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研究生：	張崇瑋 Chang, Chung-Wei
論文名稱：	化學氣相沉積法成長氮化銦奈米線及其鋰離子電池負極材料應用 Growth of Indium Nitride Nanowires by Chemical Vapor Deposition and Their Applications to Lithium Ion Battery as Anode Electrode
指導教授：	劉全璞 Liu, Chuan-Pu
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	86
中文關鍵詞：	氮化銦、化學氣相沉積法、奈米線、鋰離子電池
外文關鍵詞：	Indium nitride, CVD, Nanowire, lithium ion battery
相關次數：	點閱：63 下載：5
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本論文主軸為氮化銦奈米線成長討論，並於末節討論氮化銦奈米結構應用於鋰電池負極的未來性。在製程氮化銦奈米線的實驗中，成功改良製程方式使用低製程成本的熱化學氣相沉積法的方式成長於矽(111)及不鏽鋼錠上，經由SEM分析顯示為無方向性散亂成長之一維奈米線，並同時存在堆疊的塔狀結構及帶狀結構，並能由高解析TEM分析，於高倍率影像中能觀察到因VLS機制而存在的球狀顆粒，並由擇區電子繞射結果顯示塔狀結構奈米線沿著[0002]方向成長而帶狀奈米線則是沿著[101 ̅0]方向成長，於實驗中藉由改變製成溫度、工作壓力、氣體流量、催化劑厚度……等因素探討對氮化銦奈米結構純度、線密度的影響，以材料動力學探討造成其形貌差異之因素，製程的過程為VLS(vapor liquid solid))及SLS(solid liquid solid))機制的結合，故以SVLS(solid vapor liquid solid)機制稱之，於段落末段提出其成長地圖(growth map)。電性特性的量測利用電子束微影的方式進行單根量測，測量其導電率位於十的負四次方歐姆公分。
於末節的實驗中將成長於不鏽鋼錠極片上組成硬幣電池進行鋰電池充放電循環測試，探討一維及三維材料對循環測試造成的差異及氮化銦成為新一代負極材料的未來性，經由理論電容量的計算氮化銦的理論電容量高達1164.6 mAh/g，約為目前商用炭材的三倍，實驗中亦能達到886 mAh/g。
此次研究展示了一個新的製程概念，藉由預先蒸鍍的方式使得合金相的產生更為直接，並利用了VLS機制的低基板選擇性及氮化銦奈米線本質低的電阻率，展現出氮化銦成為高電容量的鋰二次電池負極材料的可行性。

InN nanowires with random orientations are grown densely on Au/In-coated Si (111) and stainless steel substrates by a modified thermal chemical vapor deposition method. Scanning electron microscopy images show that the as-grown nanowires are characterized by either parallel or sawtooth sides. High resolution transmission electron microscopy images and selected area electron diffraction patterns reveal that both types of nanowires contain Au catalytic particles on tops and the growth direction is along the [0001] and [101 ̅0] axis for sawtooth and parallel-sided nanowires, respectively. Through e-beam lithography, resistivity of single nanowires taken by four-point probe method all falls on the order of 10-4 Ω•cm, demonstrating to own great conductivity. For the application in lithium ion battery, coin cells are assembled using the InN nanowires grown on stainless substrate as negative electrodes and cycle performance testing is performed. The capacity could reach 886 mAh/g, which is more than two times of the commercial carbon materials. InN nanowires are testified to be promising in battery applications.

中文摘要......................................................................................................I
Extended abstract.......................................................................................II
誌謝........................................................................................................ VII
總目錄.................................................................................................... VIII
表目錄.......................................................................................................XI
圖目錄......................................................................................................XII
第一章 緒論..............................................................................1
1-1 前言..................................................................................................1
1-2 研究動機與論文架構..............................................................................2
第二章	理論基礎與文獻回顧........................................................................3
2-1 氮化銦簡介..............................................................................3
2-2 氮化銦之晶體結構與物理特性..........................................................3
2-2.1 氮化銦之光學特性.............................................................7
2-2.2 氮化銦之電學性質..............................................................................10
2-3 一維氮化銦奈米結構製作方法..........................................................11
2-3.1 氣-液-固(Vapor-Liquid-Solid, VLS)成長機制............................11
2-3.2 氣-固(Vapor-Solid, VS)成長機制...................................15
2-3.3 固-氣-固(Solid-Liquid-Solid, SLS)成長機制............................................16
2-3.4 無觸媒選區磊晶(Catalyst-free selective area epitaxial, SAE)成長機制.....17
2-4 化學氣相沉積法........................................................................19
2-5 鋰二次電池操作原理.................................................................21
2-6 負極電極材料之簡介.................................................................23
 2-6.1 傳統碳材與高電容量碳材................................................................25
2-6.2 非碳材........................................................................................27
 2-6.2.1 鋰合金.........................................................................................27
 2-6.2.2 氮化物.......................................................................................28
 2-6.2.3 矽..........................................................................................29
 2-6.2.4 氧化物..........................................................................................29
第三章 實驗步驟與分析儀器..........................................................30
3-1 化學氣相沉積法成長氮化銦奈米結構...................................................30
3-1.1 自組裝CVD系統.........................................................................30
3-1.2 基板及金屬源準備及前處理..........................................................31
3-1.3 氮化銦奈奈米結構參數設置..........................................................32
3-2 微結構、成分及表面分析..........................................................33
3-2.1 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) ...........33
3-2.2 高解析穿透式電子顯微鏡 (High resolution transmission electron  microscopy,TEM).................................35
3-2.3 粉末X光繞射儀(Powder XRD).............................37
3-2.4 微觀拉曼光譜量測系統(micro-Raman Spectrometer, μ-Raman)  ............38
3-3 單根電性元件製作.........................................39
3-4 鋰電池充放電性質量測.....................................41
 3-4.1 Coin Cell 電池組裝..................................41
 3-4.2 測試方法............................................41
第四章 結果與討論............................................42
4-1 氮化銦奈米線結構及材料分析................................42
4-1.1 掃描及穿透式電子顯微鏡分析..............................42
4-1.2 光致螢光光譜及拉曼光譜分析..............................47
4-2 製程參數改變造成之影響與變化...............................49
4-2.1 製程溫度及工作壓力對結構之影響...........................49
4-2.2 反應氣體流量、製程時間與金催化劑厚度對結構之影響.............55
4-3 以動力學探討不同形貌奈米線成長機制..........................61
4-4 單根氮化銦奈米線電性量測..................................65
4-5 鋰二次電池陰極材料探討....................................70
第五章 結論..................................................81
參考文獻..................................................82

                                    

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校內：2019-08-07公開
校外：2024-01-01公開

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