臺灣博碩士論文加值系統

本實驗為利用聚苯乙烯微球(polystyrene sphere)進行電泳法製作三維結構基板，並於基板常壓電鍍碲化鉍熱電材料，探討不同熱處理方式對熱電性質(載子濃度、遷移率、電阻率)與結構之影響。實驗操作因子分別為改變沉積電位(-80mV~-140mV)來找出符合Bi2Te3組成之條件、聚苯乙烯微球移除率對熱電材料性質影響、不同熱處理方式對熱電性質之改善、分析聚苯乙烯微球粒徑對熱電性質的影響。實驗結果顯示，當沉積電位為-0.12Ｖ時，電沉積之碲化鉍才符合Bi2Te3之化學計量數比例。聚苯乙烯球若移除不完全，當熱處理溫度過高時，會破壞碲化鉍3D結構，造成Seebeck係數與Power factor驟降之現象。為了增進熱電優值，故希望藉由熱處理來消除晶格缺陷，使得碲化鉍結構更加完整，進而促使Seebeck係數提升。從實驗結果發現，電流輔助退火可以有效的消除晶格缺陷，使得結晶性上升，且效果優於一般傳統退火方式。實驗結果指出，以300nmPS球為模板電沉積之Bi2Te3膜經過305℃、外加電流150 mA之電流輔助退火處理持續5分鐘，其Power factor值由未經退火之97.86μV/mK2上升至最大值233.37μV/mK2。

This study was to investigate the preparation of a three-dimensional (3-D) thermoelectric material of bismuth telluride (BixTey) by electrodepositing bismuth telluride in a 3-D polystyrene (PS) template. The 3-D PS template was made of electrophoretic depositing PS sphere on the ITO glass substrate. The 3-D structure morphology was observed and several thermoelectric properties were measured including Seebeck coefficient (S), carrier concentration (n), resistivity (ρ), and mobility (μ) to investigate the influence of different thermal treatments on the thermoelectric material. Three methods have been employed to enhance the power factor (S2/ρ)： (1) changing the depositing potentials (-80mV~ -140mV) to adjust the stoichiometry close Bi2Te3, (2) investigating the influence on the thermoelectric properties whether the PS sphere template was removed or not, (3) applying two types of thermal treatments to improve the thermoelectric properties, (4) analyzing the effect of pore size of the 3-D PS template on the thermoelectric properties. It was found that when -0.12V was set as the depositing potential, the stoichiometry of the Bismuth Telluride films met Bi2Te3. Besides, if the PS sphere template was not entirely removed, as the annealing temperature reaching high enough the 3-D structure would be destroyed causing the plunge of the Seebeck coefficient and power factor. In order to enhance the figure of merit, the thermal treatments were employed to reduce the structural imperfection. The analysis of XRD presented the current-assisted annealing could eliminate crystal lattice defects more effectively than the conventional thermal annealing and enhance the crystallinity. The results showed that the power factor of the 3-D Bi2Te3 films with 300nm pore size treated with current-assisted annealing at a current of 150 mA and 305℃ for 5 minutes increased from 97.86μV/mK2 to 233.37μV/mK2.

