Thin Solid Films 595 (2015) 5–11

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Thin Solid Films

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Sulfurization of sputtered Ag–In precursors for AgInS2 solar cell

absorber layers
M. Anantha Sunil a, Narayana Thota b, K.G. Deepa a, Nagaraju Jampana a,⁎
a
Energy and Health Monitoring Instrumentation Laboratory, Department of Instrumentation & Applied Physics, Indian Institute of Science, Bangalore 560012, India
b
Advanced Materials Research Laboratory, Department of Physics, Yogi Vemana University, Kadapa 516003, India

a r t i c l e i n f o a b s t r a c t

Article history: Silver indium sulfide (AgInS2) thin films are deposited by sequential sputtering of metallic precursor [Ag/In]
Received 17 June 2015 followed by sulfurization. Effect of substrate temperature (Tsub ) during sulfurization process on the
Received in revised form 9 October 2015 film growth is studied by varying the substrate temperature from 350 to 500 °C. Films prepared above
Accepted 21 October 2015
350 °C showed a mixture of orthorhombic and tetragonal phases of AgInS2 with tetragonal phase being
Available online 23 October 2015
dominant. Better crystalline, nearly stoichiometric and p-type films are obtained at a substrate tempera-
Keywords:
ture of 500 °C. The characteristic A 1 mode of AgInS 2 chalcopyrite structure is observed in the Raman
AgInS2 (AIS) spectra at 274 cm− 1 for the films prepared above 350 °C. The grain size of the film increases from 489
DC-sputtering to 895 nm with the increase in substrate temperature. The binding energies of the constituent elements
Sulfurization are determined using XPS. The band gap of AgInS2 films is in the range of 1.64–1.92 eV and the absorp-
P-type films tion coefficient is found to be N104 cm− 1. Preliminary studies on the AgInS 2/ZnS solar cell showed an
Absorption coefficient efficiency of 0.3%.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction on the properties of AgInS2 films prepared by spray pyrolysis technique.

Thin film solar cells have gained great attention of researchers
owing to their potential to reduce manufacturing costs and material
utilization. Over the years, materials belonging to I–III–VI 2 group
(CuInSe2, CuInS2, Cu (In, Ga) Se2) have been studied extensively by
various techniques in order to enhance the performance of thin
film solar cell. As on date, Cu (In, Ga)Se2 based solar cell holds the
record for highest efficiency of ~ 20.5% [1]. AgInS 2 is a unique
semiconductor material belonging to I–III–VI 2 group which exists
in both chalcopyrite and orthorhombic phase. It has direct band
gap of 1.8 eV and its absorption coefficient is greater than
104 cm − 1 . AgInS 2 is used for wide range of applications such as
photo-electrochemical, optoelectronic and photovoltaics [2–4].
AgInS2 is a solid candidate for both single junction and tandem
solar cells. The band gap of this material could be brought down by
controlling the composition of films.
AgInS2 thin films are deposited using both physical and chemical
methods. Wang et al. [5] deposited AgInS2 films on fluorine tin oxide
(FTO) substrates by using one-step electro-deposition. Jin et al. [6] syn-
thesized the AgInS2 films on TiO2/FTO substrate by hydrothermal route
and demonstrated the performance of photo-electrode. Lopez et al. [7]
studied the effect of growth temperature and chemical composition
⁎ Corresponding author.
E-mail address: solarjnr@gmail.com (N. Jampana).
Lin et al. [2] deposited AgInS2 thin films by chemical bath technique
and demonstrated the ability to control the compositions of
multi-component semiconductor thin films. Jia et al. [7] and Lei
et al. [8] have carried out studies on hybrid solar cells using Ag2S
and In 2S 3 as electron acceptors by wet-chemical sulfurization.
A few other research groups have studied the properties of AgInS2
films by varying spray parameters like substrate temperature,
deposition time and concentration of precursor solution using pneu-
matic and ultrasonic spray pyrolysis technique [9–14]. Akaki et al. [15]
studied the properties of AgInS2 films on glass substrates using single
source thermal evaporation of Ag2S and In2S3 powders. Cheng et al.
[16] prepared AgInS2 films by sulfurization of thermally evaporated
Ag and In metal precursors. Arredondo et al. [17] prepared AgInS2
films using co-evaporation method. They used Ag, In and a tantalum
effusion cell for sulfur as sources to form AgInS2 films. You et al. [18]
prepared AgInS2 films using hot wall epitaxy method where shot type
Ag, In and S were used as the sources. Here, growth of AgInS2 thin
films by sulfurization of sputter deposited Ag/In metallic layer is
presented. The advantages of this method are highly crystalline,
stoichiometric and reproducible films could be achieved. Thickness
could be controlled by varying deposition rate. No toxic gases are used
for sulfurization and uniform deposition over large area substrates
is realistic. The structural, morphological, optical and electrical prop-
erties of AgInS2 thin films as a function of substrate temperature are
presented. A trial for fabrication of solar cell is done using the
optimized sample with ZnS as window layer.

