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A simple hydrothermal method for the growth of Bi2Se3 nanorods

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2006 Nanotechnology 17 1700

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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY
Nanotechnology 17 (2006) 1700–1705 doi:10.1088/0957-4484/17/6/026

A simple hydrothermal method for the

growth of Bi2Se3 nanorods
Jyoti R Ota1 , Poulomi Roy1 , Suneel K Srivastava1 , R Popovitz-Biro2
and Reshef Tenne2
1
Inorganic Materials and Nanocomposite Laboratory, Department of Chemistry,
Indian Institute of Technology, Kharagpur-721302, India
2
Department of Materials and Interfaces, Weizmann Institute, Rehvot 76100, Israel

E-mail: sunit@chem.iitkgp.ernet.in

Received 9 January 2006

Published 27 February 2006
Online at stacks.iop.org/Nano/17/1700
Abstract
Bi2 Se3 nanorods have been synthesized through a simple hydrothermal
reduction approach. The nanorods formed were ≈10 nm in diameter and
100–200 nm in length. XRD characterization suggested that the product
consisted of the hexagonal phase of pure Bi2 Se3 . EDX and XPS studies
further confirmed the composition and purity of the product. A possible
mechanism for the reaction is proposed, where Bi2 Se3 microsheets are
presumed to be the intermediate for the formation of the nanorods. The effect
of solvent on the morphology of the final product is discussed, where, in the
presence of aprotic solvent DMF, nanoparticle formation is observed. A
bandgap of 2.25 eV is observed from the UV–visible absorption spectra.

1. Introduction dimensional nanostructures have been the subject of intense

In the past few years, studies of materials with
layered structures such as transition metal dichalcogenides
(TMDCs) [1, 2], metal chalcogenides of AV VI
2 B3 [3], A2 X3 -
M2 X3 -M X (A = Ga, In; M = trivalent metal; M = divalent

metal; X = S, Se) [4, 5], clay minerals [6] etc have received
ever-increasing attention. Among all of these, work on metal
chalcogenides of AV VI
2 B3 has attracted much attention due
to their wide application in thermoelectric, optoelectronic
devices as well as in television cameras, IR spectroscopy
etc [7, 8]. For a material to be useful for application in
thermoelectric devices, the figure of merit ( Z = S 2 σ/κ )
plays an important role, where the increase in Z is
accompanied by a corresponding increase in the electrical
conductivity (σ ) and decrease in the thermal conductivity (κ ).
It has been reported that the thermal conductivity decreases at
the nano-level, without deteriorating the electrical conductivity
due to the lattice-phonon blocking effect [9]. An enhancement
in optical and electrical properties is also expected as a
result of the quantum size effect. Some recent studies have
revealed that nanostructures, quantum wells and quantum
wires can be better thermoelectric materials than their bulk
counterparts [10, 11]. Hence, the synthesis of nanomaterials
and their proper application has remained a challenge for
developing better thermoelectric materials. In particular, one-
research during the last few years, due to their unique
electrical, optical, and magnetic properties, and their potential
application in devices [12]. In this regard, Bi2 Se3 , a low
bandgap semiconductor, has received thorough attention in the
past few years. Moreover, Bi2 Se3 has a quasi-layered structure
with two Bi and three Se layers forming one unit cell, which
are connected by weak van der Waal’s forces [13]. This unique
feature makes it suitable to grow into different one-dimensional
nanostructures such as nanorods, nanowires, nanotubes,
etc [14]. However, no significant progress has been made in
the synthesis of Bi2 Se3 nanomaterials. Wang et al [15] used
a solvothermal approach to prepare nanocrystals of Bi2 Se3 ,
using ethylenediamine as a solvent and NaI as a reducing agent.
Single-crystalline nanorods of Bi2 Se3 have been reported by
means of a convenient solvothermal route using ethylene
glycol both as a solvent and a reducing agent [16]. Recently,
thermoelectric nanosheets and nanotubes of Bi2 Se3 have been
synthesized by a hydrothermal co-reduction method [13]. Zhu
and coworkers prepared Bi2 Se3 nanocrystals with controllable
morphology and nanospheres using a sonochemical [17] and
a photochemical [18] synthetic method, respectively. The
formation of nanorods using alumina as the template was also
reported [18]. In addition to this, the synthesis of bismuth
chalcogenides in nanocrystalline form using various methods
such as solvothermal [19], conventional evaporation [20],

