2.0 Semiconductor materials 2.

1 Elemental and compound semiconductors ---Periodic Table of some elements--II Mg Zn Cd III B Al Ga In IV C (6) Si (14) Ge (32) Sn V N P As Sb VI O S Se Te

Atomic number = Number of electrons Electron configuration of elemental semiconductors 1. C (diamond): (1s)2/(2s)2(2p)2, inner orbital / outer orbital 2. Si: (1s)2(2s)2(2p)6/(3s)2(3p)2 3. Ge: (1s)2(2s)2(2p)6/(3s)2(3p)6(3d)10/(4s)2(4p)2

Commom character of semiconductor ----outer orbital, (ns)2(ns)2------

Electronic configuration of the respective elements

Metal Electron Energy of Na

Semicondu ctor

Semicondu ctor

Pauli Exclusion principle (two electrons of opposite spin can occupy each energy level)

Compound Semiconductor (Man-made materials)

Equivalent electron number (outer orbital) =4 Ga: (1s)2(2s)2(2p)6/(3s)2(3p)6(3d)10/(4s)2(4p)1 As: (1s)2(2s)2(2p)6/(3s)2(3p)6(3d)10/(4s)2(4p)3

A. Elemental semiconductors B. Compound Semi. III-V

II-VI IV-IV C. Calcogen/Spinelmagnetic Semi.) D. Rare-earth, magnetic Semi.) E. Amorphous Semi. F. Organic Semi.

CdiamondSi, Ge, Te,Sn GaAs, GaPGaN, InSb, InAs, InP, AlP

ZnS, ZnSe, ZnO, CdS, CdSe, CdTe, SiGe, SiC, (V-VI Bi2Te3) CdCr2Se4, CdCrS4 EuO, EuS, EuSe Ge, Te, Se, GeTe, As2Te TCNQ

For optical devices like LED, LD, compound semiconductors are very useful.

2.2 Covalent bond and diamond structure

Covalent bond simplest case---Hydrogen molecule, H2, There are only three elements which form a crystal with a covalent bonddiamondCsilicon(Si)germanium(Ge)
Covalent bond--one 3s orbital and three 3p (px, py, pz) orbital consist of a new sp3 hybrid orbital

Tetrahedron structure Electron distribution of sp3 hybrid orbital

Diamond structure

Crystal structure of GaAs and GaN

Zinc-blend structure

Wurzite structure

<Crystal Structure>
Classification of Material structure
(a) Amorphous---no ordered atomic arrangement (b) Polycrystallineshort range atomic order usually in small crystalline grains (10Afew m) (c) crystalline long range, ordered, atomic arrangement, repeating unit cell All important semiconductor devices are based on crystalline materials (Si especially) because of ---?

Silicon ingot and wafer

2.3 Electron Energy in the crystal (The difference in the electrical characteristics among Metal, Semiconductor and Insulator can be explained with the
Problems: How does the electron energy change from atom to crystal? New concept of energy band (Quantum theory of soild )

2.3.1 Energy band by a qualitative model ---in case of electron Energy of Na crystal (Metal)
Energy level of outer electron (3s level) sprits into N (number of Na atoms) levels with very narrow distance-----called Energy Band While, energy levels of inner electron (2p, 2s and 1s) does not sprit and N levels overrapp.
Electron energy

Electron energy

To form a crystal

Atom distance

Electron energy of Na atom

Electron energy of Na crystal

2.3.2 Energy band model (general model)

Vacuum level
Inside crystal Outside crystal

Calculate the electron energy in the crystal under periodic condition using Schrodinger equation

periodic potential
E, Electron Energy Allowed energy band

Forbidded energy band Energy level of inner orbit K, wave number

A large number of energy levels = Number of atoms

2.3.4 Band diagram of (a) metal, (b) semiconductor, and (c) insulator.
Conduction band (half full) Conduction band (almost empty) Conduction band Completely empty)

EG: Energy Gap Electron Hole

Filled band Valence band (completely full) Valence band (almost full) Valence band Completely full)

2.3.5 Energy band of Si and GaAs

Indirect semiconductor

Direct semiconductor

Electron Energy [eV]

Electron Energy [eV] Energy Band structure of GaAs

Energy Band structure of Si

2.3.6 Electron effective mass, mn

E vs. k relation (E: electron energy, k: wave number)
-------parabolic---------

E=(k)2/2mn

(2.12)

Where

1 1 2 = ( ) 2 2

(2.13)

called electron effective mass (the second derivative of E with respect to k) For GaAs narrow conduction band, mn = 0.07m0, (m0:electron rest mass) whereas for Si with a wider conduction band, mn = 0.19m0. ** Electron effective mass depends on crystal direction If we introduce the electron effective mass, electrons in the crystal under electric field behave like as a single particle with effective mass.
(2.14)

