Phys. Status Solidi RRL, 19 (2016) / DOI 10.1002/pssr.

201510423

Simple solar cells of 3.5% efficiency

with antimony sulfide-selenide
thin films
Diego Prez-Martnez, Jos Diego Gonzaga-Snchez, Fabiola De Bray-Snchez,
Geovanni Vzquez-Garca, Jos Escorcia-Garca, M. T. S. Nair, and P. K. Nair*

Instituto de Energas Renovables, Universidad Nacional Autnoma de Mxico, Temixco, Morelos-62580, Mxico

Received 21 November 2015, revised 22 March 2016, accepted 24 March 2016

Published online 6 April 2016

Keywords chemical deposition, thermal evaporation, Sb2SxSe3x, compound semiconductors, thin films, solar cells

*
Corresponding author: e-mail pkn@ier.unam.mx, Phone: 52 (55) 56229742

Thin films of antimony sulfide-selenide solid solutions
(Sb2SxSe3x) were prepared by chemical bath deposition and
thermal evaporation to constitute solar cells of a transparent
conductive oxide (FTO)/CdS/Sb2SxSe3x/CAg. The cell pa-
rameters vary depending on the sulfide-selenide composition
in the films. The best solar cell efficiency of 3.6% was ob-
tained with a solid solution Sb2S1.5Se1.5 prepared by thermal
evaporation of the precipitate for which the open circuit volt-
age is 0.52 V and short circuit current density, 15.7 mA/cm2
under AM 1.5G (1000 W/m2) solar radiation. For all-
chemically deposited solar cells of Sb2S1.1Se1.9 absorber,
these values are: 2.7%, 0.44 V, and 15.8 mA/cm2, and for
Sb2S0.8Se2.2, they are: 2.5%, 0.38 V and 18 mA/cm2.

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1 Introduction Among novel photovoltaic absorber
materials, antimony sulfide-selenide solid solutions occupy
a favorable position in view of their low-toxicity, low-cost
and long term availability [1]. Antimony sulfide (Sb2S3)
and antimony selenide (Sb2Se3) are of orthorhombic crys-
talline structure and they possess direct optical band gaps
(Eg) of 1.88 eV and 1.1 eV, respectively [2]. Thus, solid
solutions of Sb2SxSe3x may take up wide-ranging composi-
tions (x, 0 to 3) while maintaining the same crystalline
structure and Eg, which would vary in the interval,
11.88 eV [3]. Thin film solar cells of Sb2SxSe3x prepared
by chemical deposition on transparent conductive oxide
(TCO) of commercial fluorine-doped tin oxide (FTO) and
chemically deposited CdS and PbSe thin films reached an
efficiency of conversion () of solar radiation to electric
energy of 2.5% in 2013 [4]. We report in this work, of
2.73.5% in simpler solar cells of FTO/CdS/Sb2SxSe3x/
CAg, in which the antimony chalcogenide film is pre-
pared by chemical deposition or thermal evaporation, re-
spectively. Perspective of the use of antimony chalco-
genide in solar cell technology is presented.
2 Experimental
2.1 Thin film deposition Solar cell structures of
CdS/Sb2SxSe3x in this work are developed on FTO sub-
strates with nominal sheet resistance of 13 (TEC-13
supplied by Sigma-Aldrich, USA). These substrates are
washed with neutral soap solution, rinsed with distilled wa-
ter, and dried under air flow. Thin films of CdS of 80 nm
in thickness with Eg of 2.6 eV are used as n-layer in the so-
lar cell. They are deposited at 80 C during 55 min from a
chemical bath containing cadmium-citrate complex, as first
reported in 1994 [5]. Under illumination, the n-type
electrical conductivity () of this film is approximately
0.01 1 cm1. Thin films of Sb2SxSe3x are of p-type elec-
trical conductivity. Hence an n-CdS/p-Sb2SxSe3x photo-
voltaic junction is formed when the latter film is deposited
on the CdS thin film [4].
2.1.1 Sb2SxSe3x thin films A solution of sodium se-
lenosulfate, Na2SeSO3 (SS), is prepared by refluxing dur-
ing 5 h at a temperature of 96 C 4 g of Se powder
(ASARCO, 99.9%) and 12 g of sodium sulfite (Na2SO3
Baker Analyzed) in 100 mL of distilled water. The result-
ing clear solution is of approximately 0.4 M in SS with an
excess of sodium sulfite. A chemical solution mixture is
prepared by mixing 8.3 mL of 0.1 M potassium antimony
tartrate (K2Sb2C8H4O12 3H2O), 3.3 mL of 3.7 M triethanol-
amine (TEA), 1 mL of approx. 15 M ammonia (aq.), and
10 mL of 105 M silicotungstic acid (STA, H4Si(W3O10)4).

