IEEE PUBLICATION (Conference Book) TITLE: '07 Int'l Thermoelectric Conference (ICT'07)
Thermoelectric Characteristics of Solvothermally Prepared (Bi,Sb)2Te3 Mats Containing Nanosize of
Sheet-Tubes
Chia-Jyi Liu,1 Gao-Jhih Liu,1 Chun-Wei Tsao,1 Yu-Feng Lu,2 Li-Shin Chang2
1
Department of Physics, National Changhua University of Education, Changhua 500, Taiwan
2
Department of Materials Engineering, Nationla Chung Hsing University, Taichung, Taiwan
liucj@cc.ncue.edu.tw, +886-4-723-2105 ext-3337
Abstract
We report thermoelectric characterization of Bi2-xSbxTe3
(x = 0.5, 1.0, and 1.5) synthesized by a solvothermal method
using DMF as solvent. For Bi2Te3, the size of the edge and
thickness of the hexagonal nanoplatelets are 200-250 nm and
20-25 nm, respectively. Bi2Te3 nanosheets appear to grow
epitaxially from the surface of the Te tubes, which forms in
the first step and acts as the template for the formation of the
nanostructure. Upon doping with Sb, the morphology of
Bi1.5Sb0.5Te3 changes to a cluster of nanoparticles with the size
of ~100 nm. The morphology of Bi0.5Sb1.5Te3 consists of
mainly nanoplatelets with a size of less than 100 nm and
warped nanosheets growing along the Te tube. The nominal
composition of Bi2Te3 mats containing sheet-tubes shows a
negative thermopower of ca. -94 μV/K at 280 K, whereas
Bi0.5Sb1.5Te3 shows a positive thermopower of ca. 200 μV/K
at 280 K.
Introduction
Thermoelectric materials are characterized by the figure of
merit Z = σS2/, where σ, S, and  are the electrical
conductivity, thermopower, and thermal conductivity,
respectively. Turning the current best thermoelectric materials
into nanosize or nanostructure might help improve
thermoelectric figure of merit by increasing the thermoelectric
power as a result of an enhanced density of states and by
reducing thermal conductivity as a result of an increased
phonon scattering. [1,2] Bismuth alloys show the highest
dimensionless figure of merit ZT around room-temperature
and are one of the most commercialized thermoelectric
materials. Epitaxial growth of Bi2Te3 nanoplatelets from the
surface of Te tube wall has been achieved via a two-step
process using a solvothermal process. [3,4] Nanotubes of
Bi2Te3 having diameters smaller than 100 nm and spiral tube-
walls were added to zone-melted commercial n-type Bi2Te3 to
form a nanocomposite. The hot-pressed nanocomposite
exhibited enhanced thermoelectric figure of merit, which was
ascribed to a reduced thermal conductivity as a result of the
efficient phonon blocking effect. [5] In this paper, we present
the electrical conductivity and thermopower as a function of
temperature of Bi2-xSbxTe3 (x = 0, 0.5, 1.0, and 1.5) mats.
Experimental
Nominal composition of Bi2-xSbxTe3 (x = 0, 0.5, 1.0, and
1.5) were prepared by quantitatively mixing the Te powder,
BiCl3, SbCl3, EDTA (ethylenediaminetetraacetic acid
disodium salt), and NaBH4 with DMF in a PTFE-lined high
pressure bomb, which was then stirred at room temperature for
1 h. Appropriate amount of KOH was then added to the above
solution, which was stirred for another 0.5 h and heated at
140 C for 36 h. For Sb-substituted sample (x ≠0), NaBH4 is
required to inhibit the formation of Bi2O3. The molar number
of EDTA is twice the total molar number of Bi and Sb. The
resulting powders were washed by DI water and then absolute
ethanol, followed by drying at 80 C. The resulting powders
were compacted into parallelepiped and then sealed in an
evacuated Pyrex ampoule. Sintering was carried out at 300 C
for 10 h. Powder X-ray diffraction (XRD) patterns were
obtained using a Shimadzu XRD-6000 diffractometer
equ ipped wi t
h Fe Kα r adiati
on . The morphology of the
samples was observed by a field emission scanning electron
microscope (JEOL JSM-6700F). Electrical resistivity was
carried out using a quasi-dc technique with a four-wire
configuration between 300 and 10 K in an Oxford closed
cycle cooler cryostat. A Cernox sensor was used to monitor
the ambient temperature of the sample. Temperature-
dependent thermopower data were collected between 300 and
80 K using a steady technique. The thermally generated
Seebeck voltage across the sample was measured using a
Keithely 2182 nanovoltmeter. The temperature gradient across
the sample was monitored using a type E differential
thermocouple. Temperature gradients were typically between
0.5 and 1 K. The TEP of the sample was obtained by
subtracting the TEP of Cu Seebeck probes.
Results and discussion
Figure1 shows the x-ray diffraction pattern of Bi2-xSbxTe3
(x = 0, 0.5, 1.0,and 1.5) parallelepipeds which were
compacted and sintered at 300 C in an evacuated Pyrex
ampoule. All of the samples are of single phase. All the
reflection peaks can be indexed based on a rhombohedric
lattice with the space group of R3 m . For both the x = 0 and
1.5 samples, enhanced (0015) reflection is clearly observed,
indicating that the aggregate is textured and shows a preferred
orientation. This texture might be associated with the
observation that Bi2Te3 sheets grow along the [003] direction.
[4] It should be noted that the texture appears only after the
as-prepared powders are compacted and sintered. Figure 2
shows the SEM micrograph of Bi2Te3 obtained solvothermally.
The nanosheets appear to grow epitaxially along the surface of
Te tubes, being consistent with those reported in the literature.
[3,4] The size of the edge and thickness of the hexagonal
nanoplatelets are estimated to be 200-250 nm and 20-25 nm,
respectively. However, the morphology of the Sb-doped (x =
0.5) sample is no longer sheet-tubes, instead clusters of
nanoparticles with the size of ~100 nm are observed, which is
similar to the Bi2(Te,Se)3
 IEEE PUBLICATION (Conference Book) TITLE: '07 Int'l Thermoelectric Conference (ICT'07)

