡ Ñ InP on W . Concentration is measured in cm-3,
field − in V/cm and thickness W − in μm.
54 Photodiodes - From Fundamentals to Applications

Figure 7. Dependence of avalanche breakdown voltage V BD of homogeneous p + − n − n + structure on dopant concen‐

tration N in base: solid line − (31) and (32), dotted line − expressions (10) and (11). In lower inset: dependence of
relative voltage ΔV (rel ) = V BD / V BD (0, W ) − 1 normalized to concentration Ñ (W ) at N ≤ 4 × Ñ (W ). In upper inset: de‐
*
pendence of effective ΔV max = X ε−3/7 × X g6/7 × V BD − V BD (0, W ) max
(InP )
≡ ΔV max on base thickness W . Voltage is measured
in V, thickness W − in μm.
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 55
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*
Figure 8. Dependence of effective avalanche breakdown voltage V BD = X ε−3/7 × X g6/7 × V BD ≡ V BD
(InP )
of homogeneous
p + − n − n + structure on thickness of its base W for three values of effective concentration N * = X ε4/7 × X g6/7 × N ≡ N InP :
1 − N * = 3 × 1016cm-3, 2 − N * = 3 × 1014cm-3, 3 − N * = 3 × 1012cm-3. In inset is shown dependence W̃ on N *. Concentra‐
tion is measured in cm-3, voltage − in V, thickness W − in μm
56 Photodiodes - From Fundamentals to Applications

3.6.2. To сorrelation between values of impact ionization coefficients of electrons and holes

In Section 3.4 is shown that there is reason to suppose existence of some correlation between
values of impact ionization coefficients of electrons α(Е) and holes β(Е), and form of required
relation (expression (33) and (45)) is proposed. It is obvious from Fig. 9 that values Z 0 ≡ ε 3 / Eg6
may differ by many orders of magnitude in different semiconductors. At the same time, for
presented in Fig. 9 Ge, Si and GaP , function c(Е) (see relations (33) and (45)) in range of fields
where α(Е) and β(Е) vary in several orders of magnitude (Okuto & Crowell, 1975), remains, as
it follows from (33) and (45), of the order of unity. Calculations based on experimental de‐
pendences α(Е) and β(Е) (Cook et al, 1982) show that in InP value c(Е) is some more closely to
1. It is evident from Fig. 10 that for GaAs , regardless of orientation of crystal with respect to
electric field, function c(Е) depends weakly on Е in comparison with impact ionization coeffi‐
cients of charge carriers (which values are taken from (Lee & Sze, 1980)), and differs from uni‐
ty by no more than 2-3 times. A similar situation takes place in Ge (Fig. 11, according to
(Mikawa et al, 1980)). As shown in (Kobajashi et al, 1969) dependences α(Е) and β(Е) meas‐
ured in (Miller, 1955), (McKay & McAfee, 1953) in the range of fields Е = (1.5 ÷ 2.7) × 105 V/cm
can be described in Ge by formulas α(Е)=7.81 × 10−34 × Е 7, β(Е) ≅ 2α(Е). This result agrees well
with expression (33). Note that, c(Е) differs from unity approximately by the same factor, as
values α(Е) and β(Е) for the same material obtained by different authors differ, respectively,
from each other (Sze, 1981), (Tsang, 1985), (Forrest et al, 1983), (Grekhov & Serezhkin, 1980),
(Sze & Gibbons, 1966), (Stillman & Wolf 1977), (Dmitriev et al, 1987), (Tager & Vald-Perlov,
1968), (Cook et al, 1982), (Okuto & Crowell, 1974), (Okuto & Crowell, 1975), (Lee & Sze, 1980),
(Mikawa et al, 1980), (Kuzmin et al, 1975). Using procedure described in Section 3.4, we can al‐
so determine relation between α(Е) and β(E ) = K (E) × α(E) in the case when relations (11) and
(13) are not satisfied (Grekhov & Serezhkin, 1980). It seems, relation required for such case, i.e.
under assumption of power dependence α on Е and K (E) = const, was obtained for the first
time in (Shotov, 1958).

3.6.3. To Miller’s relation

From (48), (55) and (67) follow that, exponents in Miller’s relation (46) for multiplication fac‐
tors of electrons and holes are given by

nn ´ ln v = ln é( K0v - 1) / ( K0 - 1) ù ,
x

êë úû (74)

é K x ù
np ´ ln v = ln ê 0 (1 - K0- v ) ú , (75)
K
ëê 0 - 1 ûú

where ξ = 4, 5 and 7 for stepwise p − n junction, linear p − n junction and very thin (66)
p + − n − n + structure (situation 1, 2 and 3, respectively). If thickness of base in p + − n − n + struc‐
ture is not very small, i.e., W 0 < W < W̃ (situation 4) then as it follows from formula (60), ex‐
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 57
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Figure 9. Dependence Z (E) [relation (33)] in Ge, Si, and GaP for α(E) and β(E) from (Okuto & Crowell, 1975)

ponents nn and nр are also expressed by (74) and (75) but in right side of those expressions ṽ
substitutes v and ξ = 8. Value of exponent ñ lies between values nn and nр . From (1) and (2)
apparent that when α = β then factors M n , M p and M̃ coincide with each other, i.e., nn =nр =ñ =
n , and, as it follows from expressions (74) and (75), regardless of bias voltage applied, n = 4, 5
and 7 for situations 1, 2 and 3, respectively. Exponents in Miller’s relation have the same val‐
ues when V < < V BD , more exactly, when |lnK 0 / lnv| < < ξ , regardless of ratio
K 0 = β(E0) / α(E0). When V → V BD or more exactly, if

Δv = 1 − v < < min { ξ | lnK1 | ; ξ1 }, M > > 1

0

Then for these situations

ln K0 ln K0
nn = nnB º x ´ K0 ´ , np = npB º x ´ . (76)
( K0 - 1) ( K0 - 1)
58 Photodiodes - From Fundamentals to Applications

Graphs in Fig. 4 allow comparing numerical values of exponents nnB and nрB calculated in (Le‐
guerre & Urgell, 1976) nB(c) and analytical nB(a) computed by formulas (76) for asymmetrical
stepwise p − n junction. Like as in (Leguerre & Urgell, 1976), experimentally determined func‐
tional dependencies α(E0) and β(E0) (Sze & Gibbons, 1966) were used in calculations of de‐
pendences nB(a). As follows from (46), when M > > 1, then ratio of analytical value of
multiplication factor M (a) to calculated M (c) equals to ratio nB(c) to nB(a) (Fig. 11-13). It obviously
from Fig. 11-13 that for all considered semiconductors (with curves α(Е) and β(Е) taken from
(Sze & Gibbons, 1966)), dependences M (a)(V ) and M (c)(V ) do not differ by more than 50 %. De‐
pendences of exponents nn(a) and np(a) on voltage and nnB (a) (a)
and n pB on ratio K = β / α are illustrat‐
ed in Fig. 3 and 14, respectively. It should be noted that numerical values of exponent in
Miller’s relation, as well as, value V BD depend, obviously, on what functions α(Е) and β(Е) are
used in (1) and (2) in calculations. Let’s take the simplest case when α(E) = β(E) and p − n junc‐
tion is stepwise. Varying expressions (1) and (2), we find that under considered conditions

ee0
nB = ´ a( EBD ) ´ EBD , (77)
500 ´ q ´ N eff

where E BD = E (0) at V = V BD is determined from condition

EBD
100
ò a( E)dE =
ee0
´ N eff (78)
0

In Fig. 15a are shown dependences nB (N eff ) calculated from relations (77) and (78) for four
values α(E ) = β(E ) obtained for GaAs by different authors (Grekhov & Serezhkin, 1980),
(Okuto & Crowell, 1975), (Kressel & Kupsky, 1966), (Nuttall & Nield, 1974). It is seen that
analytical value nnB = n pB = 4 calculated by formulas (76) approximately equals to mean value
with respect to curves 1-4 in Fig. 15a. According to obtained above results expressions (48)-
(53) are not valid when concentration

N eff > (N eff )max ≅ 2 × 1017 × (Еg )2 × Еion

−4/3
(79)

which for many semiconductors is of the order of 1017 cm-3. At such high concentrations, as it
follows from Section 3.4 and (Kholodnov, 1988-1) and relations (1) and (2), for stepwise p − n
junction

nn =
(
ln ( K0v - 1) / ( K0 - 1) ) ,n = nn +
1- v
ln K0 , (80)
p
ln v ln v
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Figure 10. Dependence С(E) at different orientations of GaAs crystal with respect to electric field for values α(E) and
β(E) from (Lee & Sze, 1980)
60 Photodiodes - From Fundamentals to Applications

Figure 11. Dependence of ratio between analytical values of avalanche multiplication factors М (а) of electrons and
holes and numerical values М (с) (Leguerre & Urgell, 1976) in stepwise asymmetric Ge p − n junction on value of multi‐
plication factor М = М (а) of charge carriers. Solid lines – electrons, dashed – holes. Dopant concentration in high-resis‐
tivity part of p − n junction N , cm-3: 1 − 1015, 2 − 3 × 1015, 3 − 1016, 4 − 3 × 1016, 5 − 6 × 1016. Values K (E), as in (Leguerre
& Urgell, 1976), are taken from (Sze & Gibbons, 1966)
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Figure 12. Dependence of ratio between analytical values of avalanche multiplication factors М (а) of electrons and
holes and numerical values М (с) (Leguerre & Urgell, 1976) in stepwise asymmetric Si p − n junction on value of multipli‐
cation factor М = М (а) of charge carriers. Solid lines – electrons, dashed – holes. Dopant concentration in high-resistivity
part of p − n junction N , cm-3: 1 − 1015, 2 − 3 × 1015, 3 − 1016, 4 − 3 × 1016, 5 − 6 × 1016. Values K (E), as in (Leguerre &
Urgell, 1976), are taken from (Sze & Gibbons, 1966)
62 Photodiodes - From Fundamentals to Applications

Figure 13. Dependence of ratio between analytical values of avalanche multiplication factors М (а) of electrons and
holes and numerical values М (с) (Leguerre & Urgell, 1976) in stepwise asymmetric GaAs (solid lines) and GaP (dashed
lines) p − n junctions on value of multiplication factor М = М (а) of charge carriers. Solid lines – electrons, dashed – holes.
Dopant concentration in high-resistivity part of p − n junction N , cm-3: 1 − 1015, 2 − 3 × 1015, 3 − 1016, 4 − 3 × 1016, 5 −
6 × 1016. Values K (E), as in (Leguerre & Urgell, 1976), are taken from (Sze & Gibbons, 1966)
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Figure 14. Dependence of limiting values nB = lim n(V ) of exponents in Miller’s relation for electron nn and holes np
V →V BD

for "thick" abrupt р − n junction on K = β / α

64 Photodiodes - From Fundamentals to Applications

moreover

nnB = K0 ln ( K0 / ( K0 - 1) ) = K0 ´ npB . (81)

Figure 15. Dependences nB (N eff ) in GaAs calculated on the base of different dependences α(E)=β(E), taken from: 1 −
(Shabde & Yeh, 1970), 2 − (Grekhov & Serezhkin, 1980), 3 − (Okuto & Crowell, 1975), 4 − (Kressel & Kupsky, 1966), 5 −
(Sze & Gibbons, 1966). Dashed lines − analytical values

For comparison, in Fig. 15b are presented dependences of nB(c)(N eff ) and nB(a)(N eff )=1 for the
case α = β , when nnВ = nрВ = nВ . It is seen that value nB(a)(N eff )= 1 is approximately equal to mean
value with reference to curves 2, 3 and 5 in Fig. 15b plotted on the base of numerical data. Note
that starting from N eff ≅ (N eff )max breakdown voltage V BD dependence on N eff becomes, with
growth N eff , more and more weaker than that described by equation (49), and in limit tends to
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value V BD = Eion / q. This conclusion accords with results of studies (Grekhov & Serezhkin,
1980), (Nuttall & Nield, 1974). Obtained results agree well with experimental results for a num‐
ber of p − n structures, including based on Ge, Si, GaAs, GaP (Sze, 1981), (Tsang, 1985), (Still‐
man et al, 1983), (Miller, 1955), (Grekhov & Serezhkin, 1980), (Sze & Gibbons, 1966), (Stillman &
Wolf, 1977), (Bogdanov et al, 1986), (Cook et al, 1982), (Shotov, 1958). We present here three
cases of studies. In experimental study (Miller, 1955) of breakdown in Ge stepwise p − n junc‐
tion was found that measured values of exponents in Miller’s relation were lying in range from
3 to 6.6. The same values of exponents are obtained from expressions (74) and (75) with ξ = 4 if
we take into account that in Ge with doping levels used in (Miller, 1955) К0 ≅ 2 ÷ 3 (Sze, 1981),
(Tsang, 1985), (Miller, 1955), (Grekhov & Serezhkin, 1980), (Stillman & Wolf, 1977), (Shotov,
1958). In experimental study (Bogdanov et al, 1986) of APD based on MIS structure (metal-in‐
sulator-semiconductor APD) multiplication of charge carriers occurs in thick p − Si substrate.
From point of view of avalanche process this structure is similar to asymmetric stepwise n + − p
junction. Therefore, avalanche process in MIS APD can be described by expressions (74)-(76)
with ξ = 4. Concentration of shallow acceptors in substrate of investigated structure was 1015
cm-3. At this doping avalanche breakdown in Si occurs when electric field near insulator-semi‐
conductor interface reaches value E BD ≅ 3 × 105 V/cm (Sections 3.1 and 3.2, (Sze, 1981), (Osipov
& Kholodnov, 1987), (Sze & Gibbons, 1966)), and therefore К0 ≅ 10−2 (Sze, 1981), (Tsang, 1985),
(Grekhov & Serezhkin, 1980), (Sze & Gibbons, 1966), (Stillman & Wolf, 1977), (Kuzmin et al,
1975). Measured in (Bogdanov et al, 1986) value nn at V BD − V < < V BD was found equal to 0.2.
From formulas (76) with К0 ≅ 10−2 follows that nnВ = 0.186. In Tables 1 and 2 are presented ex‐
perimental (Shotov, 1958) and calculated by formulas (48) and (55) values of multiplication fac‐
tors of electrons M n (V ) and holes M p (V ) in Ge stepwise and linear p − n junctions. Obviously,
for these p − n junctions, experimental and analytical values of multiplication factors differ
from each other by less than 20 % in whole voltage V range used in measurements.

Mp
V/VBD Experiment
Theory
(Shotov, 1958)

0.65 1.35 1.30

0.70 1.50 1.44
0.75 1.75 1.65
0.80 2.10 1.98
0.85 2.65 2.55
0.90 3.70 3.71
0.95 7.00 7.30

Table 1. Experimental (Shotov, 1958) and computed [from Equation (48)] hole avalanche multiplication factor M p in
step-wise p − n junction in p − Ge for different ratios of applied voltage to avalanche breakdown voltage V / V BD . It is
assumed that K 0 = 2 (Shotov, 1958)
66 Photodiodes - From Fundamentals to Applications

Mp Mn
V/VBD K0 (*)
Experiment (*) Theory Experiment (*) Theory
0.65 1.25 1.19 1.12 1.09 2.10
0.70 1.40 1.28 1.20 1.14 2.00
0.75 1.60 1.44 1.30 1.22 2.00
0.80 1.85 1.70 1.40 1.33 2.10
0.85 2.40 2.13 1.70 1.56 2.00
0.90 3.50 3.10 2.20 2.00 2.10
0.95 6.80 5.89 3.90 3.45 2.00
0.975 13.00 11.64 7.00 6.32 2.00
0.98 - 14.52 - 7.76 2.00
0.985 - 19.33 - 10.16 2.00
0.99 30.00 28.90 - 14.97 2.00

Table 2. Experimental (*) (Shotov, 1958) and computed [from Equation (55)] avalanche multiplication factors M p and
M n for holes and electrons in Ge linear p − n junction for different ratios of applied voltage to avalanche breakdown
voltage V / V BD (Shotov, 1958)

Finally, it is interesting to analyze application of expressions (45) and (76) to describe ava‐
lanche process in InSb. The fact is that dependence α(Е) in InSb was quite well known al‐
ready in 1967 (Baertsch, 1967), but no one could obtain information about dependence β(Е)
(Dmitriev et al, 1987), (Dmitriev et al, 1983), (Dmitriev et al, 1982), (Gavrjushko et al, 1968).
Substituting in (45) dependence α(Е) for InSb (Baertsch, 1967), (Dmitriev et al, 1983), (Dmi‐
triev et al, 1982), (Gavrjushko et al, 1968), we find that ratio K = β(E) / α(E) is vanishingly
small up to electric field E ≅ 4 × 104 V/cm resulting in extremely high value nрВ when at the
same time value nnВ is extremely small. It means that M n (V ) becomes much larger than uni‐
ty, even at voltages V b noticeably lower avalanche breakdown voltage V BD , and value
M p (V ) remains equal to unity up to values V b very close to V BD . Effect obtained from appli‐
cation of relations (45) and (76) accords very well with experimental data (Baertsch, 1967),
(Dmitriev et al, 1983) and explains why multiplication of holes in InSb is extremely hard to
observe (Dmitriev et al, 1987), (Baertsch, 1967), (Dmitriev et al, 1983), (Dmitriev et al, 1982),
(Gavrjushko et al, 1968).

4. Tunnel currents in avalanche heterophotodiodes

4.1. Calculation of tunnel currents in approximation of quasi-uniform electric field and

conditions of its applicability

In act of interband tunneling electron from valence band overcomes potential barrier ABC
(Fig. 16a). The length of tunneling lT , i.e. length on which energy of bottom of conduction
band Ес (x) changes by value equal to Еg is found by solving integral equation
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x + lT ( x )
Eg = q ´ ò E( x ')dx ' (82)
x

If variation of electric field within length of tunneling ΔЕ < < Е , i.e. specific length of varia‐
tion of field lE > > lT , then expanding function Е(x ′) in Taylor series around point x ′ = x , we
find that in the first order of parameter of smallness lT / lE equation (82) takes the form

Eg
lT = (83)
qE( x) ´ [1 - (lT / 2 E) ´ ¶E / ¶x ]

When N (x) = const then equation (83) is exact. As can be seen from Fig. 16a, if

C¢C º DlT << lT , C¢B¢ º DEc << Eg , (84)

then true ABC barrier coincides to high degree of accuracy with triangle ABC′ to which cor‐
responds uniform field Е(х) (Fig. 16b).

It follows from (83) and Poisson equation that inequalities (84) are satisfied if

N ( x) ´ Eg
d( x) º << 1, (85)
2ee0 ´ E2 ( x)

at that

Eg
lT (Eg , E ) = (86)
q × E (x)

As shown below, due to large values of field Е at avalanche breakdown of p − n structures,

inequality (85) is valid for almost all materials up to concentration N = 1017 cm-3 and even
high.

Under these conditions specific rates of charge carriers’ tunnel generation gTi (x) in layers I
and II of structure can be described by expression

1 ¶J é a ù
gTi ( x) º ´ Ti = ATi ´ E2 ( x) ´ exp ê - i ú , (87)
q ¶x ë E( x) û
68 Photodiodes - From Fundamentals to Applications

Figure 16. Physical meaning of quasi-uniform field approximation: a − band diagram, b − field distribution on length
of tunneling. ABC − true potential barrier, ABC' − potential barrier used de facto. Dashed lines − Е(х) = const

obtained in (Kane, 1960) (see also (Burstein & Lundqvist, 1969)) for Е(х) = const, in which

q2 2 mi* p
ATi = ´ , ai = ´ 2 mi* ´ Egi 3 . (88)
(2 p)3 ´ h 2 Egi 4q ´ h

Here ℏ, Еgi and mi* = 2mc × mv / (mc + mv ) – crossed Plank constant, gaps and specific effective
masses of light charge carriers in proper layers. Approximation of quasi-uniform field (87)
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and expressions (6)-(9) result in convenient formula for analysis of primary interband tunnel
current density

2
J T = ∑ J Ti =
i=1
2×q 3
(2π)3 × ℏ2
×
2
∑
i=1
mi*
E gi
×L Ti × Ei
2 × exp ( )
−
ai
Ei
, (89)

where characteristic dimensions of areas of charge carriers’ tunnel generation in layers I and II

L Ti (Ei , {
W i ) = min W Ti ≡
ε0εi × Ei 2
q × ai × N i
}
, Wi . (90)

Equation (89) is valid under conditions

N i ´ Egi Ei
di º 2
< << 1, (91)
2ee0 ´ Ei ai

E gi
lTi ≡ lT (E gi , Ei ) = < < li . (92)
q × Ei

These conditions mean the following. If inequalities (91) for gTi (E) are satisfied then expres‐
sion (87) is valid, at least in the neighborhood of field value E = Ei . When right side of in‐
equalities (91) is satisfied then tunnel generation drops sharply with decreasing E , and
therefore I Ti at W Ti < W i is mainly determined by tunneling in areas 0 ≤ x ≤ W T 1 and
W 1 ≤ x ≤ W 1 + W T 2.

Fulfillment of conditions (92) is necessary at punch-through of proper layers of structure for

neglecting tunneling through its hetero-interfaces which is not accounted for by formula
(89). We show further, that at avalanche breakdown, inequalities (91) and (92) are valid for
almost all real values of material parameters, concentrations N i and layers’ thicknesses W i
of heterostructure. Avalanche breakdown occurs when one of fields Ei becomes close to
breakdown field EiBD of proper layer of structure ((Sze, 1981), (Tsang, 1985), (Grekhov &
Serezhkin, 1980), Sections 3.1-3.3).

Breakdown fields EiBD can be obtained by formula (14) (Osipov & Kholodnov, 1987), (Osi‐
pov &, Kholodnov, 1989), i.e.,

1/ s
é Ni ù
EiBD ( N i , Wi ) = Ei BD (0, Wi ) ´ ê1 + ú , (93)
%
êë N i (Wi ) úû
70 Photodiodes - From Fundamentals to Applications

where

1/( s -1) s /( s -1)

æ A ´e e ö % (W ) = æç Ai ´ ei e 0 ö÷
EiBD (0, W ) = Ai ´ çç i i 0 ÷÷ , N (94)
i i ç sqW ÷
è sqWi ø è i ø

(s and Ai – some constants).

For many semiconductors including I nx Ga1−x ASy P1− y alloy which is one of the main materi‐
als for avalanche heterophotodiodes fabrication (Tsang, 1981), (Stillman, 1981), (Filachev et
al, 2010), (Kim et al, 1981), (Forrest et al, 1983), (Tarof et al, 1990), (Ito et al, 1981), (Clark et al,
2007), (Hayat & Ramirez, 2012), (Filachev et al, 2011), (Stillman et al, 1983), (Ando et al,
1980), (Trommer, 1984), (Woul, 1980)

3/ 4
1.2 ´ q æ Egi ö
s = 8, Ai = ´ç ÷ ´ 1010. (95)
ei e0 çè 11q ÷ø

From expressions (93) and (94) when relations (95) are satisfied we find the following.
1. When

8.9 × 1019
N i ≤ N i(1) = 4 , cm-3, W i ≥ W i(1) = Χmi
3.5
× Χεi3 × Χgi6 × 1.4 × 10−4, μm, (96)
X mi × X εi4 × X gi6

then ratio Еi to ai is less than 0.1, where Χmi = 0.06 / mi0*, Χεi = 12.4 / εi , Χgi = 1.35 / E gi (for InP
which is often used for growing of wide-gap layers of heterostructure (Tsang, 1981), (Still‐
man, 1981), (Filachev et al, 2010), (Kim et al, 1981), (Forrest et al, 1983), (Tarof et al, 1990),
(Ito et al, 1981), (Clark et al, 2007), (Hayat & Ramirez, 2012), (Filachev et al, 2011), (Stillman
et al, 1983), (Ando et al, 1980), (Trommer, 1984), (Woul, 1980)), X mi = X εi = X gi = 1, mi0* = mi* / m0
(m0– free-electron mass)

2. When

X gi0.4 × 1.8 × 10−2

0.2
N i ≤ N i(2) = Χmi × Χεi1.6 × Χgi0.4 × 3.3 × 1017, cm3, W i ≥ W i(2) = 0.7 , μm (97)
X mi × X εi1.9

then under avalanche breakdown of proper layer of structure ratio δi to ЕiBD / ai is not exceed
unity, moreover, even when N i = N i(2)

0.6
δi < Χmi × Χεi1.2 × Χgi0.8 × 10−1. (98)
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3. When

1.8 × 10−2
Wi > > , μ m, (99)
X εi × 6 X gi

then length of tunneling lTi at Ei = EiBD is much shorter than thickness W i of this layer.

In expressions (96)-(99) Еgi is measured in eV. Analysis shows that under avalanche break‐
down of heterostructure inequities (91) and (92) are satisfied for real values of N i and W i
and Ei < EiBD , i.e. in layer which does not control avalanche breakdown also. As can be seen
from Fig. 17, when punch-through of layer nwg stops then, obviously, conditions (91) and
(92) become no longer valid. Note that calculations of tunnel currents in approximation of
quasi-uniform field lead to some overestimation of actually available. In fact, due to high
+
doping of рwg layer, tunnel current in it can be ignored; this is situation similar to MIS struc‐
tures (Anderson, 1977). In n type layers electric field decreases with increasing distance from
metallurgical boundary of p + − n junction (Fig. 1b), and because gradient of potential is ex‐
pressed as dφ / dx = − E then slope of zones Еc (x) and Еv (x) decreases with increasing x . It is
shown from Figure 16a that use of quasi-uniform field approximation means underestimat‐
ing of thickness of actual barrier ABC. As expected, numerical calculations in WKB approxi‐
mation (Anderson, 1977) give a somewhat smaller value of tunnel currents than formula
(89). Since tunnel currents are strongly dependent on parameters of material, which in real
samples, usually, more or less different from those used in calculations (moreover, exact
dopant’s distribution profile N i (x) and hence shape of barrier ABC are usually unknown),
then slight overestimation of tunnel currents values provides some technological margin
that is needed for development of devices with required specifications.

4.2. Features of interband tunnel currents in p + − n heterostructures under avalanche

breakdown

Analysis of expression (89) under avalanche breakdown of p + − n heterostructure, i.e., when

either E1 = E1BD or E2 = E2BD , shows that in contrast to homogeneous p − n junction (Stillman,
1981), (Ando et al, 1980) density of initial tunnel current J T , as a rule, is not a monotonic
function N 1. An increase in N 2 cause, for some values of N 1 and W i , the rise of tunnel cur‐
rent and vice versa – decrease of tunnel current when N 1 and W i have different values. De‐
pending on gap E gi of heterostructure’s layers and their thicknesses W i the following
situations are possible.

4.2.1. Independent doping levels of wide-gap and narrow-gap n type layers

I.

s ( s -1)/ s
W1 æ e ´ A1 ö é N % (W ) ù
º W1/ 2 ³ W1/* 2 = çç 1 ÷÷ ´ ê 2 2
. (100)
W2 e ´ A ê N + N% (W ) úú
è 2 2 ø ë 2 2 2 û
72 Photodiodes - From Fundamentals to Applications

Figure 17. Dependence of generalized parameters of smallness δ2* and lT*2 in quasi-uniform field approximation on
concentration N 1, at М ph = 100, in case, when charge carriers multiplication occurs in nwg : InP layer. Solid lines − δ2*,
dashed − lT*2. Values W 1, μm: 1 − 0.5, 2 – 2, 3 − 8. N 1 pt − maximal concentration N 1 at which punch-through of nwg
layer is possible; δ2 = (N 2 / 1016) × (ε2 / ε1) × E g 2 × δ2*; lT 2 = (ε2 / ε1) × E g 2 × lT*2; E g 2- eV, concentration − cm-3.

In this case, at any concentration N 1, field E1 = E1BD ( N 1, W 1), and E2 < E2BD , i.e., avalanche
breakdown is controlled by nwg layer.

As follows from (6)-(9), (89) and (93), if

exp −
a1
E1BD (0, W 1)
× 1− (
ε2 × а2
ε1 × а1
) < < 1, (101)

which is fulfilled with large margin at a2ε2 < a1ε1 due to large ratio of a1 to E1BD (0, W 1) (1-2
orders of magnitude) while
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1/ 2
æ 2 e1 ö
N1 < N% 1(T ) @ s ´ çç ´ ´ E1BD (0, W1 ) ÷÷ % (W ) µ W -( s + 0.5)/( s -1)
´N 1 1 1
(102)
è s - 1 e 2 ´ a2 ø

then tunnel current is almost independent on N 1.

If s sufficiently large ((Sze, 1981), (Osipov & Kholodnov, 1987), (Sze & Gibbons, 1966), Sec‐
tions 3.1-3.3), then with further increase of N 1 tunnel current is monotonically falling. How‐
ever, in most real cases, for example, when relations (95) is valid, tunnel current at N 1 > Ñ (T
1
)

first decreases and then increases.

One can see that at minimum of tunnel current, as a rule, the following inequality is valid

E1BD (0, W 1) κ (s−2)/(s−1) y

ξ≡ < × 2 , (103)
a1 s 1/(s−1) f (y)

where

1/s
a2 × ε2 N1
f (y) = (y + r −1) , r = (κ × s)s/(s−1), κ = 1 − , y=
a1 × ε1 r × Ñ 1

When (103) is fulfilled then W T 1 < W 1.

(T )
Therefore, as it follows from (6)-(9), (89), (90) and (93), concentration N 1 = N 1min at which J T
reaches minimum is defined by equation

y x
+ 1-(2/ s) ´ é s ´ f ( y ) - r 1-(1/ s) ´ y ù ´ ln[L( y ; x)] = 1, (104)
f ( y) r ë û

where

f 3−s (y)
(
1 − ξ × r 1/s × f (y) × s − 4 +
s
r×y
)
Λ(y; ξ) = B × × ,
y × f (y) − κ × y 2 × κ × s − f 1−s
(y) 4r
1+ξ× × f (y) − κ × y
(1 − κ) × κ × s

3/ 2 5/ 2
æ m* ö æ Eg1 ö N 2 (1 - k)2
B = ç 1* ÷ ´ç ÷ ´ ´ . (105)
çm ÷
è 2ø
ç Eg 2 ÷ N% r
è ø 1

Expression (105) is valid when inequality W T 2 < W 2 is fulfilled. This inequality and inequali‐
ty (103) also are fulfilled at minimum of tunnel current in the most practically interesting
cases. Below is explained difference between situations W T 2 > W 2 and W T 2 < W 2 at
74 Photodiodes - From Fundamentals to Applications

(T )
N 1 = N 1min . Equation (104) can be solved by successive approximations using parameters of
smallness ξ and 1 / s .

As a result we find

s
é e e ´ A1 æ e ´ a ö ù s -1 ìï 1 - k 1/ s y ´ ( k ´ s ´ y0 + 1) üï
(T )
N1min =ê 1 0 ´ çç 1 - 2 2 ÷÷ ú ´ y0 ´ í1 - x ´ ´ r ´ ln éë L( y0 ; 0) ûù ´ 0 + 0(x) ý , (106)
ëê q ´ W1 è e 1 ´ a ú
1 øû îï k ( s - 1) ´ k ´ y 0 + 1 þï

where

1 æ 1ö
y0 = 1 + + 0 ç 2 ÷.
2
(107)
k´s ès ø

(T )
It is shown from (105) and (106) that N 1min is decreased with growth W 1 and, also, although
weakly, with increase N 2.

(T )
When N 1 = N 1min then density of tunnel current

e1e0 ´ q 3 E14BD (0, W1 ) é C1 ´ a1 ù

JT ( N1 ) = JT min = C0 ´ ´ ´ L - n1 ( y0 ; 0) ´ exp ê - ú ´ ëé1 + 0(1) ûù , (108)
2 p4 ´ h ´ Eg21 % (W )
N 1 1 ë 1BD (0, W1 ) û
E

Where

y0 × κ × (s − 1) + 1
C0 = y03 × × (κ × s)(4−s)/(s−1), C1 = y0 × (κ × s)1/(s−1) −1
,
(s × κ − 1) × y0 + 1

y0 × (1 − κ)
n1 = .
(s − 1) × κ × y0 + 1

From (94), (105) and (108) follow that J T min decreases sharply with increasing W 1. Value
J T min decreases also, although weakly, with increasing N 2. Ratio

n
JT min é N2 ù 2 é a1 ù
µê ´ exp ê -(C1 + k - 1) ´ ú, (109)
% (W ) úú
JT ( N1 ) N £ N% ( T ) ëê N E (0, W )
1 1
1 1 û ë 1BD 1 û

Where

y0 × (κ × s − 1) + 1
n2 = ,
(s − 1) × κ × y0 + 1
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drops sharply, same as J T min, with increase W 1, but it increases with increasing N 2. Value of
this ratio is usually several orders of magnitude less than unity. For example, for combina‐
tion of layers nwg : InP / nng : I n0.53Ga0.47 As, differential of currents, as can be shown, does not
exceed values (N 2 / 1018)0.9 × 2 × 10−4, where N 2 is measured in cm-3.

When concentrations

e 2 ´ a2 W (T )
N2 < ´ 1 ´ N1min (110)
e1 ´ a1 - e 2 ´ a2 W2

then in minimum of J T (N 1) takes place punch-through of narrow-gap layer, i.e. non-equili‐

+ (T )
brium SCR reaches nwg layer. When N 1 > N 1min then tunnel current increases with increasing
N 1, and at the same time, non-equilibrium SCR will penetrate into narrow-gap layer until
concentration N 1 reaches value

N 1 = N 1 pt = ( A1 × ε1ε
qW 1
0
) s/(s−1)
(T )
× 1 + 0(1) > N 1min (111)

Nature of above dependence J T on N 1 is competition between tunnel currents in wide-gap

and narrow-gap layers of heterostructure (Fig. 1a). When N 1 ≤ Ñ (T )
1 then field E = EI (W 1) in
nwg layer at its heterojunction (Fig. 1b) coincide with very high accuracy with E1BD . Due to
relatively large field E2 = (ε1 / ε2)×E1BD , current density J T is determined by tunneling of
charge carriers in narrow-gap layer, i.e. J T ≈ J T 2 (Fig. 1a). With increasing N 1, field E2 and
therefore current J T 2 decrease due to fall EI (W 1) (Fig. 18). Decrease EI (W 1) with increase N 1
is caused by requirement (1) of constancy of photocurrent gain M ph = M р . Indeed, increase
N 1 for given M ph should lead to growth E1. Otherwise, due to growth | ∇ Е(х) | with in‐
creasing N 1, field would be reduced everywhere in SCR, which in turn would lead to a de‐
crease M ph . However, increase E1 should not be too large, and it should be such that Е(х) at
х greater than some value in interval 0 < x < W 1 is decreased. In other words, Е(х) anywhere
in SCR would increase, that, evidently, would increase M ph . It can be seen directly from (1)
and (2). Note that for sufficiently large values of multiplication factors M ph , field E1 is prac‐
tically independent on M ph and very close to breakdown field E1BD (N 1, W 1) when value of
integral m (2) is equal to unity. This allows to use value E1 = E1BD (N 1, W 1) (93) instead of
true value Е1(N 1, W 1, M ph ). When N 1 > Ñ (T )
1 , then variation of field Е(х) at distance W 1 in
nwg layer is still very insignificant, but it is enough to affect value J T 2. Due to decrease E2
with growth N 1 (especially when N 1 > Ñ 1), current is more and more determined by tunnel‐
(T )
ing of charge carriers in nwg layer, therefore when N 1 > N 1min , current density J T ≈ J T 1 in‐
76 Photodiodes - From Fundamentals to Applications

creases with increase N 1 because E1BD grows with increase N 1. Initial plateau (Fig. 18a) on
the graph J T (N 1) is caused by extremely weak dependences E1BD on N 1 (93) and Е on х in
nwg layer when N 1 < Ñ (T )
1 . Reducing of value J T min (108) with growth N 2 is due to increasing
length of tunneling in narrow-gap nng layer (Fig. 1). Indeed, in this layer ∇ Е ~ − N 2 < 0, and
E2 under these conditions does not depend on N 2. It means, that Е(х) everywhere in nng
d Ec d Ev dφ
layer, except of point x = W 1, falls with increase N 2 (1b). Since = = = − E < 0, then
dx dx dx
slopes of Ec (x) and Ev (x) everywhere in nng layer, except of point x = W 1, decrease also with
increasing N 2, that leads to increase length of tunneling. Reducing of J T is more significant
(T )
with growth N 2 when N 1 < N 1min (Fig.18b), because current density J T 2 increases with de‐
crease N 1 while J T 1 decreases. When N 1 < Ñ (T
1
)
then current density J T 1 ≤ J T 2, and if
(T )
N 1 = N 1min it exceeds J T 2. Therefore, ratio of J T min to J T | (109) increases with increas‐
N 1<Ñ (T
1
)

(T ) (T )
ing N 2. Because at N 1 = N 1min value J T 1 > J T 2, then, naturally, concentration N 1min (106)
slightly decreases with increasing N 2 (Fig. 18b). For small values N 2, when W T 2 > W 2, Е(х) in
nng layer coincides with E2 with high accuracy. Therefore, length of tunneling in this layer,
(T )
and hence J T also, do not depend on N 2. Reducing of values N 1min (106) and J T min (108)
with increasing W 1 (Figure 18a) is due to the fact that the more is W 1 then the less is E1BD
and the greater is fall of field Е(х) in depth of nwg layer.

II.

Condition (100) is not satisfied. For example, for combination of layers nwg : InP /
nng : I n0.53Ga0.47 As such situation takes place when

7 /8
W1 æ N2 ö
´ ç1 + 15
´ W2 8/7 ÷ < 21.5, (112)
W2 è 2.2 ´ 10 ø

where N 2 and W i are measured in cm-3 and μm, respectively. Under this condition, when
N 1 < N̄ 1, where N̄ 1 satisfies equation

e2 1/ s q ´ N1 ´ W1 % (W ) ù1/ s ,
´ A2 ´ éë N 2 + N% 2 (W2 ) ùû + = A1 ´ éë N1 + N 1 1 û (113)
e1 e1e0

avalanche breakdown is controlled by nng layer, i.e. E2 = E2BD (N 2, W 2), and E1<E1BD and it
increases linearly with N 1. Therefore, strictly speaking, when N 1 < N̄ 1 then tunnel current in‐
creases with increasing N 1. At the same time, J T 2 does not depend on N 1 under following
conditions.
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Figure 18. Dependence of tunnel current density on concentration N 1 in case of independent doping levels of
nwg : InP and nng : I n0.53Ga0.47 As layers at W 2 = 2 μm. a − N 2 = 1014cm-3; W 1, μm: 1 − 0.1, 2 − 0.2, 3 − 0.5, 4 − 1. b −
(T )
neighborhood of value N 1 = N 1min ; W 2 = 2 μm; N 2, cm-3: 1 − 1014, 2 − 1015, 3 − 1016, 4 − 1017
78 Photodiodes - From Fundamentals to Applications

1. If

1/( s -1)
æW ö s-1
ç 1/ 2 ÷ > 1- , (114)
ç W* ÷ 2 s2
è 1/ 2 ø

then at N 1 < N̄ 1,J T 2 > > J T 1 with margin of several orders of magnitude, and therefore with
very high accuracy J T (N 1) = const. If N 1 > N̄ 1 then due to decrease E2 and hence J T 2 also, den‐
sity of tunnel current J T (N 1) begins drop sharply and, reaching minimum value (108) at
concentration (106), then starts to grow again due to growth J T 1(N 1).

2. If

1/( s -1)
æW ö s-1
ç 1/ 2 ÷ << 1 - , (115)
ç W* ÷ 2 s2
è 1/ 2 ø

then after initial plateau J T (N 1) grows monotonically. It is due to monotonic increase in com‐
ponent of tunnel current density J T (N 1), which at N 1 ≥ N̄ 1 is considerably superior to J T 2.

3. If

( )
W 1/2
*
W 1/2
1/(s−1)
≈ 1−
s −1
2s 2
, (116)

then for small enough thicknesses W 1 of layer nwg dependence J T (N 1) has distinct maximum
at N 1 = N̄ 1, however, at least in this case minimum is not deep. This is due to the fact that
components of tunnel current density J T 1 and J T 2 are equal to each other in order of magni‐
tude at small enough W 1. Characteristics of tunnel currents in heterostructure with inde‐
pendent doping of nwg and nng layers are illustrated in Fig. 18. Note that if in case I increase
N 2 leads to decrease J T at all values N 1, then in case II, increase N 2, when N 1 is small
enough, leads to increase of tunnel current, but at sufficiently large N 1 tunnel current de‐
(T )
creases, particularly, in the vicinity of concentration N 1 = N 1min .

4.2.2. Equal doping levels of wide-gap and narrow-gap n type layers

Under this condition density of tunnel current is given by expression (89), where N 1= N 2= N

i.
s
W1 æ e1 ´ A1 ö
³ç ÷ (117)
W2 çè e 2 ´ A2 ÷ø

At this relation of parameters avalanche breakdown is controlled by nwg layer, i.e. E1=
E1BD (N 1, W 1), and E2<E2BD (N 2, W 2) regardless of doping. Dependence J T on N has identi‐
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cal character with J T (N 1) | N in the case of 4.2.1. I, and is caused by the same physical
2=const

grounds. The only difference is that when N < N 2, then curves J T (N ) lie higher on plotting
area, and when N > N 2 – lower, than curves J T (N 1) | N in the case of 4.2.1. I.
2=const

This occurs because at given value E2 length of tunneling in narrow-gap layer is the greater
the higher is level of doping of this layer.

ii. Condition (117) is not satisfied.

Then, till N < N̄ , (where N̄ is determined by equation (113), where N̄ 1= N 2= N̄ ) avalanche

breakdown is controlled by nng layer, i.e. E2=E2BD (N , W 2), and E1<E1BD (N , W 1) and increas‐
es linearly with N . Dependence J T (N ) has, in contrast to situation 4.2.1, not only deep mini‐
mum, but high maximum also (Fig. 19a). This is due to the fact that when N < N̄ then E1
grows and E2 grows also reaching at N = N̄ maximal value (Fig. 19b). As a result, when
N < N̄ then J T 1 grows with increase N and J T 2 grows also. Note that when doping of nwg
(T )
and nng layers are equal then concentration N = N min , at which tunnel current density J T has
minimal value, is determined by formula (106) with accuracy up to small corrections of or‐
der ξ = E1BD (0, W 1) / a1 < < 1, as in the case of independent doping of nwg and nng layers. For‐
(T )
mula for J T minmay be obtained from expression (108), if we replace N 2 by N min in it.

5. Basic performance of avalanche heterophotodiode

5.1. Responsivity

In punch-through conditions of absorber nng , current responsivity SI (λ) of heterostructure

under study can be described by relation (4). In calculating quantum efficiency η of hetero‐
structure, we take into account that optical radiation is not absorbed in its wide-gap layers.
Let’s assume that light beam falls perpendicularly to front surface of heterostructure (Fig. 1),
and absorption coefficient in narrow-gap layer γ (λ ) does not depend on electric field. Quan‐
tum efficiency is ratio of number of electron-hole pairs generated in sample by absorbed
photons per unit time to incident flux of photons.

Therefore, (Fig. 20a)

(1 - R1 ) ´ (1 - R2 )
h= ´ h1 , (118)
1 - R1 ´ R2

where reflection coefficient of light from illuminated surface R1 = ( εex − ε1)

2
/( εex + ε1)
2

and from interfaces of heterostructure R2 = ( ε2 − ε1)2/( ε2 + ε1)2; εex – relative dielectric

80 Photodiodes - From Fundamentals to Applications

Figure 19. Dependences of tunnel current density (a) and fields Е (b) on dopant concentration N in case of equal
doping levels of nwg : InP and nng : I n0.53Ga0.47 As layers, at W 2 = 2 μm. W 1, μm: 1 – 10, 2 – 1, 3 – 0.1, Curves 1', 2', 3' –
Е2(N ); curve 4 − Е1(N ), weakly dependent on W 1
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constant of environment; and quantum efficiency η1 with respect to light ray which has pe‐
netrated into narrow-gap layer is written

h1 = 1 - z + h2 ´ z ; (119)

quantum efficiency η2 with respect to light ray which has reached to second interface of het‐
erostructure,

R1 R2(1 − R2)2ζ (1 − R2)2 R3

η2 = R2(1 − ζ) + R22ζ(1 − ζ) + η2(ζR2)2 + (1 − ζ + η2ζ) + ×
1 − R1 R2 1 − R2 R3
(120)
R1(1 − R2)2ζ
2
× (1 − ζ)(1 + R2ζ) + η2R2ζ + (1 − ζ + η2ζ) ,
1 − R1 R2

ζ = exp( − γW 2), R3 – reflection coefficient of light from not illuminated (backside) surface.
From expressions (118)-(120) follow, that

1 + R23 exp( -gW2 )

h( gW2 ) = h(¥) ´ éë1 - exp( -gW2 ) ùû ´ (121)
1 - R12 R23 exp( -2 gW2 )

where

(1 - R1 )(1 - R2 )
h(¥) = , (122)
1 - R1R2

Ri (1 - R j ) + R j (1 - Ri )
Rij = , i , j = 1,2,3. (123)
1 - Ri R j

Particularly,

ì 1 - exp( -gW2 )
ïh(¥) , at R3 = R1 ,
ï 1 - R12 exp( -gW2 )
h( gW2 ) = í (124)
ïh(¥) 1 - exp( -2 gW2 ) , at R3 = 1.
ï 1 - R12 exp( -2 gW2 )
î

Dependence η on W 2 for heterostructure InP / I n0.53Ga0.47 As / InP is shown in Fig. 20b. It

should be noted that since in operation, electric field is high even in absorption layer, then,
82 Photodiodes - From Fundamentals to Applications

due to Franz-Keldysh effect, quantum efficiency is slightly higher than given in Fig. 20b.
This is especially true when absorbing layer W 2 is very thin.