中文摘要‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧I
Abstract‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧II
目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧IV
圖目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧VIII
表目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧X
第一章 緒論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧1
第二章 文獻回顧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧3
2.1 熱電材料‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧3
2.1.1 引言‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧3
2.1.2 熱電現象與運作原理‧‧‧‧‧‧‧‧‧‧‧‧3
2.1.3 西貝克效應(Seebeck effect) ‧‧‧‧‧‧‧‧‧‧3
2.1.4 皮爾特效應(Peltier effect) ‧‧‧‧‧‧‧‧‧‧4
2.1.5 湯姆森效應(Thomson effect) ‧‧‧‧‧‧‧‧‧5
2.1.6 熱電優值‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧8
2.1.7 熱電材料‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧10
2.1.8 製備Bi2Te3熱電材料之方法‧‧‧‧‧‧‧‧‧14
2.1.9 碲化鉍電鍍法‧‧‧‧‧‧‧‧‧‧‧‧‧‧17
2.2 模板介紹‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧22
2.2.1 奈米材料的製作‧‧‧‧‧‧‧‧‧‧‧‧‧22
2.2.2 聚苯乙烯(PS)球模板與二氧化矽(SiO2)模板‧‧‧‧23
2.3 模板製程技術‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧25
2.4 聚合聚苯乙烯奈米粒子‧‧‧‧‧‧‧‧‧‧‧‧28
2.4.1 聚苯乙烯膠體粒子的合成簡介‧‧‧‧‧‧‧‧28
2.4.2 乳化聚合法‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧29
2.4.3 懸浮聚合法‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧32
2.4.4 分散聚合法‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
2.5 熱處理‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
第三章 實驗方法與步驟‧‧‧‧‧‧‧‧‧‧‧‧35
3.1 實驗藥品‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
3.2 實驗儀器‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧36
3.3 實驗流程‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧37
3.3.1 實驗架構‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧37
3.3.2 基材清洗‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧38
3.3.3 聚合單一粒徑PS球‧‧‧‧‧‧‧‧‧‧‧‧40
3.3.4 電泳披覆PS球模板‧‧‧‧‧‧‧‧‧‧‧‧44
3.3.5 電鍍液配製‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧46
3.3.6 碲化鉍電鍍‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧46
3.3.7 移除PS球模板‧‧‧‧‧‧‧‧‧‧‧‧‧‧48
3.3.8 熱處理三維結構碲化鉍‧‧‧‧‧‧‧‧‧‧‧49
3.3.9 分析儀器及原理‧‧‧‧‧‧‧‧‧‧‧‧‧50
第四章 結果與討論‧‧‧‧‧‧‧‧‧‧‧‧‧‧57
4.1 電泳披覆PS球模板‧‧‧‧‧‧‧‧‧‧‧‧‧57
4.2 常壓定電位電鍍三維結構碲化鉍‧‧‧‧‧‧‧‧‧59
4.3 熱處理前後形貌與組成分析‧‧‧‧‧‧‧‧‧‧60
4.4 相同粒徑下熱處理溫度對結晶性的影響‧‧‧‧‧‧63
4.5 電沉積三維結構碲化鉍經熱處理之熱電性質分析‧‧‧66
4.5.1 相同粒徑下熱處理對Seebeck係數影響‧‧‧‧‧66
4.5.2 相同粒徑下熱處理對電阻值影響‧‧‧‧‧‧‧‧68
4.5.3 相同粒徑下熱處理對載子濃度與遷移率影響‧‧‧‧69
4.5.4 相同粒徑下熱處理對Power factor值影響‧‧‧‧‧71
4.6 相異粒徑PS膜板下電流輔助退火之三維結構Bi2Te3分析‧72
4.6.1 不同粒徑下熱處理溫度對結晶性影響‧‧‧‧‧‧72
4.6.2 不同粒徑下熱處理溫度對電阻率影響‧‧‧‧‧‧76
4.6.3 不同粒徑下熱處理溫度對遷移率與載子濃度影響‧‧77
4.6.4不同粒徑下熱處理溫度對結晶性影響‧‧‧‧‧‧79
4.6.5 不同粒徑下熱處理溫度對power factor影響‧‧‧‧81
4.7電流輔助退火之電流密度計算‧‧‧‧‧‧‧‧‧‧82
第五章 結論與未來展望‧‧‧‧‧‧‧‧‧‧‧‧83
5.1 結論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧83
5.2 未來展望‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧84
參考文獻‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧85
附錄一‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧97

[1] 周雅文，＂熱電技術應用產品及發展現況分析＂，熱電技術發展及系統應用研討會，集思會議中心，P.57，2010.

[2] 周雅文，＂熱電技術應用產品及發展現況分析＂，熱電技術發展及系統應用研討會，集思會議中心，P.41，2010.

[3] T. C. Harman, “Special Techniques for Measurement of Thermoelectric Properties” , J. Appl. Phys, 29, 1373-1374(1958).

