Journal of Physics and Chemistry of Solids 74 (2013) 867871

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Journal of Physics and Chemistry of Solids

journal homepage: www.elsevier.com/locate/jpcs

Hydrothermal synthesis of CuInSe2 nanoparticles in acetic acid

Jang Bo Shim, Chang Gyoun Kim, Dong Ju Jeon, Taek-Mo Chung, Ki-Seok An, Sun Suk Lee, Jong Sun Lim,
Seok Jong Jeong, Bo Keun Park, Young Kuk Lee n
Thin Film Materials Research Group, Korea Research Institute of Chemical Technology, Sinseongno 19, Yuseong-gu, Daejeon 305-600, Republic of Korea

a r t i c l e i n f o

abstract

Article history:
Received 9 March 2012
Received in revised form
24 October 2012
Accepted 3 February 2013
Available online 11 February 2013

The CuInSe2 nanoparticles for thin-lm solar cells were successfully synthesized using a simple
hydrothermal method with acetic acid as a mineralizer. The CuInSe2 nanoparticles with high purity
were formed with acetic acid concentration of 5 M, reaction temperature of 200 1C, and reaction time of
12 h. The concentrations of acetic acid signicantly affected the phase, morphology, and size of the
prepared particles. The crystallinity and the particle size also increased as a function of the reaction
temperature and the reaction time. Room-temperature Raman spectra shows that the single-phased of
CuInSe2 nanoparticles were obtained via the hydrothermal synthesis with acetic acid. We proposed the
one-step reaction mechanism for the CuInSe2 nanoparticles based on the X-ray diffraction and the
scanning electron microscopy data.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
A. Nanostructures
B. Crystal growth
B. Chemical synthesis
D. Phase transitions

1. Introduction
The ternary IIIIVI2 semiconductor of CuInSe2 (CIS) is one of
the potential materials as the optical absorber layer for thin-lm
solar cells. Because of its high absorption coefcient, the thickness
of the absorption layers can be reduced to several micrometers. In
addition, CIS is known for high performance, low cost, low band
gap (1.05 eV), good radiation stability, and easy conversion of n/pcarrier type [14]. Over the past few years, various methods have
been developed for CIS fabrication including sputtering [5],
evaporation [6], electrodeposition [7,8], and pyrolysis of molecular
single-source precursors [9]. However, these approaches required
complicated facility, high processing temperature, and some of
them use toxic reagents such as organometallic compounds or
H2S. To avoid these drawbacks, solvothermal methods have been
widely studied for the preparation of CIS particles at much lower
temperature [10,11]. However, the required synthesis time was
long, and the required ethylenediamine solvent was costly and
easily evaporated [12]. To solve this problem, the hydrothermal
synthesis was investigated to prepare CIS particles in this study.
H2O was used as the solvent in the hydrothermal synthesis, and it
was more environmental friendly than ethylenediamine.
In this paper, we report on the CIS nanoparticles fabricated by
the hydrothermal synthesis using acetic acid (CH3COOH) as a
mineralizer. The formation of the CIS nanoparticles from the
elemental Cu, In, and Se powders in acetic acid solution by the

Corresponding author. Tel.: 82 42 860 7357; fax: 82 42 861 4151.

E-mail address: leeyoung@krict.re.kr (Y.K. Lee).

0022-3697/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jpcs.2013.02.002

hydrothermal synthesis has not yet been reported. The inuence

of acetic acid concentration, reaction temperature, and reaction
time on the structural characterization of the synthesized particles was investigated. On the basis of these results, we discuss a
mechanism for the synthesis of CIS nanoparticles.

2. Experimental
The CIS nanoparticles were prepared using the hydrothermal
synthesis with acetic acid (99.5%) as the solvent. Copper powder
(99.5%, Aldrich), indium powder (99.99%, Aldrich), and selenium
powder ( Z99.5%, Aldrich) were used as source materials. The
reagents were loaded into a 320 ml autoclave with Teon-liner
and lled with acetic acid aqueous solution up to 80% of the total
volume. The concentrations of acetic acid were varied from 0 M to
5 M. The molar ratio of Cu, In, and Se was xed at 1:1:2. The
reaction temperature of the autoclave was controlled from 180 1C
to 220 1C for 8 h to 16 h. The prepared products were washed
with distilled water and dispersed in ethanol. The obtained
products were then dried at 80 1C for 5 h in an oven.
Powder X-ray diffraction (XRD, Rigaku D/Max-2200 V diffractometer) was employed to examine the formed phases of the
prepared particles using Cu Ka radiation at 40 kV and 40 mA. The
morphology and size of the particles were investigated by eld
emission scanning electron microscopy (FESEM) (Hitachi S-4700,
operated at 20 kV). Energy dispersive X-ray (EDX, Bruker, Quantax 200) analysis was performed to determine the elemental
composition. Raman spectra were measured from 100 to
350 cm  1 at room temperature using the 514 nm line of an Ar
laser beam (inVia, Renishaw).