Figure 20. Layout view of multiple internal reflections and absorptions of light beam in heterostructure (a) and de‐
pendence of quantum efficiency η of structure InP / I n0.53Ga0.47 As / InP on absorption layer thickness W 2, μm (b): 1 −
R3 = R1 2 − R3 = 1. It is assumed that relative dielectric permittivity of environment εex = 1
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5.2. Noise

It was noted above that in order to achieve the best performance of SAM-APD special dop‐
ing profile is formed in heterostructure which facilitates penetration of photogenerated
charge carriers with higher impact ionization coefficient into multiplication layer. In this
case, at given voltage bias on heterostructure, current responsivity SI (λ) is maximal, and ef‐
fective noise factor F ef ,i (M ph ) is minimal (Tsang, 1985), (Filachev et al, 2011), (Artsis & Kho‐
lodnov, 1984), (McIntyre 1966), and hence, as it is evident from expression (5), noise spectral
density SN is also minimal. If α = β , then (Tsang, 1985), (Filachev et al, 2011), (Artsis & Kho‐
lodnov, 1984), (McIntyre 1966) F ef (M ph ) = M ph , and therefore
3
SN = 2q ´ A ´ JT ´ M ph . (125)

In InP ratio K (E ) = β / α in interval of fields of interest E = (3.3 ÷ 7.7) × 105 V / cm varies from
2.3 to 1.4 (Tsang, 1985), (Filachev et al, 2011), (Cook et al, 1982). Therefore, noise spectral
density of heterostructure with InP multiplication layer and optimal doping is slightly less
than value given by formula (125). When N 1 > N̄ 1, (where N̄ 1 satisfies equation (113) (see
Fig. 21), in which Ñ i (W i ) is defined by formula (94) for i = 1, 2) then avalanche multiplica‐
tion of charge carriers in narrow-gap layer does not occur. Under these conditions, field val‐
ue at metallurgical boundary of p + − n junction (х = 0, Fig. 1) equals to E1 = E1B (N 1, W 1) (see
(93) and (94)). For many semiconductors (see Sections 3.1-3.2) including I nх Ga1−х Asy P1− y ,
values s and Ai are defined by relations (95). In the case of heterostructure InP /
I n0.53Ga0.47 As / InP , in first approximation in parameters of smallness

E1BD (0, W1 ) 2.786 ´ 10 -2 1 1

d1 º = 1 7
, d2 = 2 = (126)
a1 W1 s 64

(T )
we find that value of concentration N 1 = N 1min at which function J T (N 1) reaches its mini‐
mum
W10,49
JT (W1 , N 2 ) = 2.19 ´ 108 ´ ´ exp( -27.88 ´ W11 7 ), A / cm2 , (127)
min
N 20,07

is given by

2.33 ´ 1016 é 2.52 ´ 10 -2 æ N ´ W 8 7 öù

(T )
N1min (W1 , N 2 ) = ´ ê1 - ´ ç ln 2 1
- 1.41 ÷ ú , cm -3 (128)
W18 7 êë W1 17 ç 3.69 ´ 10 15 ÷ú
è øû

Formulas (127) and (128) are valid when W T 2 ≤ W 2, i.e., as follows from Section 4.2.1, when

5
N 2 ´ W2 ³ Q(W1 ) = ´ 1014 , (129)
W12 7
84 Photodiodes - From Fundamentals to Applications

where concentration and thicknesses, as in (127) and (128), are measured in cm-3 and μm,
respectively.
(T )
If inequality (129) is not satisfied, then values N 1min and J T min will be again determined by
(127) and (128), in which N 2 is replaced by Q(W 1) / W 2. It is shown from (127) and (128) that
(T )
N 1min and J T min are decreasing, moreover J T min sharply, with increase W 1 (see Fig. 21, 22),
(T )
and, also, although weakly, with increase N 2. Decrease of values N 1min and J T min with in‐
crease W 1 is caused by situation when the thicker W 1 the less E1BD and the greater fall of
(T )
field E (x) on nwg layer thickness. Slight decrease N 1min and J T min with growth N 2 is due to
increasing of length of interband tunneling lTng in narrow-gap nng layer with increase N 2
and the fact that at minimum J T 1 > J T 2. For small values either N 2 or W 2, field E (x) is so
weakly dependent on x in nng layer, that value lTng in it is almost constant. Therefore, when
(T )
N 2W 2 < Q(W 1) then values N 1min and J T min do no longer depend on N 2 and slightly decrease
with increase W 2 due to reducing the length of tunneling generation region in narrow-gap
material. In high performance diode, absorber should be punched-through when voltage
bias V b on heterostructure is less than voltage of avalanche breakdown V BD . This eliminates
dark diffusion current from narrow-gap layer and increases operational speed. Condition of
punch-through of absorber, as follows from 4.1 and 4.2 is given by:

e 0 e1
N1 ´ W1 + N 2 ´ W2 < ´ E1BD ( N1 , W1 ). (130)
q

Allowable intervals of concentrations and thicknesses of heterostructure layers are shown in

Fig. 21. As can be seen from Fig. 20b, even, when R1 = R3 quantum efficiency reaches almost
its maximal value when W 2 = 2 μm. Therefore, for development of concentration – thickness
nomogram in Fig. 21, namely this value W 2 was selected. Note that decrease in dispersion in
N 2 results in increase in dispersion N 1 and W 1, while increase gives the opposite result. Val‐
ue of noise current density I N ≤ 10−12A/Hz1/2 corresponds to J T ≤ 1.8 × 10−5А/сm2, and value
I N ≤ 10−13 А/ Hz1/2 corresponds to J T ≤ 1.8 × 10−7А/сm2.

5.3. Operational speed

Minimal possible time-of-response of this class of devices

(
t = 2 ´ ttr 1 ´ f ( M ph ) + ttr 2 ) (131)

is determined by time-of-flight of charge carriers through multiplication layer τtr 1 and ab‐
sorber τtr 2, and also by value of function f (M ph ), which is close to 1 when K > > 1, and is
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 85
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Figure 21. Concentration-thickness nomogram for avalanche InP / I n0.53Ga0.47 As / InP heterophotodiode when
N 2 = (1 ÷ 5) × 1015cm-3, W 2 = 2 μm, М ph = 15, cross-section area A = 5 × 103 μm2. When noise current I N = SN ≤ 10−13
A/Hz1/2, then allowable set of points in space (N 1, W 1) lies inside figure a-b-c-d; when I N = SN ≤ 10−12 A/Hz1/2 − inside
(T )
figure a-e-f-g. Dashed and dash-dot curves − dependences N 1min (W 1) and N̄ 1(W 1), respectively: 1 − N 2 = 1015cm-3, 2 −
N 2 = 5 × 1015cm-3. N 1 is measured in units of 1016cm-3, W 1 − in μm
86 Photodiodes - From Fundamentals to Applications

Figure 22. Dependences of minimal tunnel current J T min, A/cm2 of avalanche heterophotodiode InP / I n0.53Ga0.47 As
/ InP on multiplication layer thickness W 1, μm: 1 − N 2 = 1013cm-3, 2 − N 2 = 1015cm-3, 3 − N 2 = 1017cm-3

equal to M ph when K = 1 (Tsang, 1985), (Filachev et al, 2011), (Emmons, 1967), (Kurochkin &
Kholodnov, 1996). It was noted above that in InP 1 < K ≤ 2.3. Therefore, in InP /
I nx Ga1−x Asy P1− y / InP SAM-APD

(
t @ 2 ´ ttr 1 ´ M ph + ttr 2 .) (132)

As is evident from Fig. 20b, in InP / I n0.53Ga0.47 As / InP heterostructure quantum efficiency
value η lies in interval 0.5 ≤ η ≤ 0.686 when R3 = 1 and W 2 ≥ 0.5 μm. It means that, because of
not so much loss in quantum efficiency η compared to maximal possible (only 27 % less),
time-of-response value τtr 2 = 5 ps can be achieved by forming absorber with thickness
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W 2 = 0.5 μm and fully reflecting backside surface. Minimal value τtr 1 is determined by maxi‐
mum allowable minimal value W 1min. When J T ≤ 10−6 A/cm2, then as follows from Fig. 22,
W 1min ≅ 2 μm, and therefore τmin ≅ (4M ph + 1) × 10−2 ns.

6. Analytical model of avalanche photodiodes operation in Geiger mode

We consider possibility to describe transient phenomena in p − i − n APDs by elementary

functions, first of all, when initially applied voltage V 0 is greater than avalanche breakdown
voltage V BD . Formulation of the problem is caused by need to know specific conditions of
APDs operation in Geiger mode. Simple expression describing dynamics of avalanche Gei‐
ger process is derived. Formula for total time of Geiger process is obtained. Explicit analyti‐
cal expression for realization of Geiger mode is presented. Applicability of obtained results
is defined. APDs in Geiger mode (pulsed photoelectric signals) make possible detection of
single photons (Groves et al, 2005), (Spinelli & Lacaita, 1997), (Zheleznykh et al, 2011), (Stop‐
pa et al, 2005), (Gulakov et al, 2007). It is worked at reverse bias voltages V b > V BD . Different
types of devices are realized on APDs in Geiger mode (Groves et al, 2005), (Spinelli & Lacai‐
ta, 1997), (Zheleznykh et al, 2011), (Stoppa et al, 2005), (Gulakov et al, 2007). At the same
time, review of publications shows that theoretical studies have tendency to carry out in‐
creasingly sophisticated numerical simulations. In (Vanyushin et al, 2007) was proposed dis‐
crete model of Geiger avalanche process in p − i − n structure. Obtained iterative relations
allow to determine, although fairly easy, but only by numerical method, options for realiza‐
tion of Geiger mode when ratio K ≡ β / α differs very much from unity, where α(EiGE ) and
β(EiGE ) – impact ionization coefficients of electrons and holes and EiGE – electric field in i –
layer (base 0 < x < W iGE , Fig. 23). "Continuous" model (Kholodnov, 2009) developed in this
section admits value К = 1. Considered below approach allows also to describe conditions of
realization of Geiger mode and its characteristics by mathematically simple, graphically il‐
lustrative relations. It is adopted that photogeneration (PhG) is uniform over sample cross-
section area S transverse to axis x (Fig. 23). Then, in the most important single-photon
process, area S , according to uncertainty principle, shall not exceed in the order of magni‐
tude, square of wavelength of light λ . Under these conditions, it is allowably to consider
problem as one-dimensional (axis x , Fig. 23). There are grounds to suppose that go beyond
one-dimensional model at local illumination make no sense. Single-photon case arises itself
when S > > S1 ≈ π × λ 2. The matter is that charge, during Geiger avalanche process, as show
estimates below, has no time to spread significantly over cross section area. Consider serial
circuit: p − i − n diode – load resistance R – power supply source providing bias V b > V BD . Let
p and n regions are heavily doped, so that prevailing share of bias falls across base i . Then
after charging process voltage on it can be considered equals to V 0 = V b. When electron-hole
pairs appear in the base then occurs their multiplication that results in decrease V i due to
screening of field EiGE in base by major charge carriers inflowing into p and n regions (Fig.
88 Photodiodes - From Fundamentals to Applications

23) in quantity N n and Pp and voltage drop across load resistor V R and, hence, current in
external circuit arise

VR Vb −Vi
IR = ≡ . (133)
R R

Figure 23. Avalanche process in p − i − n structure: “-“ − acceptors charge in boundary i − p layer (cathode plate − Cath‐
ode); “+” − donors charge in boundary i − n layer (anode plate − Anode); ⊖ and ⊕ − generated in i − region avalanche
photoelectrons and photoholes; N n and Pp − inflowing in n − and p − regions avalanche photoelectrons and photo‐
holes; Ес and Еv – energy of conduction band bottom and valence band top; hν − photon energy

In present structure charge is mainly concentrated in thin near border n − i and p − i layers
(let's call them plates, Fig. 23). Therefore, as in (Vanyushin et al, 2007), field EiGE will be as‐
 Physical Design Fundamentals of High-Performance Avalanche Heterophotodiodes with Separate Absorption… 89
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sumed uniform. Numerical value EiGE = E BD when V i = V BD for a number of materials can be
quickly determined by formulas given in Section 3. As in (Vanyushin et al, 2007), we restrict
consideration by PhG in base only, we neglect recombination in it, and we assume that cur‐
rents of electrons I N and holes I P are determined by their drift in electric field with velocity
of saturation vs , i.e.,

I N ( x , t ) = q ´ vs ´ N ( x , t ), I P ( x , t ) º I ( x , t ) - I N ( x , t ) = q ´ vs ´ P( x , t ), (134)

where N and P – linear density (per unit length) of electrons and holes, I – full conductive
current, q – absolute value of electron charge, t - time.

Substituting volume charge density from Poisson equation in continuity equation for I and
integrating over depletion layer (DL) we obtain that, in approximation of zero-bias current,
in quasi-neutral parts of structure

Wd
¶Vd 1
I R = Cd ´
¶t
+ < I d > , < I d >= GE ´
Wi
ò I( x , t)dx (135)
0

where V d – voltage on DL, Cd = εε0 × S / W d and W d – DL capacity and thickness, ε0 –

dielectric constant of vacuum, ε – dielectric permittivity, < I d > let’s call avalanche current
I av .

Relation (135) generalizes well-known theorem of Rameau (Spinelli & Lacaita, 1997), it takes
into account key feature of Geiger mode – variation over time of voltage across DL, and it is
valid for any distribution profile of dopant. In our formulation of the problem (in p − i − n
structure) i – layer can be considered as DL, i.e., d in (135) and below should be replaced by
i . By integrating continuity equation for I N and I P with respect to x from 0 to W iGE and
marking linear density of photogeneration rate as G(x, t) we obtain equations

¶N i (t )
q´ = a ´ I%N (t ) + b ´ I%P (t ) + I N (WiGE , t ) - I N (0, t ) + q ´ G% (t ), (136)
¶t

¶Pi (t )
q´ = a ´ I%N (t ) + b ´ I%P (t ) - I P (WiGE , t ) + I P (0, t ) + q ´ G% (t ), (137)
¶t

WiGE WiGE WiGE WiGE

Ni = ò N ( x , t )dx , Pi = ò P( x , t )dx , I%N , P (t ) = ò I N , P ( x , t )dx , G% (t ) = ò G( x , t )dx (138)
0 0 0 0
90 Photodiodes - From Fundamentals to Applications

Because plates are very thin, then generation and recombination in them can be neglected.
Now by integrating same equations with respect to thickness of plates, we find that in ap‐
proximation of absence of minority carriers in p and n regions

∂ Nn ∂Vi
I N (0, t) = I R + q × = I R − Ci × = I P (W iGE , t), I P (0, t) = I N (W iGE , t) = 0 (139)
∂t ∂t

Strictly speaking, equations (139) are valid when r1 ≡ Pp / N n = 1, from which

r2 ≡ | Pi − N i | / N n = 0. Therefore, let’s assume uniform PhG along x . Then, at К = 1, symmetry
requires r1 = 1. Equations (139) are correct in concern of the order of magnitude both when К
is not too big and when small also. This follows from quasi-discrete computer iterations in
uniform static field. Computer iterations are performed in several evenly spaced points of
PhG xg succeeded by averaging with respect to xg and take into account much more number
acts of impact ionization by holes than similar iterations in (Vanyushin et al, 2007). Iteration
procedure performed in interval equals to several time-of-flight of charge carriers through
base ttr gives 0.6 <r1< 1, and r2< 0.4 (Fig. 24a), which corresponds to approximation of uni‐
form field. Note that smallness r2 does not mean smallness Pi + N i (curve 3 in Fig. 24a).

Relations (133)-(139) allow obtaining equations

¶ 2 VR ïì 1 ïü ¶V v 2 ´ vs
F[VR ;(1 / ti )] º + í - vs ´ Y[ EiGE (VR )]ý ´ R - s ´ Y[ EiGE (VR )] ´ VR = q ´ G% (t ) ´ , (140)
¶t 2 ïî ti ïþ ¶t ti Ci ´ WiGE

with initial conditions

t
¶VR 2 vs
VR (0) = 0, = ´ lim q ´ ò G% (t ')dt ' (141)
¶t t =0 Ci ´ WiGE t ®0
-t

where

Y ( EiGE ) = C( EiGE ) - (2 / WiGE ), X = a( EiGE ) + b( EiGE ), EiGE = (Vb - VR ) / WiGE , ti = RCi , Ci = ee0 ´ (S / WiGE ) (142)

At delta-shaped time-evolving illumination G̃ i (t) = N ph × δ(t) relations (140) and (141) are
converted into

¶VR q ´ 2 vs ´ N ph
F[VR ;(1 / ti )] = 0, VR (0) = 0, = AGE º (143)
¶t t =0
ee0 ´ S

where N ph – number of absorbed photons.

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Figure 24. Evaluation of applicability of quasi-uniform field approximation. (a) − Results of quasi-discrete computer
iterative procedure rj (K ): r1=Pp / N n , r2= | Pi − N i | / N n , r3=(Pp + N n ) / (Pi + N i ). (b) − Dependence of error ER during deter‐
mination of breakdown field on K = β / α ; accepted (Tsang, 1985), (Grekhov & Serezhkin, 1980)
α(E) = A GE × exp( − B / E ), where A GE , 1/μm: 1 − 200, 2 − 400, 3 − 800, 4 − 2000, 5 − 5000
92 Photodiodes - From Fundamentals to Applications

If we take R = 0 and limG̃ i (t) = const ≠ 0 then we find that breakdown is determined by condi‐
t→∞

tion W iGE × Χ(EiGE ) = 2, which at К ≠ 1 gives another value for breakdown field EiGE = Eav than
EiGE = E BD obtained directly from solving of stationary problem in Section 3. However, dis‐
crepancy between Eav and E BD is no more than 20 %, if К is different from 1 by no more than
two orders of magnitude (Fig. 24b). Equation (140) admits only numerical solution. Howev‐
er, Geiger mode can be described without solving this equation, by using physical grounds
and limit R → ∞ , when

¶DVi ¶DVi
I av = Ci ´ , F[DV ; 0] = 0, EiGE = Vi / WiGE º [Vb - DVi (t )] / WiGE , DVi (0) = 0, = AGE (144)
¶t ¶t t =0

and problem is solved in quadratures. To solve in elementary functions let’s approximate

exact dependence Y EiGE (ΔV i ) by piecewise-linear function passing through principal
point ΔV i = Dav ≡ V b − V av = V b − Eav × W iGE (Fig. 25 and 26), where Y =0, and I av reaches its peak
during tav .

Figure 25. Form of approximation of function Y (ΔV ). Dependences (1 - exact, 2 - approximate) are plotted for Ge
with orientation <100> (Tsang, 1985) taken W iGE = 1 μm, Dav = 4 V
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Figure 26. Ratio of approximate dependence Ỹ (ΔV ) to exact Y (ΔV ) for Ge with orientation <100>; δ = ΔV / (ΔV )max;
− W iGE =1 μm, − W iGE =2 μm; Dav , V: 1 − 0.25, 2 − 0.5; 3 − 1

Suppose, for simplicity X (Eb) ≤ 4 / W iGE , where Eb = V b / W iGE . Then ΔV imax ≡ limΔV i (t) is not
t→∞

more than value of break point ΔV k of piecewise-linear approximation (Fig. 25). Under
these conditions

Zt / tav - 1 ln Z ee ´ S ´ Yb ´ Dav
DVi (t ) = DVi max ´ , DVi max = 2 Dav , tav = ,Z º 0 >> 40, (145)
Zt / tav + Z vs ´ Yb q ´ N ph

where Y b = Y b(Eb). Geiger mode occurs when during time R × Ci of inverse recharge of ava‐
lanche diode, avalanche is able to develop and cancel itself in full. As seen from (145) it is
happened when R ≥ Rmin ≅ tav / Ci . Maximal voltage drop on load equals to V Rmax = ΔV imax.
Since ttr <<tav , then results of computer evaluation of uniform field approximation applicabil‐
ity can be considered reasonable. To evaluate transverse charge spreading let’s use expres‐
94 Photodiodes - From Fundamentals to Applications

sion (21) from (Pospelov et al, 1974). It determines dependence χ(t) ≡ r / r0, where r(t) and r0
– current and initial radii of charge "drop" of parabolic type. Implying under capacity in
(Pospelov et al, 1974) value Ci and putting W iGE = 1 μm, r0 = λ = 1 μm, in the case of single-
photon process we get χ(tav )< 21/4 ≅ 1.2. This justifies our assumption that charge spreading
˜
over sample cross-section during avalanche Geiger process is not intensive.

7. Conclusions

The above analysis shows that to create high performance SAM-APD (in particular, based
on widely used InP / I nx Ga1−x Asy P1− y / InP heterostructures) it is necessary to maintain close
tolerances on dopants concentration in wide-gap multiplication layer I – N 1 and in narrow-
gap absorption layer II – N 2, and also on thickness W 1 of wide-gap multiplication layer (Fig.
1). This is due to strong dependence of interband tunnel current in such heterostructures on
N 1, N 2 and W 1. Allowable variation intervals of values N 1, N 2 and W 1, and, optimal thick‐
ness of absorber also, can be determined using results obtained in Sections 4 and 5. Value of
minimal possible time-of-response τmin depends not only on photocurrent’s gain М ph but on
allowable noise density at preset value of photocurrent’s gain also. The lower noise density,
the larger is value τmin. For example, for heterostructure InP / I n0.53Ga0.47 As / InP minimal
time-of-response equals to τmin ≈ 0.6 ns, when noise current equals to 3.3×10−11 А/Hz1/2 and
current responsivity 10.3 A/W. Analysis shows that operational speed can be slightly in‐
creased by means of inhomogeneous doping of wide-gap multiplication layer. To ensure op‐
erational speed in picosecond range it is necessary to use as multiplication layer
semiconductor layer with low tunnel current and impact ionization coefficients of electrons
and holes much different from each other, for example, indirect-gap semiconductor silicon.
As has long been known maximal operational speed is achieved by APD if light is absorbed
in space-charge region. In this case, as it was shown in Section 6, when bias voltage V b ex‐
ceeds breakdown voltage V BD of no more than a few volts, then, for K ≡ β / α values lying in
interval from a few hundredths to a few tens, elementary relations (145) can be used for ap‐
proximate description of Geiger mode in p − i − n APD. Moreover if cross-section area
S > S1 ≈ π × λ 2, then we can expect that in single-photon case under S in (145) should imply
value of order S1. This is due to finite size of single-photon spot S1 and not intensive spread‐
ing of charge during time of avalanche Geiger process tav when photogeneration of charge
carriers occurs in i – region of p − i − n structure depleted by charge carriers. Proposed ap‐
proach allows describing Geiger mode by elementary functions at voltages higher V b as
well. Note that equation (140) and physical grownds allow to expect three possible process
modes at pulse illumination under V b > V BD . When RC < < tav then generated photocurrent
will tend to reach some constant and flow indefinitely (unless, of course, ignore energy loss‐
es). When RC = tav then generated photocurrent will be of infinitely long oscillatory charac‐
ter. When RC > > tav then Geiger mode is realized.
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Author details

Viacheslav Kholodnov1 and Mikhail Nikitin2

1 V.A. Kotelnikov Institute of Radio Engineering and Electronics Russian Academy of Scien‐
ces, Moscow, Russia

2 Science & Production Association ALPHA, Moscow, Russia

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 Section 2

Fabrication and Measurements

 Chapter 3

Fabrication of Crystalline Silicon Solar Cell with Emitter

Diffusion, SiNx Surface Passivation and Screen Printing
of Electrode

S. M. Iftiquar, Youngwoo Lee, Minkyu Ju,

Nagarajan Balaji, Suresh Kumar Dhungel and
Junsin Yi

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/51065

1. Introduction

The amount of solar energy incident on the earth surface every second (1650 TW) is high‐
er than the combined power consumption by using oil, fossil fuel, and other sources of en‐
ergy by the entire world community (< 20 TW) in 2005. The solar photovoltaic power
generation are ever increasing in capacity, yet at a lower scale. Thus there is a scope of fur‐
ther use of solar energy to produce more electricity. For this purpose a demand for a large
scale commercial production of solar cells have emerged. There is a large variety of solar
cell structures proposed with various types of materials, of which p-type c-Si solar cell has
been one of the most popular and widely used in commercial production with screen print‐
ing technique.

Looking back to the history of solar cell, one can find that, in 1839 Becquerel observed a light
dependant voltage between two electrodes, that were immersed in an electrolyte. In 1941,
first silicon based solar cell was demonstrated and 1954 is the beginning of modern solar cell
research. Since then there has been several proposals for solar cell design, that can lead to
various photovoltaic (PV) conversion efficiencies (η) of the solar cells. A conventional Si so‐
lar cell gives 14.7% PV efficiency[1], whereas other designs, for example, back surface field
(BSF) 15.5% [2], rear local contact (RLC) solar cell efficiency ~20%, as reported by NREL.
However these values are not the theoretical or experimental limit, and there is a continuous
effort in improving the efficiency.
106 Photodiodes - From Fundamentals to Applications

The c-Si solar cells fabricated on the high quality silicon wafers, having selective emitter on
the front and local contact on the rear surface [3] shows higher η, but the required additional
measures to be taken for the production of such solar cells may substantially increase the
production cost.

Presently the cost of the silicon wafer alone covers >20% of the total cost of solar cell produc‐
tion, so there may be a technology available in future, by which a large scale production of
silicon solar cells from a thin wafer ( < 200μm) will be possible

2. Fabrication Process for Industrially Applicable Crystalline Silicon

Solar Cells

The fabrication of our c-Si solar cell starts with a 300μm thick, (100) oriented Czochralski Si
(or Cz-Si) wafer. The wafers generally have micrometer sized surface damages, that needs to
be removed. After the damage removal, the wafer surface shows high optical reflectivity, for
which an anti-reflection coating (ARC) is necessary. Furthermore, the top surface was tex‐
tured by chemical etching before an ARC was deposited.

For a p-type c-Si substrate, an n-type top layer while for an n-type c-Si substrate a p-type top
layer acts as emitter. A thermal diffusion is commonly used for emitter diffusion [4]. After
the emitter diffusion, the edge isolation was carried out, as otherwise the top and the bottom
surfaces of the wafers remain electrically shorted.

A suitable thin dielectric coating at the front and back of the wafers were given to passivate
surface defects. As the wafer becomes covered with a dielectric layer, an electrical connec‐
tion to the cell becomes necessary. Ag and Al metal electrodes were formed by using screen
printing of Al pastes and co-firing at a suitable temperature.

2.1. Wafer Cleaning and Saw Damage Removal

In order to remove the organic contaminants from the c-Si wafer surfaces, we used 12% NaOCl
solution and cleaned the wafers ultrasonically at room temperature (RT) for five minutes.
This cleans the wafer surface with an approximate Si etching rate of 500nm/min [5]. The sur‐
face damages to the wafers were removed through isotropic etching with a concentrated sol‐
ution of NaOH in de-ionized water (DI-W). DI-W helps the NaOH to break in Na+ and OH-
ions in the solution. An 8% NaOH solution, at 80°C temperature for about 7 minutes of etching
removes the surface damages. This saw damage removal step, etches out about 5 micro me‐
ter Si from wafer surface. After that the wafers were rinsed in HCl(10%) for 1 min, DI-W for
1 min, HF(10%) for 1 min, DI-W for 1 min.

2.2. Surface Texturing

Anisotropic chemical etching of Si (100) oriented wafers give rise to textured surface. The
characteristics of the etching depends upon, time of etching, etching rate, temperature, com‐
 Fabrication of Crystalline Silicon Solar Cell with Emitter Diffusion, SiNx Surface Passivation and Screen Printing of 107
Electrode
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ponents of the solution and its concentration. With a dilute NaOH solution containing iso-
propyl alcohol (IPA) and DI-W, the Si(100) oriented smooth wafers can grow pyramidal
surface texture at 80°C temperature [6]. The surface texturing was performed by asymmetric
etching of front surface of the wafers, in a dilute alkaline solution, as against the concentrat‐
ed solution used for saw damage removal. The loss in mass of each wafer were estimated
from the mass of the wafer measured with a microbalance before and after texturing, which
subsequently led to the estimation of the etched thickness of the wafer and hence etch rate.
Optical microscopic observations, SEM images, and laser scanning were the tools that were
used for the characterization of the textured surface morphology. Ultraviolet visible (UV-
Vis) spectrophotometry was used to estimate the retro-reflectivity of the textured surface.
The etching depends mainly on two processes. One is the rate of the reaction at the surface,
and the other is the rate at which reactants diffuse into the surface. These two processes con‐
trol the overall rate of the micro structural growth during the etching. The anisotropic etch‐
ants is expected to etch (110) plane at a faster rate than the (100) plane while the (111) plane
etches at a slowest rate [7]. However if chemical composition of the etchant is such that
some insoluble residue is formed during etching process (like oxides etc.) then diffusion of
etchant into the Si will be hindered and hence etching will not happen as expected.
IPA enhances surface diffusion, so a rapid etching can take place in presence of IPA in the
solution [8]. The NaOH etches silicon crystal planes differently, mostly because of different
atomic concentration in different crystallographic planes. So, at a lower NaOH concentration
the selective etching process helps to create textured surface of the wafer. The chemical reac‐
tion that takes place is as follows,

Si + 2NaOH + H 2 O ® Na 2SiO3 + 2H 2 (1)

The sodium silicate (Na2SiO3) is soluble in water and thus Si surface remains devoid of any
deposition. At 80oC temperature, (100) planes etch about two orders of magnitude faster
than (111) planes [9]. For a (100) silicon wafer, a solution of NaOH, IPA, DI-W creates square
based four sided pyramids consisting of sections of (111) planes which form internal angles
of 54.7° with the (100) surface.
The degree of isotropy is sensitive to the concentration of the solution. While a 8% NaOH
solution at 80°C temperature etches silicon isotropically to achieve a polished wafer surface,
a 2% NaOH, 8% IPA solution at 80°C temperature etches anisotropically to a square based
pyramidal surface texture.

2.3. Phosphorus Diffusion for p-n Junction Formation

The thermal diffusion of phosphorus is necessary to create an n-type emitter to the p-type
wafer. The diffusion depends on various factors, of which temperature and gaseous envi‐
ronment is most important [10]. In oxygen environment and at 850°C temperature, the diffu‐
sion coefficient (D) can be approximated as D~0.0013μm2/hr. The phosphorus diffusion
108 Photodiodes - From Fundamentals to Applications

leads to formation of n+ type emitter at the top surface of the wafer. The diffusion was car‐
ried out in two stages, pre-deposition and drive-in [11-13]. At the pre-deposition stage, liq‐
uid POCl3 was evaporated by bubbling N2 gas into the liquid. The POCl3 evaporates and
gets deposited at the surface of the wafers. In presence of oxygen, phosphosilicate glass
(PSG) is formed at the 850°C temperature. Phosphosilicate glass or PSG is phosphorus dop‐
ed silicon dioxide, a hard material formed at the top surface of Si wafer. PSG formation rate
is about 15nm in 30 minutes.

After that, in the drive-in stage, the wafers were heated at 850°C temperature for 7 mins,
0.3Torr pressure in presence of oxygen, when the P atoms from the n+-type top layer diffus‐
es deeper into the wafer, forming a deeper junction. Details of the reaction is given below

POCl3(liquid) + N2(bubble) → POCl3(vapor) (pre − deposition) (2)

4POCl3 + 3O 2 ® 2P2 O5 + 6Cl2 (3)

2P2O5 + 5Si → 4P + 5SiO2 (drive-in) (4)

P + 3Si → n − type doped Si (5)

For gaseous diffusion with POCl3, the p-type silicon wafers were loaded into a quartz boat,
which was slowly moved into the middle of a fused quartz tube in a heated horizontal fur‐
nace. The boat, which can hold tens of wafers, was moved slowly into the tube so that the
wafers do not suffer large temperature gradients and warping. Furnace temperature for the
diffusion was held at about 800°C, with a variation across the length of the boat of not more
than 2°C.

When the PSG was deposited in the pre-deposition stage, the dopant profile leads to a shal‐
low junction depth and a high surface concentration. In the drive-in stage, a deeper junction
was formed as phosphorus atoms diffuse deeper, thus thicker emitter and a lower surface
concentration of dopant was achieved. The junction depth is defined as the depth where the
phosphorus and boron concentrations are equal (as boron already existed in p-Si wafers).

Table 1 shows details of P-diffusion process. A shorter pre-deposition of only 7 minutes at

850°C and a drive-in of about 20 min at 850°C temperature, shows good result. It is to be
noted that, a relatively deeper junction and the dead layer near the top wafer surface de‐
grade blue response of solar cells. The PSG was removed by washing the wafer in a 10% HF
solution for one minute.

The heated quartz tube, used for pre-deposition and drive-in, were periodically cleaned
with HCl vapor in an N2 stream.
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Table 1. A typical condition for phosphorus diffusion used in this study, using POCl3 vapor as a source gas, here ‘lpm’
stands for liter per minutes.

2.4. Edge Isolation by Wet Chemical Etching

The edge isolation was carried out after screep printing of acid barrier paste as a mask, by
the reactive ion etching [14-15]. However, it can also be performed by wet etching [16-17]
with HF, HNO3 and CH3COOH acidic solution in the 1:3:1 volume ratio. Then the wafers
were dipped into the acid solution for 1.5 – 2 minutes, after which the stack was rinsed in
DI-W. Then the wafers were thoroughly rinsed with DI-W for five minutes and later spin
dried to make it ready for silicon nitride film deposition.

2.5. Antireflection Coating and Front Surface Passivation

Light reflection as well as electronic defects at the front surface are undesirable, that needs
to be minimized. The hydrogenated SiNx layer also acts as a high quality silicon surface pas‐
sivator [18]. It has been observed that, more than 35% of the incident light gets reflected
back from a bare silicon surface, and a significant amount of incident light reflects from the
silicon surface even after surface texturing. For a single layer ARC, the wavelength (λ0) at
which the anti-reflection is most effective at normal incidence, can be expressed as: λ0 = 4μl
dl, where μl and dl are refractive index, and thickness of the ARC respectively. The reflec‐
tance R of the top surface of a solar cell is given by : R = [(μl 2 –μoμ2 ) / (μ1 2 + μ0μ2)] 2, where
μo and μ2 are the refractive indices of the medium above the ARC and that of the substrate
below the ARC, respectively. For zero reflectance, i.e. R = 0, it gives: μl = (μoμ2) ½. At λ = 550
nm, the desired thickness of silicon nitride film with μ1 = 1.96 would be 700 Å, taking air (μ =
1) as ambient above the cells [19]. The thicknesses and refractive indices of the SiNx films
prepared by PECVD under different gas flow ratios were characterized by Spectroscopic El‐
lipsometry.
The parameters for the SiNx depositions were: chamber pressure 0.6 Torr, deposition tem‐
perature 300°C, RF power density 0.08 W cm-2 at a 13.56 MHz frequency, silane (SiH4) and
ammonia (NH3) source gases, deposition time 4 minutes, with deposition rate of 3 Å/s. The
Si atom of SiNx mostly comes from silane source gas in RF PECVD process, following the
reaction, 3 SiH4 + 4NH3 → Si3N4 + 12H2.
110 Photodiodes - From Fundamentals to Applications

SiNx can also be deposited on Si surface through forming gas annealing at a higher tempera‐
ture. Forming gas is a mixture of hydrogen (H2) and nitrogen (N2), that were obtained by
dissociating ammonia (NH3) at high temperature. In this case the Si atom of SiNx come from
the surface atoms of Si wafer. However, due to higher process temperature, this method was
avoided, as a higher process temperature may alter distribution of phosphorus atoms and
hence the junction depth.

The recombination rate (Us) at the surface, with surface recombination velocity (S), is related
to excess concentration of minority carriers (∆ns) at the surface. Us ≡ S ∆ ns. Therefore, the
recombination can be minimized by a reduction of minority carrier type at the surface. Us‐
ing high-low junction n+pp+ structure the minority carriers at the surface can be reduced
[20]. This technology, known as back surface field (BSF), is widely used at the rear surface of
solar cells. Another method is the field effect passivation. The fixed charges in a passivation
layer repel the minority carriers or the extremely large fixed charges bend the energy band,
resulting in an inverting layer at the surface.

The effective lifetime of charge carrier can reflect total effect of bulk and surface recombina‐
tion. For the p-type silicon wafer of thickness W and diffusion coefficient of electron Dn, hav‐
ing front and back surfaces equally passivated, the effective lifetime ( τeff) can be expressed
as

(6)

and

(7)

where τb is minority carrier lifetime at the back surface. By combining the two cases, the ef‐
fective lifetime can be calculated by using above equations with about 5 % deviation from
the exact solution [21]

(8)

If the parameters, such as bulk lifetime of silicon (Π), wafer thickness, and diffusion co-effi‐
cient of electron are considered to be constant, the measure of effective lifetime gives the di‐
rect measure of S. As the S is an indicator of surface passivation, the measured τeff can also
be used as an indicator of the quality of surface passivation in silicon substrate.
 Fabrication of Crystalline Silicon Solar Cell with Emitter Diffusion, SiNx Surface Passivation and Screen Printing of 111
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2.6. Metallization

In order to reduce the production cost of the photovoltaic solar cell, metallization was realiz‐
ed by screen-printing of metal paste on the SiNx coating, followed by a co-firing. Another
competing technology for solar cell production is buried-contact technology, that involves
laser grooving and metal plating, which is a bit complex procedure, time consuming and
may result in a significantly high number of faulty solar cells, because of small imperfection
in metallizations, a kind of imperfection that does not make screen printed solar cells faulty.

Screen-printing (SP) is cost effective, robust, simple, inexpensive, and fast method of metalli‐
zation of the solar cells [22-23]. It can also be easily automated with a high throughput (ex‐
ceeding about 1,000 wafers per hour). This technique has been widely used for solar cell
fabrication since the early 1970s.

For selective emitter formation at the back, etchant material was screen printed before
screen printing the metal paste. During the co-firing process the necessary electronic connec‐
tion of the cell layers with the electrodes were formed. We used the Ferro- 53-102 aluminum
paste and Ferro-33-462 as Ag paste.

Baking of the screen printed wafers were carried out immediately after each printing step in
a separate conveyor belt furnace at 150°C. A burn-out process removes the organic binders
from the paste and it was carried out between 350 ~ 510°C.

The thickness of the Al over the entire back surface of the cell was maintained almost uni‐
form with a variation of ± 2 μm. Wafer bowing is a problem with full Al printing at the back
of the wafer, that was minimized to a level below 0.5 mm due to the use the low bow, lead
free paste and a thicker wafer (300μm). Bowing happens mainly due to difference in the
thermal expansion coefficients of Si and Al pastes (αSi = 7.6 K-1, αAl = 23.8 K-1) and can be
avoided by the local back contact (LBC) approach. For the application of this LBC technique
in industrial production, an addition step of Ag / Al printing in a pattern of two wide bus
bars on the back surface was introduced in order to make back metal contact solderable dur‐
ing the module making process. Despite the simplicity and technical advantages of this
process for making fully covered back metal contact and surface passivation through back
surface field (BSF) in a single shot, the emerging trend of using thinner wafers to meet the
challenges posed by depleting silicon feedstock may put this process at stake.

A problem of Aluminum ball formation was observed during the co-firing process, that was
mostly eliminated by flowing sufficient oxygen during the co-firing and also by applying a
rapid cooling approach at the end of co-firing.

Metallization is a very important step for device fabrication because it strongly affects per‐
formance of the solar cell on its short circuit current density (Jsc), open circuit voltage (Voc),
series resistance (Rs), shunt resistance (Rsh), and fill factor (FF). At the front surface the metal‐
lization creates electrical connection to thin n+ layer that is covered with SiNx. At the back
surface it provides an electrical connection and at the same time it creates a p+ layer. A glass
frit present in the Ag paste makes a superior metallization through SiNx film. However, op‐
timization of the co-firing process is critical in obtaining desired metal contact. The peak tem‐
112 Photodiodes - From Fundamentals to Applications

perature and ramp-up rate during the co-firing process are crucial along with the belt speed
that determines residual time of the wafers to various temperature zones. A cylindrical proc‐
ess zone has different local temperature setting and the belt carries the Si wafers at a cer‐
tain speed. The grid pattern of the front electrode has a significant influence on Rs and FF,
that demands optimization of co-firing process. With an increase in the sheet resistance (Rsheet)
of the emitters, Voc decreases, however Jsc increases, which may be because of the improve‐
ment of blue-response, more light entering the solar cell active region and the reduction of
recombination in the front surface. At a faster co-firing condition BSF layers and Ohmic front
contacts can preferably be established, because the Rsheet of emitters may remain nearly un‐
changed. We observed a Voc of around 622mV and FF of 80.6% by Suns-Voc measurement.
Suns-Voc measurement is a method of estimating open circuit voltage from decay character‐
istics of photo generated charge carriers. This method is generally adopted when physical
dimension of solar cell is different from its standard cell structure. Using the result, we ob‐
tain an optimized co-firing process.
Fig 1 shows important components of screen printing. The screen is made up of an interwo‐
ven mesh kept at a high tension, with an organic emulsion layer defining the printing pat‐
tern. Fig. 1(a) shows a microscopic image of the screen. Printing pattern of the front metal
contact with optimized dimensions (finger width, finger spacing, busbar width, maximum
defined finger length) was developed in the form of a computer- aided – design (CAD) as
shown in Fig. 1(b). The screen printer is equipped with optical vision system for proper
alignment. The co-firing was carried out in a conveyor belt furnace (Sierratherm).

Figure 1. a) Microscopic image of the screen used in SP. (b) Design of the front metal printing pattern for the single c-
Si wafer of size 125mm × 125mm (pseudo square).

2.6.1. Back Metallization by Screen printing

Rear surface of solar cells were screen printed with Aluminum paste (Ferro- 53-102). The
thickness of the printed metal was maintained 20μm, with a variation of ±2μm. The average
gain in mass of the wafer after back printing and drying was ~ 6 mg /cm2.
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2.6.2. Co-firing of Screen Printed Pastes

Co-firing of printed metal paste was followed in three major steps, baking, burn- out, and
sintering. Baking refers to the process of evaporating solvents of the pastes to avoid the gas
bubbling and cracks formation during the high temperature treatment. The baking is carried
out immediately after each metal printing step in a separate conveyor belt furnace at 150oC.
Burn- out process removes the organic binders from the paste and it was carried out at
350-510oC.

The temperature profile for the co-firing cycle can be decided on the basis of the studies of
Kim et. al [24]. With improper temperature and the belt speed settings of the co-firing, the
metal electrodes can penetrate across the p-n junction, as schematically shown in Fig. 2, thus
making the cell unusable.

The belt furnace used in this system was equipped with the facility to observe and adjust the
actual front and back surface temperatures of the wafer by real time measurement, with two
different thermocouples. As suggested in ref [24], we tested the co-firing with different tem‐
peratures of front and back surface. However, such a temperature difference may lead to
bending of the wafer. So we prefer keeping the temperature of both the surfaces as equal.
Proper Ohmic contact formation on the front and Al-Si alloying at back surface for proper
BSF generation are the two significant accomplishments of this single shot method.

