本論文利用反應性射頻磁控濺鍍法在室溫下於SiO2/Si
基板上製備氧化鋅(ZnO)薄膜， 並藉由熱退火處理來改善其
發光特性。在薄膜物性研究方面， 藉由SEM 及XRD 分析，
探討氧化鋅薄膜於不同熱退火處理後微結構之變化，並利用
化學分析電子光譜儀(ESCA)分析薄膜化學組態。在光學性質
方面， 藉由光致螢光光譜儀(PL)， 分析在不同熱退火條件處
理後所得薄膜之光激發光特性。
由實驗結果得知，在不同熱退火處理後薄膜內部化學組
態有不同的變化；氧化鋅薄膜的光激發光特性會受到薄膜內
部化學組態影響而得到不同波段之特性發光。在空氣900℃
下退火， 薄膜內部氧空缺比例最高， 其綠光特性最佳，而在
氧氣900℃ 下退火其O-Zn 鍵結比例最高，薄膜的紫外光特性
為最佳。

In this study, the reactive rf magnetron sputtering was used to deposit zinc oxide (ZnO) thin films on SiO2/Si substrate at room temperature. The thermal treatment procedure was carried out to improve the luminescence characteristics of ZnO thin films. The physical characteristics of ZnO thin films with different post
annealing process were obtained by the analyses of XRD and SEM. The electron spectroscopy for chemical analysis (ESCA) was used to analyze the chemical states of ZnO thin films. In optical properties, the photoluminescence spectrometer was used to measure the photoluminescence characteristics (PL).
According to the results of experiments, the chemical states of ZnO thin films were changed after different post annealing. The photoluminescence characteristics were obtained at different wavelength, and the results indicated that they were affected by the chemical states of ZnO thin films. With 900℃ annealing, the strongest green emission and UV emission intensity can be obtained under the air ambient and the oxygen ambient, respectively. The reason was due to the variation of the proportion of oxygen vacancies and O-Zn bond within the ZnO thin films.

