338
FORMATION OF CRYSTAL QUALITY OF CuInS
2
THIN FILMS FOR
PHOTOVOLTAIC APPLICATIONS
THANH
THAI
TRAN
1,3
,
THI
LAN
ANH
LUU
1
,
MATEUS
MANUEL
NETO
4
NGOC
TRUNG
NGUYEN
1
,
THI
BICH
VU
2
AND
THACH
SON
VO
1
1
Institute of Engineering Physics, Hanoi University of Science and Technology, No. 1, Dai Co Viet Road, Hanoi,
Vietnam
2
Center for Quantum Electronics, Institute of Physics, VAST10, DaoTan Road, Hanoi, Vietnam
3
Quy Nhon University, 170 An Duong Vuong, Quynhon, Binhdinh, Vietnam
4
Laboratory of Photovoltaic House Luanda, University Agostinho Neto, Luanda, Angola
Abstract. CuInS
2
(CIS) is a promising absorber material for thin film photovoltaic which has recently
attracted considerable attention due to its suitability to reach high efficiency solar cells by using low cost
techniques. In this work, the CIS thin films have been grown by repeated spray pyrolysis (RSP) onto glass
substrates using different composition solutions. Structural, optical and electrical properties of CIS films
were analyzed by X-ray diffraction, Raman spectroscopy, optical spectroscopy and Hall-effect. Repeated
spray CIS films are polycrystalline with a chalcopyrite structure and no remains of secondary phases were
found after spraying and spraying and heat treatment in suitable conditions. An optical gap of about 1.48 eV
was found for as-sulfurized CIS films. The optical absorption coefficient was found to be about 10
5
cm
-1
.
The results obtained in this work show the possibility of having the p-type CIS thin films with a wide range
of resistivity and suitably to be used in photovoltaic structures.
Introduction
Satisfying world’s growing energy demand is one
of the most significant challenges facing society. Today,
major share of the energy produced by mankind comes
from fossil fuels. The Earth’s fossil energies are on the
decline, and that green house gases are known to
contribute to global warming, there is urgent need to rely
on technologies that are economically feasible and
environmental friendly. The good news is that these
problems can be solved by solar energy as it is clean,
quiet and renewable [1-6]. Recently, one approach is
development of thin film solar cells based on absorber
CuInS
2
(CIS) and related alloys. CIS is a semiconductor
in group I-III-VI
2
with crystallizes in the chalcopyrite
structure. This compound exhibits optical band gap of
1.5 eV, absorption coefficient of 10
5
cm
-1
in visible
spectrum range, and the environmental consideration [1-
4]. For economical reasons, it will be useful to prepare
thin films using a low-cost deposition technique. One of
such methods is spray pyrolysis technique, which is a
promising method fore scale-up production under
ambient air condition with relative simplicity and low
cost [2,3]. In the present work, we report on the growth
properties of CIS thin films with various Cu/In molar
ratios in the starting solution made by spray pyrolysis
(SP) technique. However, difficulty in the usage of this
method is in deposition of thick films (>1µm) by
spraying large volumes of solution in a single stretch.
This always results in the formation of CIS thin film
with lots of pinholes. But, a trial has been made to
deposit the film by repeated spray pyrolysis (RSP)
technique using small volumes of solution and this
technique has helped to repair all the film non-uniform
having lots of pinholes on it.
Hence in this study, properties of CuInS
2
films
deposited at different Cu/In ratio using RSP were
systematically studied.
Experimental
The CIS thin films were deposited from aqueous
solution containing CuCl
2
(MERCK), InCl
3
(ALDRICH)
and (NH
2
)
2
CS (MERCK). Molar ratio of precursors Cu/In
in the precursor solution was varied in the range of 0.8 - 1.2
keeping S/Cu ratio at 5. We sprayed precursors onto a glass
substrate at the constant substrate temperatures of 360
o
C.
The films were kept at the same temperature for twenty
minutes after each sprayed and this process was repeated
six times. The nozzle to substrate distance was about 30 cm.
The transfer rate of aqueous solution was kept at 0.5
ml/min, and nitrogen for industry was used as a carrier gas.
After deposition, the CIS
thin films were introduced with
sulfur powder (99.99% purity) in a Pyrex tube. The films
were then annealed at 350
o
C for 30 min by leading the N
2
flow through the melted sulphur.
The surface morphology and composition of the
films were characterized by Field Emission Scanning
Electron Microscopy image (FESEM; Hitachi S-4800)
and Energy Dispersive X-ray analysis (EDX; FEI-Quanta
200). X-ray diffraction (XRD) patterns were recorded
with a X’PERT PRO-PANalytical Diffractometer using
the Cu-Kα radiation (λ=1.54056 A
o
). The conductivity
type was determined by the hot probe method and
resistivity of the film were determined by the Hall-effect
measurements, and the band gap was determined from
optical transmittance spectra in the UV region of 200 -
900 nm as measured with a Carry 100 Spectrophotometer.
The Raman spectrum was collected on a Renishaw in via
Raman microscope at room temperature with the