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2 D. Prez-Martnez et al.: Simple solar cells of 3.5% efficiency
Typically 3 mL of 1 M thioacetamide, CH3CSNH2 (TA),
and variable quantities of the 0.4 M (SS) solution, and dis-
tilled water are added to constitute the deposition bath of a
total volume of 80 mL. The molar ratio TA:SS in the de-
position bath was varied: 15 :1, 13 :1, 11.5 :1 to produce
solar cells, which would be referred to by labels A, B and
C, respectively. Solar cell D is produced by using TA:SS
molar ratio in the bath of 7.5 :1, and an addition of 1 mL of
1 M sodium thiosulfate solution in the bath. Thus, the
deposition of solar cell A requires 3 mL of 1 M TA and
0.5 mL of 0.4 M SS and solar cell D requires 3 mL of 1 M
TA and 1 mL of 0.4 M SS. We shall find from the compo-
sitional assay of the Sb2SxSe3x thin films presented in the
Results and Discussion that the Se-content is greatly en-
hanced during chemical deposition, for example S/Se ratio
of 15 :1 (bath) drops to 2.75 :1 (film) in solar cell A.
2.1.2 Chemical deposition of solar cells Anti-
mony chalcogenide thin films of approximately 160 nm in
thickness are deposited at 80 C during 3.5 h on the CdS
substrate layer (already deposited on the TEC 13 glass) for
the solar cell. A second deposition for the same duration
takes the Sb2SxSe3x film thickness to nearly 220 nm. We
found that a partial dissolution of the already deposited
film in the second bath is not avoided. We have reported
[4] that the chemically deposited Sb2S3 or Sb2SxSe3x thin
films are amorphous (in X-ray diffraction XRD), but
they crystallize when heated at 300 C for 30 min. This
also causes loss of the film thickness of 55 nm due to sub-
limation and compacting. In the present case we expected
film thickness of crystalline Sb2SxSe3x, of 150170 nm.
The thickness may be slightly more under carbon electro-
des painted on the film prior to heating for solar cell fabri-
cation because loss due to sublimation may be inhibited.
Overall, solar cells AD have relatively thin absorber films
of Sb2SxSe3x, when it is considered that in thin film poly-
crystalline solar cells the absorber films are of 1000 nm or
more in thickness [6].
2.1.3 Solar cells by thermal evaporation The
precipitate that settled to the bottom of the deposition bath
A was filtered out, rinsed in de-ionized water and dried.
This precipitate served as the powder source for thermal
Figure 1 Electrode configurations of solar cells AD prepared by chemical deposition and EG by thermal evaporation, shown along
with TEC-13/CdS substrate/window placed on a ruled paper with line spacing at 5 mm apart. Current voltage characteristics are re-
ported for the best cells on which silver paint was applied. XRD and optical measurements were made outside of the electrode-area
(where the cell labels are placed in this photo).
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evaporation. In a molybdenum boat-crucible 200, 400 or
600 mg of this powder was placed. The crucible was fixed
to the copper electrode posts in a vacuum thermal evapora-
tion system (Torr International). The CdS-coated TEC-13
substrates were placed on a sample holder placed 40 cm
above the crucible to assure uniform film thickness. The
substrate was heated to 400 C during the thermal evapora-
tion lasting 30 min. Thickness of crystalline Sb2SxSe3x thin
film produced this way was 110, 175, and 250 nm for
source masses 200600 mg. The solar cells produced from
these films are labelled as E (110 nm), F (175 nm) and G
(250 nm), respectively.
2.2 Fabrication of solar cells On the FTO/CdS
(80 nm)/Sb2SxSe3x stack, six electrodes of colloidal graph-
ite paint (SPI 05006-AB) of 56 mm 6 mm (area, 0.30
0.36 cm2) are hand-painted on the antimony chalcogenide
film using a thin paint brush. In most cases 2 electrodes of
10 mm 10 mm (area, 1 cm2) are also painted-on. These
FTO/CdS/Sb2SxSe3x/C cells are heated at 300 C during
30 min in a nitrogen atmosphere at a pressure of 20 Torr in
a vacuum (MTI Vacuum). Upon cooling down, the open
circuit voltage (Voc) and short circuit current density
(Jsc = Isc/cell-area) are assayed under the sun on all the
electrodes. On the best cells of AG, the cell structure is
completed by applying silver paint (DuPont-PV428) on the
graphite electrodes. Heating of the silver-paint electrodes
at 80 C during 60 min in a drying oven completes the cell-
making. By using wood-splint soaked in dilute acid,
the thin film adjoining the cell is etched out to access the
TEC-13 TCO, which would be the n-side electrode of the
cell. The graphite or graphiteAg electrode is the p-side
electrode of the cell. The solar cell-scheme described here
is shown in Fig. 1, which illustrates the electrode sizes
of the solar cells with respect to the ruled paper with
line spacing of 5 mm and the features of the TEC-13 glass
and CdS film of 80 nm in thickness on which the solar
cells are developed. In solar cells AD, the Sb2SxSe3x film
is prepared by chemical deposition and in EF, the thin
film is prepared by thermal evaporation. The Sb2SxSe3x
absorber films are of high electrical resistivity, of
108 cm, as reported in Ref. [4]. For a thin film of 150
250 nm in thickness, the sheet resistance exceeds a G.
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Phys. Status Solidi RRL (2016)
We have determined that there is no need for an area-
restricting mask (as done in Ref. [4]) or etching the film
around the cell area because there is no contribution to
light-generated current from the area surrounding the
graphite electrodes.
The JV characteristics for the cells, which will be dis-
cussed in Results and Discussion, are for the cells finished
with silver-print electrodes. Prior to making all the meas-
urements, the solar cells were exposed from the FTO-side
under the sun during 6 h in ambient conditions with inten-
sity of solar radiation of 850980 W/m2 with the tempera-
ture of the cells reaching up to 60 C during this illumina-
tion.
2.3 Characterization Film thickness was measured
on an Ambios Technology XP-200 thickness measurement