0957-4484/06/061700+06$30.00 © 2006 IOP Publishing Ltd Printed in the UK 1700


surfactant template [21] and a sonochemical route [22] have
been reported. Among all of these, the solvothermal and
hydrothermal methods have been widely used due to their ease
of use and their one-step synthesis approach.
In the present paper, we report an easy hydrothermal
approach to obtain Bi2 Se3 nanorods using Se powder, bismuth
nitrate, triethanol amine (as a complexing agent), sodium
hydroxide and hydrazine hydrate as a reducing agent. The
effect of temperature and solvent on the morphology of the
final product is also discussed. The product obtained at a higher
temperature (150 ◦ C) mainly consists of nanorods, whereas
for the same reaction at a lower temperature (110 ◦ C), some
microsheets are obtained as well as nanorods. The optical
properties of the material are examined.
2. Experimental procedure
All of the reagents were of analytical grade and used without
further purification. In a typical procedure, 7.5 mmol of
NaOH was dissolved in 20 ml of water in a 100 ml beaker,
and 3.7 mmol of Se powder was added to it under constant
stirring, followed by 0.4 ml of hydrazine hydrate. The
stirring was continued for about 1.5 h, and 1.3 mmol of
Bi2 (NO3 )3 ·5H2 O triturated in 5 ml of triethanol amine was
added to it, the stirring was continued for a further 15 min.
The resultant solution was transferred into a Teflon-lined
autoclave of 55 ml capacity, and maintained at 150 ◦ C for
about 24 h, followed by cooling to room temperature. The
product was then carefully collected and washed with water,
followed by ethanol repeatedly, then dried in vacuum at 60 ◦ C
for 4 h. The same experiment was repeated using N , N -
dimethyleformamide (DMF) and tetrahydro furan (THF) as the
solvents in place of water.
The phase analysis and structure of the material were
examined with a Philips PW-1710 x-ray diffractrometer
(40 kV, 20 mA) (XRD) using Cu Kα radiation (λ = 1.5418 Å).
The morphology of the sample collected from the surface
was studied using a JEOL (JSM-5800) scanning electron
microscope with an accelerating voltage of 20 kV. An electron
microprobe analyser (OXFORD ISIS-300 model) was used
to determine the chemical composition of the sample. TEM
micrographs and electron diffraction (ED) were carried out on
a Philips CM 120 (120 kV) transmission electron microscope.
High-resolution transmission electron microscopy (HRTEM)
was carried out on a Tecnai F30 (300 kV) (FEI). The
x-ray photoelectron spectra (XPS) were collected on an
ESCALab MKII x-ray photoelectron spectrometer, using non-
monochromatized Mg Kα x-ray as the excitation source.
A Perkin–Elmer lambda 20 UV/VIS spectrophotometer was
used for the optical measurement of the sample, dispersed in
ethanol.
3. Results and discussion
The phase analysis of the as-prepared sample was examined by
XRD, and is shown in figure 1. All of the peaks can be indexed