Figure 1: X-ray diffraction pattern of Bi2-xSbxTe3 (x = 0, 0.5, Figure 3: SEM image of solvothermally synthesized
1.0 and 1.5) compacted mats, which were sintered in an Bi1.5Sb0.5Te3 powders.
evacuated Pyrex ampoule at 300 C for 10 h.

00 15
Fe K x=0

00 21
10 10

10 13

11 15
01.11

02 10
10 16

01 20
015
Intensity (arb.units)

110
003

205
006

125
x = 0.5

x = 1.0

x = 1.5

10 20 30 40 50 60 70 80 90
2(degree)
Figure 4: SEM image of solvothermally synthesized BiSbTe3
powders prepared from hydrothermal methods. [6] The powders
change of morphology strongly suggests that formation of the
Sb-doped samples has been switched to a different growth
mechanism, which is probably due to the addition of the
reducing agent NaBH4 for suppressing formation of the oxide
impurity phase. As shown in Figs. 4 and 5, nanoplatelets
instead of clusters with a size of less than 100 nm evolve as
the major product with increasing content of Sb. Interestingly,
similar sheet-tubes microstructure can be found in the x = 1.5
sample. As shown in Fig. 6, the nanosheets growing along the
Te tube is more irregular and warped in shape (something like
leaves growing off a stalk) as compared to the x = 0 sample. It
seems that the appearance of preferred orientation of (0015)
lattice plane shown in the XRD pattern is related to the sheet-
tube nanostructure.

