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Article Analysis, Synthesis and Characterization of Thin Films of a-Si:H (n-

type and p-type) Deposited by PECVD for Solar Cells Applications

Article in Materials · October 2021

DOI: 10.3390/ma14216349

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 materials
Article
Analysis, Synthesis and Characterization of Thin Films of
a-Si:H (n-type and p-type) Deposited by PECVD for Solar
Cell Applications
Abel Garcia-Barrientos 1, *, Jose Luis Bernal-Ponce 2 , Jairo Plaza-Castillo 3 , Alberto Cuevas-Salgado 4 ,
Ariosto Medina-Flores 5 , María Silvia Garcia-Monterrosas 2 and Alfonso Torres-Jacome 6

1 Facultad de Ciencias, Universidad Autónoma de San Luis Potosi, San Luis Potosi 78295, Mexico
2 Departamento de Ingeniería Mecánica, Instituto Tecnológico de Orizaba, Orizaba 94300, Mexico;
[email protected] (J.L.B.-P.); [email protected] (M.S.G.-M.)
3 Facultad de Ciencias Básicas, Universidad del Atlántico, Barranquilla 081001, Colombia; [email protected]
4 Departamento de Ingeniería Mecánica, Instituto Tecnológico de Tlalnepantla,
Tlalnepantla de Baz 54070, Mexico; [email protected]
5 Instituto de Investigación en Metalurgia y Materiales, Universidad Michoacana de San Nicolás de Hidalgo,
Morelia 58030, Mexico; [email protected]
6 Departamento de Electrónica, Instituto Nacional de Astrofísica, Óptica y Electrónica (INAOE),
Tonantzintla 72840, Mexico; [email protected]
* Correspondence: [email protected]



Abstract: In this paper, the analysis, synthesis and characterization of thin films of a-Si:H deposited


by PECVD were carried out. Three types of films were deposited: In the first series (00 process), an
Citation: Garcia-Barrientos, A.; intrinsic a-Si:H film was doped. In the second series (A1–A5 process), n-type samples were doped,
Bernal-Ponce, J.L.; Plaza-Castillo, J.; and to carry this out, a gas mixture of silane (SiH4 ), dihydrogen (H2 ) and phosphine (PH3 ) was
Cuevas-Salgado, A.; Medina-Flores,
used. In the third series (B1–B5 process), p-type samples were doped using a mixture of silane
A.; Garcia-Monterrosas, M.S.;
(SiH4 ), dihydrogen (H2 ) and diborane (B2 H6 ). The films’ surface morphology was characterized
Torres-Jacome, A. Analysis, Synthesis
by atomic force microscopy (AFM), while the analysis of the films was performed by scanning
and Characterization of Thin Films of
electron microscopy (SEM), and UV–visible ellipsometry was used to obtain the optical band gap
a-Si:H (n-type and p-type) Deposited
by PECVD for Solar Cell Applications.
and film thickness. According to the results of the present study, it can be concluded that the best
Materials 2021, 14, 6349. https:// conditions can be obtained when the flow of dopant gases (phosphine or diborane) increases, as seen
doi.org/10.3390/ma14216349 in the conductivity graphs, where the films with the highest flow of dopant gas reached the highest
conductivities compared to the minimum required for materials made of a-Si:H silicon for high-
Academic Editor: Laura Calvillo quality solar cells. It can be concluded from the results that the magnitude of the conductivity, which
increased by several orders, represents an important result, since we could improve the efficiency of
Received: 7 September 2021 solar cells based on a-Si:H.
Accepted: 21 October 2021
Published: 24 October 2021 Keywords: a-Si:H; PECVD; solar cells

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in
published maps and institutional affil-
1. Introduction
iations.
The principal task to diminish the disturbance of energetic needs due to the nature
of humans is the generation of renewable energy. Additionally, energy consumption
is growing steeply and is directly proportional to global population growth. The high
efficiency of solar cells has always been sought after for effective light management. Today,
Copyright: © 2021 by the authors.
the manufacture of materials to produce high-efficiency solar cells has been a key factor
Licensee MDPI, Basel, Switzerland.
in the development of innovative electrical devices. In recent decades, amorphous silicon
This article is an open access article
(a-Si) has been an innovative material in the microelectronic industry, due to its fabrication
distributed under the terms and
being cheap in comparison with that of crystalline silicon (c–Si). Amorphous silicon is
conditions of the Creative Commons
Attribution (CC BY) license (https://
the non-crystalline form of silicon, and it has a band gap of around 1.7 eV. Hydrogenated
creativecommons.org/licenses/by/
amorphous silicon (a-Si:H) materials have received a great deal of attention for their
4.0/). potential to produce inexpensive solar cells, particularly in the polycrystalline growth