to the pure hexagonal phase of Bi2 Se3 , with cell parameters
a = 4.134 Å and c = 28.542 Å (space group: R 3m ) and are
close to the reported values (JCPDS 33-0214; a = 4.1396 Å
and c = 28.636 Å). Peaks corresponding to Bi, Se or other
A simple hydrothermal method for the growth of Bi2 Se3 nanorods
015
Intensity (arb.unit)
110
101
1010
006
205
116
104
1115
0210
1016
021
10 20 30 40 50 60 70
2θ, degrees
Figure 1. XRD pattern of the Bi2 Se3 nanorods synthesized at 150 ◦ C.
Bi–Se compounds are not observed in the diffraction pattern,
suggesting that the product is of high purity. The composition
of the final product was further confirmed by energy dispersive
x-ray analysis (EDX), in which the atomic ratio of bismuth
(41%) to selenium (59%) was found to be approximately 2:3,
confirming the product to be Bi2 Se3 .
XPS characterization of the sample was done to evaluate
the composition and purity of the nanorods. The binding
energies obtained in the XPS analysis are standardized for
specimen charging using C1s as the reference at 284.6 eV. The
complete range scan is shown in figure 2(a), where only peaks
for Bi, Se, O and C are found. It should be mentioned that the
presence of trace amounts of C and O during the synthesis of
nanorods is not uncommon, and that could be due to adsorbed
CO2 , O2 or H2 O on the surface of the sample [16], confirming
further the formation of a high purity product in our case.
Figure 2(a) shows that there is an overlap of Bi 4f and Se 3p
peaks at around 160 eV; but compared to the Se 3p peak, Bi 4f
is of higher intensity. The high-resolution spectrum of the Bi
4f presented in figure 2(b) shows that peaks appear at 156.0 eV
(Bi 4f7/2 ) and 161.3 eV (Bi 4f5/2 ) with a splitting of 5.3 eV,
which is in agreement with the previous reports [8, 16]. In this
case, there is no change in spin–orbit splitting. However, a
small chemical shift (0.6 eV) compared to the peak positions
in the case of elemental Bi is clearly visible [23]. Moreover,
this corresponds to around 2 eV shift for Bi 4f7/2 and Bi 4f5/2
peaks compared to that reported for Bi2 Se3 in the compound
form [16, 24]. The presence of a broad peak at 51.7 eV in
figure 2(c) corresponds to the Se 3d level. It can be noted that
the Se 3d peak also has a shift around a similar value as in
the case of the peaks for Bi. All such shifting of the peaks is
also well matched to the report by Thuler et al [25]. Taking
into account the atomic sensitivity factor of each element, the
stoichiometry calculated from the peak area of the Bi 4f and Se
3d is in agreement with the formula Bi2 Se3 .
The morphology of the product was examined using a
transmission electron microscope. A typical TEM image,
shown in figure 3(a), reveals the nanorods with diameters
around 10 nm and lengths around 100–200 nm. The ED pattern
of the product is shown in the inset of this figure, revealing
1701
J R Ota et al

