由於鍺奈米顆粒獨特的光學性質，以及在矽基光電子元件應用上的潛力，近年來大量的研究投入於合成鍺奈米顆粒，及其他 IV、VI族元素之半導體奈米結構材料於非晶質介電層之中。然而，也由於該等半導體奈米結構材料的組成、鍵結、以及缺陷形成等行為相當複雜，各研究團隊間的結果也常出現互異的現象，致使得其發光機制仍有待更進一步的探討。有鑑於此，在本論文研究中，係利用離子佈植技術於二氧化矽薄膜中植入鍺元素，並加以退火熱處理製程，合成鍺奈米顆粒，以製備常溫下具有強光致發光特性的奈米結構材料。同時，並藉由改變佈植劑量、退火溫度、以及熱處理的外在氣體氛圍，觀察不同的製程參數下，材料光致發光特性的變化。所使用的特性分析儀器包括有：穿透式電子顯微鏡、傅立葉轉換紅外光譜、以及拉曼光譜儀，藉以分析材料內部的顯微結構與特殊鍵結。研究結果顯示：（一）隨著鍺奈米顆粒的生成，其發光強度會有顯著的上升，且峰值的位置與奈米顆粒的尺寸以及製程參數無關；由此說明發光的機制並非來自於量子侷限效應，而是由於鍺奈米顆粒與基材介面的氧空乏中心缺陷合成所致。（二）退火氣體中所含有的氧氣，會導致基材中鍺元素的氧化，生成非劑量型的二氧化鍺奈米顆粒（GeOx，0 < x < 2）。GeOx奈米顆粒不但會影響低溫下的光譜強度，鍺氧之間的鍵結形成亦會減少高溫下鍺奈米顆粒的數量，導致使用不同退火氣體的測試間，在 800 oC 以下光致發光強度的差異。（三）離子佈植的製程中，會在材料內部生成大量的缺陷，而非輻射性復合的缺陷將大幅降低材料的發光強度。（四）奈米顆粒與基材的介面特性會影響發光中心的合成數目，因此具備整合性界面的小尺寸與單純鍺元素構成的鍺奈米顆粒會擁有較佳的發光特性。總結而言，藉由選用適當的佈植劑量以及熱處理的外在氣體，可避免鍺元素在低溫時的氧化與粗化現象，製備具有良好粒徑分佈的鍺奈米顆粒，並獲致最佳的發光強度。

Due to the unique optical properties as well as the potential in developing silicon-based optoelectronic device applications, enormous studies have been conducted investigating on the synthesis of group IV and VI nanoscale semiconductor materials in amorphous dielectric materials. However, the possible origin of the luminescence induced by these nanoscale semiconductor materials are indefinite and still in debate because of the complex mechanisms and inconsistent results reported by various research teams. In this study, ion implantation and following annealing process were employed to synthesize Ge nanoparticles in SiO2 thin film in order to achieve a strong room-temperature luminescence originating from nanostructure material. By changing the implantation dose, annealing temperature, and annealing ambient gas, we can clarify the correlations between photoluminescence properties and experimental parameters. Furthermore, transmission electron microscopy and Fourier transform infrared spectroscopy, Raman spectroscopy was employed to examin the microstructure and specific chemical bonding configurations of Ge nanoparticles. The results revealed that the luminescent characteristics originate from the oxygen deficient defects at the interface between Ge nanoparticles and SiO2 matrix. Moreover, according to the independence of peak position on nanoparticle size distribution, we can exclude the possibility of quantum confinement effect which dominates this luminescence band in Ge-implanted SiO2 film. Also, the oxygen gas existing in high-temperature annealing ambient would cause the oxidation of germanium. The formation of nonstoichiometry germanium oxide (GeOx) nanoparticles leads to an improvement in low temperature PL intensity, and decreases available germanium content. Based on the oxidation degree as well as the number of Ge nanoparticles, PL spectra showed

an inconsistent trend in different gas atmospheres. In addition, a large number of defects were produced by the collision of incident ions during the ion implantation process. Non-radiative recombination defects significantly reduce the emission intensity of material. Due to the fact that the luminescence centers are dependent on the interface between nanopariticles and SiO2 matrix, smaller and unoxidized Ge nanoparticles have a much better photoluminescence efficiency than GeOx particles do. In conclusion, particle size, density, and oxidation degree of Ge nanoparticles should play a crucial role in determining the effective intensity of the luminescence. Therefore, by optimizing the implantation dose, annealing temperature, and annealing ambient gas, we can suppress the oxidation and coalescence of Ge nanoparticles, so as to enhance photoluminescence intensity in the case of well separated small Ge nanoparticles. These results can be a useful guidance in light emission in UV-blue region from Ge-implanted SiO2.

中文摘要 i
英文摘要 ii
致謝 iv
表目錄 viii
圖目錄 ix
第一章 前言 1
第二章 文獻回顧 3
2.1 矽基奈米結構材料的發展歷史 3
2.2 鍺離子佈植二氧化矽材料的優勢 4
2.3 鍺離子佈植二氧化矽的各種發光機制理論 5
2.3.1 量子侷限效應 6
2.3.2 奈米結構材料內部的缺陷 7
2.4 鍺奈米顆粒的合成技術 15
2.4.1 試樣的元素分佈及品質 16
2.4.2 製程對材料內部缺陷的影響 20
2.4.3 退火熱處理的影響 22
第三章 實驗原理與方法 25
3.1 離子佈植 25
3.2 SRIM 電腦模擬計算程式 27
3.3 特性量測 29
3.3.1 拉曼光譜系統 29
3.3.2 二次離子質譜儀 34
3.3.3 穿透式電子顯微鏡 37
3.3.4 螢光光譜儀分析 42
3.3.5 傅立葉轉換紅外線光譜分析儀 48
3.4 退火熱處理製程 51
第四章 結果與討論 53
4.1 離子佈植元素分佈 53
4.1.1 SRIM 蒙地卡羅電腦模擬程式 54
4.1.2 SIMS 鍺元素分佈結果 57
4.2 光學特性分析 60
4.2.1 退火參數對 PL 光譜的影響 60
4.2.2 佈植劑量對 PL 光譜的影響 63
4.2.3 退火氣體對 PL 光譜的影響 67
4.2.4 基材差異對 PL 光譜的影響 74
4.2.5 本節整理 77
4.3 顯微結構分析 78
4.3.1 熱處理製程對顯微結構的影響 78
4.3.2 基材與退火氛圍對顯微結構的影響 86
4.3.3 奈米顆粒的介面特性 90
4.4 傅立葉轉換紅外線光譜分析 92
4.5 拉曼光譜分析 94
4.6 綜合討論 98
4.6.1 鍺佈植二氧化矽材料之發光中心 98
4.6.2 鍺元素在基材中的氧化行為 99
4.6.3 鍺奈米顆粒的生成條件與介面特性 100
4.6.4 製程參數與 PL 光譜的關係 100
第五章 結論 102
第六章 建議 104
參考文獻. 106

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