Journal of Crystal Growth 343 (2012) 68–72

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Journal of Crystal Growth

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

Characterization of single phase copper selenide nanoparticles and their

growth mechanism
D. Patidar n, N.S. Saxena
Semi-conductor and Polymer Science Laboratory, 5 & 6, Vigyan Bhawan, Department of Physics, University of Rajasthan, Jaipur 302055, India

a r t i c l e i n f o a b s t r a c t

Article history: The high quality Cu3Se2 phase of copper selenide nanoparticles was synthesized through the solution-
Received 19 April 2011 phase chemical reaction between copper and selenium. In this synthesis process, hydrazine hydrate
Received in revised form acts as reducing agent whereas ethylene glycol controls the nucleation and growth of particles. An
10 January 2012
effort has been made to explain the growth mechanism to form copper selenide nanoparticles through
Accepted 14 January 2012
the coordination of selenium to the Cu2 þ complexes with OH groups of ethylene glycol. Result indicates
Communicated by K. Nakajima
Available online 25 January 2012 the formation of Cu3Se2 single phase nanoparticles. The particles with the average particle size 25 nm
are spherical in shape having tetragonal structure. The particles are well crystallized having 94% degree
Keywords: of crystallinity. An effort has also been made to determine the energy band gap of copper selenide
A1. Electron diffraction
nanoparticles through the absorption spectra.
A3. Growth mechanism
& 2012 Elsevier B.V. All rights reserved.
B1. Copper selenide
B2. Absorption spectrum

1. Introduction
In the past few years, interest to nanoscale materials has been so
high that every possible method of their production is tried out.
These efforts have been due to the variety of new physical properties
of nano sized particles as compared to their bulk counterparts with
the same chemical constituents. The creation of ordered nanostruc-
tured materials and new devices based on them has been seen as the
development of modern science and technology. Currently semicon-
ductor nanoparticles have received great attention due to their wide
range of applications in the electronic and optoelectronic devices.
Copper selenide is one of the most important semiconductor
materials, which has been widely used as solar cells [1], super ionic
material [2], thermoelectric cooling material [3] and optical filters [4].
Interestingly, copper selenide can exist in a wide range of stoichio-
metric compositions [5–7] such as CuSe, Cu2Se, CuSe2, Cu3Se2,
Cu5Se4, Cu7Se4, etc. and non-stoichiometric compositions (Cu2 xSe)
with various crystallographic forms [8] (monoclinic, cubic, tetrago-
nal, hexagonal, etc.). Copper selenides are ideal candidates for
scientific research due to their special constitutions and properties
of compositions. The thermal stability and energy band gap of
copper selenides vary with their stoichiometric composition or
phases [9,10], which depend on the method of preparation. There-
fore, considerable research by the various researchers has been done
to explore the synthesis of copper selenides including thermolysis of
Cu and Se powder mixtures at 400–470 1C in the presence of flowing
argon [11] and mechanical alloying of Se and Cu in a high energy ball
mill [12]. Besides these, copper selenides have also been synthesized
through solvothermal process [13], gamma irradiation [14], micro-
wave-assisted heating [15], sonochemical method [16], hydrother-
mal method [17], vacuum evaporation [18], electro-deposition [19],
template-directed synthesis [20] and solution-phase chemical
reaction [21].
The wet chemical method for copper selenide has many advan-
tages over the other synthesis techniques such as simplicity, no
requirement for sophisticated equipments, non-toxic operation, low
cost and potential for large-scale production. In view of this, Kumar
et al. [22] and Kumar and Singh [23] have used this method to
prepare different phases (CuSe, Cu2 xSe, b-Cu2Se, Cu2Se) of copper
selenide taking chloride, sulfate, nitrate etc. of copper and elemental
copper as copper source with elemental selenium. However, to the
best of our knowledge, there are no reports of preparing Cu3Se2
phase of copper selenide taking elemental copper and elemental
selenium through this method. In this paper, an effort has been
made to prepare Cu3Se2 phase of copper selenide nanoparticles
taking elemental copper and elemental selenium in the presence of
hydrazine hydrate and ethylene glycol and investigate its reaction
mechanism, structural and optical properties.
2. Experimental details
2.1. Synthesis of copper selenide nanoparticles

n
Corresponding author. Tel./fax: þ 91 141 2704056. Copper selenide nanoparticles were synthesized by the wet
E-mail address: dinupatidar@gmail.com (D. Patidar). chemical method. All the reagents used were of analytical grade

