ECS Journal of Solid State Science and Technology, 2 (4) Q69-Q73 (2013) Q69

2162-8769/2013/2(4)/Q69/5/$31.00 The Electrochemical Society

Antimony Chalcogenide/Lead Selenide Thin Film Solar Cell with

2.5% Conversion Efficiency Prepared by Chemical Deposition
M. Calixto-Rodriguez, Harumi Moreno Garca, M. T. S. Nair,,z and P. K. Nair
Centro de Investigacion en Energa, Universidad Nacional Autonoma de Mexico, Temixco, Morelos 62580, Mexico

Antimony sulfide-selenide solid solutions offer optical band gaps, Eg , in the 11.88 eV interval; and lead selenide offers Eg
upward of its bulk value, 0.28 eV, depending on the extent of quantum confinement. In this work, thin film solar cells of
SnO2 :F/CdS/Sb2 (Se/S)3 /PbSe/C-Ag are developed by chemical deposition of the thin films on transparent conductive oxide (TCO)
glass. To prepare the solar cell, first a CdS thin film of 100 nm in thickness is deposited on the TCO from a solution containing
Cd(II)-citrate complex. On this, a thin film is deposited from a solution containing potassium-antimony tartrate, thioacetamide and
selenosulfate, which upon heating at 280 C in nitrogen ambient results in a Sb2 S1.2 Se1.8 film of 150 nm in thickness with an Eg
of 1.67 eV. PbSe thin film 110 nm in thickness is deposited on it from a solution of Pb-citrate complex and selenosulfate, with
crystalline grain diameter 10 nm, and Eg of 1.86 eV. The cell shows open circuit voltage (Voc ), 454 mV, short circuit current density
(Jsc ) 12.5 mA/cm2 , fill factor (FF) 0.44 and conversion efficiency () 2.5%. The observed cell parameters are backed by a tentative
energy level diagram and an estimate for the light generated current density.
2013 The Electrochemical Society. [DOI: 10.1149/2.027304jss] All rights reserved.

Manuscript submitted January 15, 2013; revised manuscript received February 5, 2013. Published February 21, 2013.

