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Materials Research Bulletin 48 (2013) 1939–1945

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Materials Research Bulletin

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AgSb(SxSe1x)2 thin films for solar cell applications

J.O. González a, S. Shaji a,b, D. Avellaneda a,b, A.G. Castillo a, T.K. Das Roy a, B. Krishnan a,b,*
a
Universidad Autónoma de Nuevo León, Facultad de Ingenierı´a Mecánica y Eléctrica, San Nicolás de los Garza, Nuevo León 66450, México
b
Universidad Autónoma de Nuevo León-CIIDIT, Apodaca, Nuevo León, México

A R T I C L E I N F O A B S T R A C T

Article history: Silver antimony sulfoselenide (AgSb(SxSe1x)2) thin films were prepared by heating glass/Sb2S3/Ag layers
Received 20 December 2012 after selenization using sodium selenosulphate solution. First, Sb2S3 thin films were deposited on glass
Accepted 23 January 2013 substrates from a chemical bath containing SbCl3 and Na2S2O3. Then Ag thin films were thermally
Available online 30 January 2013
evaporated onto glass/Sb2S3, followed by selenization by dipping in an acidic solution of Na2SeSO3. The
duration of selenium dipping was varied as 30 min and 2 h. The heating condition was at 350 8C for 1 h in
Keyword: vacuum. Analysis of X-ray diffraction pattern of the thin films formed after heating showed the
A. Thin films
formation of AgSb(SxSe1x)2. Morphology and elemental analysis were done by scanning electron
microscopy and energy dispersive X-ray detection. Depth profile of composition of the thin films was
performed by X-ray Photoelectron Spectroscopy. The spectral study showed the presence of Ag, Sb, S, and
Se, and the corresponding binding energy analysis confirmed the formation of AgSb(SxSe1x)2.
Photovoltaic structures (PV) were prepared using AgSb(SxSe1x)2 thin films as absorber and CdS thin
films as window layers on FTO coated glass substrates. The PV structures were heated at 60–80 8C in air
for 1 h to improve ohmic contact. Analysis of J–V characteristics of the PV structures showed Voc from 230
to 490 mV and Jsc 0.28 to 5.70 mA/cm2, under illumination of AM1.5 radiation using a solar simulator.
ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction
For the last few decades intense research has been going on
worldwide to achieve low cost thin film photovoltaic technology
by developing new thin film materials composed of abundant and
non-toxic elements, using low cost deposition techniques. In this
facet, CZTS (optical band gap, Eg = 1.5 eV) is the one that has been
gained attention [1,2] recently. However, there are other materials
such as CuSbS2 (Eg = 1.5 eV), SnS (Eg = 1.1 eV), Cu2SnS3
(Eg = 1.15 eV), AgSbSe2 (Eg = 1 eV) which were suggested as
promising candidates for solar cell applications due to their ideal
optical properties as well as relatively low cost preparation
methods [3–6]. Among these, AgSbSe2 was proved its perspective
as an absorber material in a photovoltaic structure glass/SnO2:F/n-
CdS/Sb2S3/p-AgSbSe2/Ag-print, showing Voc = 550 mV and
Jsc = 2.3 mA/cm2 under 2000 W/m2 illumination [7,8]. AgSbSe2
has an optical band gap of 1 eV and a high absorption coefficient
of 104 cm1 [6]. This material commonly crystallizes in NaCl
structure, in which Ag and Sb randomly occupy the same
crystallographic Wyckoff position [9]. Even though AgSbSe2 is
known to be a thermoelectric material with a narrow band gap of
* Corresponding author at: Universidad Autónoma de Nuevo León, Facultad de
Ingenierı́a Mecánica y Eléctrica, San Nicolás de los Garza, Nuevo León 66450,
México. Tel.: +52 8114920380.
E-mail addresses: kbindu_k@yahoo.com, bkrishnan@fime.uanl.mx (B. Krishnan).
0.5 eV [10], in the thin film form the transmittance and reflectance
measurements showed an optical band gap of nearly 1 eV [6,8].
Formation of amorphous AgSbSe2 thin films by thermal evapora-
tion and their transition to polycrystalline form was reported
[9,11]. Preparation of p-type AgSbSe2 thin films by heating
multilayers of glass/Sb2S3/Ag2Se in close contact with a chemically
deposited Se thin film at 300 8C for 30 min in N2 was described [7].
Our group reported the formation of AgSbSe2 and AgSb(S,Se)2 thin
films by heating multilayers of glass/Sb2S3/Ag2Se/Se/Ag and glass/
Sb2S3/Ag2Se/Ag respectively [6]. With the purpose to explore full
potential of this material, for PV application, further studies are
needed to improve their optical and electrical properties and thus,
device performance.
In this paper, we report the preparation of AgSb(SxSe1x)2 alloy
thin films via heating selenized glass/Sb2S3/Ag layer structures by
dipping in sodium selenosulphate solution. First, Sb2S3 thin films
were deposited by chemical bath deposition onto which Ag was
thermally evaporated. Then, the glass/Sb2S3/Ag layers were
directly dipped in Na2SeSO3 solution (pH 4.5) for different
durations. These selenized glass/Sb2S3/Ag samples were heated
at 350 8C for 1 h in vacuum. The thin films formed at various
conditions were characterized using X-ray diffractometer (XRD),
X-ray Photoelectron Spectrometer (XPS), Scanning Electron
Microscope (SEM) associated with an Energy Dispersive X-ray
detector (EDX), UV–vis-NIR spectrophotometer and photocurrent
measurement set up. Further, PV structures using AgSb(SxSe1x)2
thin films as absorber and chemical bath deposited CdS as window

