本研究藉由共沉澱法來製備銦錫氧化物 (ITO) 奈米粒子，選用的起始材料為硝酸銦 (In(NO3)3) 以及氯化錫 (SnCl4)，沉澱劑採用氨水 (NH4OH)。過往之研究中指出某些聚電解質高分子可提供一有效之途徑來改變奈米粒子形態。因此在本實驗中選用陰離子型聚電解質高分子 poly(styrene sulfonic acid) (PSS) 來作為 ITO 奈米粒子表面形態之生長導向劑，經由調控 PSS 上磺酸基離子化的程度以及 PSS 的濃度來探討 ITO 奈米粒子之表面形態的變化。
由實驗結果顯示，當固定 SO3H/In 的莫耳比 (1/10)，改變三乙醇胺的添加量 (0 ~ 6 ml)時，ITO precursor 奈米粒子的形態會隨著 pH 值而變化，由球狀粒子變為部分球狀部分方塊狀，當 pH 值到達11.53時粒子形成約長500~800 nm、寬100 nm以及厚度約為5~10 nm的片狀粒子。而當固定 pH 值，改變 SO3H/In 的莫耳比 (0.5/10、1/10、2/10、5/10以及 10/10) 時，粒子之形態會從桿狀變成由約2 nm的小粒子結合在一起形成約30~50 nm的粒子，所製備的 ITO precursor 奈米粒子在經500 °C高溫煆燒後均形成 ITO 奈米粒子。

This study utilized the co-precipitation method to prepare ITO nanoparticles, the starting materials were indium nitrate, tin chloride, and ammonium hydroxide. The previous research showed that polyelectrolytes can offer an effective route to alter morphologies of nanoparticles, hence an anionic polyelectrolyte, poly (styrene sulfonic acid) (PSS), was used a structure-directing agent to prepare ITO nanoparticles. Various morphologies of ITO nanoparticles via adjusting the ionization degree of sulfonic acid and the concentration of PSS were observed.
The results indicated that when the molar ratio of SO3H/In was fixed (1/10) and the value of triethanolamine was changed (0~6 ml) ITO precursor nanoparticles varied from nanospheres to nanocubes. As the pH value was equal to 11.53, ITO precursor nanoparticles became nanosheets, which length, width and thickness are 500 ~ 800 nm, 100 nm, and 5 ~ 10 nm, respectively. However, while the value of pH was fixed (pH=11.53) and molar ratios of SO3H/In were varied (0.5/10, 1/10, 2/10, 5/10 and 10/10), the ITO precursor nanoparticles changed from nanosheets to nanoparticles. The prepared ITO precursor nanoparticles formed the ITO nanoparticles through calcined at 500°C.