Theoretical analyzes relating optical bandgap (Eg ) to solar en-
ergy conversion efficiency shows that semiconductor materials with
Eg in the 1.21.4 eV interval offers prospects as efficient pho-
tovoltaic absorbers.1,2 Antimony sulfide (Sb2 S3 ) and antimony se-
lenide (Sb2 Se3 ) with direct-Eg for bulk materials at 1.88 and 1 eV,
respectively3 produce solid solutions of Sb2 Sx Se3x with Eg within
this interval.4 Thin film solar cells of CdS/Sb2 S3 /PbS,5 and
CdS/Sb2 Se3 /PbS,6 as well as CdS/Sb2 S3 /PbSe,7 with conversion effi-
ciencies of up to 1% have been previously reported by us. In hybrid
hetero-junction solar cells using antimony sulfide as the absorber, con-
version efficiency of up to 3.9% are reported.8 Here we present thin
film solar cells using antimony chalcogenide (Sb2 Sx Se3x ) and PbSe
obtained by sequential chemical deposition with conversion efficiency
of up to 2.5% - the highest so far reported for this type of solar cell.
Experimental
Thin film deposition. For optical and electrical characterization,
thin films of CdS, Sb2 Sx Se3x , and PbSe are deposited on Corning
microscope glass slides of 7.5 cm x 2.5 cm, 1 mm in thickness.
Solar cell structures of CdS/Sb2 Sx Se3x and CdS/Sb2 Sx Se3x /PbSe
are developed on TEC-15 substrate (Pilkington, Toledo, USA) of a
transparent conductive oxide (TCO) coating of SnO2 :F on glass, with
nominal sheet resistance of 15 . The CdS thin films used as n-layer in
the cell is 100 nm in thickness with Eg 2.6 eV, deposited for 1 h at 80 C
from a chemical bath containing cadmium-citrate complex, reported
first in 1994.9 For the deposition of Sb2 Sx Se3x and PbSe thin films,
a sodium selenosulfate solution was first prepared by refluxing 4 g of
Se powder (ASARCO, 99.9%), 12 g of sodium sulfite (Na2 SO3 -Baker
Analyzed), and 100 mL of distilled water at a temperature near 100 C
for 5 h. The clear solution is of approximately 0.4 M in selenosulfate.
Sb2 Sx Se3x films. 16.6 mL of 0.1 M potassium antimony tartrate
(K2 Sb2 C8 H4 O12 3H2 O); 6.6 mL of 3.7 M triethanolamine (TEA),
2 mL of 15 M ammonia (aq.), 20 mL of 105 M silicotungstic acid
(STA, H4 Si(W3 O10 )4 ), 6.6 mL of 1 M thioacetamide (TA), 2 mL of
0.4 M selenosulfate solution, and distilled water to take the mixture
to 160 mL in volume in a 250 mL beaker. Substrates are vertically
mounted in this bath mixture. The basic idea for this formulation
comes from the work reported for Sb2 S3 thin films10,11 and later on
used for solar cells.12 This formulation works well to deposit anti-
mony chalcogenide thin films at 80 C in for 3 h on a CdS substrate
layer; it is not found suitable for depositing a film directly on a bare
glass substrate. The starting solution is clear with a pH 10.3. After
Electrochemical Society Active Member.
z
E-mail: mtsn@cie.unam.mx
the deposition, the filtered clear solution has a pH 9.6. When the
film is heated at 280 C for 30 min, an amorphous-to-crystalline trans-
formation produces an Sb2 Sx Se3x film of 150 nm in thickness. A
TCO/CdS/Sb2 Sx Se3x solar cell is completed by applying colloidal
graphite paint (SPI 05006-AB) over 5 mm x 5 mm area (0.25 cm2
in cell area) on the antimony chalcogenide film before heating. A
TCO/Sb2 Sx Se3x /PbSe solar cell has in addition a PbSe film deposited
on the heated antimony chalcogenide thin film, as described below.
PbSe thin film. For depositing this film, a chemical bath is pre-
pared by mixing solutions of 1 mL of 1 M Pb(NO3 )2 , 7 mL of 0.4 M
sodium citrate, 2 mL of 4 M NH4 OH, 1 mL of the selenosulfate, and
distilled water to complete a volume of 80 mL. The film is deposited on
Corning glass slides with a ZnS film (50 nm in thickness) as substrate
layer13 or on TCO/CdS/Sb2 Sx Se3x stack already heated at 280 C. A
PbSe thin film of 110 nm in thickness is deposited in 90 min, when the
bath is maintained at 40 C. To complete a TCO/CdS/Sb2 Sx Se3x /PbSe
cell structure, colloidal graphite paint of 0.25 cm2 in area is applied on
the PbSe film and heated at 60 C for 30 min. On TCO/Sb2 Sx Se3x /C-
as well as TCO/CdS/Sb2 Sx Se3x /PbSe/C- cells, colloidal silver paint