unit by using the step created by the acid etch shown in
Fig. 1. The thickness for the Sb2SxSe3x thin film is arrived
at by subtracting 80 nm (of CdS film) from the measured
step-height. The SnO2 :F film is not etched by a dilute acid.
Grazing Incidence X-ray diffraction (GIXRD) pattern of
the cell structure FTO/CdS/Sb2SxSe3x was recorded for the
region outside of the electrode area (seen in Fig. 1) at 1
incidence with respect to the plane of the sample for Cu K
radiation ( = 0.15406 nm). The sampling depth into
Sb2SxSe3x for this GIXRD is typically 180 nm, which may
be evaluated as described in Ref. [7]. For this study a Ri-
gaku ULTIMA IV X-ray diffractometer was used. The
composition analysis for the Sb2SxSe3x thin films was
done in the 2 interval of 1020. In this interval are
placed at 17.523 and 16.874, the diffraction peaks due to
(120) orthorhombic crystallographic planes with d-values
of 0.5057 (powder diffraction file PDF 42-1393) and
0.5250 nm (PDF15-0861) for Sb2S3 and Sb2Se3, respec-
tively. In the case of a solid solution, Sb2SxSe3x, the value
of x is determined by assuming the proportional variation
of the d-value with the composition. Thus, if the (120) dif-
fraction peaks would be at 2 of 17.35, 17.19 and 17.06
the d-values are 0.5105, 0.5153, and 0.5192 nm, and they
correspond to solid solutions, Sb2S2.25Se0.75, Sb2S1.5Se1.5,
and Sb2S0.75Se2.5, respectively. We chose (120) diffraction
peak because it does not have nearby overlapping peaks
from Sb2SxSe3x, CdS or SnO2 of TEC-13 glass. We expect
that the composition of the Sb2SxSe3x thin film situated
underneath the graphite-paint electrodes would be slightly
different from these because the sublimation process would
differentiate loss of these elements from the film in open
area and under the electrode.
Optical transmittance (T) and specular reflectance
(R, measured at an angle of incidence of 5) spectra of the
Sb2SxSe3x films were measured in the cell structure using
3101PC Shimadzu UVVISNIR spectrophotometer. This
may give acceptable results for the absorber film because
the underlying CdS or SnO2 :F of TEC-13 may not modify
the characteristics near the onset of the optical absorption
in Sb2SxSe3x films, which is expected in the 11.88 eV in-
terval of photon energy. Neither CdS nor the SnO2 have
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optical absorption in this spectral region. We have deter-
mined that by having the measurement made on the
absorber thin films rightly integrated into the solar cell
structure is a good way to assay the optical properties of
the Sb2SxSe3x. The optical absorption coefficient () of the
absorber material was computed from T, and R data by
considering multiple reflections within the thin film of
thickness d [8]: T = (1 R)2 ed/(1 R2 e2d).
The currentvoltage (IV) characteristics of the stabi-
lized solar cells were measured in the dark and for an
intensity of illumination of approximately 1000 W/m2 from
a tungsten halogen lamp. The light-characteristics were
normalized using values of Jsc of the cells measured di-
rectly under the sun, with intensity of radiation at our site
of 910980 W/m2 during 11.3013.30 h local time in Feb-
ruaryMarch 2016. The sun is located at approximately
45 from the zenith and made normal incidence on the
cells during the measurement. The normalized Jsc of the
cells is arrived at from the measured current (I) under the
sun: Jsc = I (measured in mA)/[cell-area (cm2) (0.91, 0.98
etc.)]. The values were also verified in a SCIENCETECH
(Canada) Photovoltaic Testing System (PTS) by recording
the currentvoltage (IV) characteristics under simulated
solar radiation of air-mass 1.5 Global spectrum of intensity
1000 W m2 from a xenon arc-lamp. The external quantum
efficiency (EQE) of the solar cells was determined under
short-circuit conditions in the PTS with a monochromator,
which was calibrated using a standard silicon solar cell.
3 Results and discussion
3.1 Composition of Sb2SxSe3x solid solutions
from GIXRD Figure 2 shows the GIXRD patterns re-
corded at = 1 for the Sb2SxSe3x films in the cells AG
(after heating these at 300 C) for the 2 interval 1020.
The pattern for the film E of thickness 110 nm prepared by
thermal evaporation is displayed in the 2 interval 1070,
which shows that the peaks due to SnO2 (FTO) (or of CdS
film) are located at 2 above 20. Thus, they do not inter-
fere with the analysis of the XRD patterns of the solid
solutions in the 1020 interval to establish their composi-
tion. The location of the XRD peaks in the entire 2 inter-
val for E is in between those of the standard patterns for
Sb2S3 (shown in red, online) and Sb2Se3 (dark red) as seen
for the diffraction from (221) planes indicated in the bot-
tom panel. The XRD peaks for FTO films (of thickness
500 nm) or of CdS (80 nm) do not make any overly domi-
nant presence in the XRD pattern of E because the sam-
pling depth into the solid solution is approximately 180 nm
[7], which is occupied in large part by the Sb2SxSe3x film
of thickness 110 nm.
In all cases analysis in an interval of 1020 in 2
helps establish a composition assay based on the (120)
peak position, as labelled in each case. Thus, in cells AD
prepared by chemical deposition, the composition (esti-
mated as described in Section 2) varies as: Sb2S2.6Se0.4 for
A, and Sb2S1.1Se1.9 for C. In case C, the TA/SS molar ratio,
assumed as S/Se ratio in the bath, is 11.5, but in the thin
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Figure 2 GIXRD patterns (recorded at 1) for Sb2SxSe3x thin films forming the cell structure: FTO/CdS/Sb2SxSe3x of different com-
positions, AD prepared by chemical deposition and EG by thermal evaporation recorded after heating them in nitrogen at 300 C.
The PDF patterns for Sb2S3 and Sb2Se3 are given; the positions of diffraction peaks for (110), (020)/(200) and (120) crystallographic
planes for Sb2S3 and of (120) planes for Sb2Se3 are given by the dotted lines. The position of the (120) peak of a solid solution gives
the composition assay for Sb2SxSe3x for the solar cells AG specified on the patterns in each case.

