臺灣博碩士論文加值系統

本研究乃利用共沈澱法來製備銅鋁氧化物(Copper Aluminum Oxide, CAO)粉末，並以此粉末藉由陶瓷加工的程序製備CAO靶材，最後再以自製之CAO靶材利用RF磁控濺鍍製程，製備p型之透明導電薄膜。除此之外，亦探討共沉澱條件及濺鍍製程參數對CAO粉末、靶材及濺鍍薄膜之性質影響。
由研究結果證實，以共沉澱法在pH=6.5進行沉澱所製備之前驅沉澱物，經水洗、過濾及乾燥等步驟後，在1100℃至1200℃煆燒2小時，確實可製備出結晶性的CuAlO2粉末，而這些粉末經由球磨、造粒、乾壓成形、冷均壓強化、脫臘及高溫燒結等步驟，可製備出緻密度約為90%且電阻係數為40-650Ω-cm之CAO靶材。而共沉殿之條件(pH值、濃度、銅鋁配比等)不僅會對沉澱物的性質有所影響，更對煆燒後所得CAO粉末及燒結後之CAO靶材之性質(結構、成份組成及導電特性)有所影響。而以這些靶材利用RF磁控濺鍍在玻璃基板上鍍膜，雖可獲得透光率不差(>75%)的透明薄膜，但因無法形成結晶性之CAO薄膜，即使基板溫度高達300℃，其薄膜的導電能力不佳。

The objectives of this research are to prepare powders of copper aluminum oxide (CAO) by co-precipitation method, to produce CAO sputtering targets through ceramic processing using these powders, and to deposit p-type transparent conducting CAO thin films by RF magnetron sputtering. In addition, the effects of the co-precipitation parameters and the sputtering process conditions on the characteristics of the powders, targets, and sputter-deposited thin films are also investigated.
From the experimental results, it was shown that crystalline CuAlO2 powders could be prepared by calcining at 1100℃ to 1200℃ for two hours the precursor precipitates that were co-precipitated at pH=6.5, washed, filtered, and dried. CAO targets with theoretical density around 90% and electrical resistivity ranging from 40 to 650 Ω-cm could also be prepared from these CAO powders through ball-milling, granulation, dry pressing, cold isostatic pressing, de-waxing, and sintering processes. It was also found the process conditions of co-precipitation had influence not only on the properties of the precipitates but also on the characteristics of the calcined CAO powders and sintered CAO targets. The optical transmittance of the transparent RF-sputtered thin films deposited from the CAO targets was above 75%. Being unable to form crystalline CAO thin films, the electrical conductivity of these thin films was poor even with the glass substrate temperature as high as 300℃.

