臺灣博碩士論文加值系統

本論文研究是以水溶液共沉澱透過水熱法製備Ba(FeNb)0.5O3(BFN)並且添加NaOH水溶液進行Ba2+、Fe3+和Nb5+進行濕式化學反應是有利於製備BFN奈米粉末，製備出奈米粉末的優點可以增加提升塊材的比表面積，來達到降低陶瓷樣品的燒結溫度和活化能，並且在實驗流程則可以省略PVA之製備流程，避免燒結後由PVA揮發掉所產生孔隙率達到陶瓷樣品的最佳緻密度，透過水熱法來製備陶瓷樣品其目的是要模擬在地底下高溫及高壓製造結晶的環境，並且研究與討論其介電常數、介電損失和複雜的內部阻抗分析。
在XRD可以觀察到陶瓷樣品具有單一相複合型鈣鈦礦結構，陶瓷樣品燒結溫度在1200 oC具有緻密的微結構和一致的顆粒大小，並且提升BFN陶瓷樣品之介電常數。陶瓷樣品介電常數會隨著頻率的增加而降低，證實陶瓷樣品為典型鐵電材料，陶瓷樣品複雜的阻抗是由Cole-Cole plot來分析，並且觀察到兩個半圓的存在，是由於陶瓷樣品內部晶粒和晶粒邊界異質結構的組成，晶粒和晶粒邊界響應出非常高介電常數，並且證實陶瓷樣品為多重消散性的遲緩過程。

In this study, the preparation of Ba(FeNb)0.5O3(BFN) by co-precipitation percolation via hydrothermal method and the addition of NaOH aqueous solution for Ba2+, Fe3+ and Nb5+ wet chemical reactions are beneficial to the preparation of BFN nanopowders. The advantage of preparing nano powder can increase the specific surface area of the bulk material. To reduce the sintering temperature and activation energy of the ceramic sample and to omit the preparation process of PVA in the experimental procedure.To avoid the defects such as Porosity produced by the volatilization of PVA after sintering to achieve the best density of ceramic samples. The purpose of preparing a ceramic sample by a hydrothermal method is to simulate a high-temperature and high-pressure crystallization environment under the ground and results and discuss its dielectric constant, dielectric loss, and complex internal impedance analysis.
In the XRD it can be observed that the ceramic sample has a single-phase composite perovskite structure. Ceramic sample sintering temperature at 1200 oC has a dense microstructure and average particle size and has a higher dielectric constant. The dielectric constant of the ceramic sample decreases as the frequency increases, confirming that the ceramic sample is a typical ferroelectric material.
The complex impedance of ceramic samples was analyzed by the Cole-Cole plot and Observe the existence of two semicircles. Due to the composition of the internal grain and grain boundary heterostructure of the ceramic sample. Grain and grain boundaries respond to very high dielectric constants and confirm the ceramic process as a multiple-dissipative relaxation
Process.

摘要.....i
Abstract.....ii
誌謝.....iv
目錄.....v
表目錄.....vii
圖目錄.....viii
第一章 緒論.....1
1-1 前言.....1
1-2鈦酸鋇之介電材料.....2
1-3研究動機.....2
1-4 研究目的.....3
第二章 基礎理論.....8
2-1 介電理論.....8
2-1-1 介電原理.....8
2-1-2 極化機制.....8
2-1-3 介電損失.....9
2-1-4 介電特性.....10
2-2 強介電理論.....10
2-2-1 強介電性質.....10
2-2-2 強介電性之晶體結構.....11
2-2-3 強介電性材料之應用.....11
2-3 複合型鈣鈦礦.....12
2-3-1複合型之組成結構.....12
2-3-2結構置換作用.....13
2-3-3容忍因子.....13
2-3-4弛緩性質.....13
2-4 缺陷化學與掺雜物之特性.....14
2-4-1 陶瓷缺陷.....14
2-4-2 Kröger-Vink缺陷化學符號.....14