Materials 2021, 14, 6349. https://doi.org/10.3390/ma14216349 https://www.mdpi.com/journal/materials

Materials 2021, 14, 6349 2 of 9

regime. In this material, the atoms are not located at a specific distance or specific angles;
therefore, it has a random network. In [1], it was indicated that in hydrogen added to
amorphous silicon, it is possible to find a beneficial effect. Thus, [2,3] showed that silicon
has semiconducting properties when combined with a dopant gas such as phosphine or
diborane. Amorphous silicon has been deposited through various techniques such as
sputtering, and, with better results, plasma enhanced chemical vapor deposition (PECVD)
has been implemented since, with this technique, it is possible to adjust the optoelectronic
properties to the variation in the ambient temperature, the RF frequency and some other
parameters of the process [3–5]. However, a-Si:H films have several drawbacks such as
poor electron transport properties, low carrier mobility, a large number of defects and poor
stability against radiation, which limit their applications in new and high-performance
devices. In [6], the evolution of the a-Si:H to nc-Si:H transition of hydrogenated silicon
films deposited by trichlorosilane was presented. In this aspect, there are some studies that
have explored the optimization of the deposition conditions of a-Si:H films by the PECVD
technique, where the goal is to improve its performance characteristics and to produce other
materials with different structural, electrical and optical properties [7–10]. The preparation
and measurement of highly efficient a-Si:H single-junction solar cells were presented
in [11–13], and the impact of the deposition rate on metastability was discussed in [14].
The practical applications of building integrated photovoltaic systems were presented
in [15–20]. Moreover, in [21], plasmonic light trapping phenomena in thin-film silicon
solar cells with improved self-assembled silver nanoparticles were discussed. Additionally,
high-efficiency a-Si:H/µc-Si:H solar cells by optimizing a-Si:H and µc-Si:H sub-cells were
presented in [22], and the optical modeling of a-Si:H-based solar cells on textured substrates
was discussed in [23,24]. Similarly, in [25], a study on n- and p-type doping of PECVD
a-SiC:H obtained under silane starving plasma conditions with and without hydrogen
dilution was presented. Some recent research reports [26,27] have provided a complete
and comprehensive analysis of the thin-film amorphous silicon solar cell market focusing
on revenue, growth patterns, market trends and the overall volume, along with a detailed
analysis of all of the significant factors affecting the marketplace development of the
industry and demand forecast to 2027. Moreover, a review on approaches to improve
the power output of building integrated photovoltaic systems was presented in [28–31].
Therefore, in this research work, the analysis, synthesis and characterization of thin films
of a-Si:H (n-type and p-type) deposited by PECVD were carried out, where the objective
of this study was to find an optimized semitransparent a-Si:H thin film for solar cell
applications. This optimization was analyzed by a-Si:H thin films that have been doped
with phosphane (PH3 ) (n-type) and with diborane (B2 H6 ) (p-type). The procedure was
repeated with different values for the flow of PH3 and H2 for n-type films and B2 H6 and
H2 for p-type films.

2. Materials and Methods

Three types of films were deposited: an intrinsic a-Si:H thin film (00 process), called
the first series, and two series of a-Si:H films doped by the PECVD technique. In the second
series (A1–A5 process), n-type samples were doped using a gas mixture of SiH4 , H2 and
PH3 . In the third series, p-type films were doped using a mixture of SiH4 , H2 and B2 H6
(B1–B6 process). In both series, samples were made of glass (Corning Glass 2974 and 1737).
We used the AMP-3300 Plasma II PECVD Deposition System. The invariant deposition
conditions for series A and B were ambient pressure 600 mTorr, a power of 300 W, power
density of 90 mW/cm2 , temperature of 300 ◦ C and 30 min treatment time. Flows of H2 ,
SiH4 and PH3 gases in the second series or H2 , SiH4 and B2 H6 in the third series were
adjusted according to some requirements, as shown in Table 1.
Materials 2021, 14, 6349 3 of 9

Table 1. Gas flows of H2 , SiH4 , PH3 and B2 H6 for the first, second and third series.

Process 1 H2 (sccm) SiH4 (sccm) PH3 (sccm) B2 H6 (sccm)

00 1000 50 0 0
A1 200 50 4 0
A2 1000 50 5 0
A3 1000 50 6 0
A4 1000 50 8 0
A5 1000 50 10 0
B1 200 50 0 4
B2 1000 50 0 5
B3 1000 50 0 6
B4 1000 50 0 8
B5 1000 50 0 10
1 Pressure 600 mTorr, power 300 W, power density 90 mW/cm2 , time 30 min and temperature 300 ◦ C.