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1940 J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945

layer were fabricated. We analyzed the J–V characteristics of the of 500 nm thickness were obtained. The thickness was measured
PV structures formed after a post heating treatments. using a confocal microscope (ZEISS, Axio CSM 700).

2. Experimental 2.1.2. Ag thin films

2.1. Glass/Sb2S3/Ag layer structures and their selenization
2.1.1. Sb2S3 thin films
These films were deposited on cleaned corning glass substrates
of dimension 7.5  2.5 cm. First 0.650 g of SbCl3 were dissolved in
2.5 ml of acetone in a 100 ml beaker, then 25 ml of 1 M Na2S2O3
solution was added followed by 72.5 ml of preheated deionized
water at 40 8C, and the solution was mixed for 30 s [6]. The glass
substrates were placed horizontally on a Petri dish and the solution
was poured to it and maintained the bath at 40 8C. After 2
consecutive deposition of 1 h each, uniform orange Sb2S3 thin films
On Sb2S3 thin film, 70 nm of silver was coated by thermal
evaporation. Silver wire of purity of 99.999% 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.
2.1.3. Selenization
The samples of glass/Sb2S3/Ag were selenized using a solution
method at room temperature conditions. Selenium bath was
prepared by dissolving 2.2 ml of acetic acid (25% volume) in 40 ml
of deionized water at room temperature. Then, 7 ml of 0.1 M

