Thin Solid Films 515 (2007) 5777 – 5782

www.elsevier.com/locate/tsf

Antimony sulfide thin films in chemically deposited thin

film photovoltaic cells
Sarah Messina ⁎, M.T.S. Nair, P.K. Nair
Department of Solar Energy Materials, Centro de Investigación en Energía, Universidad Nacional Autónoma de México, Temixco, Morelos 62580, Mexico

Available online 16 December 2006

Abstract

Antimony sulfide thin films of thickness ≈500 nm have been deposited on glass slides from chemical baths constituted with SbCl3 and sodium
thiosulfate. Smooth specularly reflective thin films are obtained at deposition temperatures from −3 to 10 °C. The differences in the film thickness
and improvement in the crystallinity and photoconductivity upon annealing the film in nitrogen are presented. These films can be partially
converted into a solid solution of the type Sb2SxSe3 − x, detected in X-ray diffraction, through heating them in contact with a chemically deposited
selenium thin film. This would decrease the optical band gap of the film from ≈ 1.7 eV (Sb2S3) to ≈1.3 eV for the films heated at 300 °C.
Similarly, heating at 300 °C of sequentially deposited thin film layers of Sb2S3–Ag2Se, the latter also from a chemical bath at 10 °C results in the
formation of AgSb(S/Se)2 with an optical gap of ≈ 1.2 eV. All these thin films have been integrated into photovoltaic structures using a CdS
window layer deposited on 3 mm glass sheets with a SnO2:F coating (TEC-15, Pilkington). Characteristics obtained in these cells under an
illumination of 850 W/m2 (tungsten halogen) are as follows: SnO2:F–CdS–Sb2S3–Ag(paint) with open circuit voltage (Voc) 470 mV and
short circuit current density (Jsc) 0.02 mA/cm2; SnO2:F–CdS–Sb2S3–CuS–Ag(paint), Voc ≈ 460 mV and Jsc ≈ 0.4 mA/cm2; SnO2:F–CdS–Sb2Sx
Se3 − x–Ag(paint), Voc ≈ 670 mV and Jsc ≈ 0.05 mA/cm2; SnO2:F–CdS–Sb2S3–AgSb(S/Se)2–Ag(paint), Voc ≈ 450 mV and Jsc ≈ 1.4 mA/cm2. We
consider that the materials and the deposition techniques reported here are promising toward developing ‘all-chemically deposited solar cell
technologies.’
© 2007 Elsevier B.V. All rights reserved.

Keywords: Chemical deposition; Antimony sulfide; Thin films; Photovoltaic structures