The thickness and band gap energy of the samples in the three series are shown in
Table 2.

Table 2. Thickness and energy gap of the three series.

Process Thickness (Å) Eg (eV)

00 583 1.97
A1 1066 1.71
A2 941 1.71
A3 995 1.82
A4 910 1.79
A5 955 1.78
B1 601 1.83
B2 860 1.74
B3 985 1.70
B4 1030 1.69
B5 1079 1.67

Sample characterization and process evaluation were performed by the measurements

of absorption coefficients, the conductivities, the activation energies and the thicknesses of
the films. Ultraviolet–visible (UV–Vis) transmittance measurements were performed in
a Perkin-Elmer Lambda 3B spectrometer (Boston, MA, USA) in the range of 300–900 nm.
Activation energy and conductivities were obtained by using measurements of current–
voltage in a wide range of temperatures (300 to 400 K). For the electrical characterization,
a micro-spike system Model LTMP-2, “MMR Technology Inc” (San Jose, CA, USA), was
used. Spectroscopic ellipsometry was used to obtain the measurements of the imaginary
part of the pseudo-dielectric function of the films, data which were useful to obtain their
thicknesses. For this, a Jobin Yvon ellipsometer-MWR UVISEL UV/Vis (Villeneuve-d’Ascq,
France) was used.

3. Results
Figure 1 shows the FTIR spectra for a-Si:H in the second and third series of a-Si:H
thin films (Figure 1a shows n-type films with different processes, A1–A5, and Figure 1b
shows p-type films with different processes, B1–B5). The spectrum of a-Si:H consisted of
typical absorption bands for different types of hydrogen bonding to nitrogen and silicon
and silicon−nitrogen-related bands. One can observe a peak around 640 cm−1 , which
corresponds to Si–H rocking/waging modes, and the band around 800–950 cm−1 is related
to SiH2 or SiH3 bonding with low intensity. The main trend is that the intensity of the
bands assigned to SiHn decreases with the increase in the ammonia content in PECVD.
The spectra of transmittance with respect to the wavelength of the doped n-type films are
shown in Figure 2a, and in Figure 2b for the p-type films. Here, it is observed that, in
 SiH2 or SiH3 bonding with low intensity. The main trend is that the intensity of the bands
SiH 2 or SiH
assigned bonding
to3 SiHn with low
decreases with intensity.
the increaseThe in main
the trend
ammonia is that the intensity
content in PECVD. of theThebands
spec-
assigned to SiHn decreases
tra of transmittance with the
with respect toincrease in the ammonia
the wavelength content
of the doped in PECVD.
n-type Theshown
films are spec-
Materials 2021, 14, 6349 tra of transmittance
in Figure 2a, and inwith Figure respect
2b fortothe thep-type
wavelength of the itdoped
films. Here, n-type that,
is observed filmsinare 4 range
of 9
theshown
in Figure
from 300 2a, andnm,
to 550 in Figure 2b for film
the intrinsic the p-type
showsfilms.a greater Here, it is observedHowever,
transmittance. that, in the fromrange550
from
to 900300 nm, tothe 550doped
nm, the intrinsic
films, eitherfilm n-typeshows a greater
or p-type, showtransmittance.
almost double However, from 550
the transmittance
theto 900
inrange nm,
comparison
from the300doped
to to films,
the550 nm,either
intrinsic the film.n-type or p-type,
The refractive
intrinsic film shows show
index almost
with
a greater double
respect to the
transmittance. the transmittance
wavelength
However, is
in comparison
shown in Figure to the
3 intrinsic
(for doped film.
n-type The refractive
films in Figure
from 550 to 900 nm, the doped films, either n-type or p-type, show almost double index3a, with
and respect
for p-type to the
films wavelength
in Figure is
the3b).
shown
It can in
be Figure
seen, in3 (for
regionsdoped of n-type
the films
spectrum in Figure
where the
transmittance in comparison to the intrinsic film. The refractive index with respect to 3a, and
material for p-type
does notfilms in
absorb Figure
light, 3b).
that
theItthe
can be seen,is
refractive
wavelength inshown
indexregions
tendsinof tothe spectrum
decrease
Figure 3 (forwith
dopedwhere the material
increasing
n-type wavelength.
films does The
in Figure not
3a,absorb
and forlight,
absorption that
coeffi-
p-type
the
cient
films refractive
in vs. phonon
Figure index
3b). It tends
can beto
energy decrease
forseen,
the two with
seriesincreasing
in regions of the
of wavelength.
thinspectrum
films: (a) where
n-type The absorption
films
the coeffi-
with different
material does
cient vs.
processes, phonon
A1–A5, energy
and (b) for the
p-type two
films series
with of thin
different films:
not absorb light, that the refractive index tends to decrease with increasing wavelength. (a)
processes, n-type
B1–B5, films
is with
shown different
in Figure
processes, A1–A5, and (b) p-type films with different processes,
The absorption coefficient vs. phonon energy for the two series of thin films: (a) n-typefor
4a,b, respectively. In Figure 5, one can see the relation between B1–B5, is
conductivity shown and in Figure
1/kT
4a,b,
thewith
films respectively.
two series
different In Figure
of thin films 5,
processes, (in one canand
Figure
A1–A5, see thep-type
5a (b)
for relation
the n-type between
films films,
withandconductivity
in Figure
different and
5b for
processes, 1/kT thefor
B1– p-
the
B5,type two series
films).in
is shown of thin
In Figure
general, films
it can
4a,b, (in Figure 5a
be observedInthat
respectively. for the n-type
the deposited
Figure films,
5, one canfilms and in
see with Figure
less flow
the relation 5b for the
of H2 (200
between p-
type
mTorr),films).
conductivity forandIn general,
both 1/kT foritthe
doped can be observed
series,
two exhibit
series ofthe that
thin the deposited
opposite
films Figurefilms
(inbehavior 5ainforwith
each less
the type
n-type flow of Hand
of films,
doped 2 (200
film;
inmTorr),
this
Figure forfor
means,
5b boththedoped
while series,
the n-type
p-type films). exhibit
film Inshows theaopposite
general, greater
it can be behavior
observedinthat
transmittance each a type
at the greater of doped
depositedwavelength, film;
films
this
with means,
theless
p-type
flowfilmwhile
of H 2 the
(200n-type
shows little
mTorr), film forshows
transmittance aat
both doped greater
a great transmittance
wavelength,
series, exhibit the atopposite
the alatter
greater wavelength,
having
behavior a similar
in
the p-type
behavior tofilm
the shows
one little
observed transmittance
in process at
00 a great
(intrinsic wavelength,
film).
each type of doped film; this means, while the n-type film shows a greater transmittance at the latter having a similar
behavior
a greater to the one observed
wavelength, the p-typeinfilm process
shows 00little
(intrinsic film).
transmittance at a great wavelength, the
latter having a similar behavior to the one observed in process 00 (intrinsic film).
0.09 0.05
Si-H bending Si-H bending
0.09 ~ 630 cm A1 0.05 ~ 630 cm
0.08
-1 -1
B1
Si-H bending A2 Si-H bending
B2
0.08 ~ 630 cm -1 A1
A3 0.04 ~ 630 cm -1
B1
0.07 B3