film, the S/Se atomic ratio is 0.58. Thus, SS is very effec-
tively used up as the selenide source in the deposition. For
the cells E and G prepared by thermal evaporation of the
precipitate from bath A, the composition is: Sb2S2.1Se0.9 for
E and Sb2S1.5Se1.5 for G. Here TA/SS molar ratio in the bath
is 15, but the S/Se atomic ratio in the film is 2.3 for E and 1
for G. We observe here a dependence of the mass of the
powder source used in the thermal evaporation on the com-
position of the deposited film, the higher the mass (600 mg),
the higher is the Se incorporation into the film. In all cases,
the Se content in the films prepared by thermal evaporation
is superior to that of the corresponding film (Sb2S2.6Se0.4)
prepared from bath A. This suggests that Se is enriched in
the precipitate, the mechanism of which need to be investi-
gated further. In this work we did not strive to corroborate
the composition of the Sb2SxSe3x film by other techniques
or analyze the composition of the film by GIXRD on a re-
gion underneath a peeled-off graphite electrode. Thus, the
compositional values are taken as approximate to enable
more exact determination later on. Average crystallite
grain diameter (D) evaluated using the Scherrer equation,
D () = (0.9 1.5406 180)/((2) cos ) from the
Bragg angle and full width at half maximum (2) of the
diffraction peaks, is in the interval 1620 nm for the
Sb2SxSe3x thin films in the cell structures.
3.2 Optical properties Figure 3(a) and (b) show T, R
data for representative solar cells of FTO/CdS/Sb2SxSe3x
as a function of the wavelength measured for film-side in-
cidence on the electrode-free area (see Fig. 1). In all cases
(except in A), T values have dropped to near-zero before
the onset of optical absorption near 500 nm due to CdS.
The R-values are considerably larger in the same spectral
region because the high-frequency relative permittivity
(r) of 8.5 for Sb2S3 and 14.8 for Sb2Se3 [2] suggests re-
fractive indices (n = r1/2) of 2.93.84 for Sb2SxSe3x. Hence