http://dx.doi.org/10.1016/j.tsf.2015.10.050
0040-6090/© 2015 Elsevier B.V. All rights reserved.
6 M. Anantha Sunil et al. / Thin Solid Films 595 (2015) 5–11

2. Experimental

2.1. Substrate cleaning

Prior to deposition, soda lime glass (SLG) substrates are dipped in

chromic acid solution (10 g of chromic acid dissolved in 100 ml of DI
water) for 10 min. In order to remove any oil traces present on the sub-
strate, the substrates are cleaned in IPA bath for 10 min and dried with
nitrogen flush.

2.2. Deposition of metallic layer [Ag/In]

Thin films of silver (Ag) and indium (In) are deposited layer by layer
on SLG substrates using 3- target 4-holders DC magnetron sputtering
system (Tecport sputter coater, USA).The sputtering targets are placed
in such a way that deposition takes place in sputter up configuration.
Prior to deposition the chamber is evacuated to an ultimate vacuum
of 10− 6 mbar using turbo-molecular pump. During the deposition,
ultra pure argon gas is used to maintain the sputtering pressure of
1 × 10− 3 mbar and the gas flow is monitored using a mass flow con-
troller. Contaminants on the surface of the targets are removed by Fig. 1. X-ray diffraction patterns of AgInS2 films at different Tsub (a) AIS350, (b) AIS400,
(c) AIS450, (d) AIS500.
pre-sputtering in argon environment. Deposition of Ag and In is carried
out at room temperature under rotation conditions to achieve uniform
deposition. All this process is carried out in Class 1000 environment.
Table 1 shows the deposition parameters for the preparation of Ag-In area of 0.03 cm2 are deposited over ZnS layer by sputtering, which
layer used in the present study. acts as top electrode.

2.5. Characterization
2.3. Sulfurization
X-ray diffraction (XRD) measurements are performed using Bruker
A two-zone tubular quartz furnace of 1.2 mL with 50 mm ID and
D8 operated at 40 kV and 40 mA. Cu Kα line having a wavelength
55 mm OD (INDFURR) is used for sulfurization. One end of the quartz
of 1.54 Ǻ is used as the radiation source and the diffraction pattern
tube is connected to the rotary pump whereas the other end is connect-
is recorded from 20 to 90°. Raman scattering analysis is carried out
ed to the nitrogen gas cylinder which is used as carrier gas. The molyb-
using Jobin Yvon LabRAM HR. Argon ion laser having a wavelength
denum boat containing sulfur (S) powder is kept at zone I and Ag/In
of 514 nm is used as the excitation source and the spectrum is
deposited film is kept in a graphite holder at zone II. The temperature
recorded from 50 to 500 cm−1. Scanning Electron Microscopy (SEM)
of zone I is kept constant at 130 °C (melting point of sulfur). The temper-
and Energy Dispersive X-ray Analysis (EDX) are carried out using FEI
ature at zone II is varied from 350 to 500 °C in steps of 50 °C and the
ESEM quanta-200. SEM of sample surface is taken with an acceleration
samples are named as AIS350, AIS400, AIS450 and AIS500. Sulfurization
potential of 20 kV. EDX measurement is carried out over an area of
process in zone II is maintained for 1 h at each temperature. The temper-
5 × 5 μm2 in a collection time of 20 s. Atomic force microscopy (AFM) im-
ature of the quartz tube is cooled naturally to room temperature.
ages of the AgInS2 films are obtained using Bruker Dimension Icon Sys in
Base pressure of 20 mbar is maintained in the tube with the help of
rotary pump.

