Powder Technology 172 (2007) 63 – 66

www.elsevier.com/locate/powtec

Synthesis of Bi2Te3 nanopowders by vacuum arc plasma evaporation

Xingkai Duan, Junyou Yang ⁎, Wei Zhong, Wei Zhu, Siqian Bao, Xi'an Fan
State Key Lab for Plastic Forming Simulation and Dies Technology, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074, PR China
Received 1 March 2006; received in revised form 20 September 2006; accepted 12 October 2006
Available online 24 October 2006

Abstract

Starting from elemental bismuth and tellurium, bismuth telluride (Bi2Te3) nanopowders were successfully prepared by vacuum arc
plasma evaporation (VAPE) technique for the first time. The phase composition in the obtained nanopowders is closely related with the
Bi:Te atomic ratio in starting precursor. The microstructure and morphology of the samples were characterized via X-ray diffraction
(XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Compositional analysis was also carried
out by energy dispersive analysis of X-rays (EDAX). The as-synthesized Bi2Te3 nanopowders have a rhombohedral crystal structure with
lattice parameters a = 4.381 Å and c = 30.310 Å. The average particle size is about 35 nm obtained from TEM and confirmed from XRD
results.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Bismuth telluride; Nanopowder; Vacuum arc plasma evaporation

1. Introduction organic solution approach. S. A. Sapp et al. [22] and A. L. Prieto

Bismuth telluride based materials, the most important semi-
conductor compound candidates for thermoelectric application
around room temperature, receive more and more attention for
their versatile potential in micro and opto-electronics and other
high-tech fields [1–4]. Currently the main problem for them is
their lower thermoelectric efficiency. Although many efforts
have been made to improve thermoelectric properties, less
exciting progress has been achieved to bulk Bi2Te3 based
materials [5–11]. However, properties of nanostructured or low-
dimensional thermoelectric materials could be greatly improved
owing to the quantum size effect [12–16].
Currently several methods have been developed for prepa-
ration of nano-sized Bi2Te3 materials: Solvothermal synthesis is
a novel and effective method to synthesize nano-sized powders
at relative low temperature. Works on solvothermal synthesis of
Bi2Te3 have been reported recently [17–20]. Weigang Lu et al.
[21] reported a synthesis of discrete, single-crystal, defect-free,
and hexagonal Bi2Te3 nanoplatelets using a high-temperature
et al. [23] synthesized bismuth telluride nanowires by electro-
deposition method in conjunction with template synthesis
techniques within the pores of alumina template membranes.
E. E. Foos et al. [24] reported that nanocrystallines Bi2Te3 could
be synthesized with a controllable size using a reverse micelle
process. Electro-deposition was also employed to synthesize
Bi2Te3 at room temperature [25–28].
However, these methods often require some complicated
conditions (e.g. high pressure), need long time or some special
precursors. VAPE method has been proved to be a very powerful
method for preparation of nanostructured metals and their
compounds [29–33] with superfine size. To our knowledge, it
has not been used for preparation of Bi2Te3 nanopowders by
VAPE technique. In this paper, nanostructured Bi2Te3 powders
Table 1
The atomic percentage of Bi and Te
Elements Atomic%
a b c d e f

⁎ Corresponding author. Tel.: +86 27 87540944; fax: +86 27 87543076. Bi 40 45 50 55 60 65

Te 60 55 50 45 40 35
E-mail address: jyyang@public.wh.hb.cn (J. Yang).

