Photovoltaic structures using AgSb(S x

Se1−x )2 thin films as absorber

J. O. González, S. Shaji, D. Avellaneda,

G. A. Castillo, T. K. Das Roy &
B. Krishnan

Applied Physics A
Materials Science & Processing

ISSN 0947-8396

Appl. Phys. A
DOI 10.1007/s00339-014-8411-6

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 Author's personal copy
Appl. Phys. A
DOI 10.1007/s00339-014-8411-6
Photovoltaic structures using AgSb(SxSe12x)2 thin films
as absorber
J. O. González • S. Shaji • D. Avellaneda •
G. A. Castillo • T. K. Das Roy • B. Krishnan
Received: 22 December 2013 / Accepted: 25 March 2014
Ó Springer-Verlag Berlin Heidelberg 2014
Abstract Photovoltaic structures were prepared using
AgSb(SxSe1-x)2 as absorber and CdS as window layer at
various conditions via a hybrid technique of chemical bath
deposition and thermal evaporation followed by heat
treatments. Silver antimony sulfo selenide thin films
[AgSb(SxSe1-x)2] were prepared by heating multilayers of
sequentially deposited Sb2S3/Ag dipped in Na2SeSO3
solution, glass/Sb2S3/Ag/Se. For this, Sb2S3 thin films were
deposited from a chemical bath containing SbCl3 and
Na2S2O3. Then, Ag thin films were thermally evaporated
on glass/Sb2S3, followed by selenization by dipping in an
acidic solution of Na2SeSO3. The duration of dipping was
varied as 3, 4 and 5 h. Two different heat treatments, one at
350 °C for 20 min in vacuum followed by a post-heat
treatment at 325 °C for 2 h in Ar, and the other at 350 °C
for 1 h in Ar, were applied to the multilayers of different
configurations. X-ray diffraction results showed the for-
mation of AgSb(SxSe1-x)2 thin films as the primary phase
and AgSb(S,Se)2 and Sb2S3 as secondary phases. Mor-
phology and elemental detection were done by scanning
electron microscopy and energy dispersive X-ray analysis.
X-ray photoelectron spectroscopic studies showed the
depthwise composition of the films. Optical properties
were determined by UV–vis–IR transmittance and reflec-
tion spectral analysis. AgSb(SxSe1-x)2 formed at different
J. O. González  S. Shaji  D. Avellaneda 
G. A. Castillo  T. K. Das Roy  B. Krishnan (&)
Facultad de Ingenierı́a Mecánica y Eléctrica, Universidad
Autónoma de Nuevo León, 66450 San Nicolás de los Garza,
Nuevo León, Mexico
e-mail: kbindu_k@yahoo.com
S. Shaji  B. Krishnan
Universidad Autónoma de Nuevo León-CIIDIT, Apodaca,
Nuevo León, Mexico
conditions was incorporated in PV structures glass/FTO/
CdS/AgSb(SxSe1-x)2/C/Ag. Chemically deposited post-
annealed CdS thin films of various thicknesses were used
as window layer. J–V characteristics of the cells were
measured under dark and AM1.5 illumination. Analysis of
the J–V characteristics resulted in the best solar cell
parameters of Voc = 520 mV, Jsc = 9.70 mA cm-2,
FF = 0.50 and g = 2.7 %.
1 Introduction
Over the past two decades, chalcogenide thin films have
been investigated for solar cell applications due to the early
success of CuInSe2 thin films as absorber in high-efficiency
solar cells [1–3]. Among them, Cu(In,Ga)Se2 and CdTe
light absorber materials have been dominated till now. The
concerns of high toxicity of cadmium and scarcity of
indium in those materials have driven the research to
concentrate on other absorber materials made from earth
abundant, environment benign precursors. In this context,
AgSbSe2 and its alloys stand out to be promising candi-
dates for solar cell applications, due to their optical
absorption coefficient of 104 cm-1 with a band gap of
0.9–1.1 eV [4]. Photovoltaic structures using AgSbSe2
absorber thin films prepared by heating multilayers of
Sb2S3/Ag2Se in contact with a chemically deposited Se thin
film and CdS window layer showed promising results [5].
Our group reported the preparation of AgSb(SxSe1-x)2 thin
films by heating layered structure of glass/Sb2S3/Ag after
dipping in sodium selenosulfate solution [6]. These thin
films were used as absorber in the PV structures of glass/
SnO2:F/n-CdS/p-AgSb(SxSe1-x)2/Ag-print, showing Voc =
410 mV, Jsc = 5.7 mA cm-2, FF = 0.35 and g = 0.81 %.
To improve the optical and electrical characteristics of
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J. O. González et al.

