本研究使用共析出法已成功製備摻雜鐵、鈷及鎳之氧化銦錫粉末，其摻雜濃度分別為3.8at.%及6at.%，並探討摻雜離子對氧化銦錫粉末之晶相及顏色影響。實驗結果，由XRD繞射儀，各種摻雜離子不會改變氧化銦錫之特徵峰值。摻雜鐵、鈷及鎳形成淡黃綠色、褐灰及藍灰色。另外，粉末經氫氣還原和真空高溫加熱，摻雜鐵離子之ITO粉末形成藍灰色；摻雜鈷及鎳離子之顏色與未加熱前相同，因為鈷及鎳離子進入晶體結構之中加強了與氧的鍵結，導致不易產生氧空缺。

The present study has been successful fabricated the 3.8 at.% and 6 at.% Fe, Co, Ni -doped ITO powder using by co-precipitation method, and probed the effect of crystal phase and colour of doped ITO powder. The experimental results showed that the doped ions would not change the ITO’s characteristic diffraction peaks using by XRD diffraction analysis, but the doped ions will change the powder’s colour due to colour center effect which doped iron, cobalt and nickel will form the light yellow-green, gray-brown, and blue-gray, respectively. In addition, the powder thought hydrogen reduced and vacuum heating treatment, the colour of Fe-doped ITO powder turns into the blue-gray, and the colour of Co- and Ni- doped ITO powder are change less due to the cobalt and nickel ions diffused into the crystal structure and then strengthen the bonding with oxygen, that result effect of the oxygen vacancies more difficult to form.

總目錄 
中文摘要...........................................................................................I 
英文摘要..........................................................................................II 
總目錄.............................................................................................III 
圖目錄............................................................................................VI 
表目錄...........................................................................................VIII 
符號說明.........................................................................................IX 
壹、導論.........................................................................................1 
1.1 前言..........................................................................................1 
1.2 文獻回顧....................................................................................2 
1.2.1 氧化銦In2O3介紹......................................................................2 
1.2.2 氧化銦錫介紹............................................................................3 
1.2.2.1 導電性質...............................................................................4 
1.2.2.2 能隙結構...............................................................................6 
1.2.2.3 Sn的摻雜濃度對ITO的影響......................................................7 
1.2.2.4 光學性質...............................................................................8 
1.2.3 ITO粉末的製備方法..................................................................12 
1.2.3.1 傳統粉碎法..........................................................................12 
1.2.3.2 固相反應法..........................................................................13 
1.2.3.3 水熱法.................................................................................13 
1.2.3.4 溶膠凝膠法..........................................................................14 
1.2.3.5 沉澱法.................................................................................16 
1.3 動機目的.....................................................................................18 
貳、實驗設計....................................................................................26 
2.1實驗材料與設備...........................................................................26 
2.1.1 實驗材料..................................................................................26 
2.1.2 實驗設備..................................................................................26 
2.2 實驗步驟....................................................................................27 
2.2.1 ITO奈米粉體製作.....................................................................27 
2.2.2 ITO粉末氫還原及真空處理........................................................28 