Ag Metal

n+ Silicon
( 0.1 – 0. 8 μm )

Spiking
Junction
Interfacial short

P-silicon

Figure 2. P-N junction of a typical solar cell with Ag metallization on front surface showing the possible cases of
shunting through the p-n junction during co-firing as well as good sintering.
114 Photodiodes - From Fundamentals to Applications

The co-firing was carried out in the condition of sufficient dry and filtered air flow into the
furnace. It is one of the most sensitive steps of the solar cell fabrication. Any non-uniformity
in surface cleaning, texturing, doping, or even ARC can have detrimental effect on the per‐
formance of the fabricated cells as well, especially in industrial process. If co-firing is done at
a temperature below optimum temperature profile, it results in high series resistance and
hence low FF due to poor Ohmic front contact and poor BSF, whereas over – co-firing at a
higher temperature profile may result in junction shunting and degradation in surface and
bulk passivation. Thus, finding an optimum co-firing temperature profile should be always
the first priority in the industrial process.

An advantage of an LBSF compared to the standard full Al-BSF is the lower consumption of
expensive printing pastes. In order to accomplish the local back contact in solar cells, many
techniques have already been employed. It has been shown that the hybrid buried contact
solar cell with photo lithographically defined rear contacts achieves an increase in Voc by
30mV [25] as compared with a standard buried contact cell with conventional aluminum al‐
loyed BSF, which may result in a high rear surface recombination velocity. Koschier et al.
[26] also demonstrated a 30 to 40mV increase in open circuit voltage relative to conventional
buried contact solar cells using the thyristor structure device on the rear which incorporates
a grown p+ layer in localized regions of the passivating oxide. However, both these rear con‐
tact schemes require the use of photolithography to remove regions of the oxide to expose
the underlying surface for contact, which may not be suitable for large-scale commercial so‐
lar cell fabrication processes. Other techniques of creating small area contacts such as laser
firing have been demonstrated to be feasible [27].

2.6.3. Study of rear surface passivation with SiNx film

Recombination of charge carriers at the rear surface in a solar cell can be suppressed by dep‐
osition of a silicon dioxide (SiO2) layer at the back surface, grown in a high-temperature
(≥900°C) oxidation process [28-29]. Additionally, the SiO2/Al stack at the rear should act as a
reflector for the near band gap photons, that leads to improved light trapping properties
and hence the Jsc of the solar cell may improve as well. Thermally grown SiO2 layers are
manufactured using a time and energy intensive high temperature process, they may not be
a good choice for mass production, although they possibly provide a good thermally stable
passivation [30]. Hence, an alternative low temperature surface passivation became necessa‐
ry for future industrial production of high efficiency Si solar cells, which should have prop‐
erties comparable to the SiO2 passivated solar cells.

One way of achieving this is deposition of SiNx layer by PECVD technique. It has been ob‐
served that this gives comparably low surface recombination velocity (SRVs) as compared to
that with a thermal SiO2 on low resistivity p-type silicon [31-32]. However, conventional
studies have mentioned certain limitations of a SiNx layer on p-type substrates [33]. When it
was applied to the rear of a PERC (Passivated Emitter and Rear Cell) solar cell, the short cir‐
cuit current density (Jsc) reduced as compared to a SiO2 passivated cell [34]. This effect has
been attributed to the large density of the fixed positive charges in the SiNx layer, inducing
an inversion layer in the c-Si near the SiNx layer. A capacitance-voltage (C-V) measurement
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of SiNx layer having variation of refractive index may demonstrate a part of improvement
with Si-rich SiNx thin film. This may be because of field created by positive charges fixed at
its surface. It is clear that a positive fixed charge is suitable for the n-type substrate, while a
negative fixed charge is suitable for the p-type c-Si wafer substrate.

In this respect formation of local back contact is a promising technique, where a highly dop‐
ed p-type local back contact can reduce the potential barrier that charge carriers may face
before reaching the metal electrode.

Protection of the back surface of the Si-wafer may be achieved in two possible different
ways, one is a complete coverage with Al back contact, and the other is with SiNx anti reflec‐
tion coating. The problem with full metal coverage with thinner Si wafers is the cracks and
lattice defects formed during high temperature co-firing when there is high possibility of
wafer bending. Thus partial coverage of the back surface with metal electrode and the rest
covered by SiNx ARC surface passivator is a better alternative.

Figure 3. Comparison of SEM micrograph of the (a) saw damaged wafer surface, unclean and (b) saw damage re‐
moved clean surface of Cz-Si wafer.

3. Measurement Results for c-Si Solar Cells

3.1. Wafer Cleaning and Saw Damage Removal

The scanning electron microscopic (SEM) surface image of one of the cleaned and surface
damage removed wafers is shown in Fig. 3. It shows image of untreated as well as wet
chemical etched wafer surface where saw damages have been removed.

3.2. Surface Texturing

Since the concentration limit for anisotropic etching of surface texturing is 1.6 to 4 wt.%, the
concentration of NaOH (wt. %) in the etchant solution was chosen as 2 wt.%. At a different
etching time the resulting surface texture and specular reflection were different. For an etch‐
116 Photodiodes - From Fundamentals to Applications

ing/texturing time of 25, 30, 35, 40 mins, the average specular reflectivities were 17.2, 17.0,
16.1, 15.1%.

Fig. 4 (a ), (b ), ( c ) and ( d ) shows textured wafers with the four different texturing times
and depict the increase in pyramid size with increase in etching time. The average heights of
the pyramids on the surface textured for 25, 30, 35, and 40 min were estimated to be ~ 3, 5, 7,
and 10 μm, respectively.

(a) (b)

(c) (d)

Figure 4. SEM micrographs of the silicon surface textured for (a) 25 min, (b) 30 min, ( c ) 35 min, and (d ) 40 min in and
solution containing NaOH ( 2 wt. %) in DI-W water and IPA ( 6 wt. %) at 82°C.

3.3. Phosphorus Diffusion for p-n Junction Formation

After the texturing, the emitter diffusion and PSG removal were carried out. Then the wa‐
fers were rinsed in DI-W and spin dryed. A secondary ion mass spectrometric (SIMS) depth
profiling was carried out to measure the emitter junction depth. Fig. 5 shows depth profiling
of P atoms observed by (SIMS) into the c-Si wafer. 5×1015 cm-3 seems to be the boron concen‐
tration of the p-type wafer, with junction depth of about 300 nm from the top surface.
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Figure 5. Variation of phosphorus (P) concentration with the distance from the emitter surface into the wafer, As ob‐
served by SIMS depth profiling.

The diffusion profile can be expressed as a complimentary error function.

3.4. Antireflection Coating and Front Surface Passivation

There is a trade off between good antireflective property and surface passivation. From high
frequency capacitance-voltage (C–V) measurements with metal-insulator-semiconductor
(MIS) structure as Al/SiNx:H /p-type Si, one can get the electrical properties of the SiNx film.
It was observed that there was a distinct charge accumulation, depletion and inversion re‐
gion in the MIS capacitor. The forward and reverse traces of the C–V curve exhibits anti-
clockwise hysteresis, which indicates the injection of holes into the silicon nitride film
[35-36], which can also be associated with silicon dangling bonds (Si-N3) [37]. The interface
state density can be calculated using Terman’s analysis [38] from the high frequency C–V
measurements. Properties of deposited SiNx films are given in Table 2. The energy depend‐
ent trap densities (Dit) for as deposited SiNx films, and that fired at 600, 700, 800°C tempera‐
tures were 8.0 × 10 11, 1.4 × 1011, 5 × 10 10, 1.1 × 1010 cm2/eV respectively, for SiNx film of
thickness 700 Å and refractive index 2.0. The effect of surface passivation on sheet resistance
is shown in Table 3. It shows that at a higher O2/POCl3 flow rate the sheet resistance be‐
comes lower. When the wafers were annealed at a temperature of 600°C, the Dit of the SiNx
films with refractive indices 1.9, 2.0, 2.1, 2.2, 2.3 were 8.16 × 1010, 1.40 × 1011, 3.36 × 1011, 5.00 ×
1011, 8.60 × 1011 cm2/eV.
118 Photodiodes - From Fundamentals to Applications

NH3 Flow SiH4 Flow Refractive Deposition rate

(sccm) (sccm) index (Å /s)

60 18 1.8 2.33
60 30 1.9 2.86
60 45 2.0 4.10
60 60 2.1 4.26
60 66 2.2 4.05
60 75 2.3 4.00

Table 2. Gas Composition in the plasma and the corresponding properties of the as- deposited films. Pressure 1 Torr,
substrate temperature 450°C, thickness 80nm.

[O] [POCl3] Rsb (Ω/sq) Rsa (Ω/sq)

300 600 70.5 65.5

400 800 69 64.5

500 100 68.7 63.0

600 1200 65.5 62

Table 3. Comparison of emitter sheet resistance before and after the drive in step for the various different gas flow
rates, where [O] is O2 flow rate and [POCl3] is POCl3 flow rate in sccm, Rsb is sheet resistance before passivation, Rsa is
sheet resistance after passivation.

3.4.1. Carrier lifetime measurement

Carrier lifetime measurement can provide valuable information. We used a μ-PCD system
of Semilab (WT-1000) in order to measure the carrier lifetime of the silicon wafers at various
stages, with a measurement precision of ± 0.01 μs. A 940 nm wavelength laser pulse was
used for generation of the photo carriers, and all the measurements were carried out in auto‐
matic parameter setting mode. The minority carrier effective lifetime of the bare wafers were
measured first, thereafter (prior to metallization) the measurements of effective lifetime of
silicon wafer were carried out.

3.4.2. Effect of different passivating layer on carrier lifetime

Different passivating layers such as silicon nitride (SiNx), silicon oxide (SiOx), amorphous
silicon (a-Si), microcrystalline silicon (μc-Si), oxidized aluminum nitride (AlON), and oxi‐
dized porous silicon (PS) were deposited on the surfaces of the wafers. Minority carrier life‐
time was measured at least three different places of each wafer and mean of the results were
taken. The results were then compared with the minority carrier effective lifetime of the bare
wafer for further analysis.

We observed that the effective lifetime of each of the wafers increases by ~ 2 μs after clean‐
ing and texturing. This improvement is attributed to the removal of contaminants and struc‐
tural defects from the silicon surface after cleaning and saw damage removal. A significant
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improvement in lifetime, from ~ 6 μs to more than 10 μs, was observed after the phosphorus
diffusion. This improvement reflects the increase in bulk as well as surface recombination
lifetime during phosphorus diffusion. The thermal oxide passivation step after phosphorus
diffusion causes further improvement in lifetime of about ~ 3 μs. This improvement can be
attributed to the decrease of surface recombination velocity due to the passivation of surface
by the thermally grown SiO2 layer. The subsequent process of edge isolation by SF6 plasma
causes degradation in the lifetime by ~ 1 μs. Such a degradation is basically due to plasma
induced damages, especially near the edges of the wafers that indicates the formation of re‐
combination centers on the surface during the process. A sharp rise in lifetime by ~ 3 μs was
observed after deposition of non-stoichiometric TiOx films [39-40]. It is likely that fixed posi‐
tive charges in these films bend the semiconductor energy bands near the surface of the wa‐
fer, which improves the effective surface passivation [41]. A good surface passivation can be
achieved by growing a thin thermal SiO2 passivation layer over TiO2 [39,42,43]. The varia‐
tion in the minority carrier lifetime during the solar cell fabrication, indicates that the sur‐
face conditions play a vital role than the bulk of the Cz-Si wafers. During the solar cell
fabrication and before metallization there might have been the improvement in the lifetime
due to gettering of the impurities from the bulk during phosphorus doping. The SiNx films
had a refractive index between 1.90 and 2.13 and a thickness of 65 nm after annealing in the
673-1173 K temperature range. The effective lifetime of the samples became maximum for
the samples annealed at 773 K, while the lifetime of almost all samples, covered with as-
grown film, showed a minimum value.

The out-diffusion of hydrogen from the Si-SiNx interface might cause degradation of life‐
time of the samples if annealed above 773 K in vacuum. The maximum recorded effective
lifetime for the sample passivated with SiNx with a refractive index of 1.94, annealed at 773
K was 55.21 μs whereas a minimum lifetime of 6.3 μs was found for the sample with as-de‐
posited SiNx film with refractive index 1.9.

The minority carrier lifetime with different passivating films as AlON, Bare Si, Poly Si, μc-Si,
SiOx, a-Si, SiNx were 9.6, 10.1, 21.5, 23.6, 43.4, 51.0, 55.2 μs respectively, where all the sam‐
ples were annealed at 773 K in vacuum.

The comparison of surface passivation of the electronic grade Cz-Si wafers with the different
passivating layers indicates that the SiNx film is superior to other films. In order to identify
the appropriate properties and annealing condition of the SiNx films for solar cell applica‐
tion, the effective lifetimes of samples, coated with PECVD grown SiNx film, were measured
after annealing at a pressure of ~ 105Pa for ~ 90sec and at temperatures, varying from 500 to
900°C in air ambience of a belt furnace. The minority carrier effective lifetime of the silicon
wafers, after the surface passivation with SiNx films and annealed at 500, 600, 700, 800,
900°C results in the lifetime of 42, 43, 85, 115, 64μs respectively. The annealing temperature
for optimized carrier lifetime was found to be the same (760°C) as the set temperature of the
belt furnace at which c-Si solar cell was earlier optimized for co-firing to ensure good Ohmic
contact on the front and back surfaces in conjunction with the proper back surface field
( BSF) generation. Minority-carrier lifetime is a critical parameter for all solar cell designs. If
the silicon wafers to be used for the fabrication of solar cell has a low minority carrier life‐
120 Photodiodes - From Fundamentals to Applications

time, therefore a short diffusion length, most of the minority carriers cannot be collected,
and the solar cell will suffer from low conversion efficiency.

The results of this study indicate that the proper surface as well as bulk passivation in con‐
junction with gettering of defects during phosphorus diffusion can lead to a substantial gain
in minority carrier effective lifetime of silicon wafers, provided the degradation of wafer
surface condition during edge isolation is prevented.

3.5. Metallization

3.5.1. Effect of Co-firing Temperature on Solar Cell Performance

In order to optimize the co-firing we defined four different temperature zones in the fur‐
nace. We investigated each zone, changed stay time of the wafers in each zone, by varying
the belt speed and the temperature of the zones. Emitters were formed with the sheet resist‐
ance in the range of 30 to 60Ω/sq. A uniform 80nm thick SiNx layer deposited on the front
side served as an anti-reflection coating. Back and front contacts were screen printed on the
wafers and baked. The back contacts were screen printed first, using Al paste, and then the
wafers were dried at 150°C for 4min in a belt dryer. Then the front contacts were printed
with Ag paste and the same post-printing treatment was carried out. Then the wafers were
co-fired in a conventional belt-type furnace with four different temperature zones. For the
maximization of the Suns-Voc we varied the temperatures T1, T2, T3, and T4 of the four ther‐
mal zones. When an optimum temperature distribution was found, we investigated differ‐
ent belt speeds keeping the temperature unchanged. By measuring Suns-Voc, we determine
the effect of peak temperature change on the FF and Voc. We measured the co-firing temper‐
atures on the wafers directly in the belt-type furnace with a Datapaq 9000 system, which has
a thin, sensitive thermo couple tip and a thermally insulated measuring system pack for re‐
cording the firing conditions of a wafer with a thermo couple tip on it. In the first set of ex‐
periment, without a front electrode, we varied the temperatures T1, T2, T3, and T4 in the
four thermal zones and measured the Suns-Voc.

In the second set of experiments, we examined the effect of varying only the belt speed 170,
140, 165 and 160 inch per minute (IPM) on the Voc for the same sheet resistance. In this step,
we used wafers of 2–4 μm texture, sheet resistance of 35 to 40 Ω/sq. and 80μm width of fin‐
ger with 2.4mm spacing metallization.

In the third set of experiments, we investigated the variation in the Voc with the changes in
the sheet resistance, as obtained in different drive-in operations. In this step, we used wafers
that have 2–4μm texture, sheet resistance of 30, 40, 50, and 60Ohm/sq and 80μm as width of
finger with 2.2mm spacing of the metallization. The peak temperature was 759.5°C, the
melting duration was 4.5s, and the belt speed was 170 IPM.

In the fourth set of experiment, we investigated firing conditions that determines sheet re‐
sistance, by varying belt speed, and temperature. We found a co-firing process window that
resulted in a fill factor greater than 77%. For the metallization of the front side, we used Fer‐
ro 33-501 Ag paste with a peak temperature 700°C and a firing time <1–3s.
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In the fifth set of experiment, we examined the relationship between the number of grid
lines to the series resistance, fill factor, and shading loss in a single-crystal, 5-inch (125mm X
125mm, 154.83cm2) Czochralski-type solar cell. The grid model, as in ref [44], was used to
optimize the grid line design in terms of resistance and shading loss.
In order to obtain higher Voc by BSF layer, we observed that it is necessary to have the ramp-
up rate higher than 70°C/s, that resulted in an average Voc higher than 620mV [45], as shown
in Table 4. At a higher ramp-up rate and proper belt speed setting made it possible to get a
higher Voc by reducing the deterioration caused by the effects of the thermal stress on the
wafer. For further improvement in Voc, a densely packed Al layer or uniformly formed BSF
layer created by a high ramp-up rate would also be helpful.
However, as the heat increases, micro-cracks in a wafer or bowing of the wafer may occur,
leading to an increase in leakage current. Large defects or poor features of a wafer increase
the surface recombination and leakage current.
For sheet resistance of 40, 50, 60Ω/sq, the carrier lifetimes were 14, 14.9, 17.2μs and surface
recombination velocities were 660, 480, 425cm/sec respectively. We observed that, as the
emitter sheet resistance increases, the carrier lifetime increases with the decrease in surface
recombination velocity. To a certain degree, the variation in sheet resistance is dependant
upon the surface doping density, which is related to electron mobility and its lifetime in a
silicon bulk [46].

Sample numbers → #1 #2 #3 #4

Belt Speed (IPM) 170 140 165 160

Temp. Slope ( C/s)o

70.82 64.13 69.15 72.8

Peak Temp. ( C)
o
756.5 759.5 765.0 753.0

Average Voc (mV) 620.3 617.7 619.0 621.7

FF (%) 79.2 78.9 78.1 80.6

Table 4. High temperature firing specifications.

To investigate the effects of different drive-in operations, we examine the variation in Voc
and the Jsc according to the sheet resistance changes. As different drive-in operations for
dopant diffusion can lead to changes in sheet resistance. In this step, we used wafers of 24-
μm texture, sheet resistance of 30, 40, 50, or 60Ω/sq. and 80 μm width of finger with 2.2 mm
spacing shows the Voc as 621, 622, 623, 627mV and Jsc as 34.6, 34.9, 35.0, 35.3mA/cm2 respec‐
tively. The peak temperature was 759.5°C, the melting duration was 4.5s, and the belt speed
was 170 IPM.
As the emitter layer becomes thinner the sheet resistance increases, it becomes difficult to
fire the electrode to a moderate depths (i.e., near the pn junction). So the higher sheet resist‐
ance means thinner emitter and it is more likely to lead to a short circuit of electrodes that
penetrate through the emitter. With low sheet resistance (i.e., a heavy doping) by the over-
122 Photodiodes - From Fundamentals to Applications

fired sites such a situation is less likely. Fig. 6 shows a safe operating zone for the range of
belt speed (Fig. 6(a)) and firing temperature (Fig. 6(b)), it gets narrower as the sheet resist‐
ance increases. While the duration of firing was investigated, we found that the shorter the
firing time, the more was the minority carriers lifetime. Thus shorter firing time results in
increased number of minority carriers and as a result increased Voc. It is known that mobility
is dependent on the effective minority carrier lifetime. We also investigated the relationship
between the number of fingers and the series resistance, fill factor, and shading loss in a sin‐
gle-crystal, 5inch (125mm×125mm, 154.83cm2) Czochralski-type solar cell. We used two dif‐
ferent finger spacings 1.8mm and 2.4mm.

Figure 6. Firing process window from the firing conditions according to the variations of the sheet resistances, the (a)
belt speeds and (b) the firing temperatures. Hatched area indicates the range (min.–max.) that has larger than 77% of
the fill factor by the combination of variations of the sheet resistances (drive-in operations), the belt speeds and the
firing temperatures.

The screen printed and metalized front side shading loss is relatively large, in the range of
8–10% [47]. A grid model suggested in [44] can be used to optimize the grid line design, con‐
sidering resistance and shading loss. The finger width was as usual 80 μm in the case of the
fired Ferro 33-501 Ag paste grid lines. Consequently, the number of grid lines compared to
the original grid line design increased by 17. With the new grid line design, the finger spac‐
ing decreased from 2.4 to 1.8 mm. This led to a decrease in the total series resistance and an
improvement in the fill factor. The design of the metal grid line was essentially a matter of
finding the separation between the fingers that resulted in the best compromise between
shading losses and resistive ones [48]. The contribution to the series resistance from the dif‐
fused sheet was 0.192Ω.cm2 for 2.4mm spacing and 0.108Ω.cm2 for 1.8mm spacing, so that
emitter resistance (Re) improved by 0.084Ω.cm2. Each 1Ω.cm2 in series resistance caused a
decrease of about 0.041 in the fill factor (assuming a moderately high shunt resistance) [48],
the total calculated improvement in fill factor due to the increase in emitter sheet resistance
was 0.0078Ω. We also investigated the relation between the variations of Rsheet and spacing
for the available range of more than 77% of the fill factor. As shown in Fig. 7, the narrower
the spacing, the wider range of Rsheet can give a better solar cell. By shortening the spacing
between the grid lines, the series resistance decreased and the FF increased, but the addition
of extra fingers caused a 1% increase in shading loss as well as lowering the short circuit cur‐
rent. As a result of these drops, cell efficiency reduced from 17.18% to 16.92%.
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Figure 7. The relation between the sheet resistance with finger spacing for the available range of more than 77% of
the fill factor.

3.5.2. Study of rear surface passivation with SiNx film

Cell Condition Carrier Lifetime (μs) Cell Condition Carrier Lifetime (μs)

SiNx ARC PECVD ONO

As-deposited 100 As-deposited 110

FGA 125 FGA 70

Co-firing 180 Co-firing 165

Si rich SiNx SiON/Si-rich SiNx

As-deposited 205 As-deposited 120

FGA 320 FGA 225

Co-firing 11 Co-firing 20

Table 5. Temperature dependence of different passivating films. FGA – forming gas annealing, ONO – silicon -oxide -
nitride -oxide.

For the fabrication of local back contact structure with little modification on conventional
cell process, adaptation of rear passivating film on c-Si solar cell should address two issues
which are
1. temperature dependence as shown in Table 5,

2. grid pattern on rear metallization.

In order to carry out a comparative investigation about the effectiveness of Al-BSF and die‐
lectric passivation on rear surface, solar cells were fabricated with and without dielectric
passivation in conjunction with screen printed Al grid pattern with different rear metal cov‐
ered area. Comparative analysis show that the role of the rear surface passivation with SiNx
film becomes dominant when the metal coverage area is below 45% of total surface area.
But, as the metal coverage area goes above 45%, the quality of passivation degrades first
124 Photodiodes - From Fundamentals to Applications

then starts improving due to the dominating effect of Al BSF over the passivation with SiNx.
As the metal coverage area on the rear surface reaches as high as 85%, an improvement in
infrared response with net improvement in Isc by ~ 0.16 A has been observed. This indicates
that there is dominance of Al-BSF passivation in comparison to the dielectric passivation on
the cells fabricated with screen printed local back contact, especially when the rear metal
coverage reaches 45% or more but when the metal coverage comes below 45%, the effect of
the dielectric passivation becomes dominant.

All the results suggest that the passivation with dielectric film on the rear surface is a must
for local back contact formation by screen printing of Al paste whereas the role of such die‐
lectric passivation becomes significant for Al printed local back contact only if the metal cov‐
ered area on the rear surface goes below 45%. These results indicate a suitable rear metal
covered area for high efficiency thin c-Si solar cells with local back contact in conjunction
with dielectric passivation with dielectric film of SiNx and were found to be in accordance
with the results obtained by simulation in ref [28].

Figure 8. Comparison of the illuminated current-voltage (LIV) characteristics of the cells fabricated with local back
contact through the opening in SiNx film on rear surface by varying the peak temperature of the co-firing profile, as
indicated with the traces.

Tp (oC) Rs (mΩ) FF (%) η (%) Voc(mV) Isc (Amp)

825 12 67 11.5 576.2 4.40

850 11 71 12.4 575.6 4.45

875 8 75 13.0 576.8 4.38

890 24 60 10.1 574.0 4.35

912 16 67 8.4 564.5 3.77

Table 6. Comparison of the performance parameters of the cells fabricated with local back contact through the
opening window on SiNx film on rear surface by varying the peak temperature of the co-firing profile, where Tp is
peak firing temperature.
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When the cells were co-fired keeping peak temperature below 875°C, the problem of Al
bead formation was found to have reduced but the cells were found to have under-fired due
to which the series resistance of the cells increased appreciably. The comparison of LIV char‐
acteristics of the cells with local back contact through the opening in SiNx film, fabricated by
varying the peak co-firing temperature is shown in Fig. 8 and the comparative analysis of
the performance parameters of the cells is shown in Table 6. The co-firing profile with peak
temperature of 875°C was found to be the best for SiNx passivation layer in terms of per‐
formance parameters despite the formation of the Al beads on the rear surface when the cell
was co-fired at this temperature.

The minimum Rs of 8 mΩ and maximum FF of 75% among the cells compared are the evi‐
dences of the improved front metal contact without over-heating of Ag finger lines in the
case of the cell co-fired with a peak temperature 875°C. The bead formation could be mini‐
mized with the increased belt speed keeping peak temperature fixed at 875°C but that test
could not be carried out in our system because of the limitation to increase the belt speed
beyond 180 IPM.

4. Summary and Future Direction for Thin Silicon Wafer Processing

4.1. Summary

Figure 9. Process sequence of wafer cleaning, saw damage removal and surface texturing of c-Si wafer.

Wafer cleaning for saw damage removal is a fundamental step for c-Si solar cell fabrication.
Texturing the top surface of the wafer reduces reflection loss of incident light, as well as in‐
creased effective surface area of the wafer for light trapping, light absorption, carrier collec‐
tion inside the wafer. Surface passivation with silicon nitride layer increases carrier lifetime
and further reduces reflectivity of the top surface as it also works as an anti-reflection coat‐
126 Photodiodes - From Fundamentals to Applications

ing. It also gives protection of the sensitive and thin top n+ layer from environmental degra‐
dation. Co-firing at two different temperatures for the top and the bottom surface of the
wafer may be necessary as top surface needs lowed co-firing temperature than the bottom
one. Because of the thin n+ layer at the top of the cell and thin silicon nitride layer, the Ag
top contact may make electrical shorting through the n+/p interface, if co-firing is done at
higher temperature. The Al/Ag paste that is used for back contact works for electrical con‐
tact as well as p+ doping of Si at the back surface. Al is a group III element in the periodic
table so it works as a p-type dopant for Si. After the high temperature co-firing, the Si-Al
alloy that is formed at the back of the cell acts as a p+ layer and creates strong back surface
field so the photo generated holes are efficiently collected during light illumination.

Figure 10. Process flow for doping or emitter diffusion of cleaned and textured wafer. The PSG removal can be carried
out after the pre-deposition (as shown above), or it it can be done after the drive in operation. In the latter case the
drive-in can be the third step (the PSG removal will be the fourth step), and all other steps remain in order. The emitter
diffusion for this latter case has been depicted in Table 1.

Figure 11. SiNx, ARC deposition on the wafer by RF PECVD.

Out of several approaches to improve the Voc and FF, increasing the ramp-up rate of temper‐
ature and setting the belt speed along the heating furnace properly, makes it possible to get
a higher Voc. This increase in Voc may be because of reduction in the deterioration due to the
effect of thermal stress on the wafer. In presence of excess thermal stress small cracks in the
wafer may develop, resulting in a high sheet resistance and low open circuit voltage. Thus
optimizing the drive-in condition for low sheet resistance is necessary. The faster belt speed
 Fabrication of Crystalline Silicon Solar Cell with Emitter Diffusion, SiNx Surface Passivation and Screen Printing of 127
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in the co-firing stage, results in higher ramp-up rate for temperature, that greatly enhances
Voc. By studying the results of our five sets of experiments, we determined certain ap‐
proaches for improving the open circuit voltage and fill factor:
1. As the temperature ramp-up rate went higher, we could obtain better uniformity of the
BSF layer.

2. A higher belt speed tends to reduce the overall leakage current of a wafer.

3. As the emitter sheet resistance increases, the open circuit voltage decreases with the de‐
crease in dopant concentration in the emitter, although the short circuit current is in‐
creased, that is attributed to the improvement of the short wavelength response, more
light entering the cell active region and to a reduction of recombination in the front sur‐
face.

4. The peak temperature of the wafer was optimized for the shorter the firing time. It re‐
sults in increased minority carrier density, which in turn increases the open circuit volt‐
age. We investigated the optimal firing conditions for different sheet resistance,
temperature, and belt speed, and within the profile window of the firing process, we
obtained a high Voc (>620 mV) and fill factor (>77%) for a range of different sheet resist‐
ance emitters.

5. By narrowing the spacing between gridlines, the series resistance and the fill factor of
the cell got enhanced.
However, the short circuit current falls because of shadow effect of the metal electrodes. In
the case of low series resistance, we can expect to improve the fill factor, while the short cir‐
cuit current decreased because of the shading loss.

Figure 12. Process steps for metallization of the solar cell by screen printing (SP). In our system, the peak temperature
was 759.5°C.
128 Photodiodes - From Fundamentals to Applications

4.2. Future Direction for Thin Silicon Wafer Processing

Thin silicon wafer is more economical because it consumes less Si material, and results in
more efficient solar cell because of higher built in field. Cost of silicon is one of the major
expenses in c-Si solar cell production and thus with less consumption of semiconductor
mass in the form of thinner wafer, the cost of production can be significantly reduced.

One problem that thin wafer may face is bowing during the co-firing process, and hence cre‐
ation of additional structural defects. Due to unequal thermal expansion of Si and Al back
electrode these defects may be created in the wafer. The LBC approach may be more suita‐
ble for such cells.

Resistance of screen printed front electrode provides additional element to the series resist‐
ance. Each electrode creates a shadow to the cell that reduces total number of electron-
hole pair generation under constant illumination. Thus, although decreasing the spacing
among the electrodes help reducing series resistance, yet shadow effect leads to reduced
total number of electron-hole pair generation. For this, a finger with good conducting ma‐
terial and a high aspect ratio is preferable. Usually glass frit Ag/Al paste is used in the elec‐
trode design. If Ag/Al particles in the frit is bigger in size and less dense, and firing
temperature profile is not best suited then an insulating layer between Si and Ag/Al elec‐
trode may form. This may be avoided by using Ag/Al nano-particles in the paste, with a
higher number density of the particles.

Another method that has partly been adopted in commercial production is selective emitter
design. In this method a local doping pattern is designed before phosphorus doping
through diffusion chamber treatment. Ag electrodes at the front surface are fabricated over
this so that a highly doped local semiconductor region is formed around the Ag-electrode
after high temperature co-firing. In this way a barrier potential at metal semiconductor junc‐
tion can be reduced. This electrode structure may bring the screen printed solar cell technol‐
ogy close to buried contact solar cell with one additional process step.

Author details

S. M. Iftiquar1, Youngwoo Lee1, Minkyu Ju1, Nagarajan Balaji2, Suresh Kumar Dhungel1 and
Junsin Yi1,2*

*Address all correspondence to: [email protected]

1 College of Information and Communication Engineering, Sungkyunkwan University, Re‐

public of Korea

2 Department of Energy Science, Sungkyunkwan University, Republic of Korea

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 Chapter 4

LWIR Photodiodes and Focal Plane Arrays Based on

Novel HgCdTe/CdZnTe/GaAs Heterostructures Grown
by MBE Technique

V. V. Vasiliev, V. S. Varavin, S. A. Dvoretsky,

I. M. Marchishin, N. N. Mikhailov, A. V. Predein,
I. V. Sabinina, Yu. G. Sidorov, A. O. Suslyakov and
A. L. Aseev

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/50822

1. Introduction

Thermal imagers based on the photo detectors for infrared (IR) wavelength range of 3–12
μm are required for applications both in the military equipment for systems of night vision,
detection and guidance as well as in the national economy for the medical, agricultural,
chemical, metallurgical, fuel industries and others. Nowadays, the leading place among ma‐
terials for the production of IR photo detectors is occupied by mercury–cadmium–telluride
(MCT) solid solutions. This fact is due to the physical properties of these solutions (high
speed, the possibility of varying an MCT band gap within a wide range, and high quantum
efficiency in the range of overlapping wavelengths). For the last 25 years, the technology of
MCT production has been developed intensively, which has made it possible to pass from
manufacturing bulk single crystals of relatively small diameters (less than 10 mm) to epilay‐
ers on large in diameter substrates (up to 150 mm). The MCT epilayers on large-diameter
substrates are necessary for the production of IR PD arrays with a large number of elements
for enhancing the production efficiency and reducing the cost of devices. According to this,
stringent requirements are imposed on the epitaxial technologies of producing such an MCT
material. They include a high structural quality and uniformity of photoelectric characteris‐
tics over the entire area. MCT layers on alternative substrates primarily due to its low
growth temperatures (~180 ºC), which prevents the diffusion of impurities from the sub‐
strate and reduces the background doping with these impurities. The great successes had
134 Photodiodes - From Fundamentals to Applications

been reached in development of growth MCT HES by MBE on GaAs and Si large in diame‐
ter substrate. The decision of fundamental physical and chemical investigations and techno‐
logical developments allows to fabricate high quality MCT HES on GaAs substrate. Such
MCT HES are widely used for developments and production of different formats linear and
matrix IR detectors sensitive in separate spectral IR ranges.
In this chapter the results of studies of technological processes at growth MCT HES on
(013)GaAs by MBE, the developments of HES design and fabrication on its basis of high
quality IR detectors of different applications for IR radiation registration in spectral long
wavelength range (LWIR) 8-11 μm.

2. The technological processes of MCT HES growth on (0130GaAs

substrates

Fig. 1 showed the scheme of MCT HES included ZnTe and CdTe buffer and adsorber layers
in sequence grown on (013)GaAs substrate by MBE.

Figure 1. The scheme of MCT HES on (013) GaAs substrate.

The technology of growth MCT HES includes the following processes:

• the preepitaxial preparation of surface substrate;

• the growth of ZnTe and CdTe buffer layers;
• the growth of MCT absorber layer with special design.

2.1. The preepitaxial preparation of surface substrate

The GaAs substrate surface before epitaxial growth must be atomically smooth and clean.
 LWIR Photodiodes and Focal Plane Arrays Based on Novel HgCdTe/CdZnTe/GaAs Heterostructures Grown by MBE 135
http://dx.doi.org/10.5772/50822

For this purpose the preepitaxial substrate surface preparation included the chemical etch‐
ing process and thermal cleaning process in ultra-high vacuum at 500600 0С.
We used (013)GaAs substrates 2” and 3” in diameter which initially prepared as epiready.
Nevertheless it is necessary to remove the defects surface layer which prevents the epitaxial
growth of high quality MCT HES. The study of chemical etching of GaAs in sulfuric acid etch‐
ant [1] allows to determine optimal conditions for preparation GaAs surface. Fig. 2 represents
the density of luminous points which appeared after chemical etching of GaAs substrates [2].

Figure 2. The dependence of number luminous points on etching depth (013) GaAs.

It is clear that the density of luminous point changes with etching depth increases more that
one order of magnitude from initial values reaches maximum at 10-15 μm. So we deter‐
mined the optimal etching depth for epitaxial growth MCT HES which is equal to ~20 μm.
It was determined that carbon contamination does not evaporate at thermal treatment in ul‐
tra-high vacuum. The presence of 0,06 monolayer carbons coating on the GaAs surface is
disturb epitaxy [3-5]. It necessary to create a continence protective layer more than monolay‐
er thickness which must not adsorbs carbon and desorbs at low temperatures. It was found
by SIMS that at treatment of etching GaAs surface in HCl solution in spirit lead to decrease
of carbon on the surface less 0.5 % monolayer [6]. At this procedure the arsenic oxides and
gallium oxides were removed at room temperature from the GaAs substrate leading to stoi‐
chiometric surface with elemental arsenic coating.
We used the procedure of final etching in boiling HCl solution in isopropyl alcohol for for‐
mation elemental arsenic coating.
So, the chemical procedure of GaAs surface preparation before the growth includes the etch‐
ing in H2SO4/ H2O2/H2O (3:1:1) mixture at 35-40 0C during 6-10 min. and final and in boil‐
ing HCl solution in isopropyl alcohol during 10 min.
136 Photodiodes - From Fundamentals to Applications

Figure 3. The diffraction reflections intensity dependences on temperature at thermal heating (001)GaAs: curves 1
and 3 in [011] azimuth, curves 2 and 4 in [01̄1] azimuth.

After chemical etching GaAs substrates are attached to special holder and then loaded into
loading-unloading vacuum chamber of ultra-high MBE set.

The procedure of thermal heating of GaAs substrate in vacuum are developed using (001)
GaAs together with monitoring by high energy electron diffraction (HEED) and single
wavelength automatic ellipsometer (AE) LEF-755. Usually before the thermal treatment it is
seen weak diffraction patent from (100)GaAs in [11] and [01̄1] azimuths (weak diffraction
reflection). The increasing of brightness of diffraction reflection is observed at increasing
temperature GaAs substrate up to 250  300 0С. The diffraction background is practically
disappeared at temperatures more than 500 0С with appearance diffraction strikes and su‐
perstructures 2×1 and 3×1 types.

Fig. 3 showed the typical dependences of diffraction reflection intensity of (100)GaAs sur‐
face (curves 1 and 2 for [11] и [ 01̄1] azimuths) normalized to diffraction background on tem‐
 LWIR Photodiodes and Focal Plane Arrays Based on Novel HgCdTe/CdZnTe/GaAs Heterostructures Grown by MBE 137
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perature. The curves 3 and 4 shows the intensity distribution along diffraction strikes in [11]
and [01̄1] azimuths respectively. The sharp increasing of diffraction reflection intensity was
observed at GaAs substrate thermal heating from 20 0С to 300 0С that connected with de‐
sorption of volatile arsenic oxides [1]. The following sharp increasing of diffraction reflec‐
tion intensity with formation strikes was observed at temperature more 540 0С that means
the formation atomic smooth GaAs surface. The further temperature increasing or exposing
during 0.5 hour of GaAs substrate 570580 0С leads to transfer diffraction strikes to diffrac‐
tion reflections connected with roughening surface.

Figure 4. The dependences ψ and Δ on temperature at thermal heating and cooling for 3 samples (001)GaAs. The
rows show the direction of changing of ellipsometric parameters.

The typical changing of ellipsometric parameters ψ and Δ were measured at thermal heating
(001)GаAs up to 580 0С and cooling to room temperature (see Fig. 4).
The dependence of ψ on substrate temperature showed has reversible character because of
that determined by GaAs optical constants. The dependence of Δ on temperature showed
non-monotone character that determined by the GaAs surface roughness. The increasing of
Δ at thermal heating to ~ 150 0С was conditioned by desorption of adsorbed gases from
(001)GaAs surface. Further changing Δ was determined by desorption arsenic oxides [1] and
138 Photodiodes - From Fundamentals to Applications

optical constant temperature dependence. Then we observed the sharp increasing Δ con‐
nected with desorption of gallium oxides [1]. The ellipsometric parameter Δ was increased
at cooling to room temperature that сonnected with the changing of GaAs optical constants.
The ellipsometic measurements of (001)GaAs surface at thermal treatments are in a good
agreements with REED measurements.

These data given the understanding of technological process of preparation atomic smooth
and clean (001)GaAs surface by thermal heat treatments. The technological process of prepa‐
ration (013)GaAs atomic smooth and clean surface is analogous ones. We observed analo‐
gous changing of REED pattern and ellipsometric parameters ψ and Δ at thermal heat
treatments of (013)GaAs in vacuum.

2.2. The growth of ZnTe/CdTe buffer layer

The buffer layer on (013)GaAs was fabricated by sequence growth of ZnTe and CdTe layers. At
first the 20 – 300 nm ZnTe layer was grown on atomic smooth and clean GaAs surface from sep‐
arate molecular beam Te2 and Zn. This procedure is necessary to growth of only one (013) ori‐
entation. At CdTe growth on GaAs surface there was observed the growth of mixture
orientation [7] that determined with large lattice mismatch 14,6 % between CdTe и GaAs.

Figure 5. The changing of ellipsometric parameters Ψ and at growth of high quality ZnTe layer at optimal growth con‐
ditions. The points – experimental data. The rows show the direction of changing Ψ and Δ at increasing ZnTe thickness.

The optimization of ZnTe growth was carried out with monitoring technological processes
by AE in situ. At growth of high quality ZnTe in optimal conditions the undamped periodic
changing of ellipsometric parameters Ψ and Δ (ligth radiation AE λ=6328 Å) are observed
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λ
that determined by interference with period d0 = where n – refractive index of
2
2 n − sinϕ
ZnTe, φ - angle of incidence of AE laser beam on GaAs surface (see Fig. 5).

The deviation from optimal conditions leads to surface roughness or adsorption to changing
optical constants because of inclusion in layer volume at ZnTe growth.

Figure 6. The calculation data of changing of ellipsometric parameters Ψ и Δ at ZnTe growth on GaAs: a – roughness
changes from 0 nm up to 5 nm А; b – absorption factor k=0.05; c – roughness changes from 0 nm up to 2,5 nm, ab‐
sorption factor k=0.03.
140 Photodiodes - From Fundamentals to Applications

Fig. 6 shows the results of calculations of changing of ellipsometric parameters Ψ and Δ at

surface roughness and changing optical constants. The ellipsometric variation of Ψ and Δ in
Ψ-Δ plane is little by little move to decreasing Δ at relief evolution (see Fig.6 a). The ellipso‐
metric curve amplitude is decreased at growth of weakly adsorption layer с k=0,05 (see Fig.
6b). Fig. 6c shows the changing of Ψ и Δ at developing roughness and absorption factor (k)
of growing ZnTe layer.

These data were used for determination of growth mechanism ZnTe on (013) GaAs at
growth conditions. The behavior of ellipsometric parameters Ψ and Δ at 2 D and 3D growth
is similar as shown in Fig. 6a and Fig. 6b respectively.

Fig. 7 represents the experimental data of the ZnTe growth on (013) GaAs at different tem‐
peratures and different molecular fluxes of zinc and tellurium (JZn/JTe2).

5,5

4,5 2-d growth

4
J Zn/Te2, arb.un.

3,5

2,5

2 3-d growth

1,5

1
240 260 280 300 320 340
Substrate temperature 0C,

Figure 7. The phase diagram of ZnTe growth mechanism: triangular – 2D growth; points – 3 D growth; solid curve –
the boundary of growth conditions between 2D and 3 D growth.

Following these data we determined the optimal conditions for growth of high quality ZnTe
layer on GaAs. The temperature of substrate is situated in range 2800С - 2950С at molecular
fluxes relations JZn/JTe2 in range 3 - 8.

The studies of CdTe growth on (001) and (013)ZnTe/GaAs substrates were carried out with
monitoring by AE in situ. Fig. 8 shows the spiral variation of experimental and calculated
ellipsometric parameters Ψ and Δ in Ψ-Δ plane at CdTe growth on (001) GaAs.
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Figure 8. The variation of ellipsometric parameters Ψ и Δ at CdTe growth (001)GaAs for 3 samples: squares, triangular
and crosses– experimental data; solid lines – calculation data. Figures near curves – CdTe layer thickness. In insert – the
dependence of adsorption factor on thickness for case of essential differences (triangular) and good agreement
(squares) between experiment and calculation respectively.

In case of good agreement of experimental and calculated data Ψ and Δ (curves 1 and 3) al‐
lows to determine the growth rate and the thickness of growing CdTe layer.

The differences of experimental and calculated Ψ and Δ data at initial stage (up to 200 nm)
we observed at growth at non optimal growth condition (curve 2). REED pattern shows the
presence of (001) and (111) orientation. At further growth the experimental and calculated Ψ
and Δ data becomes near one another.

The observed differences of experimental and calculated Ψ and Δ data свидетельствуют,

that optical constants o CdTe for this case are differed from analogous data for bulk CdTe.
Really the calculation (see Fig. 8 in insert triangular) shows that adsorption coefficient high‐
er at initial growth stage and reached the bulk data at thickness 200 nm. The higher values
of k are explained by poor crystalline performance at initial stage of CdTe on GaAs [8]. Re‐
fractive index n = 3 does not depend on growth condition of CdTe growth. These studies
determined necessity of ZnTe growth on GaAs before CdTe growth.

The optimal conditions for growth of high quality CdTe on (013)ZnTe/GaAs substrate were de‐
termined during investigation of technological processes at different growth temperature and
molecular cadmium and tellurium fluxes(JCd/JTe2) relationships with monitoring by AE in situ.
142 Photodiodes - From Fundamentals to Applications

Figure 9. The changing of ellipsometric parameter Δ at CdTe growth.

