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.

Lin et al. [2] deposited AgInS2 thin films by chemical bath technique
Thin film solar cells have gained great attention of researchers and demonstrated the ability to control the compositions of
owing to their potential to reduce manufacturing costs and material multi-component semiconductor thin films. Jia et al. [7] and Lei
utilization. Over the years, materials belonging to I–III–VI 2 group et al. [8] have carried out studies on hybrid solar cells using Ag2S
(CuInSe2, CuInS2, Cu (In, Ga) Se2) have been studied extensively by and In 2S 3 as electron acceptors by wet-chemical sulfurization.
various techniques in order to enhance the performance of thin A few other research groups have studied the properties of AgInS2
film solar cell. As on date, Cu (In, Ga)Se2 based solar cell holds the films by varying spray parameters like substrate temperature,
record for highest efficiency of ~ 20.5% [1]. AgInS 2 is a unique deposition time and concentration of precursor solution using pneu-
semiconductor material belonging to I–III–VI 2 group which exists matic and ultrasonic spray pyrolysis technique [9–14]. Akaki et al. [15]
in both chalcopyrite and orthorhombic phase. It has direct band studied the properties of AgInS2 films on glass substrates using single
gap of 1.8 eV and its absorption coefficient is greater than source thermal evaporation of Ag2S and In2S3 powders. Cheng et al.
104 cm − 1 . AgInS 2 is used for wide range of applications such as [16] prepared AgInS2 films by sulfurization of thermally evaporated
photo-electrochemical, optoelectronic and photovoltaics [2–4]. Ag and In metal precursors. Arredondo et al. [17] prepared AgInS2
AgInS2 is a solid candidate for both single junction and tandem films using co-evaporation method. They used Ag, In and a tantalum
solar cells. The band gap of this material could be brought down by effusion cell for sulfur as sources to form AgInS2 films. You et al. [18]
controlling the composition of films. prepared AgInS2 films using hot wall epitaxy method where shot type
AgInS2 thin films are deposited using both physical and chemical Ag, In and S were used as the sources. Here, growth of AgInS2 thin
methods. Wang et al. [5] deposited AgInS2 films on fluorine tin oxide films by sulfurization of sputter deposited Ag/In metallic layer is
(FTO) substrates by using one-step electro-deposition. Jin et al. [6] syn- presented. The advantages of this method are highly crystalline,
thesized the AgInS2 films on TiO2/FTO substrate by hydrothermal route stoichiometric and reproducible films could be achieved. Thickness
and demonstrated the performance of photo-electrode. Lopez et al. [7] could be controlled by varying deposition rate. No toxic gases are used
studied the effect of growth temperature and chemical composition 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
⁎ Corresponding author. presented. A trial for fabrication of solar cell is done using the
E-mail address: [email protected] (N. Jampana). 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 parallel to the optic axis and E type are excited only for light polarized
Raman modes of AgInS2 films grown at different Tsub. perpendicular to the optic axis.
Sample Name Observed modes (cm−1) Fig. 2 shows the Raman spectrum of AgInS 2 films and modes
A1 B2, E1 E1 Cu–Au 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
AIS350 – – 64 327
peaks at 64 and 327 cm− 1. The peak at 327 cm− 1 corresponds to
AIS400 274 – 340 64, 305 –
AIS450 274 – 340 64, 305 – 3F 2g Raman active mode of AgIn 5 S 8 structure. The presence of
AIS500 274 225 340 64, 305 – 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
tapping mode configuration. Absorption spectra are recorded from 300 AgInS 2 . The peaks at 225 and 340 cm − 1 corresponds to B 2 or E 1
to 1000 nm using UV–VIS spectrophotometer (Specord S600UV-VIS) modes of vibration respectively. In addition, two modes at 64 and
and electrical properties are determined using four-point probe method 305 cm− 1 are present which does not belong to chalcopyrite struc-
(Four dimensions probe meter model 280). X-ray photoelectron spec- ture. The mode of vibration corresponding to these peaks is not
troscopy studies are carried using Axis DLD photoelectron known clearly. These modes have been observed in other I-III-VI2
spectrometer at a pressure of 2.6 × 10− 9 Pa. Aluminum (Al) k-alpha group chalcopyrite semiconductors as well [12,20]. One of the rea-
energy of 1.486 keV is used as the X-ray source at operation conditions sons for the appearance of these modes is the Cu–Au ordered
of 15 kV and 10 mA. Acceleration voltage is 3.8 kV. Ar+ ions are used as structure and Cu-poor films. In the present work, appearance of
the sputtering source to etch the films for depth profiling. The these modes could be due to silver poor films. The absence of this
sputtering is done with beam energy of 4 keV and current density of mode in the film AIS350 which has higher Ag concentration, con-
140 μA/cm2. The fabricated solar cell is characterized using Oriel sol3 firms this assumption. The orthorhombic phase observed in the
A™ solar simulator under AM1.5 condition. The cell is illuminated XRD pattern is due to the Cu–Au ordered structure. With increase in
from the top side and area under illumination is 0.03 cm2. Tsub, intensity of A1 mode increased in proportion to the crystallinity
of the sample.