[4] L. D. Hicks and M. S. Dresselhaus, “Thermoelectic figure of merit of a one-dimensinal conductor” , Phys. Rev. B, 53, 16632-16634(1993).

[5] T. Huber, A. Nikolaeva, D. Gitsu, L. Konopko, and M. Graf, “Quantum confinement and surface-state effects in bismuth nanowires”, Physica E: Low-dimensional Systems and Nanostructures, 37, 194-199(2006).

[6] D. M. Rowe, “CRC Handbook of Thermoelectric”, Boca Raton, Chap.7(1994).

[7] R. T. Delves, A. E. Bowley, D. W. Hazelden, and H. J. Goldsmid, “Anisotropy of the Electrical Conductivity in Bismuth Telluride”, Proc. Phys. Soc., 78, 5(1961).

[8] B. Yehuda, Y. Gelbstein, Z. Dashevsky, R. Shuker, and M. P. Dariel, “Improved power factor of Bi0.4Sb1.6Te3 – based samples prepared by cold pressing and sintering.”, Thermoelectrics, ICT '06. 25th International Conference on(2006).

[9] Y. Tong, F. J. Yi, L. H. Liu, P. C. Zhai, and Q. J. Zhang, “Molecular dynamics study of mechanical properties of bismuth telluride nanofilm” , Physica B, (2010).

[10] L. D. Hicks, T. C. Harman, X. Sun, and M. S. Dresselhaus, “Experimental study of the effect of quantum-well structures on the thermoelectric figure of merit”, J. Phys. Rev. B., 53, 10493-10496 (1996).

[11] R. Venkatasubramanian, M. N. Touzelbaev, P. Zhou, and K. E. Goodson, “Thermal characterization of Bi2Te3/Sb2Te3 superlattices.” , Journal of Applied Physics, 90, 763-767(2001).

[12] A. Boukai, K. Xu, and J. R. Heath, “Size-Dependent Transport and Thermoelectric Propeties of individual Polycrystalline Bismuth nanowires”, Adv. Mat. 18, 864-869(2006).

[13] A. I. Hochbaum, R. Fan, R. R. He, and P. D. Yang, “Controlled Growth of Si Nanowire Arrays for Device Integration”, Nano Letters, 5, 3, 457-460(2005).

[14] G. Chen, S. G. Volz, T. B. Tasciuc, T. Zeng, D. Song, K. L. Wang, and M. S. Dresselhaus, “Thermal conductivity and phonon engineering in low-dimensional structures”, Mater. Res. Soc. Symp. Proc., 357-368(1999).

[15] Z. B. Zhang, D. Gkhtman, M. S. Dresselhaus, and Jackie Y. Ying, “Processing and Characterization of Single-Crystalline Utrafine Nanowires”, Chem. Mater, 11, 1659-1665(1998).

[16] A. J. Yin, J. Li, W. Jian, A. J. Bennett, J. M. Xu, “Fabrication of Highly Ordered Metallic Nanowire Arrays by Electrodeposition”, Appl. Phys. Lett., 79, 1039-1041(2001).

[17] M. S. Sander, R. Gronsky, T. Sands, and A. M. Stacy, “Structure of Bismuth Telluride Nanowire Arrays Fabricated by Electrodeposition into Porous Anodic Alumina Templates”, Chem. Mater, 15, 335-339(2002).

[18] J. Redwing, T. Mayer, S. Mohney , and A. Mizel, “Building Blocks for Nanoscale Electronics,” NSF Nanoscale Science and Engineering Grantees Conference, Dec 11-13, 2002.

[19] L. Li, Y. W. Yang, X. H. Huang, G. H. Li, and L. Zhang, “Pulsed Electrodeposition of Single-Crystalline Bi2Te3 Nanowire Arrays”, Nanotechnology, 1706-1712(2006).

[20] F. Xiao, B. Y. Yoo, K. H. Lee, and N. V Myung, “Electro-transport studies of Electrodeposited (Bi1-xSbx)2Te3 Nanowires”, Nanotechnology, 335203(5pp) (2007).