Figure 10. The dependence of FWHM on CdTe thickness.

Fig. 9 represents the changing of ellipsometric parameter Δ at CdTe growth at temperature

2900С and constant molecular tellurium flux. The ellipsometric parameter Δ practically does
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not changed at stationary stage of CdTe growth at JCd/JTe2 = 3,5. A large excess of cadmium at
JCd/JTe2 = 27 it was observed weak decreasing of ellipsometric parameterΔ. In condition of
stoichoimetric relationship JCd/JTe2=1 it was observed sharp decreasing of ellipsometric pa‐
rameter Δ that determined by sharp surface roughening.

It well-known that a large dislocation density in CdTe/ZnTe interface [9] was formed and
decreased with increasing of CdTe thickness [10]. The growth of CdTe layers with different
thickness were carried out at optimal condition. Fig. 10 shows the dependence of full width
of half maximum (FWHM) of rocking curves on CdTe layer thickness.

It is clear that FWHM sharply decreased at increasing of CdTe thickness reaching practically
stationary values less 3 angle minutes at 6 μm.

So we determined the optimal conditions for growth of high quality CdTe layer on
(013)ZnTe/GaAs. The temperature of substrate is situated in range 2800С - 2950С at molecu‐
lar fluxes relations JCd/JTe2 in range 5 - 7. The thickness of CdTe layer is 5 – 7 μm.

The AFM measurements showed that grown CdTe surface roughness less than 10 нм.

2.3. The growth of MCT layers

The growth of MCT layer was carried out on (013)CdTe/ZnTe/GaAs substrates from separate
molecular sources of elemental Cd, Te и Hg. The original construction of molecular sources ant
their unique location in vacuum chamber allows to grow MCT layer with high uniformity over
the surface area of 3” in diameter GaAs substrate without rotation (see Fig. 11).

Figure 11. The MCT composition uniformity over the surface area of 3” in diameter GaAs substrate measured by
transmission spectra. The mean value <XCdTe>=0.2164 and standard deviation δ<XCdTe>=0,0036.
144 Photodiodes - From Fundamentals to Applications

It is clear that MCT composition mean value <XCdTe>=0.2164 and standard deviation
δ<XCdTe>=0,0036. So during the growth of MCT layer we used for monitoring technological
process AE in situ.

It is necessary to remark that the MCT growth conditions differ from molecular regime.
There is exist high mercury pressure 10-3 - 10-4 torr at growth MCT layer because low stick‐
ing coefficient. The tellurium adsorbed on the growth surface as diatomic molecules with
formation solid phase MCT through reaction with cadmium and mercury. There is the pos‐
sibility to formation solid phase of tellurium at growth temperatures 185-190 0С for case of
mercury deficit for some reasons. The thermodynamic analysis reveals the possibility of ex‐
isting two solid phases – MCT and tellurium. Consequently, the processes on the growing
surface determined by crystallization tellurium with formation of high quality MCT layer or
solid phase of tellurium which leads to defect structure [11,12]. So we determined the opti‐
mal growth condition with the purpose to decrease appearance defects as minimal as possi‐
ble. In opposite case there is possibility of irreversible decreasing of surface roughness and
crystalline perfection of epitaxial structure.

At initial stage of MCT growth the changing of ellipsometric parameters Ψ and Δ in Ψ-Δ
plane represents by convergent spiral curve (Fig. 12).

Figure 12. The evolution of ellipsometric parameters Ψ and Δ in Ψ-Δ plane at initial stage of growth: triangular – ex‐
perimental data; dotted line –calculated data. The цифры – MCT thickness.
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This dependence allows to determine the growth rate and MCT composition. These data al‐
lows in further to provide monitoring of MCT thickness and MCT composition and its
changing at stationary growth stage in situ. Note that (013) substrate orientation is appropri‐
ate for MCT layer growth of different composition without essential changing technological
conditions. This circumstance allows to grow MCT HES with special design to improve the
parameters of detectors and to simplify their technological process of fabrication.

Fig. 13 shows the MCT HES in which there is graded wide gap layer on the boundaries of
absorber layer. Widegap layers created built-in electric fields in which non-equilibrium car‐
rier’s drive back into the volume from surfaces with high recombination velocities and acted
as passivating coatings. Wide gap layers lead to the essential increase of minority lifetime. In
insert it is shown the variation of growth temperature measured by polarized pyrometer. It
is seen that the variation of growth temperature lies in interval 186 -188 0C that gives the
variation of MCT composition less than 0,001 mole fraction of CdTe. This data were sup‐
ported by measurement of transmission spectra with layer-by-layer chemical etching which
in a good agreement with ellipsometric measurement of MCT composition in situ.

Figure 13. The distribution of MCT composition throughout the thickness measured by AE in situ. Open circles – MCT
composition measured by transmission spectra at layer-by-layer chemical etching. In insert – variation of growth tem‐
perature during MCT growth.

We suggested the novel MCT HES allows to decide the problem of high sequence resistance
for matrix focal plane arrays (FPA) based on p-type absorber layer.

The construction of absorber layer for p-type MCT HES used for matrix photovoltaic (PV)
FPA includes additional MCT layer with high conductivity. The additional MCT layer with
146 Photodiodes - From Fundamentals to Applications

high conductivity must be fabricate by intentional doping of more wide gap layer or grow‐
ing more narrow layer than absorber ones during the growth MCT HES.

Figure 14. Novel construction of MCT HES for matrix PV FPA.

Fig. 14 shows the MCT composition distribution throughout the thickness for novel MCT
HES for large format matrix PV FPA.

MCT HES includes the following layer which is growing in sequence technological process:

• the high conductivity layer n-type with In doping up to more than n=5*1016cm-3;

• the barrier excluded cross-talking between high conductivity layer and absorber ones;

• graded wide gap layers on the boundaries of absorber layer.

Figure 15. MCT composition profile throughout the thickness with narrowgap+widegap layer at the interface and wi‐
degap at the surface measured by AE in situ. In insert – variation of MCT composition in MCT volume.
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The MCT composition in this layer is slightly more than for absorber layer. These high con‐
ductivity layer decreases of sequence resistance and serves as short wavelength cut off filter
for cooling PV FPA. It was determined by photoconductive measurement the minimal
height of barrier layer 0,05 mole fraction CdTe. Fig. 15 illustrates a novel MCT HES MBE
with variation of MCT composition on boundaries of absorber layer. In Fig. 15 the MCT
composition profile with narrowgap layers at the interface and widegap layer at the surface
is shown. There is a barrier layer as wide gap layer between narrowgap and absorber layers.
Narrowgap layer sharply decreases diodes series resistance.

2.4. Electrical parameters MCT HES

Electrical characteristics were determined from Hall measurements at 77 K by Van der

Paw method. As grown MCT HES MBE with construction represented in Fig. 12 had n-
type conductivity. The electron concentration and mobility and minority carrier lifetime
were 1014-1015 cm-3 and over 105 cm2/V sec and 2-10 μs for composition ХCdTe~0,20-0,22 re‐
spectively. For conversion of as-grown n-type MCT HS’s MBE to p-type annealing in heli‐
um atmosphere was carried out at 200-2500С and low mercury vapor pressure. After
annealing hole concentration and mobility were (5 - 20)×1015 cm-3 and 400 - 700 cm2/V s
for composition ХCdTe~0,20-0,22.

3. The design and parameters IR detectors

3.1. The graded widegap layer at the boundaries of MCT absorber layer

The graded widegap layer at the boundaries of MCT absorber layer allows to improve IR
detectors and simplify the technology of their development and fabrication.
We studied the influence of widegap layers at the boundaries of absorber layer on minority
lifetime by numerical calculation and supported this effect by experimental investigations.

The distribution of non-equilibrium carrier was determined by decision of one dimension‐

al diffusion equation taking into account the generation-recombination processes and
built-in electric in graded widegap layer. The dependence of hole current j p on the thick‐
ness position y in homogeneous MCT n-type in approximation of low generation ex‐
pressed by following [13]:

d d
jp (y) = μp (y) p(y)kB T lnni2(y) − μp (y)kB T p(y) (1)
dy dy

where μ p- hole mobility, p – carrier concentration, n i – intrinsic carrier concentration, T -

temperature, k B – Boltzmann constant.

The equation of non-equilibrium hole in MCT n-type expresses by

148 Photodiodes - From Fundamentals to Applications

kB T d p(y) − po (y)
j (y) − G(y) + =0 (2)
e dy p τ(y)

where e – electron charge, p o- equilibrium hole concentration. The generation rate is ex‐
pressed by equation

(∫ )
y

G(y) = α(y)Fexp − α(y ©)d y © (3)

0

where F - photon flux of radiation, α - absorbtion factor, τ - the recombination time of charge
carriers. At homogeneous MCT composition this time τ A is determined by Auger processes
A1 [14]. For calculation of recombination time τ d limited by dislocation density n d we used
the expression of empirical model [15]:

Cd
τd = (4)
nd

where где C d – fitting parameter depended chemical composition of semiconductor, tech‐

nology of fabrication and dislocation nature.

So the recombination time in (2) is detemined by expression:

1 1 1
= + (5)
τ τA τd

The boundary conditions are expresses by [11]:

jp (0) = − eso p(0) − po (0) , jp (L ) = esL p(L ) − po (L ) (6)

where L- MCT layer thickness, s o, s L – the recombination velocity at interface y=0 and at the
surface y=L.of MCR absorber layer.

The equation 2 is decided by difference method. Further the effective lifetime τ eff is deter‐
mined from the following equation through the non-equilibrium carrier Δp as:

L L

∫ ∫
τeff G(y)dy = Δp(y)dy
0 0
(7)

The calculations were done for photoconductor fabricated on basis of MCT HES with MCT
distribution throughout the thickness represented in Fig. 12. The thickness of absorber layer
and widegap layers is equal to L=10 and 1 μm respectively. The MCT composition in absorb‐
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er layer is x CdTe = 0.2. The MCT composition on the surface is varied. The electron concentra‐
tion is n=4 1014 cm-3 at 77 К. The surface recombination velocity at interface with CdTe and at
the MCT surface is s 0 = 105 cm/с and s = (0 - 107 cm/с). We measured the dislocation densities
and lifetime in 2-х MCT HES for С d determination. We calculate using (4) С d = 40-80 с/cm2
at measured n d (4 -6) 107 cm-2 and lifetime 0.4-0.8 μs.

Follow τ eff calculation we found that the graded widegap layer leads to decrease of the in‐
fluence of surface recombination because of existing built-in electrical field (see Fig. 16).

Figure 16. The effective lifetime τeff in MCT HES. The dislocation density- 5 107 cm-2, C d=60 s/cm2. The surface recombi‐
nation velocity: 1 - 103 cm/s, 2 - 105 cm/s.

It is needed only Δx Cd = x Cd s - x Cd b = 0.05 for suppression of surface recombination which

compared to analogous ones in [16].

We compared the calculated lifetime τ calc and experimental lifetime τ exp at 77 K measured by
photoconductive relaxation in MCT HES with graded widegap layers (Table 1).

Sample n τexp τcalc nd opt

×10 cm
14 -3
μs μs ×107 cm-2

1 3.8 1.4 1.4 4

2 2.5 1.1 1.4 5.3

3 8.6 1.2 0.9 2.3

4 1.3 0.75 1.5 8

Table 1.
150 Photodiodes - From Fundamentals to Applications

Here τ exp – experimental lifetime and τ calc - calculated lifetime determined by Auger and
dislocation recombination lifetime for С d =60 с/cm2 и n d=4 107 cm-2. n d opt - fitting dislocation
density for calculated and experimental data lifetime. It is apparently clear a good agree‐
ment between calculated and experimental lifetime.

Fig. 17 demonstrates the calculation of changing lifetime at etching layer-by-layer upper

graded widegap layer at the surface MCT HES. It is seen that τ eff sharply decreases at com‐
pletely moving.graded widegap layer from the surface.

Figure 17. The changing of effective lifetime τeff on etching graded wide gap layer thickness d for MCT HES: x Cd s = 0.3,
n d = 5 107 cm-2. The surface recombination velocity: 1 - 103 cm/s, 2 - 105 cm/s.

Figure 18. The temperature dependences of lifetime for n-type MCT HES with MCT composition in absorber layer 0,215
mole fraction CdTe: 1) – with graded wide gap layers; 2) – after chemical moving of upper graded wide gap layer.
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The testing of influence of graded widegap layers on lifetime was checked experimentally at
measurement non contact super high frequency conductivity relaxation before and after
chemical etching moving of upper graded widegap layer. Fig. 16 represents the temperature
dependences of MCT HES with graded widegap layers at the boundaries of absorber layers
(curve 1) and after chemical etching of upper graded widegap layer (curve 2). One can see
that the experimental data of measurement lifetime supported the calculation ones at tem‐
peratures lower than 150K. It means that the presence of graded widegap layers at bounda‐
ries of absorber layer is very important for cooled IR detectors.

3.2. Surface leakage

One important spurious component of p-n junction dark current is leakage current (LC)
which limited the threshold characteristics. At low carrier concentration inside p-n junction
volume LC current is mainly the surface LC determined by the carrier generation-recombi‐
nation, tunneling, ohmic conductivity and etc. The surface LC can be expressed by the fol‐
lowing equation [17]:

I = Is exp q(V − IRs) / βkT) + 1 + (V − IRs) / Rsh + IT (8)

where Is – saturation current; Rs – sequence resistance; Rsh – shunt resistance; V – bias volt‐
age; IT ~ exp[-4(2m)1/2Eg 3/2/3qħE] for triangular potential barrier; β = 1 at diffusion current
(DC) component ID~ni 2 ~ exp(-Eg/kT); β = 2 at generation-recombination current ((G-R)C))
component IGR~ ni ~ exp(-Eg/2kT); Eg – band gap; k – Boltzmann constant; T- temperature.

It is clear that DC or/and (G-R)C decrease exponentially with Eg and falls 108 and 105 times
respectively yet in case of changing of MCT composition from XCdTe = 0.22 up to XCdTe = 0.3. It
means that the presence of widegap layers at the boundaries of active layer suppress effec‐
tively surface LC. It is necessary to notice that these widegap layers eliminate the influence
of surface on minority lifetime as remembered earlier.

3.3. The role of high conductivity layer in MCT HES

Sequence resistance (Rs) is other parameter which influence on p-n characteristics and deter‐
mine the IR detector operating frequency range, operating point of heterodyne IR detector
and analogous ones of different pixels of FPA etc. In last case it is equivalent of increasing of
cross-taking and noise current. Really, Rs reaches several units (MWIR) or tens kilo-ohms
(LWIR) for IRD with p-type MCT absorber layer with optimal values p77К ≤ 1016 cm−3, μ77К =
400-600 cm 2/В×с and thicknesses less than 10 μm and pixel size 20-40 μm. We suggested de‐
creasing Rs due to narrow gap layer at the interface between absorber and buffer layers of
MCT HES. But the presence only narrow gap layer leads to decreasing of quantum efficien‐
cy (QE). This problem was solved by the special MCT composition with the growing se‐
quent narrow gap and wide gap layers at interface (Fig. 14). The numerical calculation of QE
for different MCT composition distribution at the interface and with wide gap layer at the
surface (Fig. 19) was carried out [18,19].
152 Photodiodes - From Fundamentals to Applications

Figure 19. MCT composition (X) distribution throughout the thickness with graded widegap layer at the surface and
different layer at the interface: type 1– widegap (solid line); type 2 – narrowgap (dotted line); type 3 – narrow gap +
widegap (pointed line).

The calculated A/W sensitivities (Sj) normalized to λсo is presented in Fig. 19.

Figure 20. The calculated (solid 1,2,3) and experimental (dashed 1’,2’, 3’) A-W of diodes sensitivity (Sj) normalized to
λc. Numerals are mean number MCT type on fig.19. Crosshatched region is deviation for type 2.

Apparently clear essential decreasing Sj for MCT HES type 2 especially near λсo in compar‐
ing with MCT HES’s type 1 and type 3. We fabricated testing diodes on the basis of three
types MCT HES and measures V-dependences, differential resistances on bias voltage and
spectral responses at 77K. The experimental data is in good agreement with calculated ones.
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We found that Rs is equal to approximately several Ohms for MCT HS type 3 and at the
same time several hundreds Ohms for MCT HS type 3. It means that the presence of narrow
+wide gap layer allows to decrease Rs without IRD performance degradation. Really the typ‐
ical characteristics of photodiodes with maximum wavelength at λp = 7 μm and cut-off λco =
9,1 μm were as following: Rs ~1 Ом, R0А=100 Ohm×cm2, S(λp) = 3,5 А/Вт, D* *(λp, 500 K, 1200
Hz, 1 Hz)= 6,5×1011 cmHz1/2W-1.

As mentions above there is the problem of sequence resistance at developments of different

PV type IR detectors.

For IR detector operated at high frequency the limiting frequency is determined by Rs×C,
where Rs – sequence resistance and С – p-n junction capacity. For IR FPA n+-p type the in‐
creasing of hole concentration in absorber layer more 2×1016 cm-3 leads to decreasing of
threshold diode parameters at forward bias, decreasing electrons diffusion length and corre‐
spondingly decreasing of quantum efficiency. The bulk MCT p-type with the thickness ~ 1
mm and hole concentration 2×1016 cm-3 used for IR PV detectors (10.6 μm) operated at fre‐
quencies more than 1 GHz and has a high quantum efficiency when MCT provides wave‐
length cut off more 12 μm. For MCT HES p-type a sequence resistance is about kΩ unit that
at С ~ 1 – 10 pF gives receiving radiation at frequencies lower than 1 GHz.

For large format PV FPA it is necessary to create the same condition (the same bias voltage)
for central and edge diodes. At high sequence resistance there is the possibility of so called
“debiasing substrate” or “boublik” effects that observed by this time for 128× 128 PV FPA.

The problem of sharp decreasing of sequence resistance is decided by growing MCT HES
with high conductivity layer which does not influence on threshold PV FPA.

The numerical calculation of n+-p diodes current of matrix PV FPA based on MCT HES with p-
type absorber layer were carried out. For this n+-p junction the minority charge carriers (elec‐
trons) are collected by p-n junction, while the excess holes moves to base contact at periphery
of FPA. The continuity equation of hole current is described by following expression:

∂p 1
∂t = Gp − U p − q ∇ ⋅ J p (9)

where G p –generation rate; U p- recombination velocity (cm-3/s), q- electron charge, J p – hole

current density.

The hole current density is expressed by

J p = qμp pE − qDp ∇ p (10)

where μ p – hole mobility, р – hole concentration, Е- electric intensity, D p – hole diffusion

coefficient.

For 2-D FPA the stationary equation for homogeneous hole current through the thickness d
and taking into account G p - U p = J S /d at low generation rate (Δр<<p) is described by
154 Photodiodes - From Fundamentals to Applications

d 2φ d 2φ
2 + = ρs J S (11)
dx dy2

where φ(x,y) – the potential in absorber layer, ρ S – surface resistance ρS =1/qμ p pd.

The surface current density J S=I×N, where I – diode current; N – density of surface state. For
ideal n-p junction the current is expressed by

I = I ph + I S e ( qV
kT
−1 ) (12)

where Iph – photocurrent; V = -(φd-φ(x,y)) and φ d – potential at diode from multiplexer and
boundary condition φ(x,y)=0 at the base contact.

Fig 21 shows the calculation data of distribution of diodes current for the case of appearance
of positive voltage bias at central part of FPA due to voltage drop because of large summed
current in absorber layer.

Figure 21. The numerical calculation data of changing of output diodes current at homogeneous radiation of central
part of 128× 128 FPA.

This data demonstrates “debiasing substrate” or “boublik” effect which means the breaking
of central diodes that observed experimentally (Fig. 22).
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Figure 22. The experimental image at homogeneous radiation of central part of 128× 128 PV FPA n-p type.

For decreasing or elimination of “debiasing substrate” or “boublik” effect we suggested

high level doping (Fig. 14) or narrow gap layer (Fig. 15) during growing MCT HES.

Figure 23. The numerical calculation data of potential distribution in 640×512 PV FPA p-type on dependence of resist‐
ance of high conductivity layer. The photocurrent of diodes is 20 nA.

In case of fabricating high conductivity layer by doping during the growth the thickness
d and MCT composition can be chosen for creating cooled short wavelength cur off filter.
156 Photodiodes - From Fundamentals to Applications

The results of numerical calculation of potential distribution in the absorber layer for
640×512 PV FPA is shown in Fig. 23 with the following parameters: I d =20 nA;
А=6.25×10-6 cm2; ρ s=2 kΩ/ (р=8×1015 cm-3, μ р=400 cm2/(V×s); d=10 μm); n-p junction be‐
tween n-type layer and barrier layer is ideal with the density of saturation current J S =
1.6×10-7 A/cm2; ground potential to base contact.

The good values of voltage drop lower 70-110 mV reached at resistance 10-100 Ω/ of high
conductivity layer thickness 3 μm doping by In up to (1-5)×1016 cm-3.

3.3. MCT HES p-P design

The special dual layer absorber construction of MCT HES p-P type (p in narrowgap part
of absorber layer; P in widegap of absorber layer) (see Fig.24) allows to decrease dark cur‐
rent and photocurrent that leads to increase of wavelength cut off in range 8-12 μm or
operating temperature [20].

Figure 24. The MCT distribution throughout the thickness in p-P MCT HES: Δx – barrier between narrowgap and wide‐
gap parts of absorber layer; zj – position of n+-P junction.

The quantum efficiency η and R 0 A product (R 0 – differential resistance at 0 bias voltage; A -

diode area) was numerical calculated for p-P MCT HES taking into account only diffusion
current in which the lateral diffusion current contribution becomes essential [21,22].

Fig. 25 shows the scheme of PV diode for calculation η and R 0 A. The MCT of narrow gap p
and wide gap P layers is equal to 0.22 mole fraction CdTe and 0.22+Δx mole fraction CdTe
respectively. N+ -p junction located in P layer.
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Figure 25. The scheme of n+-P-p diode fabricated in p-P MCT HES.

The diffusion current is determined from decision of stationary continuity equation for ex‐
cess electron in р range. The valence band location in p-P absorber layer is permanent (com‐
mon anion rule). The р-range is quasi neutral. The current in n+ range does not take into
account. The stationary continuity equation in cylindrical coordinates at constant electron
mobility and lifetime is expressed by

∂2 n ′ 1 ∂ n ′ ∂2 n ′ d
∂r 2 + r ∂r +
∂z
∂n ′
2 − dz (ln ni (z) ) ⋅ ∂ z −
2 d2
dz 2
(
ln ni2(z) +
1
L n2
)
⋅n′= −
g(z)
Dn
(13)

∫
whereg(z) = α(z)Qexp( − α(t)dt) g(z)- generation function and α(z) – adsorption coefficient;
0

Q – the density of flux of radiation, n ′ - excess electron concentration, Dn - electron diffusion

coefficient; L n- electron diffusion length, ni - intrinsic carrier concentration. The boundaries
conditions are the following:

1. ∂n ′
= 0at r = 0 and r = r j+ 5L n
∂r

2. n ′ = n p0(exp(qV / kT ) − 1) on n+-p junction borders

3. ∂n ′
= 0 on the planar borders of absorber layer at z = 0 и z = H.
∂z

The incident radiation from back side of diode has wavelength for maximal ampere-watt
sensitivity at 78 К.
158 Photodiodes - From Fundamentals to Applications

∂n ′
The diode current I is determined after equation decision by integration of jN = qDn and
∂z
∂n ′
jL = qDn on planar and lateral surfaces of n+-p junction. The R 0 A product is deter‐
∂r
kT
mined from dark diffusion current I as R0 A = A, where A = πrj2- area of n+-p junction. The
qI
Ip
quantum efficiencyη = is determined by calculated photocurrent I p.
qQA

Figure 26. The R0A and η для 1D and 3D diodes on Δx at z j=8 μm, L n=25 μm and r j = 5 μm.

Fig. 26 represents the dependence of R 0 A and η on Δx. The Δx increasing leads to decreas‐
ing of diffusion current and changes the relationship between volume and lateral compo‐
nents from comparing R 0 A and η for 3D and 1D diodes.

Fig. 27 (a, b) shows the influence of n+-p position and relationship rj/L n on diffusion current.

So the anyone using suggested model could be carried out the calculation and/or taking the
data in Fig. 25, 26 to determine the MCT HES p-P construction (Δx, rj and poison n+-p junc‐
tion) which allows to fabricate IR detector with definite low diffusion current.
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Figure 27. The diffusion current dependences on position of n+-p junction in P region (a) and relationship rj /L n (b).

4. The technology and parameters of IR detectors

4.1. Linear LWIR 288х4 FPA

The linear 288×4 PV FPA has been fabricated by planar technology described in [23] using
MCT HES with graded widegap layer at absorber layers boundaries represented in Fig. 13.
The FPA has 288 channels of four pixels, on which time delay and integration (TDI) is per‐
formed through the readout integrated circuit (ROIC). The size of each pixel is 25 μm (scan
direction) per 28 μm (cross-scan direction). The in-scan pitch is 43 μm and the cross-scan
pitch is 28 μm. The diodes were formed by the implantation of B+ ions with the energy ~50
keV and a dose ~3×1013 cm–2 into p-MCT structures. The spectral response of one of the ele‐
ment in the array is shown in Fig. 28, (STD = 0.1 μm).

Current-voltage characteristics of 30 diodes have been measured at random with the help of
the microprobe device cooled by the liquid nitrogen vapour. The typical dark current was
equal to 5.3 nA at the reverse bias voltage 150 mV.

A defect diode can be detected by its high dark current, and the deselection function of the
ROIC allows us to switch such a diode off. The time delay integration is performed over the
entire 4-diode channel thus, the presence of a single defect diode does not influence the
160 Photodiodes - From Fundamentals to Applications

channel operation. Additionally, there is an option in the ROIC to use the average dark cur‐
rent value for deselected defect diodes.

1,0

0,8
Response, arb.un.

0,6

0,4

0,2

0,0
2 4 6 8 10 12
Wavelength, mm

Figure 28. The typical spectral response of one of the sensitive element in 288×4 PV FPA.

In Fig. 29, the typical I-V curvе and differential resistance R versus bias voltage at 77 K are
shown. The values of R 0, R max, and of the product R 0 A were equal to 1.6×107 Ω, 2.1×108 Ω,
and 70 Ω cm2, respectively.

Figure 29. The typical current (1 – the photocurrent,2 - the dark current) and the differential resistance (3) depend‐
ence on the bias voltage.
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The experimentally measured I-V curves of photodiodes has been modelled with the help of
the carrier balance equations approach [24,25], assuming the presence of in-gap donor-type
trap level with the energy E t ≈0.7Е g and taking into account the trap-assisted tunnelling and
the Shockley-Read-Hall (SRH) generation/recombination as two current mechanisms. The
other relevant current mechanisms, that do not involve the trap levels, have been taken into
account additively. The modelling has shown that at a small reverse bias (less than –0.25 V)
the dark current is limited by the diffusion current and the SRH current outside the n–p-
junction. At the reverse bias larger than –0.25 V, the dark currents were determined by the
tunnelling and thermal generation from the trap levels. Interband tunnelling as well as the
other recombination mechanisms do not contribute substantially at the operational bias val‐
ues. The modelling has shown that these heterostructures are of the n + -n – -p type, with the
n-p junction shifted into n-region that is characterized by long carrier lifetimes and low con‐
centration of recombination centres (due to the compensation of the Hg vacancies). The use
of the varyband potential at the surface of the heteroepitaxial MCT structure allows us to
increase the effective carrier lifetime by means of diminishing the influence of the surface
recombination, as well as by suppressing the surface leakage currents [26].

Experimentally, our average diodes have shown current-voltage characteristics that are
practically limited by the diffusion current mechanism for ideal diodes. Such characteristics
make possible to realize the FPA operating in a BLIP regime.

The multiplexer was designed using the 1.0-μm CMOS technology with two polysilicon and
two metallic layers. The multiplexer provides a bidirectional TDI scanning, random pixel
deselecting, anti-blooming and background skimming, and testing analogue part of a circuit
without connection to photodiodes. The output charge capacity of the multiplexer exceeds
2.5 pC at the nonlinearity lower than 2%.

Figure 30. The photo view 288×4 PV FPA hybrid assembly.

162 Photodiodes - From Fundamentals to Applications

The 288×4 PV FPA was fabricated by hybrid assembling of the photosensitive array and
the ROIC, with the help of indium bumps group welding at 120ºС. After hybridization,
the total height of In bumps was equal to ~10 μm [27]. In Fig. 30, a photo of the 288×4 PV
FPA hybrid assembly is presented.

Figure 31. An example of the thermal image 288×4 PV FPA.

Figure 32. The histogram of NETD.

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The measurement of PV FPA parameters were carried out in a cryostat at 77 K, the input
signal was coming through the GaAs substrate (FOV 32º, 295 K). The integration time was
20 μs. Typical values of responsivity and detectivity at the maximum of the spectral sensitiv‐
ity were equal to 2.27×108 V/W and 2.13×1011 cm×Hz1/2×W–1 at STD 6.7% and 15.3%, respec‐
tively. The example of a 576×610 thermal image by PV FPA (FOV = 32º, F = 1/1.6) is
presented in Fig. 31.

The NEDT histogram is shown in Fig. 32. The average NETD value is about 9 mK.

4.2. Matrix LWIR 320х256 PV FPA

We developed the technology of fabricating 320×256 (320×240) and 320×240 PV FPA operat‐
ed in wavelength ranges 8-12 μm at 77 K. The MCT HES composition distribution through‐
out the thickness used for FPA is analogous presented in Fig. 14.

Figure 33. The photo view 320×240 PV.

Figure 34. Spectral responsivity 320×240 PV FPA.

164 Photodiodes - From Fundamentals to Applications

The topology 320×256 (320×240) FPA is matrix with pixel pitch 30 μm in X и Y directions.
Fig. 33 shows photo view of 320×240 FPA (photosensitive pixels array in left corner).

The typical spectral response is present in Fig. 34.

The low dark current is equal to 1.5-2 nA and is constant up to reverse bias voltage 200 mV
for best diodes. The product R0 A=40 Ohm×cm2 for such diode (optical area А=8×10-6 cm2) is
compatible to the best literature data for n + -p photodiodes [17].The readout integrated cir‐
cuit 320×256 design is based on a silicon CMOS technology. The charge capacity is very
large - more then 20 pC. This multiplexer can operate with LWIR photodiodes for spectral
range to 14 μm, that have large dark and background current. Developed multiplexer oper‐
ate with two formats: 320×256 and 320×240 elements. IR FPA was fabricated by hybrid cold
welding by indium bumps of photodiode array and silicon ROIC under pressure. The F/1,6
NEDT and thermal images with the help of LWIR 320×240 FPA are shown in Fig 35, 36.

Figure 35. NEDT histogram of 320×240 PV FPA.

Figure 36. Thermal images 320×240 PV FPA.

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4.3. Heterodyne LWIR detector

The HF PD threshold heterodyne detection power (Pt) taking into account real parameters
described by the expression (1)

Pd2 ℏωs
Pt = + (14)
2Pg η (ωs − ωg )

where Pd – threshold power at baseband detection;

Pg – heterodyne power, ωs – frequency of detected radiation,

ωg – heterodyne frequency, η(ωs- ωg) – quantum efficiency.

In Fig. 37 the calculation solid curves (1-3) of Pt dependences on Pg for different Pd are shown.

Figure 37. The dependences of Pt on Pg of HF PD for detection 10,6 µm wavelength radiation at η = 0,5: 1 - Pd = 10-13
W/Hz1/2; 2 - Pd = 10-12 W/Hz1/2; 3 - Pd = 10-11 W/Hz1/2.

The dashed line is typical experimental data. It is clear that theoretically Pt values reach min‐
imum value at essentially smaller Pg for PD’s with the minimal Pd values. Experimental Pt
values for PD’s based on bulk p-type HgCdTe (dashed line) has analogous dependence on
Pg. But at Pg> 10-3 W Pt begin increases that connected with changing optimal condition oper‐
ation because of PD heating. So it is necessary to fabricate PD with smaller Pd values for fa‐
vorable operation condition. And it is maybe important for multi-channel system having
low heterodyne radiation power. We fabricated HF PD on the basis of p-type MCT HES (see
166 Photodiodes - From Fundamentals to Applications

Fig. 15) with thickness of absorber ~ layer 10 μm. The calculations and experimental data
were shown that it is necessary to grow wide gap layer between high conductivity narrow
gap layer and absorber to reach limiting PD and HF PD parameters [23]. The QE of PD on
the basis HgCdTe HS MBE without antireflection coating η≅ 0.65. The Rs< 10 Ω and Ro×A =
100130 Ω cm2. The Sv (λ=15.0 μm) and D* (λ=15.0 μm) were (57)×105 V W-1 and (68) ×1010
cm Hz1/2 W-1 at FOV=300 and Tbackground 295К.

The specification of single element HF PD and PC is the following:

PD PC

Element size, µm 250 100×100

λmax, µm 10 15

λ0,1, µm 11 19

Pd (λmax), W/Hz 1/2

2×10 -13
1×10-13

Pt (λmax), W/Hz 10-19 10-18

operating temperature, K 77-78K

frequency range, GHz ≥1

Table 2

HF PD and PC mounted into LN2 cooled Dewar (Fig. 38).

Figure 38. The view HF PD into LN2 Dewar.

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4.4. Matrix LWIR 128×128 PV FPA

We fabricated 128×128 PV FPA by planar low temperature technology on the basis of р-P
MCT HES (see Fig. 24). N+ - P junctions were fabricated by B+ implantation and located into
MCT P-layer. The photodiode parameters were as following: λc = 10,6 μm; dark current 0,8
nA at V= −200 mV at 77K. The diodes pitch was 40 μm. The diode size was 17×17 μm. The
wavelength cut off was 10,3μm. The diode design and band diagram was shown in Fig. 39.

CdTebuffer heterojunction
layer
GaAs substrate n+
illumination

contact

p-type rj
active
layer surface graded
layer

surface graded (à)

layer
Eg Fermi level

(b)

Figure 39. Photodiode base on p-P MCT HES : (a) design and (b) band diagram.

The ratio signal to noise (S/N) of hybrid FPA expressed by well-known equation

S / N = Is / IУ × (k × Q / q)1/2 (15)

where Is – the signal photocurrent, IУ – total current, equal to sum of dark current and back‐
ground current (neglecting the signal current), k – the charging of accumulating capacitance
coefficient, Q – charge capacitance, q – electron charge.

The relation S/N of FPA based on P-p NCT HES does not depend on barrier height because
of decreases at presence of potential barrier at the same manner of photo- and dark currents
at diffusion approximation. Nevertheless, in real diode frequently there is existed an excess
1/f noise and dark current caused by generation and tunneling processes inside space-
charge region. In this situation large photocurrent through high-resistance p-absorber to
ground bus leads to large differences of voltage biases of FPA photodiodes at the center and
periphery. It appears as an additional noise increase. Moreover ROIC added noise according
to In = Vn/Rd, where In – noise current, Vn – bias noise voltage, Rd – differential resistance
168 Photodiodes - From Fundamentals to Applications

which may be essential values at small Rd. So, in real FPA values S/N is usually lower than
calculated one by formula (1). This difference is increase with the increase total diode cur‐
rent. The potential barrier at P-p MCT HES leads to decrease of total diode current of FPA
and eliminates negative phenomena described previously. We showed from measurement
of noise spectrum that frequency cut off of 1/f noise for photodiode on the basis of P-p MCT
HES is equal up to less than 10 Hz. These 1/f values are essentially lower than for FPA based
on MCT epitaxial structure without P-p heterojunction. It means that S/N of FPA on the ba‐
sis P-p heterojunction will approach to values given by equation 16.
128×128 hybrid FPA was package inside cooled cryostat with ZnSe window. We meas‐
ured the FPA parameters in range 77 – 300K, at FOV 450, black body temperatures 300 -
500К and background temperature 295K. The temperature at measurement maintained
with accuracy 0,5К. We measured the black body’s diode signal and noise. The signal
storage time satisfied by k = 0,8. The S/N experimental (squares) data of FPA on the basis
of P-p MCT HES are given in Fig. 40.

- calculation
S/N, arb. un.

- FPA with barrier

- FPA without barrier
0,1

0,01
70 80 90 100 110 120 130
T,K

Figure 40. The ratio of S/N on temperature. Squares – FPA on p-P MCT HES. Triangles – FPA on p-type MCT HES. Solid
curve – calculation.

In the same Figure the calculated S/N dependence is shown for analogous FPA without
barrier at the same measurements regime. The S/N calculation was carried out in follow‐
ing approximations:
• the dark current was calculated by diffusion model;
• the velocity of surface recombination on boundaries was zero;
• the carrier collection area at fixed temperature was determined by geometric size of n-re‐
gion and carrier diffusion length but was no more than pixel size;
 LWIR Photodiodes and Focal Plane Arrays Based on Novel HgCdTe/CdZnTe/GaAs Heterostructures Grown by MBE 169
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• quantum efficiency value was taken to be 0.7;

• 1/f noise was zero;
• the accumulation time was chosen from the above condition of charging of accumulation
capacitance.
In the same Figure measured S/N values are given for few FPA on the basis of MCT layer
without P-p barrier with λc in range 10,5-10,7 мm at T=77 K.
The experimental S/N values of FPA on the basis of P-p DLHJ with barrier more closely
correspond to calculated dependence in comparison with FPA on the basis of MCT layer
without P-p barrier. This can be explained as follows. At temperatures near 77 K lower
S/N ratio of FPA on the basis of MCT layer without P-p barrier is associated to excess
currents (generation and tunneling current) and to presence of 1/f noise. When the tem‐
perature increases in range 77 -130K the diodes differential resistance of FPA diodes de‐
creases and total current increases. The first leads to increase of ROIC noise and diodes
noise. The second leads to additional noise determined by strong mutual coupling of pho‐
todiodes. All this factors decrease the S/N ratio faster than calculated one. It means that
FPA for operating at elevated temperatures must be fabricated on the basis of P-p DLHJ
with barrier. The behavior of S/N will analogous ones which given in Fig.4 for at increase
of wavelength cut off at constant operating temperature.

5. Conclusion

The technology of fabrication of mercury cadmium telluride (MCT) heterostructure (HES) at

growth by molecular beam epitaxy (MBE) was developed. The MBE ultra vacuum set allows
to grow high quality n-type MCT HES with monitoring in real time. Thermal treatments are
used for fabrication high quality p-type MCT HES for LWIR photovoltaic (PV) devices.
We suggested different MCT HES design with graded widegap layers, high conductivity
layer and p-P structures.
We demonstrated the four cooled LWIR detectors for spectral range 8-11 μm based on
these MCT HES:
• linear 288×4 PV FPA on the basis MCT HES with graded widegap layers on the bounda‐
ries of absorber layer;
• matrix 320×256(240) PV FPA on the basis MCT HES with high conductivity layer (grow‐
ing by doping) to eliminate “debiasing” effect;
• matrix 128×128 PV FPA on the basis MCT HES with p-P absorber layer which successfully
operated at elevated temperature;
• one elements heterodyne detector on the basis MCT HES with high conductivity layer
(growing narrowgap layer) operating at GHz frequencies.

The parameters of these devices are limited by background radiation.

170 Photodiodes - From Fundamentals to Applications

Author details

V. V. Vasiliev1, V. S. Varavin1, S. A. Dvoretsky1*, I. M. Marchishin1, N. N. Mikhailov1,

A. V. Predein1, I. V. Sabinina1, Yu. G. Sidorov1, A. O. Suslyakov1 and A. L. Aseev1

*Address all correspondence to: [email protected]

1 A.V. Ryhanov Institute of Semiconductor Physics, Siberian branch of the Russian academy
of sciences, Russia

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dorov, Yu. G., Suslyakov, A. O., Yakushev, M. V., & Aseev, A. L. (2003). HgCdTe epi‐
layers on GaAs: growth and devices. Opto-Electronics Review, 11, 99-111.
 Chapter 5

Photodiodes as Optical Radiation Measurement

Standards

Ana Luz Muñoz Zurita, Joaquín Campos Acosta,

Alejandro Ferrero Turrión and Alicia Pons Aglio

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/51462

1. Introduction

Photodiodes for optical radiation measurements are used without reverse bias in most ap‐
plications since this operation yields the lowest dark current. To obtain photodiodes that op‐
erate at a low bias and have a low dark current, it is necessary to produce epitaxial layers
that are pure and have few defects (such as dislocations, point defects, and impurity precipi‐
tates). Furthermore, a planar device structure requires that a guard ring be used to keep the
electric field around the photoreceptive area from increasing too much. Fabrication and
processing technologies such as impurity diffusion, ion implantation, and passivation play
important roles in the production of reliable photodetectors.

From a radiometric point of view, the photodetectors important characteristics are: Speed of
response (characterized by the bandwidth of the frequency response or the Full Width Half
Maximum (FWHM) of the pulse response), responsivity (determined as the ratio of current
out the detector to the incident optical power on the device), sensitivity (defined as the mini‐
mal input power that can still be detected which, as a first approximation, is defined as the
optical power which generates an electrical signal equal to that due to noise of the diode)
and response linearity. These quantities defined the basic radiometrical behavior of any de‐
tector. For those detectors having large area, as it may be the case for some photodiodes,
knowing the response uniformity of the sensitive area is important too, especially when the
incident beam diameter is much smaller than the detector sensitive surface. A high nonuni‐
formity would produce measurement errors when the detector is used at different positions,
errors that have to be taken into account for the final accuracy of the measurement.
174 Photodiodes - From Fundamentals to Applications

To determine those radiometric features in photodiodes and learn how they change with
wavelength, for instance, it is a good approach to start by analyzing. The physical phenom‐
ena involved in the detection. When light impinges on a detector, various physical processes
occur; part of the incident light is reflected at the sensitive surface, while the rest passes in‐
side the detector, where can be partially, because of losses due to absorption, converted into
an electronic signal. Then the photodetector response is conditioned by the amount of absor‐
bed light, but for evaluating the incident power one has to know the ratios of the reflected,
absorbed, and converted power as well. Taking into account these phenomena, the short cir‐
cuit response of a photodiode can be written as

λ
I (λ ) = I 0 + (1 − ρ (λ ))ε (λ ) k ∅ (λ ) (1)

Where I 0 is the dark response, ρ(λ) is the photodiode’s reflectance, λ is the radiation wave
length, ε (λ) is the photodiode’s internal quantum efficiency,k is a constant that takes into ac‐
count other fundamental physical constants and ϕ (λ) is the spectral radiant flux incident on
the photodiode. According to this equation, the incident radiant flux can be determined from
measuring the photodiode’s response as far as its spectral reflectance and internal quantum ef‐
ficiency are known. Then photodiodes are good devices for radiant flux standards.

Silicon and InPphotodiodes from different manufacturers have got rather low noise lev‐
el, good response uniformity over the sensitive surface and a wide dynamic range. There‐
fore they are good devices to build radiometers in the visible and NIR spectral region in
many different applications, particularly for building up spectroradiometric scales for ra‐
diant flux measurements.

Back to equation (1), if photodiode’s reflectance and internal quantum efficiency were
known, the photodiode’s responsivity would be known without being compared to another
standard radiometer; i. e. the photodiode would be an absolute standard for optical radia‐
tion measurements [1, 2, 3].

This idea was firstly developed for silicon photodiodes in the eighties, once the technology
was able to produce low defects photodiodes [4]. Following this reference, the reflectance
could be approached from a superimposed thin layers model. By knowing the thicknesses of
the layers and the optical constants of the materials, it is possible to determine the device
reflectance. However, this information is not completely available for InP photodiodes: the
actual thickness of the layers is not known and optical constants of materials are only ap‐
proximately known for bulk. Nevertheless it’s possible to measure reflectance at some wave‐
lengths and to fit the thicknesses of a layer model that would reproduce those experimental
values.

The internal quantum efficiency cannot be determined as for Si. Since InP photodiodes are
hetero-junctions rather than homo-junctions as silicon photodiodes are. In the other hand,
since the internal structure is not accurately known, it is not possible to model the internal
quantum efficiency without having experimental values for it.
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Therefore the attainable scope at present is just to obtain a model to be able to calculate spec‐
tral responsivity values at any wavelength. To get this, a model has been developed to cal‐
culate reflectance values from experimental ones at some wavelengths and another model
has been developed to interpolate spectral internal quantum efficiency values from some
values got from reflectance and responsivity measurements at some wavelengths. Both
models will be presented in this chapter.

2. Spectral responsivity scale in the visible range based on single silicon

photodiodes.

A spectral responsivity scale means that the responsivity is known at every wavelength
within the response range of interest and it would be desirable to know it for all the other
parameters associated with a beam: angle of incidence, divergence or polarization.