(a.u)
A2
A4
(a. u)

B2
B4
A3
A5 0.04
0.07
0.06 B3
(a.u)
B5
A4
(a. u)

Absorbance 0.03 B4
A5
0.06
Absorbance

0.05 B5
0.03
Absorbance
Si-O absorption Si-O absorption
P-H stretching P-H stretching
Absorbance

-1 -1
0.05
0.04 ~ 1100 cm
~ 2320 cm -1 0.02
~ 1100 cm
~ 2320 cm -1
Si-O absorption Si-O absorption
-1 P-H stretching -1 P-H stretching
~ 1100 cm ~ 1100 cm
0.04
0.03 Si-H2 bending Si-H2 stretching~ 2320 cm
-1
0.02 Si-H2 bending Si-H2 stretching ~ 2320 cm
-1

-1 ~ 2080 cm -1 -1 ~ 2080 cm -1
0.03
0.02 ~ 890 cm
Si-H2 bending Si-H2 stretching 0.01 ~ 890 cm
Si-H2 bending Si-H2 stretching
-1 ~ 2080 cm -1 -1 ~ 2080 cm -1
0.02
0.01
~ 890 cm 0.01 ~ 890 cm

0.00
0.01
0.00
0.00
0.00 600 800 1000 1200 2000 2200 2400 600 800 1000 1200 2000 2200 2400
-1 -1
600 800 Wavenumber
1000 1200 (cm2000) 2200 2400 600 800 Wavenumber
1000 1200 (cm2000) 2200 2400
-1 -1
Wavenumber (cm ) Wavenumber (cm )
(a) (b)
(a) (b)
Figure 1. FTIR spectra for a−Si:H for two series of thin films: (a) n−type films with different H2 and PH3 contents; (b) p−type
films1.with
Figure
Figure different
1.FTIR
FTIR spectraHfor
spectra 2 and
for a−BSi:H
a−Si:H2H6for
contents.
fortwo series
two of thin
series films:
of thin (a) n−type
films: (a) n−films with different
type films H2 andH
with different PH 3 contents;
2 and (b) p−type
PH3 contents;
films with different H 2 and B 2H 6 contents.
(b) p−type films with different H2 and B2 H6 contents.