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2012.01.026
 D. Patidar, N.S. Saxena / Journal of Crystal Growth 343 (2012) 68–72
and used without further purification. In the synthesis process,
copper (99.99%) and selenium (99.99%) in the powder form were put
into the round bottom (RB) flask. The ratio of Cu and Se concentra-
tion plays an important role in phase formation of copper selenide.
The ratio of Cu and Se can be changed to obtain the different phases
of copper selenide [17,21] such as 0.25 for CuSe, 0.5 for Cu3Se2, from
0.5 to 2 for mixed Cu2 xSe and Cu3Se2 and 2 for Cu2 xSe phase. The
phase diagram of CuSe system was given by Chakrabarti and
Laughlin [24] and Glozov et al. [25]. The CuSe system has the large
number of stoichiometries and phases. This is because copper exists
in more than one oxidation states such as þ1,þ2,þ3 and þ4.
Copper also makes the spinal system with the VI group element. The
Se is a member of the VI group element and CuSe makes the spinal
system in which Cu ions occupy tetrahedral and octahedral holes
(voids) in the close packed arrangement of selenium ions. The
number of tetrahedral and octahedral sites occupied may be ordered
and random, which is responsible for large number of stoichiome-
tries and phases of CuSe system. In the present case, the ratio of Cu
and Se concentration was taken as 0.5 to obtain Cu3Se2 tetragonal
phase. The deionized water, ethylene glycol and hydrazine hydrate
were added in the RB flask in the volume ratio of 10:3:1, respectively.
Then this solution was refluxed at 80 1C for 24 h under vigorous
stirring resulting in dark chocolaty precipitate. This precipitate was
centrifuged at 5000 rpm for 5 min and then washed several times
with ethanol and hot distilled water for the removal of excess
ethylene glycol and hydrazine hydrate. Finally washed precipitate
of copper selenide nanoparticles was dried at room temperature
under vacuum (10  2 Torr). To obtain the fine powder of dried
copper selenide nanoparticles, precipitate was crushed by mortar
and pestle. The nanoparticles of copper selenide were then char-
acterized through the X-ray diffraction (XRD), transmission electron
microscope (TEM) and optical spectroscopy.
2.2. Characterization techniques
XRD measurement was performed with Philips X’pert X-ray
diffractometer at a scanning rate of 31/min between 10 and 601.
The source used for this study was CuKa (l ¼1.5406 Å) operated
at 40 mA and 45 kV.
The transmission electron microscope (TEM) measurements
were performed on Tecnai G2 30 U-Twin system operating at an
accelerating voltage of 300 kV. The sample for TEM measure-
ments has been prepared by dissolving the copper selenide
nanoparticles in tetrahydrofurane (THF) solvent using ultra soni-
cator. A drop of prepared solution was placed on the carbon
coated copper grid. Before the TEM measurement, solvent was
removed from the sample by evaporation at room temperature.
The optical absorption spectrum of copper selenide nanopar-
ticles was recorded over the wavelength range 250–600 nm using
an USB 2000 spectrophotometer. In this spectrophotometer,
absorption spectra were obtained directly through the computer
using OOIBase32 software. This measurement was done in the