2-4-3 離子摻雜之特性.....14
2-5 共沉澱法及水熱法.....15
2-5-1 共沉澱法機構.....15
2-5-2 水熱法機構.....15
2-6燒結過程及理論.....16
2-6-1燒結基本原理.....16
2-6-2 幾何形狀的考量.....16
2-6-3 粉末顆粒大小對燒結行為的影響.....17
2-6-4 晶粒成長.....17
2-6-5 晶粒成長的發生及驅動力.....17
2-6-6 晶粒成長的類型.....17
2-8 晶障型電容.....18
2-8-1晶域與晶界.....18
2-9 阻抗分析原理.....18
第三章 實驗流程.....32
3-1 實驗目的.....32
3-2 實驗藥品.....32
3-3 實驗流程.....32
3-4 材料結構與特性量測.....32
3-4-1 X光繞射儀.....32
3-4-2 場發射掃描式電子顯微鏡.....33
3-4-3 X射線光電子能譜儀 / 化學分析電子能譜儀.....33
3-4-4 比重密度天秤.....33
3-4-5 阻抗分析儀.....33
第四章 結果與討論.....37
4-1 以水熱法製備Ba(FeNb)0.5O3之鈣鈦礦結構.....37
4-1-1 Ba(FeNb)0.5O3之晶體結構.....37
4-1-2密度量測.....37
4-1-3 FE-SEM表面結構分析.....38
4-1-4 不同燒結溫度對氧空缺及Fe2+/Fe3+的影響.....38
4-1-5 介電性質分析.....39
4-1-6 阻抗分析量測.....40
第五章 結論.....56
5-1-1 Ba(FeNb)0.5O3結構分析.....56
5-1-2 Ba(FeNb)0.5O3介電分析.....56
參考文獻.....58
Extended Abstract.....62

[1]林士欽，“陶瓷晶片電容性質介紹及在電源模組上之應用”，工業材料雜誌，178期P .93
[2]薛立人，“超高電容器的應用深遠弘廣”，工業材料雜誌，128期 P.133
[3]M. Yokosuka, “Dielectric Dispersion of the Complex Perovskite Oxide Ba(Fe1/2Nb1/2)O3 at Low Frequencies”, Jpn. J. Appl. Phys. 34 (1995) 5338.
[4]S. Saha, T. P. Sinha, “Low-temperature scaling behavior of BaFe0.5Nb0.5O3”, Phys. Rev. B: Condens. Matter 65 (2002) 134103.
[5]V. A. Bokov and I. E. Myl，nikova, 1961,“Electrical and Optical Properties of Single Crystals of Ferroelectric with a Diffuse Phase Transition”, Sov. Phys. Solid State 3[3] 613.
[6]G. A. Smolenskii and A. I. Agranovskaya, 1960, “Dielectric Polarization of a Number of Complex Compounds”, Sov. Phys. Solid State 1 1429.
[7]S. L. Swartz,T. R. Shrout,W. A. Schulze and L. E. Cross, 1984, “Dielectric Properties of Lead-Magnesium Niobate Ceramics”, J. Am. Ceram. Soc. 67 311.
[8]T. T. Fang and H. K. Shiau, 2004, “Mechanism for Developing the Boundary Barrier Layers of CaCu3Ti4O12” J. Am. Ceram. Soc., 87 2072.
[9]S. Saha and T. P. Sinha, 2002, “Structure and dielectric of Ba(FeNb)0.5O3” J. Phys. Condens Matter, 14 249-258.
[10]Z. Wang, X. M. Chen, L. Ni, Y. Y. Liu and X. Q. Liu, 2007, “Dielectric relaxations in Ba(Fe1/2Ta1/2)O3 giant dielectric constant ceramics”, Appl. Phys. Lett. 90 102905.
[11]M. Yokosuka,1995,“Dielectric Dispersion of the Complex Perovskite Oxide Ba(Fe1/2Nb1/2)O3 at Low Frequencies”, Jpn. J. Appl. Phys. 34 5338.
[12]S. Saha and T. P. Sinha, 2002, “Low-temperature scaling behavior of BaFe0.5Nb0.5O3”, Phys. Rev. B: Condens. Matter 65 134103.
[13]鍾朝宇，2005，“複合型鈣鈦礦Ba1-xAx(Fe0.5Nb0.5)1-x/4O3(A=La、Bi)之介電性質研究”，國立成功大學材料科學及工程博士論文
[14]廖琨逢，2009，“低價數補償Ba1-xMx(Fe0.5Nb0.5)+x/4O3(A=Na、K)系列之介電性質研究”，國立虎尾科技大學光電與材料所碩士論文
[15]A. Dutta and T.P. Sinha, 2011, “Structural and dielectric properties of A(Fe1/2Ta1/2)O3 [A = Ba, Sr, Ca] ”, Mater. Res. Bull. 46 518-524.