2.3 性質測試....................................................................................28 
2.3.1 X光繞射分析...........................................................................28 
2.3.2 EDAX分析..............................................................................29 
参、結果與討論.............................................................................32 
3.1 摻雜離子進入ITO晶體.................................................................32 
3.1.1 X光繞射分析............................................................................33 
3.1.2 EDAX成分分析.......................................................................33 
3.2 製作過程中引發顏色的改變...........................................................34 
3.3 熱處理造成的顏色變化................................................................36 
3.3.1 在450℃空氣中熱處理後顏色的改變............................................36 
3.3.2 在250℃氫氣中熱處理後顏色的改變............................................39 
3.3.3 在400℃真空中熱處理後顏色的改變............................................40 
肆、結論.................................................. ........................................56 
伍、參考文獻............................................... ...................................58 

圖目錄 
圖1.1 In2O3晶體結構圖..................................................................19 
圖1.2 CaF2晶體結構圖...................................................................19 
圖1.3 In2O3中b site及d site銦離子周圍的氧離子配置........................20 
圖1.4 Nath等人製造的ITO薄膜和In2O3薄膜XRD比較圖.......................21 
圖1.5 In2O3摻錫的能隙模型............................................................22 
圖1.6 不同摻錫濃度及氧分壓下處理的ITO薄膜的載子濃度.................23 
圖1.7 典型ITO薄膜穿透、反射及吸收光譜圖.....................................24 
圖1.8 In2O3與摻雜Sn之後的拋物線能隙結構....................................25 
圖2.1 使用共析出方法製作ITO粉末之流程圖.......................................31 
圖3.1 摻雜離子在In2O3晶體結構中可能置換的位置示意圖.................41 
圖3.2 摻雜離子進入In2O3晶體結構後造成的影響..............................42 
圖3.3 不同摻雜濃度Fe ITO粉末之XRD繞射分析圖...........................43 
圖3.4 不同摻雜濃度Co ITO粉末之XRD繞射分析圖...........................43 
圖3.5 不同摻雜濃度Ni ITO粉末之XRD繞射分析圖............................44 
圖3.6 使用共析出方法製備摻雜鐵ITO之顏色變化...............................45 
圖3.7 使用共析出方法製備摻雜鈷ITO之顏色變化...............................46 
圖3.8 從溶液取出清洗烘乾後的摻雜ITO粉末之顏色改變.....................47 
圖3.9 使用共析出方法製備摻雜鎳ITO之顏色變化...............................48 
圖3.10 摻雜的ITO粉末在450℃熱處理前之XRD繞射分析圖...................49 
圖3.11 摻雜的ITO粉末在450℃熱處理後之XRD繞射分析圖...................49 
圖3.12 ITO粉末經氫還原後及真空加熱後之照片...............................50 
圖3.13 ITO粉末經真空油壓機加熱加壓後之照片...............................50 
圖3.14 摻雜3.8 at.% Fe ITO粉末經氫還原及真空加熱之照片...........51 
圖3.15 摻雜6 at.% Fe ITO粉末經氫還原及真空加熱之照片..............51 
圖3.16 摻雜3.8 at.% Co ITO粉末經氫還原及真空加熱之照片...........52 
圖3.17 摻雜6 at.% Co ITO粉末經氫還原及真空加熱之照片..............52 
圖3.18 摻雜3.8 at.% Ni ITO粉末經氫還原及真空加熱之照片............53 
圖3.19 摻雜6 at.% Ni ITO粉末經氫還原及真空加熱之照片...............53 

表目錄 
表3.1 各種摻雜ITO粉末經不同熱處理之顏色變化.............................54 
表3.2 6 at.% 摻雜Fe ITO粉末之EDAX.............................................55 
表3.3 6 at.% 摻雜Co ITO粉末之EDAX.............................................55 
表3.4 6 at.% 摻雜Ni ITO粉末之EDAX..............................................55

[1]K. Badeker, “Uber die elektrische Leitfahigkeit und die thermoelektrische Kraft einiger Schwermetallverbindungen,” Ann. Phys. (Leipzig), 22 (1907), pp.749-766.
[2]楊明輝，透明導電膜，藝軒圖書出版社，(2006)，pp.34-37，pp.54-58。
[3]I. Hamberg and C.G. Granqvist, “Evaporated Sn-doped In2O3 films : Basic optical properties and applications to energy-efficient windows”, J. Appl. Phys., 60, R123 (1986).
[4]S.-H. Chen, “Work function changes of treated indium-tin-oxide films for organic light emitting diodes investigated using scanning surface potential microscopy”, J. Appl. Phys., 97 (7) (2005), 073713.
[5]H. Odaka, Y. Shigesato, T. Murakami, and S. Iwata, “Electronic Structure Analyses of Sn-doped In2O3”, J. Appl. Phys., 40 (2001),  pp.3231-3235.
