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Electrochimica Acta 87 (2013) 153157

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrodeposition and characterization of copper bismuth selenide


semiconductor thin lms
Jiyu Li a , Liangxing Jiang a , Bo Wang b , Fangyang Liu a,,1 , Jia Yang a , Ding Tang a , Yanqing Lai c, , Jie Li c
a
b
c

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.

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J. Li et al. / Electrochimica Acta 87 (2013) 153157

four-electron reduction of Se(IV) to Se(0) (Eq. (1)); and the peak A2


relates to the six-electron reduction of Se(IV) to Se(II) (Eq. (2)).
The product Se(II) then undergoes a comproportionation reaction
with Se(IV) in the solution (Eq. (3)), leading to the chemical formation of Se(0) [22]. It is also observed from the inset in Fig. 1 that
there is an initial reductive feature starting from 0.05 V before
the peak A1. This weak reduction current corresponds to the predeposition of selenium on SnO2 substrate as the same reaction via
Eq. (1) [14,22], which is related to a cementation process. As in the
cementation process, the electroactive species Se(IV) react at the
surface of the substrate to form a Se layer which reduces its activity
by diffusing into the substrate. No anodic current is detected and no
anodic peaks appear, because the potential is not positive enough
for the development into an anodic peak for selenium oxidation.
H2 SeO3 + 4H+ + 4e  Se + 3H2 O
+

Fig. 1. Cyclic voltammograms of SnO2 -coated electrode in (a) Se solution containing


4.0 mM SeO2 and 0.6 M NH4 Cl; (b) BiSe solution containing 2 mM Bi(NO3 )3 , 4 mM
SeO2 and 0.6 M NH4 Cl; (c) CuBiSe solution containing 2 mM CuCl2 , 2 mM Bi(NO3 )3 ,
4 mM SeO2 and 0.6 M NH4 Cl.

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)

H2 SeO3 + 2H2 Se  3Se + 3H2 O

(3)

For binary BiSe solution containing 2 mM Bi(NO3 )3 , 4 mM


SeO2 and 0.6 M NH4 Cl, the similar reductive feature for the predeposition of selenium beginning with 0.05 V is found again from
the inset. When the potential reaches 0.12 V, the reduction current shows a much steeper increase abruptly than that of unitary
Se solution, then forming a cathodic peak B1 at about 0.30 V
which should involve the reduction of Bi(III). It is indicative that
the pre-deposited Se(0) induces the reduction of Bi(III) by Eq. (4)
because of the large Gibbs free energy release of the formation
of BiSe compounds. For instance, the value of the Gibbs free
energy of the formation of Bi2 Se3 is 211.43 kJ/mol, therefore, the
redox potential of the reaction in Eq. (4) is shifted by an amount
of G/6F = + 0.365 V theoretically with respect to the standard
deposition potential of metallic bismuth. Whatever the stoichiometry of bismuth selenide is, Bi2 Se3 is presented here for simplicity.
With further potential scan, the peak B2 at 0.72 V is associated
with the further reduction of bound Se in BiSe compounds to
soluble Se(II) and Bi(0) [23,24].
When the potential sweeps to the positive direction, two anodic
peaks observed at about 0.06 V (B3) and 0.28 V (B4) may correspond
to the anodic stripping of free Bi(0) to Bi(III), Bi2 Se3 to Bi(III) and
Se(IV) [24], respectively.
2Bi3+ + 3Se + 6e  Bi2 Se3

(4)

For ternary CuBiSe solution that contains 2 mM CuCl2 , 2 mM


Bi(NO3 )3 , 4 mM SeO2 and 0.6 M NH4 Cl, three cathodic peaks are
observed at about 0.08 V (C1), 0.22 V (C2) and 0.80 V (C3),
respectively. From the inset, the peak C1 before the pre-reduction of
Se may correspond to the reduction of Cu(II) to Cu(I) as Eq. (5) [25].
In comparison with the curve of binary solution, the appreciably
positive shift of the peak C2 and the increase in peak current density is found, revealing that the pre-deposited Se can also induce the
reduction of Cu(I). On the basis of previous analysis, C2 should correspond to the reactions involving the co-deposition of Cu, Bi and
Se (Eq. (6)) conrmed from the results of EDS composition analysis
(Fig. 2). Regardless of the stoichiometry of copper bismuth selenide
compounds, CuBiSe2 is presented here for simplicity. When the
potential sweeps beyond 0.65 V, the reduction peak C3 may indicate a further reduction of CuBiSe2 to form Cu(0), Bi(0) and soluble
Se(II).
On the anodic scan, two anodic waves observed at about 0.01 V
(C4) and 0.32 V (C5), but these peaks are difcult to be assigned
to specic anodic reactions due to the complexity of electrolyte
system.
Cu2+ + e  Cu+