3. Results and discussion Table 3 shows the composition of AgInS2 films grown at different
Tsub. Sample AIS350 is rich in In concentration, there by resulting in
Fig. 1 shows the XRD pattern of AgInS2 films deposited at different the AgIn5S8 and In2S3 phases that is observed in XRD pattern. The sam-
substrate temperatures (Tsub). Films deposited at Tsub = 350 °C ples are found to be nearly stoichiometric with the increase in Tsub. It is
exhibited cubic spinel AgIn5S8 structure along with traces of In2S3 observed that sulfur is incorporated into the metallic precursor layers
phase. Preferential orientation is along the (422) plane of AgIn5S8 [Ag/In] (Table 1). The precursor ratio [S/(Ag + In)] for sample AIS500
(JCPDS 26-4177). With the increase in Tsub, all the samples showed is equal to 1 which shows films are completely sulfurized.
AgInS2 phase with preferential orientation along (112) plane. Films ex- Surface morphology of AgInS2 thin films are analyzed using SEM and
hibited peaks corresponding to (103), (200), (004), (211), (220), (204), AFM. Fig. 3 shows the surface morphology of AgInS2 thin films. With the
(301), (312), (116), (316) and (424) planes of tetragonal structure increase in substrate temperature, the grain size increases from 489 nm
(JCPDS 75-0117). In addition, peaks corresponding to (202) and (200) to 895 nm. The highest grain size is obtained for sample AIS500. Fig. 3
planes of orthorhombic structure of AgInS2 (JCPDS 25-1328) are shows that surface of sample AIS350 is inhomogeneous in shape,
observed. No binary phases are detected for samples prepared at which might be due to the non-stoichiometry and presence of binary
Tsub N 350 °C. Crystallinity of films improved with the increase in phases in the film. Shape of the grains changed from spherical to flowers
substrate temperature. XRD pattern shows that sample AIS500 has the and rods with Tsub N 350 °C. The grain size of the AgInS2 films became
highest intensity along (112) plane. Films are found to be porous in larger with increase in substrate temperature and the maximum grain
nature when Tsub N 500 °C and hence studies have not been carried size of 895 nm is obtained for sample AIS500. Larger grain size helps
out beyond this temperature. in reducing the grain boundary scattering and thereby improving the
Raman spectroscopy is used to determine both the structure and efficiency of the solar cell.
different vibration modes in the sample. The Raman active modes of Fig. 4 shows the AFM images of AgInS2 thin films deposited at differ-
vibrations for I-III-VI2 chalcopyrite structure [19] is represented as. ent Tsub. There is a significant variation in the shape of the grains with
the composition. Ag-rich film (AIS350) showed pyramidal shaped
Γvib ¼ A1 þ 3B1 þ 3B2 þ 6E ð1Þ grains and In-rich films (AIS400–AIS500) showed spherically shaped
grains. The AFM images of AgInS2 thin films confirm the increase in
Here, A1 mode corresponds to the vibration of anions (S) in the x-y grain size with the increase in substrate temperature. The grain
plane with cations (Ag and In) at rest. The frequency of this mode is size depends on initial nucleation density and recyrstallization process.
associated with the mass of anion and the bond-stretching force of Recrystallization into larger and non-aggregated grains is enhanced
anion-cation bonds. B1 mode corresponds to the frequency of vibration at higher temperatures. Similar phenomenon was observed in growth
of cations (Ag and In) in anti-phase. B2 and E mode reflects the vibration of CuInS2 thin films by spray pyrolysis [21]. With the increase in sub-
of In-S atoms in anti-phase. B2 type modes are excited for light polarized 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 9

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 conductivity. The conductivity type calculated is in agreement with
spectra recorded over the wavelength range from 300 to 1000 nm. Hall measurements.