this material and thus the performance of the PV structures,
further studies were needed. Motivated by the high per-
formance of CIGS and CdTe-based solar cells as a result of
intense research in various aspects to achieve ideal opto-
electronic properties and thus the device performance, we
focused to increase the AgSb(SxSe1-x)2 thin film thickness
and to study their optical and electrical properties, also to
incorporate this material formed at different conditions in
PV structures using CdS window layers. The present work
is a continuation of our earlier work [6] towards the effort
to improve the performance of the PV devices using
AgSb(SxSe1-x)2 thin films.
2 Experimental
In this paper, we report the preparation of AgSb(SxSe1-x)2
thin films by heating layered precursor structures consisting
of chemical bath deposited Sb2S3 and thermally evaporated
Ag after dipping in sodium selenosulfate solution for var-
ious durations. Selenium dipping time and the heating
conditions were varied. The crystalline structure, mor-
phology, composition, optical and electrical properties of
the films formed under different conditions of heating
using two kinds of precursor layers glass/Sb2S3/Ag/Se and
glass/Sb2S3/Ag/Se/Ag/Se were analyzed using X-ray dif-
fractometer (XRD), scanning electron microscope (SEM)
associated with an energy dispersive X-ray detector (EDX),
X-ray photoelectron spectrometer, UV–Vis–NIR spectro-
photometer and photocurrent measurement set-up. Further,
these thin films were incorporated into photovoltaic struc-
tures using chemical bath deposited CdS thin films as
window layer. The effects of thickness as well as post-
deposition treatments on CdS on the PV performance were
studied.
2.1 Precursor thin films
Sequentially deposited antimony sulfide and silver (Sb2S3/
Ag) thin films selenized via a solution method were used as
the precursor films. Three different precursor types were
prepared to study the effect of selenization time in the
structural characteristics and physical properties of the
AgSb(SxSe1-x)2. In all the cases, Sb2S3 thickness was the
same. Ag was coated either in single step before
Fig. 1 A schematic diagram to show the structures of precursor
layers. a glass/Sb2S3/Ag/Se, b glass/Sb2S3/Ag/Se/Ag/Se