90 90

90
80 90
80

80
70 80
70
Transmittance (%)
(%) (%)

70
60 70
60
Transmittance (%)
Transmittance

60
50 60
50
Transmittance

50
40 50
40
40
30 00 40
30 00
A1 B1
30
20 00A2 30
20 00B2
A1A3 B1B3
A2A4 B2B4
20
10 20
10 B3B5
A3A5
A4 B4
100 A5 100 B5
300 400 500 600 700 800 900 300 400 500 600 700 800 900
0 Wavelength (nm) 0
300 400 500 600 700 800 900 300 400 500Wavelength
600 (nm)
700 800 900
Wavelength (nm) Wavelength (nm)
(a) (b)
(a) (b)
Figure
Figure 2. Transmittance
2. Transmittance vs.vs. wavelength
wavelength forfor
twotwo series
series ofofthin
thinfilms:
films:(a)
(a)n-type
n-typefilms
filmswith
withdifferent
differentH
H22 and
and PH33 contents;
contents;(b)
p-type
Figure films
2. with different
Transmittance vs. H2 and B
wavelength
2 H6 contents.
for two
(b) p-type films with different H2 and B2 H6 contents.series of thin films: (a) n-type films with different H 2 and PH 3 contents; (b)
p-type films with different H2 and B2H6 contents.
 Materials 2021, 14, x FOR PEER REVIEW 5 of 9
Materials 2021, 14, x FOR PEER REVIEW 5 of 9
Materials 2021, 14, x FOR PEER REVIEW 5 of 9
Materials 2021, 14, 6349 5 of 9

6.0 6.0
00
00
6.0 A1 6.0
5.5 A2
5.5 B1
00 B2
A3 00
6.0
5.5 A1
A4
6.0
5.5 B1
B3
5.0 A2 5.0 B4

Refractive Index
Refractive Index

00 A5 B2
A3 00 B5
A1 B3
5.5
5.0 A4
A2
5.5
5.0
B1
B4

Index
Index

4.5 A5
A3
4.5 B2
B5
B3
A4
5.0
4.5 5.0
4.5 B4

Index
Index

A5
4.0 4.0 B5

Refractive
Refractive

4.5
4.0 4.5
4.0
3.5 3.5

Refractive
Refractive

4.0
3.5 4.0
3.5
3.0 3.0
3.5
3.0 3.5
3.0
2.5 2.5
300 400 500 600 700 800 900 300 400 500 600 700 800 900
3.0
2.5 3.0
2.5 Wavelength (nm)
300 400 500 Wavelength
600 (nm)
700 800 900 300 400 500 600 700 800 900
2.5 2.5 Wavelength (nm)
Wavelength (nm)
300 400 500 600
(a) 700 800 900 300 400 500 600
(b) 700 800 900
Wavelength (nm) Wavelength (nm)
(a)vs. wavelength for two series of thin films: (a) n-type films with(b)
Figure 3. Refractive index different H2 and PH3 contents;
(b) p-type films with (a)
different H 2 and B2H6 contents. (b)
Figure 3. Refractive index vs. wavelength for two series of thin films: (a) n-type films with different H2 and PH3 contents;
(b) p-type
Figure films with different H2 and B2Hfor
6 contents.
Figure 3.3.Refractive
Refractive index
index vs.wavelength
vs. wavelength twoseries
for two seriesofofthin
thinfilms:
films:(a)
(a)n-type
n-typefilms
filmswith
withdifferent
differentHH 2 and PH3 contents;
2 and PH3 contents;
(b) p-type films with different H 2 and B2H6 contents.
(b) p-type6 films with different H2 and B2 H6 contents. 6
10 10
6 6
10 10

Absorption coefficient (cm )

Absorption coefficient (cm )

-1
-1

6 6
10 10 ) -1)
) -1)