(DuPont PV428) is printed on the dried graphite electrodes and al-
lowed to dry at 60 C for 1 h. These cell structures are found to be sta-
ble during repeated measurement under sunlight for over eight months
so far.
Characterization. Film thickness is measured on an Ambios
Technology XP-200 thickness measurement unit. Grazing Incidence
X-ray Diffraction (GIXRD) patterns of a TCO/CdS/Sb2 Sx Se3x /PbSe
cell structure are recorded with the X-ray beam making an angle ()
of 0.2, 0.4, 0.6, and 1 with the plane of the sample. A Rigaku D-Max
2000 X-ray diffractometer using Cu-K radiation ( = 1.5406 )
is used for this measurement. The optical transmittance at normal
incidence (T) and specular reflectance spectra (R) of the films are
measured with a JASCO-670 spectrophotometer in the UV-VIS-NIR
region, at 2502500 nm wavelength range. To record the dark- and
photo- conductivity of the films, a bias of 10 V is applied across pairs
of silver print electrodes of 5 mm in length at 5 mm separation. The
current is recorded in the dark for 20 s and then under illumination
(800 W/m2 of intensity from a tungsten-halogen lamp) for another
20 s followed by a 20 s dark decay. The current-voltage (I-V) charac-
teristics of the cells are recorded in the laboratory using an intensity
of illumination 1000 W/m2 from a tungsten-halogen lamp. The Voc
and Jsc of the cells were then normalized using direct measurements
on the cell outdoor under 1000 50 W/m2 intensity of solar radiation
of nearly1.5 air-mass during mid-day.
Q70
(a)
900
Intensity (cps)
600
300
0 in the cell structure as Sb2 S1.2 Se1.8 . The presence of the PbSe and
20
1750
d = 0.5250 nm
(b)
1500
(002)
(110)
1250
Intensity (cps)
1000
750
500
250
(120)
0
10 20
Figure 1. (a) GIXRD patterns for the cell structure SnO2 :F/CdS/
Sb2 Sx Se3x /PbSe shown in the inset recorded at  = 0.2 and 0.4 ; (b) those
recorded at  = 0.6 and 1 .
Results and Discussion
Structural characterization. The GIXRD patterns on the cell
structure (see the inset) SnO2 :F/CdS/Sb2 Sx Se3x /PbSe are given in
Fig. 1a to analyze the PbSe film and in Fig. 1b to analyze the solid
solution, Sb2 Sx Se3x . At  = 0.2 and 0.4 , the patterns in Fig. 1a
are dominated by the top-lying PbSe thin film (110 nm). They match
the powder diffraction file (PDF) 060354 for the mineral clausthalite
(PbSe from a mine in Clausthal, Germany). The sampling depths
(SD) for the films for Cu-K radiation are estimated from the lin-
ear absorption coefficient for the X-ray for the constituent elements14
and the mass density of the substance,15 as described in previous
reports.7,16 For PbSe the SD at  = 0.2 is 23 nm and is 45 nm at
 = 0.4 . The peak positions of the sample maintain the same as that
in the standard powder pattern, but a tendency for preferential growth
with texture coefficient (TC >1) sets-in as the growth proceeds. This
leads to crystalline planes in the grains arranged perpendicular to
[111]: TC is 1.7 for the top 23 nm of the film, and 1.5 for the top
45 nm film and toward the Sb2 Sx Se3x /PbSe interface (Fig. 1b). Av-
erage grain diameter of the crystallites estimated using the Scherrer
formula for the top 23 nm is 10 nm and about 9 nm into the depth of
the PbSe film. Peaks seen in the 2 region of 3040 in the pattern
recorded at  = 0.4 correspond to underlying materials.
The diffraction patterns recorded at  = 0.6 (PbSe-SD: 70 nm)
and  = 1 (PbSe-SD: 115 nm) shown in Fig. 1b are also dominated
by PbSe diffraction peaks. Since the PbSe film thickness (110) is
approximately covered by the SD in both cases, the PbSe peak heights
for (111), (200) and (220) planes are not altered in intensity. However,
ECS Journal of Solid State Science and Technology, 2 (4) Q69-Q73 (2013)
increase in intensity is notable for the (110), (200) and (201) planes of
(200)
GIXRD: = 0.2 1 SnO2 for the pattern recorded at  = 1 compared with that recorded
( at  = 0.6 . The prominent (002) peak of CdS-hex9 overlaps with the
PbSe 110 nm (110) peak of SnO2 , and hence cannot be distinguished. The position
(111)
Sb2SxSe3-x150 nm of the antimony chalcogenide (221) peak located in between that of