Fig. 2 XRD patterns of

precursor layers of a glass/
Sb2S3/Ag/Se, b glass/Sb2S3/Ag/
Se/Ag/Se

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Photovoltaic structures using AgSb(SxSe1-x)2
Fig. 3 XRD patterns for multilayers of a glass/Sb2S3/Ag/Se (3 h)
annealed at 350 °C for 20 min in vacuum followed by 325 °C for 2 h
in Ar, b glass/Sb2S3/Ag/Se (4 h) annealed at 350 °C for 20 min in
vacuum followed by 325 °C for 2 h in Ar, and c glass/Sb2S3/Ag/Se/
Fig. 4 XPS survey spectrum of multilayers of glass/Sb2S3/Ag/Se/
Ag/Se (5 h) annealed at 350 °C for 1 h in Ar
Ag/Se (5 h in total, 2.5 h each) annealed at 350 °C for 1 h in vacuum.
Standard patterns of AgSb(S,Se)2(pdf#46-1355), AgSbSe2(pdf#12-
0379), AgSbS2(17-0456) are included
selenization or in two steps, one before and another after
selenization, keeping the total thickness of Ag constant.
Dip-selenization was done for 3–5 h, either as single or two
consecutive dips. Each type of precursor material was
deposited as follows:
2.1.1 Sb2S3 thin films
These films were deposited on clean glass substrates by
chemical bath deposition. For this, first 0.650 g of SbCl3
was dissolved in 2.5 ml of acetone in a 100 ml beaker, and
then 25 ml of 1 M Na2S2O3 solution was added followed
by 72.5 ml of preheated deionized water at 40 °C, and the
solution was mixed for 30 s [6]. Clean glass substrates
were placed horizontally on a Petri dish and the solution
was poured to it and maintained at 40 °C. After three
consecutive deposits of 1 h each, uniform orange Sb2S3
thin films of *700 nm thickness were obtained. The
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Fig. 5 High-resolution spectrum of a Ag-3d, b Sb-3d, c S-2p and d Se-3d
thickness was measured using a confocal microscope
(ZEISS, Axio CSM 700).
2.1.2 Ag thin films
On Sb2S3 thin film, silver was coated by thermal evapo-
ration. Silver wire of 99.999 % purity was evaporated onto
Sb2S3 coated glass substrates (glass/Sb2S3) placed in a high
vacuum system (INTERCOVAMEX-TE12P). Thickness of
silver layer was measured using a quartz crystal thickness
monitor incorporated in the deposition system. In one case,
100 nm of silver was deposited in one step on Sb2S3 (glass/
Sb2S3/Ag). In other case, after 50 nm coating of Ag, the
glass/Sb2S3/Ag thin films were selenized (glass/Sb2S3/Ag/
Se) followed by another 50 nm coating (glass/Sb2S3/Ag/
Se/Ag). The precursor layer structures are schematically
represented in Fig. 1.
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J. O. González et al.
2.1.3 Selenization
The precursor layer structures of Sb2S3/Ag were selenized
using a solution method at room temperature conditions.
Selenization bath was prepared by dissolving 2.2 ml of
acetic acid (25 % volume) in 40 ml of deionized water.
Then, 7 ml of 0.1 M Na2SeSO3 was dissolved in 33 ml of
deionized water and finally both solutions were mixed in a
100 ml beaker [6]. For glass/Sb2S3/Ag/Se multilayers, the
selenium dipping times were 3 and 4 h, whereas for glass/
Sb2S3/Ag/Se/Ag/Se the dipping time was 5 h, double dip-
ping of 2‘ h each, after each silver deposition.
2.1.4 Heating
The selenized multilayers were heated at different condi-
tions. Glass/Sb2S3/Ag/Se was heated at 350 °C for 20 min,
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Photovoltaic structures using AgSb(SxSe1-x)2
Fig. 6 Depth profile of Ag-3d,
Sb-3d, S-2p, Se-3d and Si-2p
in low vacuum (10-3 torr), followed by a post-heat treat-
ment at 325 °C for 2 h in Argon. In the case of Glass/
Sb2S3/Ag/Se/Ag/Se layered structure, the heating was done
at 350 °C for 1 h in Argon (TM Vacuum Products Model
No V/IG-803-14).
2.2 Fabrication of PV structures (glass/SnO2:F/CdS/
AgSb(SxSe1-x)2/C/Ag)
Preparation of PV structures involved various steps. Firstly,
CdS thin films were deposited by chemical bath deposition
from a solution containing CdCl2, TEA, NH4OH and
thiourea at 70 °C for 20 min [7] on SnO2:F coated glass
substrates (Pilkington). Then, AgSb(SxSe1-x)2 thin films
were grown at different conditions on the CdS layers, by
varying selenization time as 3, 4 and 5 h as mentioned
earlier. To study the effect of CdS thickness on the pho-
tovoltaic performance of the PV structures, the CdS
deposition time was varied as 90, 120 and 150 min. Fur-
ther, another set of PV structures were prepared, in which,
CdS thin films with 20 min of deposition time were
annealed at 400, 450 and 500 °C for 1 h in air prior to the
deposition of the absorber material.
2.3 Characterization
XRD patterns of the thin films were recorded by PANa-
lytical (Empyrean) diffractometer using Cu Ka1 radiation
(k = 1.54059 Å). The scan range (2h) was 10°–70°.
Morphological features were examined using scanning
electron microscope FEI Nova NanoSEM 200. Surface and
depthwise composition was determined by X-ray photo-
electron spectrometer thermo scientific XPS (K-alpha
model). The optical transmittance (T) and the specular
reflectance (R) of the thin films were recorded using a
Shimadzu UV-1800 spectrophotometer in the wavelength
range of 300–1,100 nm. Electrical measurements were
done using Keithley 6487 Picoammeter/Voltage source
interfaced with a computer. For the DC conductivity
measurements, the contacts used were two planar elec-
trodes of 3 mm in length and 3 mm in separation using
carbon paint. Hall effect measurements were done using
Van der Pauw Ecopia HMS-3000 system. The J–V char-
acteristics of the PV structures were measured in the dark
