Inorganic Chemistry Communications 7 (2004) 319–321

www.elsevier.com/locate/inoche

Size-controllable sonochemical synthesis of thermoelectric

material of Bi2Se3 nanocrystals
Xiao-feng Qiu a, Jun-Jie Zhu a,*
, Lin Pu b, Yi Shi b, You-Dou Zheng b, Hong-Yuan Chen a

a
State Key Laboratory of Coordination Chemistry and Laboratory of Mesoscopic Materials Science,
Department of Chemistry, Nanjing University, Nanjing 210093, PR China
b
National Laboratory of Solid State of Microstructures, Department of Physics, Nanjing University, Nanjing 210093, PR China
Received 17 September 2003; accepted 17 November 2003
Published online: 8 January 2004

Abstract

We report the sonochemical synthesis of thermoelectric materials of Bi2 Se3 nanocrystals in the 6.9–15.2 nm size regime. In this
method, the size of Bi2 Se3 nanocrystals can be easily controlled by varying the concentration of EDTA in aqueous solution.
Ó 2003 Elsevier B.V. All rights reserved.

Keywords: Thermoelectric materials; Bi2 Se3 ; Sonochemistry; Nanocrystals

The performance of thermoelectric devices depends
on the figure of merit (ZT ) of the material, given by
ZT ¼ S 2 rT =j, where T is the temperature, S is the
thermoelectric power (or Seebeck coefficient), r is the
electrical conductivity, and j is the thermal conductivity
[1], and Z characterizes the electrical and thermal
transport properties of the materials [2]. The best ther-
moelectric materials are alloys of AV VI
2 B3 binary com-
pounds such as Bi2 Te3 , Sb2 Te3 , Bi2 Se3 , with traces of
other elements to dope these narrow bandgap semi-
conductors. The ZT values of these materials are about
1, which is only acceptable for certain specialized ap-
plications, but to be economically competitive with the
refrigerators and air-conditions, a thermoelectric air-
condition would require ZT P 3 at room temperature.
More recently, attention has been focused on the ther-
moelectric structures based on dimensional confinement
quantum wells [2], dots [3], and wires [4]. These results
suggest that nanoengineering of thermoelectric materials
could result in higher value of ZT than more efficient
thermoelectric devices.
For AV VI
2 B3 binary compounds, there are some recent
works on the template-synthesis of Bi2 Te3 nanowires
*
Corresponding author. Tel.: +86-25-3594976; fax: +86-25-3317761.
E-mail address: jjzhu@nju.edu.cn (J.-J. Zhu).
with diameters of 40 and 250 nm, and some groups re-
ported the synthesis of Bi2 Te3 nanopowders with the
diameters of 30–50 nm [5]. It is evident that the same
interest is focused on the size-controllable fabrication of
these functional materials in the size regime beyond the
limit of todayÕs electron beam lithograph for the pur-
pose of enhancing size-induced quantum confinement
effect. Nevertheless, controlling the size of nanoparticles
is of great technological and scientific importance due to
particlesÕ size-determined properties of electric, mag-
netic, optical, melting points, specific heats and surface
reactivity resulted from the quantum confinement effect
[6]. In the case of nanocrystalline Bi2 Se3 , it was usually
synthesized by the methods such as metallurgical melt
processing [7], travelling heater method [8], Bridgman
method [9] at high temperature (>500 °C) and solvo-
thermal method in ethylenediamine. [10] However,
controlled synthesis of the nanocrystalline Bi2 Se3 in a
mild reaction condition is still a great challenge. Based
on these views, we report a simple sonochemical route to
synthesize Bi2 Se3 nanocrystals in aqueous solution.
Sonochemistry arises from acoustic cavitation phe-
nomenon, that is the formation, growth and implosive
collapse of bubbles in a liquid medium [11]. The ex-
tremely high temperatures (>5000 K), pressures (>20
MPa), and very high cooling rates (>107 K s
1 ) attained

1387-7003/$ - see front matter Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2003.11.015
320 X.-f. Qiu et al. / Inorganic Chemistry Communications 7 (2004) 319–321

during acoustic cavitation lead to many unique prop- 6

erties in the irradiated solution. The remarkable ad-

100
vantages of this method include a rapid reaction rate, 5

Intensity ( arb.unit)
the controllable reaction condition and the ability to
4

110
form nanoparticles with uniform shapes, narrow size
distributions and high purities [12]. 3
In current study, we use high-intensity ultrasound