[21] S. H. Kim , B. K. Park, “ Solvothermal synthesis of Bi2Te3 nanotubes by the interdiffusion of Bi and Te metals” Materials Letters, 64, 938-941(2010).

[22] O. Yamashita, S. Tomiyoshi, and K. Makita, “Bismuth telluride compounds with high thermoelectric figures of merit.” , Journal of Applied Physics, 368 (2003).

[23] R. A. Laudise, W. A. Sunder, R. L. Barns, R. J. Cava, T. Y. Kometani, and Czochralski, “Growth of doped single-crystals of Bi2Te3.” , Journal of Crystal Growth, 53 (1989).
[24] J. Y. Yang, X. A. Fan, R. G. Chen, W. Zhu, S. Q. Bao, and X. K. Duan, “Consolidation and thermoelectric properties of n-type bismuth telluride based materials by mechanical alloying and hot pressing.” , Journal of Alloys and Compounds, 416, 1-2(2006).

[25] L. D. Zhao, B. P. Zhang, J. F. Li, H. L. Zhang, and W. S. Liu, “Enhanced thermoelectric and mechanical properties in textured n-type Bi2Te3 prepared by spark plasma sintering.” , Solid State Sciences, 10 ,651 (2008).

[26] I. Chowdhury, R. Prasher, K. Lofgreen, G. Chrysler, S. Narasimhan, R. Mahajan, D. Koester, R. Alley, R. Venkatasubramanian, "On-chip cooling by superlattice-based thin-film thermoelectrics," Nature Nanotechnology, 4, 235-238(2009).

[27] 鍾昌浩，林昭任，「利用聚苯乙烯微球模板與電沉積來製備三維結構碲化鉍熱電材料之研究」，國立中正大學化學工程系，2011.

[28] Y. H. Shing, Y. Chang, A. Mirshafii, L. Hayashi, S.S. Roberts, J, Y. Josefowicz and N. Tean, “Sputtered Bi2Te3 and PbTe thin films”, Journal of Vacuum Science and Technology A, 1, 503 (1983).

[29] E. Sayed and H. E. A., “Structural and optical properties of thermally evaporated Bi2Te3 films.” , Applied Surface Science, 250 ,70 (2005).

[30] http://projects.ece.utexas.edu/ece/mrc/groups/street_mbe/mbechapter.html

[31] A. Boulouz, A. Giani, P. D. F., M. Boulouz, A. Foucaran, and A. Boyer, “Preparation and characterization of MOCVD bismuth telluride thin films.” , Journal of Crystal Growth, 194(3-4), 336 (1998).

[32] 胡啓章，電化學原理與方法，第30~35頁，五南圖書出版股份有限公司，2002.

[33] B.Y. Yoo, C. K. Huang, J. R. Lim, J. Herman, M. A. Ryan, J. P. Fleurial, N.V. Myung, “Electrochemically Deposited Thermoelectric N-type Bi2Te3 Thin Films”, Electrochim. Acta., 50, 4371-4377 (2005).

[34] O. D. Iyore, B.S. “Interface characterization of contacts to bulk bismuth telluride alloys.” , The University of Texas at Dallas, (2009)

[35] M. Takahashi, M. Kojima, S. Sato, N. Ohnisi, A. Nishiwaki, K.Wakita, T. Miyuki, S. Ikeda, and Y. Muramatsu, “Electric and thermoelectric properties of electrodeposited bismuth telluride (Bi2Te3) films”, Journal of Applied Physics, 96, 5582-5587(2004).

[36] Q. H. Huang, W. Wang, F. L. Jia, Z. R. Zhang, “Preparation of Bi2-xSbxTe3 thermoelectric films by electrodeposition”, J. Univ. Sci. Technol. Beijing, 13, 277-280(2006).

[37] V. Richoux, S. Diliberto, N. Stein, C. Boulanger, “ Characterization of Bi2Te3 thin films grown by pulse electroplating.” , Names, 3rd France-Russia Seminar(2007).
[38] M. Takahashi, Y. Kayou, K. Nagata, and S. Futura, “Composition and Conductivity of Electrodeposited Bi-Te Alloy Films”, Thin Solid Films, 240, 70-72(1994).

