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研究生： 洪智晟
Hung, Chih-Cheng
論文名稱： 熱蒸鍍法生長多孔ZnO及Zn2GeO4奈米線
Growth of porous ZnO and Zn2GeO4 nanowires by thermal evaporation
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： 2009
畢業學年度： 97
語文別： 中文
論文頁數： 88
中文關鍵詞： 熱蒸鍍法 、Zn2GeO4奈米線 、多孔ZnO奈米線
外文關鍵詞： porous ZnO nanowires, Zn2GeO4 nanowires, thermal evaporation
相關次數： 點閱：90  下載：3 
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    • 本研究分為兩個部份，其一是分別將硫化鋅奈米線在空氣中氧化以及在銀的催化下熱蒸發硫化鋅粉末，來生成具多孔結構的氧化鋅奈米線。硫化鋅奈米線先藉由熱蒸鍍的方式熱蒸發硫化鋅粉末，在1100℃以及氬氣的氣氛下，隨後在空氣中退火並設定在不同的溫度，硫化鋅奈米線會分別在600-700℃下轉變成硫化鋅-氧化鋅的核-殼奈米線，以及700-750℃下會形成多孔結構的氧化鋅奈米線。較高的退火溫度或是較高的氧氣分壓氣氛會抑制氧化鋅中多孔結構的生成。而在1100℃下熱蒸發硫化鋅粉末可以在溫度750-800℃有沉積銀顆粒的矽基板上直接生成具多孔結構的氧化鋅奈米線而不需要進行退火的過程。由於二氧化硫高於氧化鋅的形成速率，以及在磊晶氧化鋅及硫化鋅介面的不相容結構，此兩種因素對於從硫化鋅奈米線模板在空氣中退火以及藉由銀催化的方式來生成多孔氧化鋅奈米線有相當的幫助，而藉由此兩種方式來生成多孔氧化鋅奈米線的機制將在本文被探討。另一部分則是探討氧分壓及矽基板上的銅膜對於熱蒸鍍法熱蒸發硫化鋅及鍺粉末在1100℃以及氬氣的氣氛下生長Zn2GeO4奈米線的影響。Zn2GeO4奈米線可以在氬氣中650-800℃下在純矽基板上生長，而鍍有銅的基板可以稍微促進Zn2GeO4奈米線的生長，並形成摻雜銅的Zn2GeO4奈米線。這兩種奈米線均是遵循自催化vapor-liquid-solid機制來生長。氧氣於氬氣中比例在3%的時候，會生成GeO2的顆粒而非Zn2GeO4奈米線，顯示若氧分壓較高的時候會促進GeO2的生長。摻雜銅的Zn2GeO4奈米線的PL訊號鋒要比Zn2GeO4奈米線的540nm往藍位移的方向移動15nm左右。

    The growth of porous ZnO nanowires (NWs) by thermal oxidation of ZnS NWs in air and by the Ag catalyst via thermal evaporation of ZnS powder in Ar, respectively, was studied. The ZnS NWs were first synthesized by thermal evaporation of ZnS powder at 1100℃ in Ar. On subsequent annealing in air, the ZnS NWs transformed to porous ZnS-ZnO core-shell NWs and porous ZnO NWs at 600-700℃ and 700-750℃, respectively. Higher annealing temperature or oxygen partial pressure suppressed the formation of porous ZnO NWs. On Ag-coated Si substrates, porous ZnO NWs could directly grow at 750-800℃ by thermal evaporation of ZnS powder at 1100℃ in Ar without subsequent annealing. Two factors, the higher formation rate for SO2 than for ZnO and the incompatible structure at the interface of epitaxial ZnS and ZnO, are beneficial to the formation of porous ZnS NWs from ZnS templates on annealing in air or by the Ag-catalytic growth in Air. The mechanisms for the formation of porous ZnO NWs by the two methods were explored, respectively. Another part of this study focused on the effects of oxygen partial pressure and a Cu layer on Si substrates on the growth of Zn2GeO4 NWs by thermal evaporation of ZnS and Ge powders at 1100˚C in Ar. The Zn2GeO4 NWs could grow on the bare Si substrates at 650-800˚C in Ar, while the deposited Cu layer further enhanced the growth of Zn2GeO4 NWs, forming the Cu-doped Zn2GeO4 NWs. The growth of Zn2GeO4NWs and Cu-doped Zn2GeO4 NWs followed the self-catalyzed vapor-liquid-solid (VLS) process. In Ar/O2(3%), GeO2 particles instead of Zn2GeO4 NWs formed on the Si substrates, revealing that higher oxygen partial pressure in Ar enhanced the growth of GeO2. The photoluminescence (PL) peak of Cu-doped Zn2GeO4 NWs showed a blue shift of about 15 nm as compared with that, 540 nm, of undoped Zn2GeO4 NWs.