1010
irradiation to prepare highly dispersed Bi2 Se3 nano- 2

101

205
crystals in the 6.7–15.2 nm size regime. Changing the

116

1115
0210
006
concentration of EDTA can control the size of prepared 1

1016
021
Bi2 Se3 nanoparticles. The as-prepared Bi2 Se3 nano-
crystals are characterized by X-ray powder diffraction 0
(XRD), transmission electron microscopy (TEM) and 20 30 40 50 60 70
high-resolution transmission electron microscopy 2θ (Degrees)
(HRTEM).
At room temperature, bismuth nitrate, ascorbic acid Fig. 1. A typical XRD pattern of the prepared bismuth selenide.
(AA) and freshly prepared Na2 SeSO3 in the presence of (c ¼ 1:0 g/L, average size ¼ 9.3 nm).
EDTA were dissolved to give a final concentration of
0.05 mol/L Bi(NO3 )3 , 0.15 mol/L AA and 0.08 mol/L more. EDTA is known to react strongly with Bi3þ
Na2 SeSO3 . The concentration of EDTA is varied in yielding a complex. The equilibrium constant for the
order to control the size of Bi2 Se3 nanocrystals. The pH formation of the complex is log K ¼  27:8: It is sug-
value of the resulting solution was adjusted to 11 with gested that Bi3þ ions react with Se2
ion in the solution
5 mol/L NaOH solution. In a sonochemical procedure, a upon the dissociation of the complex. Simultaneously
high-intensity ultrasonic probe (Xinzhi Co., China, EDTA molecules are also released and they act as
JY92-2D, 0.6 cm diameter, Ti horn, 20 kHz, 60 W/cm2 )
was directly immersed in the solution. Typically the
solution was sonicated for 1 h. The resultant black
precipitate was centrifuged, then washed three times
with distilled water and dried in air. The phase purities
of final products were examined by X-ray diffraction
(XRD) using a Shimadzu XD-3A X-ray diffractometer.
The morphologies and sizes of the products were ex-
amined with TEM (JEOL, JEM 200CX) and high-
resolution TEM (JEOL JEM 2010).
All of the reflections of the XRD pattern can be in-
dexed to a pure rhombohedral phase of Bi2 Se3 with
lattice constants a ¼ 4:1396 A,  c ¼ 28:636 A  (JCPDS
33-214) as shown in Fig. 1. This XRD pattern indicates
that the product can be obtained with high purity.
The TEM morphologies of the prepared Bi2 Se3
nanocrystals are shown in Fig. 2(a–c). The corresponding
size distributions of the Bi2 Se3 nanocrystals are extracted
from the TEM images (Fig. 2(d–f)). The dotted lines
represent Gaussian fits to the particle diameter distribu-
tion curves. Benefit to the particlesÕ high dispersal, we
counted 200 particles in each image and calculated a
particleÕs diameter based on sphere approximation by
extracting its area from the TEM image. The results are
15.2  3.9, 10.3  4.5 and 6.9  2.9 nm, corresponding to
the EDTA concentrations (c) of 0.5, 1.0 and 1.5 g/L, re-
spectively, which can be fit in an exponential relation of Fig. 2. TEM images and size distributions of the Bi2 Se3 nanoparticles
Dp ¼ 23:2 expð
1:7cÞ þ 4:6 (Fig. 3). Therefore, it is evi- fabricated under different concentration of EDTA. (a) 0.5 g/L; (b) 1.0
g/L; (c) 1.5 g/L. The count numbers of all the size distributions are 200
dent that the size of nanoparticles is sensitive to the
particles and the dotted curves are the Gaussian fits of the data. The D
concentration of EDTA. When the concentration of values are the diameters of nanocrystals based on the sphere approx-
EDTA reaches a certain value, the quantity of EDTA imation. Note the arrow in (c) points to a particle with the diameter of
does not influence the size of Bi2 Se3 nanoparticles any- 2 nm. All the TEM images have the same scale: 100 nm.
 X.-f. Qiu et al. / Inorganic Chemistry Communications 7 (2004) 319–321
Dp = 23.2exp(-1.7c) + 4.6
16
14
12 Dp (nm)
10
8
6 Acknowledgements
Concentration of EDTA : c (g/L)
1 2
Fig. 3. The exponential relation of the preferred particleÕs diameters
(Dp ) and the EDTA concentrations (c).
Fig. 4. High-resolution TEM image of the as prepared Bi2 Se3 crystals
 (0 1 2 0).
(Sample b in Fig. 2). the lattice plane index to d ¼ 1:33 A
stabilizers promoting the formation of Bi2 Se3 nanopar-
ticles [13]. So the shape and size of Bi2 Se3 nanoparticles
can be effectively controlled via varying the concentra-
tion of EDTA.
Fig. 4 shows the high-resolution TEM morphologies
of the prepared Bi2 Se3 nanoparticles. The image reveals
a single crystalline nature of the synthesized bismuth
selenide, which is in agreement with the results indicated
by XRD analysis. We found that most of the Bi2 Se3
nanoparticles had a crystal structure like what is shown
in Fig. 4. By the analysis of the TEM morphologies of
the Bi2 Se3 nanoparticles (Fig. 2), it is found that large
quantities of particles have limited diameters (note some
sharp peaks in Fig. 2(d–f)). Therefore, our synthesis
method may provide an effective way to control the size
of Bi2 Se3 nanocrystal and obtain highly dispersed
nanocrystals with a high yield.
In summary, we have successfully synthesized highly
dispersed Bi2 Se3 nanocrystals in the presence of EDTA
and AA via a sonochemical method. The size of the
prepared Bi2 Se3 nanoparticles can be controlled by
changing the concentration of EDTA. The method is
321
simple and nontoxic. The products may provide a proto
typical material for future self-assemble of low-dimen-
sional thermoelectric structures such as quantum dot
superlattices [2].
This study was financially supported by the National
Natural Science Foundation of China ( No. 60206001,
No. 90206037), and ‘‘863’’ Project (No. 2003AA302740).
We are also grateful to Mr. YiÕnong Lu, from Department
of Materials Science and Engineering, Nanjing University
of Technology, for extending his facilities to us.
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