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Phys. Status Solidi RRL (2016)
Figure 3 (a) Optical transmittance (T) and (b) reflectance (R) versus wavelength plots for solar cells AG obtained by chemical depo-
sition or thermal evaporation. (c) Optical absorption coefficient () versus photon energy. (d) and (e) Analysis of the forbidden transi-
tion across direct gap for the Sb2SxSe3x absorber films.
R = [(1 n)/(1 + n)]2 is of 2434% for these filmair inter-
faces. However, in the operation of the solar cells, the solar
radiation incidence is from glassFTO side with a reduc-
tion in such reflection loss. The optical absorption coeffi-
cients for the AG films are plotted in Fig. 3(c). Interpola-
tion of these plots toward photon energy (h)-axis indicate
Eg of 1.6 eV for Sb2S1.5Se1.5 (G), which increases toward
1.85 eV for Sb2S2.6Se0.4 (A). This variation is nearly as ex-
pected from a proportional variation of Eg within the inter-
val 1.1 eV (Sb2Se3)1.88 eV (Sb2S3) in Sb2SxSe3x solid
solutions, which would give an Eg of about 1.5 eV for crys-
talline Sb2S1.5Se1.5. Analyses of the optical absorption for
the films in (h)2/3 versus photon energy in Fig. 3(d) and
(e) render the data into straight lines showing that the elec-
tronic transitions are forbidden, taking place across direct
band gaps [8]. The intercepts of these plots on the h-axis
help determine more exactly the Eg for these absorber films,
1.58 eV for G and 1.85 eV for A. We found that the
proportional variation of Eg with composition is not always
followed because, for crystalline grain diameters of
1620 nm some contribution from quantum confinement of
the exciton in such crystalline grains would increase the Eg.
3.3 Solar cell characteristics Figure 4 shows the
JV characteristics of the small-area (0.30.36 cm2, Fig. 1)
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cells AD and EG measured in the dark and under light
for solar radiation (1000 W/m2) for bias interval 0.8 V.
Figure 5(a) gives the IV characteristics for the large area
cells C, D, F and G and in (b) the JV characteristics for
the corresponding small-area cells measured using the
photovoltaic test system using illumination from a Xe-arc
lamp and filters for air-mass (AM 1.5) solar radiation
(1000 W/m2). The JV characteristics in the dark in Fig. 4
assure the rectification characteristics of the cells AG.
The JV characteristics (light) measured for these cells un-
der solar radiation compares well with those given in
Fig. 5(b), with simulated solar radiation. Both these results
also compare well with characteristics in Fig. 5(a) for cells
C, D, F and G of 1 cm2 in area. However, some differences
exist among the values of solar cell parameters, which are
summarized in Table 1, given along with the material pa-
rameters of the Sb2SxSe3x thin films. A clarification on the
spread of values of the parameters among the six small-
area cells (Fig. 1) is pertinent here. The variation in Voc
values among these cells, measured prior to placing silver
paint on the best electrode, is typically by 2%. When we
report a Voc of 0.52 V, the spread of values is within 0.51
to 0.52 V. The best cell is chosen for its higher Jsc, for
which the spread of values is by 5%, typically from
12 mA/cm2 to 12.6 mA/cm2. When a silver paint electrode
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6 D. Prez-Martnez et al.: Simple solar cells of 3.5% efficiency
is placed on the chosen graphite electrode, Jsc increases by
23%, toward a Jsc of 13 mA/cm2 in this case.
The best Voc of 0.580 V is for cell E, but its of 0.95%
is the least among all the cells. Among the chemically de-
posited solar cells, the best value for of 2.7% is for the
cell C, even though the best Jsc of 18.3 mA/cm2 belongs to
cell D. Figure 5(c) shows the EQE measured under short-
circuit in cell C. The onset of EQE is at a wavelength of
900 nm, which corresponds to photon energy of 1.38 eV,
lower than an Eg of 1.64 determined for this absorber in
Fig. 3. We consider that the material underneath the graph-
ite electrode may be richer in Se and may be more crystal-
line than in the area outside it hence with an Eg closer
toward 1.1 eV for Sb2Se3. It is possible that diffusion of
carbon in the semiconductor/graphite electrode occurs dur-
ing heating at 300 C with the graphite electrode in place
in the FTO/CdS/Sb2SxSe3.x/C solar cells. Without such
heating, Jsc of the solar cells are nearly one-fifth the values
reported here. The C-doping of Sb2S3 has been reported
previously, in which a thin film of carbon deposited on a
Sb2S3 film and its subsequent heating at 300 C in nitrogen
(as done here) resulted in the reduction of electrical resis-
tivity of the Sb2S3 from 108 to 102 cm (p-type) [9]. Sharp
rise immediately after the onset of the curve at the long
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Figure 4 JV characteristics of
small-area cells AD (by chemical
deposition) and EG (by thermal
evaporation) finished with silver
paint (shown in Fig. 1), measured
under the Dark and in Light (for so-
lar radiation of AM 1.5 of intensity
1000 W/m2 outdoor). Sb2SxSe3x ab-
sorber thickness in nm is 110 (E)
250 (G). Solar cell parameters are
summarized in Table 1.
wavelength, typical of high efficiency solar cells [6] lacks
in C or in other solar cells presented here. Thus, the mate-
rial quality, mainly in crystalline grain diameter needs to
improve to facilitate collection of photogenerated charge
carriers at the back electrode. It is also important to opti-
mize the CdS (or other) window film to inhibit the drop in
EQE at wavelength shorter than 500 nm.
The best solar cell parameters are obtained for the solar
cells produced by thermal evaporation of the Sb2SxSe3x
precipitate from chemical bath A. Here, for solar cells F
and G with film thickness 175250 nm, Voc is close to
0.525 V and is near 3%. The best value of 3.63% is for G
in small area and 2.97% for large area. This discrepancy
mainly arises from the drop in fill factor from 0.44 (small
area, Fig. 5(b) to 0.37 (large area, Fig. 5(a) because in
these proof-of-concept cells, we did not paint a silver elec-
trode on the FTO all around the large cell to improve the
collection of the photo-generated electrons. When this is
assured, an efficiency of 2.97% would improve by a factor
(0.44/0.37) toward 3.53%. In these cells, the series resist-
ance is 3060 cm2, which is an order of magnitude
higher than for high efficiency CdTe solar cells [10], thus
limiting the value of the fill factor (FF) to 0.40.44. Better
cell design may improve these values toward 0.6, hereby
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= 20%, rs is 0.30 cm2 and rp, 8801605 cm2 with FF