(5)

J. Li et al. / Electrochimica Acta 87 (2013) 153157

Fig. 2. Atomic composition of as-deposited lms at various potentials between


0.2 V and 0.6 V from the solution containing 2 mM CuCl2 , 2 mM Bi(NO3 )3 , 4 mM
SeO2 and 0.6 M NH4 Cl.

Cu+ + Bi3+ + 2Se + 4e  CuBiSe2

(6)

The results of the cyclic voltammetry above represent that the


suitable potential range for the preparation of CuBiSe compound
thin lms is between 0.10 V and 0.60 V.

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.

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J. Li et al. / Electrochimica Acta 87 (2013) 153157

Fig. 4. X-ray diffraction patterns of SnO2 -coated substrate, as-deposited and


annealed lm.

in this experimental system can be conrmed to be 0.22 V in


combination with CV, EDS and ESEM studies.
Fig. 4 displays the typical X-ray diffraction patterns measured
for the electrodeposited and annealed lms, where the electrodeposited lm was obtained at the optimal deposition potential.
Annealing treatment at 450 C does not change lm composition
obviously. The electrodeposited lm is found to have poor crystallinity without any diffraction peaks observed, except for the
peaks of SnO2 (JCPDS card no. 77-0452) coming from the substrate. After annealing, sharp diffraction peaks are visible, which
can match well with the triclinic structure Cu1.6 Bi4.8 Se8 phase
(JCPDS card no. 80-1592). This phase does not match exactly with
the chemical composition determined by EDS, which is probably
caused by crystal defects and additional unitary or binary second
phases.
Fig. 5 shows the optical absorption coefcient () of the
annealed lm as a function of photon energy (h), which is converted from the transmission spectra recorded in the wavelength
range of 4001100 nm, without taking into account the reection
loss. The optical band gap of the thin lm was determined by applying the Tauc and Menths law [15] given by:
h = A(h Eg )

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.

where h is the photon energy, Eg is the band gap energy and A is


a proportionality constant which is related to the effective masses
associated with the valance and conduction bands. The value of n
is equal to 1/2 for a direct band gap and 2 for indirect gap material.
As observed in Fig. 5, the value of absorption coefcient is found in
the range of 0.51.2 105 cm1 that supports the direct band gap
nature of semiconductor material [15,27], which is in good agreement with earlier report [17]. Based on the allowed direct interband
transition, the optical band gap is estimated to be about 1.50 eV by
extrapolating the linear portion of the plot relating (h)2 versus h
to (h)2 = 0, as depicted in the inset of Fig. 5. The value of band gap
is quite close to that value of 1.51 eV prepared by chemical bath
deposition [17], which satises theoretical optimal value of light
absorber for a single junction solar cell.
Photovoltaic performance of the light-absorber materials can be
readily tested in a photoelectrochemical (PEC) cell. This method is
popular because the liquid electrolyte provides nearly ideal contact
to the half cell, avoiding problems such as interface contact with the
full device architecture. Therefore, in order to assess the photoactivity and PV-potential of prepared lms, the photoelectrochemical
characterization was carried out in an aqueous PEC cell containing
0.5 M H2 SO4 . Fig. 6 illustrates the photocurrentpotential curve by
PEC test of the annealed lm. The cathode photocurrent increases
as the cathode potential shifts to the negative direction, which
shows the characteristic of a p-type semiconductor [28,29]. Seen
from the inset of Fig. 6, the obvious and stable photoresponse
indicates the good quality and stability of the prepared lms. The
photocurrentpotential and potentialtime behaviors suggest that
the prepared copper bismuth selenide thin lm would be a competitive candidate in the fabrication of photovoltaic devices.
4. Conclusion

Fig. 5. Optical absorption coefcient () of the annealed lm as a function of photon


energy (h). The inset shows the plot of (h)2 vs. h.

Copper bismuth selenide thin lms have been obtained on tin


oxide glass substrates by potentiostatical electrodeposition and
post annealing treatment. The electrochemical behavior of electrodeposition was investigated by cyclic voltammetry (CV). The
inuence of deposition potential on lm composition and morphology was also studied. The suitable deposition potential for
lm preparation was determined to be about 0.22 V combining
with CV, composition and morphology analysis. The annealed lm
exhibited improved crystallinity with a basic structure of triclinic

J. Li et al. / Electrochimica Acta 87 (2013) 153157

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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