Fig. 1. XRD patterns for multilayers of (a) as-deposited glass/Sb2S3/Ag, (b) as-deposited glass/Sb2S3/Ag/Se (2 h), (c) glass/Sb2S3/Ag/Se (½h) annealed at 350 8C for 1 h in
vacuum and (d) glass/Sb2S3/Ag/Se(2 h) annealed at 350 8C for 1 h in vacuum. Standard patterns Ag (pdf#04-0783), Ag2Se (pdf#24-1041), AgSb(S,Se)2 (pdf#46-1355), AgSbSe2
(pdf#12-0379), AgSbS2(17-0456) are included.
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J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945
Na2SeSO3 was dissolved in 33 ml of deionized water and finally
both solutions were mixed in a 100 ml beaker [6]. Glass/Sb2S3/Ag
multilayers were placed vertically in the solution for different
durations of ½ and 2 h.
2.2. Heating
The selenized multilayers, glass/Sb2S3/Ag/Se, were heated at
350 8C for 1 h, in low vacuum (103 torr), in a vacuum furnace (TM
Vacuum products model No V/IG-803-14).
2.3. Fabrication of the PV structures glass/SnO2:F/CdS/AgSb(SxSe1x)2/
C be due to the formation of a solid solution of AgSb(SxSe1x)2 by
For this, first CdS thin films were deposited from a solution
containing CdCl2, TEA, NH4OH and thiourea at 70 8C for 20 min [12]
on SnO2:F coated glass substrates. These thin films were annealed
at 400 8C for 1 h in vacuum prior to the deposition of the absorber
films. Then, the samples of glass/SnO2:F/CdS were coated with
Sb2S3 and Ag followed by dipping in Na2SeSO3 solution for 2 h as
described earlier, to produce PV structures using (AgSb(SxSe1x)2 of
x = 0.51, the thin films of better photosensitivity. These multilayer
structures were heated at 350 8C for 1 h in low vacuum
(4  103 torr). For measuring current-voltage characteristics,
ohmic contacts were made using carbon suspension (SPI Sup-
plies1). The area of contact varies from 0.04 to 0.06 cm2. The PV
structures using AgSb(SxSe1x)2 absorber formed by ½ and 2 h
selenium dipping conditions were post-heated at different
temperatures 60–80 8C in air for 1 h. The photovoltaic parameters
were evaluated, and thus the performance.
2.4. Characterization
X-ray diffraction (XRD) patterns of the thin films were recorded
by PANalytical (Emperian) diffractometer using Cu Ka1 radiation
(l = 1.54059 Å). The scan range (2u) was 10–708. X-ray photoelec-
tron spectroscopy was done using thermo scientific XPS (K-alpha).
Morphological studies were done using scanning electron micro-
scope FEI Nova NanoSEM 200, elemental analysis using an energy
dispersive X-ray detector associated with the SEM. The optical
transmittance (T) and specular reflectance (R) of the films were
recorded using a Shimadzu 3100 PC spectrophotometer in the
250–2500 nm wavelength range. Electrical measurements were
carried out using Keithley 6487 Picoammeter/Voltage source
interfaced with a computer. For the DC conductivity measure-
ments the contacts used were two planar electrodes of 3 mm in
length and 4 mm in separation using carbon paint. The J–V
characteristics of the PV structure under dark and illuminated
conditions were measured using carbon contact. Solar cell
characterization was performed using an Oriel solar simulator
under an AM1.5 radiation of intensity 1000 W/m2.
3. Results and discussion
Fig. 1(a) shows the XRD pattern of as-deposited multilayers of
glass/Sb2S3/Ag. From the figure, well defined peaks at 2u = 38.158,
44.318 and 64.458 match the standard pattern of cubic silver
(pdf#04-0783) corresponding to crystallographic planes: (1 1 1),
(2 0 0) and (2 2 0) respectively. No peaks of Sb2S3 were observed
since as-deposited Sb2S3 thin film was amorphous [13]. Fig. 1(b)
displays the diffraction pattern of glass/Sb2S3/Ag after dipping
in Na2SeSO3 solution for 2 h (glass/Sb2S3/Ag/Se (2 h)). In this
case, all the silver peaks disappeared and new peaks were
detected at 2u = 22.968, 26.808, 30.938, 32.768, 33.498, 34.738,
36.988, 40.048, 42.658, 43.368, 45.038, 45.358, 46.748 and 48.378.
These peaks coincide with standard pattern of orthorhombic Ag2Se
1941
(pdf#24-1041 Naumannite) as indicated by (0 0 2), (1 1 1), (1 0 2),
(1 2 0), (1 1 2), (1 2 1), (0 1 3), (0 3 1), (1 1 3), (2 0 1), (0 3 2), (2 1 1),
(0 0 4) and (1 2 3) planes respectively in the figure. This implies the
formation of Ag2Se thin film by the reaction of silver layer with
selenium from the Na2SeSO3 bath during the dipping process. Also,
relative intensities of the experimental pattern of Ag2Se follow that
of the standard pattern. Fig. 1(d) shows the diffraction pattern of
glass/Sb2S3/Ag/Se (2 h) after heating at 350 8C 1 h in vacuum. In the
figure, we can observe distinct peaks at 2q = 26.948, 31.208, 44.848,
53.128 and 55.608. When the experimental pattern was compared
with that of the standard pattern of the possible phase of AgSbSe2,
we found a consistent right shift in 2q for all the peaks. This might
comparing with that of cubic AgSbSe2 (pdf#12-0379, solid vertical
line) and cubic AgSbS2 (pdf#17-0456, dotted line). To find the
value of x, we applied the empirical relation stated by Vegard’s law
[14] in our experimental data. The law states that in an alloy, the
lattice constant is approximately equal to the composition-
weighted average of the lattice constant of the pure materials
[14]. Using this law, aAgSb(S,Se)2 = (x)aAgSbS2 + (1x)aAgSbSe2, in
which ‘‘a’’ is the lattice constant. From this empirical relation,
the value of x was determined as 0.51. Shift in the case of typical
(1 1 1) peak is shown in the inset of the figure.
Fig. 1(c) shows the diffraction pattern recorded after heating
glass/Sb2S3/Ag/Se (½h) at 350 8C 1 h in vacuum. Analysis of the
pattern explained that the thin film formed consists of two phases,
cubic AgSb(SxSe1x)2 and monoclinic AgSb(S,Se)2. From the figure,
the major peaks at 2u = 26.928, 31.218, 44.818 corresponds to the
formation of AgSb(SxSe1x)2 as the primary phase marked by
planes: (1 1 1), (2 0 0) and (2 2 0), respectively. The value of x was
estimated as 0.52 from the shift in 2u as given in the inset. The
minor peaks detected at 2u = 13.558, 25.638, 27.628 and 31.948
were that of AgSb(S,Se)2 (pdf#46-1355) as marked by (0 0 2),
(1 1 2), (4 0 0) and (2 0 4) planes, secondary phase in the thin film.
Average crystallite size of the AgSb(SxSe1x)2 thin films formed
was evaluated using the line broadening analysis of the diffraction
patterns given in Fig. 1(c) and (d). The diffraction peak broadening
can be due to small grain size as well as micro strain present in the
thin films [14]. The size and strain effects can be separated by the
Williamson–Hall plot [14] in which (b cos u)/l vs (sin u)/l are
plotted, b and l being the full width at half maximum (FWHM) of
the diffraction peak located at 2u and the X-ray wavelength
(1.54059 Å) respectively. By fitting a straight line to this plot, the
inverse of its intercept on (b cos u)/l axis gives the ratio of the
crystalline grain diameter (D) from which the value of D is
Fig. 2. XPS survey spectrum of multilayers of glass/Sb2S3/Ag/Se (2 h) annealed at
350 8C for 1 h in vacuum.
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1942 J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945