above-mentioned wavelength range at room temperature by
dissolving the copper selenide nanoparticles in dimethyl sulfox-
ide (DMSO) solvent. The light source was a deuterium lamp. From
the absorption spectrum, the optical band gap of copper selenide
nanoparticles was determined.
3. Results and discussion
3.1. Reaction mechanism
In this study, copper selenide nanoparticles were formed from
the elements Cu and Se through redox reaction, with hydrazine
hydrate acting as reducing agent whereas ethylene glycol solvent
69
plays an important role in controlling nucleation and growth of
copper selenide nanoparticles. The source of Se ions was pro-
duced through the reduction of Se by hydrazine hydrate. The
highly reactive Se is easily converted into Se ions as shown in
Eq. (1). At the initial stage of reaction, copper ions obtained by the
oxidation of Cu produce glycolate through the formation of
Cu’OH coordination bonds [26] due to the presence of ethylene
glycol molecules in the reaction medium. The mono-chelate
glycolate is formed by the chelation of two OH groups of ethylene
molecules with Cu2 þ ions. The chelation involves dative cova-
lencies in which hydroxyl oxygen donates a pair of electrons to
Cu2 þ to produce the adduct complex. Here, hydroxyl oxygen acts
as a Lewis base whereas Cu2 þ works as a Lewis acid. Chelation
continues to form the more stable tri-chelate octahedral glycolate
complex [27] as shown in Scheme 1 and Eq. (2). Cu2 þ complexes
could predominate [28] due to presence of the reducing agent
(hydrazine hydrate), which also prevents the oxidation reaction of
Cu particles with oxygen. The solvent molecule may act as a
bidentate ligand in the solvent solution to form relatively stable
Cu2 þ complexes. The stability of Cu2 þ complexes is expected to
decrease with the increase of temperature. At some temperature,
for example 80 1C in the present case, selenium may coordinate to
the Cu2 þ complexes with OH groups of ethylene glycol to form a
copper selenide nanoparticles (Eq. (3)) and volatile coordinated
ligands are gradually lost. In the formation of copper selenide
nanoparticles, this bidentate ligand complex could serve as a
molecular template in the control of copper selenide crystal
growth.
2Seþ4OH  þN2H4  H2O-2Se2  þ5H2OþN2 (1)
Cuþ2C2H6O2 þ4H2O-Cu(OH)26 þ þ 2OH  þ2C2H6 (2)
3Cu(OH)26 þ þ 2Se2  þ 2OH  -Cu3Se2 þ10H2Oþ5O2 (3)
3.2. XRD study
The X-ray diffraction pattern of copper selenide nanoparticles
is shown in Fig. 1. The presence of sharp structural peaks in this
XRD pattern confirms the crystalline nature of the material. The
experimental values of d (lattice spacing) for copper selenide
nanoparticles are determined using the Bragg’s relation [29] by
taking the y value from the peak position of XRD pattern. These
values of d are compared with the standard (ASTM) values of dn.
The experimental values of d and values of dn from ASTM data are
in good agreement as shown in Table 1. XRD result corresponds to
the characteristic pattern of Cu3Se2 phase [30]. The cell constants
were determined to be a ¼6.392 Å and c ¼4.297 Å, which are also
Scheme 1.
70 D. Patidar, N.S. Saxena / Journal of Crystal Growth 343 (2012) 68–72