2.4 Extrinsic Semiconductors, n-type and p-type

2.4.1 Donors
Excess electron submitted from phosphorus atom

Conduction band

Positively ionized phosphorus atom

Valence band

Donor concentration :Nd [cm-3] Electron concentration: n

n=Nd p=ni2/Nd

(2.23) (2.24)

Intrinsic carrier concentration: ni

Breaking Si-Si bond, an electron is emitted and it is captured by boron atom, completing covalent bond hole

2.4.2 acceptors

An missing electron leaves a hole Negatively ionized boron atom

Acceptor concentration: Na [cm-3] Hole concentration: p

p=Na n=ni2/Na

(2.25) (2.26)

(at room temperatures)

2.4.3 intrinsic carrier concentration i

Constancy of p product

p=ni2
ni={NcNv}1/2

150 100 500 10190 0 18 10

T() 200 100

27 0

-50

(2.21) ni (cm-3)

1017
1016 1015 1014 1013 1012 Si

exp(-EG/2kT)
(2.22)

Ge: 2.40x1013cm -3 at 300K Si: 1.45x1010cm -3 at 300K GaAs: 1.79x106cm -3 at 300K

1011 1010
109 108 107 GaAs

1.451010

1.79106
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 1000/T(K-1)

106

2.4.4 Temperature dependence of electron concentration

At low temperatures (<100K), Electrons become electrically inactive, i.e., electrons are bound with donor atoms.

Absolute Temperature [K]

200K<T < 500K (For Si) Electrons are completely ionized, i.e., electrons are free from donor atoms. (2.27) n=Nd

At high temperatures, for n-type semiconductors, (2.28) neutrality: n=p + Nd np product constancy: np=ni2 (2.29)

2.5 Carrier Transport in the electric field

2.5.1 mobility
No Electric Field Electric Field, Ex

Electron

In no electric field, free electrons and holes move through the crystal due to random thermal motion ------ Thermal velocity : vth =107 cm/s When the electric field, Ex is applied, carriers move very slowly as compared with thermal velocity. This situation seems to drift. Its velocity is called drift velocity.

 Electron can be regarded as particle using effective mass. Ex: Electric field in x direction, Vx: velocity of electron, mn: effective mass of electron

qExt Then, vx=vxo mn

dvx mn = q Ex . dt

(2.30)

(2.31)

(vxo: initial velocity of electron at t=0)

Above equation indicates the increase of electron velocity with time. However, real situation in the movement of many electrons differs. Electrons are scattered and collide with host atoms (Si) or other electrons. Average time between collision is called average relaxation time .
(2.32)

vd=n Ex,

(2.33)

where n = q
mn

(2.34)

This average velocity called drift velocity vd . The proportional factor n is called mobility.

<Mobility of Si and GaAs as a function of dopant concentration>

Si

GaAs

2.5.2 Drift Current, Conductivity, and Ohms law

Electron drift curent Jnx =qnvx=qnnEx Hole drift current Jpx =qpvx=qppEx Total drift current J= Jnx + Jpx , =q (nn + pp) Ex , where conductivity = q (nn + pp) Then, J= Ex ,
(2.39) (2.35) (2.36)

(2.37) (2.38)

called Ohms law

(2.40) (2.41)

In n-type semiconductor, n>>p, then = q nn In p-type semiconductor, p>>n, then = q pp

Resistivity =1/
(2.42)

2.5.3 Diffusion current----important in pn junction-- Flux F is proportional to the concentration gradient (dc/dx). This is called Ficks first law. dc F=D D: diffusion coefficient (2.43) dx c: concentration, x: distance In semiconductor, diffusion current is generated due to the nonuniform distribution of carrier concentration .

dn dn Electron diffusion current Jdn=(q) (Dn )=q Dn dx dx dp dp ) = q D Hole diffusion current Jdp=(q) (Dp p dx dx

(2.44) (2.45)

Total current
Electron current
(2.46)

Hole current
Total current J = Jn + Jp
(2.48)

(2.47)

Relationship between Mobility (Drift) and Diffusivity (Diffusion) Einsteins Relation

(2.49)

2.7 Carrier generation and recombination

In thermal equilibrium, electron-hole pairs are always generated and recombine. In net, carrier concentrations are maintained at certain values at temperatures. Consider that light is irradiated on a p-type semiconductor substrate uniformly. We investigate the generation and recombination of the minority carrier (here, electron) concentration. During the irradiation of light, excess electron-hole pairs are generated. GL: generation rate of electron-hole pairs
: time constant for excess carrier to return to the thermal equilibrium

Time variation of electron concentration (minority carrier) in p-type semiconductor is given by

(2.50) (2.51)

At steady state(t<0), dn/dt=0

Then n=n0 + n GL
(2.52)

light

semiconductor
X: distance

time

If light is off (GL=0) at t=0, electron concentration returns to the thermal concentration n0 with time constant .
(2.53)

Summary of semiconductor materials--1

Summary of semiconductor materials--2