Aspectral responsivity scale in the visible range can be created by calibrating a silicon trap
detector at several laser wavelengths against ahigh accuracy primary standard such as an
electrically calibrated cryogenic radiometer. This method provides a very certain value for
the responsivity at specific wavelengths as those of lasers (for instance 406.7 nm, 441.3 nm,
488.0 nm, 514.5 nm, 568.2 nm, 647.1 nm and 676.4 nm). From there single elements detectors,
most suitable for some applications, can be calibrated against that trap detector at those
wavelengths to define the working scale.

The spectral responsivity of silicon photodiodes is given by the well-known equation

λ
R (λ ) = (1 - ρ (λ ))ε (λ ) k (2)

This chapter describes the results obtained for the responsivity of the photodiodes by using a
model to calculate the diode’s reflectance from experimental measurements and a model for
the internal quantum efficiency, which is also fitted to experimental values. Based on the mod‐
els, the fitting errors and the uncertainty of reflectance and responsivity measurements, the
uncertainty of the responsivity scale is calculated according to the ISO recommendations.

3. Reflectance evaluation of silicon photodiodes

From the reflectance point of view, a silicon photodiode can be considered as a system
formed by a flat transparent film over an absorbing medium. The flat film is the silicon ox‐
ide and the absorbing medium is the silicon substrate. The reflectance of such a system is
given by [5]
176 Photodiodes - From Fundamentals to Applications

r122 + ρ232 + 2r12ρ23cos(ϕ23 + 2β )

ρ= (3)
1 + r122ρ232 + 2r12ρ23cos(ϕ23 + 2β )

where r12 is the amplitude of the reflection coefficient from air to silicon oxide, ρ23 is the
amplitude of the reflection coefficient from silicon oxide to silicon, φ23 is the phase change
at the interface silicon oxide–silicon and β = 2πn2h cos(θ2)/λ0, with h the thickness of SiO2,
n2 the refractive index of SiO2 and θ2 the refraction angle at the air–oxide interface. These
variables change with the angle of incidence and the light polarization, so the reflectance
value will be known if the silicon oxide thickness, the angle of incidence, the refractive index
and the light polarization status are known. This reflectance model has been already tested
for another type of silicon photodiode from the same manufacturer [6].
Spectral values of the refractive index are available in the literature. In this work values have
been obtained from those given in [7]. The index of refraction of silicon oxide has been inter‐
polated by fitting a polynomial to data; the real part of the refractive index of silicon has
been obtained by fitting a polynomial in 1/λ and the imaginary part by fitting an exponen‐
tial decay in λ.Reflectance was measured with an angle of incidence of 4 in our reference
spectrophotometer, using p-polarized light, at the laser wavelengths for which the diodes
were calibrated against the trap: 406.7 nm, 441.3 nm, 488.0 nm, 514.5 nm, 568.2 nm, 647.1 nm
and 676.4 nm. By fitting equation 3 to measurement results, the silicon oxide thickness was
obtained for every photodiode, as shown in table 1. The fitting error in this table is the pa‐
rameter given by the fitting software.

Photodiode SiO2 thickness/nm Fitting error/nm

CIRI 29.58 0.19

SiN 28.84 0.17

Si1 29.93 0.19

Table 1. Silicon oxide thickness fitted to reflectance measurements

The fitting is very good for wavelengths longer than 500 nm, getting worse for shorter
wavelengths, as can be seen in figure 1 for one of the photodiodes studied. The same results
are obtained for the three photodiodes studied in this work.
This agrees also with [2]. Probably it is due to the measurement bandwidth. For conven‐
ience, the reflectance was measured in our reference spectrophotometer with a bandwidth
of 5 nm in order to have a good signal-to-noise ratio at the shortest wavelengths. But in this
region the first and second derivatives of reflectance are higher than in the middle visible, so
the increased bandwidth produces an effective reflectance value that differs significantly
from the spectral value. For this reason, reflectance values below 500 nm were not used in
the final fitting process to obtain the thickness.
Using thickness values given in table 1, the reflectance of the photodiodes at normal inci‐
dence can be calculated, and from them and the responsivity values measured against the
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trap detector, the photodiodes’ internal quantum efficiency can be calculated according to
(2). Using a model based in physical laws rather than experimental equations allows obtain‐
ing the physical quantity for different circumstances, such as different angles of incidence,
for instance.

Figure 1. Spectral reflectance values of photodiode CIRI and fitted values according to equation (3).

5. Internal quantum efficiency of silicon photodiodes

To spectrally know the internal quantum efficiency we have used the model developed by
Gentile et al [2], based on that from Geist and Baltes [14] and improved by Werner et al [15].
The internal quantum efficiency is given by

1 − Pf 1 − Pb
ε (λ ) = Pf + α (λ )T
{1 − exp − Tα (λ ) } − (D − T )α (λ )
{exp − Tα (λ ) − exp Dα (λ ) } −
(4)
Pbexpexp hα (λ ) + Rback exp hα (λ ) Pb

where Pf is the collection efficiency at the front, T is the junction depth, Pb is the collection
efficiency at the silicon bulk region, which starts at depth D, h is the photodiode’s length,
Rback is the reflectance at the photodiode’s back surface and α is the absorption coeffi‐
cient.According to Gentile et al [2] a simplified model can be used if the model is to be ap‐
plied to wavelengths shorter than 920 nm. This model is obtained from the previous
equation by deleting the last two terms. Then, the quantum efficiency can be obtained from
178 Photodiodes - From Fundamentals to Applications

e ( l ) = Pf + ( 1 - Pf ) /a ( l ) T {1 - exp ëé -Ta ( l ) ûù} - ( 1 - Pb ) / ( ( D - T ) a ( l ) ) {exp ëé-Ta ( l )ûù - exp ëéDa ( l )ûù} (5)

This model has been fitted to the calculated internal quantum efficiency values by a non-lin‐
ear squared method.
The parameters’ initial values were taken from Gentile et al [2]. The goodness of the fit can
be seen in figure 2, where values for one of the studied photodiodes are shown. The same
results are obtained for the three photodiodes studied in this work. The main difference be‐
tween the fitted values of the internal quantum efficiency and those calculated from the re‐
sponsivity and reflectance measurements is about 10-3, which agrees well with results given
by other authors, e.g.[2,9].

Figure 2. Experimental internal quantum efficiency values ofphotodiode SiN and fitted values according to equation
(5) againstthe absorption coefficient.

Another point that can be discussed is how far the internal quantum efficiency can be ex‐
trapolated. Using this simplified model and fitting with values corresponding to wave‐
lengths shorter than 700 nm, quantum efficiency values continue to increase very slightly to
900 nm at least. This is not what really happens in the photodiode, so there will be an upper
limit for the extrapolation. This limit will depend on the uncertainty allowable to the re‐
sponsivity value and will be discussed in the following section.

6. Spectral responsivity values of silicon photodiodes

Responsivity of detectors has been calculated with the model described previously and the
parameters obtained by the fitting process by using (2), (3) and (5). The agreement between
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the calculated values and those measured against the trap is excellent as can be seen in fig‐
ure 3 for one of the photodiodes studied. This result is just a check of the consistency of the
method. Nevertheless, it can be seen that most calculated values are smaller than the meas‐
ured ones. This might be due to the independent fitting of reflectance and quantum efficien‐
cy values and their functional forms, but it may also be due to the presence of a systematic
error in the measurements. Some research will have to be done in the future to clarify this.

Figure 3. Spectral Difference between calculated and measured spectral responsivity values for photodiode CIRI as a
function of wavelength.

7. Spectral responsivity scale in the near IR range based on single InP/

InGaAs photodiodes

As in the visible range, semiconductor photodiodes are the best choice for establishing spec‐
tral responsivity scales in the near IR range. The first attempt was to use germanium photo‐
diodes, since its gap allowed to obtain a device responding to wavelengths lower than 1.6
μm, approximately, depending on temperature. However germanium photodiodes have got
a rather high dark current and lower shunt resistance than silicon, then they are not so use‐
ful for optical radiation detection. Since optical communications were demanding better de‐
tectors to enlarge their use, other photodiodes were developed in this spectral region of
great interest. Since no other single element semiconductor was possible, semiconductor
hetero-junctions were developed. A hetero-junction is a junction formed between two semi‐
conductors with different band-gaps. Of course building such devices is not straightforward
since the lattice parameters have to be matched, but this is not the subject of this chapter and
many good references may be found in literature [17].
180 Photodiodes - From Fundamentals to Applications

The group known as III-V hetero-structures has yield different photodiodes in the near IR
range, particularly those based on InP/InGaAs has yield very good devices for the spectral
range covered by germanium photodiodes. This hetero-structure has got two junctions in
fact. The InGaAs material, having a lower gap, is kept in between two layers on InPwhose
gap is bigger and hence transparent to the wavelength region used in optical communica‐
tions: the nondispersion wavelength (1.3μm) and the loss minimum wavelength (1.55μm).
The radiometric characteristics of these InP-based photodetectors are superior to those of
conventional photodiodes composed of elemental Germanium. Because of that they have re‐
placed germanium in almost every application.

By using a hetero-structure, which hadn’t been used in group IV elemental semiconductors

such as Si and Ge, new concepts and new designs for high performance photodetectors have
been developed.For example, the absorption region for a specific spectral range can be con‐
fined to a limited inner layer, avoiding typical high recombination rates of charge carriers at
the first interfaceof the photodiode and getting a higher internal quantum efficiency.

Recently InGaAs/InP avalanche photodiodes (APDs) with a SAM (separation of absorption

and multiplication) configuration have become commercially available. The SAM configura‐
tion is thought to be necessary for high performance APDs utilizing long wavelengths.

InGaAs/InPphotodetectors are used for maintaining the scale of spectral responsitivityup to

1.7 μm in many laboratories [17, 19].In addition they are exploited in instruments for meas‐
uring optical radiation within the near infrared (NIR) range (800 nm -1600 nm). From this
point of view, these photodiodes are like other and their response is given by equations (1)
and (2). Therefore to know their reflectance and internal quantum efficiency is the key for
defining the spectral responsivity scale in this range.

Next experimental values for those properties measured in our laboratory for devices built
by different manufacturers will be presented.

8. Measurement of InP photodiode’s reflectance

To realize our experiments related to measuring the reflectance of InGaAs/InP photodiodes

the experimental set-up presented in figure 4 hasbeen arranged.

An incandescence lamp is the white light source imaged at the input slit of the monochro‐
mator. This lamp was able to cover the spectral range from 800 nm to 1600 nm and appro‐
priate blocking filters for second – order wavelengths were added to the monochromator.
After the monochromator, a linear polarizer and a beam splitter, which serves to monitor
temporal power fluctuations,were placed. A germanium photodiode was used as the moni‐
toring reference photodetector. More details can be seen in reference [20].

The experimental set-up included an optical system of mirrors, which consists of two parts.
An upper part (see mirror 7 and germanium photodiode 9) realized monitoring temporal
fluctuations of light power. A bottom part (see mirrors 8, 11; InGaAs/InP-photodiode 10,
 Photodiodes as Optical Radiation Measurement Standards 181
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and and germanium photodiode 12) formed an image of the monochromator’s exit slit on
the sensitive surfaces of photodiodes. The angle of incidence was equal to 7.4 º which was
accepted as the normal incidence in this train of measurements.

Figure 4. Experimental set-up for measuring the reflectance InGaAs/InP photodiodes

The measurement method consists in comparing the response from a germanium photo‐
diode to the radiation reflected by the InGaAs/InP photodiode with the response from an
aluminum standard mirror whose reflectance is measured as in [21], so that [20]:

I p (l )
r (l ) = rm (l ) (6)
I m (l )

Here,I p (λ) is the response to the light reflected by

the InGaAs/InP, I m (λ)is the response to the light reflected by the mirror, and ρm(λ) is the
reflectance of a standard mirror. With this method the reflectance of photodiodes from dif‐
ferent manufacturers hasbeen measured. One part of detectors had a round active area of 5
mm in diameter and the other part had a quadratic active area of 8 mm x 8 mm.

9. Analysis of Reflectance of InP Photodiodes

The polarization degree of light at the output the monochromator was different with vary‐
ing the wavelength.The figures 5and 6 illustrate spectral dependences of the reflectance,
which had been obtained from photodetectors belonging to three different manufacturers.
Two types (photodiodes 1 and 4 and photodiodes 2 and 5) are 5 mm in diameter sensitive
182 Photodiodes - From Fundamentals to Applications

area and the third is an 8 mm in diameter sensitive area especially commercialized some
years ago for developing spectral responsivity scales and no longer available in the market.
Figure 5a, and 5b show that the reflectance of 5 mm in diameter detectors from both manu‐
facturers has got a minimum in the region 1000 nm to 1600 nm, and they both are related to
a structure of layers providing maximal responses in the spectral interval of mayor utility of
these detectors in near IR:Optics communication [17]. The first photodiode, see Figure 5a,
whose reflectance was minimized, is more efficient that the second one, see figure 5b.

Figure 5. Detector with an active area 5 mmin diameter

Reflectance in figure 6 is associated with a photodiode with rectangular active area. In

this case the reflectance has two minima at 1000 nm and 1600 nm, but the reflectance has
a maximum between these minima. This photodiode is older than previous ones, and it
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was produced by another manufacturer. One can remark that maybe it was produced with‐
out good enough control, because the structure of layers on the sensitive surface modi‐
fies the reflectance.

0.36
0.34
Reflectance

0.32
0.30
0.28
0.26
800 1000 1200 1400 1600
Wavelenght (nm)

Figure 6. Detector with a rectangular aperture of 8 x 8mm

0.25
0.20
Reflectance

0.15
0.10
0.05
0.00
800 1000 1200 1400 1600
Wavelenght (nm)

Figure 7. Spectrum of reflectance for photodiodes 1 and 4 from the same manufacturer.

The spectrum of reflectance for photodiodes 1 and 4, manufactured by the same company, is
presents in figure 7. The reflectance was measured with linearly polarized and non-polar‐
184 Photodiodes - From Fundamentals to Applications

ized lights, and these pair of measurements gives quite similar results. In fact, the difference
was equal to approximately 2% for the angle of incidence used in this work. The same re‐
sults are depicted for the photodiodes 2 and 5, manufactured by a second company. It is im‐
portant that the results do not depend on the polarization state of the incident light when
the angle of incidence is smaller than 10 degrees [22].

0.18
0.16
0.14
Reflectance

0.12
0.10
0.08
0.06
800 1000 1200 1400 1600
Wavelenght (nm)

Figure 8. Spectrum of reflectance of photodiodes 2 and 5 from the same manufacturer.

0.35
0.30
0.25
Reflectance

0.20
0.15
0.10
0.05
0.00
800 1000 1200 1400 1600
Wavelenght (nm)

Figure 9. Comparison of reflectance of all photodiodes measured in this work.

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All spectrums of reflectance are presented in Figure 9, with linearly polarized and non po‐
larized light, so that it is possible to see the different behavior of the photodiodes in the near
infrared wavelength. In fact, in this chapter we are studying the behavior of the photodetec‐
tors in the near infrared with the linearly polarized and non polarized light in the case of the
polarized light the angle of incidence is smaller 10 angular degrees and is possible to ob‐
serve the reflectance doesn’t change its spectral behavior.

10. New Quantum Internal Efficiency Model of some InPphotodetectors.

To determine the internal quantum efficiency of a photodiode it is necessary to know its re‐
sponsivity (2). In this work, the responsivity, R(λ), was measured by direct comparison to an
electrically calibrated pyroelectric radiometer (ECPR), obtaining responsivity values with an
uncertainty of 1.2 % approximately, roughly the uncertainty of the ECPR. Spectral respon‐
sivity values of one photodiode from every manufacturer obtained from measurements are
shown in figure 10 (analogous results are obtained for the other photodiode from the same
manufacturer). From now on, the photodiodes will be identified as Ham, GPD and POL.
Ham and GPD are photodiodes from different manufacturers and were identified before as
photodiode 2 and photodiode 1, respectively. Both have got a 5 mm in diameter active area.
Photodiode POL was identified before as photodiode 4 and has got an 8 mm side square ac‐
tive area. Figure 10 shows there is a noticeable difference in responsivity between them.

Figure 10. Spectral responsivity values of InPphotodiodes.

10.1. External quantum efficiency

It is obtained from the responsivity values according to the equation:

186 Photodiodes - From Fundamentals to Applications

R ( l ) hc
Q (l ) = (7)
le

Where h, c and e are the usual physical constants andλis the wavelength.Values ob‐
tained are presented in figure 11 for the same detectors as before. It can be clearly
seen that the oldest detector (identified as POL) presents a lower external quantum ef‐
ficiency than the other and that detector GPD presents a higher external quantum effi‐
ciency than detector HAM, which starts to decrease its quantum efficiency at a shorter
wavelength. However, detector POL decreases less its quantum efficiency at wave‐
lengths lower than the corresponding to the InGaAs gap. Perhaps this is mainly due
to the tailoring of the hetero-structure done by the manufacturer. Detector POL was de‐
veloped for realizing spectral responsivity scales, while the other two were developed
for a better performance in the optical communications spectral range.

Figure 11. Spectral external quantum efficiency obtained from responsivity values

Figure 12. Internal Structure used in this work to model internal quantum efficiency of InP photodiodes
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10.2. Internal quantum efficiency

Internal quantum efficiency is obtained from responsivity and reflectance by using (2).
However those quantities have been measured at some wavelengths only, then it is necessa‐
ry to develop a model to interpolate them at every wavelength within the response range.
To develop such a model it is necessary to know the internal structure of the photodiode, as
it was done for the silicon photodiode, but a enough precise structure is not available in the
open literature. Since a structure has to be assumed to develop the model, the simplest one
from literature has been adopted in this work (Fig. 12). It is more than likely that detector
POL has particularly got a different structure.

The first layer made on NSi is transparent in the wavelength range considered in this work.
Probably it is placed in the photodiode as a passivation layer. Its thickness may be tailored
by the manufacturer to spectrally adjust the device’s reflectance.

Considering a structure as shown before (Fig. 12) and a simple model for the collection effi‐
ciency of carriers in every region given by a constant value: Pf,lower than 1 in the first re‐
gion, 1 in the depletion region (mainly InGaAs) and Pb in the back region, and an “infinite”
thickness for the diode, ε (λ) can be calculated by [23]:

e ( l ) = Pf ( 1 - exp ( -a T ) ) + exp ( -a T ) - exp ( -a T ¢ ) + exp ( -a ¢T ¢ )

(8)
- exp ( -a ¢D¢ ) - exp ( -a D¢ ) + exp ( 1 - Pb ) exp ( -a D )

Where T is the thickness at which collection efficiency becomes 1, T’ is the thickness at

which InGaAs region starts, D’ is the the thickness at which the InP (S) starts and D is the
thickness at which depletion region ends. By fitting this model to internal quantum efficien‐
cy values, the following parameters are obtained for every photodiode [23].

Photodiode Pf T T’ D’ D Pb

HAM 0 0.44 2.19 2.19 11.96 0.844

GPD 0 0.32 1.65 1.62 4351.16 0.960

Table 2. Parameters fitting the model to experimental internal quantum efficiency

Internal quantum efficiency values calculated from responsivity and reflectance (dots) and
adjusted values following (8) are shown in figures1 3 and 14 for photodiodes HAM and
GPD, respectively. It can be seen that photodiode GPD has got an internal quantum efficien‐
cy very close to unity in the region from 1 μm to 1.6 μm, approximately. Both photodiodes
have got internal quantum efficiency in this region nearly independent of wavelength.
These two results are very important in order to try to develop an absolute radiometer
based on InP photodiodes in the future.
188 Photodiodes - From Fundamentals to Applications

The model does not fit well in the short wavelength region. Possibly this is because the
structure of the detector is actually more complex or, perhaps, refraction index are not accu‐
rately known.

Figure 13. Internal quantum efficiency of photodiode HAM experimental values (dots) and fitted values (solid line)
according to the model shown below.

Figure 14. Internal quantum efficiency of photodiodes GPD experimental values (dots) and fitted values (solid line)
according to the model shown below.

11. Interpolation of spectral reflectance

Finally, to have the spectral responsivity scale, it is necessary to interpolate spectral reflec‐
tance at any wavelength, what can be done by using a multilayer model [11]. Complex re‐
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fraction index of the materials and thickness of the layers have to be known for
interpolation. Refraction index has been obtained from [13] and other sources cited in there
and are shown in figure 15.

Figure 15. Materials’ refraction Index

Thickness of the different layers is obtained by a nonlinear fitting of the experimental

values of reflectance to a multilayer model. The model did not worked out well for pho‐
todiode POL, then results are not given for it. Perhaps its structure is very different
from that of figure 12. Table 3 shows the thickness obtained from the fitting for photo‐
diodes Ham and GPD. The last layer, the deeper one regarding light absorption, was
considered to be infinite.

Photodiode NSi InP (Zn) InGaAs

HAM 162.17nm 1213.35nm 1593.2nm

GPD 159.99nm 1200.54nm 1536.7nm

Table 3. Thickness of layers of InGaAs photodiodes

12. Conclusions

Silicon photodiodes in the visible up to 950 nm and InP/InGaAs photodiodes in the NIR up
to 1.6 μm are widely used for optical radiation measurements in many different applications
because of their good radiometric properties. They have got high internal quantum efficien‐
cy, therefore they are very useful for realizing spectral responsivity scales.
Perhaps in a near future a model be developed for the internal quantum efficiency of InP/
InGaAs photodiode as it was done for the silicon, so that its responsivity may be accurately
190 Photodiodes - From Fundamentals to Applications

known in their spectral interval of response. Some more work is also needed to know the
structure of the device and improve the fitting of reflectance via a multilayer model.

Author details

Ana Luz Muñoz Zurita1, Joaquín Campos Acosta2, Alejandro Ferrero Turrión2 and
Alicia Pons Aglio2

1 Universidad Autónoma de Coahuila, Campus Torreón, Faculty of Enginering Mechanical

and electrical. Torreón, Coahuila, México

2 Consejo Superior de Investigaciones Científicas (CSIC), Instituto de óptica “Daza de

Valdés”, Madrid, España

References

[1] Ferrero, J. Campos, A. Pons, and A. Corrons “New model for the internal quantum
efficiency of photodiodes based on photocurrent analysis”. Applied Optics, Vol. 44, Is‐
sue 2, 208-216 (2005).

[2] Gentile T.R., Houston J.M., and Cromer C.L. “Realization of a scale of absolute spec‐
tral response using the National Institute of Standards and Technology High-accura‐
cy Cryogenic Radiometer. Appl. Opt. 35 4392-403 (1996).

[3] J. Campos, A. Corróns, A. Pons, P. Corredera, J.L. Fontecha and J.R Jiménez “Spectral
responsivity uncertainty of silicon photodiodes due to calibration spectral band‐
width". Meas. Sci. Technol, 12, 1936-1921, (2001).

[4] J. Campos, A. Corróns, and A. Pons, “Response uniformity of silicon photodiodes“.

Applied Optics, 27, 24, 5154-5156, (1988).

[5] E.F. Zalewski and J. Geist, “Silicon photodiode absolute spectral response self-cali‐
bration”. Applied Optics, 19, 8,1214-1216, (1980).

[6] R. Schaefer, E.F. Zalewski, and Jon Geist, “Silicon detector nonlinearity and related
effects”. Applied Optics, 22, 8, 1232-1236, (1983).

[7] E.F. Zalewski and C.R. Duda”Silicon photodiode device with 100% external quantum
efficiency”. Applied Optics, 22,18, (1980).

[8] J. Campos, A. Pons and P. Corredera., “Spectral responsivity scale in the visible
range based on single silicon photodiodes. Metrologia 40 S181-S184. (2003).

[9] Kholer R., Goebel R. and Pello R. “Results of an international comparison of spectral
responsivity of silicon photodetectors”. Metrologia 32 463-8 (1995).
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[10] E.F. Zalewski and J. Geist “Silicon photodiode absolute spectral response self-calibra‐
tion”. Appl. Opt., Vol. 19, No. 8 pag. 1214-1216. (1980).

[11] Born M. and Wolf E. 1989 “Principles of Optics. Electromagnetic Theory of Propaga‐
tion, Interference and Diffraction of Light”. 6th ed. (Oxford: Pergamon) p 633.

[12] Haapalinna A., Karha P. and Ikonen E. “Spectral reflectance of silicon photodiodes”.
Appl. Opt. 37 729-32 (1998).

[13] Palik E.D. 1985 Handbook of Optical Constants of Solids. (New York: Academic Press).

[14] Geist J. and Baltes H. “High accuracy modeling of photodiode quantum efficiency".
Appl. Opt. 28 3929-39 (1989).

[15] Werner L, Fischer J, Johannsen U. and Hartmann J. “Accurate determination of the

spectral responsivity of silicon trap detectors between 238 nm and 1015 nm using a
laser-based cryogenic radiometer”. Metrologia 37 279-84, (2000).

[16] O. Wada, H. Hasegawa, InP-Based materials and devices : physics and technology. New
York. John Wiley & Sons, 1999.

[17] P. Corredera, M.L. Hernanz, M. González-Herráez, J. Campos “Anomalous non-line‐

ar behaviour of InGaAs photodiodes with overfilled illumination”. IOP Metrología 40,
S181-S184, (2003).

[18] P. Corredera, M.L. Hernanz, J. Campos, A. Corróns, A. Pons and J.L Fontecha. “Com‐
parison between absolute thermal radiometers at wavelengths of 1300 nm and 1550
nm”. IOP Metrología. 37. 237-247, (2000).

[19] J M Coutin, F. Chandoul, J. Bastie,“Characterization of new trap detectors as transfer

standards”. Proceedings of the 9th international conference on new developments and appli‐
cations in optical radiometry, (2005).

[20] A.L. Muñoz Zurita, J. Campos Acosta, A. PonsAglio. A.S. Shcherbakov. “Medida de
la reflectancia de fotodiodos de InGaAs/InP”. Óptica Pura y Aplicada (Spain), 40(1),
105-109 (2007).

[21] Campos, J. Fontecha, J. Pons, A. Corredera, P. Corróns, A., Measurement of standar‐

daluminiummirrors, reflectance versus light polarization. Measurement Science and
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[22] A.L. Muñoz Zurita, J. Campos Acosta, A. S. Shcherbakov, A. Pons Aglio, “Differen‐
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[23] Ana Luz Muñoz Zurita1, Joaquín Campos Acosta2, Ramón Gómez Jimenez1, Rodri‐
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ODES”. Proc. of SPIE. Vol. 7726, pag. 772628-1- 772628-6.
192 Photodiodes - From Fundamentals to Applications
 Section 3

Device Applications
 Chapter 6

Si-Based ZnO Ultraviolet Photodiodes

Lung-Chien Chen

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/48825

1. Introduction

Semiconductor-based ultraviolet (UV) photodiodes have been continuously developed that

can be widely used in various commercial, civilian areas, and military applications, such as
optical communications, missile launching detection, flame detection, UV radiation calibra‐
tion and monitoring, chemical and biological analysis, optical communications, and astro‐
nomical studies, etc. [1-2]. All these applications require very sensitive devices with high
responsivity, fast response time, and good signal-to-noise ratio is common desirable charac‐
teristics. Currently, light detection in the UV spectral range still uses Si-based optical photo‐
diodes. Due to the Si-based photodiodes are sensitive to visible and infrared radiation, the
responsivity in the UV region is still low [3-5]. To avoid these disadvantages, wide-bandgap
materials (such as diamond, SiC, III-nitrides and wide-bandgap II–VI materials) are under
intensive studies to improve the responsivity and stability of UV photodiodes, because of
their intrinsic visible-blindness [6].

Among them, zinc oxide (ZnO) is another wide direct bandgap material due to its sensitive
and UV photoresponse in the UV region [7-9]. ZnO has attracted attention as a promising ma‐
terial for optical devices, owing to its large direct band gap energy of 3.37 eV and a large ex‐
citon binding energy of 60 meV at room temperature compared to other II-VI semiconductors
[10-12]. Therefore, ZnO is promising for use in light-emitting diodes (LEDs), laser diodes
(LDs), ultraviolet (UV) detection devices [12-15]. Several deposition methods have been em‐
ployed for the growth of ZnO layers, including metal-organic chemical vapor deposition
(MOCVD), molecular beam epitaxy (MBE), pulsed laser deposition (PLD), sol-gel and spray
pyrolysis [16-20]. The synthesis of p-type ZnO films with acceptable stability and reproduci‐
196 Photodiodes - From Fundamentals to Applications

bility by means of indium and nitrogen codoping or other group-III elements and nitrogen
codoping has recently been demonstrated [21-24].

Since the quality of ZnO materials plays a key role in determining the performance of UV
photodiodes. This chapter reviews the recent progress in Si-based heterostructure (UV) pho‐
todiodes, including p-ZnO/n-Si UV photodiodes, and p-ZnO/SiO2 ultrathin interlayer/n-Si
UV photodiodes. Furthermore, the optoelectronic and the magneto-enhanced characteristics
(so called magneto-optical multiplication effects) of UV photodiode placed in a strong mag‐
netic field were elucidated.

2. ZnO/Si UV photodiodes

Fabrication of a p-ZnO/n-Si heterojunction photodiode was reported [25]. An N-In codoped

p-type was deposited on a (111)-oriented silicon substrate by ultrasonic spraying pyrolysis
method. Three aqueous solution, Zn(CH3COO)2 2H2O (0.5 mol/l), CH3COONH4 (2.5 mol/l),
and In(NO3)3 (0.5 mol/l), were as the source of zinc, nitrogen, and indium, respectively. The
atomic ratio of Zn/N is 1:2 for N-doped film, and Zn/N/In is 1:2:0.15 for N-In codoped film
[21]. The n-type Si (111) wafers were used as the substrates, which were etched with HCl for
5 min before deposition. The aerosol of precursor solution was generated by the commer‐
cial ultrasonic nebulizer. P-type N-In codoped ZnO films were obtained by heating the sub‐
strate to 650 C, and were subsequently studied by Hall measurement. The hole concentration
and mobility of p-ZnO were around 1×1017 cm-3 and approximately 46 cm2/V-s, respectively.
P-ZnO/n-Si structures were then fabricated. The Ni/Au ohmic contact layer was evaporated
onto the p-type ZnO film as the anode electrode, and a Ti/Pt/Au electrode was formed on the
backside of the n-type Si substrate as the cathode electrode. Then, the cross section of the com‐
pleted structure is shown in Figure 1. The ZnO film with thickness of about 1.3 μm was formed
on silicon substrate.

Figure 2(a) shows the plots of the I-V characteristics of the photodiodes measured in the
dark (dark current) and under illumination (photocurrent, λ=530 nm) at reverse biases from
0 to 1 V. As shown in Fig. 2(a), it was found the photocurrent approximately 3.9×10-7 A and
the dark current was approximately 8.87×10-9 A at a bias of 1 V. Therefore, it was found that
a photocurrent to dark current contrast ratio is around two orders of magnitude. Figure 2(b)
shows the plot of responsivity as a function of the wavelength for a p-ZnO/n-Si heterostruc‐
ture photodiode at a bias of 1 V. The photodiodes exhibited two higher responsive regions
denoted as A and B, respectively. Region A at wavelength approximately from 400 nm to
700 nm was owing to ZnO film absorption occurring through the band-to deep level [26],
and region B at wavelength approximately from 700 nm to 1000 nm was owing to Si sub‐
strate absorption occurring through the band edge.
 Si-Based ZnO Ultraviolet Photodiodes 197
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Figure 1. Schematic cross section of the completed structure. [25].

Responsivity R is given by [27]

q
R = I ph / Pinc = η (A / W ) (1)
hν

where I ph is the photocurrent, P inc is the incident power, and η, q, ν and h are the QE, the elec‐
tron charge, the frequency of incident light, and Planck’s constant, respectively. Using Eq. (1),
the values of responsivity and QE at 530 nm at biases of 1 V were 0.204 A/W and 47.73%, re‐
spectively. The values of responsivity and QE at 850 nm at biases of 1 V were 0.209 A/W and
30.49%, respectively. In contrast to conventional Si-based photodetectors, the ZnO film has
been improved the responsivity in UV/blue region. However, the responsivity was degrad‐
ed in near infrared region (700-1100 nm). This result means that the portion of light with high‐
er energy, such as 400–500 nm, was absorbed by ZnO film and the portion of light with lower
energy, such as 800-1000 nm, can completely incident into Si substrate and was absorbed.
However, the responsivity owing to the ZnO film absorption occurring through the band-to-
band did not observe in this work.
198 Photodiodes - From Fundamentals to Applications

Figure 2. a) The dark and illuminated (λ=530 nm) I-V characteristics of the p-ZnO/n-Si heterostructure photodiode. (b)
The responsivity as a function of the wavelength for a p-ZnO/n-Si heterostructure photodiode at a bias of 1 V [25].

Figure 3. a) Schematic showing the configuration of the photoresponse measurement system used for the n-ZnO
(shell)/p-Si (core) radial nanowire photodiodes. (b) A typical cross-sectional SEM image of the n-ZnO/p-Si NW arrays.
(c) A magnified image showing the bottom region of a ZnO/Si NW [28].

Kim et al. [28] were demonstrated utilizing radial heterojunction nanowire diodes (RNDs)
array consisting of p-Si/n-ZnO NW core/shell structures which were fabricated using confor‐
mal coating by atomic layer deposition (ALD). Vertically dense Si NW arrays were prepared
by Ag-induced electroless etching of p-type Si wafers. After formation of the Si NW arrays,
the ALD technique was used to conformably coat a n-type ZnO thin film on the high aspect
ratio Si NWs, as shown in figure 3(a). The properties of long (6 μm) and short (2 μm) nano‐
wire photodiodes, denoted as RND2 and RND6, respectively. The typical diameter of the n-
ZnO/p-Si NW arrays was 350-400 nm, which consisted of a 100 nm thick shell and a 150-200
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nm thick NW core. The aspect ratios of the RNDs, which were calculated using the averaged
values of the lengths and diameters, were ~10 and 30 for RND2 and RND6, respectively. A
magnified image showing a ZnO/Si NW, in which the ZnO shells were partly peeled off
during the sample preparation. A uniform thickness of ZnO over the Si core is observed.
The yellow dashed lines indicate the position of the interface between ZnO and Si, as shown
in Figs. 3(b) and 3(c).

Figure 4(a) shows the photoresponsivity spectra under a forward bias of 0.5 V. It is clear the
UV responsivities of RND2 and RND6 are higher than that of the planar thin film diode (PD)
under a forward bias. Such as compared to a PD, a RND2 (6 μm) resulted in a ~2.7 times en‐
hancement of the UV responsivity at λ=365 nm in the forward bias. In addition, the en‐
hanced UV photoconductive response in ZnO NWs may be attributed to the presence of
oxygenrelated hole-trap states at the NW surface [29]. As a result, RNDs can improve the
UV photodetection sensitivity due to the high surface area to volume ratio. In this case, the
UV responsivities at λ=365 nm were detected to be 0.23, 0.42, and 0.63 A/W for PD, RND2,
and RND6, respectively. Owing to the short penetration depth, the carrier generation normal‐
ly occurs near the surface. It indicates surface scattering and recombination decrease the car‐
rier lifetime. Figure 4(b) shows the photoresponsivity spectra of RNDs compared to the PD
under a reverse bias. The values of the visible/UV responsivity at λ=700 nm and 365 nm were
17.2 A/W for RND6 and 0.86 A/W for PD. It appears that the ZnO surface can be depleted
by the surface oxygen absorption according to the hole-trapping mechanism [29]. There‐
fore, both the UV and visible photoresponsivities of the RNDs were better than that of a pla‐
nar PD, owing to the enlarged surface area to volume ratio, efficient carrier collection, and
improved light absorption.

Figure 4. Photoresponsivity spectra of the RNDs and PD measured under (a) forward and (b) reverse biases. Their en‐
ergy band diagrams and charge transport mechanisms are also depicted in the insets [28].
200 Photodiodes - From Fundamentals to Applications

3. ZnO/SiO2/Si UV photodiodes

3.1. Ultrathin SiO2 films

Many the various types of photodiodes which include homojunction, heterojunction and met‐
al-semiconductor-metal (MSM) photodiodes much attention has been paid in recent years to
metal-oxide-semiconductor (MOS) structures [30-33]. An ultrathin silicon dioxide (SiO2) films
has been the most commonly used material for diffusion barriers and insulating layers for
various applications in MOS devices due to its properties such as low defect density, high
thermal stability, high resistivity, high electric insulating performance, high reliability, and
reasonable dielectric constant [34,35]. In general, an ultrathin SiO2 films (≤ 1 nm) was formed
on the silicon substrate that the silicon/SiO2 interface becomes crucial for good transistor be‐
havior. Several fabrication methods have been employed for the formed of ultrathin SiO2
films, such as rapid thermal oxidation (RTO) [36], oxidation with excited molecules and ions
[37,38], plasma oxidation [39,40], photo-oxidation [34,41], ozone oxidation [43], metal-promot‐
ed oxidation [44], anodic oxidation [45,46] and nitric acid (HNO3) vapor oxidation [47,48] etc.
When a reverse bias is applied to a MOS photodiode, the energy bands in the semiconduc‐
tor bend and a potential well is formed between the oxide and the semiconductor. Electron-
hole pairs generated near the junction by incident light will be stored in the potential well,
and current transport occurs through the oxide layer via tunneling.

Recently, Chen et al. [49-51] reported the p-ZnO/SiO2 ultrathin interlayer/n-Si substrate struc‐
ture photodiodes. An ultrathin SiO2 film as interlayer was formed on a (111)-oriented sili‐
con substrate by heating the substrate in wet oxygen ambient at 650 C for 10 min to improve
the performance of ZnO/Si photodiodes by inserting a SiO2 ultrathin interlayer.

3.2. ZnO/SiO2/Si UV photodiodes

In 2003, Jeong et al. [52] presents n-ZnO/p-Si photodiodes through use of a SiO2 ultrathin ox‐
ide interlayer that unintentionally doped n-ZnO thin films were deposited on p-type Si sub‐
strates by RF magnetron sputtering. A schematic cross-section of the complete structure is
shown in Figure 5 (a). The n/p heterojunction has a thin SiO2 layer about 3 nm at the n-ZnO/p-
Si interface and hence the photoelectrons may face a transport barrier. The result indicates that
n-ZnO/p-Si photodiodes could detect UV photons in the depleted n-ZnO and simultaneous‐
ly detect visible photons in the depleted p-Si. Figure 5 (b) presents the spectral responsivity
curves obtained from the n-ZnO/p-Si photodiode. The responsivity of a photodiode for visi‐
ble light was as high as ~0.26 A/W at 5 V and 0.4 A/W at 30 V. The UV-driven responsivity
spectra are quite different, showing a noticeable increase with voltage. Higher responsivity is
found for more energetic UV photons from the photodiode. For the 310 nm UV photons, the
n-ZnO/p-Si photodiode shows responsivity of 0.09 A/W at 5 V and 0.5 A/W at 30 V. Howev‐
er, they show relatively weak response near 380 nm, which is the band gap of ZnO.
 Si-Based ZnO Ultraviolet Photodiodes 201
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Figure 5. a) Energy-band diagram of a reverse-biased n-ZnO/p-Si structure. (b) Spectral responsivity curves obtained
under the reverse biases [52].

Additionally, we found that an intermediate SiO2 ultrathin film can improve the quantum ef‐
ficiency and the responsivity by decreasing the surface state density and increase the tunnel‐
ing photocurrent [49-51]. Figure 6 (a) shows a schematic cross-section of the complete
structure. The inset in this figure shows a schematic cross-sectional TEM image of nanostruc‐
ture p-ZnO/SiO2 ultrathin interlayer/n-Si substrate. The ZnO film had an anomalous nano‐
scale columnar structure with a diameter of 50-80 nm. The ultrathin oxide layer between the
ZnO film and the Si substrate had a thickness of approximately 26 Å, as estimated from the
TEM image in Fig. 6(b) taking the area A in Fig. 6(a).

Figure 6. a) Schematic cross-section of the complete structure. (b) Cross sectional TEM image of p-ZnO/SiO2 ultrathin
interlayer/n-Si structure [49,51].

Figures 7(a) and 7(b) present a schematic band diagram to elucidate the current components.
Based on Figure 7(a), the dark current can be described as [30,53]

J dark = J Sp + J Tp + J Sn + J Tn (2)
202 Photodiodes - From Fundamentals to Applications

where J Sp is the hole current through surface states, J Tp is the hole tunneling current, J Sn is
the electron current tunneled through surface states, and J Tn is the electron current through
surface states. As shown in Figure 7(b), the photocurrent mechanisms can be written as

J light = J Tn + J Dn + J Ln + J Tp + J Dp + J Lp (3)

where J T is the tunneling current, J D is the current in the depletion region, and J L is the
photo-generated current. The subscripts n and p indicate electron and hole, respectively.

Figure 7. Schematic energy-band diagram of the p-oxide-n tunnel diode system under (a) dark and (b) illuminated
conditions [49].

Figure 8(a) plots the responsivity as a function of (I-V) characteristics of photodiodes that
were measured in the dark and under illumination (λ = 530 nm) with a 250 W xenon arc
lamp at reverse biases from 0 to 1 V. At a reverse bias of 1 V, for the p-ZnO/n-Si structure,
the photocurrent was ~3.9×10-7 A and the dark current was ~8.87×10-9 A. For the p-ZnO/SiO2
ultrathin interlayer/n-Si structure, the photocurrent and the dark current were ~4.99×10-5 A
and ~4.98×10-10 A, respectively. It can be noted that the photocurrent-to-dark-current con‐
trast ratios improved from two orders of magnitude to five orders of magnitude. Evidently,
the p-ZnO/SiO2 ultrathin interlayer/n-Si structure improves the photocurrent-to-dark-cur‐
rent contrast ratio by passivating the surface states and enhancing the tunneling current, as
shown in Figures 8(a) and 8(b).

Figure 8(b) plots the as a function of wavelength for both a p-ZnO/n-Si and a p-ZnO/SiO2 ultra‐
thin interlayer/n-Si photodiode, measured throughout this work at a reverse bias of 1 V. The
photodiode responsivities can be divided into three regions of around wavelengths of 400 nm,
530 nm, and 850 nm, denoted A, B, and C. Region A, at a wavelength of around 400 nm, corre‐
sponds to excitonic absorption in the ZnO film [54,55]. Region B, which is defined as the wave‐
length range from about 400 nm to 700 nm, corresponds to band-to-deep level absorption in
the ZnO film [26]. Region C (wavelengths between 700 nm to 1000 nm) corresponds to band
edge absorption in the Si substrate. According equation (1), for the p-ZnO/n-Si structure, in re‐
gion A, B, and C, the responsivity (R) and quantum efficiency (QE) were 0.147, 0.204, 0.206
A/W and 45.57, 47.73, 30.05 %, respectively. However, for the p-ZnO/SiO2 ultrathin interlayer/
n-Si photodiode, the R and QE were 0.225, 0.252, 0.297 A/W and 69.75, 58.96, 43.33 %, respec‐
 Si-Based ZnO Ultraviolet Photodiodes 203
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tively. As shown in Figure 8 (b), the use of an intermediate oxide film resulted in a greater R in
the UV/visible/IR region than was measured for the p-ZnO/SiO2 ultrathin interlayer/n-Si struc‐
ture photodiodes. This result suggests that the intermediate oxide ultrathin film passivates
surface states and increases the tunneling photocurrent, thus improving both QE and R.

Figure 8. p-ZnO/SiO2 ultrathin interlayer/n-Si and p-ZnO/n-Si structure photodiodes. (a) Dark and illuminated (λ = 530
nm) (I-V) characteristics (b) Responsivity as a function of wavelength at a bias of -1 V [49].

4. ZnO/SiO2/Si UV photodiodes in a strong magnetic field

Figure 9. shows the cross-section of the p-ZnO/SiO2 ultrathin interlayer/n-Si structure completed configuration in a
strong magnetic field [50].

In recent years, diluted magnetic semiconductors (DMSs) are attracted much great scientific
interest because of their unique spintronics properties with potential technological applica‐
tions. Consequently, the high Curie temperature ferromagnetism of ZnO and related materi‐
204 Photodiodes - From Fundamentals to Applications

als, doped with transition metal (TM) ions, is also expected to have applications in
spintronics, including in information storage and data-processing devices [56]. The electron‐
ic, optical and magnetic properties of TM-doped ZnO and related materials have been stud‐
ied extensively [57-64]. However, the behavior and characteristics of ZnO optoelectronic
devices in a magnetic field have seldom been investigated. Photodiodes with a p-ZnO/SiO2
ultrathin interlayer/n-Si structure in a magnetic field (Faraday configuration) as shown in
Figure 9 were studied [50,51].