and illumination under an AM1.5 radiation of intensity
90 mW cm-2 from an Oriel solar simulator. For measuring
current–voltage characteristics, ohmic contacts were made
using carbon and silver suspensions (SPI SuppliesÒ). The
contact area was 0.06 cm2.
3 Results and discussion
Figures 2 and 3 show the XRD patterns of the precursor
layers and the thin films formed after heating at different
conditions. In Fig. 2a, b, all the diffraction peaks present in
pristine samples of glass/Sb2S3/Ag/Se and glass/Sb2S3/Ag/
Se/Ag/Se match orthorhombic Ag2Se phase (PDF#24-
1041) as marked. This implied that by dipping Na2SeSO3
bath, Ag layer reacted with selenium to form Ag2Se, being
chemical bath deposited pristine Sb2S3 thin film was
amorphous [6]. Figure 3a, b shows the patterns for the thin
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Fig. 7 Scanning electron micrographs of multilayers of a glass/
Sb2S3/Ag/Se (3 h) annealed at 350 °C for 20 min in vacuum followed
by 325 °C for 2 h in Ar, b glass/Sb2S3/Ag/Se (4 h) annealed at
films formed after heating glass/Sb2S3/Ag/Se(3 h) and
glass/Sb2S3/Ag/Se(4 h) at 350 °C for 20 min in vacuum,
followed by a post-heat treatment at 325 °C for 2 h in
Argon. Figure 3c depicts the pattern for the multilayers of
glass/Sb2S3/Ag/Se/Ag/Se(5 h) heated at 350 °C for 1 h in
Ar. In all cases, the diffraction peaks located at 2h values of
27.04°, 31.30°, 44.87°, 53.12° and 55.62° showed a con-
sistent shift with respect to those of standard AgSbSe2
(pdf#12-0379, solid vertical line) and AgSbS2 (pdf#17-
0456, dotted vertical line in the figure) peaks. This shift can
be due to the formation of AgSb(SxSe1-x)2 solid solution.
From the figures, the thin films formed after heating the
diffraction patterns showed the presence of the solid
solution as major phase independent of the precursor
configuration and the heating conditions. The value of ‘‘x’’
was estimated using the empirical relation as stated by
Vegard’s law [6, 8]. Applying this law,
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J. O. González et al.
350 °C for 20 min in vacuum followed by 325 °C for 2 h in Ar, and
c glass/Sb2S3/Ag/Se/Ag/Se (5 h in total, 2.5 h each) annealed at
350 °C for 1 h in vacuum, at a magnification of 910,000
aAgSb(S,Se)2 = (x)aAgSbS2 ? (1-x)aAgSbSe2, in which ‘‘a’’ is
the lattice constant. Using this relation, the value of ‘‘x’’
was determined as 0.53, 0.58 and 0.61, respectively, for
AgSb(SxSe1-x)2 thin films formed by heating glass/Sb2S3/
Ag/Se(3 h), glass/Sb2S3/Ag/Se(4 h) and glass/Sb2S3/Ag/
Se/Ag/Se(5 h). Further, in all samples, peaks indexed (002)
and (400) match the standard pattern of monoclinic
AgSb(S,Se)2 (pdf#46-1355). Also, minor peaks represented
by (200), (120), (310), (221), (410), (420), (520) and (630)
planes indicate the presence of un-reacted Sb2S3 of
orthorhombic structure (pdf#42-1393), as indicated by
solid squares in the figures.
Average crystallite size of the AgSb(SxSe1-x)2 thin films
formed was evaluated using the line broadening analysis of
the diffraction patterns given in Fig. 3. Considering the
effects of the particle size and the lattice strain in the dif-
fracted peak broadening, the Williamson–Hall plot [8] in
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Photovoltaic structures using AgSb(SxSe1-x)2
Fig. 8 Optical characteristics for AgSb(SxSe1-x)2 thin films formed by 3, 4 and 5 h selenium dipping: a transmittance (%T) and reflectance
(%R) spectra; b optical absorption coefficient; c band gap analyses
Fig. 9 Photocurrent response for AgSb(SxSe1-x)2 thin films for 3, 4
and 5 h Se
which (bcosh)/k vs. (sinh)/k were plotted as given in the
insets if Fig. 2, b and k being the full width at half maxi-
mum (FWHM) of the diffraction peak located at 2h and the
X-ray wavelength (1.54059 Å), respectively. By fitting a
straight line to each plot, the inverse of the intercept on
(bcosh)/k axis in each case gave the crystalline grain
diameter (D). From the slope of the fitted line, the value of
the microstrain (e) was evaluated. The plots were drawn by
assigning Lorentzian shape for the prominent diffraction
peaks from (111), (200) and (220) planes. Grain size and
microstrain values obtained from the plot were in the range
of 20–22 nm and 0.001–01 the thin films.
Figure 4 shows the survey scan XPS spectra of
AgSb(SxSe1-x)2 sample with x = 0.61. The peak patterns
corresponding to the presence of Ag, Sb, S and Se elements
were identified, at the surface of the sample. The C-1s peak
detected was that of adventitious carbon due to the exposure
of the sample to the atmosphere. This C-1s peak at binding
energy (B.E) 284.6 eV, was used to correct the spectral shift
due to the surface charging effect in addition to the charge
compensation by the flood gun implemented in the spec-
trometer. Figure 5a–d shows the high resolution spectra for
Ag-3d, Sb-3d, S-2p and Se-3d core levels, respectively,
recorded after etching the surface for 10 s. The Shirley
method was used to compute the background of these high
resolution spectra. In Fig. 5a, we observed that the Ag-3d
spectrum consisted of the spin–orbit doublet of Ag-3d5/2 at
367.72 eV and Ag-3d3/2 at 373.72 eV. When the binding
energy values were compared with those of elemental Ag-
3d doublet [Ag-3d5/2(368.3 eV) and Ag-3d3/2(374.3 eV)
[9]], the peaks showed a chemical shift indicating the for-
mation of a compound. According to our previous work [6]
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J. O. González et al.