CdS 100 nm Sb2 Se3 to the left and Sb2 S3 to the right, indicated in Fig. 1b, helps to
(220)
SnO2:F 500 nm estimate the chemical composition of this material.
To estimate the value of x in the Sb2 Sx Se3x solid solution, we
assume a linear variation of inter-planar spacing d(221) of 0.2868 nm
0.4
for Sb2 Se3 (PDF:06-0354) and 0.2765 nm for Sb2 S3 (PDF:42-1393)
in the GIXRD patterns of the cell structure at  = 0.6 and 1 . The
GIXRD peak for the solid solution is located at 2 = 31.86 , corre-
0.2 sponding to d(221) of 0.2807 nm, which is seen almost independent of
PbSe 06-0354 the sampling depth. This leads to the designation of the solid solution
40 60 SnO2 peaks in the patters at the exact locations with reference to the
2 (degree) respective PDFs supports that there is no peak shift caused by any
sample height mis-alignment in the measurement. Hence, the chemi-
cal composition estimated for the solid solution is reliable. We have
d = 0.2868 nm
d = 0.2765 nm
* SnO2 46-1088 observed that the content of selenosulfate in the deposition bath for
CdS 41-1049 Sb2 Sx Se3x can shift the value of x in the solid solution. The present
Sb2S3 42-1393 method of preparing the Sb2 Sx Se3x solid solution is distinct from that
(200)
reported by us earlier4 - in which a chemically deposited Sb2 S3 thin
(201)
*
* film was heated in contact with a chemically deposited selenium thin
*
film. The crystallite grain diameter for the Sb2 S1.2 Se1.8 thin film in
the cell structure is estimated from the non-overlapping peak of the
1 solid solution located to the right of (120) peak of standard Sb2 Se3
indicated in Fig. 1b; it is about 16 nm. The GIXRD patterns in Fig. 1a
Sb2S3 (221)
and 1b also confirms that the cell structure is composed of stratified
layers of CdS and Sb2 Sx Se3x underneath the PbSe thin film.
0.6
Optical and electrical properties of the Sb2 S1.2 Se1.8 and PbSe thin
(221)
Sb2Se3 06-0354 films. Figure 2 shows the T, R, and T+R spectra of: (a) PbSe
30 40 50 60 70 (110 nm) and (b) Sb2 S1.2 Se1.8 (150 nm) thin films. At wavelength
( > 1000 nm), T+R remain fairly constant at approximately 95%,
2 (degree) suggesting that the band-to-band optical absorption has not set in, and
any loss due to diffuse reflectance on a powdery surface is minimal
(up to 5%). At a wavelength below 750 nm, optical absorption across
a bandgap occurs. The optical absorption coefficients () for photon
energy (h) of the materials are calculated by taking into account
multiple reflections within the film of thickness d: 17
 1/2
  2
1 (1 R)2 (1 R)2
= ln + +R 2
[1]
d 2T 2T
These values are plotted in Fig. 2c, which indicate Eg for the materials
(for 0): 1.84 eV for PbSe and 1.69 eV for Sb2 S1.2 Se1.8 . The inset
(d) shows parts of (h)2/3 vs. h plots at which optical absorption
sets-in. This analysis is restricted to photon energy below 2.5 eV for
Sb2 S1.2 Se1.8 to avoid the optical absorption in the CdS substrate layer
and below 3.0 eV for PbSe film to avoid that in the ZnS substrate
layer. The straight line plots confirm that the optical transitions are of
the forbidden type across a direct bandgap18 of 1.86 eV for PbSe and
1.67 eV for Sb2 S1.2 Se1.8 thin film. These values of Eg will be used in
further discussion.
Discussion on the Eg . Quantum confinement of excitons and
consequent increase in Eg of PbSe19 and PbS20 nanocrystals (of a few
nanometers in diameter) are well studied. With a large Bohr radius
near 45 nm for the exciton ground state, drastic increase in Eg occurs
in these materials when crystallite diameter descend toward 10 nm
and less. In photovoltaic structures using PbSe quantum dots (QDs),
solar energy conversion efficiencies of up to 3.4% have been reported
when the QD diameters are below 2 nm.21,22 Consideration of PbSe
with a direct Eg of 0.278 eV at room temperature at the L-point of
the fcc-Brillouin zone23 as a solar cell absorber owes to increase in
Eg from 0.4 eV to 1.4 eV and consequent increase in Voc as the QD
diameter drops from 10 nm toward 2 nm.19 At QD diameters above
 ECS Journal of Solid State Science and Technology, 2 (4) Q69-Q73 (2013) Q71