Fig. 3. High resolution spectrum of (a) Ag 3d, (b) Sb 3d, (c) S 2p and (d) Se 3d.

extracted. From the slope of the line, the value of the microstrain
(e) is evaluated. The Williamson–Hall plots for AgSb(SxSe1x)2 thin
films formed by heating precursor samples of glass/Sb2S3/Ag/
Se(½h) and glass/Sb2S3/Ag/Se(2 h) are given in the insets of Fig. 1(c
and d) respectively. The graphs were drawn by assigning
Lorentzian shape for the prominent diffraction peaks from
(1 1 1), (2 0 0) and (2 2 0) planes. Grain size and microstrain
evaluated from the plot were 34 nm and 3.5  103, 31 nm and
4.2  103 respectively for AgSb(SxSe1x)2 thin films formed by
heating 2 h and ½ h selenized samples.
Fig. 2 shows the survey scan XPS spectra of AgSb(SxSe1x)2
samples with x = 0.51. The binding energy peaks of Ag 3d, 3p, 3s, Sb
3d, 3p, S 2p and Se 3d, 3p, 3s were identified, confirming the
presence of these elements on the surface of the sample, along with
C1s which can be attributed to the exposure of the sample to the
atmosphere. The spectral shift due to the surface charging effect

Fig. 4. Depth profile of Ag 3d, Sb 3d, S 2p, Se 3d and Si 2p.