Fig. 10 J–V characteristics of

photovoltaic structures glass/
SnO2:F/CdS/AgSb(SxSe1-x)2/C/
Ag for x = 0.53, 0.58 and 0.61
with a CdS deposition time of
20 min: a represents a typical
dark characteristic of the PV
structures, b under illumination

Fig. 11 J–V characteristics of

photovoltaic structures glass/
SnO2:F/CdS/AgSb(SxSe1-x)2/C/
Ag for x = 0.61, in which CdS
deposition time was 20 min and
an annealing at 400, 450 and
500 °C was applied to the CdS
prior to the deposition of the
absorber: a represents a typical
dark characteristic of the PV
structures, b under illumination

and other reports on B.E values for binary compounds such
as AgO (367.2 eV) and Ag2Se (367.6 eV) [9], we assigned
the shift to the formation of AgSb(SxSe1-x)2. Peaks from
Sb-3d, S-2p and Se-3d were de-convoluted using Gaussian–
Lorentzian sum function. Figure 5b illustrates the B.E.
curve for Sb-3d, two major peaks located at binding ener-
gies 528.73 and 538.08 eV corresponding to Sb-3d5/2 and
Sb-3d3/2, respectively. By comparing the B.E. values with
those reported for elemental Sb-3d (528 and 537 eV) and
our previous work, the shift may be due to the formation of
AgSb(SxSe1-x)2 [6]. There were also two weak peaks
labeled I (527.59 eV) and II (536.92 eV) that can be
assigned to Sb-3d5/2 and Sb-3d3/2, respectively. Figure 5c
shows the high resolution spectrum for S-2p. After de-
convolution of the curve, two closely spaced peaks at
161.26 and 162.43 eV were assigned to S-2p3/2 and S-2p1/2

