International Journal of Mechanical Engineering and Technology (IJMET)

Volume 9, Issue 13, December 2018, pp. 182–191, Article ID: IJMET_09_13_019
Available online at http://www.iaeme.com/ijmet/issues.asp?JType=IJMET&VType=9&IType=13
ISSN Print: 0976-6340 and ISSN Online: 0976-6359

© IAEME Publication Scopus Indexed

PULSE PLATED CuInGaSe2 THIN FILMS AND

THEIR CHARACTERISTICS
V. Chitra
Dept. of Physics, Sri Ramakrishna Institute of Technology, Coimbatore, India

S.Vasantha
Dept. of Physics, CIT, Coimbatore, India

ABSTRACT
Copper Indium Gallium selenide films of different composition were deposited by the
pulse electrodeposition technique at 50 % duty cycle at room temperature and at a
deposition potential of – 0.8 V (SCE). The films exhibited single phase chalcopyrite
structure. Optical band gap of the films varied in the range of 1.11 eV to 1.62 eV as the
gallium concentration increased. Room temperature resistivity of the films varied from
0.8 ohm cm to 23.52 ohm cm as the gallium concentration is increased.
Key words: Thin films, I-III-VI2, Semiconductors, Chalcopyrite
Cite this Article: V. Chitra and S.Vasantha, Pulse Plated CuInGaSe2 Thin Films and Their
Characteristics, International Journal of Mechanical Engineering and Technology, 9(13),
2018, pp. 182–191
http://www.iaeme.com/IJMET/issues.asp?JType=IJMET&VType=9&IType=13

1. INTRODUCTION
In recent years, quaternary chalcopyrite compound CuInxGa1-xSe2 (CIGS) has been one of the
most promising absorber materials for high efficiency thin film solar cells [1]. Thin film solar
cells based on co-evaporated CIGS absorbers (x close to 0.3) have reached up to 20.0%
conversion efficiencies at the laboratory scale, by using a process requiring high vacuum
[2].From ‘Lab to Large-Scale Production’, one of the main challenges is to find an alternative
deposition method using non-vacuum equipment that yields economically viable solar cells and
is easily scalable. From this point of view, electrochemical deposition is a simple and non-
vacuum technique and has a natural advantage of large-area deposition [3]. Therefore, over the
last two decades, there has been considerable work done on the growth of CIGS thin films using
electrode position technique [4, 5]. So far all electrodeposited (ED) CIGS films need a
selenization step under a Se-containing atmosphere to recrystallize the films, as in most
cases electrode position is employed at low temperature. In this work, the pulse electrode position
technique was employed for the deposition of CIGS films. Characteristics of these films are
presented in this paper.

http://www.iaeme.com/IJMET/index.asp 182 editor@iaeme.com

 V. Chitra and S.Vasantha

2. EXPERIMENTAL METHODS
CuIn1-xGaxSe2 films of different composition (0< x <1), were pulse electrodeposited on indium
tin oxide coated glass substrates at 50 % duty cycle and at room temperature. The precursors
used were 20 mM SeO2, 30 mM CuCl2 and the concentration of the Indium chloride and
gallium chloride precursors were varied as shown in Table-1, to obtain films of different
composition. The deposition potential was maintained at – 0.8V (SCE). The pH was maintained
at 1.5 by HCl. A microprocessor controlled pulse plating unit was used. Thickness of the films
measured by Mitutoyo surface profilometer was in the range of 0.5 – 1.4 micrometer with
increase of Indium concentration. The films were characterized by Xpert analytical x-ray
diffraction unit with Cu kα radiation. Optical measurements were recorded using a Hitachi UV-
VIS-IR spectrophotometer. Composition of the films was estimated by EDAX attachment to
JOEL SEM. X-ray photoelectron spectroscopic (XPS) studies were made using VG MK II
system with Mg kα radiation. Surface morphology of the films was studied by molecular
imaging atomic force microscope.