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J.B. Shim et al. / Journal of Physics and Chemistry of Solids 74 (2013) 867871

3. Results and discussion

20

30

40

30

40

20

40

50

In(OH)3

In(OH)3

Se
In(OH)3

Se

In(OH)3

Se In(OH)3

In(OH)3
Se
Se
In(OH)3
Se

70

80

60

70

80

CIS(312/116)

CIS(204/220)

50

50

60

CIS(316/332)

CuSe

60

CIS(008/400)

In(OH)3

30

CuSe

20

CIS(112)

Intensity (a.u.)

Se

Se
In(OH)3

In(OH)3

The inuence of acetic acid concentration on the formation of

CIS nanoparticles with a xed reaction temperature of 200 1C and
reaction time of 12 h studied. Fig. 1 shows the X-ray diffraction
patterns of nanoparticles employing acetic acid with 1 M and 5 M

70

80

2 theta (degree)
Fig. 1. XRD patterns of the CIS nanoparticles at 200 1C for 12 h with (a) 1 M,
(b) 3 M, and (c) 5 M acetic acid in the hydrothermal synthesis.

concentrations. In our experimental set-up, the CIS cannot be

found as a phase without acetic acid. As shown in Fig. 1(a), when
the acetic acid concentration was 1 M, a small amount of CIS was
found to coexist with the phases of In(OH)3 and Se. At acetic acid
concentration of 3 M, the intensity of CIS diffraction peaks was
increased and the peak intensity of In(OH)3 phase was decreased
(Fig. 1(b)). As the acetic acid concentration increased to 5 M
(Fig. 1(c)), the single-phased CIS was obtained and In(OH)3 phase
and Se phase disappeared. At less than 5 M of acetic acid
concentration, In3 ions tend to combine with OH  ions rather
than Se2  ions. The diffraction peaks of the nanoparticles prepared with 5 M acetic acid were in good agreement with the data
reported in JCPDS card no. 87-2265. The nanoparticles were
conrmed to have the chalcopyrite structure belonging to the I42d space group [13]. This reveals that acetic acid could prevent
the synthesis of In(OH)3 phase and as a result the single-phased
CIS can be formed.
The qualitative analysis of the particles prepared at 200 1C for
12 h with 1 M acetic acid concentration was analyzed using an
EDX spectrum in Fig. 2. It was found that the chemical compositions of the particles with a cubic shape were indium. The Cu and
Se elements were also detected. This result, in accordance with its
XRD patterns of Fig. 1(a), implies cubic shaped particles are
deduced to be In(OH)3. The nanoparticles of plate shape were
CIS phase and the nanoparticles of spherical shape were Se phase.
To understand the reaction temperature effects on the structure and morphology of CIS nanoparticles, the hydrothermal
reaction was carried out from 180 1C to 220 1C for 12 h with
5 M acetic acid. The XRD patterns of the CIS nanoparticles
prepared at different reaction temperatures are shown in Fig. 3.
When the reaction temperature was 180 1C, the CIS phase was
found to coexist with a small amount of CuSe and Se phases

Fig. 2. (a) SEM image of the particles prepared at 200 1C for 12 h with 1 M acetic acid in the hydrothermal synthesis, and (b)(d) elemental mapping of Cu, In, and Se
in a particles.