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Photovoltaic structures using AgSb(SxSe1-x)2
doublet; another doublet at 159.4 and 165.5 eV, respec-
tively, match with those of Se-2p3/2 and Se-2p1/2. Also, the
presence of selenium peaks was confirmed by the Se-3d
doublet located at 53.58 and 54.39 eV in the deconvoluted
spectrum given in Fig. 5d. As in the case of Sb and Ag
peaks, both S-2p and Se-2d the B.E values showed chemical
shifts which did not coincide with those of any of their
binary compounds. This implied the formation of a
AgSb(SxSe1-x)2 in agreement with the XRD results. Fig-
ure 6 shows the depth profile of the sample where the
presence of Ag, Sb, S and Se was detected uniformly
throughout the thin film from the surface to the glass
substrate.
Morphology of AgSb(SxSe1-x)2 thin films formed at 3, 4
and 5 h of Se, are depicted in Fig. 7a–c, respectively. From
micrograph (Fig. 7a), we noticed compact structures of
interconnected spherical grains. Similar grains with surface
porosity were observed in micrograph (Fig. 7b) for the thin
films formed by 4 h dip-selenization, while for the films
formed by 5 h dip, compact spherical grains of smaller size
were seen (micrograph Fig. 7c).
Figure 8a shows the optical transmission (%T) and
reflection (%R) spectra of AgSb(SxSe1-x)2 thin films
formed after heating 3, 4 and 5 h dip-selenized precursor
samples recorded over a wavelength range of 300–100 nm.
Using the transmission (%T) and reflection (%R) values
from the spectra, absorption coefficient (a) at each wave-
length was computed using the following relation [10]:
" #
1 ð1  RÞ2
a ¼ In ð1Þ
d T
where, d is the thin film thickness and the value was
*1,000 nm for the thin films. Figure 8b demonstrates the
absorption spectra for the AgSb(SxSe1-x)2 thin films. From
the spectra, the optical band gap values of the thin films
were evaluated using the formula [10]:
ðahmÞ1=2 ¼ Aðhm  Eg Þ ð2Þ
where Eg is the optical band gap for an allowed indirect
transition, a is the absorption at frequency m and A is a
constant. To estimate the Eg values, the Tauc plot of (ahm)1/2
vs. hm was drawn for all the thin films as given in Fig. 8c,
showing a good linear fit for n = 1/2. This implied that the
fundamental optical absorption in AgSb(SxSe1-x)2 thin
films was dominated by an indirect allowed transition. From
these curves, the value of band gap for each sample was
estimated by extrapolating the linear region of the respec-
tive plot to a = 0, as shown in the figure. The value was
1.0 eV for AgSb(SxSe1-x)2 thin films of x = 0.53 and
x = 0.58, respectively, and 1.1 eV for the sample with
x = 0.61. The increase in the band gap from 1.0 to 1.1 eV
as x increased was due to the lower effective ionic radium of
sulfur (1.84 Å) than that of selenium (1.98 Å) reducing the
lattice parameter of AgSb(SxSe1-x)2 and thus lowering the
valance band maximum [11–13].
Figure 9 shows the photocurrent response curves of
AgSb(SxSe1-x)2 thin films corresponding to x = 0.53, 0.58
and 0.61, respectively. To measure the photo-generated
current, a bias voltage of 5 V was applied and the current
through the sample was measured for a period 10 s under
dark (Io), 20 s under illumination (I) and 10 s after
switching off the illumination, respectively. Samples with
x = 0.53 and 0.58 showed a dark conductivity in the order
of *10-3 (X cm)-1. In the case of sample with x = 0.61,
the conductivity increased to 10-1 (X cm)-1. We observed
an improvement in the electrical properties of AgSb(Sx-
Se1-x)2 thin films as the Se deposition time was increased.
Hot probe test was performed on the samples to determine
the type of conductivity, all the samples showed p-type
conductivity [6]. The carrier concentrations evaluated from
the Hall effect measurements were 9 9 1013, 7.8 9 1014
and 4.6 9 1015 cm-3, respectively, for samples with
x = 0.53, 0.58 and 0.61 correspondingly. Specific studies
on electrical conduction mechanism in AgSbSe2-based
alloys or solid solutions were not reported so far. However,
in analogous with other sulfo-selenides such as CuIn(Sx,
Se1-x)2 [11] and CZT(SxSe1-x)4 [12], the p-type conduc-
tivity of AgSb(SxSe1-x)2 may be due to the presence of
fully ionized S2- and Se2- interstitials as prominent
defects. In our samples as x, S/(S ? Se), increased, the
presence of S2- could also be increased, resulting in higher
hole concentrations (two orders) as evidenced from the
Hall effect measurements, and hence the conductivity
raised by two orders of magnitude.
Based on the above studies, photovoltaic structures
were fabricated using AgSb(SxSe1-x)2 thin films as
absorber material and CdS thin films as window material.
Figure 10 shows the J–V characteristics of photovoltaic
structures of glass/SnO2:F/CdS/AgSb(SxSe1-x)2/C/Ag for
x = 0.53, 0.58 and 0.61 and CdS of deposition time