[39] M. Gonzalez, M. S., A. L. Prieto, R. Gronsky, T. Sands and A.M. Stacy, “Insights into the Electrodeposition of Bi2Te3”, J. Electrchemical Society, 149, 546-554(2002).

[40] L. Scidone, S. Diliberto, N. Stein, C. Boulanger, and J. M. Lecuire, “Electroless method for Bi2Te3 film deposition” , Materials Letters, 59, 746- 748(2005).

[41] 吳東峰，林昭任，「應用超臨界二氧化碳電鍍鐵鎳合金與利用PS球為模板電鍍碲化鉍熱電材料之研究」，國立中正大學化學工程系，2010.

[42] 蔡鎮安，林昭任，“應用超臨界二氧化碳電鍍碲化鉍熱電奈米線之 研究”，國立中正大學化學工程學系，2009。

[43] P. Zhong, W. X. Que, and J. Zhang, ” Fabrication of regular TiO2 nanoporous films derived by combining nanoimprint technique with sol-gel method.” , J. Nanosci Nanotechnol, 10, 7574-7577 (2010).

[44] X. Z. Gong, J. N. Tang, J. Q. Li, and Y. K. Liang, “Preparation and characterization of La-Co alloy nanowire arrays by electrodeposition in AAO template under nonaqueous system” , Trans. Nonferrous Met. Soc. China 18(2008)

[45] E. Ge´raud, V. Pre´vot , and F. Leroux, “ Synthesis and characterization of macroporous MgAl LDH using polystyrene spheres as template ” , Journal of Physics and Chemistry of Solids, 67, 903–908(2006).

[46] S. Bauer, J. G. Brunner, H. Jha, Y. Yasukawa, H. Asoh, S. Ono, H. Böhm, J. P. Spatz, and P. Schmuki, “Ordered nanopore boring in silicon: Metal-assisted etching using a self-aligned block copolymer Au nanoparticle template and gravity accelerated etching” , Electrochemistry Communications, 12, 565-569(2010).

[47] J. Ding, J. N. Gao, F. Q. Tang, “Fabrication of Colloidal Crystal Array by Self-Assembly Methods” , Progress in chemistry, 16, 321-326(2004).

[48] Y. Xia, and B. Gates, “Monodispersed Colloidal Spheres：Old Materials with New Applications” , Adv. Mater., 12, 693-713(2000).

[49] D. H. Kim and G. H. Lee, “Effect of Rapid Thermal Annealing on Thermoelectric Properties of Bismuth Telluride Films Grown by Co-sputtering.” , Materials Science and Engineering B , 131, 106-110 (2006).

[50] S. J. Jeon, M. Oh, H. Jeon, S. Hyun, and H. J. Lee, “Effect of Post-annealing on Thermoelectric Properties of Bismuth-telluride Thin Films Deposited by Co-sputtering.” , Microelectronic Engineering, doi:10.1016/j.mee.2010.06.036(2010).

[51] T. Y. Yang, I. M. Park, B. J. Kim, and Y. C. Joo, “Atomic Migration in Molten and Crystalline Ge2Sb2Te5 under High Electric Field” , Appl. Phys. Lett., 95, 032104(2009).

[52] K. M. Liou and C. N. Liao, “Electric Current Enhanced Defect Elimination in Thermally Annealed Bi-Sb-Te and Bi-Se-Te Thermoelectric Thin Films.” , Journal of Applied Physics, 108, 053711 (2010).

[53] S. Chen, C. C. Chang, G. Lin, C. C. Chan, and R. F. Louh, 「電泳自組裝技術製作具有不同粒徑聚苯乙烯微球之光子晶體模板與光學性質之分析」, 國科會計畫編號：NSC 95-2221-E-035-065.

[54] 廖建能，”奈米晶碲化鉍合金之熱電傳輸性質”，熱電技術發展及系統應用研討會，集思會議中心，P.36，2010.

[55] 陳奕瑞，”熱電性能量測技術”，熱電技術發展及系統應用研討會，集思會議中心，P.2，2010.