J.B. Shim et al. / Journal of Physics and Chemistry of Solids 74 (2013) 867871

CIS(316/332)

CIS(008/400)

CuSe

CIS(312/116)

CuSe

CIS(204/220)
Se
CuSe

CuSe
Se
CuSe
CuSe

Se

CIS(112)

(Fig. 3(a)). The as-prepared nanoparticles can be indexed to

hexagonal CuSe (JCPDS card no. 89-7391). The CuSe phase with
hexagonal structure is the intermediate formed with 180 1C
reaction temperature. This result clearly indicates that the reaction temperature is an important factor in this study. When the
reaction temperature is lower than 180 1C, this reaction proceeds
to produce CuSe and cannot continue to form CIS because of the
low reactivity of In [14]. After the reaction temperature of 200 1C

30

40

50

60

70

80

20

30

40

50

60

70

80

20

30

40

50

60

70

80

Intensity (a.u.)

20

2 theta (degree)
Fig. 3. XRD patterns of the hydrothermal synthesized CIS nanoparticles prepared
at (a) 180 1C, (b) 200 1C, and (c) 220 1C for 12 h with 5 M acetic acid.

869

was employed, the intensity of CIS increased with corresponding

decrease in the intensities of CuSe and Se. The single-phased CIS
was formed as shown in Fig. 3(b). As the reaction temperature
was increased to 220 1C, CIS form as the main phase. However, a
small amount of CuSe phase was also found (Fig. 3(c)). Studies of
the hydrothermal synthesis pathway of the reappeared CuSe
phase are in progress.
Fig. 4 shows the SEM images of CIS nanoparticles prepared by
the hydrothermal synthesis at various reaction temperatures. The
particle size of the 180 1C synthesized particles was mixed size
between some mm and several hundreds of nm as shown in
Fig. 4(a). The CuSe nanoparticles synthesized at 180 1C were small
and the CIS particle shows abnormal form of overgrowth. On
increasing the reaction temperature to 200 1C, the particles with
approximately 400 nm were obtained (Fig. 4(b)). The nanoparticles exhibited uniform and spherical shape. In the conventional
solvothermal processes, the CIS powders prepared in ethylenediamine had a whisker-like shape with a length of 3080 nm [15].
On further increasing the reaction temperature to 220 1C, the
particle size of CIS particles was increased to approximately
400 nm and approximately 800 nm (Fig. 4(c)). The sizes of the
synthesized CIS nanoparticles increased with increase in reaction
temperature.
The inuence of reaction time on the size of CIS nanoparticles
with a xed reaction temperature of 200 1C and acetic acid
concentration of 5 M was also studied. Fig. 5 shows the XRD
patterns of CIS particles for various reaction times. The CuSe and
Se phases appear in the reaction time of 8 h and disappear over
the reaction time of 12 h. It indicates that the second phases and
CIS phase simultaneously formed below the reaction time of 8 h
and single-phased CIS formed over the reaction time of 12 h.
As the reaction time of the hydrothermal synthesis was further
increased to 16 h, the crystallinity of CIS was further enhanced.
The required reaction time for preparing single-phased CIS
powders via the conventional solvothermal route is at least 15 h
[15]. In this study, the preparation time for the pure CIS phase in

Fig. 4. SEM images of the CIS nanoparticles prepared at (a) 180 1C for 12 h, (b) 200 1C for 12 h, (c) 220 1C for 12 h, (d) 200 1C for 8 h, and (e) 200 1C for 16 h in the
hydrothermal synthesis.

172

CIS(316/332)

260

20

30

40

50

60

70

80

20

30

40

50

60

70

80

20

30

40

50

60

70

80

Intensity (a.u.)

CIS(008/400)

CuSe

CIS(312/116)

CIS(112)
CuSe
Se
CuSe

Se

Intensity (a.u.)

CuSe

J.B. Shim et al. / Journal of Physics and Chemistry of Solids 74 (2013) 867871

CIS(204/220)
Se
CuSe

870

100

150

200

250

300

350

100

150

200

250

300

350

100

150

200

250

300

350

Raman shift

2 theta (degree)

(cm-1)

Fig. 5. XRD patterns of the hydrothermal synthesized CIS nanoparticles prepared

at 200 1C for (a) 8 h, (b) 12 h, and (c) 16 h with 5 M acetic acid.