1. Introduction Chemically deposited antimony sulfide thin films have also

Chemical deposition of thin films of antimony sulfide has
been reported by many authors since early 1990s [1–3]. When
heated at 300 °C, these films show well defined crystal structure
identical with that of the mineral stibnite (Sb2S3), of the
orthorhombic system [2]. The optical band gap of this material
is 1.88 eV (direct gap) [4]. Heating a chemically deposited
Sb2S3–CuS layer at 350–400 °C (nitrogen, ≈ 40 Pa) results in
the formation of CuSbS2 thin film, which occurs in nature as the
mineral chalcostibite. An optical band gap of ≈ 1.5 eV and p-
type conductivity of 0.03 (Ω cm)− 1 have been reported for this
material [5]. Photovoltaic structures, SnO2:F–CdS–Sb2S3–
CuSbS2 [6], have shown an open circuit voltage, Voc, of
≈ 350 mV and a short circuit current density, Jsc, ≈ 0.2 mA/cm2.
⁎ Corresponding author.
E-mail address: mtsn@cie.unam.mx (S. Messina).
0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2006.12.155
featured in Schottky barrier and heterojunction solar cells [7,8].
Preparation of AgSbSe2 thin films is possible through the
reaction of Sb2S3–Ag layer at 200–300 °C in selenium vapor
evolved from a chemically deposited Se thin film [9].
Photovoltaic structures of SnO 2:F:CdS–Sb2S 3–AgSbSe 2
[10,11] showed Voc N 500 mV and Jsc ≈ 2 mA/cm2. Heating an
Sb2S3 film at 200–400 °C in contact with a chemically
deposited Se thin film produces solid solutions of Sb2SxSe3 − x
with the optical band gap decreasing to 1.2 eV [12], which
would be an attractive feature for solar cells.
In this paper we report a new methodology to produce
antimony sulfide thin films of thickness N500 nm from a single
bath. The formation of Sb2SxSe3 − x, CuSbS2 and AgSbSe2
through the reactions of Sb2S3/Se, Sb2S3–CuS and Sb2S3–
Ag2Se/Se, respectively are illustrated. The application of these
films as absorbers in chemically deposited photovoltaic
structures is presented subsequently. The results indicate that
antimony chalcogenides and related ternary or quaternary
5778 S. Messina et al. / Thin Solid Films 515 (2007) 5777–5782
materials offer prospects as absorber materials in chemically
deposited solar cells.
2. Experimental details
2.1. Thin film deposition
2.1.1. Sb2S3 thin films
Thin films of Sb2S3 were obtained from a chemical bath
prepared by dissolving 650 mg of SbCl3 (Aldrich) initially in
2.5 ml of acetone and subsequently adding 25 ml of 1 M
Na2S2O3 (Baker Analyzed) solution and sufficient water to
make the volume to 100 ml. For the deposition of thin films of
Sb2S3 reported by this method [2], clean microscope glass
slides were placed in the bath, supported vertically on the wall
of the beaker. Final film thickness of 200 nm was achieved in
4 h deposition inside a refrigerator at 10 °C. In the present
work the glass slides were placed in the bath horizontally in
order to avoid temperature and concentration gradient in the
bath. The bath with the substrates was placed in a temperature
controlled circulation bath at − 3, 1, 5 or 10 °C. In all cases the
temperature was initially set at 10 °C. Subsequently, the
temperature was decreased in steps of 2 °C every 15 min to
reach a final deposition temperature of − 3 to 5 °C. Without
this gradual decrease in temperature, the film would detach
from the glass substrates during rinsing for depositions made
at temperatures b5 °C. At 1 °C, a film of ≈ 550 nm in
thickness was deposited on glass with a transparent conductive
oxide (TCO) of SnO2:F or SnO2:F–CdS substrates in 6 h. This
condition of deposition was followed for most studies
presented here.
2.1.2. Se thin films
These thin films required as source of Se vapor in the
processing of the thin films reported here were deposited on
microscope glass slides coated with a thin film of ZnS,
following the procedure described in [9]. The chemical bath for
Se-deposition was prepared using 10 ml of a 0.1 M solution of
Na2SeSO3, 70 ml of water, and 2 ml of ∼ 4.4 M acetic acid. A
Se thin film of ≈ 300 nm in thickness was deposited from this
solution in 8 h at 10 °C in a refrigerator. In order to control the
evolution of the Se vapor in the heat treatments of Sb2S3 and
Sb2S3–Ag2Se layer, a ZnS thin film was further deposited on
the Se film, as suggested in a recent report [13].
2.1.3. Ag2Se thin films
The deposition mixture was prepared by dissolving 100 mg
of AgNO3 (Baker Analyzed) in 10 ml of water. Then 4 ml of
7.5 M of ammonia (aq.), 81 ml of deionized water and 5 ml of a
0.1 M solution of Na2SeSO3 were added [14]. Silver selenide
thin film was deposited at 10 °C in a refrigerator on a thin film
of Sb2S3. Under this condition, a thin film of 150 nm in
thickness was deposited in 45 min.
2.1.4. CuS thin film
This film was deposited on Sb2S3 thin films using a chemical
bath containing 10 ml of 0.5 M CuCl2, 8 ml of triethanolamine
Fig. 1. Growth curve of antimony sulfide thin films deposited at − 3, 1, 5 and
10 °C.
(TEA) 50%, 8 ml of 15 M ammonia (aq.), 10 ml of 1 M NaOH,
6 ml of 1 M thiourea, and water for 100 ml bath. In 1 h at
30 °C, a CuS thin film of estimated thickness 120 nm was
deposited on the Sb2S3 film. The latter film was deposited at
1 °C and heated in air at 200 °C to prevent peeling in the CuS
deposition bath.
2.2. Heat treatments
Individual thin films as well as multilayer films and device
structures were heated in air, or in nitrogen (40 Pa) in a vacuum
oven. For the formation of Sb2SxSe3 − x solid solution or the
ternary compound AgSbSe2, a ZnS–Se–ZnS layer is held
facing the Sb2S3 film or Sb2S3–Ag2Se layer and the assembly
kept intact using Teflon sealing tape. Here, ZnS remains stable
at temperatures up to 350 °C and does not incorporate into the
adjacent film — it merely controls the evolution rate of Se
vapor for the reaction [13].
2.3. Characterization
X-ray diffraction (XRD) patterns of the films were recorded
on a Rigaku D-Max 2000 diffractometer using Cu-Kα
(λ = 1.5406 Å) radiation in standard mode (θ–2θ) and grazing
incidence angles of θ = 0.5°, 1.5° and 3°. X-ray fluorescence
(XRF) spectra were obtained on Philips Magi-X PRO using a
pentaerythrite (002) analyzer crystal for Sb-Lβ and S-Kα and a
PX1 layered analyzer crystal (2d = 5.1 nm) for Se-Lα fluores-
cence emission. The optical transmittance and specular
reflectance spectra of the films were obtained using a Shimadzu
UV 3100 PC spectrophotometer in the wavelength range 250–
2500 nm. Air or front aluminized mirror, respectively, was used
in the reference beams. For the electrical characterization, we
printed silver paint electrodes (5 mm length at 5 mm separation)
on the film surface. A tungsten halogen lamp was used for the
illumination. It produced an intensity of illumination 850 W/m2
at the sample plane. The samples were placed in the
measurement chamber and maintained in the dark to stabilize
the current before a voltage was applied across the electrodes
 S. Messina et al. / Thin Solid Films 515 (2007) 5777–5782 5779