[6]CaF2 晶體結構圖， 2012/7/29取自http://zh.wikipedia.org/zh-tw/File:CaF2_polyhedra.png。
[7]透明導電膜之技術，日本學術振興會 透明酸化物光．電子材料第116委員會編，Ohmsha，（1999），pp.84。
[8]G. B. Gonzalez, T. O. Mason, J. P. Quintana, O. Warschkow, D. E. Ellis, J.-H. Hwang, and J. P. Hodges, “Defect structure studies of bulk and nano-indium-tin oxide”, J. Appl. Phys., 96 (7) (2004), pp.3912-3920.
[9]J. C. C. Fan and F. J. Bachner, “Properties of Sn-Doped In2O3 Films Prepared by RF Sputtering”, J. Electorchem. Soc., 122 (12) (1975), pp.1719-1724.
[10]P. Nath and R. F. Bunshah, “Preparation of In2O3 and Tin-Doped In2O3 Films by a Novel Activated Reactive Evaporation Technique”, Thin Solid Films, 69(1980), pp.63-68. 
[11]J.-H. Hwang , D.D. Edwards , D.R. Kammler , T.O. Mason, “Point defects and electrical properties of Sn-doped In-based transparent conducting oxides”, Solid State Ionics, 129 (2000), pp.135–144.
[12]M. Buchanan, J. B. Webb and D. F. Williams, “Preparation of Conducting and Transparent Thin Films of Tin-Doped Indium Oxide by Magnetron Sputtering”, Appl. Phys. Lett., 37 (2) (1980), pp.213-215.
[13]T. Karasawa and Y. Miyata, “Electrical and Optical Properties of Indium Tin Oxide Thin Films Deposited on Unheated Substrates by DC Reactive Sputtering”, Thin Solid Films, 223 (1) (1993), pp.135-139.
[14]W. F. Wu and B. S. Chiou, “Properties of Radio-Frequency Magnetron Sputtered ITO Films without In-Situ Substrate Heating and Post-Deposition Annealing”, Thin Solid Films, 247 (1994), pp.201-207.
[15]J. C. C. Fan and J. B. Goodenough, “X-Ray Photoemission Spectroscopy Studies of Sn-Doped Indium-Oxide Films”, J. Appl. Phys., 48 (8) (1977), pp.3524-3531.
[16]R. L. Weiher, “Electrical Properties of Single Crystals of Indium Oxide”, J. Appl. Phys., 33 (9) (1962), pp.2834-2839. 
[17]N. Nadaud, N. Lequeux, M. Nanot, J. Jove and T. Roisnel, “Structural studies of tin-doped indium oxide (ITO) and In4Sn3O12” J. Solid State Chem., 135 (1998), pp.140–148.
[18]洪文進，許登貴，萬明安，郭書瑋，蘇昭瑾，“ITO 透明導電薄膜：從發展與應用到製備與分析”，CHEMISTRY，63 (3) (2005)，pp.409-418。
[19]M. Quaas, C. Eggs and H. Wulff, “Structural studies of ITO thin flms with the Rietveld method”, Thin Solid Films, 332 (1998), pp.277-281.
[20]G. Frank and H. Kostlin, “Electrical Properties and Defect Model of Tin-Doped Indium Oxide Layers”, Appl. Phys. A, 27 (4) (1982), pp.197-206.
[21]陽明輝，“金屬氧化物透明導電材料的基本原理”，工業材料，第179期，(2001)，pp.134-144。
[22]M. Fox, Optical Properties of Solids, Oxford University Press, (2001).
[23]I. Hamberg, C. G. Granqvist, K. F. Berggren, B. E. sernelius and L. Engstrom, “Band-gap widening in heavily Sn-doped In2O3”, Phys. Rev. B, 30 (1984) , pp.3240-3249.