-5
100 (a) 10
T+R PbSe (110 nm) PbSe (110 nm)
80
-6
10
T, R (%)

-1
60 Sb2SxSe3-x

( cm)
T
(150 nm)
40 R -7
10

20

-8
0 10
500 1000 1500 2000 2500 0 20 40 60 80 100 120
(nm) time (sec.)

Figure 3. Photoconductivity response plots for PbSe (110 nm) and

100 (b) Sb2 Sx Se3x (150 nm) thin films under an intensity of illumination, 800 W/m2
T+R Sb2SxSe3-x (150 nm) from a tungsten-halogen lamp.
80
For Sb2 S1.2 Se1.8 thin film, a linear variation of Eg in the 1.0 eV
(Sb2 Se3 ) 1.88 eV (Sb2 S3 ) range3 would mean an Eg of 1.31 eV
T, R (%)

60 R
for the solid solution, in case quantum confinement does not exist at
crystalline grain diameter 16 nm (result from GIXRD). The high static
40 T relative permittivity of > 100 for antimony chalcogenides,3 however,
brings-in a large Bohr radius for the exciton ground state for the solid
20 solution, just as in lead chalcogenides. This could explain why the Eg
of 1.64 eV determined from Fig. 2c for Sb2 S1.2 Se1.8 is more than that
is expected for Sb2 S1.2 Se1.8 based only on the chemical composition.
0
500 1000 1500 2000 2500 Electrical conductivity. In the photoconductivity response plots
(nm) given in Fig. 3 for both the absorber materials, the electrical conduc-
tivity under illumination is 1.9 107 ( cm)1 for Sb2 S1.2 Se1.8 film
6
10
and 2.4 106 ( cm)1 for the PbSe film. Thermoelectric measure-
(c) ment on the PbSe film suggests that it is a p-type material. Due to the
Sb2SxSe3-x PbSe high electrical resistivity of Sb2 S1.2 Se1.8 , its conductivity type could
5
10 not be ascertained. We assume that it is of n-type as reported for Sb2 S3
films deposited from chemical bath containing silicotungstic acid and
used in solar cells.12 The majority carrier concentration (nn for n-type
4 6
10 and pp for p-type) in the thin films under the illumination may be
2/3
-1

(d)
(cm)

(h) ,10 (cm eV)

5
Sb2SxSe3-x PbSe estimated by assuming carrier mobility of 10 cm2 V1 s1 a usual
-1

4 value for polycrystalline semiconductor materials with crystallite di-

3
10 3 ameters < 20 nm. Such estimates give nn , 1011 cm3 for Sb2 S1.2 Se1.8
3

2 and pp , 1012 cm3 for PbSe. The intrinsic carrier concentrations (ni )
2/3

are estimated from the optical band gaps from Fig. 2d using standard
1.69 eV

1
1.84 eV

2
10
0
1.67 eV
1.0 1.5
1 h (eV)
10
1.0 1.5 2.0 2.5
h (eV)
Figure 2. (a) Optical transmittance T and reflectance R versus wavelength
plots for PbSe film and (b) Sb2 S1.2 Se1.8 thin film; (c) optical absorption coef-
ficient versus photon energy plots for the films; inset (d): bandgap analysis for
the films.
4 nm, the prospects for such application is reported to disappear. In the
case of PbS, a compilation of data on the QDs suggests that in order
to bring Eg above 1.0 eV, the diameter has to be below 5 nm.20 Thus,
it is intriguing that in the present case an Eg of 1.86 eV is estimated
from the optical T and R data for a PbSe thin film, 110 nm in thickness
(Fig. 2) for which the XRD data suggest an average crystalline diam-
eter of 9-10 nm (Fig. 1). However, such a high Eg may be accepted
as possible if one considers that unlike in the case of QDs in which
the experimental methodology for their preparation provides the QD
diameter distribution strongly peaked near the stated value, no such
control exists in the chemical bath deposition for PbSe reported here.
1.86 eV procedure,24 and are 104 cm3 for Sb2 S1.2 Se1.8 and 3 102 cm3 for
2.0 2.5 3.0 PbSe. The approximate positions of the quasi-Fermi levels can thus
be determined as 1.25 eV above the valence band for Sb2 S1.2 Se1.8 and
3.0 3.5 0.36 eV above the valence band for PbSe thin films. Overall, the char-
acteristics of the PbSe thin film seen here are markedly different from
that reported by us earlier for those used in TCO/CdS/Sb2 S3 /PbSe so-
lar cells which showed Eg of 0.690.85 eV and electrical conductivity
0.5 ( cm)1 . In that work the chemical formulations used for PbSe
thin film deposition were distinct.
Energy level diagram. A tentative energy level diagram for
the present case may be set up following the approach described
previously7,25 from the electron affinity26 and ionization energy27 of
the constituent elements of the semiconductor compounds. The elec-
tronegativity (EN) of the element is the arithmetic mean of its electron
affinity and the ionization energy, and the EN of the compound is the
geometric mean of the EN of the constituent elements, considered
to coincide with the intrinsic Fermi level of the substance. Thus, an
estimate for the electron affinity () of the substance with respect to
vacuum level is, EN Eg /2, which is, 5.52 eV for Sb2 S1.2 Se1.8 and
5.00 eV for PbSe. A value of , 4.5 eV for SnO2 is assumed,25
which also represents its work function, for being a TCO. Electron
Q72 ECS Journal of Solid State Science and Technology, 2 (4) Q69-Q73 (2013)