(a) of about 10–12 lattice fringes, and the interlayer separation

Bi 4f(Se 3p) estimated from the line profile is 0.474 nm. The above distance
80k corresponds to the (006) plane of Bi2 Se3 , so the preferential
growth along this plane is consistent with the growth of the
one-dimensional nanostructures along the (00) direction [12].
Figure 3(c) shows a TEM of a complete nanorod, where well-

Bi 4d3/2
Bi 4d5/2

Bi 4p3/2
60k defined fringes can be observed without any disarrangement
(dislocation). The FFT (fast Fourier transform) of this nanorod,

O 1s
Intensity (cps)

showing clear spots, is shown in the inset. The spots identified

refer to the 006 plane (0.474 nm), and are equal to the
C 1s

40k calculated average fringe width. Figure 3(d) shows a HRTEM

image from part of a nanorod with the 003 (0.96 nm) lattice
fringes, corresponding to one layer of Bi2 Se3 , marked.
We also carried out the reaction using DMF and THF as
Se 3d

20k the solvents. The SEM image of the product prepared using
Bi 5d

DMF as a solvent is shown in figure 4(a). It can be seen

that hexagonal particles in the size range of a few hundred
nanometres to one micrometre are the structures of these
0k
0 200 400 600 800 1000 products, and no nanorods are formed. The TEM image of this
Binding energy / eV sample, shown in figure 4(b) shows the presence of some clear
(b) hexagonal particles of around 100–300 nm. The ED of this
Bi 4f7/2
(156.0 eV)
Bi 4f5/2 nanoparticle in the inset of this figure has random spots that are
(161.3 eV) difficult to index, indicating the formation of a polycrystalline
product. It appears that the interaction of ions with the reaction
Intensity (arb. unit)

media controls the rate of crystal growth, which is responsible

for the formation of such particles. The hydrazine acts as a
reducing agent in our process, converting (reducing) elemental
selenium to HSe− , that in turn is converted to Se2− by OH−
provided by sodium hydroxide [26]. Thus, Bi3+ through the
controlled release from the TEA-Bi complex, reacts with Se2−
to give Bi2 Se3 . The slow reaction rate favours the formation of
one-dimensional nanstructures [27]. The aprotic nature of the
0 150 155 160 165 170 DMF could increase the activity of the ionic species, thereby
(c) Binding energy / eV increasing its reaction rate. Thus, the diffusion of the ions in
Se 3d DMF at 150 ◦ C is more rapid than in water, i.e. protic, and
(51.7 eV) can interact with the charged species effectively. Hence, the
reaction is completed in a shorter time in an aprotic solvent,
and the product is in a growing process for the rest of the
Intensity (arb. unit)

time (Ostwald ripening) [27]. As a result, the morphology of

45 50
Binding energy / eV
Figure 2. XPS spectra of the Bi2 Se3 nanorods: (a) wide scan spectra;
(b) high-resolution spectra of Bi 4f and (c) high-resolution spectra of
Se 3d.
clear diffraction spots that correspond to the hexagonal phase
of Bi2 Se3 . The nanorods formed are short, but nearly uniform
in dimension. A TEM image of part of a nanorod is shown
in figure 3(b), along with the line profile of the marked
region (inset). It is clearly evident that each nanorod consists
the product changes from a rod-like shape to the hexagonal
particles of Bi2 Se3 , controlled by its crystal habit. However,
when water is used as the solvent, the slow reaction rate affects
the structure of the product resulting in nanorods. In this case,
the ionic activity is likely to decrease due to the protic (polar)
water and as result, the reaction rate remains slow giving rise
to preferential growth along one direction, thereby forming
nanorods. The morphological evolution of the Bi2 Se3 nanorods
reflects its inherent crystal structure. It crystallizes in structure
55 60 65 where hexagonal sheets of cation and anion are arranged in
a close-packed chain-like manner. In this typical structure,
different layers are arranged vertically to each other extending
along the c-axis. This anisotropy in the crystal structure makes
the material suitable for growth in a specific orientation to
give rod-like structures. However, formation of Bi2 Se3 is
significantly low when THF is used as a solvent under similar
conditions.
When the same reaction was carried out in the presence of
water at a lower temperature i.e. below 110 ◦ C, some particle
were found floating on the upper surface. EDX analysis of
these confirmed the Bi:Se atomic ratio to be 2:3, and the

1702
 A simple hydrothermal method for the growth of Bi2 Se3 nanorods

a b

c d

Figure 3. TEM images of the Bi2 Se3 nanorods synthesized at 150 ◦ C: (a) low magnification TEM image and the corresponding SAED pattern
(inset); (b) high magnification TEM image of part of a nanorod showing a profile of the lattice fringes marked by a line (inset); (c) high
magnification TEM image of a complete nanorod and FFT (fast Fourier transform) of the region marked by a square (inset). (d) HRTEM
image of a part of a nanorod with the 003 (0.96 nm) lattice fringes marked.