2.4. Fabrication of solar cell

Solar cell is fabricated on ITO coated glass plates having a sheet

resistance of 8 Ω/□, which act as bottom electrode. AgInS2 films are
deposited on ITO substrates by sulfurization of sputter deposited Ag-In
metallic layer. 70 nm thick zinc sulfide (ZnS) is deposited on AgInS2
films using thermal evaporation technique. Ag electrodes having an

Table 1
Sputtering conditions of Ag–In layer.

Sputter process parameter Ag In

Sputtering Target 99.999% pure 99.99% (76 mm

(70 mm diameter diameter and
and 6 mm thick) 6.35 mm thick)
Substrate Glass/Ag Glass/Ag/In
Target to substrate distance (cm) 7.5 7.5
Pre-sputtering time (min) 2 5
Deposition time (min) 16 13
Sputter power (W) 25 60
Rotation (rpm) 10 10
Fig. 2. Raman scattering of AgInS2 films at different Tsub (a) AIS350, (b) AIS400, (c) AIS450,
Argon (sccm) 50 50
(d) AIS500.
 M. Anantha Sunil et al. / Thin Solid Films 595 (2015) 5–11 7

Table 2
Raman modes of AgInS2 films grown at different Tsub.
Sample Name Observed modes (cm−1)
A1 B2, E1 E1 Cu–Au
AIS350 – – 64
AIS400 274 – 340 64, 305
AIS450 274 – 340 64, 305
AIS500 274 225 340 64, 305
tapping mode configuration. Absorption spectra are recorded from 300
to 1000 nm using UV–VIS spectrophotometer (Specord S600UV-VIS)
and electrical properties are determined using four-point probe method
(Four dimensions probe meter model 280). X-ray photoelectron spec-
troscopy studies are carried using Axis DLD photoelectron
spectrometer at a pressure of 2.6 × 10− 9 Pa. Aluminum (Al) k-alpha
energy of 1.486 keV is used as the X-ray source at operation conditions
of 15 kV and 10 mA. Acceleration voltage is 3.8 kV. Ar+ ions are used as
the sputtering source to etch the films for depth profiling. The
sputtering is done with beam energy of 4 keV and current density of
140 μA/cm2. The fabricated solar cell is characterized using Oriel sol3
A™ solar simulator under AM1.5 condition. The cell is illuminated
from the top side and area under illumination is 0.03 cm2.
3. Results and discussion
Fig. 1 shows the XRD pattern of AgInS2 films deposited at different
substrate temperatures (Tsub). Films deposited at Tsub = 350 °C
exhibited cubic spinel AgIn5S8 structure along with traces of In2S3
phase. Preferential orientation is along the (422) plane of AgIn5S8
(JCPDS 26-4177). With the increase in Tsub, all the samples showed
AgInS2 phase with preferential orientation along (112) plane. Films ex-
hibited peaks corresponding to (103), (200), (004), (211), (220), (204),
(301), (312), (116), (316) and (424) planes of tetragonal structure
(JCPDS 75-0117). In addition, peaks corresponding to (202) and (200)
planes of orthorhombic structure of AgInS2 (JCPDS 25-1328) are
observed. No binary phases are detected for samples prepared at
Tsub N 350 °C. Crystallinity of films improved with the increase in
substrate temperature. XRD pattern shows that sample AIS500 has the
highest intensity along (112) plane. Films are found to be porous in
nature when Tsub N 500 °C and hence studies have not been carried
out beyond this temperature.
Raman spectroscopy is used to determine both the structure and
different vibration modes in the sample. The Raman active modes of
vibrations for I-III-VI2 chalcopyrite structure [19] is represented as.
Γvib ¼ A1 þ 3B1 þ 3B2 þ 6E
Here, A1 mode corresponds to the vibration of anions (S) in the x-y
plane with cations (Ag and In) at rest. The frequency of this mode is
associated with the mass of anion and the bond-stretching force of
anion-cation bonds. B1 mode corresponds to the frequency of vibration
of cations (Ag and In) in anti-phase. B2 and E mode reflects the vibration
of In-S atoms in anti-phase. B2 type modes are excited for light polarized