Fig. 6. Room-temperature Raman spectra of the hydrothermal synthesized CIS

nanoparticles prepared at 200 1C for (a) 8 h, (b) 12 h, and (c) 16 h with 5 M
acetic acid.

the hydrothermal synthesis was shortened to 12 h. Acetic acid can

react with each other in the nanoparticles within a short time.
Fig. 4 shows the change of morphology synthesized at 200 1C
according to the change of reaction time. The hydrothermal
synthesized nanoparticles exhibited spherical shape. When the
reaction time is increased from 8 h to 12 h, the particle size
increases from approximately 200 nm to approximately 400 nm,
respectively (Fig. 4(d) and (b)). On further increasing the reaction
time to 16 h, the particle sizes of CIS were increased to approximately 600 nm (Fig. 4(e)). It is clear that the size of particles is
signicantly affected by the reaction time.
Fig. 6 shows the Raman spectra of CIS particles prepared at
200 1C with 5 M acetic acid for various reaction times. In the
reaction time of 8 h, two peaks were observed at 172 and
260 cm  1. Very strong signal measured at 172 cm  1 for CIS
nanoparticles corresponds to the A1 optical phonon mode in
tetragonal CIS crystal. The A1 mode in CIS results from the motion
of the Se atom, and the Cu and In atoms remain at rest [1618].
An additional mode appears at 260 cm  1, which is assigned to the
A1 mode of CuSe [19]. Over the reaction time of 12 h, only the
Raman spectra belonging to CIS were observed, and no other
peaks were detected. This result clearly indicates that the CIS
nanoparticles with single-phase were obtained via the hydrothermal synthesis.
The proposed reaction mechanism for the CIS nanoparticles in
this hydrothermal synthesis using acetic acid can be summarized
by the following equations:

it might be that CIS was synthesized not through the formation of

CuSe. No In phase was observed in solid-state intermediates by
XRD and Raman in acetic acid of 5 M. This indicates that In
intermediate remains in solution until CIS formation step. In
Inductively Coupled Plasma-Atomic Emission Spectrometer analysis for the solution after cooling step, high volume of In ion was
detected at low reaction temperature. It is expected that the nonsynthesized remaining source materials are In ion. Moreover,
although the reaction temperature was high enough to melt In
(melting point: 157 1C), In and Se did not produce In2Se3 under
our experimental conditions. Over the reaction time of 12 h at the
reaction temperature of 200 1C, the existence of liquid In may
motivate this solid solution to grow CIS nanoparticles. On the
basis of these results, we proposed a one-step reaction mechanism. In our hydrothermal synthesis with Cu, In, and Se by using
acetic acid as a mineralizer, a one-step reaction could directly
yield CIS nanoparticles.

Cu2 Se2  -CuSe

(1)

Cu In3 2Se2  -CuInSe2

(2)

Under our hydrothermal synthesis conditions, acetic acid was

used as the attacking reagent to release Cu , In3 , and Se2  . The
nanoparticles of CuSe phase form upon reaction of solvated Cu2
and Se2  species. The CuSe phase was observed at the low
reaction temperature and for a short reaction time and formed
as an intermediate compound. The CuSe synthesis temperature
should be kept lower than CIS reaction temperature. Due to the
low activity of CuSe compared with the newly produced CuSe,

4. Conclusions
The pure CIS nanoparticles of high crystallinity have been
successfully synthesized using the hydrothermal method with
acetic acid concentration of 5 M, reaction temperature of 200 1C,
and reaction time of 12 h. The CIS nanoparticles with approximately 400 nm were obtained. Acetic acid as a mineralizer could
prevent the synthesis of In(OH)3 phase and as a result the singlephased CIS can be formed. The crystallinity and the particle size of
single-phased CIS nanoparticles were increased with increase in
the reaction temperature and the reaction time. Over the reaction
time of 12 h, the only Raman spectra belonging to CIS at
175 cm  1 were observed, and no other peaks were detected. To
explore the reaction mechanism, different synthetic reaction
systems such as various acetic acid concentrations, reaction
temperature, and reaction time were investigated, and a onestep reaction mechanism was proposed. Consequently, the nanosized CIS particles created by the hydrothermal method with
acetic acid as a mineralizer show great promise for use in thinlm solar cell devices using simple and environmental friendly

J.B. Shim et al. / Journal of Physics and Chemistry of Solids 74 (2013) 867871

route, low processing temperature, controllable nanoparticle size,

and low cost.

Acknowledgments
This work was supported by the IT R&D program of MKE/KEIT.
[KI002130, Development of high quality GaN single crystal and
wafer for white LED].
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