目錄
中文摘要......................................................................................................................Ⅰ
英文摘要......................................................................................................................Ⅱ
目錄..............................................................................................................................Ⅲ
表目錄..........................................................................................................................Ⅴ
圖目錄..........................................................................................................................Ⅵ
第一章 緒論
1-1 前言.................................................................................................................1
1-2 研究動機與目的.............................................................................................4
第二章 原理與文獻
2-1 銦錫氧化物.....................................................................................................5
2-1-1 銦錫氧化物的導電性.........................................................................7
2-1-2 銦錫氧化物的光學性質.....................................................................9
2-2 濕式成膜法製備 ITO 透明導電膜............................................................12
2-3 銦錫氧化物奈米粒子的製備.......................................................................15
2-4 奈米粒子的表面有機物修飾.......................................................................25
第三章 實驗部份
3-1 實驗藥品.......................................................................................................29
3-2 實驗步驟.......................................................................................................31
3-3 材料性質分析與測試條件………………………………….……………..33
第四章 結果與討論
4-1 奈米粒子晶相分析.......................................................................................37
4-2 分子結構分析……………………………….……………………………..44
4-3 結構鑑定…………………………………….……………………………..56
4-4 表面形態鑑定………………………………..……………….……………75
IV
第五章 結論…………………………………………………………………………89
參考文獻......................................................................................................................90
附錄..............................................................................................................................92
V
表目錄
表3-1 實驗條件………………………………………………..…………………35
表4-1 改變三乙醇胺添加量所製備 ITO precursor 奈米粒子的特徵吸收波長位置………………………………………………………..............................................50
表4-2 改變磺酸基/銦莫耳比所製備 ITO precursor 奈米粒子的特徵吸收波長位置………………………………………………………..............................................55
VI
圖目錄
圖2-1 (a) cubic-In(OH)3 和 (b) bixbyite-In2O3 晶體結構…………………………..6
圖2-2 在立方晶體的氧化銦 (In2O3) 結構中陽離子所佔據的位置……………….7
圖2-3 一典型之ITO穿透、反射與吸收之光譜圖………………………………….10
圖2-4 載子濃度增加時 ITO 薄膜穿透率之變化圖譜……………………………11
圖2-5 電阻值隨著薄膜厚度之變化圖………………………………………….….14
圖2-6 In(OH)3 轉變至 In2O3的過程中，隨不同溫度變化的經驗分子式….......…18
圖2-7 帶結晶水的 ITO precursor 奈米粒子在120 oC下乾燥之FTIR圖譜以及在空氣中300 oC，2小時的煆燒處理後成為 ITO 奈米粒子的FTIR圖譜………………19
圖2-8 pH=6.75時 ITO precursor 奈米粒子經 (a) 600oC煆燒以及在 (b) 400oC下的混合氣體(N2+2%H2) 中作還原處理後的 ITO 奈米粒子之TEM圖….….20
圖2-9 不同pH值環境下所製備出之ITO precursor經300 oC煆燒............................21
圖2-10 反應槽溫度為40o C與100o C之 ITO precursor 的X光繞射圖譜……..22
圖2-11 ITO 桿狀奈米粒子之生長模型……………………………………………22
圖2-12 ITO 薄膜的近紅外光穿透圖譜 (A) 玻璃 (B) ITO 薄膜…………….…23
圖2-13 由共沉澱法以及經300oC煆燒後之 ITO 奈米粒子……………………23
圖2-14 共沉澱法製備之 ITO precursor奈米粒子的DSC圖……………………..24
圖2-15 由水熱法所製備出之單分佈ITO 奈米粒子……………………………24
圖2-16 PSS高分子鏈分子間連結之結構圖……………………………..…………27
圖2-17 PSS 改變粒子表面形態的機制示意圖……………………………………27
圖2-18 Bi2WO6花狀粒子形成過程的示意圖…………………………………...….28
圖2-19 球狀及方塊狀 ITO precursor 奈米粒子表面形態之SEM圖………...….28
圖3-1 製備ITO奈米粉體流程圖………………………………………………..….36
圖4-1 不同三乙醇胺添加量之反應條件下所製備的ITO precursor奈米粒子的XRD圖……………………………………………………..………………….…39
VII
圖4-2 不同三乙醇胺添加量之反應條件下所製備的ITO奈米粒子的XRD圖...40
圖4-3 不同磺酸基/銦莫耳比之反應條件下所製備的ITO precursor奈米粒子的XRD圖……………………………………………………………………............42
圖4-4 不同磺酸基/銦莫耳比之反應條件下所製備的 ITO 奈米粒子的XRD圖….……………………………………………………………………………..…...43
圖4-5 不同三乙醇胺添加量所製備之ITO precursor 奈米粒子之FTIR圖…………………………………………………………………………………..…46
圖4-6 不同三乙醇胺添加量所製備之 ITO precursor 奈米粒子之FTIR圖 (波長範圍: 1800 ~ 400 cm-1)………………………...………………………..…...............47
圖4-7 pH= 11.53所製備之 ITO precursor 奈米粒子的FTIR圖 (波長範圍: 1450 ~ 400 cm-1) ………………………………………………………………..…...............48
圖4-8 不同三乙醇胺添加量所製備之 ITO 奈米粒子之FTIR圖…………........49
圖4-9 不同磺酸基/銦莫耳比所製備之ITO precursor 奈米粒子之FTIR圖…………………………………………………………………………………….52
圖4-10 樣品 SO3H/In=5/10 以及 10/10 之FTIR圖…………………………......53
圖4-11 不同磺酸基/銦莫耳比所製備之ITO奈米粒子之FTIR圖……………....54
圖4-12 PSS高分子鏈在不同pH值的水中所呈現的型態之TEM圖…………..….58
圖4-13 pH 值為2.63時，所製備之ITO precursor的形態........................................59
圖4-14 pH 值為8.83時，所製備之ITO precursor的形態........................................60
圖4-15 pH 值為10.11時，所製備之ITO precursor的形態………………......……61
圖4-16 pH 值為11.39時，所製備之ITO precursor的形態…………………..……62
圖4-17 pH 值為11.46時，所製備之ITO precursor的形態………………….…….63
圖4-18 pH 值為11.53時，所製備之ITO precursor的形態…………………….….64
圖4-19 pH 值為11.53時，所製備之ITO precursor 奈米粒子的d-spacing…….…65
VIII
圖4-20 pH 值為11.53時，所製備之ITO precursor，經300 O C，1.5小時煆燒後成為ITO 奈米粒子……………………………….....................................................66
圖4-21 pH 值為11.67時，所製備之ITO precursor的形態………………………..67
圖4-22 隨著不同PSS的pH值，PSS鏈上負電荷之變化……………….................68
圖4-23 SO3H/In=0.5/10時，所製備之ITO precursor的形態………………...…….70
圖4-24 SO3H/In=1/10時，所製備之ITO precursor的形態……………………..…..71
圖4-25 SO3H/In=2/10時，所製備之ITO precursor的形態…………………..…….72
圖4-26 SO3H/In=5/10時，所製備之ITO precursor的形態………………………....73
圖4-27 SO3H/In=10/10時，所製備之ITO precursor的形態……………….………74
圖4-28 PSS水溶液 pH=2.63 時之ITO奈米粒子之表面形態……………………76
圖4-29 PSS水溶液pH=8.83時之ITO奈米粒子之表面形態……………..……….77
圖4-30 PSS水溶液pH=10.11時之ITO奈米粒子之表面形態…………………….78
圖4-31 PSS水溶液pH=11.39時之ITO奈米粒子之表面形態………………….…79
圖4-32 PSS水溶液pH=11.46時之ITO奈米粒子之表面形態………………….…80
圖4-33 PSS水溶液pH=11.53時之ITO奈米粒子之表面形態………………….…81
圖4-34 PSS水溶液pH=11.67時之ITO奈米粒子之表面形態……………….……82
圖4-35 SO3H/In=0.5/10時ITO奈米粒子之表面形態..............................................84
圖4-36 SO3H/In=1/10時ITO奈米粒子之表面形態….............................................85
圖4-37 SO3H/In=2/10時ITO奈米粒子之表面形態….............................................86
圖4-38 SO3H/In=5/10時ITO奈米粒子之表面形態…………………………….…88

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