[24]羅吉宗，戴明鳳，林鴻明，鄭振宗，蘇程裕，吳育民，奈米科技導論，全華科技圖書股份有限公司，(2003)，pp.3-41 - 3-49。
[25]Hong-Ming Lin,奈米材料合成技術, 2012/2/28取自http://nano.mse.ttu.edu.tw/html/doc/Class02_produ/3.pdf。
[26]劉吉平，郝向陽，奈米科學與技術，世茂出版社，(2003)，pp.26-41。
[27]徐國財，張立德，奈米複合材料，五南圖書出版公司，(2004)，pp.81-96。
[28]K. Fukui, K. Kanayama, M. Katoh, T Yamamoto and H Yoshida, “Synthesis of indium tin oxide powder by solid-phase reaction with microwave heating”, Advanced Powder Technology, 20 (5) (2009), pp.488–492
[29]S.G. Chen, Y.F. Huang, H.N. Xiao, H.W. Liao, C.G. Long, C. Ye and Q. Xia, “Sodium dodecyl benzene sulfonate (SDBS)-aid hydrothermal synthesis of indium–tin oxide (ITO) precursor intersecting-rods”, Materials Letters, 61 (2007), pp.1937–1942.
[30]C.P. Udawatte and K. Yanagisawa, “Fabrication of low-porosity indium tin oxide ceramics in air from hydrothermally prepared powder”, J. Am. Ceram. Soc., 84 (1) (2001), pp. 251–253.
[31]X. Li and G.M. Kale, “Urea-based hydrothermal synthesis of ITO nanopowders”, J. Phys.: Conf. Series, 26 (2005), pp. 319–322.
[32]蔡裕榮，周禮君，“以溶膠凝膠法製備透明導電氧化物薄膜的探討”，CHEMISTRY，60 (3) ( 2002)，pp.307-318。
[33]Z.-H. Li and D.-Y. REN, “Preparation of ITO transparent conductive film by sol-gel method”, Trans. Nonferrous Met. SOC. China, 16 (6) (2006), pp.1358-1361.
[34]B.C. Kim, S.M. Kim, J.H. Lee and J.J. Kim, “Effect of phase transformation on the densification of coprecipitated nanocrystalline indium tin oxide powders”, J. Am. Ceram. Soc., 85 (8) (2002), pp. 2083–2088.
[35]S. M. Kim, K. H. Seo, J.H. Lee, J. J. Kim, H. Y. Lee and J. S.Lee, “Preparation and sintering of nanocrystalline ITO powders with different SnO2 content”, Journal of the European Ceramic Society, 26 (2006), pp.73-80.
[36]S. Tang, J. Yao, J. Chen and J. Luo, “Preparation of indium tin oxide (ITO) with a single-phase structure”, Journal of Materials Processing Technology, 137 (2003), pp. 82–85. 
[37]S.G. Chen , C.H. Li , W.H. Xiong , L.M. Liu and H. Wang ,” Preparation of indium-tin oxide (ITO) nano-aciculae by a simple precipitation near boiling point and post-calcination methode”, Materials Latters, 59 (2005), pp.1342-1346.
[38]N. C. Pramanik, S. Das and P. K. Biswas, “The effect of Sn(IV) on transformation of co-precipitated hydrated In(III) and Sn(IV) hydroxides to indium tin oxide (ITO) powder”, Materials Letters, 56 (2002), pp.671–679. 
[39]W.L. Bragg, “The Diffraction of Short Electromagnetic Waves by a Crystal”, Proc. Camb. Philos. Soc., 17 (1913), pp.43–57.
[40]M. Schultz, “Diffraction for Materials Scientists”, Prentice–Hall Englewood Cliffs, N. J., (1982), pp.226.
[41]Ja Eun Song, Young Hwan Kim and Young Soo Kang, “Preparation of indium tin oxide nanoparticles and their application to near IR-reflective film”, Curr. Appl. Phys., 6 (4) (2006), pp.791-795.