of 0.77 [11], again suggesting a need to improve the mate-
rials and electrodes of the present cells.
Estimates for the photo-generated current density (JL)
for solar cell absorbers of direct band gap shows that the
maximum achievable current density (and hence of Jsc) is
obtained for absorber film thickness of 200 nm for CdTe,
GaAs and CuInSe2 of approximately 27, 31, 42 mA/cm2,
respectively [12]. Because is relatively lower for semi-
conductors with direct-forbidden Eg as in Sb2SxSe3x
films, estimates made as in Ref. [12] shows that to achieve
a 90% of maximum JL, the cell requires a film thickness of
400 nm. At such thickness, JL (and hence Jsc) of the cells
may be 2030 mA/cm2 for Sb2SxSe3x solar cells. Table 1
shows that for different cells, the thickness falls short of
this requirement. Larger film thickness also leads to higher
values of parallel resistance, which may improve the FF
and hence the . These tasks are taken up in the work-in-
progress on these cells.

3.4 On the simplicity of the cell structure and

Figure 5 (a) Current density (I) for AM 1.5 G simulated solar ra-
diation of intensity 1000 W m2 versus applied bias 0 to 0.6 V at
the graphite/Ag electrode for cells C, D, F and G of area 1 cm2;
(b) JV characteristics under such illumination for the corre-
sponding small-area cells. (c) External quantum efficiency (EQE)
of the short-circuited small-area solar cell C.
making a 50% improvement of the efficiency of the cell
possible, toward 5%. In CdTe solar cell of = 15.7%, rs is
1 cm2 and rp, 30005000 cm2 with FF of 0.77 [10].
For high efficiency Cu(InGa)Se2 thin film solar cell of
material perspectives Major merit of the antimony
chalcogenide solar cells reported here with a conversion
efficiency of 0.93.5%, is the simple four-step process
used in its preparation:
(i) Deposition on a commercial FTO of a CdS film of
80 nm in thickness during 55 min at 80 C.
(ii) Deposition at 80 C in about 3.5 h the desired
Sb2SxSe3x solid solution from the bath mixture AD or any
modification of these, followed by a second deposition of
the same; or in the case of thermal evaporation recovery by
filtering of the precipitate from these baths and evaporation
of typically 400600 mg of this material placed in a mo-
lybdenum boat for cells F and G.
(iii) Application of a commercial colloidal graphite
paint on the Sb2SxSe3x thin film defining a cell area and
heating it in an oven at 300 C during 30 min and finally.