摘要............................................................................ Ⅰ
目............................................................................ Ⅲ
圖表目錄.................................................................... Ⅵ
第一章 前言.............................................................. 1
第二章 理論分析....................................................... 6
2.1 電致發光元件..................................................................... 6
2.1-1 電致發光元件之結構與動作原理............................ 7
2.1-2 雙絕緣層EL 元件結構與各層材料的需求.............. 8
2.2 發光.................................................................................... 11
2.2-1 發光之簡介.............................................................. 11
2.2-2 發光中心之種類與原理........................................... 13
2.3 螢光材料............................................................................. 14
2.3-1 螢光材料之簡介....................................................... 14
2.3-2 螢光材料的種類與應用........................................... 15
2.4 氧化鋅薄膜......................................................................... 18
2.4-1 氧化鋅之簡介.......................................................... 18
2.4-2 氧化鋅薄膜的發光機制........................................... 19
2.4-3 氧化鋅薄膜的光學性質........................................... 22
2.5 薄膜沈積原理..................................................................... 22
2.5-1 沈積現象.................................................................. 22
2.5-2 薄膜表面及截面結構............................................... 23
2.6 反應性射頻磁控濺鍍原理.................................................. 23
2.6-1 直流輝光放電.......................................................... 24
2.6-2 磁控濺射.................................................................. 24
2.6-3 射頻濺射.................................................................. 25
2.6-4 反應性濺射.............................................................. 25
第三章 實驗.............................................................. 27
3.1 薄膜的製作......................................................................... 27
3.1-1 基板的清洗步驟....................................................... 27
3.1-2 濺鍍系統與薄膜沈積............................................... 28
3.2 熱處理製程......................................................................... 29
3.3 薄膜特性分析..................................................................... 29
3.3-1 X 光繞射(X-Ray Diffraction, XRD)分析................... 29
3.3-2 掃描式電子顯微鏡(Scanning Electron Microscopy,
SEM)分析................................................................. 30
3.3-3 原子力顯微鏡(Atomic Force Microscopy, AFM)分析
.................................................................................. 30
3.3-4 化學分析電子光譜儀(Electron Spectroscopy for
Chemical Analysis，ESCA)分析............................... 31
3.3-5 光致螢光光譜儀(Photoluminescence Spectrometer,
PL)分析.................................................................... 31
第四章 結果與討論................................................... 33
4.1 室溫沈積之氧化鋅薄膜...................................................... 33
4.1-1 沈積速率.................................................................. 33
4.1-2 薄膜表面結構與粗糙度........................................... 34
4.1-3 薄膜結晶性分析....................................................... 34
4.1-4 PL 量測.................................................................. 35
4.2 不同溫度熱退火處理之影響.............................................. 36
4.2-1 薄膜表面結構與粗糙度........................................... 36
4.2-2 薄膜結晶性分析....................................................... 37
4.2-3 薄膜化學組態分析................................................... 38
4.2-4 PL 量測.................................................................. 39
4.3 不同氣氛熱退火處理之影響.............................................. 40
4.3-1 薄膜表面結構.......................................................... 41
4.3-2 薄膜結晶性分析....................................................... 41
4.3-3 薄膜化學組態分析................................................... 42
4.3-4 PL 量測.................................................................. 42
4.4 不同持溫時間熱退火處理之影響....................................... 43
4.4-1 薄膜表面結構.......................................................... 43
4.4-2 薄膜結晶性分析....................................................... 43
4.4-3 PL 量測.................................................................. 44
第五章 結論.............................................................. 45
參考文獻.................................................................... 46
圖表目錄
圖1-1 平面顯示器種類.............................................................. 53
圖1-2 EL 元件的種類及特性..................................................... 54
圖2-1 薄膜型EL 元件的基本構造圖......................................... 55
圖2-2 EL 元件的發光原理......................................................... 55
圖2-3 EL 元件加偏壓時電子撞擊激發之能帶圖....................... 56
圖2-4 雙絕緣層EL 元件之等效電路......................................... 56
圖2-5 以矽做為基板之EL 元件................................................ 57
圖2-6 由紫外光區至紅外光區的電磁光譜................................ 57
圖2-7 激發能在發光材料中的吸收與轉換................................ 58
圖2-8 氧化鋅(ZnO)結構............................................................. 58
圖2-9 在固定壓力350mtorr 下，以脈衝雷射沉積在兩種不同基
板上的ZnO 所量測到的PL 光譜，(a) (001)之sapphire，
(b) (100)之p-type 的Si.................................................... 59
圖2-10 自由載子濃度、氧空缺及綠光PL 隨著不同退火溫度的
變化情形.......................................................................... 60
圖2-11 E. G. Bylandern 所提出氧化鋅之缺陷能階圖................. 61
圖2-12 B. Lin 所提出氧化鋅之缺陷能階圖................................ 61
圖2-13 薄膜沈積步驟，(a)成核、(b)晶粒成長、(c)晶粒聚結、(d)
縫道填補、(e)薄膜的沉積............................................... 62
圖2-14 濺鍍參數對沈積薄膜之影響............................................ 62
圖2-15 直流輝光放電結構與電位分佈圖.................................... 63
圖2-16 平面型圓形磁控之結構圖............................................... 64
圖2-17 平面磁控結構及電子運動路徑........................................ 64
圖2-18 反應性濺射之模型........................................................... 65
圖3-1 射頻磁控濺鍍系統構造圖............................................... 66
圖3-2 射頻磁控濺鍍系統操作之流程圖.................................... 67
圖3-3 光致螢光光譜實驗系統................................................... 68
圖4-1 室溫下沈積氧化鋅一小時之SEM 剖面圖....................... 69
圖4-2 室溫下沈積氧化鋅一小時之SEM 表面圖....................... 69
圖4-3 室溫下沈積氧化鋅薄膜之AFM 之3D 圖....................... 70
圖4-4 室溫下沈積氧化鋅薄膜之XRD 圖.................................. 70
圖4-5 室溫下沈積氧化鋅薄膜之PL 圖..................................... 71
圖4-6 不同溫度(200~500℃)空氣熱退火處理後之氧化鋅薄膜
之SEM 表面圖................................................................ 72
圖4-7 不同溫度(600~900℃)空氣熱退火處理後之氧化鋅薄膜
之SEM 表面圖................................................................ 73
圖4-8 不同溫度(600~900℃)空氣熱退火處理後氧化鋅薄膜之
AFM 量測之3D 圖.......................................................... 74
圖4-9 不同溫度(RT~500℃)空氣熱退火處理後氧化鋅薄膜之
XRD 圖............................................................................ 75
圖4-10 不同溫度(600~900℃)空氣熱退火處理後氧化鋅薄膜之
XRD 圖............................................................................ 76
圖4-11 不同溫度(200~900℃)空氣熱退火處理後氧化鋅薄膜之
XRD-ZnO(002)繞射峰強度統計圖................................... 77
圖4-12 氧化鋅薄膜經RTA600℃空氣退火後之ESCA 分析的
Survey 圖......................................................................... 77
圖4-13 氧化鋅薄膜經RTA600℃空氣退火處理後之ESCA 分析
的Multiplex 圖................................................................ 78
圖4-14 氧化鋅薄膜經RTA600℃空氣退火後之ESCA 分析的
Multiplex 圖使用Gaussian fit 後的O 1s peak 結果........ 78
圖4-15 不同溫度(600℃~900℃)空氣熱退火處理的氧化鋅薄膜其
O 1s 的相對面積關係圖.................................................. 79
圖4-16 不同溫度(RT~500℃)空氣熱退火處理後氧化鋅薄膜之PL
圖..................................................................................... 80
圖4-17 不同溫度(600~900℃)空氣熱退火處理後氧化鋅薄膜之
PL 圖............................................................................... 81
圖4-18 不同氣氛900℃熱退火處理後氧化鋅薄膜之SEM 圖.... 82
圖4-19 不同溫度(600~900℃)氧氣氛熱退火處理後氧化鋅薄膜
之SEM 表面圖................................................................ 83
圖4-20 不同溫度(600~900℃)真空氣氛熱退火處理後氧化鋅薄
膜之SEM 表面圖............................................................ 84
圖4-21 不同氣氛900℃熱退火處理後氧化鋅薄膜之XRD 圖..... 85
圖4-22 不同氣氛900℃熱退火處理後氧化鋅薄膜O 1s 的相對面
積關係圖.......................................................................... 86
圖4-23 不同氣氛900℃熱退火處理後氧化鋅薄膜之PL 圖........ 87
圖4-24 不同持溫時間(15-90mins)空氣氣氛熱退火處理後氧化鋅
薄膜之SEM 表面圖......................................................... 88
圖4-25 不同持溫時間(15-90mins)空氣氣氛熱退火處理後氧化鋅
薄膜之XRD 圖................................................................ 89
圖4-26 不同持溫時間(15-90mins)空氣氣氛熱退火處理後氧化鋅
薄膜之PL 圖................................................................... 90
表一 交流電薄膜電致發光元件之優缺點(ACTFEL).................. 91
表二 低電壓彩色螢光粉的特性.................................................. 91
表三 二六族化合半導體能隙表.................................................. 92
表四 氧化鋅(ZnO)基本特性表................................................... 93
表五 反應性射頻濺鍍系統沈積ZnO 薄膜之系統參數.............. 94
表六 氧化鋅(ZnO)的JCPDS Data............................................... 95
表七 鋅(Zn)的JCPDS Data ......................................................... 95

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