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研究生： 林柏凡
Lin, Po-Fan
論文名稱： In摻雜及製程條件對ZnO奈米板生長及光學性質影響之研究
Effects of In doping and processing parameters on the growth and optical properties of ZnO nanodisks
指導教授： 林文台
Lin, Wen-Tai
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： 2005
畢業學年度： 93
語文別： 中文
論文頁數： 95
中文關鍵詞： 氧化鋅 、氧化銦 、奈米 、奈米板 、製程條件 、光學性質
外文關鍵詞： nanodisk, nano, In2O3, ZnO
相關次數： 點閱：47  下載：2 
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    • 中文摘要
    本研究將氧化鋅粉末摻雜氧化銦，並以熱碳還原法在900-1000℃通入氬氣製作銦摻雜的氧化鋅奈米板，並研究冷卻速率、氬氣中的氧分壓以及（氧化鋅，氧化銦）/碳粉混合粉末中碳粉濃度等製程參數的影響。在900-970℃可發現由六個{10-10}面圍成的六邊形氧化鋅奈米板，以及由六個{10-10}與六個{11-20}面所包圍的十二邊形氧化鋅奈米板。在1000℃則僅有六邊形的氧化鋅奈米板存在。生成溫度及銦的摻雜是影響氧化鋅奈米結構外型的主要因素。在氬氣中生長並空冷的氧化鋅奈米板，由於氧空缺及銦摻雜所造成的缺陷，導致光學分析中的綠光強度增加。爐冷製程使得氧化鋅奈米板中的氧空缺能在緩慢降溫過程達到室溫的氧空缺平衡濃度，因此比空冷製程的奈米板具有較少的氧空缺，而有較高的紫外光/綠光相對強度。然而爐冷後的氧化鋅奈米板由於生成非晶質，導致紫外光絕對強度下降。在氧化鋅奈米板生長及爐冷中，於氬氣中添加0.5-10%的氧濃度，能顯著改善紫外光絕對強度以及紫外光/綠光的相對強度。這是由於通氧後減少氧空缺，奈米板尺寸較大，及促進氧化鋅奈米板的生長。當氧濃度高於25%則無氧化鋅奈米板生長。紫外光/綠光的相對強度在氧濃度0.5-1%逐漸上升，在2-10%則漸差。這是由於在氧化鋅奈米板生長過程的氬氣中添加氧能減少氧空缺，然而過量的氧濃度則會造成鋅空缺使綠光增強。在（氧化鋅，氧化銦）/碳粉的混合粉末中，過高的碳粉濃度會降低紫外光/綠光相對強度，這是由於過多的碳粉會使氧化鋅奈米板尺寸減小，並在氧化鋅奈米板中形成較多的CO2。

    Abstract
    The growth and optical properties of In-doped ZnO nanodisks grown via carbothermal reduction of ZnO/In2O3 powders at a temperature of 900-1000℃ in flowing Ar as functions of cooling rate, oxygen partical pressure into the Ar flow, and carbon concentration in the (ZnO,In2O3)/carbon powders were studied. The hexagonal ZnO nanodisks enclosed by {10-10} facets and twelve-sided ones enclosed by {10-10} and {11-20} facets were grown at a temperature of 900-970℃. At 1000℃ only hexagonal nanodisks were formed. The growth temperature and In doping act as important roles in determining the morphology of ZnO nanostructures. For ZnO nanodisks grown in Ar and then subjected to air cooling green emission was enhanced due to the oxygen vacancies and defects induced by In doping. Furnace cooling allowed the equilibrium concentration of oxygen vacancies at room temperature to be readily reached, resulting in the decrease of oxygen vacancies in the ZnO nanodisks as compared with the air-cooled samples, and thus increased the ultra-violet (UV)/green emission ratio. However, the intensity of UV emission was concurrently decreased because of the formation of amorphous zinc oxides in the samples. Upon growth and subsequent furnace cooling in the Ar/O2 flow with the O2 concentration in the range of 0.5-10% the UV intensity and UV/green ratio were significantly increased. The reasons can be attributed to the decrease of oxygen vacancies, the larger grain size, and enhanced growth of ZnO nanodisks. With the O2 concentration above 25% no ZnO nanodisks were grown. The UV/green ratio first increased with the O2 concentration in the range of 0.5-1% and then decreased in the range of 2-10%. The introduction of O2 in the Ar flow during growth can decrease the oxygen vacancies in the ZnO nanodisks; however, higher O2 concentration can induce the formation of zinc vacancies and thus enhance green emission. Higher carbon concentration in the (ZnO,In2O3)/carbon powders decreased the UV/green ratio of ZnO nanodisks because of the reduction of grain size and the formation of more CO2.