Figure 2: SEM image of solvothermally synthesized Bi2Te3

powders. The sheet-tube structure is clearly observed. Figure 5: SEM image of solvothermally synthesized
Bi0.5Sb1.5Te3 powders. The major product has the shape of
nanoplatelets with the size of less than 100 nm.
 IEEE PUBLICATION (Conference Book) TITLE: '07 Int'l Thermoelectric Conference (ICT'07)

Figure 6: SEM image of solvothermally synthesized Figure 8: Thermopower as a function of temperature for Bi2-
Bi0.5Sb1.5Te3 powders. Sheet-tube microstructure can be also xSbxTe3 (x = 0, 0.5, 1.0, and 1.5), which was sintered in an
found in this sample. As compared to the x = 0 sample, the evacuated Pyrex ampoule at 300 C for 10 h.
nanosheet is more irregular and curved in shape.
300
x = 1.5

200

Thermopower (V/K)
100 x = 0.5

0 x=0

-100
x = 1.0

-200
50 100 150 200 250 300
Temperature (K)

Bi2-xSbxTe3 (x = 0, 0.5, 1.0 and 1.5) as a function of

Fig. 7 shows the electrical resistivity of Bi2-xSbxTe3 (x = 0,
0.5, 1.0 and 1.5) as a function of temperature between 300 and
10 K. The electrical resistivity decreases with decreasing
temperature below 250 K for all the samples, a characteristic
of metal-like temperature dependence. The x = 0 sample
shows the lowest resistivity in this series of materials, whereas
the x = 1.0 sample shows the maximum resistivity. This trend
seems to be opposite to the electrical conductivity
perpendicular to the trigonal c-axis of (Bi,Sb)2Te3 crystals. [7]
This result could be associated with the morphology of the
sample. It should be noted that fine grained samples with the
size less than 0.1 would affect the electrical conduction via
boundary scattering. [8] Fig. 8 shows the thermopower of
Figure 7: Electrical resistivity as a function of temperature for
Bi2-xSbxTe3 (x = 0, 0.5, 1.0, and 1.5), which were sintered in
an evacuated Pyrex ampoule at 300 C for 10 h.
temperature between 300 and 80 K. The absolute value of
thermopower decreases with decreasing temperature below
250 K for all the samples, being also a characteristic of
metal-like temperature dependence. Both the samples of x = 0
and 1.0 exhibit negative thermopower, whereas x = 0.5 and
1.5 positive thermopower. The size of thermopower of x = 0 is
smaller than that of hydrothermally synthesized and hot-
pressed sample. [6] However, the resistivity of our x = 0
sample is slightly lower than the latter around room
temperature. The size of thermopower for x = 1 is twice that
perpendicular to the trigonal c-axis of a BiSbTe3 crystal. [7]
The size of thermopower of x = 1.5 sample can be improved
to 200 μV/K at 280 K by sintering at 360 C. The negative
thermopower of x = 1.0 sample is unusual, which could be due
to that the real composition of the sample deviates from the
nominal composition or the inhomogeneity of the composition.
The composition analysis of the samples and the sintering
effects are in progress.

0.019
0.018 x = 1.0 Conclusions
0.017
0.016 We have synthesized Bi2-xSbxTe3 (x =0, 0.5, 1.0, and 1.5)
0.015 x = 1.5 by a solvothermal method using DMF as solvent. The
0.014
0.013 morphology of Bi2Te3 exhibits epitaxial growth of nanosheets.
Resistivity (-cm)

0.012
0.011 The morphology transforms to clusters of nanoparticles with a
0.010 size less than 100 nm for x = 0.5 and nanoplatelets for x = 1.5.
0.009
0.008 Warped nanosheets are also found in the x = 1.5 sample. The
0.007 x = 0.5
0.006 trend of electrical resistivity for our Sb-doped samples seems
0.005 to be opposite to that perpendicular to the trigonal c-axis of
0.004 x=0
0.003 (Bi,Sb)2Te3 crystals, which could be attributed to the
0.002
0.001 boundary scattering of carriers. The negative thermopower of
0.000 x = 1.0 sample is unusual, which might be due to the sample
0 50 100 150 200 250 300 inhomogeneity. Further studies on the synthesis and sintering
Temperature (K) temperatures of the samples are in progress, which are thought
to affect the composition, morphology and homogeneity of the
samples.
 IEEE PUBLICATION (Conference Book) TITLE: '07 Int'l Thermoelectric Conference (ICT'07)

Acknowledgments
This work is supported by the National Science Council of
Taiwan, ROC, grant No. NSC 95-2112-M-018-006-MY3.
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