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IEEE PUBLICATION (Conference Book) TITLE: '07 Int'l Thermoelectric Conference (ICT'07

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Thermoelectric Characteristics of Solvothermally Prepared (Bi,Sb)2Te3 Mats Containing Nanosize of Sheet-Tubes
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Chia-Jyi Liu,1 Gao-Jhih Liu,1 Chun-Wei Tsao,1 Yu-Feng Lu,2 Li-Shin Chang2 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 μ V/K at 280 K, whereas Bi0.5Sb1.5Te3 shows a positive thermopower of ca. 200 μ V/K at 280 K. Introduction Thermoelectric materials are characterized by the figure of merit Z = σ S2/ , 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 tubewalls 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 e q u i p p e dw i t hF eK αr a d i a t i o n . 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. Temperaturedependent 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 R 3 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, 1.0 and 1.5) compacted mats, which were sintered in an evacuated Pyrex ampoule at 300 C for 10 h.
Fe K
00 15

Figure 3: SEM image of solvothermally synthesized Bi1.5Sb0.5Te3 powders.

x=0

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11 15 00 21 01 20 125

10 10 01.11 110

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x = 0.5 x = 1.0

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powders prepared from hydrothermal methods. [6] The 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 sheettube nanostructure. Figure 2: SEM image of solvothermally synthesized Bi2Te3 powders. The sheet-tube structure is clearly observed.

Figure 4: SEM image of solvothermally synthesized BiSbTe3 powders

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 Bi0.5Sb1.5Te3 powders. Sheet-tube microstructure can be also found in this sample. As compared to the x = 0 sample, the nanosheet is more irregular and curved in shape. Figure 8: Thermopower as a function of temperature for Bi2xSbxTe3 (x = 0, 0.5, 1.0, and 1.5), which was sintered in an evacuated Pyrex ampoule at 300 C for 10 h.
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x = 1.5
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x = 0.5

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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.
0.019 0.018 0.017 0.016 0.015 0.014 0.013 0.012 0.011 0.010 0.009 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0.000 0 50 100

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 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 hotpressed 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 μ V/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. Conclusions We have synthesized Bi2-xSbxTe3 (x =0, 0.5, 1.0, and 1.5) by a solvothermal method using DMF as solvent. The morphology of Bi2Te3 exhibits epitaxial growth of nanosheets. The morphology transforms to clusters of nanoparticles with a size less than 100 nm for x = 0.5 and nanoplatelets for x = 1.5. Warped nanosheets are also found in the x = 1.5 sample. The trend of electrical resistivity for our Sb-doped samples seems to be opposite to that perpendicular to the trigonal c-axis of (Bi,Sb)2Te3 crystals, which could be attributed to the boundary scattering of carriers. The negative thermopower of x = 1.0 sample is unusual, which might be due to the sample inhomogeneity. Further studies on the synthesis and sintering temperatures of the samples are in progress, which are thought to affect the composition, morphology and homogeneity of the samples.

x = 1.0
x = 1.5

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x = 0.5 x=0

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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. References 1. Hicks, L. D., Dresselhaus, M. S., “ Effect of quantum-well structures on the thermoelectric figure of merit, ” Phys. Rev. B, Vol. 47 (1993), pp. 12727-12731. 2. Hicks, L. D., Dresselhaus, M. S., “ Thermoelectric figure of merit of a one-dimensional conductor,” Physica B, Vol. 47 (1993), pp. 16631-16634. 3. Lu, W., Ding, Y., Chen. Y., Wang, Z. L., Fang, J., "Bismuth Telluride Hexagonal Nanoplatelets and Their Two-Step Epitaxial Growth," J. Am. Chem. Soc., Vol. 127, (2005), pp. 10112-10116. 4. Deng, Y., Cui, C. W., Zhang, N.-L., Ji, T.-H., Yang, Q.-L., Guo, L., "Fabrication of Bismuth Telluride Nanotubes via a Simple Solvothermal Process, "Solid State Commun., Vol. 138 (2006), pp. 111-113. 5. Zhao, X. B., Ji, X. H., Zhang, Y. H., Zhu, T. J., Tu, J. P., Zhang, X. B., "Bismuth Telluride Nanotubes and the Effects on the Thermoelectric Properties of Nanotubecontaining Nanocomposites," Appl. Phys. Lett. Vol. 86 (2005), pp. 062111-062113. 6. Ni, H.L., Zhu, T. J. Zhao, X.B., "Hydrothermally synthesized and hot-pressed Bi2(Te,Se)3 thermoelectric alloys," Physica B, Vo. 364 (2005), Vol. 364, pp. 50-54. 7. Stordeur, M., CRC Handbook of Thermoelectrics, CRC Press (Boca Raton, 1995), p. 243. 8. Kingery, W. D. et al., Introduction to Ceramics, John Wiley & Sons (Singapore, 1991), pp. 904-910.