proportional to the intensity of amorphous scattering. The degree

of crystallinity is about 94% in the sample. This indicates that the
prepared nanoparticles are well crystallized.
The particle size of copper selenide nanoparticles is deter-
mined using the Debye Scherrer formula [32] as given below
D ¼ 0:9l=bcos y ð4Þ
where D is the average particle size perpendicular to the reflect-
ing planes, l is the X-ray wavelength, b is the full width at half
maximum (FWHM) and y is the diffraction angle. After removing
all broadening factor from diffraction spectra such as instrumen-
tal broadening and strain broadening, the average particle size
has been determined. It is found that the average particle size of
copper selenide nanoparticles is 24 nm.

3.3. Morphology study

The morphology of copper selenide was investigated by TEM.

The TEM images are shown in Fig. 2(a) and (b) at 50 nm and
0.5 mm scale, respectively. The structure and shape of the parti-
cles are measured from the TEM measurement. The shape of
particles is spherical as observed from TEM image. It is observed
Fig. 1. XRD pattern of copper selenide nanoparticles. that the particles are aggregated and indistinguishable from each
other. The aggregation of particles took place due to the very high
surface energy. The average particle size is about 25 nm. This is in
good agreement with the value obtained from XRD pattern.
Table 1 Selected area electron diffraction (SAED) pattern is taken from
XRD data for copper selenide nanoparticles. certain selected area as mentioned in TEM image in Fig. 2(a),
which indicates tetragonal structure with the highly ordered
2y (deg.) d (Å) dn (Å) hkl
particles as shown in Fig. 2(c). The highly ordered spots in the
SAED pattern mean that the particles are well crystallized, which
20.65 4.285 4.279 001
24.95 3.566 3.558 101 is also confirmed from the XRD measurement. Fig. 2(c) also shows
27.89 3.196 3.203 200 a large shadow hiding a part of the electron diffraction pattern.
28.64 3.114 3.110 111 The large shadow in the SAED pattern is due to the beam stopper,
31.12 2.862 2.865 210 which is used for reducing the intensity of central beam in order
34.94 2.564 2.564 201
37.77 2.380 2.380 211
to avoid any damage in the sample. Some clear rings in the SAED
39.86 2.260 2.264 220 pattern are made up of some discrete spots that are due to the
42.02 2.147 2.140 002 nanocrystalline material [33]. The crystallographic planes and
44.60 2.024 2.025 310 reciprocal unit vectors in SAED pattern have been determined
45.30 2.000 2.002 221
taking [1–10] as zone axis of tetragonal copper selenide using the
46.78 1.940 1.934 112
47.59 1.909 1.911 301 method described in Ref. [34] and indicated in Fig. 2(c).
49.81 1.830 1.831 311
51.19 1.783 1.779 202 3.4. Band gap determination
53.29 1.717 1.714 212
56.01 1.639 1.641 321
57.64 1.598 1.602 400 Fig. 3 shows the absorption spectrum of copper selenide
59.29 1.557 1.555 222 nanoparticles. The absorption edge presents the band gap of
copper selenide nanoparticles. It is observed that the absorption
edge shifts towards the lower wavelength side (blueshift) as com-
consistent with the reported data [30,31]. Although there are pared to bulk material. The energy band gap is determined using
many stoichiometries of copper selenide and some stoichiome- absorption spectrum through the Tauc-relation [35] as given by
tries have different phases but each of them has its characteristic
XRD pattern. Therefore, the XRD pattern gives the most positive ahn ¼ AðhnEg Þ1=2 ð5Þ
evidence for the formation of Cu3Se2 phase having tetragonal where a is the absorption coefficient, h is the Planck constant, n is the
structure. The XRD pattern does not show any peak of elements frequency, A is a constant and Eg is the energy band gap. A graph is
Se and Cu as well as other stoichiometries. This indicates that the plotted between square of ahn and hn, for the determination of
prepared material is a single phase material, which can be energy band gap as shown in Fig. 4. The value of band gap is
produced by the controlled synthesis process. The degree of estimated by extrapolating the linear portion of the curve to
crystallinity has been evaluated through ‘High Score Plus’ soft- (ahn)2 ¼0. It is found that band gap of copper selenide nanoparticle
ware, which is based on following principle. The degree of is 4.0 eV that indicates the blueshift of 1.82 eV from the bulk band
crystallinility is the ratio of integrated intensity of crystalline gap (Eg ¼ 2.2 eV for Cu3Se2) due to quantum confinement effect.
phase and sum of the integrated intensities of both crystalline and
amorphous phases, which can be determined by drawing the line
of demarcation in such a manner as to be congruent with the XRD 4. Conclusions
pattern. The area above the demarcation curve is taken to be
proportional to the intensity of crystalline scattering and area It is concluded from the above study that Cu3Se2 phase of
between the base line and demarcation curve is taken to be copper selenide nanoparticles was formed through the reaction
 D. Patidar, N.S. Saxena / Journal of Crystal Growth 343 (2012) 68–72 71

Fig. 2. (a) TEM image of copper selenide nanoparticles at 50 nm scale, (b) TEM image of copper selenide nanoparticles at 0.5 mm scale and (c) selected area electron
diffraction pattern of copper selenide nanoparticles.

Fig. 3. Absorption spectrum of copper selenide nanoparticles.

between elemental copper and selenium in the presence hydra-
zine hydrate and ethylene glycol. Particles are well crystallized
having tetragonal structure. The band gap shifts towards higher
value by 1.82 eV as compared to bulk band gap due to quantum
confinement effect.
Fig. 4. Energy band gap determination of copper selenide nanoparticles.
Acknowledgments
Authors are thankful to the Council of Scientific and Industrial
Research (CSIR), New Delhi for providing financial assistance
72 D. Patidar, N.S. Saxena / Journal of Crystal Growth 343 (2012) 68–72
during the course of this work. Authors would also like to thank
Ms. Sonalika Agrawal, Mr. Mahesh Baboo and Mrs. Faheem
S. Naqvi for their help in various ways.
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