during 30 min in air or N2 atmosphere. During the heating there

Fig. 2. XRF peak intensities in thin films of Sb2S3: as prepared, heated at 300 °C
in air or N2 (40 Pa) and in Sb2S3 thin films heated at 300 °C in contact with a Se
thin film in air or N2 (40 Pa) as shown in the inset.
is a loss of ≈ 6–9% S and Sb, but the ratio of S/Sb intensity
remains the same. Since the XRD results show that the material
of the film is Sb2S3, this ratio is 1.5. Hence the XRF intensities
(raw data) have been multiplied by a sensitivity factor to result
in the values shown. When the Sb2S3 film is heated at 300 °C
during 30 min in the presence of Se vapor evolved from a
ZnS–Se–ZnS placed in contact with the Sb2S3 film (as shown
in the inset), the Sb-XRF intensity falls by about 9–10%, but
the S-XRF intensity falls by a greater extent. We note that
there is an incorporation of Se in the film compensating the
relative loss of S. Grazing angle XRD pattern would show that
the surface of the Sb2S3 thin film has been converted into a
solid solution, Sb2SxSe3 − x during such heating.

using a Keithley 230 programmable voltage source. The current

was measured using a Keithley 619 multimeter interfaced with a
computer. Thickness of the films was measured using Alpha
Step 100 (Tencor, CA).

3. Results and discussion

3.1. Film growth

Specularly reflective Sb2S3 thin films devoid of adhering

precipitate were obtained at the different temperatures. The
following conclusions may be drawn from the growth curve for
the films presented in Fig. 1.
The terminal (final) thickness of the films increases with
reduction in the deposition temperature: at 10 °C, a final
thickness of ≈ 470 nm is reached in 5–6 h, whereas at − 3 °C a
final thickness of 650 nm is obtained in about 7 h. At 1 °C, a
film thickness of 550 nm is obtained in 6 h. For most of the
studies, this condition has been chosen for the film deposition.
Note that the temperature was reduced in steps of 2 °C from
10 °C to the final deposition temperature. Thus, during an initial
period of 1–2 h, the temperature of the bath has not been
constant, and hence conclusion on the rate of deposition with
temperature may not be drawn from the present set of data. The
initial (1–4 h) deposition rate is greater than that in the later
period, when the bath becomes depleted of the constituent ions.
This is a feature well known in chemically deposited
semiconductor thin films. The reason for initiating the
deposition at 10 °C is to improve the adhesion of the films to
glass substrates during the nucleation phase of the deposition.
The films deposited at a constant temperature of − 3 or 1 °C,
would otherwise peel-off from the glass substrate when rinsed
in water. However, this problem is inhibited when the film is
deposited on a CdS thin film, as required for forming the
photovoltaic structure.