Table 1 Material and solar cell parameters: series resistance (rs), parallel (shunt) resistance (rp), fill factor FF, Voc (V), Jsc (mA/cm2),
and conversion efficiency () normalized for AM 1.5G solar radiation for FTO/CdS/ Sb2SxSe3x/CAg solar cells AG of area
0.30.36 cm2 from Fig. 4 and given in (bracket) for cells C, D, F and G for area 1 cm2 from Fig. 5(a) measured using photovoltaic IV
test station and solar simulator.

cell composition Eg thickness rs rp FF Voc Jsc

(eV) (nm) ( cm2) ( cm2) (V) (mA/cm2) (%)
A Sb2S2.6Se0.4 1.85 150 0.25 0.580 6.6 0.95
B Sb2S2.7Se0.3 1.68 170 0.32 0.520 9.7 1.62
C Sb2S1.1Se1.9 1.64 170 68 218 0.39 0.440 15.8 2.7
(36) (91) (0.32) (0.434) (14.1) (1.98)
D Sb2S0.8Se2.2 1.68 150 55 203 0.37 0.380 18.3 2.56
(29) (57) (0.30) (0.403) (14.5) (1.75)
E Sb2S2.1Se0.9 1.81 110 0.40 0.539 12.3 2.65
F Sb2S1.7Se1.3 1.66 175 54 403 0.40 0.520 16 3.35
(30) (220) (0.43) (0.545) (13.5) (3.12)
G Sb2S1.5Se1.5 1.58 250 42 421 0.44 0.528 15.7 3.63
(32) (125) (0.37) (0.522) (15.6) (2.97)