(cm (cm
(cm (cm

5 5
10 10
-1
-1

coefficient
coefficient

5 5
10 10
coefficient
coefficient

5 5
10 10
4 4
10 00 10 00
Absorption
Absorption

A1 B1
4 A2 4 B2
10 00
A3 10 00
Absorption

B3
Absorption

A1 B1
A4 B4
4 A2 4 B2
10 00A3 A5 10 00B3 B5
A1A4 B1B4
A2A5 B2B5
1.5 2.0 2.5 3.0 3.5 A3 4.0 1.5 2.0 2.5 3.0 3.5
B3 4.0
A4 B4
Phonon Energy (eV) A5 Phonon Energy (eV) B5
1.5 2.0 2.5 3.0 3.5 4.0 1.5 2.0 2.5 3.0 3.5 4.0
Phonon Energy (eV) Phonon Energy (eV)
(a) 3.0
1.5 3.5 4.0 2.0 2.5 1.5 2.0 2.5 (b) 3.0 3.5 4.0
Phonon Energy (eV) Phonon Energy (eV)
(a) (b)
Figure 4. Absorption coefficient vs. phonon energy for two series of thin films: (a) n−type films with different H2 and PH3
contents;
Figure (a) with different
(b) p−typecoefficient
films Henergy
2 and B2H6 contents. (b) with different H2 and PH3
Figure 4. 4. Absorption
Absorption coefficient vs.vs. phonon
phonon energy forfor
two two series
series of thin
of thin films:
films: (a) (a)
n−n−type films
type films with different H2 and PH3
contents;
Figure 4.(b)(b) p−type films
Absorption with different
coefficient H2 energy
vs. phonon and B2H 6 contents.
contents; p−type films with different H2 and B2 Hfor
6 two series
contents. of thin films: (a) n−type films with different H2 and PH3
contents; (b) p−type films with different H2 and B2H6 contents.
-3
10 10
-4

-3 -4
10 10 00 10
-4 00
B1
Conductivity ( cm )

A1
Conductivity ( cm )

-5
-1 -1

-5
-4
10
-1 -1

10-3 10
10 00 A2 10
-4 00 B2
A3 B1 B3
)

A1
)

-5
-1) -1

-5 -6
10-4 10 10 B4
-1) -1

10 00A2
A4 00B2
( cm

B5
( cm

A3 A5 -6
B1B3
-6 -7 A1 -5 10
10-5 10
10 10 B4
-1 -1

A4 B2
-1 -1

A2
( cm

B5
( cm

A5 -6 B3
-7 -8 A3 10
10-6 10
10 A4 -7
B4
Conductivity

-6 10
Conductivity

A5 B5
10 10 -7-8 -9 10
10 -7
Conductivity

10
Conductivity

-9 -10
10-810
10 -8
-7 10
-10 -11
10
10 10
10
-9
-8
10
-11
10-10
10 -8
10
-11
28 30 32 34 36 38 40 42 28 30 32 34 36 38 40
10 1/kT (eV )
-1
-1
28 30 32 34 36 38 40 42 28 30 32 1/kT (eV36)
34 38 40
-1
1/kT
(a)(eV ) (b) (eV 36
1/kT )
-1
28 30 32 34 36 38 40 42 28 30 32 34 38 40
-1
1/kT
(a) (eV ) (b) -1
1/kT (eV )
Figure 5. Relation
Figure between
5. Relation conductivity
between and 1/kT
conductivity for two
and 1/kT series
for two of thin
series of thin (a) n−
films:films: (a)type filmsfilms
n−type withwith
different H2 and
different H2 PH
and3 PH3
contents;
contents; −type
p(b) p−type
(b)Relation (a)withwith
films
films different
different H2 1/kT
H2and
andand
B2 HBfor
62H 6 contents.
contents. (b)
Figure 5. between conductivity two series of thin films: (a) n−type films with different H2 and PH3
contents;
Figure (b) p−type
5. Relation films with
between different and
conductivity H2 and
1/kTB2for
H6 contents.
two series of thin films: (a) n−type films with different H2 and PH3
contents; (b) p−type films with different H2 and B2H6 contents.
Materials 2021, 14, x FOR PEER REVIEW 6 of 9
Materials 2021, 14, 6349 6 of 9