Table- 1 Concentration of InCl3 and GaCl3 precursors for deposition of CuIn(1-x)Ga(x)Se2 films of
different composition

Composition Concentration of InCl3 (mM) Concentration of GaCl3 (mM)

0.1 90 10
0.2 80 20
0.3 70 30
0.4 60 40
0.5 50 50
0.6 40 60
0.7 30 70
0.8 20 80
0.9 10 90
In pulse electrode position [6, 7] the potential or current is alternated swiftly between two
different values. This results in a series of pulses of equal amplitude, duration and polarity,
separated by zero current. Each pulse consists of an ON-time (TON) during which potential
and/current is applied, and an OFF- time (TOFF) during which zero current is applied. It is possible
to control the deposited film composition and thickness in an atomic order by regulating the pulse
amplitude and width. They favor the initiation of grain nuclei and greatly increase the number of
grains per unit area resulting in finer grained deposit with better properties than conventionally
plated coatings. The sum of the ON and OFF times constitute one pulse cycle. The duty cycle
is defined as follows:
Duty Cycle (%) = (ON time) / (ON time + OFF time) x 100 (1)
A duty cycle of 100% corresponds to conventional plating because OFF time is zero. In
practice, pulse plating usually involves a duty cycle of 5% or greater. During the ON time the
concentration of the metal ions to be deposited is reduced within a certain distance from the
cathode surface. This so-called diffusion layer pulsates with the same frequency as the applied
pulse current. Its thickness is also related to ip but reaches a limiting value governed primarily
by the diffusion coefficient of the metal ions. During the OFF time the concentration of the
metal ions build up again by diffusion from the bulk electrolyte and will reach the equilibrium
concentration of the bulk electrolyte if enough time is allowed. These variables result in two
important characteristic features of pulse plating which make it useful for alloy plating as well
as property changes as mentioned earlier.
http://www.iaeme.com/IJMET/index.asp 183 editor@iaeme.com
 Pulse Plated CuInGaEe2 Thin Films and Their Characteristics

(i) Very high instantaneous current densities and hence very high negative potentials can be
reached. The high over potential causes a shift in the ratio of the rates of reactions with different
kinetics. This high over potential associated with the high pulse current density greatly influences
the nucleation rate because a high energy is available for the formation of new nuclei.
(ii) The second characteristic feature is the influence of the OFF time during which
important adsorption and desorption phenomena as well as recrystallization of the deposit
occurs.
Pulse plating technique has distinct advantages compared to conventional electrode position
namely, crack free, hard deposits and fine grained films with more uniformity, lower porosity
and better adhesion. It is well known that by using pulse current for electrode position of metals
and alloys it is possible to exercise greater control over the properties of electrodeposits and to
improve them by modifying their microstructures [8]. It has been reported that a significant
reduction in internal stress could be obtained when pulse current was used, compared to the use
of conventional direct current [9]

3. RESULTS AND DISCUSSION

Micro structural parameters were estimated by studying the x-ray diffract grams of Cu In (1-x)
GaxSe2 films of different composition. Fig.1 shows the x- ray diffraction patterns of CuIn (1-
x)Ga(x)Se2 films of different composition. All the figures indicate the prominent peaks
corresponding to (112), (220)/ (204), (312)/ (116). These care characteristic of the chalcopyrite
phase. No other phases were observed in the x-ray diffractograms indicating the formation
of single phase material. The peaks shifted from CuInSe2 side to CuGaSe2 side as the
concentration of Ga increased in the films. The lattice parameters were calculated using the
following relation [10]
1/d2 = (h2 + k2)/ a2 + l2/ c2 (2)
Where, ‘a’ and ‘c’ are the lattice parameters, “d” is the lattice spacing.

