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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
Advanced Coatings and Surface Engineering Laboratory (ACSEL), Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO 80401, USA
Engineering Research Center of Advanced Battery Materials, The Ministry of Education, Changsha 410083, China
a r t i c l e
i n f o
Article history:
Received 4 July 2012
Received in revised form 27 August 2012
Accepted 8 September 2012
Available online 23 September 2012
Keywords:
Copper bismuth selenide
Thin lms
Electrodeposition
Solar cell
a b s t r a c t
Copper bismuth selenide thin lms have been prepared by potentiostatical electrodeposition from an
aqueous solution containing CuCl2 , Bi(NO3 )3 and H2 SeO3 followed by post annealing treatment. Cyclic
voltammetry (CV) test was used to investigate the electrodeposition mechanism. The suitable deposition
potential for lm preparation was determined combining with CV, composition and morphology studies. The as-deposited lms are amorphous in nature and the amorphous-to-crystalline transition can
be obtained by annealing treatment at 450 C. The morphological, compositional, structural, optical and
electrical properties of the prepared lms were studied via environmental scanning electron microscopy,
energy-dispersive X-ray spectroscopy, X-ray diffraction, optical absorption and photoelectrochemical
tests, respectively. The annealed lm with triclinic structure exhibits high absorption coefcient of
0.51.2 105 cm1 , an optical band gap of 1.50 eV, a p-type conductivity and good photoactivity, indicating potential application in photoelectric conversion.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Over the past few years, the metal selenides have received considerable attention owing to their unusual structures, optical and
electronic properties [13]. Metal selenides compounds with the
nature of semiconductor, have been applied in many areas, such
as solar cells [4], light emitting devices [5], thermoelectric [6] and
superionic conductor [7]. The metal selenides in thin lm form are
one of the most important candidates for photoelectric conversion,
due to the tunable band gap to match solar spectrum, the high optical absorption coefcient and the excellent electrical properties [8].
Among these selenides materials, bismuth selenide has been paid
great attention and extensively studied, because of its suitable optical properties including a high absorption coefcient larger than
104 cm1 [9] and a narrow band gap of 0.35 eV [10]. In order to make
the band gap match with the maximum solar energy spectrum,
another compound Cu2 Se with band gap of 1.92.3 eV [11,12] is
alloyed with Bi2 Se3 to form copper bismuth selenide, which would
have the band gap between their individual band gap, similar to
Corresponding author. Tel.: +86 731 88876454; fax: +86 731 88876454.
Corresponding author. Tel.: +86 731 88830649; fax: +86 731 88830649.
E-mail addresses: liufangyang@csu.edu.cn (F. Liu), laiyanqingcsu@163.com
(Y. Lai).
1
ISE member.
0013-4686/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.09.016
the combinations of Bi2 S3 Cux S [13], Bi2 Se3 Sb2 Se3 [14,15] and
CuInSe2 CuGaSe2 [16], and has showed their applications in the
area of energy conversion and solar energy utilization due to modication in electrical and optical properties. Recently, Phok et al. [17]
reported that the chemical deposition of Cu doped BiSe thin lms
show an absorption coefcient in the range of 0.71.7 105 cm1
and the band gap ranging from 1.26 to 1.51 eV, which may open
up a new avenue as absorber layers in thin lm photovoltaic
devices.
The synthesis of metal selenides in thin lm form has been
realized by many methods, such as chemical bath deposition
[3,17], arrested precipitation technique [18], successive ionic layer
adsorption and reaction [19], electrochemical atomic layer epitaxy
[10], evaporation [4] and electrodeposition [5] etc. Among various deposition techniques, electrodeposition is attractive because
of its simplicity, low cost, mild lm growth conditions, possibility for large-scale production and its intrinsic ability to control lm
growth rate by controlling electrical quantities such as current density, charge, or deposition potential. To the best of our knowledge,
the preparation of copper bismuth selenide thin lms by electrodeposition has not been reported yet.
In this paper, the preparation of copper bismuth selenide thin
lms by electrodeposition and annealing is studied. The results of
the investigation of the deposition mechanism by cyclic voltammetry (CV), as well as lm composition, morphology, structure,
electrical and optical properties, are presented.
154
2. Experimental
The electrochemical experiments, including the cyclic voltammetry (CV) and electrodeposition were controlled by an EG&G PAR
273A Potentiostat in a simple three-electrode cell, which contained
a SnO2 -coated glass substrate (20 /) as the working electrode, a
pure graphite plate as the counter electrode and a saturated calomel
electrode (SCE) as the reference electrode. All potential values in
this study were referenced to this reference electrode. Before deposition, the SnO2 -coated glass substrates were cleaned ultrasonically
in the order of acetone, ammonia and alcohol, and then rinsed with
deionized water. The electrolytes contained 2 mM CuCl2 , 2 mM
Bi(NO3 )3 , 4 mM SeO2 and 0.6 M NH4 Cl as a stabilizing agent, and the
pH value was adjusted to 1.5 by adding drops of concentrated HCl
solution. The deposition time was xed to 30 min at room temperature. After electrodeposition, the deposited lms were removed
from the electrolyte and rinsed with distilled water. To improve the
crystallinity, the electrodeposited lms were annealed in a owing Ar atmosphere at the rate of 10 C/s from room temperature
to 450 C, then kept at 450 C for 3 min, and nally cooled to room
temperature naturally.