Figure 10 (a) plots the I-V characteristics of photodiodes that were measured in the dark (dark
current), under illumination with a xenon arc lamp at 100 W, and in magnetic fields of 0, 0.1,
0.5 and 0.7 T, at applied reverse biases ranging from 0 to 1 V at room temperature. The mag‐
netic field-induced photocurrents were 3.02×10-5, 4.89×10-5, 1.02×10-4, and 2.27×10-4 A in mag‐
netic fields of 0, 0.1, 0.5 and 0.7 T, respectively, at a reverse bias of 1 V. However, the dark
current in various magnetic fields remains almost constant (~1.27×10-8 A). Evidently, the pho‐
tocurrent/dark-current contrast ratios are about four orders of magnitude in magnetic field. A
change of the applied magnetic field does not noticeably change the total current in the dark.
However, when the photodiode was illuminated, the total current significantly increases by
approximately one order of magnitude under a strong magnetic field, such as 0.7 T.

The total current can be described as

I Total = I Dark + I Light + I Magnetism (4)

where I Dark is the dark current, I Light is the photocurrent or photo-generated current, and I
is the magnetic field-induced current or magneto-induced current.
Magnetism

Figure 10. a) The I-V characteristics of the p-ZnO/SiO2 ultrathin interlayer/n-Si structure photodiode in the dark, illu‐
minated and under an applied magnetic field. (b) Total current at a reverse bias of 1 V against various magnetic fields
[50].

Figure 10(b) a plots the total current at a reverse bias of 1 V as a function of the magnetic
field. In the case of non-illumination, applying a magnetic field only slightly changed the to‐
tal current because of the absence of photo-ionization. However, under illumination, I Magnetism
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exponentially increases with the applied magnetic field because the probability of photo-ex‐
citation increased [65,66]. This phenomenon is called the magneto-optical multiplication
effect. The magneto-optical current multiplication effect may be caused by photo-ionization
due to the quantized magnetic effect of ZnO film in the photodiode structure.
Figure 11(a) and 11(b) show the I-V characteristics of photodiodes measured under illumi‐
nation with a xenon arc lamp at various operating power levels, and in a magnetic field of
0.5 T at applied reverse biases from 0 to 1 V at room temperature. Figure 11(b) depicts the
magneto-induced current calculated in Eq. (4), showing that the magneto-induced current
increases exponentially as the reverse bias increases. Figure 11(c) plots the photocurrent as
a function of wavelength in the ranges 300-720 nm for a p-ZnO/SiO2 ultrathin interlayer/n-
Si structure photodiode, measured throughout this work at a reverse bias of 1 V. The cur‐
rent variation of the photodiode was obvious when the wavelength of incident light was
lower, around 375 nm (higher photon energy). Therefore, the photo-ionization due to quan‐
tized magnetic effect of nanostructure ZnO film is apparently the source the magneto-in‐
duced current [65,66].

Figure 11. a) and (b) Illuminated and magnetic field applied I-V characteristics of the p-ZnO/SiO2 ultrathin
interlayer/n-Si structure photodiode with a xenon arc lamp at various operating power and magnetic field of 0.5 T
applied. (c) Photocurrent as a function of wavelength in the ranges 300-720 nm [51].

Figure 12(a) plots the responsivity as a function of wavelength for a photodiode with the p-
ZnO/SiO2 ultrathin interlayer/n-Si structure, measured throughout this work at a reverse
bias of 1 V at which the system is in a stable optoelectronic regime. Peak A located at around
410 nm is interpreted as the excitonic absorption in the ZnO film. Peak B (around 470 nm)
206 Photodiodes - From Fundamentals to Applications

may be attributed to the band-to-deep level absorption in the ZnO film. Peak B (around 470
nm) may be attributed to the band-to-deep level absorption in the ZnO film. The band ab‐
sorption edge of responsivity in the absence of a magnetic field is located at a wavelength of
around 371 nm, which corresponds to the band-to-band absorption of the ZnO film [54]. In
this work, the responsivity (R) and quantum efficiency (QE) at 410 nm under an applied
magnetic field of 0.5 T are 0.25 A/W and ~76 %, respectively. R and QE at 410 nm in the ab‐
sence of an applied magnetic field are 0.20 A/W and ~61 %, respectively. Therefore, Eq. (1)
had to modify, R is given by [27]

q
R = I ph / Pinc = ηζ (A / W ) (5)
hν

where the gain factor, ζ , is governed by the magneto-optic multiplication effect. In an ap‐
plied magnetic field of 0.5 T, the band absorption edge of responsivity shifts to 370 nm. The
photon energy has shifted by approximately 9.03 meV. This result suggests that the magnet‐
1
ic field splits the conduction-band edge into Landau levels with a spacing of ℏωce , and the
2
1
valence-band edge into Landau levels with a spacing of ℏωch , as displayed in Figure 12
2
(b), where ℏ is the reduced Planck’s constant, ωce is the cyclotron resonance frequency of
electrons, and ωch is the cyclotron resonance frequency of holes. Accordingly, this process is
referred as the interband magneto-optic absorption due to the Landau splitting.

Figure 12. a) Responsivity as a function of wavelength for the photodiode with p-ZnO/SiO2 ultrathin interlayer/n-Si
structure at a reverse bias of 1 V. (b) Schematic band diagram to elucidate the responsivity [50].

Figure 13(a) plots the photocurrent as a function of wavelength in the range of 350-410 nm
for a p-ZnO/SiO2 ultrathin interlayer/n-Si structure photodiode, measured throughout this
work at a reverse bias of 1 V. All spectra were normalized to clarify the photon energy shift.
The absorption edge of photodiode without an applied magnetic field was at a wavelength
of approximately 370.5 nm. The absorption edge of photodiode with applied magnetic field
 Si-Based ZnO Ultraviolet Photodiodes 207
http://dx.doi.org/10.5772/48825

of 0.1, 0.5, and 0.7 Tesla shifted to 370, 369, and 368.5 nm, respectively, while the photon en‐
ergy shifts were approximately 4.51, 9.03, and 18.11 meV, respectively. This result suggests
that the magnetic field splits the conduction-band edge into Landau levels.

Hence, according to the discussion above, a carrier transport model can be used to descript
the magneto-induced current. Figure 13(b) shows that the dark current and photocurrent
can be respectively described as [30,49,53]

I Dark = I S + I Tp + I Tn (6)

and

I Light = I Tn + I Dn + I Ln + I Tp + I Dp + I Lp (7)

where J S is the surface recombination current through the surface states, J Tp is the hole tun‐
neling current, J Tn is the electron current through surface states, J T is the tunneling current, J
D is the current in the depletion region, and J L is the photo-generated current. The subscripts
n and p indicate electron and hole, respectively. The magneto-induced current is given by

I Magnetism = I Tm + I Dm + I Lm (8)

where the subscript m indicates magnetism. Therefore, in the case of non-illumination or

low flux irradiations, applying a magnetic field barely changed the total current. This is be‐
cause the surface recombination velocity is so fast such that the carriers cannot produce pho‐
to-ionization. However, in the case of high flux irradiations, the probability of the photo-
ionization increases as the photo-generated excess carrier increases. This phenomenon is
called as magneto-optical multiplication effect, and is caused by the photo-ionization due to
quantized magnetic effect of nanostructure ZnO film.

Figure 13. a) Photocurrent as a function of wavelength in the ranges 350-410 nm for a p-ZnO/SiO2 ultrathin interlay‐
er/n-Si structure photodiode (b) Schematic energy-band diagram of the p-ZnO/SiO2 ultrathin interlayer/n-Si system in
the presence of a magnetic field under illumination [51].
208 Photodiodes - From Fundamentals to Applications

5. Conclusions

In summary, both p-ZnO/n-Si and p-ZnO/SiO2 ultrathin interlayer/n-Si structures UV photo‐

diodes have been introduced. In the aspect of p-ZnO/n-Si photodiodes, the photoresponses
exhibited higher responsive regions at UV, visible and near infrared ranges. In the aspect of
p-ZnO/SiO2 ultrathin interlayer/n-Si photodiodes, placing in a strong magnetic field, the
magneto-induced current in photodiode increases exponentially as the reverse bias and illu‐
mination flux increases, mainly because the magnetic field induced a photocurrent by mag‐
neto-optical multiplication effects. In the various magnetic fields, the absorption tails of the
responsivity were shifted from 370.5 nm to 368.5 nm, and a blue shift of the photon energy
from 4.52 meV to 18.16 meV were observed. This shift is attributed to the interband magne‐
to-optical absorption caused by Landau splitting. Therefore, the magneto-optical current
multiplication effect may be caused by the photo-ionization owing to quantized magnetic ef‐
fect of the ZnO film. We hope all these contents may be helpful for the readers and compre‐
hend the development of ZnO/SiO2/Si UV photodiodes.

Author details

Lung-Chien Chen*

Department of Electro-optical Engineering, National Taipei University of Technology, 1, sec.

3, Chung-Hsiao E. Rd., Taipei 106, Taiwan, Republic of China

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 Chapter 7

Infrared Photodiodes on
II-VI and III-V Narrow-Gap Semiconductors

Volodymyr Tetyorkin, Andriy Sukach and

Andriy Tkachuk

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52930

1. Introduction

During the last two decades HgCdTe, InSb and InAs infrared (IR) photodiodes have de‐
veloped rapidly for utilization in second generation thermal-imaging systems. Obviously,
they are regarded as the most important candidates for development of third generation
systems as well. Despite this fact many problems still exist in manufacturing technology
as well as in understanding of physical phenomena in materials and photodiodes. As a re‐
sult, threshold parameters of commercially available IR photodiodes are far from the val‐
ues predicted theoretically.

The concept of band gap engineering have found numerous applications in the fabrication
IR devices on II-VI and V III-V semiconductors. For instance, the most important advantage
of HgCdTe ternary alloy is ability to tune its energy band gap in wide range. The spectral
cutoff of HgCdTe photodiodes can be tailored by adjusting the HgCdTe alloy composition
over the 1-30 mm range. Further application of this concept in technology of IR detectors is
closely connected with development of GaAs/AlGaAs multiple quantum well detectors and
InAs/GaInSb type-II superlattice photodiodes.

To implement the concept of defect engineering, grown-in and process-induced defects

must be minimized and passivated or eliminated. Defects in narrow-gap semiconductors are
easily introduced either intentionally or unintentionally during crystal growth, sample treat‐
ment and device processing. There are also evidences that these defects are electrically ac‐
tive. So, for controlling parameters and characteristics of infrared photodiodes on narrow-
gap semiconductors through defect engineering, it is essential to understand physical
properties of defects, mechanisms of their interaction and temporal evolution. Electronic
216 Photodiodes - From Fundamentals to Applications

properties of native defects and foreign impurities in narrow-gap semiconductors have been
of great importance for several decades. As a result of intensive investigations, the primary
native defects and the mechanisms of their formation were elucidated. Doping effect of dif‐
ferent impurities has been also recognized. This allows to develop effective methods for con‐
trolling the carrier concentration and type of conductivity in intentionally undoped and
doped materials. To some extent the carrier lifetime can be controlled by extrinsic doping.
However, in many cases electronic states of defects in these semiconductors are still to be
unknown and further investigations are needed.

For controlling properties of semiconductors through defect engineering, it is essential to

understand the mechanisms of interaction between point and extended defects (disloca‐
tions), as well as to understand their effect on device characteristics. This task seems to be
important since alternative substrates (Si, GaAs, sapphire) are widely used in epitaxial tech‐
nology of IR photodiodes. These substrates are very attractive because they are less expen‐
sive and available in large area wafers. The coupling of the Si substrates with Si read-out
integrated circuit allows fabrication of very large focal-plane arrays (FPA). Due to the large
lattice mismatch between HgCdTe, InSb and InAs and alternative substrates, photodiodes
on their base suffer from the high density of dislocations (typically of the order of 106 cm-2).
For instance, these defect densities seriously limit application of HgCdTe epitaxial layers for
manufacture of high-performance photodiodes for the LWIR and VLWIR spectral regions.
The use of buffer layers, temperature cycling and hydrogen passivation is expected to be
useful for reduction of the density of dislocations and weakening their effect on the device
performance. However, none of these methods has yet been proven to be practical.

A number of physical properties of HgCdTe, such as direct energy gap, ability to obtain
both low and high carrier concentrations, high mobility of electrons and holes, low dielec‐
tric constant and extremely small change of lattice constant with composition, makes it
possible to grow high quality layers and heterostructures. As a consequence, high-per‐
formance HgCdTe photodiodes on mead-wavelength, long-wavelength and very long-
wavelength IR regions (MWIR, LWIR and VLWIR) have been developed. The main
drawbacks of HgCdTe are technological disadvantages of this material. The most impor‐
tant is a weak Hg–Te bond, which results in bulk, surface and interface instabilities. Uni‐
formity and yield are still issues especially in photodiodes on the LWIR and VLWIR
spectral regions. InSb photodiodes on the MWIR spectral region have comparable per‐
formance with photodiodes made of HgCdTe.

Initially, the IR photodiodes were prepared by diffusion, ion implantation or other techni‐
ques which allow preparation of homojunction structures. In these photodiodes, the concen‐
tration of carriers in the lightly doped ‘base’ region was strongly controlled. With
development of epitaxial techniques, homojunction photodiodes were replaced by hetero‐
junction ones. In a heterojunction photodiode the ‘base’ region are introduced between a
wide-gap substrate and a capping layer with wider band gap. Thus, the influence of surface
recombinations on the photodiodes performance is weakened. It seems that the most suc‐
cessful application of the band gap and defect engineering concepts in technology of IR pho‐
todiodes is development of double-layer heterojunction photodiodes.
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 217
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The main objective of this article is to outline the basic properties of point and extended de‐
fects, their effect on physical properties and threshold parameters of infrared photodiodes
based on HgCdTe, InAs and InSb narrow-gap semiconductors. This article is divided into
two parts. The first part is dedicated to technological steps (crystal growth, thermal anneal‐
ing, junction formation) closely connected with defects forming in materials and devices. In
the second part original results are analyzed with emphasize on possible participation of
dislocations and point defects in the carrier transport mechanisms and recombination proc‐
esses in the photodiodes.

2. Native defects and impurities in HgCdTe, InAs and InSb

The defect structure of narrow-gap Hg1-xCdxTe (hereinafter – HgCdTe) compounds was in‐
tensively investigated both theoretically and experimentally over the past fifty years. The
current status of defect states in these semiconductors are reviewed in numerous papers and
monographs (see, e.g., Capper and Garland, 2011; Chu and Sher, 2010). HgCdTe crystalline
materials are always grown with large deviation from stoichiometry. The equilibrium exis‐
tence region in HgCdTe (x~0.2) is shown to be completely on the Te-rich side (Schaake,
1985). Thus, the most important type of native point defects in undoped materials are Hg
vacancies. Residual impurities, Hg interstitials, dislocations and Te precipitates were also
observed in as-grown materials. All these defects can exist in neutral or ionized states. Their
important characteristics, such as donor or acceptor type, ionization energy, density, spatial
location and temporal variation were investigated.

The ab initio calculation of the formation energies of native point defects in HgCdTe (x~0.2)
has been made by Berding with co-authors (Berding, 1994, 1995, 2011). The most reliable cal‐
culations are based on the local-density approximation to the density functional theory. The
calculations predict the mercury vacancy and the tellurium antisite TeHg as the dominant de‐
fects in the material grown under tellurium-rich conditions. The concentration of native
point defects was calculated as a function of Hg pressure using quasichemical formalism. In
the the calculation all defects were assumed to be equilibrated at the temperature 500 0C
and the defect concentrations were assumed to be frozen in. The 500 0C temperature is typi‐
cal of LPE growth. In the calculations the Hg vacancy and tellurium antisite TeHg are classi‐
fied as acceptor and donor defects, respectively. The calculation also predicts that the
concentration of TeHg is comparable with the mercury vacancies concentration. At the same
time, as was pointed by Berding, to date there is no experimental confirmation of the pres‐
ence of the tellurium antisite defects in HgCdTe in so large amounts. Also, the calculated
concentration of Hg interstitial was found to be too low to explain experimental data on the
self diffusion (Berding, 2011). Experimentally the defect structure in undoped HgCdTe
(x~0.2) was investigated by Vydyanath and Schaake. It has been shown that the dominant
native defects are doubly ionized acceptors associated with Hg vacancies (Vydyanath, 1981;
Schaake, 1985). This result is in accordance with the theoretical prediction. Defects in doped
HgCdTe have been reviewed by Shaw and Capper (Shaw and Capper, 2011).
218 Photodiodes - From Fundamentals to Applications

Native defects in HgCdTe, including dislocations and defect complexes, can act as Shockley-
Read-Hall (SRH) centers due to their effect on the carrier lifetime. There is a large literature
concerning the links of deep defects to the carrier lifetime in HgCdTe (Capper, 1991; Sher,
1991; Capper, 2011; Cheung, 1985, Chu and Sher, 2010). Clear evidence of SRH centers was
provided by deep level transient spectroscopy, admittance spectroscopy, thermally stimulat‐
ed current and optical modulation spectroscopy (Polla, 1981, 1981a, 1981b, 1982; Jones, 1982;
Schaake, 1983; Mroczkowski, 1981). The centers located at near midgap seems to be common
to p-type Hg1CdTe, where the doping is due to mercury vacancies. Summary of impurity
and native defect levels experimentally observed in HgCdTe has been done by Litter et. al.
(Litter, 1990). The main results of experimental findings are as follows: (i) shallow acceptor-
like levels have activation energies between 2 and 20 meV; deep levels have energies 0.25Eg,
0.5Eg and 0.75Eg above the valence band edge. The concentration of donor-like deep centers
reported by Polla and co-authors was ranged from approximately 0.1NA to 10NA, where NA
is the shallow acceptor concentration. The values of the cross section for electrons and holes
were in the range 10-15-10-16 cm2 and 10-17-10-18 cm2, respectively. The origin of the SRH cen‐
tres in HgCdTe is still not clear. The vacancy-doped materials with approximately the same
carrier concentration, but manufactured at different temperature conditions, may exhibit
different lifetimes. At the same time, the correlation has been found between the SRH re‐
combination centre densities and the Hg vacancies concentration (Capper, 2011).

The behavior of extrinsic defects in HgCdTe is important from several reasons. Manufacture
of photodiodes with improved characteristics requires intentionally doped materials with
controllable concentrations of acceptors and donors instead of vacancies-doped material.
This is caused by several reasons such as instability of the vacancy-doped material and low
ability to control the concentration of free carriers. Also, Hg vacancies or complexes with
their participation may be responsible not only for the carrier lifetime, but also they can en‐
hance the trap-assisted tunneling, giving rise to excess dark current in infrared photodiodes.
Shaw and Capper (Shaw and Capper, 2011) provides a complete summary of the work on
dopants in bulk material and epitaxial layers. Indium and iodine are most frequently used
as a well-controlled donors for preparation of n-type bulk material and epitaxial layers. Both
are incorporated as shallow single donors occupying metal and tellurium lattice sites (In
and I, respectively). Indium has moderately high diffusivity whereas diffusivity of iodine is
rather low. Group V elements have low diffusivity and hence are ideal as p-type dopants.
Approximately 100% activity is found for In and I concentrations up to ~1018 cm−3. Vydya‐
nath (1991) argued that group V elements (P, As, Sb, Bi) are incorporated as donors under
Te-rich (Hg-deficient) conditions of growth. Under Hg saturated anneal at 500 0C there is
enough energy to move these elements from metal lattice cites to Te or interstitial sites. The
group V impurities if occupy Te sites act as shallow acceptors.

Shallow impurities are known to determine the concentration of free carriers in semiconduc‐
tors. The ionization energy of a hydrogen-like donors in HgCdTe were calculated as a func‐
tion of composition and concentration of defects (Capper, 2011). Due to low effective masses
of electrons this energy is too small to be detected experimentally at 77 K (e.g., the ionization
energy is 0.30 (0.85) meV for the composition x=0.2 (0.3). The ionization energy for acceptors
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 219
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depends on the material composition, concentration of acceptors and degree of compensa‐

tion. The calculated energy for the shallow acceptors is 11(14) meV for x=0.20 (0.3).

Electronic properties of extended defects in HgCdTe, InSb and InAs are less investigated in
comparison with point defects. It is known that II-VI semiconductors are more ionically
bonded as III-V covalent semiconductors. As a result, they can be easily plastically de‐
formed at room and lower temperatures (Holt and Yacobi, 2007). The photoplastic effect,
discovered by Osipiyan and Savchenko (1968), is conclusive proof that dislocations in II-VI
materials are electrically charged and that charge is largely electronically determined. The
dislocation core contains broken bonds so the dislocation line may generally be charged
negatively. The broken bonds are chemically reactive and electrostatic interaction between
the charged dislocation lines and ionized point defects and short-range chemical bonding ef‐
fects may occur. This tends to reduce (neutralize or passivate) the electrical effects of dislo‐
cations especially in the ionically bonded II-VI compounds. The charge states of the
dislocation can be altered illumination and other means of carrier injection and this can
change dislocation line charges as well as dislocation mobility. Yonenaga (1998) compared
the dynamics of dislocations in InAs with those in other semiconductors, including narrow-
gap and wide-gap II-VI compounds. It has been shown that the activation energies for dislo‐
cation motion depend linearly on the band-gap with an apparent distinction between
different types of semiconductors. The activation energy is lower in ionically bonded II-VI
semiconductors compare to III-Vs. Thus, dislocations would be expected to be the most mo‐
bile in II-VI narrow-gap semiconductors. The long-range electrostatic interaction strength‐
ens the attraction of dislocations to their Cottrell impurity atmospheres and strengthens the
pinning effect opposing dislocation motion.

Dislocations can also act as SRH centers in HgCdTe and III-V narrow-gap semiconductors.
The electrical activity of dislocations can be attributed to Cottrell atmosphere, or to dangling
bonds in the dislocation core. The ability of the strain fields of dislocations in HgCdTe to
capture significant amounts of impurities has been investigated in the early work by
Schaake (Schaake, 1983). It has been argued that the origin of the electrical activity is dan‐
gling bond states on the dislocations rather that the impurities. The high Peierls stress ob‐
served in II-VI compound semiconductors supports this argument. This stress has been
attributed to the ability of dangling bonds to heal themselves along the dislocation core. The
reduced lifetime and mobility caused by dislocations in n- and p-type HgCdTe has been
pointed out in several papers (Lopes, 1993; Yamamoto, 1985; Shin, 1991). This reduction has
been ascribed to dangling bonds which provide SRH centers. Dislocations also affect the
dark currents in LWIR photodiodes operating at low temperatures (<77 K) because they are
believed to produce mid-gap states in the band gap (Arias, 1989; Tregilgas, 1988). The de‐
crease of the differential resistance-area product at zero bias voltage, R0A, in the presence of
high dislocations densities has been reported by Johnson et al. (Johnson, 1992). As the tem‐
perature decreases the effect of dislocations was found to be more significant. At 77 K the
decrease of R0A begins at the dislocation density of the order of 106 cm−2, whereas at 40 K it
is affected by the presence of one or more dislocations. The scatter in the R0A data may be
associated with the presence of pairs of ‘interacting’ dislocations, which may be more effec‐
220 Photodiodes - From Fundamentals to Applications

tive in reducing the R0A than individual dislocations. The excess current in photodiodes
caused by dislocations may be the source of 1/f noise.

The effect of misfit dislocations on dark currents in high temperature MOCVD HgCdTe
infrared heterostructure photodiodes has been investigated by Jóźwikowska et al. (Jóźwi‐
kowska, 2004). It was shown that the most effective current transport mechanism at high
temperature in HgCdTe heterostructures is the trap-assistant tunneling. In the photodio‐
des operated at 240 K, this mechanism is predominant at bias voltage that not exceeded
0.1 V. The best fit of experimental data with theoretical predictions for the zero bias differ‐
ential resistance versus temperature has been obtained for rather high dislocation densi‐
ties in the volume of HgCdTe layer ~5 107 cm-2. To a certain extent electrical activity of
dislocation can be reduced by passivation (Boieriu, 2006). It has been showed that incor‐
poration of H in In-doped HgCdTe (x = 0.2) epilayers, through exposure to an electron cy‐
clotron resonance (ECR) H plasma, the lifetime increases by a factor of 10. The increase
was attributed to H passivation of the dangling bonds and is only effective for high dislo‐
cation densities (~107 cm−2).

The early studies of native defects and impurities in InSb and InAs have been summarized
by Milnes (Milnes, 1973). The energy of shallow impurities in InAs and InSb was calculated
with extension of effective mass theory (Baldereschi and Lipari, 1974). Several deep donors
of undetermined origin have been observed in InSb. Copper atoms segregated at disloca‐
tions in InAs are apparently electrically inactive, but on heating they diffuse away and can
be frozen into the lattice as electrically active centers. They return to the dislocations during
the low-temperature anneal. A similar effect was observed with Cu in InSb. A number of
undetermined deep defects was found in InSb and InAs (Madelung, 2003).

The nature of intrinsic point defects in InAs single crystals has been studied by several
groups (Bublik, 1977, 1979, 1979a; Karataev, 1977; Mahony and Maseher, 1977). In special‐
ly undoped InAs single crystals grown by direct solidification and Czochralski methods
precision measurement of density and lattice constant has been made in order to deter‐
mine the type and concentration of interstitial atoms and vacancies depending on the con‐
tent of arsenic in InAs melt. The difference in concentrations of VAs and Asi for InAs was
found to be of the order of 3 1018 cm-3. For InAs grown from the melt of stoichiometric
composition, this difference does not exceed 1·1017 cm-3. It was also established the effect
of point defects on structural and recombination properties of InAs single crystals. It is
shown that InAs crystals were n-type conductivity and electron concentration increased
from 1.4·1016 to 2.5·1016 cm-3 (T = 77 K) with increasing of As content in the growth melt. It
has been concluded that the concentration of electrons is determined by intrinsic defects
and complexes composed of native defects (vacancies) and background impurities. The ef‐
fect of annealing on electrical properties of undoped indium arsenide has been investigat‐
ed by Karataev (1977). The annealing was made in the temperature range 300-900 °C for
1-100 h. It was found that the annealing increases the concentration of electrons. For ex‐
ample, for the annealing temperature ~900 °C the concentration of electrons increased
from 2·1016 cm-3 to 2·1017 cm-3.
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Impurity, structural Ionization

Type Concentration, cm-3 Reference
defect energy, meV
As divacancy+
neutral complex - (7 ± 2)·1016 Mahony, J. and Maseher, P., 1977
residual impurity
As monovacancy+ neutral
- ~ 1·1017 Mahony, J. and Maseher, P., 1977
residual impurity complex
VIn A1 EV+100 - Mahony, J. and Maseher, P., 1977
VIn A2 EV+130 - Mahony, J. and Maseher, P., 1977
VIn A3 EV+230 - Mahony, J. and Maseher, P., 1977
VAs D EC+0.03Eg - Bynin, M.A. and Matveev, Yu.A., 1985
VAs D EC-Eg/4 - Bynin, M.A. and Matveev, Yu.A., 1985
Omel’yanovskii,1975; Balagurov, 1977;
Cr D EC–160 -
Plitnikas,1982; Adomaytis,1984
S, Se, Te D EC– (2–3) - Voronina, 1999
Mn A EV + (28-30) - Adrianov, 1977; 26 Gheorghitse,1989
Zn A EV+10 - Kesamanly, 1968
Zn A EV +25 - Guseinov, 1969; Guseinov, 1997
Cd A EV+20 - Galkina, 1966
Cd A EV+11 - Iglitsyn, 1968
Mg A - - Voronina, 2004
Cu D EC-< 7 - Karataev, 1977
Pb N - - Baranov, 1992; Baranov, 1993
Be A EV+< 7 - Lin, 1997; Astahov, 1992; Dobbelaere, 1992
Ge (amphoteric) D (Ge sub.In) EC-< 7 - Guseva, 1974; Guseva, 1975
Ge (amphoteric) A (Ge sub. As) EV+14 - Guseva, 1974; Guseva, 1975
Si (amphoteric) D (Si sub. In) EC-< 7 - Guseva, 1974; Guseva, 1975
Si (amphoteric) A (Si sub. As) EV+20 - Guseva, 1974; Guseva, 1975
Structural defect - 110±20 (0.5÷10)·1014 Fomin, 1984
- - 150±20 ≤ 5·1014 Fomin, 1984
- - ~ 220 (1÷3)·1015 Ilyenkov, 1992
- - ~Eg/2 (77 К) ~ 1017 Kornyushkin, 1996
- D EC–(100-200) - Baranov, 1992
- D EC–(10-20) - Baranov, 1992
- A EV+50 - Baranov, 1992
- D EC–15 - Baranov, 1993
- A EV+50 - Baranov, 1993
- D EC– (20-30) - Voronina, 1999
- D EC–(90-100) - Voronina, 1999
- A EV+10 - Voronina, 1999a
- A EV+20 - Voronina, 1999a
- A EV+30 - Voronina, 1999a
- A EV+65 - Voronina, 1999a
- A EV+20 - Zotova, 1975
- A EV+35 - Zotova, 1975
- A EV+35 - Allaberenov, 1970
- A EV+35 - Esina, 1985
Residual impurity D EC–2 - Baranov, 1992
Dislocation (possibly) A EV+(45-50) - Anisimova, 1969

Table 1. Parameters of impurities and structural defects in InAs

222 Photodiodes - From Fundamentals to Applications

Impurity, Ionization energy, Concentration,

Type Reference
structural defect meV cm-3
Zn A EV + 8 - Ismailov, 1969
Zn A EV + 10 - Pehek and Levinstein, 1965
Ge A EV+ (16-19) - Ismailov, 1969
Ag1 A1 EV+27 - Pehek and Levinstein, 1965
Ag2 A2 EV+50 - Pehek and Levinstein, 1965
Au A EV+43 - Pehek and Levinstein, 1965
Cu A EV+ (57-64) - Valyashko, 1975
Cu A EV+(23-27) Kevorkov, 1980
Cu, Ag, Au A EV+67 3·1014 Korotin, 1976
Structural defect D EC–48 - Valyashko, 1975
- A EV+ (7-9) ≤ 6·1014 Kevorkov, 1980
- A EV+ (5-6) - Nasledov, 1962
- D EC– (7-8) - Nasledov, 1962
- D EC–55 ~ 8·1013 Laff and Fan, 1961
- D EC–60 1011 - 1013 Sipovskaya and Smetannikova, 1984
- A EV+ (50-60) ~ 1014 Zitter, 1959
- D EC- (65 ± 5) (1.3 - 7.5)·1013 Golovanov, 1973
- A EV+ (20-30) 1·1015 Guseinov, 1971
- D EC–110 - Valyashko, 1975
- A EV+ (150-170) (0.3-1.0) 1012 Tsitsin, 1975
- D EC– (50-70) - Trifonov, 1971
- A EV+ 120 - Golovanov, and Oding, 1969
- D EC– (110-120) < 7·1013 Nasledov, 1962
- D EC–120 ~ 8·1013 Laff and Fan, 1961
- D EC–140 ~ 2·1014 Volkov and Golovanov, 1967
- D EC–110 ~ 3·1013 Hollis, 1967
- D EC–71 ~ 3·1013 Hollis, 1967
- A EV+ (60-63) - Egemberdieva, 1982
- A EV+ (69-73) - Egemberdieva, 1982
- A EV+ (80-82) - Egemberdieva, 1982
- D EV+ (110-113) - Egemberdieva, 1982
- D EV+ (131-135) - Egemberdieva, 1982
- D EV+ (140-142) - Egemberdieva, 1982
- D EC–130 1013 - 2·1015 Sipovskaya and Smetannikova, 1984
- - EV+ (120±30) (0.7 - 2.3)·1015 Golovanov, 1973
- - EC–130 ~ 1.2·1014 Korotin, 1976
- - EC–220 (2 - 5)·1012 Korotin, 1976
- - EC–110 2·1014 Guseinov, 1971
- A EV+68 (3 - 4)·1013 Shepelina and Novototsky-Vlasov, 1992
- D EV+99 (6 - 8) ·1013 Shepelina and Novototsky-Vlasov, 1992
- D EV+132 (2 - 3) ·1013 Shepelina and Novototsky-Vlasov, 1992
Ini+O2 A EC-50 Zaitov, 1981

a. in Table 1 and 2 residual impurities and structural defects have unknown identity;

b. doping behavior is indicated by A, acceptor, D, donor; A1,A2 and A3 means singly, doubly and triple ionized acceptor.

Table 2. Parameters of impurities and structural defects in InSba,b

 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 223
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The greatest effect of the anneal was observed in InAs, grown from the melt with an excess
of indium or arsenic atoms. Dislocations with densities from 103 to 105 cm-2 were found to
contribute to the effective change in the concentration of electrons at the annealing process.
Investigation of defect complexes in InAs using positron annihilation has been presented by
Mahony and Maseher (1977). The neutral complexes with the concentration of (7±2)∙1016
cm-3 has been found. Moreover, these complexes are composed of two vacancies at high
temperatures whereas at low temperatures only one vacancy is participated in a complex.
Both complexes are stable up to temperatures ~850 ºC. Theoretical calculations of energy
levels related with In and As vacancies was also carried out (Mahony and Maseher, 1977). It
is shown that In and As vacancies are acceptors and donors, respectively. Growing the high
resistivity InAs LPE films doped with chromium and study its electrical and photovoltaic
properties was also reported (Omel’yanovskii,1975; Balagurov, 1977; Plitnikas,1982; Ado‐
maytis,1984). Based on investigations of deep centers in epitaxial layers of InAs, the devel‐
opment of high-quality MOS-structures with a density of surface states ≤2 1010 cm-2 eV-1 has
been realized. Linear and matrix IR photodetector hybrid assemblies with the temperature
resolution of 4 - 8 mK were prepared (Kuryshev, 2001, 2009).

The deviation from the stoichiometry in InSb has been investigated by Abaeva et al. (Abae‐
va, 1987). The authors make a precise determination of the temperature dependence of the
InSb lattice constant by Bond's method. It is shown that In and Sb vacancies are the principal
intrinsic point defects that determine the deviation from stoichiometry in InSb and reduce
the lattice constant. The mid-gap defect states were observed in InSb bulk crystals (Ehem‐
berdyeva, 1982; Shepelyna, 1992). Their energy does not depend on the chemical nature of
dopant and the doping level. Defect complex composed of indium and oxygen atoms with
energy EC-50 meV has been found by Zaitov et al. (Zaitov, 1981). The low temperature (~200
0
C) annealing in an atmosphere of inert gas or saturated vapor of lead results in 5-10 times
increasing of the carrier lifetime in n-InSb (Tsitsina,1975; Strelnikova, 1993). A model of the
conductivity type conversion with participation of fluorine has been proposed (Blaut-Bla‐
chev,1979; Kevorkov, 1980). Some parameters of impurities and deep defects in InAs and
InSb are summarized in Table. 1 and 2.

3. Defect-related manufacturing processes

3.1. Growth techniques

Various methods have been proposed for growing II-VI and III-V semiconductor crystals.
These methods can be roughly classified into the melt growth, solution and vapor growth
methods. Each of the proposed growth methods has its own advantages and disadvantages.
For growing II-VI semiconductor compounds there exist a problem of high dissociation
pressure which leads to evaporation of a volatile component and hence deviation from stoi‐
chiometry. The deviation from stoichiometry introduces lattice defects since there is a defi‐
ciency of one component. If there is a large deviation from stoichiometry, vacancies can
combine with the residual impurities or with the impurities which are later introduced into
224 Photodiodes - From Fundamentals to Applications

the crystal during a subsequent process. The number of defects is hard to control in this
case. Therefore, from the point of perfect crystallography, it is desirable to grow crystals at
temperatures as low as possible. This requirement is especially important for HgCdTe al‐
loys, since they are decomposing solids. Also, the liquidus-solidus temperatures of the mer‐
cury telluride and cadmium telluride compounds are different, which causes their
segregation as the alloy is frozen from a melt. The resultant variation of the mole fraction of
each compounds results in a consequent variation in energy gap as well as electrical and op‐
tical properties throughout the material. In contrast to HgCdTe, the III-V compounds (InSb
and InAs) melt congruently, i.e. a liquid and solid having identical compositions are in equi‐
librium at the melting point. Thus, they can be grown directly from the melt, a process com‐
monly used to grow large boules of InAs and InSb.

Further progress in IR photodiode technology is connected with epitaxial layers. Epitaxial

techniques offer the possibility of growing large area layers with good depth and lateral ho‐
mogeneity, abrupt composition and doping profiles, which can be configured to improve
the performance of photodiodes. The commonly used methods for preparation of epitaxial
films are liquid phase epitaxy (LPE), molecular beam epitaxy (MBE), metal-organic vapor
phase epitaxy (MOVPE), and metal-organic chemical vapor epitaxy (MOCVD). LPE method
is a near-thermodynamic equilibrium growth technology. It has the advantages of relatively
simple process, high utilization rate of the source material, high crystalline quality of the ep‐
itaxial films and fast growing. The weakness of LEP is that it cannot be used for precision
controlled growth of very thin films of nano-scale. In other words, it is not applicable to the
growth of superlattices or quantum-well devices and other complex micro-structure materi‐
als. In addition, the morphology of materials grown by LPE is usually worse than that
grown by MOCVD or MBE. In these techniques epitaxial growth is performed at low tem‐
peratures, which makes it possible to reduce the native defects density. Obviously, for epi‐
layers the choice of substrate is decisive for minimizing effect of misfit dislocations and
interdiffusion at the epilayer/substrate heterojunction. This problem is especially important
for InSb and InAs because of the lack of lattice-matched III-V wide-gap semiconductors
which may be used as substrates. To overcome this difficulty, the use of alternative sub‐
strates (Si, GaAs, supphire) attracts great attention. Successful implementation of epitaxy of
narrow-gap semiconductors on Si substrates can directly lead to possibility of realization of
multicolor, monolithic focal plane arrays.

3.1.1. Growth of HgCdTe

Several historical reviews of the development of bulk HgCdTe have been published (Maier
and Hesse, 1980; Capper, 1994; Capper, 1997). Bulk growth of HgCdTe is rather difficult due
to the high vapor pressure of Hg at the crystal melting point (about 950 0C), caused by weak
Hg-Te bond in a crystal. For bulk material the Bridgman, solid state recrystallization, and
travelling heater methods have been developed. The most successful implementation of the
bulk growth technique was the travelling heater method which allows to grow up to 5-cm
diameter single crystals of high structural and electrical quality. Bulk crystal growth is cur‐
rently used to support the first generation of photoconductive HgCdTe array fabrication.
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The LPE is the most matured method for preparation of high-quality HgCdTe epitaxial films
(Capper, 2011). Two different approaches have been developed: growth from Te and Hg sol‐
utions at 420-600 0C and 380-500 0C, respectively. Dipping, tipping and sliding boat techni‐
ques have been used to grow both thin and thick films. The tipping and dipping techniques
have been implemented by using both tellurium- and mercury-rich solutions, but only tellu‐
rium-rich solutions have been used with the sliding boat. Both Hg- and Te-rich LPE can pro‐
duce material of excellent compositional uniformity and crystalline quality (Capper, 2011).
MBE and MOVPE growth of HgCdTe is performed at much lower temperatures compare to
LPE. Growth temperature is typically around 200-350 0C in MOVPE and around 150-200 0C
in MBE (Garland, 2011; Maxey, 2011). Due to the weak Hg-Te bond, the evaporation of this
material is not congruent. Consequently, Hg re-evaporates from the growth surface, leaving
the surface Hg-deficient. Because of a large flux of Hg is necessary in this case, it means that
the MBE growth temperature window is extremely small for HgCdTe and precise control of
the growth temperature is highly desirable (Arias, 1994; Arias, 1994a). Furthermore, to ob‐
tain a desired cut-off wavelength within ±6%, one must control the Cd composition x within
±0.002 (Garland, 2011).
Routinely produced CdTe and CdZnTe (Zn~ 3-4%) single crystals are used as substrates for
MBE and MOVPE growth. Today, the largest commercially available CdZnTe substrates are
limited to approximately 7x7 cm2 area. At this size, the wafers are unable to accommodate
more than two 1024x1024 FPAs (Rogalski, 2009). Also, the quality of epitaxial layers is influ‐
enced by poor thermal conductivity, compositional nonuniformity, native defects, surface
roughness and imperfect surface flatness CdZnTe substrates.
The most used dopants for MBE and MOVPE growth are arsenic as the p-type dopant and
indium and iodine as the n-type dopants. There are no problems with in-situ incorporation
of indium and iodine and low-temperature post-growth annealing is used to optimize the
structural and electronic properties of the doped material, but is not required for activation
of dopants. The MBE growth of HgCdTe is optimally performed under Te-rich conditions
(Arias, 1994), thus Hg vacancies are the dominant native point defects in as-grown layers.
Due to this reason the in-situ incorporated As occupy Hg sites in a lattice and annealing is
required to its activate as a p-dopant by transferring to Te sites. The standard activation an‐
neal is 10 min at ~425 0C followed by 24h at ~250 0C under a Hg overpressure to fill the Hg
vacancies. The high-temperature annealing it limits many of the low-temperature-growth
advantages of MBE. Therefore, attempts have been made to obtain the p-type activation of
As either as-grown or after only a low-temperature anneal (Garland, 2011).
The use of alternative Si and GaAs substrates are attractive in IR FPA technology due to sev‐
eral reasons including available Si substrates with large sizes (up to 300 mm diameter), low‐
er cost and compatibility with semiconductor processing equipment. The match of the
coefficient of thermal expansion with Si readout circuit allows fabrication of very large FPAs
exhibiting long-term thermal cycle stability. Of course, the large lattice mismatch between
HgCdTe and alternative substrates (Si: 19%, GaAs: 14%) causes a high dislocation density
(typically from mid-106 to mid-107 cm−2) at the epilayer/substrate interface due to propagat‐
ing of dislocations in the growth direction. The high dislocation density is detrimental to de‐
226 Photodiodes - From Fundamentals to Applications

vice performance because of the effect of dislocations on minority carrier lifetimes (Shin,
1992). For comparison, in epitaxial layers grown on CdTe and CdZnTe substrates the dislo‐
cation density is less than mid-105 cm-2. The dislocation density below this value is believed
to be not a serious problem unless they form clusters under device contacts. Despite these
difficulties, epitaxial growth of high quality HgCdTe on 4-inch CdTe/Si substrates has been
demonstrated for MWIR applications (Maranowski, 2001). Also, large area high quality
HgCdTe epilayers were grown by MBE on 100 mm diameter (211)Si substrates with a CdTe/
ZnTe buffer layer (Bornfreund, 2007). Epilayers of HgCdTe with extremely uniform compo‐
sition and extremely low defects density were demonstrated by Peterson et al. (Peterson,
2006) on 4- and 6-inch diameter silicon substrates.

The lattice matched and alternative substrates with (100) and (211) orientations are com‐
monly used. The best crystalline quality is obtained on the substrates with the slightly mi‐
soriented surfaces. For instance, the MOVPE growth on (100) substrates misoriented from
the (100) plane by a few degrees is useful to suppress the formation of pyramid-shaped mac‐
rodefects, known as hillocks (Maxey, 2011). Today almost all growth is carried out on (211)
substrates, which have (111) terraces with (100) steps (Garland and Sporken, 2011).

The MBE and MOVPE technology of HgCdTe has developed to rather high level at which
epitaxial layers grown on bulk CdTe and CdZnTe substrates have characteristics compara‐
ble to those of LPE material.

3.1.2. Growth of InSb and InAs

Due to the relatively low melting point of (525 0C) and small saturation vapor pressure, InSb
bulk crystals can be grown using different growth techniques: Czochralski and horizontal
Bridgman technique, travelling heater method and zone melting (Hulme and Mullin, 1962;
Liang, 1966; Parker, 1965; Benz and Müller, 1975; Bagai, 1983). Technology of InSb bulk crys‐
tals are well matured. InSb is the most perfect material among the III-V semiconductors
available to data. Typically 10-100 cm-2 etch pit density is specified in a commercially availa‐
ble InSb. However, the best result is only 1 etch pit in 50 cm-2. In the ultra-high pure InSb
bulk crystals the carrier concentration can be lower 1013 cm-3.

In contrast to indium antimonide, InAs possesses an appreciable vapor pressure at the melt‐
ing point (943 0C), because of the equilibrium vapor is constituted of the more volatile com‐
ponent (As) whose condensation and sublimation temperature lies below the melting point.
However, even at this case, there is a strong tendency to form stoichiometric compound.
InAs bulk crystals can be grown using liquid covering Czochralski or vertical gradient
freeze method. Because of purification of InAs is more difficult than InSb, the residual elec‐
tron concentration of InAs bulk crystals is about of 2·1016 cm-3.