3.2. X-ray fluorescence analysis

Fig. 3. XRD patterns of: A — a) Sb2S3 thin films heated at 300 °C in N2; b)
Sb2S3 thin films heated in contact with a Se thin film and recorded at θ = 0.5°
Fig. 2 shows the intensity of XRF peaks of Sb-Lβ, and S-Kα and 1.5°. B — c) Sb2S3–CuS thin film heated at 400 °C in N2; and d) Sb2S3–
for Sb2S3 thin films (≈ 550 nm, as deposited) heated at 300 °C Ag2Se thin film heated at 300 °C in nitrogen in contact with a Se thin film.
5780 S. Messina et al. / Thin Solid Films 515 (2007) 5777–5782

AgSbSe2, (PDF # 12-0379). The reaction appears to be complete

in this case.

3.4. Optical properties

Optical transmittance spectra of Sb2S3 thin films and of

various other thin films produced from these, as described in
Fig. 3, are given in Fig. 4. The following heat treatments have
been applied: Sb2S3, heated at 300 °C in N2; Sb2SxSe3 − x
produced by heating in nitrogen at 300 °C a Sb2S3 film in
contact with ZnS–Se–ZnS thin film (Fig. 2 inset); CuSbS2
produced by heating in nitrogen at 400 °C a Sb2S3–CuS layer;
and AgSbSe2 produced by heating in air at 300 °C a Sb2S3–
Ag2Se layer in contact with a ZnS–Se–ZnS film.
Fig. 4. Optical transmittance of different crystalline thin films formed from
The optical absorption coefficient (α) for photon energies
Sb2S3 thin films; the values in the parentheses are the optical band gap obtained n
was  calculated using the equation: a ¼ d1 ln ð1−R
2
Þ
from (αhν)n versus hν plots. (hν)
 2T þ
2 1=2
g. Here d is the film thickness and T and R are
2
ð1−RÞ
2T þR2