[16]I. P. Raevski, S. A. Prosandeev, A. S. Bogatin, M. A. Malitskaya and L. Jastrabik, 2003, “High dielectric permittivity in AFe1/2B1/2O3 nonferroelectric perovskite ceramics (A=Ba, Sr, Ca ; B=Nb, Ta, Sb) ”J. Appl. Phys. 93 4130.
[17]A. P. Ramirez, M. A. Subramanian, M. Gardel, G. Blumberg, D. Li, T. Vogt and S. M. Shapiro, 2000, “Giant dielectric constant response in a copper-titanate”, Solid State Commun. 115 217.
[18]M. A. Subramanian, D. Li, N. Duan, B. A. Reisner and A. W. Sleight, 2000, “High Dielectric Constant in ACu3Ti4O12 and ACu3Ti3FeO12 Phases”, J. Solid State Chem. 151 323.
[19]S. Eitssayeam, U. Intatha, K. Pengpat, T. Tunkasiri(2006), “Preparation and characterization of barium iron niobate (BaFe0.5Nb0.5O3) ceramics”, Current Applied Physics 6 (2006) 316–318.
[20]Uraiwan Intatha a, Sukum Eitssayeam a, Kamonpan Pengpat a,Kenneth J.D. MacKenzie b, Tawee Tunkasiri a, (2007), “Dielectric properties of low temperature sintered LiF doped BaFe0.5Nb0.5O3, ”Materials Letters 61 (2007) 196–200.
[21]Zhuo Wang, Liang Liang Zhang, Yong Ping Pu(2014), “Ba0.4Sr0.6(Fe0.5Nb0.5)O3 ceramics with extended giant dielectric constant step and reduced dielectric loss, ”Journal of Alloys and Compounds 586 (2014) 420–425.
[22]P.K. Patel, K.L. Yadav, H. Singh, A.K. Yadav, “Origin of giant dielectric constantand magnetodielectric study in Ba(Fe0.5Nb0.5)O3 nanoceramics, ”J. AlloysCompd. 591 (2014) 224–229.
[23]C.-Y. Chung, Y.-H. Chang, G.-J. Chen, Y.-L. Chai, “Preparation, structure andferroelectric properties of Ba(Fe0.5Nb0. 5)O3powders by sol–gel method, ”J.Cryst. Growth 284 (2005) 100–107.
[24]Roberto Köferstein ,Stefan G. Ebbinghaus(2017), “Investigations of BaFe0.5Nb0.5O3 nano powders prepared by a lowtemperature aqueous synthesis and resulting ceramics, ”Journal of the European Ceramic Society 37 (2017) 1509–1516.
[25]吳朗，1994，“電子陶瓷-介電陶瓷”，全欣科技圖書。
[26]Z.Fan, K.Sun, J.Wang, “Perovskites for photovoltaics: a combined review of organic–inorganic halide perovskites and ferroelectric oxide perovskites”, Journal of Materials Chemistry A,Issue 37, 2015
[27]William D. Callister JR., “Materials Science and Engineering an Introduction 6/e”, WILEY (2003).
[28]A. J. Moulson and J. M. Herbert, “Electroceramics-Materials, Properties, Applications”, Chapman and Hall, 2002.
[29]黃國長，2006，“GdFeO3-GdInO3強介電磁功能性陶瓷材料之開發與性質研究”，國立東華大學材料科學與工程研究所碩士論文，p.11。
[30]M. W. Barsoum, “Fundamentals of Ceramics”, Mc Graw Hill.
[31]汪建民，1987，“精密陶瓷技術概論”，工業技術出版社，p.8-9, p.附錄 A-19。
[32]盧志權，“新世紀科技-自旋電子學與自旋電子元件簡介”，工業材料雜誌，169期 (2001) p.117
[33]吳朗，“電子陶瓷-壓電”，全欣資訊圖書 (1994)
[34]C. Ederer, N. A. Spaldin, “Recent progress in first-principles studies of magnetoelectric multiferroics”, Curr. Opin. Solid State Mater. Sci. 9 (2005) 128.