parallel to the optic axis and E type are excited only for light polarized
perpendicular to the optic axis.
Fig. 2 shows the Raman spectrum of AgInS 2 films and modes
3F2g
present are shown in Table 2. The slight shift in peaks may be
due to stress or defects in the films. Sample AIS350 showed
327
peaks at 64 and 327 cm− 1. The peak at 327 cm− 1 corresponds to
–
– 3F 2g Raman active mode of AgIn 5 S 8 structure. The presence of
– AgIn5S8 phase observed in the XRD pattern is confirmed from the
Raman spectrum. All other samples showed a prominent peak at
274 cm− 1, which is the characteristic peak of AgInS2 chalcopyrite
structure. This peak corresponds to the A1 mode of the tetragonal
AgInS 2 . The peaks at 225 and 340 cm − 1 corresponds to B 2 or E 1
modes of vibration respectively. In addition, two modes at 64 and
305 cm− 1 are present which does not belong to chalcopyrite struc-
ture. The mode of vibration corresponding to these peaks is not
known clearly. These modes have been observed in other I-III-VI2
group chalcopyrite semiconductors as well [12,20]. One of the rea-
sons for the appearance of these modes is the Cu–Au ordered
structure and Cu-poor films. In the present work, appearance of
these modes could be due to silver poor films. The absence of this
mode in the film AIS350 which has higher Ag concentration, con-
firms this assumption. The orthorhombic phase observed in the
XRD pattern is due to the Cu–Au ordered structure. With increase in
Tsub, intensity of A1 mode increased in proportion to the crystallinity
of the sample.
Table 3 shows the composition of AgInS2 films grown at different
Tsub. Sample AIS350 is rich in In concentration, there by resulting in
the AgIn5S8 and In2S3 phases that is observed in XRD pattern. The sam-
ples are found to be nearly stoichiometric with the increase in Tsub. It is
observed that sulfur is incorporated into the metallic precursor layers
[Ag/In] (Table 1). The precursor ratio [S/(Ag + In)] for sample AIS500
is equal to 1 which shows films are completely sulfurized.
Surface morphology of AgInS2 thin films are analyzed using SEM and
AFM. Fig. 3 shows the surface morphology of AgInS2 thin films. With the
increase in substrate temperature, the grain size increases from 489 nm
to 895 nm. The highest grain size is obtained for sample AIS500. Fig. 3
shows that surface of sample AIS350 is inhomogeneous in shape,
which might be due to the non-stoichiometry and presence of binary
phases in the film. Shape of the grains changed from spherical to flowers
and rods with Tsub N 350 °C. The grain size of the AgInS2 films became
larger with increase in substrate temperature and the maximum grain
size of 895 nm is obtained for sample AIS500. Larger grain size helps
in reducing the grain boundary scattering and thereby improving the
efficiency of the solar cell.
Fig. 4 shows the AFM images of AgInS2 thin films deposited at differ-
ent Tsub. There is a significant variation in the shape of the grains with
the composition. Ag-rich film (AIS350) showed pyramidal shaped
ð1Þ grains and In-rich films (AIS400–AIS500) showed spherically shaped
grains. The AFM images of AgInS2 thin films confirm the increase in
grain size with the increase in substrate temperature. The grain
size depends on initial nucleation density and recyrstallization process.
Recrystallization into larger and non-aggregated grains is enhanced
at higher temperatures. Similar phenomenon was observed in growth
of CuInS2 thin films by spray pyrolysis [21]. With the increase in sub-
strate temperature, the roughness of films increased from 81 nm to

Table 3
EDX analysis of AgInS2 films grown at different Tsub.