    中文摘要 I Abstract III 致謝感言 V 目錄 VI 圖目錄 IX 第一章 前言 1 1.1奈米材料簡介 1 1.1.1奈米表面效應 1 1.1.2量子尺寸效應 3 1.2一維奈米材料 4 第二章 文獻回顧 6 2.1奈米線製作技術 6 2.1.1熱蒸鍍法（thermal evaporation） 6 2.1.2化學氣相沉積法（chemical vapor deposition） 7 2.1.3熱碳還原法（carbothermal reduction） 9 2.1.4水熱法（Hydrothermal） 10 2.1.5雷射蒸鍍（laser ablation） 11 2.1.6模板輔助[50-58]（template-assisted） 11 2.1.7溶膠-凝膠（sol-gel） 11 2.2奈米線生長機制 12 2.2.1 Vapor-Liquid-Solid（VLS） 13 2.2.2 Vapor-Solid（VS） 16 2.2.3 Vapor-Solid-Solid（VSS） 17 2.2.4 Oxide-Assisted Growth（OAG） 18 2.2.5 Solution-Liquid-Solid（SLS） 19 2.3儀器原理 21 2.3.1 掃瞄式電子顯微鏡（Scanning Electron Microscope，SEM） 21 2.3.2 掠角X光繞射儀（Grazing Incidence X-ray Diffractometer，GID） 22 2.3.3 穿透式電子顯微鏡（Transmission Electron Microscope，TEM） 23 2.3.4 X光能量散佈分析儀（Energy Dispersive X-ray Spectrometer，EDS） 24 2.3.5 光激發光譜分析（Photoluminescence，PL） 25 2.4 研究動機 27 第三章 實驗步驟與方法 30 3.1 實驗設備及流程 30 3.1.1 ZnS奈米線試片製備 31 3.1.2 多孔ZnO奈米線試片製備 31 3.1.3 Zn2GeO4奈米線試片製備 31 3.2 基板製備與清洗與TEM試片製備 32 3.2.1基板製備與清洗 32 3.2.2 TEM試片製備 33 3.3 實驗分析 34 3.3.1掃瞄式電子顯微鏡分析 34 3.3.2 低掠角X光繞射分析 34 3.3.3 穿透式電子顯微鏡分析 35 3.3.4 光激發光譜量測 35 第四章 結果與討論 36 4.1 ZnS奈米線的生長 36 4.2 具多孔結構的ZnO奈米線的生成 36 4.2.1 在熱蒸鍍的過程通入O2來生成多孔結構ZnO奈米線 37 4.2.2 ZnS奈米線在空氣中退火來生成多孔結構ZnO奈米線 37 4.2.3 ZnS奈米線在氧氣中退火來生成多孔結構ZnO奈米線 38 4.2.4 在Ag顆粒／Si基板上熱蒸鍍ZnS粉末生成多孔結構ZnO奈米線 38 4.3 多孔結構ZnO的成長模式 39 4.3.1 ZnS奈米線在空氣中退火來生成多孔結構ZnO奈米線 39 4.3.2在Ag顆粒／Si基板上熱蒸鍍ZnS粉末來生成多孔結構ZnO奈米線 40 4.3.3多孔狀結構ZnO的PL（Photoluminescence）分析 41 4.4 Zn2GeO4奈米線的生長 41 4.4.1 Zn2GeO4奈米線在Ar氣氛下及Ar /O2氣氛下的生長 41 4.4.2 Zn2GeO4奈米線在Ar氣氛下Cu膜／Si基板上的生長 42 4.4.3 Zn2GeO4奈米線及摻雜Cu的Zn2GeO4奈米線的PL 43 第五章 結語 45 參考文獻 47 附錄 88

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