The chemical composition, surface morphology, crystalline
properties and thickness of the prepared lms were characterized
by energy dispersive X-ray spectroscope (EDS, EDAX-GENSIS60S),
environmental scanning electron microscopy (ESEM, FEI Quanta200), X-ray diffraction (XRD, Rigaku 3014, CuK1 radiation,
and step meter (Alpha-Step IQ), respectively. The
= 1.54 A)
optical properties of annealed thin lms were measured by
UVvisNIR spectrophotometer (UVvisNIR, Varian Cary 5000).
Electrical properties of the lms were characterized by photoelectrochemical (PEC) test. The PEC test (photocurrentpotential and
potentialtime transient characteristics) was carried out in 0.5 M
H2 SO4 solution. A 300 W xenon lamp was used as the light source
with the light intensity kept at 100 mW/cm2 .
3. Results and discussion
Fig. 1 shows the typical cyclic voltammograms of SnO2 -coated
electrode in the unitary Se, binary BiSe and ternary CuBiSe
solutions. For unitary Se solution containing 4 mM SeO2 and 0.6 M
NH4 Cl, it is observed that there are two remarkable cathodic
peak at about 0.45 V (A1) and 0.59 V (A2). In combination
with previous studies [2022], these two peaks can be assigned as
follows: the peak A1 corresponds to bulk Se deposition through the
(1)
H2 SeO3 + 6H + 6e H2 Se + 3H2 O
(2)
(3)
(4)
(5)
(6)
155
Fig. 2 shows the atomic composition of thin lms electrodeposited at various potentials between 0.20 V and 0.60 V. For
lms deposited at 0.50 V or more positive potentials, the composition of lm almost does not change signicantly, implying that
deposition potential plays little role in lm composition. Therefore,
the electrodeposition process should be controlled by diffusion
independent of potential in this range of 0.20 V to 0.50 V. As the
deposition potential shifts negatively to 0.60 V, the lm composition uctuates with a loss of Se, which is attributed to the further
reduction of deposited copper bismuth selenide lm to metal and
soluble Se(II).
The thickness of lms deposited at 0.20 V, 0.22 V, 0.40 V and
0.60 V is 500, 520, 620 and 660 nm, respectively. The increase of
lm thickness is owing to the higher electrode reaction rate with
the negative shift of deposition potential. Fig. 3 shows the dramatic difference of surface morphologies of electrodeposited lms
at various deposition potentials from 0.20 V to 0.60 V. It can be
observed that the lm deposited at 0.20 V exhibits many large
size grains, which is caused by slow nucleation and growth rate.
Film at 0.22 V shows a very compact and homogeneous surface
without cracks and voids. When the potential reaches 0.40 V, the
lm becomes rough and porous with a loose occulent structure. At
more negative potential of 0.60 V, the lm turns to a much poorer
surface morphology with a dendritic structure, showing a poor
adhesion to the substrate which can be easily rinsed down by water.
This morphology is probably caused by the high electrode reaction rate and excessive concentration polarization [22,26]. Hence,
the optimal potential for the preparation of CuBiSe compound
Fig. 3. The SEM micrograph of thin lm electrodeposited at different deposition potential: (a) 0.20 V, (b) 0.22 V, (c) 0.40 V and (d) 0.60 V.
156
Fig. 6. Photocurrentpotential response curve for the annealed lm. The inset is the
potentialtime transient responses at a constant current density of 10 A/cm2 by
chopping the light with 50 s on and 50 s off. Both experiments were performed in
0.5 M H2 SO4 aqueous electrolyte.
Cu1.6 Bi4.8 Se8 . The absorption coefcient and the optical band gap
were estimated to be in the range of 0.51.2 105 cm1 and about
1.50 eV using UVvisNIR characterization. Good photoactivity and
p-type conductivity were determined by PEC test. The optical and
electric properties indicate that copper bismuth selenide lms can
be considered to be a promising absorber material for photovoltaic
solar energy conversion.
Acknowledgements
This work was supported by the National High Technology
Research and Development Program of China (863 Program, no.
2012AA050703), the Fundamental Research Funds for the Central
Universities (no. 201021100029 and no. 2012QNZT022) and the
National Natural Science Foundation of China (no. 51272292).
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