臺灣博碩士論文加值系統

近年來，隨著奈米顆粒在矽基奈米結構材料的強發光現象被發現後，此類材料在光電應用領域上備受矚目。其中，以離子束合成法在二氧化矽薄膜中合成矽奈米顆粒最為普遍，乃因採取離子束合成法來控制實驗條件較為容易，且與半導體製程相容性甚佳。而接續發展的離子共佈植法，即依序佈植矽、碳離子，不只改變基材內部結構，還激發出多光源組合成的白光，為未來的光電材料開發更多應用價值。然而，有關矽、碳離子佈植二氧化矽材料的光致發光（photoluminescence，以下簡稱 PL）機制仍有待釐清，因此，本論文目標為全盤地研究矽、碳離子佈植二氧化矽薄膜經由不同的離子佈植與後續熱處理程序後，其微結構與 PL 的性質變化；另外，也比較不同佈植方式的發光性質差異。本研究以熱成長法成長於矽基板上之二氧化矽作為基質材料，矽與碳離子在室溫下以單獨或共佈植的方式植入二氧化矽薄膜之中，後續分析是以螢光光譜量測矽、碳及矽、碳共佈植二氧化矽薄膜之 PL 性質，結果顯示矽離子佈植二氧化矽薄膜之 PL 光譜出現三種不同峰值，分別為 310 nm、450 nm 及 650 nm，三者之發光來源均屬於材料內部缺陷，其中前兩者稱為氧空乏中心，後者則為未橋接氧空洞中心。與矽佈植不同的是，碳與矽-碳共佈植卻分別觀察到由 410 nm 的藍光、520 nm 的綠光及 720 nm 的紅光等發光波段，即三原色組合成的白光光源，而這三道光源係分別來自於矽-碳鍵結、碳-碳類石墨結構及矽奈米晶粒所貢獻，且其峰值強度皆隨退火溫度改變而有明顯地變化，因此可以推論矽、碳離子佈植二氧化矽材料內部受熱處理時，可能引發不同的熱效應，包括：（一）缺陷修復、（二）佈植離子鍵結以及（三）奈米晶粒的生成，導致 PL 性質的改變。此外，本研究也更進一步地使用精密儀器來分析材料的顯微結構、化學鍵結與元素分佈。

In recent years, the potential applications of Si-based nanostructured materials in the areas of optoelectronic devices have gained much attention especially since the discovery of strong luminescence from semiconductor nanoparticle-containing materials. Ion beam synthesis has been considered as one of the most promising methods to form nanoparticles due to its great processing compatibility with current semiconductor manufacturing technology as well as its excellent controllability in implantation process parameters. The method of sequential implantation of Si+ and С+ ions into SiO2 not only changes the structure of internal matrix but also excites white light emission coupling from multiple luminescent centers. Furthermore, this method creates a glorious prospect for the applications of Si-based optoelectronic materials. However, the mechanisms of photoluminescence (PL) originating from Si+/C+-implanted SiO2 are still unclear and need to be clarified. Thus, this study aims to thoroughly investigate the effects of different parameters of ion implantation and post-annealing on microstructures and PL characteristics in the Si+/C+ implanted SiO2 films. A comparative analysis was also conducted to clarify the difference of optical properties between the Si+ and Si+/C+ implanted SiO2 films. In this study, thermally-grown SiO2 films on Si substrates were used as the matrix materials. The Si+ ions and C+ ions were separately implanted into the SiO2 films at room temperature. The PL characteristics of the Si+/C+ implanted SiO2 films were analyzed using a fluorescence spectrophotometer.
The results revealed that the distinct PL peaks were observed at approximately 310, 450 and 650 nm in the Si+ implanted SiO2 films, which can be attributed to the defects, so called oxygen deficiency centers (ODCs) and Non-Bridging Oxygen Hole Center (NBOHC), in the Si+ implanted SiO2 materials. In contrast to the Si+ ion implantation, the SiO2 films which were sequentially implanted with Si+ and C+ ions and annealed at 1100°C can emit white light corresponding to the PL peaks located at around 410, 520 and 720 nm, those can be assigned to the Si-C bonding, C-C graphite-like structure (sp2), and Si nanocrystals, respectively. Moreover, the intensity of PL peaks varied with post-annealing temperature, which implied that thermal annealing treatment could induce (1) defect recovery, (2) bonding of implanted ions with matrix atoms and (3) nanocrystal formation which would influence the PL luminescence properties. Moreover, this study attempted to establish a correlation among optical properties, microstructures, and bonding configurations of the Si+/C+ implanted SiO2 films using some sophisticated experimental equipment.

目錄
摘要 i
Abstract ii
表目錄 vii
圖目錄 viii
第一章 前言 1
第二章 文獻回顧 4
2.1 矽基奈米材料的發展歷史 4
2.2 奈米顆粒製備法 6
2.2.1 離子束合成法 6
2.2.2 射頻-磁控濺射 8
2.2.3 試樣的元素分佈及品質 9
2.3 離子佈植二氧化矽材料的發光特性 11
2.4 離子佈植二氧化矽材料的發光機制 13
2.4.1 量子侷限效應（Quantum Confinement Effect） 14
2.4.2 奈米結構材料的缺陷 16
2.4.3 碳離子佈植的鍵結行為 19
2.5 退火熱處理的影響 20
第三章 實驗原理與方法 24
3.1 SRIM 電腦模擬計算程式 24
3.2 基質材料製備 26
3.3 退火熱處理 28
3.4 特性分析 29
3.4.1 螢光光譜儀分析 29
3.4.1 X射線光電子能譜儀 35
3.4.2 二次離子質譜儀 38
3.4.3 拉曼光譜儀 42
3.4.4 穿透式電子顯微鏡 46
第四章 結果與討論 49
4.1 SRIM 蒙地卡羅電腦模擬程式 50
4.2 矽離子佈植二氧化矽 54
4.3 碳離子佈植二氧化矽 58
4.4 低劑量矽-碳離子共佈植二氧化矽 62
4.5 高劑量矽-碳離子共佈植二氧化矽 66
4.6 綜合討論 69
4.6.1 碳相關結構 69
4.6.2 退火時間對PL的影響 71
4.6.3 不同佈植試片對矽奈米晶粒成核之差異 74
4.6.4 實驗參數改變對材料發光性質的影響 76
第五章 結論與未來工作 79
5.1. 結論 79
5.2. 未來建議 81
參考文獻 82

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