SEM image is shown in figure 4(c). The platelet or sheet-
like structure in the micron range can be seen clearly in the
micrograph. However, no such platelets were found floating
on the surface when the reaction was carried out at a higher
temperature (150 ◦ C). These observations clearly suggest that
the formation of nanorods takes place through the platelets, and
the reaction is completed without leaving any of these platelets
untransformed at a higher temperature.
The optical absorption spectrum was recorded in the range
1100–300 nm at room temperature by dispersing the samples
in ethanol, and the value of the optical absorption coefficient
(α ) is calculated by using the equation
1
α = − ln A
c
where c is the concentration expressed in terms of the amount
of sample dispersed per 1 ml of ethanol (2.3 × 10−4 g cm−3 )
and A is the absorbance. The value of α is found to be
of the order 104 cm−1 , supporting the presence of a direct
bandgap [28–30].
The bandgap of the material has been calculated on the
basis of the optical spectra using the following equation:
(αhν) = B(hν − E g )n
where hν is the photon energy, B is a constant and n
is the transition-dependent parameter, which is 1/2 or 3/2
for a direct bandgap material depending on whether the
transition is allowed or forbidden, respectively. Bi2 Se3 , being
a semiconducting material with direct bandgap, n can be taken
to equal 1/2. The plot of (αhν)2 with respect to hν is shown
in figure 5. Extrapolating the linear part of the curve on the
hν axis, the bandgap of the sample is found to be 2.25 eV. The
higher bandgap values of 2.3 eV [31] and 1.7 eV [32] have
been reported in the case of Bi2 Se3 thin films. Yang et al
[16] have also reported a bandgap of 1.5 eV for nanorods of
around 100 nm in diameter, which they explained as being due
to the quantum confinement effect. However, the nanorods in
our case are of much lower dimensions (10 nm), so a higher
bandgap is expected. Earlier studies by Bhosale et al [33]
on Bi2 S3 also confirmed the effect of size on the bandgap.
According to this, the bandgap of Bi2 S3 is 1.7 eV for a particle
size 224 nm, and with a decrease in particle size (130 nm)
it increased to 2.0 eV. Therefore, the increase in bandgap in
our case may be attributed to the quantum confinement effect,
although, the possibility of an additional contribution from the
surface state cannot be ruled out [34–36].

1703
J R Ota et al
a b
200 nm
c The authors would like to acknowledge the financial support
Figure 4. (a) SEM image of the Bi2 Se3 nanoparticles prepared at
150 ◦ C using DMF as the solvent, (b) TEM photograph of the
nanoparticles (inset: the corresponding SAED pattern), (c) SEM
image of the sample collected from the surface of the solution when
the reaction was carried out at 110 ◦ C using water as a solvent.
2.8
(αhν)2x 108 / (eV/cm)2
2.4
2.0
1.6
0 1 2 3
hν / eV
Figure 5. Plot of (αhν)2 versus hν for the Bi2 Se3 nanorods.
4. Conclusions
Bi2 Se3 is a typical thermoelectric material with excellent
thermoelectric properties. We have been able to synthesize
nanorods of Bi2 Se3 through the hydrothermal method to
be potentially useful for the preparation of thermo-electric
nanostructures or quantum devices by chemical self-assembly.
XRD studies confirmed the formation of hexagonal Bi2 Se3
with lattice parameters a = 4.134 Å and b = 28.542 Å.
The results of ED and TEM analysis also supported the lattice
constants calculated from XRD. The effect of solvents on the
final morphology of the sample and a possible mechanism for
the formation of the reaction product are discussed. Micro-
platelets of Bi2 Se3 appear to be a possible intermediate during
the formation of the nanorods. The purity and composition
of the sample is confirmed by both EDX and XPS. From
1704
the optical study of the nanorods, the bandgap was found
to be 2.25 eV; higher than that of the bulk sample. The
increase in the bandgap suggests that the nanorods could be
a better material for use in optoelectronic devices than the bulk
material.
Acknowledgments
by MHRD and CSIR, India to carry out this work. RT is
the Director of the Helen and Martin Kimmel Center for
Nanoscale Science and the holder of the Drake Family Chair
for Nanotechnology.
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