    本文目錄 中文摘要....................................................I Abstract .................................................... II 誌謝感言………………………………………………………………… III 本文目錄...................................................IV 表目錄…………………………………………………………………..VII 圖目錄…………………………………………………………………..VII 本文 第一章奈米材料簡介........................................1 前言....................................................1 1. 奈米材料............................................1 1.1 奈米表面效應....................................2 1.2 量子尺寸效應（Quantum Size Effect） ...............3 1.3 量子穿隧效應....................................4 第二章基本理論..............................................6 2-1 文獻回顧............................................6 2-1-1 氧化鋅薄膜之文獻回顧..............................6 2-1-1-1 直流或射頻濺鍍法（D. C or R. F Sputtering） ......6 2-1-1-2 真空蒸鍍法（vacuum evaporation） ...............6 2-1-1-3 有機金屬化學氣相沉積（MOCVD）..............7 2-1-1-4 溶膠-凝膠（Sol-gel method）....................7 2-1-2 氧化鋅奈米材料的應用與製法........................8 2-1-2-1 熱蒸發法（thermal evaporation method）...........8 2-1-2-2 水熱法（Hydrothermal Growth method）.........10 2-1-2-3 化學氣相沉積法（Chemical Vapor Deposition, CVD） .............................................11 2-1-3 氧化鋅奈米結構生長機制...........................12 2-1-3-1VLS 生長機制（Vapor –Liquid–Solid growth mechanism）..................................12 2-1-3-2 VS 生長機制（Vapor –Solid growth mechanism）..13 2-1-4 氧化鋅晶體結構與特性.............................13 2-1-4-1 氧化鋅晶體結構..............................13 2-1-4-2 氧化鋅生長趨勢..............................15 2-1-5 氧化銦晶體結構...................................15 2-2 儀器原理............................................16 2-2-1 掃瞄式/穿透式電子顯微鏡（Scanning/Trasmission Electron Microscope） .....................................16 2-2-2 能量散佈光譜儀（Energy Dispersive Spectrometer，EDS）17 2-2-3 掠角X 光繞射法（Grazing Incidence X-ray Diffraction, GID） .................................................17 2-2-4 光學性質分析（光子激發光譜儀分析，photoluminescence， PL） ............................................18 2-2-5 電子能譜儀分析（ESCA）...........................20 2-3 實驗研究動機.......................................22 第三章實驗步驟與方法......................................23 1.實驗流程圖...........................................23 2.清洗試片.............................................24 3.粉末配製.............................................24 4.以高溫爐製作試片.....................................24 5.微結構分析SEM 01002 5-35 .............................25 6.微結構分析TEM 01002 5-37 ...........................25 7.微結構分析EDS .......................................25 8.低掠角X 光繞射分析GID...............................26 9.激發光譜分析PL ......................................26 10.電子能譜儀分析ESCA.................................26 第四章結果與討論..........................................27 4-1-1 銦摻雜對氧化鋅微結構之影響.......................27 4-1-2 銦摻雜氧化鋅奈米板之生長機制.....................28 4-1-3 銦摻雜的氧化鋅奈米板之光學性質...................30 4-2 碳含量對氧化鋅奈米板生長溫度及微結構的影響.........30 4-3 冷卻速率（Cooling Rate）對氧化鋅奈米板微結構及光學性質 的影響.............................................31 4-4 在製程中摻雜氧氣對氧化鋅奈米板微結構及光學性質的影響 ...................................................33 4-4-1 摻雜氧氣對氧化鋅奈米板微結構的影響............33 4-4-2 摻雜氧氣對氧化鋅奈米板光學性質的影響.........34 4-4-3 碳含量對氧化鋅奈米板光學性質的影響...........35 4.5 氧化鋅奈米板的ESCA 分析...........................36 第五章結論................................................38 參考文獻...................................................39

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