Vacuum level 20
0
Sb2SxSe3-x/
-1 15 PbSe(110 nm)
14.8
= 4.07 eV
= 4.68 eV

JL (mA/cm2)
-2 = 4.5 eV 11.5
10
Energy (eV)

EFn= 5.1 eV
= 4.5 eV
-3 EFn= 4.7 eV EFp= 5.57 eV
7.2
= 5 eV 5
-4 Sb2SxSe3-x

-5 SnO2:F Eg= 1.86 eV /////// 0

C 0
Eg= 1.67 eV
Eg= 2.48 eV
-6
PbSe
Sb2S1.2Se1.8
-7
CdS
Figure 4. Tentative energy level diagram for the TCO/CdS/Sb2 Sx Se3x /
PbSe/C layers estimated from the results presented in Figs. (1)(3).
affinity of 4.5 eV is a typical value considered for CdS.28 Its Eg
is 2.48 eV because the thin film is subjected to heating (along with
an overlying Sb2 Sx Se3x thin film) at 280 C. The Eg of as-prepared
CdS film (100 nm) by the citrate-complex method is 2.6 eV.9 The
positions of the conduction band, valence band and the Fermi levels
(dashed lines) with respect to the vacuum level estimated this way for
the materials constituting the heterojunction are given in Fig. 4. The
difference in the Fermi levels between the CdS window (4.7 eV)
and Sb2 S1.2 Se1.8 (5.1 eV) suggests a built-in voltage (Vbi ) of nearly
400 mV for this junction. This value may be representative of the
upper limit for the Voc for the TCO/CdS/Sb2 Sx Se3x /C-Ag cell under
the illumination level considered.
With a PbSe absorber of p-type conductivity, a higher Voc could be
expected from the energy level scheme due to additional Vbi of 470 mV
across the Sb2 S1.2 Se1.8 /PbSe junction. A carbon electrode with Fermi
level at 5 eV (work function, 5 eV), is not an appropriate contact
for PbSe with its Fermi level at 5.57 eV. However, with the PbSe
film placed behind Sb2 S1.2 Se1.8 , it is at a lower illumination level and
hence the quasiFermi level will be closer to mid gap (5.00 eV). The
tentative energy level diagram proposed in Fig. 4 is a working model
and requires refining, as further results come in on the conductivity
type and chemical composition of the solid solution.
Light generated current density of solar cell absorbers. The light
generated current density (JL ) in optical absorber material represents
100 200 300 400 500
Sb2SxSe3-x thickness (nm)
Figure 5. Upper limit of the light generated current density (JL ) as a
function of film thickness expected in solar cells using Sb2 Sx Se3x and
Sb2 Sx Se3x /PbSe(110 nm) absorbers.
Sb2 S1.2 Se1.8 will absorb Nph (h) of 1.60 1021 m2 s1 and pro-
duce JL of 25.7 mA/cm2 and PbSe will absorb Nph (h) of 1.16
1021 m2 s1 and provide JL of 18.6 mA/cm2 . Values of JL for
the ITO/CdS/Sb2 S1.2 Se1.8 and TCO/CdS/Sb2 S1.2 Se1.8 /PbSe(110 nm)
cells as a function of Sb2 S1.2 Se1.8 film thickness are given in Fig. 5.
We do not consider here reflection or recombination losses, multi-
ple exciton generation, gain from any back reflection or absorption
loss in glass, TCO or CdS. For an absorber thickness of 150 nm,
ITO/CdS/Sb2 S1.2 Se1.8 will have a JL (or upper limit of Jsc ) of
11.5 mA/cm2 and that for the TCO/CdS/Sb2 S1.2 Se1.8 /PbSe(110 nm),
it is 14.8 mA/cm2 . For a single absorber thickness of 110 nm, PbSe
will give a JL of 7.2 mA/cm2 , but it adds only 3.3 mA/cm2 to the
11.5 mA/cm2 available from Sb2 S1.2 Se1.8 when placed behind the
Sb2 S1.2 Se1.8 film.
Solar cell structures. Figure 6 shows the current vs. voltage
(J-V) characteristics for the structures: (a) TCO/CdS/Sb2 Sx Se3x /C-
Ag showing an open-circuit voltage (Voc ) of 438 mV, short-circuit cur-
rent density (Jsc ) of 8.68 mA/cm2 , fill factor (FF) of 0.38, and conver-
sion efficiency () of 1.45%; and (b) TCO/CdS/Sb2 Sx Se3x /PbSe/C-
Ag, with Voc of 454 mV, Jsc of 12.52 mA/cm2 , FF of 0.45, and of
2.56%. The values are normalized to represent AM 1.5 G (1000 W/m2 )
Voc Jsc FF
2
) %
J (mA/cm2)