(a) x = 0.1 (b) x = 0.5

http://www.iaeme.com/IJMET/index.asp 184 editor@iaeme.com

 V. Chitra and S.Vasantha

(c) x = 0.7 (d) x = 0.9

Figure 1 - X-ray diffraction pattern of CuIn1-xGaxSe2 f i l m s of different composition deposited at

50 % duty cycle
The grain size of the films have been calculated using Scherrer's formula [11],
D = 0.94λ/ βcosθ (3)
Where λ is the wavelength of X-ray used, β the full-width half-maximum (FWHM)
And θ the Bragg angle. The grain size varied from 30 nm to 70 nm as the Gallium
Concentration increased. The dislocation density δ, defined as the length of
Dislocation lines per unit volume of the crystal has been evaluated using the
Formula [12]
δ=1/D2 (4)
The microstructural parameters are presented in Table-2. From the table it is observed that
the dislocation density decreases with increase of grain size. Information on the particle size
and strain for the CuIn ( 1-x)GaxSe2 films was obtained from the full-width at half-maximum
of the diffraction peaks. The full- width at half-maximum β can be expressed as a linear
combination of the contributions from the particle size, D and strain, ε through the relation [13]
βcosθ/λ = 1/D + ε sinθ/λ (5)
The plot of βcosθ/λ vs sinθ/λ allows us to determine both strain and particles size from
slope and intercept of the graph. The estimated values for films deposited at different duty
cycles are listed in Table - 2. The deviation in the lattice parameter values from the bulk
value observed in the present case clearly suggests that the grains in the films are under stress.
Such a behaviour can be attributed to the change of nature, deposition conditions and the
concentration of the native imperfections developed in thin films. This results in either
elongation or compression of the lattice and the structural parameters. The density of the film
is therefore found to change considerably in accordance with the variations observed with the
lattice constant values. The stress developed at higher Ga concentrations is likely to be due
to the formation of native defects developed from the lattice misfit or dislocations. The

http://www.iaeme.com/IJMET/index.asp 185 editor@iaeme.com

 Pulse Plated CuInGaEe2 Thin Films and Their Characteristics

defects have a probability to migrate parallel to the substrate surface so that the films will have
a tendency to expand and develop an internal tensile stress.

Table 2 Microstrucral parameters of CuIn(1-x)GaxSe2 films of different composition

Lattice parameter (Å ) Dislocation

Composition Thickness Grain size Strain
density
X nm "a" "c" nm 10-4 1015cm-3
0.9 500 5.623 11.115 30 2.51 1.11
0.8 660 5.645 11.160 39 2.45 0.66
0.7 710 5.662 11.235 45 2.24 0.49
0.6 805 5.682 11.275 49 2.12 0.42
0.5 900 5.693 11.330 52 1.87 0.37
0.4 1035 5.713 11.395 57 1.48 0.31
0.3 1187 5.723 11.450 62 1.12 0.26
0.2 1308 5.748 11.507 66 1.02 0.23
0.1 1500 5.765 11.558 70 0.91 0.20
This type of change in internal stress is always predominant by the observed recrystallization
process in polycrystalline films. The stress relaxation is mainly considered as due to dislocation
glides formed in the films. The decrease of internal stress may be attributed to a decrease in
dislocation density. The reduction in the strain and dislocation density with decrease of Ga
concentration may be due to the reduction in concentration of lattice imperfections at lower Ga
concentrations. Similar behaviour was reported earlier [14]
Composition of the films was estimated by recording the EDS spectrum of the films deposited
of different composition (Table - 3). Fig.2 show the EDS spectrum of CuIn1-xGaxSe2 films
deposited at 50 % duty cycle. It is observed that films with lower concentrations of Gallium were
copper rich. As the gallium concentration increased, the films became nearly stochiometric.
This is due to the fact that at as the concentration of gallium chloride increases in the bath,
more flux of gallium ions are available for deposition compared to the flux of indium ions, which
results in higher concentration of gallium thus decreasing the Cu/(Ga + In) ratio. Based on the
defect chemistry model of ternary compounds [15], c o m p o s i t i o n a l deviations of the
CuIn1-xGaxSe2 films can be expressed by non-stoichiometry parameter (Δy = [2Se/{Cu +
3(Ga + In)}] - 1). The parameter Δy is related to the electronic defects. For Δy > 0, the film has
a p-type conductivity and it has an n-type conductivity for Δy < 0. In this study the value of Δy
is greater than zero and the films exhibit p-type conductivity

