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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

solution, which was stirred for another 0.5 h and heated at


Abstract
140 C for 36 h. For Sb-substituted sample (x ≠0), NaBH4 is
We report thermoelectric characterization of Bi2-xSbxTe3
required to inhibit the formation of Bi2O3. The molar number
(x = 0.5, 1.0, and 1.5) synthesized by a solvothermal method
of EDTA is twice the total molar number of Bi and Sb. The
using DMF as solvent. For Bi2Te3, the size of the edge and
resulting powders were washed by DI water and then absolute
thickness of the hexagonal nanoplatelets are 200-250 nm and
20-25 nm, respectively. Bi2Te3 nanosheets appear to grow ethanol, followed by drying at 80 C. The resulting powders
epitaxially from the surface of the Te tubes, which forms in were compacted into parallelepiped and then sealed in an
the first step and acts as the template for the formation of the evacuated Pyrex ampoule. Sintering was carried out at 300 C
nanostructure. Upon doping with Sb, the morphology of for 10 h. Powder X-ray diffraction (XRD) patterns were
Bi1.5Sb0.5Te3 changes to a cluster of nanoparticles with the size obtained using a Shimadzu XRD-6000 diffractometer
of ~100 nm. The morphology of Bi0.5Sb1.5Te3 consists of equ ipped wi t
h Fe Kα r adiati
on . The morphology of the
mainly nanoplatelets with a size of less than 100 nm and samples was observed by a field emission scanning electron
warped nanosheets growing along the Te tube. The nominal microscope (JEOL JSM-6700F). Electrical resistivity was
composition of Bi2Te3 mats containing sheet-tubes shows a carried out using a quasi-dc technique with a four-wire
negative thermopower of ca. -94 μV/K at 280 K, whereas configuration between 300 and 10 K in an Oxford closed
Bi0.5Sb1.5Te3 shows a positive thermopower of ca. 200 μV/K cycle cooler cryostat. A Cernox sensor was used to monitor
at 280 K. the ambient temperature of the sample. Temperature-
dependent thermopower data were collected between 300 and
Introduction 80 K using a steady technique. The thermally generated
Thermoelectric materials are characterized by the figure of Seebeck voltage across the sample was measured using a
merit Z = σS2/, where σ, S, and  are the electrical Keithely 2182 nanovoltmeter. The temperature gradient across
conductivity, thermopower, and thermal conductivity, the sample was monitored using a type E differential
respectively. Turning the current best thermoelectric materials thermocouple. Temperature gradients were typically between
into nanosize or nanostructure might help improve 0.5 and 1 K. The TEP of the sample was obtained by
thermoelectric figure of merit by increasing the thermoelectric subtracting the TEP of Cu Seebeck probes.
power as a result of an enhanced density of states and by
Results and discussion
reducing thermal conductivity as a result of an increased
phonon scattering. [1,2] Bismuth alloys show the highest Figure1 shows the x-ray diffraction pattern of Bi2-xSbxTe3
dimensionless figure of merit ZT around room-temperature (x = 0, 0.5, 1.0,and 1.5) parallelepipeds which were
and are one of the most commercialized thermoelectric compacted and sintered at 300 C in an evacuated Pyrex
materials. Epitaxial growth of Bi2Te3 nanoplatelets from the ampoule. All of the samples are of single phase. All the
surface of Te tube wall has been achieved via a two-step reflection peaks can be indexed based on a rhombohedric
process using a solvothermal process. [3,4] Nanotubes of lattice with the space group of R3 m . For both the x = 0 and
Bi2Te3 having diameters smaller than 100 nm and spiral tube- 1.5 samples, enhanced (0015) reflection is clearly observed,
walls were added to zone-melted commercial n-type Bi2Te3 to indicating that the aggregate is textured and shows a preferred
form a nanocomposite. The hot-pressed nanocomposite orientation. This texture might be associated with the
exhibited enhanced thermoelectric figure of merit, which was observation that Bi2Te3 sheets grow along the [003] direction.
ascribed to a reduced thermal conductivity as a result of the [4] It should be noted that the texture appears only after the
efficient phonon blocking effect. [5] In this paper, we present as-prepared powders are compacted and sintered. Figure 2
the electrical conductivity and thermopower as a function of shows the SEM micrograph of Bi2Te3 obtained solvothermally.
temperature of Bi2-xSbxTe3 (x = 0, 0.5, 1.0, and 1.5) mats. The nanosheets appear to grow epitaxially along the surface of
Te tubes, being consistent with those reported in the literature.
Experimental [3,4] The size of the edge and thickness of the hexagonal
Nominal composition of Bi2-xSbxTe3 (x = 0, 0.5, 1.0, and nanoplatelets are estimated to be 200-250 nm and 20-25 nm,
1.5) were prepared by quantitatively mixing the Te powder, respectively. However, the morphology of the Sb-doped (x =
BiCl3, SbCl3, EDTA (ethylenediaminetetraacetic acid 0.5) sample is no longer sheet-tubes, instead clusters of
disodium salt), and NaBH4 with DMF in a PTFE-lined high nanoparticles with the size of ~100 nm are observed, which is
pressure bomb, which was then stirred at room temperature for similar to the Bi2(Te,Se)3
1 h. Appropriate amount of KOH was then added to the above
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


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