Sample name Atomic percentage of elements Atomic ratio Grain size (nm) Band gap (eV)

Ag (%) In (%) S (%) [S/(Ag + In)] (Δy = [2S/Ag/In) − 1]

AIS350 29.02 34.01 36.97 0.58 −0.24 489.5 1.92

AIS400 23.73 27.44 48.81 0.95 −0.08 683.8 1.71
AIS450 24.70 26.63 48.5 0.94 −0.08 784.7 1.68
AIS500 22.41 26.27 51.32 1.00 0.01 895.5 1.64
8 M. Anantha Sunil et al. / Thin Solid Films 595 (2015) 5–11

Fig. 3. SEM images of AgInS2 films at different Tsub (a) AIS350, (b) AIS400, (c) AIS450, (d) AIS500.

260 nm. Large surface roughness is due to sulfurization of Ag–In morphology and uniform distribution of the grains. The average
precursor at high substrate temperatures as well as the high concentra- thickness of the films is found to be ~ 1 μm. There is no significant
tion of Indium [22]. Both the morphological studies showed similar change observed in thickness with the increase in Tsub.

Fig. 4. AFM images of AgInS2 films (10 × 10 μm2) at different Tsub (a) AIS350, (b) AIS400, (c) AIS450, (d) AIS500.
 M. Anantha Sunil et al. / Thin Solid Films 595 (2015) 5–11
Fig. 5. Absorption spectra of AgInS2 films at different Tsub (a) AIS350, (b) AIS400, (c) AIS450, (d) AIS500.
Band gap of the AIS thin films are determined from the absorption
spectra recorded over the wavelength range from 300 to 1000 nm.
The band gap of the material is calculated using Tauc relation [23]
given by.
αhυ =A(hυ − Eg)r (2)
where A is a constant, Eg is the optical band gap, r = 1/2 for direct
allowed optical transitions and 3/2 for the direct forbidden ones.
A graph is plotted between (αhυ)2 and hυ and the extrapolation of
the linear region of the graph at the x-axis gives the energy band gap.
Fig. 5 shows the absorption spectra of AgInS2 films at different substrate
temperature. With the increase in Tsub, the band gap decreased from
1.92 eV to 1.64 eV. Band gap for the sample AIS350 is higher due to
the formation of AgIn5S8 phase [24]. The decrease in band gap for
other samples is due to the improvement in crystallinity of films with
the increase in substrate temperature.
From the electrical characterization studies, the carrier density, type
of conductivity and resistivity of the films are obtained and is shown
in Table 4. AIS350, AIS400, and AIS450 showed n type conductivity
whereas AIS500 is p type in nature. This change in conductivity is
attributed to the change in the composition of AgInS2. Interstitials of
In (Ini) and vacancy of S (Vs) are the defects which result in n-type
conductivity [26]. Even though sample AIS500 is slightly In rich, it
showed p type conductivity. EDX analysis showed that sample AIS500
is S rich and Ag poor in composition. Acceptor type of defects such as
vacancy of Ag (VAg) and S interstitials (Si ) are likely to be formed
in these films. The presence of these defects results in p type conduc-
tivity of films. It is in good agreement with Hattori et al. [25]. The
type of conductivity in CuInS2 films was calculated using the formula
(Δ y = [(2S/Cu + 3In) − 1] based on atomic values of each element
[26]. Films with Δ y N 0 will act as p type whereas films with Δ y b 0
will behave as n type. For AgInS2 films, (as per the above formulae)
Cu is replaced by Ag in order to determine the conductivity type.
EDX analysis showed that AgInS2 films prepared at Tsub = 500 °C is
sulfur rich with Δ y N 0, resulting in p type conductivity. Δ y b 0 for
samples deposited at temperatures below 500 °C resulted in n type
9
conductivity. The conductivity type calculated is in agreement with
Hall measurements.
The carrier densities of AgInS2 thin films measured at room temper-