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J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945 1943

was corrected by taking C1s photoelectron peak at binding

energy (284.6 eV) as reference value, in addition to the charge
compensation by the flood gun associated with the spectrometer.
Fig. 3a–d show the high resolution scans of Ag 3d, Sb 3d, S 2p and
Se 3d respectively, the sample recorded after etching the surface
layer. The Shirley method was used to compute the background of
high resolution scans of Ag 3d, Sb 3d, S 2p and Se3d. Peaks from Sb
3d, S 2p and Se 3d were de-convoluted using the Gaussian–
Lorentzian sum function. In Fig. 3a, we can observe that the high
resolution scan of Ag 3d consists of two peaks at 367.98 and
373.98 eV which correspond to spin-orbit doublet of Ag 3d (Ag
3d5/2 and Ag 3d3/2, respectively). When these energies were
compared with the reported values for elemental Ag 3d5/
2(368.3 eV) and Ag 3d3/2(374.3 eV) [15], these peaks are shifted
towards lower energies, indicating the formation of a compound.
There are no reports of XPS studies on AgSb(SxSe1x)2 surface.
Hence, we looked for phases such as AgO (367.2 eV), Ag2Se
(367.6 eV) and Ag2S (366.9 eV), but no one matched. Thus, the
presence of these binary phases in our sample was ruled out. So,
we assigned these Ag peaks to the formation of AgSb(SxSe1x)2.
Fig. 3b shows the B.E curve for Sb 3d where the two strong peaks
located at 529.11 eV and 538.5 eV were assigned to Sb 3d5/2 and
Sb 3d3/2, respectively. From the curve, the peak positions are
shifted comparing with the values reported for Sb2S3 [15,16] and
this shift can be attributed to the formation of AgSb(SxSe1x)2.
Further, the presence of three peaks labelled as I (527.93 eV), II
(529.62 eV) and III (537.13 eV)respectively were attributed to Sb
3d5/2, O 1s and Sb 3d3/2. The result indicates that the surface is
oxidized slightly in the air. Fig. 3c shows the high resolution scan
for S 2p. Two strong peaks at 161.26 and 162.43 eV with an energy
separation of 1.17 eV were assigned to S 2p3/2 and S 2p1/2,
respectively. Fig. 3d shows the high resolution scan for Se 3d. Two
peaks at 53.58 and 54.39 eV are assigned to Se 3d5/2 and Se 3d3/2,
respectively. As in the case of Sb and Ag peaks, both S 2p and Se 2d
B.E values showed chemical shifts which were not corresponding
to their binaries, indicating the formation of a new compound
namely AgSb(SxSe1x)2. These results were in agreement with
the XRD results. Fig. 4 shows the depth profile of the sample
showing the presence of Ag, Sb, S and Se uniformly from the
surface to substrate. The peak of Si was originated from the glass
substrate.
Morphology of precursor samples (glass/Sb2S3/Ag/Se (2 h)
before heating) and AgSb(SxSe1x)2 thin films formed are depicted
in Fig. 5. From Fig. 5(a) the surface features of the precursor thin
film corresponds to irregular shaped Ag2Se grains formed by the
reaction of Ag and selenium during the dipping process, in
agreement with the XRD analysis. After heating, compact structure
with spherical interconnected grains were observed in both the
AgSb(SxSe1x)2 thin films which were formed by heating precursor
thin films of glass/Sb2S3/Ag/Se (½h) and glass/Sb2S3/Ag/Se (2 h)
respectively, in Fig. 5(b and c).
Atomic percentage of Sb/Ag and S/Se were estimated from EDX
measurements. In both thin films of AgSb(SxSe1x)2, Sb/Ag was
1.4 as expected since both had the same precursor layer thickness
of Sb2S3 and Ag. The S/Se ratios were 1.2 and 1.4 respectively for
the thin films formed by heating 2 h and 30 min selenized samples.
From these ratios, x was estimated as 0.55 and 0.58 respectively.
These values are close to the values obtained from the XRD
analysis.
Fig. 6(a) shows the optical transmission (%T) and reflection (%R)
Fig. 5. Scanning electron micrographs of multilayers of (a) as-deposited glass/Sb2S3/
spectra of AgSb(SxSe1x)2 thin films formed after heating 30 min
Ag/Se (2 h), (b) glass/Sb2S3/Ag/Se (½h) annealed at 350 8C for 1 h in vacuum and (c)
and 2 h selenium dipped precursor samples recorded in a glass/Sb2S3/Ag/Se (2 h) annealed at 350 8C for 1 h in vacuum, at a magnification of
wavelength range of 250–2500 nm. From the spectra, we observed 20,000.
that both thin films showed an average of 40% reflection and 50%
transmission in the non-absorbing region of 1200–2500 nm. Well
defined interference peaks in this wavelength range implied that
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1944 J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945