[35]P. Q. Mantas, “Dielectric Response of Materials: Extension to the Debye Model”, J. Eur. Ceram. Soc. 19 (1999) 2079.
[36]陳建宏，“強介電記憶體之發展”，工業材料雜誌，155期 (1999) p.147
[37]J. L. Chen, M.Y. Shieh, H. H. Yu, C. Liao, H. M. Chang, B. H. Yang and Z. P. Zhao, “Asymmetric reflectivity from surfaces with distributed dipoles and IR experiments on poled polyvinylidene difluoride films”, Appl. Phys. Lett. 93 (2008) 011902.
[38]Y. Y. Liu, X. M. Chen, X. Q. Liu and L. Ni, “Giant dielectric response and relaxor behaviors induced by charge and defect ordering in Sr(Fe1/2Nb1/2)O3 ceramics”, Appl. Phys. Lett. 90 (2007) 192905.
[39]Y. J. Hsiao,Y. S. Chang,T. H. Fang,Y. L. Chai,C. Y. Chang and Y.H. Chang, “High dielectric permittivity of Li and Ta codoped NiO ceramics”, J. Phys D: Appl. Phys. 40 (2007) 863.
[40]吳朗，“電工材料”，滄海圖書 (1998)
[41]基特，(Charles Kittel)原著，洪連揮，劉立基，魏榮君譯，“固態物理學導論(第七版) ”，高立 (2004)
[42]彭成鑑，“強介電薄膜材料技術專題導言”，工業材料雜誌，155期 (1999) p.120
[43]林淑萍，“LaMnO3粉末之製備及其性質之研究”，國立成功大學材料科學及工程碩士論文，全國碩博士論文資訊網。
[44]S. Yangyun and R.J. Brook, 1985, “Preparatiom of Zirconia-Toughened Ceramics by Reaction Sintering”, 17 [1] 35-47.
[45]Y. C. Liou, 2004, “Effect of heating rate on properties of Pb(Mg1/3Nb2/3)O3 ceramics produced by the reaction-sintering process”, Mater. Lett. 58 944-947.
[46]Y. C. Liou and C. T. Wu, 2008, “Synthesis and diffused phase transition of Ba0.7Sr0.3TiO3 ceramics by a reaction-sintering process”, Ceram. Int. 34 517-522.
[47]Y. C. Liou, C. T. Wu and T. C. Chung, 2007, “Synthesis and microstructure of SrTiO3 and BaTiO3 ceramics by a reaction-sintering process”, J. Mater. Sci. 42:3580-3587.
[48]于若軍，1985，“現代陶瓷工程學”，全華圖書。
[49]蕭富山，2000，“修正型統計燒結理論評估位添加、氧化鎂及氧化鋯添加氧化鋁燒 結行為及顯微結構演進”，國立成功大學材料科學及工程博士論文。
[50]R. L. Coble, “Sintering Crystalline Solids. Ⅰ. Intermediate and Final State Diffusion Models” J. Appl. Phys. 32 (1961) 787
[51]C. Greskovich and J. H. Rosolowski, “Sintering of Covalent Solids” J. Am. Ceram. Soc. 59 (1976) 336C. Herring, “Effect of Change of Scale on Sintering Phenomena” J. Appl. Phys. 21 (1950) 301.
[52]Z. Wang, Y.F. Wen, H.J. Li, M.R. Fang, C. Wang, Y.P. Pu, “Excellent stability and low dielectric loss of Ba(Fe0.5Nb0.5)O3 synthesized by a solution precipitationmethod, ”J. Alloys Compd. 656 (2016) 431–438.
[53]Subrat Kumar Kar, Sridevi Swain, Sonia, Pawan Kumar*(2015), “High dielectric constant and low optical band gap studies of La-modified Ba(Fe0.5Nb0.5)O3 ceramic”, Materials Chemistry and Physics 155 (2015) 171-177.
[54]D. W. Budworth, “Theory of Pore Closure during Sintering” Trans. Brit. Ceram. Soc. 69 (1970) 29.
[55]C. Herring, “Effect of Change of Scale on Sintering Phenomena” J. Appl. Phys. 21 (1950) 301.