20 min, measured under dark and illumination conditions.
The dark characteristics, demonstrated typical diode
behavior of rectification of the PV structures as seen from
Fig. 10a. Figure 10b shows the photovoltaic behavior of
the structures under illumination. The PV parameters such
as Voc, Jsc, FF and the conversion efficiency g were
evaluated from the curves. The respective values were in
the range of: Voc = 410–490 mV, Jsc = 5.17–7.71
mA cm-2 and FF = 0.32–0.44. The better conversion
efficiency achieved was 1.42 %, which corresponds to the
PV structure with x = 0.61. The improvement in effi-
ciency may be attributed to the reduction of ohmic losses
which depend directly on the electrical properties of the
absorber material (the higher the conductivity, the lower
the ohmic losses).
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For further studies, PV structures glass/SnO2:F/CdS/
AgSb(SxSe1-x)2/C/Ag for x = 0.61 were fabricated, using
CdS thin films annealed at 400, 450 and 500 °C for 1 h in
air, prior to the absorber layer deposition. Figure 11 shows
the J–V characteristics of the photovoltaic structures using
the pre-annealed CdS layers, measured under dark and
illumination conditions. Again, the typical diode behavior
of the PV structures was displayed as given in Fig 11a. The
performance of the PV cells under illumination is illus-
trated in Fig. 11b along with the values of photovoltaic
parameters such as Voc, Jsc, FF and g. From the analysis of
the J-V curves, we observed that as the CdS annealing
temperature increased, the PV device performance
decreased. The deterioration in the performance may be
due to the CdS thinning at higher temperatures which can
create current leakage between the TCO and the absorber
material [14]. The best values were obtained for the device
formed using 400 °C annealed CdS thin film, giving
Voc = 520 mV, Jsc = 9.70 mA cm-2, FF = 0.50 and
g = 2.77 %. Hence, due to pre-annealing of CdS, the PV
conversion efficiency was increased from 1.42 to 2.77.
Mathew et al. [14] reported the effect of CdS annealing on
the device performance of CdS/CdTe of PV structures.
When CdS thin films were annealed in oxygen, a barrier
against diffusion between CdS/CdTe is created (diffusion
hardening), avoiding the formation of undesired phases
such as CdS1-yTey which lowers the band gap of CdS
reducing the amount of solar radiation that reaches the
absorber, and thus reducing photocurrent and device per-
formance. Also, it was proven that annealing CdS in oxy-
gen enhances the device performance, specially the open
circuit voltage [14]. In our case, the annealing might play
the similar role of ‘grain hardening’ effect resulting an
interlayer diffusion barrier in CdS/AgSb(SxSe1-x)2 junc-
tion, thus avoiding the formation of alloys which would be
detrimental for the PV performance.
It should be pointed out that the optimization of the cell
structure and material performance were yet to be done by
incorporating wider band gap oxide window layers and
also, by taking passivation and antireflection measure-
ments. However, the initial results may open up the scope
of AgSb(SxSe1-x)2 thin films as PV absorber as well as the
hybrid technique using CBD, dip-selenization and metal
evaporation techniques for their deposition for large-scale
industrial production of solar cells.
4 Conclusions
In this work, we prepared AgSb(SxSe1-x)2 thin films by
heating multilayers of glass/Sb2S3/Ag/Se and glass/Sb2S3/
Ag/Se/Ag/Se at different heating conditions. Different
techniques were used to determine the structure,
123
J. O. González et al.
morphology, optical and electrical properties of these thin
films. XRD showed the formation of AgSb(SxSe1-x)2 thin
films, with x = 0.53, 0.58 and 0.61 for 3, 4 and 5 h of Se
dipping, respectively. The thin films showed indirect band
gap (Eg) value between 1.0 and 1.1 depending on the
x value. Dark conductivities were in the range of 10-3–
10-1 (X cm)-1 for the thin films. The AgSb(SxSe1-x)2 thin
films of various ‘x’ formed at different conditions were
incorporated in PV structures using CdS as window layer.
Also, we studied the effect of CdS annealing (prior to the
absorber deposition) on the performance of the PV struc-
tures. The best J–V characteristics were for the PV struc-
ture with x = 0.61 and an annealed CdS at 400 °C for 1 h
in air showing Voc = 520 mV, Jsc = 9.70 mA cm-2,
FF = 0.50 and g = 2.77 %. Further research is being
developed to improve the Voc, Jsc and FF of the PV
structures and the conversion efficiency.
Acknowledgments The authors are thankful to PAICYT
2010-UANL, Mexico, PROMEP-Mexico and SEP-CONACYT-
Mexico for the financial assistance, FCQ for UV–Vis–NIR mea-
surements. One of the authors, G. Jorge Oswaldo is grateful to CO-
NACYT-Mexico for providing research fellowship.
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