Fig. 6. Optical characteristics for AgSb(SxSe1x)2 thin films formed by ½ and 2 h selenium dipping: (a) transmittance (%T) and reflectance (%R) spectra, (b) optical absorption
coefficient, a, and (c) band gap analyses.

the thin film surface was uniform and specularly reflective. Using Hence analyzing our results, an effect of band gap engineering due
the transmission (%T) and reflection (%R) values from the spectra, to incorporation of S in cubic lattice of AgSbSe2 was achieved in the
absorption coefficient (a) at each wavelength was computed using present case.
the following relation [17]: Fig. 7 shows the photocurrent response curves of
AgSb(SxSe1x)2 thin films. The ohmic nature of carbon contact
" #
1 ð1  RÞ2 with the material is depicted in the corresponding I–V character-
a ¼ In (1) istics given in the inset. To measure the photo-generated current, a
d T
bias voltage of 20 V was applied and the current through the
where, d is the thin film thickness and the value was 800 nm for sample was measured in an interval of 20 s under dark (Io), under
both the thin films. illumination (I) and after switching off the illumination respec-
Fig. 6(b) shows the absorption spectra for the AgSb(SxSe1x)2 tively. Both samples showed a dark conductivity of same order
thin films. From the spectra the optical band gap of the thin films 103 (V cm)1. The photosensitivity of the thin films, which is
was evaluated using the formula [16]: defined as (IIo)/Io, was evaluated. The values were 0.7 and 0.8
respectively for AgSb(SxSe1x)2 thin films formed from 30 min and
n
ðahnÞ ¼ Aðhn  EgÞ (2) 2 h selenium dipped precursors. Hot probe test on the samples