fractional values of transmittance and reflectance. The values of

the optical band gap have been calculated from the best
3.3. Crystalline structure
straight line fits in (αhν)n versus hν plots. In general we
found that for n = ⅔ the correlation factor is the best. Thus,
XRD peaks are not observed in the case of as-deposited Sb2S3
the optical gap is direct but involves forbidden transitions
thin films [1,2]. When heated in air or N2 at temperatures above
[15].
250 °C these films produce XRD patterns matching that of the
mineral stibnite (PDF # 42-1393, as shown in Fig. 3A a). The
XRD patterns for a thin film of Sb2S3 recorded after heating in
contact with a Se thin film in N2 (or air) at grazing incidence
angles of 0.5° and 1.5°, are shown in Fig. 3A b) along with the
standard pattern for Sb2Se3 (PDF # 15-0681). The formation of
a solid solution is expected because both materials crystallize in
orthorhombic structure. It is seen in Fig. 3A b) that the top layer
of the Sb2S3 has been converted into a solid solution, with the
XRD peaks recorded at grazing incidence 0.5° staying midway
between that of Sb2S3 and Sb2Se3 in 2θ positions. The value of x
for the solid solution Sb2SxSe3 − x layer may be estimated using
Vegard's law for solid solutions, as illustrated for this material
[12]. In the present case x is b1.5 for the top layer. In the pattern
recorded at θ = 1.5°, the X-rays penetrate deeper into the layer,
and broader XRD peaks arise due to a continuous increase in x
toward the interior of the film. We have reported in [12] that
heating the layer at a higher temperature or for a longer duration
would lead to the formation of a solid solution Sb2SxSe3 − x with a
constant value of x throughout the film thickness. However, for
photovoltaic application, a film with graded composition and
hence of graded optical band gap may be more desirable.
The XRD pattern given in Fig. 3B c) is of a CuSbS2 thin
film formed by heating a Sb2S3–CuS layer in N2 at 400 °C
during 1 h, as suggested in [5]. The XRD pattern for the film
matches that of the mineral chalcostibite, (PDF # 44-1417) of
composition CuSbS2. The conversion of the layer to the
ternary compound predominates, but the presence of Sb2S3
(200) and (120) peaks suggests that the reaction is not
complete.
The reaction between Sb2S3 and Ag2Se in contact with Se
Fig. 5. Photoconductivity response curves of: a) antimony sulfide thin films
thin film at 300 °C in nitrogen results in the formation of heated in air and N2 with and without Se vapor; b) photoconductivity response
polycrystalline AgSbSe2 thin film, as shown in Fig. 3B d). The of CuSbS2 and AgSbSe2 thin films formed by heating Sb2S3–CuS and Sb2S3–
XRD peaks observed here match the standard pattern of Ag2Se layers.
 S. Messina et al. / Thin Solid Films 515 (2007) 5777–5782
3.5. Electrical properties
Antimony sulfide thin films heated with and without Se
in N2 at 300 °C shows the same order of photocurrent
response. However in the film heated in air in contact with a
ZnS–Se–ZnS film at 200 °C for 30 min, the photocurrent
response improves considerably, compared with an Sb2S3
film subjected to the same condition of heating. These results
are shown in Fig. 5. Both CuSbS2 and AgSbSe2 are also
photoconductive. The dark conductivity of these materials is
≈ 10− 3 (Ω cm)− 1, well suited to serve as p-absorbers.
4. Photovoltaic structure
Current (I)–voltage (V) characteristics of the photovoltaic
structures formed using the materials developed above are
shown in Fig. 6. The heterojunction SnO2:F–CdS–Sb2S3 was
heated in air at 250 °C during 30 min; it shows Voc = 470 mV and
Jsc = 0.02 mA/cm2 (Fig. 6a). The presence of a Se thin film
placed in contact with the structure during heating at 225 °C for
30 min in air improves the characteristics: Voc = 670 mV and
Fig. 6. I–V characteristics of the structures: a) TCO(SnO2:F)–CdS–Sb2S3; b)
TCO–CdS–Sb2S3–Sb2SxSe3 − x; c) TCO–CdS–Sb2S3–CuS; and d) TCO–CdS–
Sb2S3–AgSbSe2. In all the cases the illumination is from the TCO side and a
silver print contact of about 1 mm2 area painted over the top layer served as p-
side contact.
5781
Fig. 7. I–V characteristics of the structures TCO–CdS–Sb2S3–CuS–Ag(print)
and TCO–CdS–Sb2S3–AgSbSe2–Ag(print) in the dark and under illumination.
Jsc = 0.05 mA/cm2 (Fig. 6b). We found in this case that the silver