the upper limit of Jsc when it forms the absorber element in a solar 454 12.52 0.45 2.56
4
cell structure when illuminated with the same radiation.29 Value for
JL may be estimated for AM 1.5 (1000 W/m2 ) photon flux density30 2
Nph (h) for a single absorber of Eg1 or for two absorbers, of Eg1
0
followed at rear by another of Eg2 with film thickness d1 and d2 and -200 -100 0 100 200 300 400 500
absorption coefficients 1 and 2 , respectively as illustrated previ- -2 V (mV)
ously for Bi2 S3 /PbS31 and Bi2 S3 /Si32 heterojunction solar cells. In the
-4 Ag
TCO/CdS/Sb2 S1.2 Se1.8 /PbSe cell, absorber1 is Sb2 S1.2 Se1.8 with Eg1 (a) (b) C
1.67 eV and absorber-2 is PbSe with Eg2 1.86 eV and its JL is: -6 Ag
PbSe
 -8
(a) C
Sb2S1.2Se1.8
JL (m A/cm 2 ) = 0.1q N Ph (h)(1 e1 d1 )d E Sb2S1.2Se1.8
1.67eV -10 CdS CdS
 (b) SnO2:F SnO2:F
-12
+ 0.1q N Ph (h)e1 d1 [(1 e2 d2 )]d E
1.86eV -14 Sunlight Sunlight
[2]
Figure 6. Current density versus applied bias normalized for AM 1.5 G
Here q is the electron charge, 1.602 1019 C; Nph (h) is of (1000 W/m2 ) solar radiation for the cell type (a) and (b), illustrating the contri-
the order of 1021 m2 s1 (eV)1 ; and dE is the differential pho- bution of the PbSe thin film toward the cell performance (for layer thicknesses,
ton energy h in eV. For a single absorber with thickness d , refer to inset in Fig. 1a).
 ECS Journal of Solid State Science and Technology, 2 (4) Q69-Q73 (2013)
solar radiation. The increase in Voc when the PbSe absorber is added
is very little (16 mV). However, Jsc is enhanced by nearly 50% estab-
lishing that PbSe indeed participate in the photo-carrier generation.
The observed Jsc of 8.68 mA/cm2 is comparable with the estimate for
JL , 11.5 mA/cm2 for the Sb2 Sx Se3x (150 nm) absorber; and Jsc of
12.52 mA/cm2 is comparable with the estimate of 14.8 mA/cm2 for
Sb2 Sx Se3x (150 nm) + PbSe (110 nm) absorbers. Thus, Voc as well
as Jsc are in reasonable proximity with the values expected from the
tentative energy level diagrams in Fig. 4 and JL plots of Fig. 5.
While the conversion efficiency of 2.56% reported for
TCO/CdS/Sb2 S1.2 Se1.8 /PbSe/C cell is larger than what has been re-
ported for TCO/CdS/Sb2 S3 /PbSe/C-Ag cells (1%), the Voc in the
present case is significantly smaller than 690 mV reported for such
cells.7 We may note from Fig. 4 that it is important to identify and
apply a more adequate p-side contact with a work function of 5.57 eV
or higher to avoid collection loss at the p-side. The series resistance
of the TCO/CdS/Sb2 S1.2 Se1.8 /PbSe/C-Ag cell is high: > 10  cm2
and the parallel resistance is low, 400  cm2 , which keeps the fill
factor, FF < 0.5 and hence the conversion efficiency below 3%. For
higher efficiency cells, the series resistance is an order of magnitude
lower and FF > 0.6. The composition of Sb2 Sx Se3x may have to be
reduced in x and appropriate heating/re-crystallization process should
be established to increase the Voc .
The thickness of CdS is not yet optimized for this type of cell.
Further comments on Sb2 Sx Se3x /PbSe solar cell absorbers. We
