本論文使用原子層沉積法 (Atomic Layer Deposition, ALD)交互成長多層氧化鋅與氧化鋁薄膜於c-面藍寶石(即α-Al2O3)基板或(100)矽基板上而形成超晶格多層膜結構。為系統化找尋多層磊晶薄膜的成長條件，起始以單材質薄膜蒸鍍,首先分別由三、四個不同取向，七種不同晶面的基板找尋能取得薄膜的平整度最佳者，再由兩種基板中各取一最佳晶面，亦即α-Al2O3(0001), Si(100), 把氧化鋅對氧化鋁的循環數的比例保持在三比二，總週數期數定在為6、15、30，從而得到固定以300總循環數(number of cycles) 亦即分別為[ZnO30/AlOx20]6、[ZnO12/AlOx8]15、[ZnO6/AlOx4]30具超晶格結構的多層膜。經由X光繞射儀(X-ray Diffraction, XRD)分析後，發現週期厚度越厚，雖然繞射訊號越強，但也發現氧化鋁的含量多寡會影響氧化鋅磊晶的形成與否。因此進行另一組實驗，由於所得30:20，總周期數6的在α-Al2O3(0001)上的樣品具有晶體訊號，在此系列中僅取α-Al2O3(0001)為基板，改變氧化鋅與氧化鋁單位週期的循環數的比例，使之延伸到30:10、30:6、30:4、30:3、30:1，希望藉以找出氧化鋅薄膜出現磊晶結構時氧化鋁層的膜厚限閾值。結果發現當循環數比例為30:3與30:1時，薄膜得以磊晶長成，而且此時鋁與氧原子會沿著纖鋅礦結構堆疊，形成一具纖鋅礦結構特性的[ZnO30/AlOx3]6 與及[ZnO30/AlOx1]6的磊晶超晶格。實驗中的超晶格樣品皆藉著低掠角(grazing angle) X光反射率(X-ray Reflectivity, XRR)量測膜厚及各基板與多層膜間的粗糙度，並且由X光繞射儀的2Θ-ω、低掠角繞射(Grazing Incidence X-ray Diffraction, GIXRD)、Phi Scan、Pole Figure等掃描模式來量測氧化鋅及氧化鋁的晶性結構，透過穿透式電子顯微鏡(Transmission Electron Microscope, TEM)觀察不同週期數及不同氧化鋅與氧化鋁比例不同製程所得之晶體晶性的改變。

Attempts were made to grow epitaxial ZnO/AlOx superlattice structures by Atomic Layer Deposition (ALD) at 177˚C on (0001)-oriented sapphire (α-Al2O3) and (100)-oriented Si substrates. In order to systematically search for epitaxial growth conditions, the total numbers of the alternating cycles were first set at 300 and the ratio of the cycle numbers between the ZnO and AlOx kept at 3:2 for each period. The total periods were varied from 6, 15, to 30, ending with three series of superlattices [ZnO30/AlOx20]6, [ZnO12/AlOx8]15, and [ZnO6/AlOx4]30 on both kinds of substrates. Though diffraction signals intensified as the ZnO layer of each period got thicker, increasing numbers of the AlOx cycles would hamper the epitaxy of ZnO. Consequently, due to the sign of crystallinity of [ZnO30/AlOx20]6 on α-Al2O3(0001), another series of experiments were conducted to seek the threshold thickness ratio for epitaxy, the AlOx cycles were reduced from n(ZnO) : n(AlOx) = 30:20 to 30:10, 30:6, 3:4, 30:3 and 30:1. Samples of the cycle ratios of 30:3 and 30:1, namely, the [ZnO30/AlOx3]6 and [ZnO30/AlOx1]6 superlattices , were found to achieve the desired epitaxy, while those of [ZnO30/AlOx4]6 were not, thus putting 30:3 as a threshold ratio. Moreover, the aluminum oxide layers followed their ZnO counterparts to take the Wurtzite structure in epitaxial growth. The thickness and roughness of each layer in the superlattices were measured by X-ray Reflectivity (XRR), while the epitaxial relationships of were determined or tested by combined XRD 2Θ-ω, GIXRD, Φ-Scan, and Pole Figure measurements. High-resolution transmission electron microscope (HRTEM) was also used to investigate the related nanostructures.

論文審定書 i
致謝 ii
摘要 iii
Abstract iv
目錄 v
圖目錄 vii
表目錄 xi
第一章 簡介 1
1-1 半導體超晶格(SEMICONDUCTOR SUPERLATTICES) 1
1-2 材料介紹 3
1-2.1 氧化鋅 3
1-2.2 藍寶石基板 4
1-2.3 矽基板 6
第二章 基本原理與儀器介紹 7
2-1 原子層沉積系統 (ATOMIC LAYER DEPOSITION‚ ALD) 7
2-2 X光繞射儀(X-RAY DIFFRACTOMETER‚ XRD)] 11
2-2.1 XRD簡介 11
2-2.2 X-Ray生成原理 11
2-2.3 布拉格定理(Bragg’s law) 12
2-2.4 Bede儀器介紹 13
2-2.5 常見XRD掃描模式 14
2-3 X光反射率(X-RAY REFLECTIVITY‚ XRR) 18
2-3.1 XRR簡介 18
2-3.2 XRR量測基本原理 19
2-3.3 單層膜系統折射率 25
2-3.4 多層膜系統折射率 29
2-3.5 粗糙度(Roughness) 32
2-3.6 XRR 模擬演示 32
2-4 穿透式電子顯微鏡(TRANSMISSION ELECTRON MICROSCOPE, TEM) 36
第三章 實驗設計與前置作業 38
3-1 實驗設計 38
3-2 基板清洗 41
第四章 實驗結果與分析 42
4-1 實驗A 42
4-1.1 XRR Scan 43
4-2 實驗B 52
4-2.1 XRR Scan 53
4-2.2 XRD scan 59
4-2.3 TEM Analysis 64
4-3 實驗C 72
4-3.1 XRD scan 73
第五章 結論 76
參考文獻 77
附錄 A 83
附錄 B 86

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