In Figure 5a, one can observe that for A1 (H2 = 200 sccm), the conductivity suddenly
In Figure
dropped. This 5a,
canone can observe
be explained bythat
thefor A1 (H
effect = 200
of 2the sccm), the
hydrogen conductivity
content suddenly
in the a-Si:H thin
films. It is caused by the deteriorated interface and can be attributed to voids createdthin
dropped. This can be explained by the effect of the hydrogen content in the a-Si:H by
films. It is caused
insufficiently by the deteriorated
passivated interface
Si surface dangling and can
bonds, be attributed
voids formed bytoSiH
voids created by
2 clusters and
insufficiently
voids formed bypassivated Si surface
Si particles dangling
caused by bonds,
gas-phase voids
particle formed in
formation bysilane
SiH2 clusters and
plasma [30].
voids formed by Si particles caused by gas-phase particle formation in silane plasma [30].
4. Discussion
4. Discussion
In this study, n- and p-type a-Si:H thin films were deposited by the PECVD technique
In this study, n- and p-type a-Si:H thin films were deposited by the PECVD technique at
at a low frequency, varying the fluxes of the diborane and phosphine gases. When com-
a low frequency, varying the fluxes of the diborane and phosphine gases. When comparing
paring the intrinsic sample with the doped samples, it can be noted that the doped sam-
the intrinsic sample with the doped samples, it can be noted that the doped samples
ples
havehave
betterbetter properties
properties thanthan the intrinsic
the intrinsic sample;
sample; this is
this fact fact is evidenced
evidenced in the inconductivity
the conduc-
tivity graph where the doped samples show a higher conductivity,
graph where the doped samples show a higher conductivity, and in the fact that their and in the fact that
gap
their gap improves at a higher dopant flux. From this, it can also
improves at a higher dopant flux. From this, it can also be concluded that the best conditions be concluded that the
best conditionswith
are presented are the
presented
highestwithfluxes theofhighest
dopants, fluxes
either ofphosphine
dopants, eithergas orphosphine
diborane gas. gas orIn
diborane gas. In this way, the conductivity graph shows samples
this way, the conductivity graph shows samples with the highest flow of dopants reaching with the highest flow of
dopants reaching conductivities higher than the minimum
conductivities higher than the minimum conductivity required in a-Si: H materials for conductivity required in a-Si:
H materials
quality solarfor quality solar cells.
cells.
As
As for
for which
which of of the
the doped
doped filmsfilms (type
(type p p or
or type
type n)n) isis better
better for
for the manufacture of
the manufacture of
solar
solar cells,
cells,ititisisconcluded
concludedthat thatthetheA3A3 and andB3B3 processes
processes present
presentthe the
bestbest
results, which
results, can
which
be
canseen in the
be seen intransmittance
the transmittance and absorption
and absorption coefficient curves.
coefficient Finally,
curves. if weifanalyze
Finally, we analyzehow
the hydrogen flux during deposition influences the properties
how the hydrogen flux during deposition influences the properties of the films, it can of the films, it can be con-
be
cluded
concluded that the deposited films with a lower hydrogen flux (200 sccm) do not present aa
that the deposited films with a lower hydrogen flux (200 sccm) do not present
greater attractivenessthan
greater attractiveness thanthe thesamples
samples deposited
deposited withwith a higher
a higher hydrogen
hydrogen flux (1000flux sccm),
(1000
sccm),
since thesince thehave
latter latterbetter
have optical
better optical and electrical
and electrical properties.
properties. This can This
becan be observed
observed in the
in the conductivity
conductivity curve.curve.
In
In Figure 6, five five images
imagesobtained
obtainedby byAFM AFMare areshown,
shown, corresponding
corresponding to to
thethe morphol-
morphology
ogy of the a-Si:H films deposited over the glass substrate
of the a-Si:H films deposited over the glass substrate with flows of H2 = 1000 sccmwith flows of H 2 = 1000 sccm and
SiH
SiH44 ==5050sccm.
sccm.InInthe theimage,
image,it itcancan bebeobserved
observed that forfor
that a pressure
a pressure of of
600600 mTorr,
mTorr, there
thereis
no evidence
is no evidence of nanoclusters,
of nanoclusters, andand theytheyappear
appearfrom 1000
from mTorr,
1000 mTorr,wherewheretheir quantity
their quantityin-
increases
creases with
with thethe increase
increase inin pressure,but
pressure, buttheir
theirsize
sizedecreases
decreaseswhen whenthe thepressure
pressureincreases.
increases.
similar behavior, in a greater quantity of nanoclusters,
A similar nanoclusters, is seen in the films shown in
Figure 7. Figure
Figure Figure 88 shows
shows thethe SEM
SEM photo
photo of of the
thesample
sampleat at2000
2000mTorr,
mTorr, where nano-crystals
appear that
appear that are are approximately 1.5 nm in size.

Figure 6. Images of surface of a-Si:H films deposited over glass substrate with flows of H2 = 1000 sccm and SiH4 = 50 sccm.
Figure 6. Images of surface of a-Si:H films deposited over glass substrate with flows of H2 = 1000 sccm and SiH4 = 50 sccm.
Materials 2021,14,
2021,
Materials2021,
Materials 14,6349
14, xxFOR
FORPEER
PEERREVIEW
REVIEW 777of
ofof999

Figure7.7.Images
Figure Imagesofofsurface
surface ofa-Si:H
a-Si:Hfilms
filmsdeposited
depositedover
overglass
glasssubstrate
substrate withflows
flows of H2 2==4000
4000 sccmand
and SiH4 4==200
200
Figure 7. Images of surface ofofa-Si:H films deposited over glass substrate withwith
flows of H2of= H
4000 sccm sccm
and SiH4 =SiH
200 sccm.
sccm.
sccm.