want to highlight here that other techniques exist for the preparation of
Sb2 Sx Se3x solid solutions. Pulsed vapor-liquid-solid growth of Sb2 S3
and Sb2 Se3 or solid solutions of the materials are reported using
tris(dimethylantimony) Sb(NMe2 )3 and diethyldiselenide (Et2 Se2 )
or H2 S in an adapted atomic layer deposition set-up.33 Synthesis
of sulfurized Sb2 Se3 with composition Sb2 Se3-x Sx (0 x 2)
in a microwave-stimulated solvothermal process uses thioglycolic
acid (TGA)-ligated antimony salts and tri-n-octylphosphine (TOP)-
ligated selenium, with the sulfur content being varied by adjusting the
TGA/TOP-Se2 molar ratio.34 Solid solutions of Sb2 Sx Se3x may be
produced as well by direct evaporation of Sb2 S3 -Se powder mixture.35
The resultant materials through these routes carry distinct crystalline,
compositional and morphological features. In large area applications,
safety and toxicity issues of antimony might become relevant. A study
on antimony sulfide reported in 2002 describes the materials as rel-
atively safe, but underlines various aspects to be considered among
possible occupational hazards in handling such materials.36 Regarding
safety issues of chemically deposited lead chalcogenide (PbS) films,
a conclusion has been drawn that chemical deposition is a relatively
safe method for the thin films and that the chalcogenides as products
are relatively safer than volatile organic substances of lead.37
Conclusions
For the first time, antimony chalcogenide/lead chalcogenide thin
film solar cell has reached conversion efficiency above 2.5%, mea-
sured under solar radiation normalized to AM 1.5 G (1000 W/m2 ).
This cell without any encapsulation had remained stable over a period
of Feb. Nov. 2012, in repeated measurements; thus the cell structure
is accepted as stable. Reproducibility of the performance of the cell
in repeated trials is good. Antimony chalcogenide absorber thickness
presented is 150 nm, close to what is typically used in hybrid solar
cells substituting the Ru-dye,8 for which conversion efficiency of up
to 3.9% has been reported. Increase in the thickness of the antimony
chalcogenide absorber beyond 150 nm through a successive chemical
deposition did not yield better cell performance. This is due to the
small crystalline grain diameters, <20 nm, which would cause pre-
dominant recombination loss in the inter-grain region. Benefit from
such increased absorber thickness toward Jsc would follow an effective
re-crystallization process.
Q73
Acknowledgments
We are grateful to Mara Luisa Ramon Garca and Patricia
E. Altuzar Coello for measuring GIXRD data, Jose Campos for
the electrical characterization and to Oscar GomezDaza for assist-
ing in the film preparation and optical characterization. This work
was supported by PAPIIT-UNAM (IT112511) and SEP-CONACyT
(CB-79938), LIFYCS-CONACYT 123122, and ICYTDF 307/2009.
HMG acknowledges CONACyT-Mexico and UdG- Centro Universi-
tario de los Valles for a postdoctoral fellowship.
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