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 rrl
solidi
physica
status
8 D. Prez-Martnez et al.: Simple solar cells of 3.5% efficiency
(iv) Finishing the cell structure with colloidal silver
paint and stabilizing the cell under solar radiation for 6 h
prior to measurement.
Solar cells made this way have been found stable under
sunlight. The results presented here have been confirmed
through repeated measurements under the sun. This degree
of stability of the cell is imperative because the cell struc-
ture with the carbon electrode is developed through heating
at 300 C.
As a solar cell material, antimony chalcogenide is free
from scarcity. It is present at 0.7 ppm (compared with Si)
on the earths upper crust and at typically 1 g/L in unpol-
luted river water. Its world mine production is upward of
150000 metric tons per year in recent years; and its world
mine reserve is estimated upward of 1.8 million metric
tons [1]. Its toxicity is well studied and considered control-
lable and/or insignificant as a hazardous environmental
agent [13]. In the Sb2SxSe3x solid solutions, the molar ratio
of SS to TA in the bath is typically 0.09 (bath C), but it
goes into depositing a Sb2S1.1Se1.9 film exhibiting great ef-
ficacy of selenium utilization in chemically deposited solar
cell of , 2.7%. In bath A, from which the precipitate is re-
covered for thermal evaporation for solar cell G (, 3.6%),
the SS to S molar ratio is 0.067, but in the solid solution,
Sb2S1.5Se1.5, it is 1. Thus, the deposition of Sb2SxSe3x thin
films for solar cells by thermal evaporation reported here
also represents a high efficacy of selenium utilization. This
element is by far the costlier one in the solid solution. Se-
lenosulfate as a source for selenide has been widely used in
the chemical deposition of metal selenide thin films [14].
The presence of a Sb2SxSe3x solid solution even as in cell
B of Sb2S2.7Se0.3 helps achieve a reasonable of 1.6%. In
our previous report on solar cells of FTO/CdS/Sb2S3/CAg
with Sb2S3 thin films of 400 nm in thickness obtained
by thermal evaporation of Sb2S3 powder source, was at
best 1.27% [15]. The best conversion efficiency in anti-
mony chalcogenide thin film solar cells is 5.6%, reported
in 2015 for Sb2Se3 absorber produced by rapid thermal
evaporation, for which Voc is 0.4 V and Jsc is
25.14 mA/cm2 with Sb2Se3 absorber thickness of 380 nm
and for cell area, 0.095 cm2 [16]. Such cells have been
found to be stable under solar radiation. For a solar cell
technology to be commercially viable, its energy conver-
sion efficiency is required to reach 1820% in large area
laboratory cells [6]. Thus, further research is called for in
all these materials.
4 Conclusions We analyzed the photovoltaic behav-
ior of simple heterojunction solar-cells, FTO/CdS/
Sb2SxSe3x/CAg, produced by chemical deposition or
thermal evaporation. The composition of the films arrived
at through the analysis of GIXRD patterns of the films cor-
relate reasonably well with the optical band gap deter-
mined for the films. Best value for the conversion effi-
ciency of 3.63% accompanied by a Voc of 528 mV and
Jsc of 15.7 mA/cm2 is obtained for the FTO/CdS/
Sb2S1.5Se1.5/CAg cell produced by thermal evaporation,
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
whereas the best cell FTO/CdS/Sb2S1.1Se1.9/CAg prepared
by chemical deposition reached an efficiency of 2.7%. We
have identified that a film thickness of 400 nm instead of
110250 nm used in these solar cells would lead to better
cell characteristics. By presenting the solar cells prepared
by chemical deposition and thermal evaporation, the meth-
odology for preparing these cells is made widely accessible.
Antimony is well available on the earths crust to sustain
an antimony chalcogenide solar cell technology.
Acknowledgements We are grateful to Patricia Altuzar
for the XRD measurements, Jos Campos lvarez and to Oscar
Gomez Daza for optical and electrical measurements and for the
general assistance in the laboratory. We acknowledge the finan-
cial support provided by PAPIIT-UNAM IN116015, IT100814;
CONACYT-LIFYCS 123122 and CeMIE-Sol Project 35 and to
DGAPA-UNAM for a postdoctoral fellowship (DPM).
References
[1] M. Filella, N. Belzile, and Y.-W. Chen, Earth Sci. Rev. 57,
125176 (2002);
http://www.metalprices.com/historical/database/antimony/a
ntimony-min-99-65-sb-cif-us.
S. Sundar and J. Chakravarty, Int. J. Environ. Res. Public
Health 7(12), 4267 (2010), doi: 10.3390/ijerph7124267.
[2] O. Madelung, Data in Science and Technology: Semicon-
ductors Other than Group IV Elements and IIIV Com-
pounds, edited by R. Poerschke (Springer-Verlag, Berlin,
1992), p. 49.
[3] D. Y. Surez-Sandoval, M. T. S. Nair, and P. K. Nair,
J. Electrochem. Soc. 153, C91 (2006).
[4] M. Calixto-Rodriguez, H. Moreno Garca, M. T. S. Nair,
and P. K. Nair, ECS J. Solid State Sci. Technol. 2, Q69
(2013).
[5] M. T. S. Nair, P. K. Nair, R. A. Zingaro, and E. A. Meyers,
J. Appl. Phys. 75, 1557 (1994).
[6] I. L. Repins, M. J. Romero, J. V. Li, S.-H. Wei, D. Kuci-
auskas, C.-S. Jiang, C. Beall, C. DeHart, J. Mann, W.-C.
Hsu, G. Teeter, A. Goodrich, and R. Noufi, IEEE J. Photo-
volt. 3, 439 (2013).
[7] B. E. McCandless, Mater. Res. Soc. Symp. Proc. 865, 75
(2005);
National Institute of Standards and Technology_NIST:
http://physics.nist.gov/PhysRefData/XrayMassCoef/cover.ht
ml, accessed Nov. 2015.
[8] J. I. Pankove, Optical Processes in Semiconductors (Dover
Publ., New York, 1975).
[9] E. Crdenas, A. Arato, E. Perez-Tijerina, T. K. Das Roy,
G. Alan Castillo, and B. Krishnan, Sol. Energy Mater. Sol.
Cells 93, 33 (2009).
[10] P. Jackson, D. Hariskos, E. Lotter, S. Paetel, R. Wuerz,
R. Menner, W. Wischmann, and M. Powalla, Prog. Photo-
volt.: Res. Appl. 19, 894 (2011), DOI: 10.1002/pip.1078.
[11] X. Wu, R. G. Dhere, D. S. Albin, T. A. Gessert, C. DeHart,
J. C. Keane, A. Duda, T. J. Coutts, S. Asher, D. H. Levi,
H. R. Moutinho, Y. Yan, T. Moriarty, S. Johnston, K. Emery,
and P. Sheldon, High-Efficiency CTO/ZTO/CdS/CdTe
Polycrystalline Thin-Film Solar Cells, preprint, NREL, pre-
sented at the NCPV Program Review Meeting, Lakewood,
www.pss-rapid.com
Phys. Status Solidi RRL (2016)
Colorado 14-17 October 2001, http://www.nrel.gov/docs/
fy02osti/31025.pdf.
X. Wu, Sol. Energy 77, 803 (2004).
[12] J. Nelson, in: The Physics of Solar Cells, Thin Film Solar
Cells (Imperial College Press, London, 2003), chap. 8,
p. 211.
[13] Toxicological profile for antimony and compounds, Report,
September 1992, available at: http://www.atsdr.cdc.gov/
toxprofiles/tp23.pdf; and US EPA briefing on antimony tox-
icity of the year 1992, revised in 2000, available at:
www.pss-rapid.com
9
http://www3.epa.gov/airtoxics/hlthef/antimony.html; both
accessed Nov. 2015.
[14] G. Hodes, Chemical Solution Deposition of Semiconductor
Films (Marcel Dekker, New York, 2003), p. 56.
[15] J. Escorcia-Garca, D. Becerra, M. T. S. Nair, and P. K. Nair,
Thin Solid Films 564, 28 (2014).
[16] Y. Zhou, L. Wang, S. Chen, S. Qin, X. Liu, J. Chen, D.-J.
Xue, M. Luo, Y. Cao, Y. Cheng, E. H. Sargent, and J. Tang,
Nature Photon. 9, 409 (2015).
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