http://www.iaeme.com/IJMET/index.asp 186 editor@iaeme.com

 V. Chitra and S.Vasantha

Figure 2 EDS spectrum of CuIn0.5Ga0.5Se2 films deposited at 50 % duty cycle

Table 3 Composition of CuIn1-xGaxSe2 films of deposited at 50 % duty cycle

Composition(x
Cu (at. %) In (at %) Ga(at. %) Se (at. %) Cu/(Ga+In) Ga(Ga+In)
)
0.1 26.00 22.50 2.50 49.00 1.04 0.10
0.2 25.30 20.00 5.00 49.70 1.01 0.20
0.3 25.20 17.50 7.50 49.80 1.01 0.30
0.4 24.60 14.50 10.00 51.10 1.01 0.41
0.5 24.20 12.00 12.00 51.80 1.01 0.50
0.6 23.20 9.00 14.00 53.80 1.01 0.61
0.7 23.20 7.00 16.00 53.80 1.01 0.70
0.8 22.50 4.00 18.00 54.90 1.01 0.80
0.9 21.30 2.00 19.10 57.60 1.01 0.90
Fig.3 shows the transmission spectra of the CuIn 1-xGaxSe2 films deposited at 50% duty
cycle. The spectra exhibits interference fringes and the value of the refractive index was
estimated by the envelope method [16] as follows:

n = [N + (N2 – ns 2)] 2 (6)

N = (ns2+1)/2+ns (Tmax - Tmin)/ Tmax Tmin (7)

Where ns is the refractive index of the substrate, Tmax and Tmin are the maximum and
minimum transmittances at the same wavelength in the fitted envelope curve on a transmittance
spectrum. The value of the refractive index was calculated from the above equations. The
refractive index decreases from 2.80 to 2.35 with wavelength (FIg.4). The value of the absorption
co-efficient (α) was calculated using the relation

α = 1/d ln {(n-1) (n-ns)/ (n + 1) (n – ns)} [(Tmax/Tmin) +1]/ [(Tmax/Tmi) 2 - 1] (8)

Where‘d’ is the thickness of the film and the other parameters have the usual meaning as
given for equation (8). The band gap of the films increased from 1.11 eV to 1.62 eV as the
gallium concentration increased (from (αhν) 2 vs hν plot) (Fig.5). The increase in band gap at

http://www.iaeme.com/IJMET/index.asp 187 editor@iaeme.com

 Pulse Plated CuInGaEe2 Thin Films and Their Characteristics

lower duty cycles is due to the small crystallites. The values of the band gap agree well with the
earlier report [17].

Figure 3 Transmission spectra of CuIn1-xGaxSe2 films deposited at 50 % duty cycle

(a) X = 0.1 (b) x = 0.2 (c) x = 0.3 (d) x = 0.4 (e) x = 0.5 (f) x = 0.6
(g) X = 0.7 (h) x = 0.8 (i) x = 0.9

Figure 4 Variation of refractive index with wavelength of CuIn 1-xGaxSe2 films deposited at 50 % duty
cycle (a) x = 0.2 (b) x = 0.4 (c) x = 0.6 (d) x = 0.8