Gettering effect of lead and rare earth elements (ytterbium and gadolinium) in LPE of InAs
has been studied by several groups ( Baranov, 1992, 1993; Voronina, 1999; Gao, 1999). The
gettering effect of lead is attributed to the formation of stable insoluble aggregates com‐
posed of indium tellurides, selenides and sulphides. As a result, epitaxial films with the con‐
centration of electrons ∼15 cm-3 and mobility 9.1 104 cm2/V s at 77 K have been grown. In
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these films reduction of the concentration of structural defects was also observed. The simul‐
taneous introduction of controlled amounts of lead and rare earth elements makes it possi‐
ble to prepare high resistivity films with the compensation degree 0.6-0.9. In the
compensated films the electron concentration 3·1015 cm-3 was achieved. The defect complexes
of n-type were also observed in these films.
Various efforts have been made to adopt LPE growth of InSb (Kumagava, 1973; Mengai‐
lis, 1966; Holmes, 1980). However, there is a small number of reports on successful
growth of InSb films by this method. Recently Dixit and co-authors reported growth of
high-quality films on (001) semi-insulating GaAs substrate in a boat-slider type LPE unit
(Dixit, 2002; Dixit, 2002a).
Heteroepitaxy of InSb and InAs has been achieved on Si and GaAs substrates with MBE and
MOCVD technology (Razeghi, 2003). To overcome the lattice mismatch (>19%), the MBE of
InSb on Si substrates was performed using CaF2 and stacked BaF2/CaF2 buffer layers. The
room temperature electron mobility of 65000 cm2/V s (n ≈2 1016 cm-3) was obtained in an 8
μm-thick film grown on a Si substrate with 0.3 μm CaF2 buffer layer. The 77 K mobilities
were at least an order of magnitude lower than the room temperature values. This behavior
of electron mobility is attributed to electron scattering on dislocations arising from both lat‐
tice and thermal strains (Liu, 1997).
Epitaxial layers of InSb were grown directly on InSb, GaAs and GaAs-coated Si substrates
with MBE and a low pressure MOCVD techniques (Razeghi, 2003). The quality of epitax‐
ial films has been shown to depend critically on the growth conditions and preparation of
substrates. In order to get high crystal quality InSb and GaAs substrates, directed 20 off
the (100) toward (110) direction were used. The X-ray rocking curve FWHM, electron con‐
centration and mobility was found to depend on the thickness of films due to influence of
highly dislocated interface. In 3.6 μm thick InSb film the electron mobility was 56000
cm2/V·s at 300 K and close to 80000 cm2/V·s at 77 K. The background electron concentra‐
tion at 77 K was of the order of 1016 cm-3. Excellent uniformity (within the ±3 arcs varia‐
tion of FWHM) was detected for a 10 μm thick InSb layer grown by MBE on a 3-inch
semi-insulating GaAs substrate. The FWHM decreases with thickness as the dislocation
density decreases due to the greater distance between the surface and the highly dislocat‐
ed interface. The 300 K mobility close to that of bulk InSb (75000 cm2/V·s) was achieved in
the films with thickness more than 2 μm. The temperature dependence of the electron mo‐
bility was peaked at 77 K and decreased at lower temperatures due to the dislocation scat‐
tering at the InSb/GaAs interface (Razeghi, 2003).
The MBE growth of InAs has been reported by several groups (Yano, 1997; Kalem, 1998).
InAs epitaxial layers with thicknesses ranging from 0.5 up to 6.2 μm was grown on (100) ori‐
ented semi-insulating GaAs substrates. As in the case of InSb films, the properties of InAs
films was influenced by the growth conditions and InAs/GaAs interface structure. The elec‐
tron mobility at room temperature is 1.8 104 cm2/V·s (n=6.1 1015 cm−3) and peaks at about liq‐
uid-nitrogen temperature with a value of 5.173 104 cm2/V·s (n=3.1 1015 cm−3) for a InAs layer
with thickness of 6.2 μm. It is shown that the temperature dependence as well as the magni‐
tude of the mobility can be explained by a combined impurity-phonon-dislocation scattering
228 Photodiodes - From Fundamentals to Applications

mechanism. The dislocation densities of the order of 106 cm−2 were found. High-quality InAs
epilayers on the GaAs substrates have been grown by MBE (Chen,2000; Cai, 2003). The
growth was carried out as a two-step process: InAs layers were grown under As-rich condi‐
tions on InAs prelayers grown directly on the GaAs substrates under In-rich conditions. The
optimized growth condition for this method from the Raman spectroscopy and the low-tem‐
perature photoluminescence was the following: first InAs is grown 20 nm thick under In-
rich conditions at 500 0C with the appropriate V/III ratio of 8, then InAs is continuously
grown under As-rich conditions at 500 0C with the appropriate V/III ratio of 10–23. Also, a
two-step growth method consisting of a 400 0C prelayer followed by deposition of the thick
bulk layer at higher growth temperatures has been reported by Watkins et al. (Watkins,
1995). High purity InAs epilayers were grown on GaAs substrates by MOCVD technique.
Temperature dependent Hall measurements between 1.8 and 293 K showed a competition
between bulk and surface conduction, with average Hall mobilities of 1.2·105 cm2/V·s at 50 K.
Large changes in the temperature dependent transport data are observed several hours after
Hall contact formation and appear to be due to passivation of the surface accumulation lay‐
er by native oxide formation. The highest electron mobilities were observed in InAs films
grown by MOCVD at reduced growth temperature (Partin, 1991). Electron mobilities as
high as 21000 cm2/V·s at 300 K were obtained for a film only 3.4 μm thick. From the depth
dependence of transport properties it has been found that in the grown films electrons are
accumulated near the air interface of the film, presumably by positive ions in the native ox‐
ide. The scattering from dislocations was greatly reduced in the surface accumulation layer
due to screening by a high density of electrons. These dislocations arise from lattice mis‐
match and interface disorder at the film-substrate interface, preventing these films from ob‐
taining mobility values of bulk indium arsenide. More or less successful attempts to grow
quality InAs epitaxial films were also reported in numerous papers (Fukui, 1979; Haywood,
1990; Egan, 1995; Huang, 1995; von Eichel-Streiber, 1997; Watkins, 1997).

Technology of InSb bulk crystals is more mature than HgCdTe. Good quality substrates
with more than 7 cm diameter are commercially available (Micklethwaite, 2000). However,
technology of InSb and InAs epitaxial layers is not matured to the level suitable for device
applications.

3.2. Junction formation techniques

3.2.1. HgCdTe photodiodes

Different HgCdTe photodiode structures have been developed including mesa, planar and
lateral homojunction and heterojunction structures. The history and current status of
HgCdTe IR photodiodes has been reviewed in numerous monographs and review articles
(Capper and Elliot, 2001; Norton,1999; Rogalski, 2011; Rogalski et al., 2000; Chu and Sher,
2010; Reine, 2000; Baker and Maxey, 2001; Sher, 1991). The junctions have been formed by
numerous techniques including impurity diffusion, ion implantation, growth of doped epi‐
taxial layers from vapor or liquid phase. In the early stages of device technology Hg in- and
out-diffusion has been used for the junction formation in HgCdTe bulk material. At present
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time ion implantation is commonly used technique for formation n-on-p and p-on-n homo-
and heterojunctions. The n+-p homojunction can be formed by implantation of different ions
into a vacancy doped p–type material, but B and Be are the most frequently used for this
purpose. The doses of 1012–1015 cm–2 and energies of 30–200 keV are used for the junction
formation. First devices were fabricated on bulk p-HgCdTe single crystals with the hole con‐
centration of the order of 1016 cm–3. But in the early 1990s bulk crystals were replaced by LPE
material. To-day, epitaxial films grown by LPE on CdZnTe lattice matched substrates are the
best structural quality material, and they are successfully used in the homojunction technol‐
ogy. An ion implantation was also adapted to produce P+-n heterojunctions (P means wider
gap material). In both structures the lightly doped ‘base’ region with the doping concentra‐
tion below 1016 cm-3 determines the dark current and photocurrent. Indium is most frequent‐
ly used as a well-controlled dopant for n-type doping due to its high solubility and
moderately high diffusion. Arsenic proved to be the most successful p-type dopant that are
used for fabrication of stable junctions due to very low diffusivity. The important advantage
of P+-n structure is that the thermal generation of carriers is effectively reduced in wider
bandgap material.

The significant step in the development of HgCdTe photodiodes has been made by Arias
with co-authors (Arias, 1993). They proposed the double-layer planar heterostructure
(DLPH) photodiodes. The photodiodes were realized by incorporating a buried narrow-
bandgap active layer in the DLPH configuration. The planar devices were formed using a
Hg1–yCdyTe/Hg1–xCdxTe (y>x) heterostructure grown by MBE on CdZnTe substrate. An im‐
portant feature of the DLPH approach is a planar p-doped/n-doped device geometry that in‐
cludes a wide-bandgap cap layer over a narrow-bandgap ‘base’ layer. The formation of
planar photodiodes was achieved by selective implanting of arsenic through a ZnS mask fol‐
lowed by diffusing the arsenic (by annealing at high temperature) through the cap layer into
the narrow gap base layer. After that the structures were annealed under Hg overpressure.
The first high-temperature annealing was carried out to diffuse the arsenic into the base lay‐
er and to make the doped region p-type by substitution of arsenic atoms on the Te sub-lat‐
tice, while the second low-temperature one was carried out to annihilate Hg vacancies
formed in the HgCdTe lattice during high-temperature process. In DLPH photodiodes sig‐
nificant reduction in tunneling current and surface generation-recombination current has
been achieved. The architecture of mesa and planar heterostructure photodiodes are shown
in Fig.1. The back-illuminated heterostructure photodiodes prepared from both LPE and
MBE material grown on CdZnTe substrates have the highest performance achieved to-day
(Arias, 1993; Bajaj, 2000; Rogalski, 2000).

The serious disadvantage of CdZnTe substrates is the thermal expansion coefficient mis‐
match with Si used for the read-out integrated circuit. To overcome this problem, growth of
HgCdTe on alternate substrates such as sapphire, Si and GaAs has been developed. LPE, MBE
and MOCVD techniques were used for this purpose. However, these alternate substrate ma‐
terials suffer from a large lattice mismatch with HgCdTe, leading to a higher defect density in
the HgCdTe material and consequently reducing the detector performance (Bajaj, 2000). De‐
spite these disadvantages the large, 1024-1024 and 2048-2048, HgCdTe FPAs operating in
230 Photodiodes - From Fundamentals to Applications

SWIR and MWIR spectral bands were grown on alternative substrates (Kozlowski, 1999; Ba‐
jaj, 2000; Golding, 2003; Tribolet, 2003). Their performance is comparable to performance of
FPAs prepared on lattice matched bulk substrates, with the same spectral cut-off.

Figure 1. Schematic cross section of mesa (left) and planar (right) HgCdTe IR photodiodes. The photodiodes are illumi‐
nated through the wide bandgap substrate.

While ion implantation of As requires activation of the implanted atoms at relatively high
temperatures, an alternative technology (ion milling or plasma induced type conversion)
has received considerable attention during the past few years. Currently plasma induced
type conversion in HgCdTe is regarded as an alternative to ion implantation junction forma‐
tion technology (Agnihotri, 2002). The post-implant annealing is not needed in this technolo‐
gy. Reactive ion etching (RIE) induced type conversion and junction formation have been
observed in a vacancy doped p-HgCdTe using H2/CH4 plasma. The junction depth could be
adjusted from 2 to 20 μm.

3.2.2. InSb and InAs photodiodes

High performance InSb detectors have been fabricated with bulk material for decades. Typi‐
cally, the p-on-n junctions are prepared on bulk crystals of n-type conductivity with electron
concentration in the range 1014 - 1015 cm-3 and mobility of the order of (2-6) 105 cm2 V-1 s-1 at T
= 77 K. Be ion implantation and thermal diffusion of Zn and Cd seems to be the most fre‐
quently used technological methods which allow to obtain sharp p+-n junctions (Mozzi and
Lavine, 1970; Hurwitz and Donnelly, 1975; Rosbeck, 1981; Nishitani, 1983; Fujisada, 1985).
The current status of InSb photodiode technology have presented by Wimmers et al.
(Wimmers, 1983; Wimmers, 1988). Current manufacturing device processes require that
bulk materials should be thinned before or after the junction preparation. Using this techni‐
que, hybrid FPAs were produced (Fowler, 1996; Hoffman, 1991; Parrish 1991). An array size
of 1024-1024 was possible because the InSb detector material was thinned to <10 μm (after
surface passivation and hybridization to a readout chip) which allows it to accommodate the
InSb/silicon thermal mismatch. Certainly, the substrate thinning process is a very delicate
process that can lower the yield and the reproducibility of the photodiodes, but it is used
commercially because of LPE of InSb is not developed. Several attempts have been made to
manufacture InSb photodiodes by LPE (Kosogov and Perevyaskin, 1970; Kazaki, 1976).
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Currently the major efforts are focused on photodiodes grown by MBE and MOCVD meth‐
ods. An overview of these technologies has been done by Razeghi (Razeghi, 2003). The InSb
photodiodes were grown on 3-inch Si and (111)GaAs substrates. The InSb photodiodes typi‐
cally consisted of a 2 μm n+ region (~1018 cm−3 at 77 K), a ~6 μm unintentionally doped region
(n = 1015 cm−3 at 77 K) and a ~0.5 μm p+ (~1018 cm−3) contact layer. The crystallinity of these
structure was excellent as confirmed by the X-ray diffraction, which showed FWHM <100
arcs for structures grown on (111)GaAs and Si substrates. Photodiodes were fabricated with
400 × 400 μm2 mesa structures by photolithography and wet chemical etching. These devices
showed excellent response of about 1000 V/W, which is comparable to that of bulk detectors,
with detectivities of ~3 1010 cmHz1/2/W at 77 K. It was shown that photodiodes can operate
up to room temperature, even though they were not optimized for this purpose.

A miniaturized InSb photovoltaic infrared sensor that operates at room temperature was
developed by Kuze with co-authors (Kuze, 2007). The InSb sensor consists of an InSb p+-p--
n+ structure grown on semi-insulating GaAs (100) substrate, with a p+-AlxIn1-xSb barrier lay‐
er between p+ and p-layers to reduce diffusion of photoexcited electrons. The optimum Al
composition and thickness of AlInSb barrier layer was found to be x=0.17 and 20 nm, re‐
spectively. Typical responsivity of 1.9kV/W, output noise of 0.15 μV/Hz1/2 and detectivity of
2.8 108 cm Hz1/2/W was measured at 300K. InSb high-speed photodetectors were grown on
semi-insulating GaAs substrate with 0.1 μm GaSb buffer layer using MBE (Kimukin, 2003).
After the buffer layer a 1.5 μm thick n-InSb layer, 1.5 μm thick n-InSb layer, and finally 0.5
μm thick p- InSb layer were grown. The n-active layer was unintentionally doped to 2-3
1015 cm-3. Tellurium and beryllium were used as the n- and p-layer dopants, respectively.
Doping level was 1018 cm-3 for both highly doped layers to decrease the serial resistance.
The developed photodetectors can operate at room temperature. The responsivity 1.3 A/W
was measured at 1.55 μm wavelength at room temperature. InSb photodiodes grown by
MBE on GaAs coated Si substrates have been reported (Besikci, 2000; Ozer and Besikci,
2003). The peak detectivity of ~1·1010 cm Hz1/2 W−1 at 80 K has been measured under back‐
side illumination without anti-reflection coating. Differential resistance at 80 K is shown to
be limited by ohmic leakage under small reverse bias and trap assisted tunneling under
moderately large reverse bias.

InAs photodiodes are mainly manufactured by ion implantation and diffusion methods
(McNally, 1970; Astahov, 1992). The p-n junctions prepared by Cd diffusion into n-InAs sin‐
gle crystals were investigated by Tetyorkin et al. (Tetyorkin, 2011). The photodiodes grown
by MBE on InAs substrates have been reported (Kuan, 1996; Lin, 1997). The fabrication of
InAs photodiodes on GaAs and GaAs-coated Si substrates by MBE have also been reported
(Dobbelaere, 1992).

In conclusion, during the past ten years the impressive progress has been made in the
growth of narrow-gap semiconductors by MBE, MOVPE and MOCVD on silicon, GaAs
and sapphire substrates. It is expected that in the near future HgCdTe and InSb IR photodi‐
odes will be grown directly on silicon for the low cost detectors with bi-spectral and multi-
spectral capability.
232 Photodiodes - From Fundamentals to Applications

3.3. Thermal annealing

In HgCdTe photodiodes prepared on bulk crystals and LPE films the active absorption re‐
gion should be p-type with the hole concentration of the order of 1016 cm-3. Because of the as-
grown materials are strongly p-type with vacancy concentration p>1017 cm-3, they should be
annealed. Due to importance of annealing, it has been intensively studied in HgCdTe (Cap‐
per, 1994; Capper, 1997; Capper 2011). The most important parameters of annealing are tem‐
perature, Hg vapor pressure and annealing duration. In HgCdTe (x = 0.2) Vydyanath
determined the free hole concentration at 77 K as a function of the Hg partial pressure, PHg,
at anneal temperatures between 140 and 655 0C. The concentration of doubly-ionized vacan‐
cies [VHg] is given by (Vydyanath, 1991):

[VHg]PHg= 1.7E28 exp(-1.67 eV/kT)cm-3atm

The hole concentration at 77 K is assumed to be equal to the concentration of vacancies. It

was proved that there is no essential difference in the annealing behavior of bulk crystals
and LPE epilayers. As seen, the same vacancy concentration can be obtained by combination
of temperature and Hg vapor pressure. Obviously, samples annealed at lower temperature
and pressure conditions would also have the lower concentration of interstitials and poten‐
tially the higher minority carrier lifetime. However, to reduce density of Te precipitates and
dislocations high-temperature annealing should be performed (Capper, 2011). In epilayers
grown on lattice-matched substrates (CdTe, CdZnTe) the dislocation density is in low-104 to
mid-105 cm-2. At the same time, in epilayers grown on alternative substrates the dislocation
density exceeds 106 cm-2. In LWIR epilayers grown by MBE on (211) GaAs and Si substrates
the dislocation densities as low as 2.3 105 cm−2 have been obtained using high-temperature
cycling between 300 and 490 °C (Shin, 1992). It has been shown that epilayers grown by
MOCVD require a higher thermal annealing temperature than MBE material and the differ‐
ence in dislocation reduction between MBE and MOCVD HgCdTe materials is caused by
dislocation movement under high-temperature and thermal stress conditions. A strong cor‐
relation between minority carrier lifetime and dislocation density was observed. The effect
of temperature cycling on the dislocation density was also investigated by Farrell et al. (Far‐
rell, 2011). In-situ and ex-situ thermal cycle annealing methods have been used to decrease
dislocation density in CdTe and HgCdTe. During the MBE growth of the CdTe buffer layer,
the growth was interrupted and the layer was subjected to an annealing cycle within the
growth chamber under tellurium overpressure. During the annealing cycle the temperature
is raised to beyond the growth temperature (290 → 550 °C) and then allowed to cool before
resuming growth again. This process was repeated several times during the growth. The in-
situ thermal cycle annealing resulted in almost a two order of magnitude reduction in the
dislocation density. The decrease of dislocation density was attributed to the movement of
the dislocations during the annealing cycles and their subsequent interaction and annihila‐
tion. To decrease the dislocation density in HgCdTe layers grown on CdTe/Si composite
substrates, ex-situ annealing has been performed in a sealed quartz ampoule under a mercu‐
ry overpressure. It was found that the primary parameters that affect dislocation density re‐
duction are the annealing temperature and the number of annealing cycles.
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At last, high temperature anneal in Hg vapor is used to activate the dopant by substituting
arsenic atoms on the Te sublattice. A lower temperature anneal (200–250 0C), performed im‐
mediately after the high temperature anneal, annihilates the Hg vacancies formed in the
HgCdTe lattice during high temperature treatment.
Bulk, LPE, MOCVD and MBE grown high purity material subjected to low-temperature
(<300 0C) Hg reach annealing are converted to n-type with the electron concentration which
depends on the doping level of residual donors. In HgCdTe material for LWIR photodiodes
the minimum electron concentration that can be obtained is ~(2-10) 1014 cm-3 and the mobili‐
ty is ~6 104 cm2/V s (Chu and Sher, 2008).
Techniques for improving the control of the Hg vacancy concentration was also reported by
Yang et al. (1985), who deduced experimentally a relationship between the concentration of
Hg vacancies, the annealing temperature, and the temperature of a Hg source. They also de‐
rived theoretically an analytic expression for this relationship. The annealing for MBE
grown material can be conducted in-situ under ultra-vacuum conditions. In-situ annealing
is very useful for production purposes. The improved ex-situ and in-situ annealing process‐
es were developed for MOCVD grown films (Madejczyk, 2005).
The performance of LWIR photodiodes can be improved by post-implant annealing (Bubu‐
lac, 1998). The dramatic decrease of the dark current in LWIR photodiodes was observed
due to low temperature annealing at 120-150 °C (Ajisawa and Oda, 1995). The improve‐
ments was explained by changes in both carrier concentration profile and p-n junction posi‐
tion determined by interaction of interstitial Hg atoms with vacancies in the vicinity of the
junction during the annealing process.
Very scarce data are available in the literature concerning the annealing of InSb and InAs,
both materials and devices. The effect of rapid thermal annealing and sulfur passivation
on the quality of reactively sputtered SiO2 on InAs were investigated. Results show that
both rapid thermal processing and sulfur passivation cause a reduction in leakage current
and oxide fixed charges. Annealing at temperature higher than 400 0C caused degrada‐
tion. Also, passivation started to loose its effectiveness when structures are annealed at
500 °C (Eftekhari, 1997).

4. Carrier transport and recombination mechanisms

4.1. Tunnelling current in HgCdTe, InAs and InSb photodiodes

Tunneling current was observed by many authors in IR photodiodes made of narrow-gap

A2B6 and A3B5 semiconductors (Rogalski, 1995). However, its nature seems to be under‐
stood in rare cases. For instance, the trap-assisted tunneling (TAT) via single level in the
gap introduced by point defects was proved to be the main reason for the excess current
in HgCdTe IR photodides at rather small reverse biases followed by the direct band-to-
band (BTB) tunneling current at higher biases (Nemirovsky, 1992; Rosenfeld, 1992; He,
1996). In these photodiodes the trap-assisted tunneling current is shown to be a source of
234 Photodiodes - From Fundamentals to Applications

the low-frequency 1/f noise. Similar results were also obtained in HgCdTe MIS structures
(He, 1996). Dislocations are also known for a long time as a source of an excess current in
semiconductor devices, especially when they intersect the depletion region of the p-n
junction (Matare, 1971; Holt, 2007; Shikin, 1996; Whelan, 1969). As to InAs and InSb pho‐
todiodes the role of dislocations is not established clearly. Therefore, identification of the
type of defects participating in the carrier transport in InAs and InSb IR photodiodes is a
key problem for improvement of their performance. Usually TAT and BTB tunneling cur‐
rents were analyzed in the reverse biased IR photodiodes. This analysis performed for the
forward biased InAs and InSb photodiodes revealed new aspects of tunneling transport of
carriers.

4.2. Dislocation-assisted tunnelling current in the forward-biased InAs and InSb

photodiodes

The photodiodes were prepared on single-crystal substrates of n-type conductivity. In order

to investigate effect of dislocations on the dark current, the substrates were cut from differ‐
ent parts of ingots grown by Bridgman technique. The density of dislocations in InAs sub‐
strates measured by the etch-pit method was of the order of 104 cm-2. The damaged surface
layers were removed using dynamic chemical-mechanical polishing in solution of methanol
with 2% of Br2. The electron concentration and mobility in the initial substrates were (2-3)
1016 cm-3 and (2-2.5) 104 cm2/V·s, respectively. The dislocation density was ranged from (1-2)
104 cm-2 in the central part of ingots up to 4 ∙105 cm-2 at the periphery one. The p-n junctions
were prepared by thermal diffusion of preliminary synthesized CdAs2 into substrates in
sealed evacuated quartz ampules. The mesa structures with active area A = 7 10-3 cm2 were
delineated using standard photolithographic technique. Then Zn and In contact pads were
thermally deposited onto p- and n-type sides of the junction, respectively, followed by a
heat treatment in purified hydrogen atmosphere. InSb photodiodes were manufactured by
implantation of beryllium into appropriately prepared substrates followed by thermal an‐
nealing. In n-InSb substrates the electron concentration and mobility were of the order of
(1-2) 1015 cm-3 (6-7) 105 cm2/V·s at 77 K, respectively. The dislocation density in InSb sub‐
strates was not exceeded 5·102 cm-2. Photodiodes had planar structure with the junction
area A = 1.33 10-2 cm2.

The current-voltage characteristics are shown in Fig.2. As seen, the characteristics consist of
two exponential parts. At lower bias voltages the forward current in InAs photodiodes in‐
creases with increasing the density of dislocations, whereas at higher voltages it has approx‐
imately the same magnitude for both photodiodes. Fig. 3 shows the temperature
dependence of the forward current in InAs and InSb photodiodes measured at the bias volt‐
age 10 mV. At low temperatures T < 130 K the current is weakly dependent on temperature.
At the same time at higher temperatures it exhibits an activation character. To clarify the ob‐
served peculiarities the current-voltage characteristics were investigated in InAs photodiode
subjected to ultrasonic treatment with frequency 5-7 MHz and intensity ~0.4 W/cm2 during
four hours at room temperature, Fig. 4.
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 235
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Figure 2. Current-voltage characteristics in InAs (1,2) and InSb (3) photodiodes at 77 K. Curves (1) and (2) refer to the
dislocation density in substrates 4 104 cm-2 (1) and 2 105 cm-2, respectively.

Figure 3. Temperature dependences of the forward current measured at 10 mV in InAs (1) and InSb (2) photodiodes
236 Photodiodes - From Fundamentals to Applications

Figure 4. Current-voltage characteristics in InAs photodiodes before and after ultrasonic treatment (curves 1 and 2,
respectively), and after one-year storage (3).

The dark current as a function of bias voltage was measured immediately after ultrasonic
treatment as well as after approximately one-year storage of photodiodes at laboratory con‐
dition. It must be pointed out that the ultrasonic treatment results in pronounced increase of
the dark current at lower bias voltages, whereas those parts of the current-voltage character‐
istics measured at higher voltages were remained almost unchanged. Also, it is important to
note that after storage of samples within one year the excess current caused by ultrasonic
treatment is decreased to approximately the starting values.

An explanation of experimental results is based on the assumption that dislocations inter‐

secting the depletion region are responsible for the excess current at small forward biases.
A model for tunneling current via dislocations intersecting the depletion region of the
junction has been proposed by Evstropov et al. (Evstropov, 1997, 2000). Experimentally it
has been also investigated by Ageev with co-authors (Ageev, 2009). According to this
model, mobile carriers (holes and electrons) are moved along acceptor-like and donor-like
dislocation lines which has been modeled by a chain of parabolic potential barriers with
variable height.

In the symmetric junction the forward current flows due to direct recombination of electrons
and holes at the middle of the depletion region. The current-voltage characteristics can be
described by the formula
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 237
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I = I01exp( e(U − IRs)

E0
)+I 02exp
( e(U − IRs)
βkT
) (1)

where I01 and I02 are the pre-exponential factors, E0 is the characteristic energy; β is the ideali‐
ty factor and RS is the series resistance.

The temperature dependence of the pre-exponential factor in equation (1) is then given by:

I01 = eρνDAexp ( )
eU
E0
D
(2)

where ρ is the density of dislocations, νD is the Debye frequency, UD is the diffusion poten‐
tial. The lifetime of carriers in the depletion region τ0 was determined from the relation I02 =
eniWA/τ0, where ni is the intrinsic concentration of carriers, W is the depletion region width,
A is the junction area.

Because of in the investigated photodiodes the diffusion potential linearly depends on tem‐
perature (Sukach, 2005), the exponential dependence of I01 on temperature should be ob‐
served. Also, in accordance with Evstropov, the characteristic energy E0 is independent on
the concentration of free carriers. These consequences of the analyzed model may be used
for discrimination of the tunneling current via dislocations. For instance, by using typical ex‐
perimental data for InSb photodiodes at 77 K (I0/A = 8.85∙10-5A/sm2, UD = 160 mV, E0 = 29
meV and νD = 3.3∙1012 s-1, which was determined from the known value of Debye tempera‐
ture TD = 160 K (Madelung, 1996), the dislocation density ρ = 4.2∙104 cm-2 was estimated.
This value is almost two orders of magnitude higher than in the starting substrates. Rela‐
tively high density of dislocations can be explained by the fact that during the heat treat‐
ment the edge of the junction was not removed from the zone of radiation defects formed by
ion implantation of beryllium in InSb. However, the same discrepancy between experimen‐
tal and theoretical data was also observed in InAs photodiodes prepared by diffusion tech‐
nique. Moreover, in the investigated InAs photodiodes the characteristic energy E0 was
found to be varied from ~30 meV up to ~60 meV in contrast to theoretical predictions. It
must be stressed that values of E0 experimentally obtained in this study are close to those
observed in diodes made of wide-gap GaP and SiC (Evstropov, 1997, 2000; Ageev, 2009).
This means that the tunneling current via dislocations is characterized by the same features
independent on semiconductor materials used for manufacture of diode structures.

The observed discrepancy between theoretical and experimental data may be caused by sev‐
eral reasons. First of all, in the model developed by Evstropov dislocation lines are assumed
to be fully occupied by carriers and have a length of the order of the depletion region width.
This seems to be not typical for dislocations in semiconductors (Matare, 1971; Holt and Ya‐
cobi, 2007; Shikin, 1995). Also, the presence of jogs, inclusions of impurity atoms, kinks, etc.,
results in a loss of translation symmetry along the dislocation line and spatial localization of
mobile carriers. Thus only short dislocation segments can contribute to the direct current
conduction (Holt, 2007; Kveder, 1985; Nitccki, 1985). It is supposed that this is the main rea‐
son why the direct current conduction along dislocation cores is not clearly demonstrated so
238 Photodiodes - From Fundamentals to Applications

far (Holt and Yacobi, 2007). Further, as originally proposed by Shockley (Holt and Yacobi,
2007) and according to Labusch (Labusch, 1982) and Labusch and Schröter (Labusch and
Schröter, 1983) dislocations in semiconductors introduce one-dimensional energy bands into
the gap, located near the conduction and valence band edges. Direct recombination transi‐
tions between these bands seem to be not effective. The much more effective is the recombi‐
nation through deep defect states in the gap (Kveder, 2001; Seibt, 2009).

Further analysis of experimental data is based on assumption that the p-n junctions in the
investigated diodes are non-homogeneous and there are two conduction paths for mobile
carriers in the junction. The tunneling current flows via the dislocations intersecting the de‐
pletion region whereas the recombination current flows via homogeneous region free of dis‐
locations. At low bias voltages the tunneling current is dominant, so the forward I-U
characteristic is described by the first term in equation (1). Thus, the weak dependence of
the forward current on temperature in Fig.3 can be qualitatively understood. With increas‐
ing the bias voltage this current is masked by the recombination current which can be ex‐
plained within the well known SRH model (Sze, 1981). This change in the current
mechanism is described by the second term in equation (1).

Experimental evidences exist that the recombination rate of minority carriers at dislocations
in silicon depends strongly on dislocation decoration by transition metal impurities (Seibt,
2009). Due to the fact that the recombination of carriers captured at dislocation bands can be
substantially enhanced by the presence of small amount of impurity atoms at the dislocation
core, it is assumed that the low-temperature transport mechanism consists of several steps,
namely: a) injection of electrons into the depletion region under the forward bias, b) capture
of electrons on the dislocation core by tunneling transitions, c) electron transport along the
undisturbed segments of the dislocation core and d) recombination of electrons with holes
through the states in the gap related with ‘native’ core defects (such as jogs and kinks) or
impurity atoms segregated to the dislocation core. In the case of the dislocation core can ex‐
change electrons directly with the conduction band the energy E0 is the dislocation barrier
height. Using experimental values for the density of dislocations (~104 cm-2) and the forward
current (10-8-10-7 A) it is easy to show that dislocations form equipotential lines. If we take
into account that the dislocation resistivity is of the order of 1010 Ω/cm (Labusch, 1982), the
voltage drop along a segment of dislocation of 10-5 cm is less than 10-4 V. So, it is likely that
at low temperatures tunneling transitions of electrons to the dislocation core is the bottle-
neck for the forward current in the investigated photodiodes. Also, it is possible that these
transitions can occur via local states in the gap, associated with point defects or their precipi‐
tates surrounding dislocations. In this two-step process physical meaning of E0 should be
corrected taking into account the energy of these states. Because of in this study the pre-
threshold intensity of ultrasonic treatment was used, experimental results can be explained
by rearrangement of existing defects rather than generation of new point defects. In accord‐
ance with the vibrating string model of Granato-Luecke, the intensive sonic-dislocation in‐
teraction results in an effective transformation of the absorbed ultrasonic energy into the
internal vibration states of a semiconductor stimulating different defect reactions (Granato
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 239
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and Luecke, 1956). The driving force of the long-term relaxation of the forward current may
by stress and electric fields around dislocations.

In conclusion, the excess current experimentally observed in InAs and InSb photodiodes at
forward biases is related to dislocations intersecting the depletion region. Pronounced effect
of ultrasonic treatment on the forward current is explained by transformation of defects seg‐
regated around dislocations. A model for the carrier transport via dislocations is proposed.

4.3. Trap-assisted tunnelling current in the reverse-biased InAs and InSb photodiodes

The effect of traps in the depletion region of a photodiode on the TAT current was consid‐
ered by several authors (Wang, 1980; Kinch, 1981; Nemirovsky, 1989, 1991; Rosenfeld and
Bahir, 1992; He and Celik-Butler, 1995). The calculation of the TAT current in a reverse-
biased photodiode is carried out using several simplifying assumptions: the p-n junction is
abrupt with a linear variation of potential (constant electric field) across the depletion re‐
gion; the traps are uniformly distributed; the initial states are occupied whereas the final
states are empty. Under these assumptions, the TAT current is proportional to the trap den‐
sity, but depends exponentially on the trap-ionization energy and the electric field strength.
Within this model the observed soft reverse breakdown current-voltage characteristics were
adequately explained.

For instance, in Fig. 5 and 6 are shown typical current-voltage characteristics and 1/f noise
spectra measured in n+-p HgCdTe (x=0.22) photodiodes. The photodiodes were prepared by
boron implanting into epitaxial films grown by LPE method, followed by surface passiva‐
tion and low-temperature post-implanting anneal. In the calculation of TAT current thermal
and tunnel transitions from the valence band to deep defect states in the gap followed by
tunnel transitions to the conduction band were taken into account. That is, the TAT current
is given by

J tat = qW N t ( ω N 1+ c p
v v p 1
+
1
ωc N c + cn n1 ) −1
(3)

were ωcNc and ωvNv are the tunneling rates. In order to fit experimental and calculated data
it has been supposed that are non-uniformly distributed through the depletion region (Iva‐
siv, 1999). The best fit was obtained for the acceptor-like traps with energy Et = 0.72Eg above
the top of the valence band and the capture rates for holes and electrons Cp ≈ 10-7 - 10-6 cm3/s
and Cn = (0.1-0.01)Cp, respectively. The determined trap energy correlates well with the pre‐
viously used Et=0.75Eg in photodiodes prepared by boron implantation to bulk material
(Nemirovsky, 1991). Note that in photodiodes investigated by Nemirovsky et al., the TAT
current was dominant by donor-like traps with the capture rates Cp=(10-10-10-9cm3/s) and Cn =
(10-100)Cp. Our data are in accordance with the study performed by Rosenfeld and Bahir for
acceptor-like centers in HgCdTe photodiodes (Rosenfeld and Bahir, 1992).
240 Photodiodes - From Fundamentals to Applications

Figure 5. Measured (dots) and calculated (solid lines) current-voltage characteristics of n+-p photodiodes at 77 K. Pa‐
rameters of traps: Et=0.72Eg, Cp=1 10-7 cm3/s, Cn=0.01Cp, Nt=3.2 1015 and 4.8 1015 cm-3 for curves 1 and 2, respectively.

Figure 6. Noise spectra for the photodiodes with R0A=1.0 Ω cm2 (1) and R0A=0.3 Ω cm2 (2) at 77 K.
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 241
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The correlation was found between the TAT current at small reverse bias voltage U ≤ 0.1 V
and 1/f noise. In the case of the total dark current was completely determined by TAT mech‐
anism the 1/f noise was observed up to frequencies 104 Hz. Taking this into account the
noise current was calculated by the formula

In = α ( )
ITAT
f
(4)

From the fitting calculation the values of the constant α = 10-8 - 10-7 were found. Earlier simi‐
lar correlation was observed by Nemirovsky et al.. (Nemirovsky, 1989; Nemirovsky, 1992).

It seems that parameters of traps determined from the fitting calculations within this model
may be used for rough estimations only. More accurate calculations of the TAT current has
been performed by Krishnamurthy et al. (Krishnamurthy, 2006). The TAT current has been
calculated for a linearly varying electric field in the depletion region of the p-n junction and
self consistently obtained trap-occupation probability. The calculations showed that the re‐
verse-bias dark current changes considerably both in magnitude and in shape. For a better
interpretation of the observed dark currents and an estimation of trap density, these im‐
provements should be taken into account.

In order to explain experimental data in InAs photodiodes it has been assumed that the tun‐
neling current is controlled by small areas of the junction which are characterized by large
deviation of impurity concentration from the mean value (Sukach, 2005). For instance, non-
uniform distribution of impurity atoms can be realized around dislocations (Cottrell atmos‐
phere) or at the periphery of the junction. This results in increase of electric field in the
junction over the value given by the equation (1) for more or less uniform distribution of
charged defects in the junction. We also assumed that the tunneling current in these areas is
caused by the trap-assisted tunneling described with the modified values of the junction
area and electric field strength in the junction. For this purpose, the dislocation was modeled
by the effective area Aeff ≈1 μm2 with increased concentration of charged defects. Their con‐
centration was determined from the fitting calculation of I-U curves. The density of disloca‐
tion was assumed to be of the order of 104 cm-2. The electric field around a dislocation may
be determined from the Poisson equation. However, as the first approximation there has
been assumed that the electric field around dislocations may be estimated using formulas
for the abrupt p-n junction (Sze, 1981). Because of the tunneling rates ωcNc and ωvNv are ex‐
ponentially depend on the electric field strength, the TAT current through these regions are
exponentially large in comparison with the uniform regions of the junction. The trap-assist‐
ed tunneling current was calculated for the following cases: i) traps are exchanged with both
bands by thermal and tunnel transitions of carriers (curve 1), ii) tunnel transitions of carriers
from the valence band to traps followed by thermal and tunnel transitions to the conduction
band (curve 2), tunnel transitions of carriers from the valence band to the conduction band
through traps. The best fit was obtained for the energy of traps Et = Eg/2 and their concentra‐
tion in the range from ~1013 to ~1014 cm-3. These values seem to be reasonable for InAs. The
concentration of charged defects determined from the fit of the calculated and measured da‐
242 Photodiodes - From Fundamentals to Applications

ta was found to exceed 4·1016 cm-3. This value is more than one order of magnitude higher
than the mean value of the free carriers concentration determined from the capacitance-volt‐
age measurements.

Some arguments in favor of the measured current in InAs photodiodes is related to Cot‐
trell’s atmospheres around dislocations have been obtained from investigations of effect of
ultrasonic treatment on the current-voltage characteristics (Sukach and Tetyorkin, 2009). In
the photodiodes subjected to ultrasonic vibration with frequency 5-7 MHz and pre-thresh‐
old intensity ~0.4 W/cm2 prononced increase of the reverse current was obseved. The current
is relaxed down to the starting value during nine-month storage of photodiodes at laborato‐
ry conditions. Experimental results are explained by transformation of existing complex de‐
fects rather than generation of new point defects. Most probably that this transformation is
connected with Cottrell’s atmospheres around dislocations which intersect the p-n junction.
In accordance with the vibrating string model of Granato-Luecke (Granato and Luecke,
1966), the intensive sonic-dislocation interaction results in an effective transformation of the
absorbed ultrasonic energy into the internal vibration states of a semiconductor stimulating
different defect reactions. The driving force of the observed relaxation may be deformation
and electric fields around dislocations.

4.4. Recombination mechanisms

The carrier lifetime in HgCdTe, InSb and InAs narrow-gap semiconductors is determined
by three principal recombination mechanisms: radiative, Auger and SRH. The first two
mechanisms are intrinsic, whereas SRH recombination is not intrinsic because it is carried
out with assistant of deep defect states in the gap. In principle, SRH recombination can be
suppressed by reducing the concentration of recombination centers. Ten types of possible
band-to-band Auger recombination processes in n- and p-type semiconductors were deter‐
mined by Beattie (1962). The Auger 1 recombination mechanism in n-type material with
InSb-like parabolic band structure was firstly considered by Beattie and Landsberg (Beat‐
tie and Landsberg, 1959). The Auger 7 process is important in p-type material (Beattie and
Smith, 1967; Petersen,1970; Takeshima, 1972; Casselman and Petersen, 1980; Casselman,
1981). For the nonparabolic band structure, the |F1F2| dependence on k, and nongenerate
statistics appropriate expressions for the Auger 7 recombination process has been de‐
duced by Beattie and Smith (1967).

The well known problem in the Auger recombination processes is the uncertainty in the car‐
rier lifetime introduced by the overlap integrals F1 and F2 of the periodic part of the electron
wave functions. As was shown by Petersen (1970, 1981), the dependence of the product |
F1F2| on the wave vector k should be taken into account in p-type materials. However, in
practice the constant value of |F1F2| in the range 0.1-0.3 is used for calculations of the carrier
lifetime (Rogalski, 1995). This results in scatter of the calculated data within an order of
magnitude. The detailed analysis of recombination process in HgCdTe can be found in nu‐
merous review articles and books (Beattie and Landsberg, (1959); Petersen, 1981; Capper,
1994; Rogalski, 2011; Chu and Sher, 2010).
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 243
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Due to Capper (1994), in n-type HgCdTe for low values of composition (x<0.25) and carrier
concentrations >1015 cm-3 the Auger 1 recombination process is dominant, particularly at
high temperatures (>100 K). The SRH recombination is important at lower values of carrier
concentration and at low temperatures. In LPE material grown from Hg-rich solution higher
values of lifetime than in corresponding material grown by other techniques were observed,
presumably due to a lower level of recombination centers related with Hg vacancies. Dislo‐
cations can also contribute to the SRH recombination when present at high densities. The
measured data in p-type HgCdTe indicated that the Auger 7 recombination does not limit
the carrier lifetime. It is believed that the SRH recombination can explain most of the experi‐
mental data (Fastow, 1990).

The Auger recombination process in narrow-gap semiconductors with the three- and four-
band Kane models of band structure was reexamined by Gelmomnt et al. (Gelmont, 1978;
Gelmont, 1981; Gelmont, 1982; Gelmont and Sokolova, 1982). The appropriate calculations
of the carrier lifetime in InAs based on Gelmont’s theory has been performed by Tetyorkin
and co-authors (Tetyorkin, 2011). The calculated dependences of the lifetime as a function of
the carrier concentration in InSb is shown in Fig. 7 and 8.

The generation rate for the Auger 1 process gA1 obtained by Beattie and Landsberg is
given by

g A1 =
8(2π)5/2e 4me* | F 1 F 2 | 2no
h 3ε 2(1 + μ)1/2(1 + 2μ)
( )
kT 3/2
Eg exp − ( 11++2μμ ) kTE
g
(5)

According to Gelmont, the generation rate for the Auger 7 is

G
g A7 =
18mo (mh* h / mo )e 4
πℏ3ε 2
po ( )
kT 7/2
Eg exp − (1 +
mhl*
mhh*
Eg
) kT g(α) (6)

In these equations, ε is the static dielectric constant, mhl* and mhh

*
are the effective masses of
light and heavy holes, respectively, μ is the ratio of the electron to the heavy-hole effective
mass. In the calculation of gA1 the product of the overlap integrals |F1F2| is equal to 0.25
(Malyutenko, 1980). The calculated dependences are compared with experimental data pub‐
lished starting from the late 1950s to our days. As seen from Fig.7, the Auger 1 process is
dominant at the electron concentration n > 4·1015 cm-3, whereas at n < 1·1015cm-1 the carrier
lifetime is determined by the radiative mechanism. In p-InSb the radiative recombination is
dominant at the concentration p< 5·1015 cm-3, Fig.8. The observed scatter of experimental da‐
ta in samples with approximately the same concentration of carriers can be attributed to the
SRH recombination. The values of the carrier lifetime in samples investigated earlier were
lower than those obtained later. Thus, the relation between the improvement in technology
of InSb and the increase in the carrier lifetime is clearly seen from experimental data shown
in Fig. 7 and 8.
244 Photodiodes - From Fundamentals to Applications

Figure 7. Calculated dependences (solid lines) of the lifetime in n-InSb at 77 K. Experimental are taken from (Abduva‐
khidov, 1968; Malyutenko, 1980; Guseinov, 1971; Strelnikova, 1993; Biryulin, 2004): open square, close square, open
triangle, close triangle and open circle, respectively.