The band gap of the material is calculated using Tauc relation [23] The carrier densities of AgInS2 thin films measured at room temper-
given by. 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
αhυ =A(hυ − Eg)r (2) 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-
where A is a constant, Eg is the optical band gap, r = 1/2 for direct perature. This is attributed to charge compensation due to variation in
allowed optical transitions and 3/2 for the direct forbidden ones. the concentration of intrinsic defects. Resistivity of sample AIS500 is
A graph is plotted between (αhυ)2 and hυ and the extrapolation of high and further studies are being carried out to reduce the resistivity.
the linear region of the graph at the x-axis gives the energy band gap. XPS analysis is carried out to determine the valence states of AgInS2
Fig. 5 shows the absorption spectra of AgInS2 films at different substrate thin films deposited at Tsub = 500 °C. The sample is etched for 10 min in
temperature. With the increase in Tsub, the band gap decreased from order remove the impurities present on the surface of the sample.
1.92 eV to 1.64 eV. Band gap for the sample AIS350 is higher due to Fig. 6(a) shows the wide spectrum of AIS500. The binding energies
the formation of AgIn5S8 phase [24]. The decrease in band gap for obtained in the XPS analysis are calibrated by referencing the C1s peak
other samples is due to the improvement in crystallinity of films with to 284.5 eV. From the wide spectrum it is observed that elements Ag,
the increase in substrate temperature. In, S and O are present. High resolution spectrum with peaks marked
From the electrical characterization studies, the carrier density, type is shown in Fig. 6(b-e). Ag spectra showed binding energies of 367.8
of conductivity and resistivity of the films are obtained and is shown and 373.8 eV which corresponds to 3d5/2 and 3d3/2 levels respectively.
in Table 4. AIS350, AIS400, and AIS450 showed n type conductivity Peaks at 444.6 and 452.2 eV are observed in In spectra due to 3d5/2
whereas AIS500 is p type in nature. This change in conductivity is and 3d3/2 levels. Sulfur showed a binding energy of 161.8 eV which
attributed to the change in the composition of AgInS2. Interstitials of matches with 2p1/2 level. The binding energy values of Ag, In and S
In (Ini) and vacancy of S (Vs) are the defects which result in n-type indicated the formation of AgInS2 films [27]. The peak due to elemental
conductivity [26]. Even though sample AIS500 is slightly In rich, it oxygen appeared at 531.6 eV. The diffusion of oxygen might have taken
showed p type conductivity. EDX analysis showed that sample AIS500 place during the high temperature sulfurization process.
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 Table 4
Electrical properties of AgInS2 films.
(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 Sample name Carrier density Type of Resistivity
will behave as n type. For AgInS2 films, (as per the above formulae) (ions/cm2) conductivity (Ω-cm)
Cu is replaced by Ag in order to determine the conductivity type. AIS350 1.5 × 1022 n 3.6 × 10−4
EDX analysis showed that AgInS2 films prepared at Tsub = 500 °C is AIS400 9.6 × 1022 n 3.9 × 10−4
sulfur rich with Δ y N 0, resulting in p type conductivity. Δ y b 0 for AIS450 2.68 × 1019 n 4.6 × 10−3
AIS500 2.11 × 1013 p 4.9 × 105
samples deposited at temperatures below 500 °C resulted in n type
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 reducing the resistivity of the absorber layer and optimizing the thick-
window layer respectively. Fig. 7 shows the J–V characteristics of ness of ZnS layer, efficiency of solar cell can be enhanced.
fabricated AgInS2/ZnS solar cell under dark and AM1.5 illumination con-
ditions. Short circuit current density (Jsc) and open circuit voltage (Voc)
4. Conclusions
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
AgInS2 thin films have been successfully deposited by sputtering
found to be 0.3%. Peng et al. [28] also reported an efficiency of 0.5%
of metallic precursors followed by sulfurization process at different
using synthesis of AgInS2 nanocrystals. These results show that by
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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