Figure8.
Figure
Figure 8.8.SEM
SEMphoto
SEM photoof
photo ofthe
of thesample
the sampleat
sample at2000
at 2000mTorr,
2000 mTorr,where
mTorr, wherenano-crystals
where nano-crystalsappear.
nano-crystals appear.
appear.

5.5.Conclusions
5. Conclusions
Conclusions
In
In this
Inthis study,
study,n-type
thisstudy, n-typeand
n-type andp-type
and p-typea-Si:H
p-type a-Si:Hfilms
a-Si:H filmswere
films weresuccessfully
were successfullydeposited
successfully depositedby
deposited byusing
by using
using
the PECVD technique at a low frequency, always changing the flows of the diborane and
the
the PECVD
PECVD technique
technique at
at aa low
low frequency,
frequency, always
always changing
changing the
the flows
flows of
of the
the diborane
diborane and
and
phosphine
phosphine gases.
gases. When
When comparing
comparing the
the intrinsic
intrinsic sample
sample
phosphine gases. When comparing the intrinsic sample with the doped films, it can be with
with the
the doped
doped films,
films, it
it can
can be
be
seen
seen that
that the doped films
films present
present better
better electric
electric properties
properties than
than
seen that the doped films present better electric properties than the intrinsic film. This can thethe intrinsic
intrinsic film.
film. This This
can
can
be be evidenced
beevidenced
evidenced inthe
in ingraphs
the the
graphsgraphs of conductivity,
ofconductivity,
of conductivity, where
where where the doped
thedoped
the doped filmsfilms
films present
present present a greater
aagreater
greater con-
con-
conductivity,
ductivity,and
ductivity, and
andby bytheby the
thefact fact
factthat that
thattheir their
theirgap gap
gapbecomes becomes
becomesbetter better
betterwith with
withaagreater a greater
greaterflow flowof flow
ofdopantof
dopant dopant
gases.
gases.
gases.
Itcan
It canalsoIt can
also bealso
be be concluded
concluded
concluded thatthe
that thethat
bestthe
best best conditions
conditions
conditions canbe
can can be obtained
beobtained
obtained usinggreater
using usingflows
greater greater
flows ofof
flows
the of
dopant the dopant
gas, this gas,
being this being
either either
phosphine phosphine
or diborane.or diborane.
It was
the dopant gas, this being either phosphine or diborane. It was found that for our deposi- found It was
that found
for our that for
deposi-
our
tiondeposition
tion systemand
system and system and conditions,
conditions,
conditions, processesA3
processes processes
A3 andB3
and B3A3 and B3 the
presented
presented presented
thebest the bestoptimized
bestoptically
optically optically
optimized
optimized
a-Si:Hthin
a-Si:H a-Si:H
thinfilms, thin
films,due films,
duetotothe due to
thetransmittancethe transmittance
transmittancecurve. curve.
curve.However, However,
However,processes
processesA5 processes
A5andandB5 A5 and B5
B5presented
presented
presented
betterresults better
resultswith results
withrespect with respect
respecttototheir to their
theirconductivity.conductivity.
conductivity.With Withthis With this
thisresearch, research, it
research,ititisisconfirmed is confirmed
confirmedthat that
better
that
films films
of of amorphous
amorphous silicon
silicon withwith controlled
controlled chamber
chamber pressures
pressures and andgas gas flows
flows deposited
deposited by
films of amorphous silicon with controlled chamber pressures and gas flows deposited by
by
the the PECVD
PECVD technique
technique can canbe be obtained.
obtained. TheThe influence
influence of ofHH 2 and
and SiHSiH 4 in
in thethe deposition
deposition of
the PECVD technique can be obtained. The influence of H2 and SiH4 in the deposition of 2 4
of a-Si:H
a-Si:Hthin thin
thinfilms films
filmsby by
bythe the
thePECVD PECVD
PECVDprocess process
processcan can improve
canimprove
improvethe the efficiency
theefficiency
efficiencyof of
ofsolarsolar
solarcells. cells.
cells.
a-Si:H
Materials 2021, 14, 6349 8 of 9

Author Contributions: Conceptualization, A.G.-B. and A.T.-J.; methodology, J.P.-C. and A.C.-S.;
validation, J.L.B.-P. and A.M.-F.; writing—original draft preparation, A.G.-B. and M.S.G.-M. All
authors have read and agreed to the published version of the manuscript.
Funding: The authors acknowledge funding from CONACYT-Mexico, grant numbers 169062 and
204419, and PRODEP.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within this article.
Conflicts of Interest: The authors declare no conflict of interest.

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