http://www.iaeme.com/IJMET/index.asp 188 editor@iaeme.com

 V. Chitra and S.Vasantha

Figure 5 Tauc’s plot of CuIn1-xGaxSe2 films deposited at 50 % duty cycle (a) x = 0.1
(b) X = 0.2 (c) x = 0.3 (d) x = 0.4 (e) x = 0.5 (f) x = 0.6 (g) x = 0.7 (h) x = 0.8
(i) X = 0.9
The room temperature transport parameters were measured by Hall Van der Pauw technique
by providing gold ohmic contact. The influence of duty cycle on the resistivity of the films is
shown in Table-4. The magnitude of the resistivity increased from 0.8 ohm cm to 23.52 ohm cm
as the gallium concentration is increased. The resistivity values are comparable with an earlier
report [18]. The variation in resistivity with gallium concentration can be explained in terms of
the Cu/ (Ga+ In) ratio obtained from EDAX measurements. The Cu/(Ga + In) ratio is greater
than unity for all compositions. The films exhibit p-type conductivity, as the concentration of
gallium increases, the resistivity increases. The variation of room temperature mobility and
carrier density with increase of gallium concentration is also shown in Table-4. The increase of
resistivity can also be explained in terms of the decrease of carrier density with increase of
gallium concentration.

Table 4 Transport parameters of CuIn1-xGaxSe2 films of different composition deposited at 50 % duty

cycle
Mobility Carrier density
Concentration of Ga (x) Resistivity Ohm cm
Cm2 V-1S-1 cm-3
0.1 0.80 115.0 16
6.78 x 10
0.2 1.00 105.0 16
5.94 x 10
0.3 1.20 98.0 16
5.31 x 10
0.4 1.50 80.0 16
5.20 x 10

0.5 26.0 16
4.85 4.95 x 10

0.6 16
11.00 12.0 4.73 x 10

0.7 16
13.28 10.2 4.60 x 10

0.8 16
16.24 8.5 4.52 x 10

0.9
23.52 6.1

http://www.iaeme.com/IJMET/index.asp 189 editor@iaeme.com

 Pulse Plated CuInGaEe2 Thin Films and Their Characteristics

16
4.35 x 10

4. CONCLUSIONS
CIGS films of different composition possessing nanocrystalline grains can be deposited by the
pulse electrodeposition technique. Films with grain size in the range of 30 nm to 70 nm can be
obtained as the Gallium concentration increased. Films with resistivity in the range of 0.8 ohm
cm to 23.5 ohm cm can be prepared. Future work involves Finite element simulation so that
we can do cost effective analysis using finite element simulations [20-23]