0032-5910/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2006.10.009
64 X. Duan et al. / Powder Technology 172 (2007) 63–66
Fig. 1. XRD patterns of powders prepared at different atomic ratio: a(Bi:
Te = 4:6); b(Bi:Te = 4.5:5.5); c(Bi:Te = 5:5); d(Bi:Te = 5.5:4.5); e(Bi:Te = 6:4);
f(Bi:Te = 6.5:3.5).
were successfully prepared by vacuum arc plasma evaporation
technique, and some preliminary results were reported.
2. Experimental procedure
Elemental powders Bi and Te of high purity (99.999%) were
blended in a series of atomic ratios (as shown in Table 1) as the
starting materials to study the stoichiometric relationship be-
tween the reactant and product. A copper crucible with water-
cooling was used. The VAPE system was evacuated to a
vacuum of about 2 × 10− 5 Torr, and then high purity argon gas
(99.999%) was charged to 4 × 103 Pa as the plasma gas. The
nanopowders were deposited on the wall of water-cooled stain-
Fig. 2. XRD pattern of Bi2Te3 nanopowders synthesized at atomic ratio (Bi:
Te = 6:4).
Table 2
XRD parameters for Bi2Te3 sample
2θ (°) FWHM B(°) Bcosθ Particle size (Å)
27.7260 0.2342 0.003966 365
less steel chamber. Other experiment parameters are listed as
follows: the power for arc plasma: 3kW(U = 20 V, I = 150 A);
evaporation time: 35 min; cooling water flux: 12 L/min. The
powders were deposited at a rate of about 4.2 g/min.
The microstructure of the nanopowder samples was checked
by using X-ray diffraction (PANalytical B.V.-X'Pert PRO, Cu K
radiation with λ = 1.541 Å) with a 0.02° step over the 2θ range
of 10–80°. The morphology and particle size were investigated
with a FEI-Tecnai G2 20TEM microscope. Compositional ana-
lysis was also carried out in the transmission electron micro-
scope by using its EDAX accessory.
3. Results and discussion
Fig. 1 shows the X-ray diffractograms of nanopowders pre-
pared from different starting atomic ratios. As shown in Fig. 1a,
the starting atomic ratio of Bi:Te is just the stoichiometry of
Bi2Te3 compound, however there are some elemental Te peaks
in the XRD pattern besides those of Bi2Te3. This indicates that
some amounts excess of Te during the VAPE synthesis process.
The single phase Bi2Te3 compound nanopowders could not be
obtained by using the same starting atomic ratio as bismuth
telluride. This is because of the large difference in vapor
pressure between Bi and Te. Because the vapor pressure of Te is
higher than Bi at the same temperature, it is Te that gets
evaporated easily from the source materials. To obtain single
phase Bi2Te3 nanopowders, the Bi content in starting materials
was added gradually. Apparently, the Te peaks decreases
gradually with increasing of Bi content, and a single phase
Bi2Te3 was obtained at the atomic ratio of Bi:Te = 6:4 (Fig. 1e).
There is some amounts surplus of source materials in copper
Fig. 3. EDAX spectrum of Bi2Te3 nanopowders.
 X. Duan et al. / Powder Technology 172 (2007) 63–66 65

crucible with water-cooling after the VAPE synthesis process.

Obviously, Bi accounts for a high proportion of some amounts
surplus of source materials. Further increasing Bi content, BiTe
phase appears along with Bi2Te3 (Fig. 1f). Fig. 2 shows the
XRD pattern of Bi2Te3 compound nanopowders obtained in this
work. All the peaks of the pattern can be well indexed to those
from the rhombohedral Bi2Te3 crystal structure (ICDD PDF
card NO. 15-0863). The broadening of the diffraction peaks
indicates that the samples are nanosized. The lattice parameters
of the nanopowders were calculated using the Bragg's formula

2dsinh ¼ k: ð1Þ

The lattice parameters deduced from the diffraction angle are

a = 4.381 Å and c = 30.310 Å. These values are close to those
reported for bulk (a = 4.385 Å and c = 30.480 Å) [34–36].
The particle size of the Bi2Te3 was calculated from the XRD
using Scherer's relation [37],

D ¼ kk=Bcosh ð2Þ

where k is the constant = 0.94, λ the wavelength of radiation, B

the full-width half-maximum and θ the diffraction angle. XRD
parameters for the Bi2Te3 sample are listed in Table 2. The
calculated results indicate that the average particle size is 365 Å.
Composition of the Bi2Te3 nanopowders was verified using
the EDAX technique. The EDAX spectrum for the nanopow-
ders is shown in Fig. 3. The EDAX results are given in Table 3.
It was observed that the samples showed near stoichiometric
composition within experimental accuracy. The EDAX spec-
trum taken from the Bi2Te3 nanopowders further confirms the
compositions of Bi2Te3.
Fig. 4a shows the TEM image of the particles, which possess
irregular polyhedrons, flake, and even rod-like structure. Unlike Fig. 4. (a) TEM image of Bi2Te3 nanopowders; (b) corresponding SAED
most of metallic nanopowders prepared by VAPE, those show pattern.
spherical morphology. The irregular polyhedrons, flake and
rod-like structure are consistent with the high anisotropy of
Bi2Te3 semiconductor compound. The average particle size is 6:4, the nanopowders are a two-phase mixture of element Te
about 35 nm, which is in good agreement with the XRD an- and Bi2Te3 compound. The single phase Bi2Te3 compound
alysis. The SAED pattern clearly shows that the resulting could be obtained at the Bi:Te atomic ratio of 6:4, and BiTe +
nanoparticles are polycrystals in Fig. 4b. Bi2Te3 coexist in the nanopowders when the atomic ratio is
larger than 6:4. This route to Bi2Te3 nanopowder is simple,
convenient and effective, and holds potential for large-scale
4. Conclusions synthesis needed for commercial applications.

In this study, nanostructured Bi2Te3 powders were success- Acknowledgement

fully synthesized via a vacuum arc plasma evaporation tech-
nique for the first time. The phase composition in the obtained This work is co-financed by the national natural Science
nanopowders is closely related with the Bi:Te atomic ratio in foundation of China under Grant No.50401008, the Specialized
starting precursor. When the Bi:Te atomic ratio is lower than Prophasic Research Project of Key Basic Research Plan (No.
2004CCA03200) of China.
Table 3
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