ature are in the range of 2 × 1013− 1 × 1022 cm−3. The carrier density
decreases with increase in substrate temperature. This decrease is due
to change in conductivity type of the samples. It is observed that resis-
tivity increases from 10−3 to 105 Ω-cm with increase in substrate tem-
perature. This is attributed to charge compensation due to variation in
the concentration of intrinsic defects. Resistivity of sample AIS500 is
high and further studies are being carried out to reduce the resistivity.
XPS analysis is carried out to determine the valence states of AgInS2
thin films deposited at Tsub = 500 °C. The sample is etched for 10 min in
order remove the impurities present on the surface of the sample.
Fig. 6(a) shows the wide spectrum of AIS500. The binding energies
obtained in the XPS analysis are calibrated by referencing the C1s peak
to 284.5 eV. From the wide spectrum it is observed that elements Ag,
In, S and O are present. High resolution spectrum with peaks marked
is shown in Fig. 6(b-e). Ag spectra showed binding energies of 367.8
and 373.8 eV which corresponds to 3d5/2 and 3d3/2 levels respectively.
Peaks at 444.6 and 452.2 eV are observed in In spectra due to 3d5/2
and 3d3/2 levels. Sulfur showed a binding energy of 161.8 eV which
matches with 2p1/2 level. The binding energy values of Ag, In and S
indicated the formation of AgInS2 films [27]. The peak due to elemental
oxygen appeared at 531.6 eV. The diffusion of oxygen might have taken
place during the high temperature sulfurization process.
Table 4
Electrical properties of AgInS2 films.
Sample name Carrier density Type of Resistivity
(ions/cm2) conductivity (Ω-cm)
AIS350 1.5 × 1022 n 3.6 × 10−4
AIS400 9.6 × 1022 n 3.9 × 10−4
AIS450 2.68 × 1019 n 4.6 × 10−3
AIS500 2.11 × 1013 p 4.9 × 105
10 M. Anantha Sunil et al. / Thin Solid Films 595 (2015) 5–11
Fig. 6. XPS spectrum of etched AgInS2 films at Tsub = 500 °C : a) Survey scan and high resolution scan of (b) Ag (c) In (d) S (e) O.
As a trial, solar cell is fabricated with AIS500 and ZnS as absorber and
window layer respectively. Fig. 7 shows the J–V characteristics of
fabricated AgInS2/ZnS solar cell under dark and AM1.5 illumination con-
ditions. Short circuit current density (Jsc) and open circuit voltage (Voc)
of the device are 0.24 mA/cm2 and 0.6 V, respectively. Fill factor of the
fabricated cell is determined as 30% whereas efficiency of the cell is
found to be 0.3%. Peng et al. [28] also reported an efficiency of 0.5%
using synthesis of AgInS2 nanocrystals. These results show that by
Fig. 7. J–V characteristics of AIS500 solar cell under dark and illuminated conditions.
reducing the resistivity of the absorber layer and optimizing the thick-
ness of ZnS layer, efficiency of solar cell can be enhanced.
4. Conclusions
AgInS2 thin films have been successfully deposited by sputtering
of metallic precursors followed by sulfurization process at different
substrate temperatures. Tetragonal AgInS2 thin films with improved
crystallinity are obtained with increase in substrate temperature. Nearly
stoichiometric films with band gap of 1.64 eV at substrate temperature
of 500 °C are achieved. Films at this substrate temperature exhibited
p type conductivity and showed highest grain size of 895 nm. Initial
trial on AgInS2 /ZnS junction showed an efficiency of 0.3% which
demonstrates the potential of AgInS2 as a solar cell absorber.
Acknowledgments
The authors take this opportunity to thank CENSe (Centre for
Nanoscience and Engineering), IISc, Bangalore for providing the
facilities to carry out this work.
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