where Eg is the optical band gap and n = 2, 1/2, 2/3 respectively for
allowed direct, allowed indirect and forbidden direct transitions, a
is the absorption coefficient at frequency n and A is a constant.
Fig. 6(c) demonstrates the Tauc plot of (a hn)n vs hn for both thin
films gives good linear fit for n = 1/2. This implied that the
fundamental optical absorption in AgSb(SxSe1x)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 respective plot to a = 0, as
shown in the figure. The values were 1 eV and 1.1 eV for
AgSb(SxSe1x)2 thin films of x = 0.51 and x = 0.52 respectively.
Optical band gap value for single phase AgSbSe2 thin films were
reported in a range of 0.9 eV depending on the preparation
conditions [8,11]. In the present work, the increment in Eg value
may be due to the incorporation of sulfur (x = 0.51) in the cubic
lattice of AgSbSe2 to form AgSb(SxSe1x)2. In monoclinic structured
AgSb(S,Se)2 thin films, the band gap was reported as 1.55 eV
corresponding to a direct allowed transition. For cubic AgSbS2 thin
films prepared by laser ablation, an indirect band gap was reported
as 1.3–1.4 depending on laser fluency and irradiation time [18]. Fig. 7. Photocurrent response for AgSb(SxSe1x)2 thin films for ½ and 2 h Se.
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J.O. González et al. / Materials Research Bulletin 48 (2013) 1939–1945
Fig. 8. J–V characteristics of the photovoltaic structure glass/SnO2:F/CdS/
AgSb(SxSe1x)2/C for Se (2 h) in which the CdS layer was heated at 400 8C for 1 h
in vacuum, in dark and under illumination with post heating the PV structure at
60 8C for 1 h in air prior to form the carbon contact.
indicated p-type conductivity in both. P-type conductivity of
AgSb(SxSe1x)2 may be due to the presence of defects of Ag or Sb
vacancies (VAg or VSb), considering the valance states of the
elements, Ag+, Sb3+ and S2/Se2. By comparing with the defects
present in other chalcogenides CuInSe2 (Cu1+, In3+ and Se2), Ag
substituted Sb sites (AgSb) and selenium interstitials [10] were also
expected. In our experiments, Ag/Sb ratio was 0.7 (EDX results)
resulting less probability for the presence of AgSb substitutional
defects and hence dominant p-type defects can be Se interstitials
[6].
Fig. 8 shows the J–V characteristics of the photovoltaic structure
glass/SnO2:F/CdS/AgSb(SxSe1x)2/C, using AgSb(SxSe1x)2 formed
by 2 h selenization and the C contact was post-heat treated at 60 8C
for 1 h in air, measured under dark and illumination conditions. In
dark, the PV structure showed a diode behaviour of rectification.
The PV parameters such as Voc, Jsc, FF and conversion efficiency (h)
were evaluated from the JV curve under illumination. The PV
structure showed an Voc = 410 mV, Jsc = 5.7 mA/cm2, FF = 0.35 and
h = 0.81%.
We prepared AgSb(SxSe1x)2 alloy thin films by heating
selenized glass/Sb2S3/Ag thin films using sodium selenosulphate
solution. Compared to other techniques, this method offered better
control over Se/(Ag + Sb) and S/Se ratios to improve both optical
and electrical properties to attain better device performance for
the PV cells based on this material.
1945
4. Conclusions
In this work, we prepared AgSb(SxSe1x)2 thin films by heating
Na2SeSO3 dipped glass/Sb2S3/Ag thin films at 350 8C for 1 h in
vacuum. Different techniques were used to determine the
structure, morphology, optical and electrical properties of these
thin films. XRD showed the formation of AgSb(SxSe1x)2 thin films,
with x = 0.52 and 0.51 for 30 min and 2 h of Se dipping,
respectively. XPS showed the presence of Ag, Sb, S and Se on
the surface of the sample prepared by 2 h of Se dipping, and also
the formation of AgSb(SxSe1x)2 thin films. AgSb(SxSe1x)2 thin
films showed indirect transition across band gap (Eg) value of
1 eV. Dark conductivities were in the range 6–7  103 (V cm)1.
Photovoltaic structures were fabricated using CdS as window layer
and AgSb(SxSe1x)2 as absorber. The PV parameters were evaluated
from the J–V curves and the values are: Voc = 410 mV, Jsc = 5.70 mA/
cm2, and FF = 0.35 and h = 0.81. Further research is in progress to
improve Voc, Jsc and FF of these PV structures and thus, the
conversion efficiency, by this non toxic and simple technique.
Acknowledgements
The authors are thankful to PAICYT 2012-UANL, México,
PROMEP, México and SEP-CONACYT, México for the financial
assistance, CIMAV for recording XRD, CIE-UNAM for UV–vis-NIR
measurements. One of the authors, G. Jorge Oswaldo is grateful to
CONACYT-Mexico for providing research fellowship.
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