print electrode reacts with the top layer, probably forming a
Ag2Se layer, leading to a cell degradation. But on freshly
painted silver print electrodes the same characteristics are
obtained. This issue did not come up in cell structures with CuS
or AgSbSe2 as the top layer.
For the photovoltaic structures consisting of Sb2S3–CuS
(Fig. 6c), we used the first layer of Sb2S3 (300 nm) heated in
nitrogen at 300 °C, followed by the deposition of the second
Sb2S3 layer (300 nm) and subsequently the deposition of a
CuS thin film of 50–100 nm and heated in air at 200 °C. This
cell presents Voc = 460 mV and Jsc = 0.4 mA/cm2. For the
structure with AgSbSe2 (Fig. 6d) the Sb2S3 layer was heated
in air at 225 °C during 30 min in contact with a ZnS–Se–ZnS
film and another Sb2S3 film was deposited over this. The
Ag2Se film was deposited on this and the structure was
heated in nitrogen at 200 °C for 90 min in contact with a Se
thin film to form AgSbSe2. I–V characteristics for this struc-
ture show: Voc = 450 mV and Jsc = 1.4 mA/cm 2 . Fig. 7 shows
both I–V curves in the dark and under illumination for these
two cell structures. The presence of a high series resistance
as well as comparable parallel resistance is obvious in these
cells.
The deposition procedure described here avoided film peel-
off during sequential deposition. This process has to be
optimized in further work to improve the cell characteristics.
5782 S. Messina et al. / Thin Solid Films 515 (2007) 5777–5782
5. Conclusions
In this paper we presented a methodology to deposit Sb2S3
thin films of 500–600 nm in thickness, adequate for use in
photovoltaic structures from a single bath. This is an im-
provement over the methods reported previously, in which
multiple depositions have been used to build up the thickness
to this value. These films have been used to prepare solid
solutions of the type Sb2SxSe3 − x with graded composition and
optical band gap (≈ 1.3–1.7 eV) along the thickness, desired
in photovoltaic structures, by heating them in contact with a
chemically deposited Se thin film. Photovoltaic absorber films
of ternary compositions, CuSbS2 (band gap, 1.54 eV), and
AgSbSe2 (1.2 eV) may be produced from the Sb2S3–CuS and
Sb2S3–Ag2Se, which are photoconductive and possess dark
conductivity 10− 3 (Ω cm)− 1, suitable to serve as p-absorbers.
The use of these films in photovoltaic structures has been
illustrated. We consider that further work on the optimization
of the film thickness, thermal processing and cell con-
figurations would lead toward new solar cell technologies
using chemical bath deposition as the principal thin film
technique.
Acknowledgements
The authors are grateful to María Luisa Ramón and
Patricia Altuzar Coello, for recording the XRD and XRF
data; Oscar Gomez-Daza for the assistance in the optical
characterization and José Campos for the electrical charac-
terization. We acknowledge the financial support received
from DGAPA-UNAM (IN110906) and CONACYT (Project
40515-F and graduate fellowship for SM).
References
[1] O. Savadogo, K.C. Mandal, Sol. Energy Mater. 26 (1991) 117.
[2] M.T.S. Nair, Y. Peña, J. Campos, V.M. García, P.K. Nair, J. Electrochem.
Soc. 145 (1998) 2113.
[3] I. Grozdanov, Semicond. Sci. Technol. 9 (1994) 1234.
[4] O. Madelung, Semiconductors Other than Group IV Elements and III–V
Compounds, Data in Science and Technology, Springer-Verlag, Berlin
Heidelberg, 1992.
[5] Y. Rodríguez-Lazcano, M.T.S. Nair, P.K. Nair, J. Cryst. Growth 223
(2001) 399.
[6] Y. Rodríguez-Lazcano, M.T.S. Nair, P.K. Nair, J. Electrochem. Soc. 152
(2005) G635.
[7] O. Savadogo, K.C. Mandal, J. Phys., D, Appl. Phys. 27 (1994) 1070.
[8] O. Savadogo, K.C. Mandal, J. Electrochem. Soc. 141 (1994) 2781.
[9] K. Bindu, P.K. Nair, Semicond. Sci. Technol. 19 (2005) 1348.
[10] K. Bindu, José Campos, M.T.S. Nair, P.K. Nair, Semicond. Sci. Technol.
20 (2005) 496.
[11] K. Bindu, M.T.S. Nair, T.K. Das Roy, P.K. Nair, J. Electrochem. Solid
State Lett. 9 (2006) G-195.
[12] D.Y. Suarez-Sandoval, M.T.S. Nair, P.K. Nair, J. Electrochem. Soc. 153
(2006) C91.
[13] K. Bindu, M.T.S. Nair, P.K. Nair, J. Electrochem. Soc. 153 (2006) C526.
[14] B. Pejova, M. Najdoski, I. Grozdanov, S.K. Dey, Mater. Lett. 43 (2000)
269.
[15] R.A. Smith, Semiconductors, Second. Ed, Cambridge University Press,
Cambridge, 1978, p. 314.