[56]張益新，2004，“鈦鐵礦結構Zn1-xAxTi1-yByO3之合成及性質研究”國立成功大學材料科學及工程研究所博士論文。
[57]許志雄，2006，王木琴，許蕙如，“玻璃－排列不規則的固體”，科學發展，406 期 ，p.6。
[58]劉士山，2001，“鋁電解電容器的阻抗特性”，工業材料雜誌，176期 p.132。
[59]K. S. Cole and R. H. Cole, “Dispersion and Absorption in Dielectric”, J. Chem. Phys, 1941. 9 341.
[60]R. M. German, “Sintering Theory and Practice”, John Wiley ＆ Son, 1996.
[61]A. R. West, D. C. Sinclair and N. Hirose, “Characterization of Electrical Materials, Especially Ferroelectric, by Impedance Spectroscopy”, J. Electroceram. 1 (1997) 65.
[62]K. Lichtenecker, “Dielectric Constant of Natural and Synthetic Mixtures” ,Phys. Z.,27 (1926) p.115.
[63]G. V. Lewis and C.R.A. Catlow, J. Phys. Chem. 47 (1986) 89
[64]Macchi, C., Somoza, A., Dupasquier, A., Lopez., A Castro and M. Castro, “positron trapping in BaTiO3 perovskite”, J. Phy: Condens. Matter 13 (2001) 5717.
[65]M. Mohsen, R. K. Rehberg, A. M. Massoud and H. T. Langhammer, “Donor-doping effect in BaTiO3 ceramic using positron annihilation spectroscopy”, Radiation Phys. Chem. 68 (2003) 549
[66]F. D. Morrison, D. C. Sinclair and A. R. West, “Doping mechanisms and electrical properries of La-doped BaTiO3 ceramics”, International J. of Inorganic Mater. 3 (2001) 1205
[67]R. Moos and K. H. Härdtl, “Defect Chemistry of Donotr-Doped and Undoped Strontium Titanate Ceramics between 1000o and 1400oC”, J. Am. Ceram. Soc. 80 (1997) 2549.
[68]Z. Wang, L.L. Zhang, Y.P. Pu, “Ba0.4Sr0.6(Fe0.5Nb0.5)O3 ceramics with extended giant dielectric constant step and reduced dielectric loss”, J. Alloys Comp. 586, 420–425 (2014)
[69]B. Angadi, V. M. Jali, M. T. Lagare, V. V. Bhat, A. M. Umarji and R. Kumar, “Radiation resistance of PFN and PMN-PT relaxor ferroelectrics” , Radia. Measure. 36 (2003) 635
[70]L. Zhou, P. M. Vilarinho, P. Q. Mantas, J. L. Baptista and E. Fotunato, “The effects of La on the dielectric properties of lead iron tungstate Pb(Fe2/3W1/3)O3 relaxor ceramics” , J. Euro. Ceram. Soc. 20 (2000) 1035
[71]Y. Park, “Low-frequency-dispersion of Pb(Fe1/2Nb1/2)O3 single crystal in the region of its paraelectric ferroelectric phase transition”, Solid State Commun. 113 (2000) 379
[72]K. Kinoshita and A. Yamaji, 1976, “Grain-size effect on dielectric properties in barium titanate ceramics”, Journal of Applied Physics, 47 ,371.
[73]G. Arlt, D. Hennings and G. de With ,1985, “Dielectric properties of fine-grained barium titanate ceramics”, Journal of Applied Physice, 58 ,1619.
[74]W. H. Jung, J. H. Lee, J. H. Sohn, H. D. Nam and S. H. Cho, 2002, “Dielectric loss anomayly in Ba(Fe1/2Ta1/2)O3 ceramics” , Materials Letters, 56, 334.
[75]W. H. Jung and E. Iguchi, 1996, “Transition from hopping conduction to band conduction in LaxFexNi1-xO3” Philosophical Magazine B. 73 873.
[76]A.K Jonscher, “Dielectric relaxation in Solid”, Chelsea Dielectric Press Limited, London (1983) p.76
[77]A.R West, T.B. Adams, F.D Morrison and D.C. Sinclair, “Novel high capacitance materials: BaTiO3:La and CaCu3Ti4O12”, J. Euro. Cream. Soc., 24(2004) 1439
[78]N. Yamaoka, “SrTiO3-Base Boundary Layer Capacitors”, Am. Cream. Soc., 24(2004) 1439.