REFERENCES
[1] Abou-Ras.D, Rudmann.D, Kostorz.G, Spiering.S, Powalla.M, Tiwari.A.N. Microstructural
and chemical studies of interfaces between Cu (InGa) Se2 and In2S3 layers. J. Appl.
Phys; 2005, 97: 084908 (8 pages)
[2] Repins.I, Contreras.M.A, Egaas.B, DeHart.C, Scharf.J, Perkins.C.L, To.B, Noufi.R. 19.9 %
efficient ZnO/CdS/CuInGaSe2 solar cell with 81.2 % fill factor. Prog. Photovolt. Res.
Appl; 2008,16 : 235 - 239
[3] Lincot.D. Electrodeposition of semiconductors. Thin Sold Films, 2005, 487: 40 - 48.
[4] Dharmadasa.I.M, Chaure.N.B, Tolan.G.J, Samantilleke.A.P. Development of p+, p, i, n,
and n+- Type CuInGaSe2 Layers for applications in garded bandgap multilayer thin film
solar cells. J.Electrochem.Soc; 2007, 154: H466 – H471.
[5] Delsol.T, Simmonds.M.C, Dharmadasa.I.M. Chemical etching of Cu (InGa) Se2 laters for
device application. Sol. energy mater. Sol. cells. 2003, 77: 331 - 339.
[6] Ghaemi.M, Binder.L. Effects of direct and pulse current on electrodeposition of manganese
dioxide.J. Power Sources. 2002, 111: 248 - 254
[7] Marlot.A, Kern.P, Landolt.D. Pulse plating of Ni-Mo alloys from Ni-rich electrolytes.
Electrochim Acta. 2002, 48: 29 - 36
[8] Bahrololoom.M.E,Sani,R. The influence of pulse plating parameters on the hardness and wear
resistance of nickel – mandanese composite coatings. surf.coat.tech, 2005, 192 : 154 – 163
[9] [9] Yin.K.M. Current pulse plating of nickel on rotating ring disk electrodes. Surf. Coat.
Technol.1996, 88:252 - 262
[10] Lee.D, Park.S, Kim.J.H. Structural analysis of CIGS film prepared by chemical spray
deposition.Current Applied Physics;2011, 11: S88–S92
[11] Rincon.C.A, Hernandez.E, Alanso.M.T, Garriza.M, Wasim.S.M, Rincon.C, Leon.M. Optical
transitions near the band edge in bulk CuInGaSe2 from ellipsometric measurements.
Mater.Chem.Phys; 2001, 70: 300 - 304.
[12] Mustafa.H, Hunter.D, Pradhan.A.K, Roy.U.N, Cui.Y, Burger.A. Synthesis and
characterization of AgInSe2 films for use in thin film solzr cells. Thin solid films; 2007, 515:
7001 - 7004.
[13] Santhosh Kumar. M.C, Pradeep.B. Formation and properties of AgInSe2 films deposited by
co-evaporation. Vacuum; 2004, 72: 369 - 378.
[14] Venkatachalam.M, Kannan.M.D, Jayakumar.S , Balasundaraprabhu.R,
Muthukumarasamy.N.Effect of annealing on the structural properties of CIGS thin
films.Thin Solid Films; 2008, 516 : 6848–6852
[15] Venkatachalam.M, Kannan.M.D, Jayakumar.S , Balasundaraprabhu.R,
Muthukumarasamy.N.Effect of annealing on the structural properties of CIGS thin
films.Thin Solid Films; 2008, 516 : 6848–6852
[16] Groenik.J.A, Janse.P.H. A generalized approach to the defect chemistry of ternary
compounds. Z. Phys. Chem; 1978, 110: 17 - 28.

http://www.iaeme.com/IJMET/index.asp 190 editor@iaeme.com

 V. Chitra and S.Vasantha

[17] Joo.H.Y, Kim.H.J. Spectrophotometric analysis of aluminum nitride thin films.

J.Vac.Sci and Technol; 1999 ,A 17 : 862 - 870
[18] Huang.C.J, Meen.J.T, Lai.M.Y, Chen.W.R. Formation of CuInSe2 films on flexible
susbstrates by electrodeposition technique. Sol energy mater.sol.cells; 2004, 82: 553 - 565.
[19] Reddy.K.T.R, Chalapathy.R.B.V. Preparation and properties of sprayed CuIn0.5Ga0.5Se2
thin films. Sol.energy.mater.sol.cells; 1998, 50 : 19 – 24
[20] Prakash Marimuthu K., Thirtha, P. H. P. and Chethan, K. C. S. (2017) “Force, Stress
prediction in drilling of AISI 1045 steel using Finite Element Modelling,” IOP Conference
Series: Materials Science and Engineering, 225,12030. doi: 10.1088/1757-
899X/225/1/012030.
[21] Prakash Marimuthu K., Thirtha, P. H. P. dan Chethan, K. C. S. (2018) “3d Finite Element
Model To Predict Machining Induced Residual Stresses Using Arbitrary Lagrangian Eulerian
Approach,” Journal of Engineering Science and Technology, 13, 309-320.
[22] Prakash Marimuthu K., Thirtha, P. H. P. and Chethan, K. C. S. (2018) “Mathematical
modelling to predict the residual stresses induced in milling process,” International Journal
of Mechanical and Production Engineering Research and Development, 8, 423-428
[23] Prakash Marimuthu, K., Kumar, C. S. C., & Prasada, H. P. T. (2018). 2D finite element
thermo-mechanical model to predict machining induced residual stresses using ALE
approach. Paper presented at the Materials Today: Proceedings, 5(5) 11780-11786.
doi:10.1016/j.matpr.2018.02.147

http://www.iaeme.com/IJMET/index.asp 191 editor@iaeme.com