Figure 8. Calculated dependences (solid lines) of the lifetime in p-InSb at 77 K. Experimental data are taken from (Laff
and Fan, 1961; Volkov, 1967; Zitter, 1959): close square, open square and close triangle, respectively.
 Infrared Photodiodes on II-VI and III-V Narrow-Gap Semiconductors 245
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In conclusion, the following peculiarities of the carrier lifetime in MWIR and LWIR HgCdTe
may be pointed out: carrier lifetime can be essentially different in samples prepared by dif‐
ferent growth techniques, even if they have approximately the same carrier concentration;
correlation between the lifetime and the concentration of vacancies is observed in vacancy
doped materials; lifetime can be increased by doping with foreign impurities; SRH recombi‐
nation is more distinct at low temperatures and in samples with low carrier concentration.

It seems that the SRH recombination is also dominant in InAs and InSb at low temperatures
and low values of the carrier concentration. It should be noted that the low-temperature an‐
nealing of n-InSb leads to a significant increase in the lifetime in samples with the carrier
concentration of the order of 1014 cm-3. The highest values of the lifetime, as shown in Fig.6
(Strelnikova, 1993), were obtained in annealed samples due to significant decrease in the
concentration of recombination centers.

5. Conclusion

Despite significant advances in the development of infrared photodiodes on narrow-gap II-

VI and III-V semiconductors, theoretically predicted threshold parameters have not yet been
achieved. The main reason for this is the participation of defects of different type in the
processes of recombination and carrier transport. It is clear that further progress in develop‐
ment of IR photodiodes is closely connected with the band gap and defect engineering. The
most impressive application of these concepts, based on knowledge of fundamental physical
properties and defect states in narrow-gap semiconductors, is the development of HgCdTe
planar heterostructure photodiodes with the highest performance achieved to-day.

Author details

Volodymyr Tetyorkin1, Andriy Sukach1 and Andriy Tkachuk2

1 V. Lashkaryov Institute of Semiconductor Physics NAS of Ukraine, Ukraine

2 V. Vinnichenko State Pedagogical University, Ukraine

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 Chapter 8

Al(Ga)InP-GaAs Photodiodes Tailored for Specific

Wavelength Range

Yong-gang Zhang and Yi Gu

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/50404

1. Introduction

The sun light shining on our earth, with its main energy concentrated in visible extending to
ultraviolet (UV), has activated this planet adequately. Therefore, the spectral response fea‐
tures of life-forms including human beings, as well as plentiful artificial creatures, are linked
to those bands spontaneously and tightly. Photodiodes or photodetectors (PDs) with specific
wavelength response in UV-visible bands have many practical and potential applications in‐
cluding ocean or water related sensing and communication, medical engineering and photo‐
dosimetry, missile guidance and countermeasures, and so on. In those wavelength bands,
various groups of II-VI, III-V and VI materials could be utilized for PDs. Among them, Si PD
should be the most successful one, whereas its wide response extends to near-infrared inher‐
ently, also, the performance of Si PD is limited by its indirect and relatively narrow bandg‐
ap, which restricts its applications in certain cases. Among various optional materials in
those bands, the III-V Al(Ga)InP system, especially the ternary AlInP and GaInP, may work
well in visible or even extending to UV band. Al0.52In0.48P and Ga0.51In0.49P, which are lattice
matched to GaAs substrate, have band gaps about 2.3 eV and 1.9 eV respectively, the combi‐
nation of those two ternary materials, in conjunction with the quaternary AlGaInP system,
also gives a big room in tailoring the response of the photodiodes to a specific wavelength
region. Besides, profiting from the wider bandgap comparing to that of Si, higher working
temperature, lower dark current and better radiation hardness could be expected for those
robust materials. Furthermore, for this GaAs based III-V non-nitride system, the doping in
both n and p type is feasible, a quite mature growth and processing technology can be relied
on, so photovoltaic detectors and arrays with better performance could be presumed.

In this chapter, a simple review on the material issues of PDs in these bands will appear
first, then concentrated on the gas source molecular beam epitaxy (GSMBE) growth of the
262 Photodiodes - From Fundamentals to Applications

ternaries lattice matched to GaAs substrates, including GaInP and less-studied AlInP. The
doping, structural and optical properties of the GSMBE grown materials will be investigated
in detail, then turning into the growth of PD structures and processing of the device chips
composing of those ternaries, mainly based on our experience. Finally, the performance of
developed AlInP-GaInP-GaAs and AlInP-GaAs photodiodes tailored for specific wave‐
length range will be characterized and discussed.

2. Material Issues

2.1. UV-visible detector materials overview

In UV-visible bands normally quantum or photon type PDs, instead of thermal type PDs,
are preferable. The materials for quantum type PDs sensitive to UV-visible bands could be
chosen from group IV (e.g.: Si, SiC), group III-V (nitride, phosphide or arsenide), group II-VI
(e.g.: CdS, CdTe) and so on, mainly depending on their bandgap (e.g. Razeghi et al. 1996).
The expected sensitive wavelength region of a PD is mainly depending on its application re‐
quirements. Normally, inside the anticipant sensitive wavelength region a high response of
the detector is expected. However, outside the anticipant sensitive wavelength region a full
cutoff of the PD is preferable, because in this case the response is not a signal but noise or
interference to the applications. For a quantum type PD operating in certain wavelength re‐
gion, regardless of artificial resonate or filtering structures, the cutoff wavelength at long
wavelength side is determined by the bandgap of the sensitive material inherently. The re‐
sponse of the detector at short wavelength side is depending on the material properties, de‐
vice structures and so on. Normally, it will not cutoff sharply but drop continuously until
reaching an unacceptable level. Furthermore, a better performance of the detector could be
expected for a material with larger bandgap, regardless of some other effects. Normally the
introduction of artificial resonate or filtering structures on the detection system, regardless
of internally or externally, will increase the complexity, as well as cause losses, therefore a
PD just matched to desired wavelength region inherently is strongly expected. Based on
above considerations, when the cutoff wavelength of the detector at long wavelength side is
fixed, as a rule of thumb a material with close to but slightly longer bandgap wavelength is
expected. After that, the response of the detector could be finely tailored and optimized us‐
ing different material stacks, device structures and processing parameters.

Quantum type PDs may have different types such as photoconductive or photovoltaic; from
practical point of view photovoltaic types are more preferable because the detectors could
be operated without bias, and therefore with lower dark current. In visible wavelength
range group IV Si is definitely the most successful material to demonstrate photovoltaic de‐
tectors. However, its response is wider and extends to both near infrared (NIR) and UV
sides. Therefore for certain applications in specific wavelength region a filter or resonate
structure has to be applied to suppress the response in both long and short wavelength
sides. Also, the indirect and relative narrow bandgap will limit its performance. The CdS de‐
tector has no infrared response inherently, whereas currently it only works as a photocon‐
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 263
http://dx.doi.org/10.5772/50404

ductor and seems hard to reach high performance and high speed. Some other wide
bandgap II-VI, SiC and III-V nitrides have also attracted much attention in those bands (e. g.
Ando et al. 2002; Zhang et al. 1997; Zhang et al. 2009; Rigutti et al. 2010). Especially, various
nitride AlGaN/GaN detector structures including positive-intrinsic-negative (PIN) (e. g. Pul‐
frey et al. 2001), Schottky (e. g. Lee et al. 2012), metal-semiconductor-metal (MSM) (e. g.
Mosca et al. 2004) or metal-insulator-semiconductor (MIS) (e. g. Chang et al. 2006) have been
adopted. However, their responses are mainly restricted in the UV side, and the tailoring of
the response width is difficult. In addition to above-mentioned material systems, the III-V
AlGaInP material system, especially the ternary AlInP and GaInP, may also work well in
visible and may even extend to UV band (e. g. Zhang et al. 2005, 2010; Li et al. 2011).

Figure 1. Lattice constant and bandgap energy of AlzGaxInyP quaternary system. The shadowy bottom region indi‐
cates the indirect bandgap zone; the thick solid line in the middle indicates the quaternary alloy lattice matched to
GaAs substrate.

The calculated lattice constant and bandgap energy contours of the AlzGaxInyP (x+y+z=1)
quaternary system are shown in Figure 1. In this figure the sloping solid line and almost
aclinic dot line indicate the bandgap energies and lattice constants of this quaternary respec‐
tively. In the calculation the energy bowing of the ternary was taken into account, whereas
the bowing of the quaternary was ignored. This quaternary system is composed of three
group-III elements of Al, Ga and In, with only one group-V element of P. In this material
system the ternaries AlzIn1-zP and GaxIn1-xP are at the left and right ridges; the ternary AlzIn1-
zP could be recognized as the alloy of binaries indirect AlP and direct InP, and ternary

GaxIn1-xP as the alloy of binaries GaP and InP also with indirect and direct bandgap, respec‐
tively. The direct bandgap of AlzIn1-zP and GaxIn1-xP at 300 K could be written as Eg=3.55z
+1.34(1-z)+0.48z(1-z) and Eg=2.78x+1.34(1-x)-0.65x(1-x) respectively (Vurgaftman et al. 2001).
Those ternaries have the widest direct bandgap among common III-Vs excepting nitrides.
264 Photodiodes - From Fundamentals to Applications

Figure 2 shows the bandgap energy and band edge wavelength of the AlInP and GaInP
ternary alloys versus the indium composition x at 300 K. The materials with direct and
indirect bandgap are shown by solid and dashed lines, respectively. The indium composi‐
tion of the ternaries latticed matched to GaAs has also been indicated. The lattice con‐
stants of AlP and GaP are very close, which makes the indium compositions for GaAs-lattice-
matched AlInP and GaInP are also very close. AlxIn1-xP is lattice matched to GaAs substrate
when the indium composition is around 0.48, while ternary GaxIn1-xP is lattice matched to
GaAs substrate with indium composition around 0.49. It makes ternary Al0.52In0.48P and
Ga0.51In0.49P important epitaxial materials from both research and application points of view.
The Al0.52In0.48P on GaAs shows many similar characteristics as the AlGaAs/GaAs or AlInAs/
InP system. It has an indirect bandgap about 2.3 eV, which is the largest bandgap among
the practical non-nitride III-V alloys, so a great deal of applications could be expected on
this wide bandgap material (Gu et al. 2006, 2007). The bandgap of 2.3 eV corresponds to a
cutoff wavelength of about 540 nm, which is located in the visible band. The Ga0.51In0.49P on
GaAs has a direct band gap of 1.9 eV, corresponding to the wavelength of about 650 nm.
The combination of AlInP and GaInP two materials gives a room in tailoring the response
of the photodiodes to a specific wavelength region in visible band and even extending to
UV, but blind to infrared inherently.

Figure 2. Bandgap energy and related band edge wavelength of InxGa1-xP and InxAl1-xP ternary alloys versus the indi‐
um composition x at 300 K. The materials with direct and indirect bandgap are shown by solid and dotted lines, re‐
spectively. The indium composition when the ternaries latticed matched to GaAs has also been indicated.

2.2. Gas source MBE growth of GaInP and AlInP ternary alloys

In our growth process, a VG Semicon V80H GSMBE system was applied. The best back‐
ground vacuum achieved in this system was about 1×10-11 Torr. The elemental indium and
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 265
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gallium Thermacells, as well as aluminum standard effusion cell, were used as group III
sources, and their fluxes were controlled by changing the cell temperatures. Arsine (AsH3)
and phosphine (PH3) high-pressure cracking cells were used as group V sources, their fluxes
were pressure controlled, and the cracking temperature was around 1000 °C. Standard ber‐
yllium and silicon effusion cells were used as p- and n- doping sources, and the doping level
was also controlled by changing the cell temperatures. Before the growth, the fluxes of
group III sources were calibrated by using an in situ ion gauge.

The GaInP and AlInP layers were all grown on (100) oriented GaAs semi-insulating (S. I.)
epi-ready substrates, which were placed on In-free Mo blocks. Prior to the growth, the sur‐
face oxide desorption of the substrate was carried out under As2 flux. This process involved
a slow ramp-up of the substrate temperature until the reflection high energy electron dif‐
fraction (RHEED) pattern shown an abrupt transformation to 2×4 surface reconstruction, in
this case the substrate desorption temperature measured by thermocouple was usually
about 630 °C, then the substrate temperature was decreased to appropriate temperature to
begin the growth. Prior to the growth, an appropriate As-P flux exchange procedure with
pump down of arsenic for 1 minute before open P flux was used. The pressure in the growth
chamber during growth, which is related to the flux of group V sources, was adjusted to
about 2×10-5 Torr. The growth rate of the epi-layers was controlled to be about 1 μm/hour,
and the epi-layer thickness of all grown samples in this study was around 1 μm. After
growth, the morphology of the grown samples was observed using a Normasky microscope,
their structural characteristics were measured by using a Philips X-pert type X-ray diffrac‐
tometer (XRD) including a Ge (220) four-folded monochrometer, and the carrier concentra‐
tion of the epi-layer was determined by using Hall measurement in Van der Pauw scheme
or electrochemical capacitance-voltage (EC-V) profiler at room temperature.

Ternary GaInP material has been widely applied in visible laser diodes (e.g.: Kaspari et al.
2008) and solar cells (e.g.: Geisz et al. 2008) structures. Many efforts have been paid to the
epitaxy of GaInP, and found that the ordered degree plays a critical role in the growth. In
our GSMBE growth, the calibration growth of GaInP layers were performed as the first step,
the indium and gallium source temperatures were adjusted to grow Ga0.51In0.49P, which was
lattice matched to GaAs substrate. The lattice mismatch between epilayers and substrate
were confirmed by XRD measurements, the typical XRD rocking curve of grown Ga0.51In0.49P
on GaAs is shown in Figure 3. Since the thermal expansion coefficient of Ga0.51In0.49P is larger
than that of GaAs, the amount of lattice mismatch determined at room temperature is shift‐
ed to positive side comparing to the lattice match at growth temperature; therefore, at room
temperature a slightly positive lattice mismatch should be preferable, the estimated lattice
mismatch of +5×10 -4 at room temperature may lead to the precise lattice match of Ga0.51In0.49P
to GaAs at growth temperature. As shown in Figure 3, the XRD measurement shows that
this optimized GaInP epi-layer has a positive mismatch around +4.9×10-4 to GaAs substrate,
with a FWHM of 28.6 arcsec for the epi-layer and 18.6 arcsec for the substrate.
266 Photodiodes - From Fundamentals to Applications

Figure 3. Measured X-ray rocking curve of typical GSMBE grown Ga0.51In0.49P on (100) GaAs substrate.

After that, a series of Ga0.51In0.49P layers were grown with different silicon doping levels, in‐
cluding an unintentionally doped sample and three samples with silicon cell temperatures
of 1130 ˚C, 1150 ˚C and 1200 ˚C. The room temperature electron concentrations measured by
Hall effects were high resistance, 2.4×1017 cm-3, 1.1×1018 cm-3 and 4.6×1018 cm-3, respectively.
Photoluminescence (PL) measurements were performed for these samples and shown in
Figure 4. The samples were mounted in a continuous-flow variable-temperature helium
cryostat (using a HC-2D-1 APD Cryogenic System and a Lakeshore 330 temperature control‐
ler). A Coherent INNOVA 305 argon-ion laser (=514.5 nm) was used and the laser beam was
focused to a spot size of approximately 0.5 mm2 on the sample to excite the PL spectra. The
PL light was collected and collimated by a couple of large quartz lens, and then focused into
a Jobin Yvon THR1000 monochrometer with a 1200 grooves/mm grating, the PL signal was
detected by using a photo-multiplier-tube (PMT).

It is shown in Figure 4 that the PL emission keeps nearly the same for the samples with un‐
intentional or lower doping, the PL peaks are at 1.951 eV and the full width half-maximum
(FWHM) are about 24 meV. However, as the doping level is increased to about 1×1018 cm-3,
the PL emission wavelength is blue shifted to about 1.963 eV and the peak FWHM increases
to 38 meV. When the doping level is further increased to about 5×1018 cm-3, the PL wave‐
length is further blue shifted to about 1.972 eV and the FWHM further increases to 58 meV.
Moreover, the PL intensity for the sample with the highest silicon doping level is decreased
significantly to about 1/10. The blue shift, broad FWHM and decreased intensity can be ex‐
plained by the decreased ordered degree, which could be attributed to the high silicon dop‐
ing (Yoon et al. 1999; Longo et al. 2001).
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 267
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Figure 4. The PL spectra of Ga0.51In0.49P samples with different electron concentration levels at 10 K.

Figure 5. The AlP mole fraction versus the aluminum flux ratio ηAl in the GSMBE growth of AlInP.
268 Photodiodes - From Fundamentals to Applications

Figure 6. Measured X-ray rocking curve of typical GSMBE grown Al0.52In0.48P on (100) GaAs substrate.

In the past years, epitaxial AlInP lattice matched to GaAs has been studied for the applica‐
tions such as window/anti-reflection (AR) layer of GaInP/GaAs multi-junction solar cells
(Takamoto et al. 1997; Karam et al. 2001) and cladding layer of visible lasers and modulators
(Murata et al. 1991), mainly by using metal-organic chemical vapor deposition (MOCVD)
techniques. The GSMBE growth of relative thin AlInP layers for the tunnel junction or win‐
dow/AR layer of tandem solar cells have also been reported (Li et al. 1998). Recently, AlInP
has been found with great potential to demonstrate very low dark current avalanche photo‐
diodes (APD) (Ong et al. 2011). However, comparing with the well-developed GaInP
growth, the study of the growth process and doping characteristics of AlInP on GaAs re‐
mains quite insufficient, especially for the growth of thicker and composition diversified
layers. Compared to MOCVD, MBE yields a higher doping efficiency and less diffusion ef‐
fects for its lower growth temperatures, and the use of gas source for group V elements in
GSMBE makes the process more realizable, especially for the growth of phosphide (Gu et al.
2006& 2007).

During our GSMBE growth of ternary AlInP layers, the fluxes of aluminum and indium and
their ratio in the growth of AlxIn1-xP were investigated in detail. Figure 5 shows the XRD
measured AlP mole fraction of AlInP versus aluminum flux ratio during the growth. The
aluminum flux ratio (η Al) is defined as η Al=f Al/(f Al+f In), in which f Al and f In is the flux of
aluminum and indium cell respectively. The AlP mole fraction shows a quite linear function
with η Al in our experimental range, which could be used to predict the AlP mole fraction
before sample growth. The non-unity slope of the line shows that indium and aluminum el‐
ements have quite different sticking coefficient, at this growth temperature the sticking coef‐
ficient of aluminum is much higher than that of indium.
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Similar to GaInP/GaAs, a slightly positive lattice mismatch of AlInP epi-layer with respect to
GaAs substrate should be preferable at room temperature. The XRD measurement shows
that the optimized AlInP epi-layer has a positive mismatch around +4.3×10-4 to the GaAs
substrate as shown in Figure 6, with a FWHM of 21.6 arcsec for the epi-layer and 14.9 arcsec
for the substrate, which are among the best for epitaxial grown layers.

In this condition, a perfect mirror-like surface could be reached as shown in Figure 7(a). The
Normasky micrographs of other grown samples with larger lattice mismatch to GaAs are
shown in Figure 7 (b-d). Figure 7(b) shows the micrograph of AlInP epi-layer with large
negative mismatch around -4.7×10-3, in this condition light ripple pattern could be seen
along <01Ī> direction. At even larger negative mismatch of -6.1×10-3, a cross ripple pattern
along both <011> and <01Ī> direction could be seen as shown in Figure 7(c). In negative mis‐
match conditions, the AlInP epi-layer is affected by tensile strain from the substrate; in this
case the misfit dislocation may develop, and leads to poor morphology of the epi-wafer.
However, the positive mismatched sample shows a mirror-like surface even if the mismatch
reaches as large as +7.3×10-3 as shown in Figure 7(d). It could be deduced that the compres‐
sive strain during the growth has much weak effects on the surface morphology.

Figure 7. Normasky micrographs of the GSMBE grown AlInP epi-layers with different lattice mismatch to GaAs: (a)
nearly lattice-matched layer with positive mismatch of +4.3×10-4; (b) layer with negative mismatch of -4.7×10-3; (c) lay‐
er with even large negative mismatch of -6.1×10-3; (d) layer with positive mismatch of +7.3×10-3.

XRD rocking curves were measured for AlInP epi-layers with different AlP mole fractions,
and the FWHM of XRD epi-layer and substrate peaks as a function of AlP mole fraction is
shown in Figure 8. The AlInP samples in the condition of around lattice match have narrow‐
er FWHM values and show the better lattice quality. The FWHM of epi-layer peaks kept be‐
low 100 arcsec as the lattice mismatch was in the range of about -4×10-3 to +3×10-3, and was
270 Photodiodes - From Fundamentals to Applications

broadened abruptly when out of this range. The FWHM of substrate peaks was broadened
to about 160 arcsec as the negative lattice mismatch was increased to -6×10-3, but was still
narrower than 40 arcsec as the positive lattice mismatch was increased to +7×10-3. It could be
deduced that AlInP epi-layer with positive mismatch has better lattice quality than those
with negative mismatch. This behavior also suggests that the compressive strain has weaker
effects on lattice quality than the tensile strain during the growth.

Figure 8. FWHM of XRD peaks for AlInP epi-layers and substrates versus the AlP mole fractions.

Figure 9. Average (carrier density divided by epi-layer thickness) carrier concentration in AlInP layers versus reciprocal
temperature of Si and Be cells.
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Figure 10. a) The PL spectra of five AlInP samples with different aluminum compositions at 10 K; (b) Three peaks were
defined by using Gaussian fitting for PL spectrum of sample 3 at 10 K.

The electrical properties of AlInP were also investigated. Figure 9 shows the measured elec‐
tron or hole concentration in Si or Be doped AlInP samples as a function of the reciprocal
temperature of Si and Be cells, all those samples were around the lattice matched condi‐
tions of x=0.52. Considering that the production of two dimensional electron or hole gas is
possible for higher bandgap AlInP layer grown on GaAs substrate with lower bandgap, the
EC-V profiling was also done using a PN4300 Profiler, besides the Hall measurements. Re‐
gardless the measurement and system error (with a coefficient of about 2) for different
measurement techniques, a good correlation between the EC-V and Hall results definitely
exists. It was observed that the Hall hole concentration maintained around 1016 cm-3 as the
Be cell temperature (TBe) was below 820 °C, and increased to 1.2×1018 cm-3 when TBe was
272 Photodiodes - From Fundamentals to Applications

increased to 840 °C. Similarly, as the Si cell temperature (TSi) was below 1200 °C the Hall
electron concentration was quite lower, whereas as TSi increased to 1250 °C the electron
concentration also increased to 5.4×1018 cm-3 abruptly. At higher cell temperatures a satura‐
tion phenomenon was observed.

Figure 11. a) Excitation power dependence of the PL spectra for AlInP sample 3 at 10K; (b) Peak energy of the three
Gaussian fitting peaks versus the excitation power for AlInP sample 3 at 10 K.

The optical properties of the grown AlInP samples were studied by using PL measurements,
and the mechanisms were analyzed in detailed. Figure 10(a) shows the PL spectra of five
AlInP samples with different aluminum composition at 10 K, for consistency the same exci‐
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tation power of 13 mW was used. For sample 1-5, the measured AlP mole fractions by XRD
using strained estimation (XAl-S) are 0.38, 0.40, 0.42, 0.47 and 0.51 respectively; whereas using
relaxed estimation the AlP mole fractions (XAl-R) are 0.22, 0.28, 0.32, 0.42 and 0.49 respective‐
ly. The real AlP mole fractions of these samples should be between the strained and relaxed
values. Sample 1, 2 and 3 have direct bandgap, sample 5 has indirect bandgap, and sample 4
is near the critical condition. The lattice-mismatch between AlInP and GaAs substrate of
sample 1 is the largest, and decreases in turn for sample 2, 3, 4, 5. As shown in Figure 10(a),
several overlapped peaks, which should have different origins, could be seen in the spectra.
For sample 1-3, two main peaks appear clearly, in sample 3 a weak peak also exits at lower-
energy side. As the two strong peaks overlapped each other, Gaussian fitting was used to
determine the peak energy and intensity exactly. In the fitting two peaks were used for sam‐
ple 1 and 2, whereas three peaks for sample 3. The fitting result for sample 3 is shown in
Figure 10(b), the two strong peaks are marked as peak 1 and peak 2, the weak side-peak is
marked as peak 3.

Figure 12. PL intensity and FWHM of B-B peaks for AlInP Sample 1-3 at 10K versus strained AlP mole fraction XAl-S at
excitation power of 13 mW.

To study the origins of these emission peaks, excitation power dependence of the PL spectra
was performed on sample 3 from 1 mW to 180 mW at 10 K as shown in Figure 11(a). These
spectra were fitted by using three Gaussian peaks, and Figure 11(b) shows the peak energy
for the three peaks as a function of the excitation power. It could be seen that peak 2 shifts to
higher energy side (blue shift) as the excitation power increases, whereas no obvious shift is
observed for the other two peaks. Therefore, peak 2 is considered due to shallow donor-ac‐
ceptor (D-A) pair recombination, and this PL shift can be explained in terms of the Coulomb
interaction of donors and acceptors as a function of their separation. As the excitation power
increases, there are more probabilities for the transitions between closer D-A pairs; there‐
fore, the emission intensity increases, and the transition energy tends to move towards high‐
274 Photodiodes - From Fundamentals to Applications

er energy side [Zacks et al. 1972]. On the other hand, peak 1 is deemed to be related to band-
to-band (B-B) transition, which shows narrow width and not shifts as the excitation power
increases. The side-peak around 1.72 eV may be considered as associated with the presence
of arsenic related defects according to its peak energy and weak intensity, which may be im‐
ported by the growth background. The PL intensity and FWHM of B-B transition peak in
sample 1, 2 and 3 versus the AlP mole fraction is shown in Figure 12. As AlP mole fraction
increases, the intensity of B-B transition peak is increased and the FWHM is decreased,
which is due to the reduction of nonradiative recombination centers and increase of the ra‐
diation efficiency in smaller lattice-mismatched material.

Table 1 lists the peak energies of the two strong peaks of B-B related EBB or D-A related EDA
in the PL spectra, the separation energy between B-B and D-A transition peaks (EBB-EDA) for
sample 1-3 are also listed. For sample 1-3 both the B-B and D-A transition peaks shift to
higher energy side (blue shift) as AlP mole fraction increases, which is mainly caused by the
increase of the bandgap. By using XAl-S and XAl-R respectively, the theoretical bandgap ener‐
gies at 10 K (written as EG-S and EG-R for short) of all samples were calculated and also listed
in Table 1, for sample 1-4 the Г-valley determines the bandgap, whereas for sample 5 the X-
valley has the lowest energy. For sample 1-3, the rough fraction of strained portion in the
epi-layers (η) could be calculated by the linear interpolation using the following equation:

EG−S · η + EG−R(1 − η ) = EBB (1)

The calculated results of are also listed in Table 1. Results show that this fraction increases as
expected when the Al mole fraction increases and lattice mismatch decreases.

EBB EDA EBB-EDA EG-S EG-R η

Sample No. XAl-S XAl-R
(eV) (eV) (meV) (eV) (eV) (%)

1 0.38 0.22 1.98 1.87 104 2.15 (Г) 1.83 (Г) 47

2 0.40 0.28 2.12 2.01 117 2.19 (Г) 1.95 (Г) 71

3 0.42 0.32 2.23 2.10 140 2.24 (Г) 2.02 (Г) 95

4 0.47 0.42 NA 2.14 NA 2.34 (Г) 2.24 (Г) NA

5 0.51 0.49 NA 2.00 NA 2.36 (X) 2.35 (X) NA

Table 1. Measured and calculated data of grown AlInP samples.

It could be noticed in Figure 10(a) that the PL peaks of sample 4 and 5 have broad FWHM
and weak intensity, which is because sample 4 is around the point for bandgap turning from
direct to indirect and sample 5 is indirect bandgap material. The PL peaks of those two samples
are considered only due to the D-A transition. As shown in Figure 10(a)and Table 1, the PL
peak of sample 4 is located at 2.14 eV, whereas the peak of sample 5 is located at 2.00 eV. The
strained AlP mole fraction XAl-S is 0.47 for sample 4 and 0.51 for sample 5, the bandgap EG-S at
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10 K is around 2.34 eV and 2.36 eV for sample 4 and sample 5 respectively. It means that for
sample 4 and 5 the shift direction of the PL emission peak differs from that of the bandgap
energy. The analogous composition-dependent red shift of D-A transition PL peak was also
reported in beryllium doped AlxGa1-xAs (Morita et al. 1989). In our study, the donor ioniza‐
tion energy (ED) of sample 5 with X energy valley might be larger than that of sample 4 with
Γ energy valley, which could induce the decrease of D-A transition energy for sample 5.

Figure 13. PL intensity of the D-A transition peak for sample 1-3 versus reciprocal temperature from 10 K to above
100 K. The solid, dotted and dashed lines are the least-squares fit of the data to Eq. (2) for sample 1-3 respectively.

The thermal activation energy and nonradiative recombination mechanism of the samples
could be analyzed by the thermal quenching process of PL intensity. We have measured the
PL spectra from 10 K to above 100 K at the same excitation power of 13 mW. Figure 13
shows the PL intensity of the D-A transition peak for sample 1-3 as a function of reciprocal
temperature (in Log scale), and the intensities are normalized to the maximum intensity of
sample 1. The curves show Arrhenius behavior with two different slopes, which could be
interpreted in terms of different nonradiative recombination mechanisms respectively pre‐
vailing in two distinct temperature ranges. The slopes can give the activation energies for
the two nonradiative recombination processes. The line in Figure 13 is the least-squares fit of
the experimental data of D-A transition peak using the following equation as a function of
temperature T [Lambkin et al. 1994 and Yoon et al. 1997]:

α
I (T ) = (2)
1 + C1exp( − E1 / kT ) + C2exp( − E2 / kT )

where I(T) is PL emission intensity, α is a variable constant, and k is Boltzmann constant, C1

and C2 are the ratios of nonradiative to radiative recombination probabilities for the two loss
276 Photodiodes - From Fundamentals to Applications

mechanisms, E1 and E2 are the thermal activation energies. The fitting results of E1 and E2 for
sample 1-3 have been listed in Table 2. The obtained thermal activation energies are in the
range of E1~8-20 meV and E2~90-120 meV without significant dependence on lattice mis‐
match. The thermal activation energy of E1 is deemed to dominate at lower temperatures
and be considered related to silicon donor. On the other hand, the thermal activation energy
of E2 dominates at higher temperatures. The presence of deep acceptors, such as traps or im‐
purities, is considered to be the most likely causes of E2. Therefore, the value of E1 plus E2
should indicate the total D-A pair energy. As listed in Table 2, E1 plus E2 is 106 meV, 116
meV and 129 meV respectively for sample 1-3, which is in good agreement with the separa‐
tion energy between B-B and D-A peaks (EBB-EDA) as listed in Table 2.

Sample No. E1 (meV) E2 (meV) E1+E2 (meV)

Sample 1 17 89 106

Sample 2 8 108 116

Sample 3 10 119 129

Table 2. Thermal activation energies estimated by fitting to the temperature-dependent PL intensity of the D-A
transition peaks for sample 1-3 through Eq. (2)

2.3. Growth of Al(Ga)InP photodetector structures

Two kinds of PD epitaxy structures are grown on (100) oriented S. I. GaAs epi-ready sub‐
strates, where GaInP and AlInP are applied as absorption layers respectively (denoted as
GaInP PD and AlInP PD hereafter). The GaInP PD consists of a 0.9 m n+ GaAs buffer and
bottom contact layer, a 40 nm n+ GaInP back-surface field (BSF) layer, a 1 m n- GaInP light
absorption layer, a 60 nm p+ GaInP emitter layer, a 30 nm p+ AlInP window layer and a 0.2
m p+ GaAs top contact layer, which is quite similar to the top cell structure of the tandem
solar cells (e.g.: Karam et al 2001; Yamaguchi 2001). The growth of AlInP PD began with a 1
m n+ GaInP buffer layer, which was also for the bottom contact, and then a 50 nm n+ AlInP
BSF layer was grown. After that, a 1 m n- AlInP light absorption layer was grown, which
was lightly doped with silicon to below 1×1016 cm-3 to reach fully depletion at zero bias. Fi‐
nally, a 150 nm p+ AlInP emitter layer and a 150 nm p+ GaInP top contact layer were grown.

The grown samples all show shiny surfaces. The structural characteristics of the wafers were
measured by XRD as shown in Figure 14 and Figure 15 for GaInP and AlInP PD structures,
respectively. From the measurements, the epi-layer of GaInP PD shows a positive mismatch
of +9.0110-4 to the GaAs substrate, with a FWHM of 28.3 arcsec. For the AlInP PD structure,
the peak of AlInP absorption layer shows a positive mismatch of +4.7610-4 to the GaAs sub‐
strate with a FWHM of 22.5 arcsec as shown in Figure 15, confirming the good epitaxy quali‐
ty. After that, the grown samples were processed into PD chips for further investigation.
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Figure 14. X-ray diffraction rocking curve of the GSMBE grown GaInP PD structure.

Figure 15. X-ray diffraction rocking curve of the GSMBE grown AlInP PD structure.
278 Photodiodes - From Fundamentals to Applications

3. Performances of specific Al(Ga)InP photodetectors

The grown wafers were processed into mesa type PDs using conventional processing steps.
The detector mesas with different diameters were defined by using photolithography and
wet etching to the bottom contact layer, and then passivated by plasma enhanced chemical
vapor deposition of Si3N4. Both the top and bottom contacts were formed using photolithog‐
raphy, evaporation of TiPtAu and lift-off. After an alloy step, the wafers were diced into
chips, and then the chips were mounted into transistor outline (TO) packages and wire
bonded for further measurements. Various photodiodes tailored for UV-enhanced or blue
wavelength range was demonstrated.

3.1. UV-enhanced GaInP photodetector

As concerned in the introduction part of this chapter, many practical and potential appli‐
cations need PDs sensitive to short wavelength side of visible and extending to UV, but
blind to infrared. For GaInP PD, UV light may also be detected besides the visible light
and blind to infrared inherently, so we can call it UV-enhanced GaInP PD as demonstrat‐
ed (Zhang et al. 2005).

Figure 16 (a) shows the schematic of the GaInP detector, (b) is the capacitance-voltage (C-
V) characteristics of the PD measured at 1 MHz frequency with a HP4280A C-V meter,
the detector sensitive area is 1.0810-3 cm2. The capacitance of this detector is 40.75 pF (37.9
nF/cm2) at zero bias, including the capacitance of the package and bonding pad. In Fig‐
ure 16, the carrier concentration along the GaInP absorption layer is also plotted, which
is calculated by using N=(1/q0 rA2)[C3/(dC/dV)] and Xd=0 rA/C (where Xd=0 is at the pn
junction interface) from the C-V curve. The electron concentration of 3~61016 cm-3 in the
GaInP absorption layer is educed, which is in consistent with the quite low silicon dop‐
ing level during the growth.

The current-voltage (I-V) characteristics, which are directly correlated to the performance of
the detector, have been measured using a HP4156A precise semiconductor analyzer over
more than 6 orders of magnitude in current range. Figure 17 shows the typical dark I-V
characteristics of the detectors at room temperature and reverse bias. The dark current of
this GaInP detector is only 340 fA at reverse bias VR=50 mV, the breakdown voltage is great
than 5 V. For those GaInP photovoltaic detectors, the output voltage under illumination is
much higher than those of Si detectors, the open-circuit voltage of Voc>1.05 V is measured as
shown in the lower inset of Figure 17. The shunt resistances of the detector at 0 V bias (R0)
are also measured as shown in the upper inset of Figure 17, for this detector R0 of 120 G
(R0A=1.3108 cm2) has been reached at room temperature.
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Figure 16. Schematic of the UV enhanced GaInP photodetector (a), and measured C-V characteristics of the PD and
calculated carrier concentration profile in the Ga0.51In0.49P light absorption layer.

The response spectrum of the detector was measured by using a grating monochrometer
with lock-in technique, in the measurement a chopped deuterium/halogen combined light
source in conjunction with a standard Si detector (with known area and calibrated respon‐
sivity data at each wavelength) was used. Figure 18 shows the measured response spectrum
of the UV-enhanced GaInP PD at room temperature, the thin solid lines show the quantum
efficiency grid and dashed line shows the relative C.I.E. curve of the human eye; the detec‐
tor was under zero bias. It could be seen that, the response peak of the detector is at 550 nm,
with 10% cut-on and cut-off wavelength of 350 nm and 675 nm, respectively. The measured
responsivity of the detector at 400, 550 and 650 nm is 0.12, 0.26 and 0.19 A/W, respectively.
The quantum efficiency around 500 nm reaches 60% and drops down in both red and blue
280 Photodiodes - From Fundamentals to Applications

sides, besides the contact shading and non-optimized AR coating, the reduced efficiency in
the red side could be contributed to the insufficient GaInP absorption layer thickness,
whereas in blue side the surface recombination may play an important role. In this detector,
the infrared response was totally suppressed, the measured infrared suppression ratio is
greater than 250 (limited by the measurement system), whereas the UV response is en‐
hanced evidently, this feature is desirable in certain applications. In Figure 18 the Commis‐
sion International de l' Eclairage (C.I.E.) curve of human eye was also shown. Notice that the
response of this detector covers the C.I.E. curve quite well, so it may also find applications
in photometry.

Figure 17. Measured dark I-V characteristics of the UV-enhanced GaInP PD at room temperature and reverse bias; the
upper inset shows the I-V characteristics across the zero bias and related shunt resistance of the detector, the low inset
shows the I-V characteristics of the detector with and without illumination.

3.2. Narrow band blue AlInP Photodetector

Clear ocean water shows attenuation minimum in the blue (450-490 nm) band with trans‐
mission peak around 480 nm, while quite sensitive to particle and pollution (Pope et al.
2000). Therefore for the ocean related remote sensing applications, sensitive PDs in this band
with inherent narrow wavelength width should be needed, and photovoltaic type without
filter or resonate structure is more preferable. In addition to the traditional Si, II-VI or III-V
nitrides PD structures, the AlInP PD adopting AlInP as absorption layer works well in the
blue band.
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 281
http://dx.doi.org/10.5772/50404

Figure 18. Measured response spectrum of the UV-enhanced GaInP PD; the thin solid lines show the quantum effi‐
ciency grid and dashed line shows the relative C.I.E. curve of the human eye.

Based on the grown AlInP PD structures mentioned above, devices have been demonstrated
with the schematic structure as shown in Figure 19 (Zhang et al. 2010). The typical dark I-V
characteristics of the detectors at room temperature and reverse bias are shown in Figure 20; the
diameter of the detector is 300 m. It can be seen that the dark current of this AlInP/GaInP detector
is only 150 fA at reverse bias VR=500 mV, and the breakdown voltage is greater than 30 V.

Figure 19. Schematic drawing of the AlInP blue PD.

282 Photodiodes - From Fundamentals to Applications

Because of the lower doping level in AlInP absorption layer, at forward bias <1.78 V the
dark current remains below 30 pA, after that the diode turns on. For those GaInP/AlInP pho‐
tovoltaic detectors, the output voltage under blue light emitting diode illumination is much
higher than that of Si detectors, the open-circuit voltage of Voc>1.28 V is measured as shown
in the lower inset of Figure 20, the illumination intensity on the detector is about 2 W. The I-
V characteristics around zero bias have also been measured as shown in the upper inset of
Figure 20, from which the shunt resistances of the detector at 0 V bias (R0) are deduced. For
this detector R0 of 980 G (R0A=6.9108 cm2) has been reached at room temperature.

Figure 20. Measured dark I-V characteristics of the Ga0.51In0.49P/Al0.52In0.48P/GaAs blue photovoltaic detector at room
temperature and reverse bias; the upper inset shows the I-V characteristics around zero bias, the low inset shows the I-
V characteristics of the detector in dark and with blue illumination.

The response spectrum of the detector has been measured by using a grating monochrome‐
ter adopting lock-in technique. In the measurement an xenon light source chopped at 14 Hz
and a calibrated LiTaO3 pyroelectric detector were used. Figure 21 shows the measured re‐
sponsivity spectrum of the detector under zero bias at room temperature. It could be seen
that the detector has a Gaussian alike response spectrum, the peak response wavelength p is
480 nm with 50% cut-on and cut-off wavelength at 452 nm and 497 nm respectively, corre‐
sponding to a relative response wavelength width (FWHM/p) of 9.4%. The measured re‐
sponsivity of the detector at 480 nm and zero bias is 0.168 A/W, corresponding to an external
quantum efficiency of 43.4% for this detector without AR coating. Considering ~30% reflect‐
ing loss and ~11% top contact shadowing loss, the peak internal quantum efficiency reaches
70%. In Figure 21 the absorption feature of water is also shown, the response of the detector
matches the transmission window quite well.
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 283
http://dx.doi.org/10.5772/50404

Figure 21. Measured responsivity spectrum of the AlInP blue PD; the thin solid lines show the quantum efficiency grid
and dashed line shows the absorption feature of ocean water in this wavelength range.

The response of those detectors is fitly around blue band with intrinsic narrow response
wavelength width, which is much lower than the normal value of above 30% for other de‐
tectors in this band. This can be attributed to our epitaxy structure design adapting the
bandgap features and combination of AlInP with GaInP. At aluminum composition around
0.52 lattice matching to GaAs, AlInP is an indirect bandgap material with bandgap around
2.3 eV corresponding to wavelength about 540 nm, but enters direct bandgap around 2.6 eV
(Ishitani et al. 1997; Menoni et al. 1997; Gu et al. 2006). Therefore, the absorption at blue
band around 480 nm should be quite strong like those of direct bandgap material. At the
same time the response at short wavelength side, especially the UV parts, is restrained by
the GaInP cap layer with narrower direct bandgap of about 1.9 eV; furthermore, the re‐
sponse at long wavelength side is also suppressed by the use of a relative thin AlInP absorp‐
tion layer. The combination of all the effects forms an appropriate response characteristic
suitable for blue band detection.

For the same epitaxial structure of the detector, through the etching away of the top p+-
GaInP contact layer during the processing to open a light entrance window, the peak re‐
sponse wavelength of the PD blue shifted 10 nm to 470 nm as shown in Figure 22, the peak
response increased obviously to 0.287 A/W (Li et al. 2011). The cut-off wavelength at short
wavelength side also blue shifted 12 nm to 440 nm, whereas almost unchanged at long
wavelength side. The narrow response feature of the PD still retained (increased slightly to
about 12%), the dark current still kept at a quite low level (R0A=1.7108 cm2), which makes
this PD very useful for ocean related blue band applications.
284 Photodiodes - From Fundamentals to Applications

Figure 22. Measured responsivity spectrum of the AlInP PD when etching away of the top p+-GaInP contact layer dur‐
ing the processing.

4. Conclusion

In conclusion, based on the analysis of the material issues for the PDs in UV-visible bands
suitable for specific applications, the quaternary Al(Ga)InP system lattice matched to GaAs
substrate, especially the ternaries GaInP and AlInP, were chosen as our object. Using
GSMBE method, the growth techniques and material characteristics of ternaries GaInP and
AlInP were investigated in detail (Gu et al. 2006, 2007). The UV-enhanced AlInP-GaInP-
GaAs PD and narrow band AlInP-GaAs blue PD structures have been grown by using
GSMBE, and PDs with excellent performances have been demonstrated (Zhang et al. 2005,
2010; Li et al. 2011). The spectral responses of those PDs are tailored by the design of the
epitaxial and device structures to specific wavelength band, which are desirable for particu‐
lar applications where selective response and outstanding performances are expected.

Acknowledgements

The authors wish to acknowledge the support of National Basic Research Program of China
under grant No.2012CB619200 and Innovative Founding of Shanghai Institute of Microsys‐
tem and Information Technology, CAS.
 Al(Ga)InP-GaAs Photodiodes Tailored for Specific Wavelength Range 285
http://dx.doi.org/10.5772/50404

Author details

Yong-gang Zhang* and Yi Gu

*Address all correspondence to: [email protected]

State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Micro‐
system and Information Technology, Chinese Academy of Sciences. Shanghai, China

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