指導教授推薦書
口試委員會審定書
長庚大學博碩士紙本論文著作授權書
謝誌…………………………………...………........................…………Ⅳ
中文摘要…………………………………...………….……...…………Ⅴ
英文摘要…………………………………...………................…………Ⅵ
目錄………………………………………………....………...…………Ⅶ
圖目錄……………………………………....…………….......………ⅩⅢ
表目錄………………………...………………….…………...………ⅩⅥ
第一章 序論………………………………………..……………………1
1.1前言…………………….……………………………...……...……1
1.2研究動機………………….……………………...……………...…4
第二章 文獻回顧……………………………………………..……….…6
2.1 透明導電薄膜……………..…………………………….………...6
2.1.1 光學性質…………………………………………………..….8
2.1.2 導電性質………………………………………………….…11
2.1.3 n-type TCO…………………..………………………………12
2.1.4 p-type TCO……………………..……………………………13
2.2 銅鋁氧化物 (CAO)…………………..…………………………16
2.2.1 CAO的結構…………………………………………………16
2.2.2 CAO 的導電原理………………………...…………………17
2.2.3 CAO的光學性質……………………………....……………25
2.3銅鋁氧化物薄膜的製備……………………………….…………28
2.3.1 濺鍍法製備導電薄膜………………………………………28
2.4 簡介濺鍍原理……………………………………………...……29
2.4.1 濺射(sputtering)…………………………………………..…29
2.4.2 電漿(plasma)……………………………………………..…30
2.4.3 濺鍍沈積(sputtering deposition)……………………………34
2.5 射頻磁控濺鍍…………………………………………...………35
2.5.1 射頻濺鍍(RF sputtering)……………………………………35
2.5.2 磁控濺鍍(magnetron sputtering)…………………………...36
2.6 靶材的製備與燒結(Sintering)原理…………………..…………38
2.7 銅鋁氧化物粉末製備方式……………………………...………41
2.7.1 共沈澱法……………………………………………………42
2.7.2 CAO前驅物之共沈澱平衡及沈降程序……………………44
2.7.3兩性氫氧化物…………………………………….…………45
2.7.4溶質溶解度的影響因素……………………………..………46
2.7.5共沈澱參數對粉末之影響…………………………..………49
2.7.5.1 溶液的pH值………………………...…………………49
2.7.5.2母液初濃度之影響 …………………………………49
2.7.5.3溫度之影響……………………………..………………50
2.7.5.4共沉反應時之轉速影響………………...………………50
2.7.5.5 不同陳化條件之影響…………………….……………51
2.7.5.6 共沈澱劑之種類…………………………….…………51
2.8 研究目的……………………………………………………...…53
第三章 實驗方法與儀器原理…………………………………………55
3.1 實驗藥品與物品………………………………………………...55
3.2 實驗方法與流程………………………………...………………56
3.2.1 CAO前驅沈澱溶液及CAO粉末製備…………..…………56
3.2.2 CAO濺鍍靶材的製備過程…………………………………58
3.2.3 CAO薄膜鍍製………………………………………………59
3.3 性質分析……………………………………………………...…64
3.3.1 儀器設備……………………………………………………64
3.3.2 性質量測……………………………………………………65
第四章 結果與討論…………………………………………….………67
4.1最終沉澱pH值對CAO粉末性質影響之分析……………..……68
4.1.1濾液中殘餘金屬濃度分析……………………………..……68
4.1.2 煆燒溫度及時間對CAO粉末結晶性之影響……………...70
4.1.3 沈澱pH值對CAO粉末結晶性之影響………………….…72
4.2銅鋁比例對共沈澱法製備之CAO粉末性質影響之分析……....73
4.2.1 銅鋁比例對共沈澱法製備之CAO粉末結晶的影響…...…74
4.2.2 銅鋁比例對共沈澱法製備之CAO粉末化學組成之影響…………………………………………………………….76
4.3共沉澱條件對共沈澱法製備之CAO粉末性質影響之探討……77
4.3.1起始濃度對共沈澱法製備之CAO粉末性質影響之探討…77
4.3.1.1 CAO前驅沈澱物之粒徑分析………………………….….78
4.3.1.2 CAO前驅沉澱物及粉末之FE-SEM分析……………….79
4.3.1.3 CAO粉末之XRD探討…………………...…………….…81
4.3.1.4 CAO粉末之EDS分析…………………….....................…82
4.3.2陳化反應對CAO粉末性質影響之分…………..…………...…84
4.3.2.1 CAO前驅沈澱物之粒徑分析………………………….…84
4.3.2.2 CAO前驅沉澱物及粉末之FE-SEM探討…………….…85
4.3.2.3 CAO粉末之XRD探討…………………………………....87
4.3.2.4 CAO粉末EDS分析…………………………………….…88
4.3.3不同沈澱劑對CAO粉末性質影響之分析………………….…89
4.3.3.1 CAO前驅沈澱物粒徑分析……………………………..…89
4.3.3.2 CAO前驅沉澱物及粉末之FE-SEM分析…………….…90
4.3.3.3 沈澱劑對CAO粉末之結晶性影響探討…………………91
4.3.3.4 CAO粉末之EDS分析………………………………….…91
4.4共沉澱條件對CAO靶材性質影響之探討………………………93
4.4.1 反應物起始濃度對CAO靶材性質影響之分析…………...93
4.4.1.1 靶材之XRD探討………………………………………93
4.4.1.2 靶材之物性分析分析………………………………..…94
4.4.2 陳化反應對CAO靶材性質影響之探討…………….……..96
4.4.2.1 CAO靶材之XRD分析…………………………..……..96
4.4.2.2 CAO靶材之物性分析……………………….………….97
4.4.3 不同沈澱劑對CAO靶材性質影響之分析……………...…97
4.4.3.1 CAO靶材之XRD探討…………………………………97
4.4.3.2 靶材之物性分析……………………………………..…97
4.5 CAO薄膜性質分析………………………………………………99
4.5.1 CAO薄膜之電性分析…………………………………...…..99
4.5.2 CAO薄膜之XRD分析………………………………….…..99
4.5.3 CAO薄膜之可見光透率分析……………………………...101
第五章 結論…………………………………………….…………..…103
未來展望………………………………………….………..………..…105
參考文獻………………………………………….……………..…..…106

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