氧化鋅，由於其高exiton binding energy (60 meV)及寬能帶(~3.4 eV)之特性，使其具有在室溫下發紫外光之能力。而其易於成長的特性，及可於多數酸及鹼性溶液下蝕刻的特性，也使其易於應用於製造奈米元件。電化學沉積(Electrodeposition)是一種可在低溫下直接成長高品質薄膜的方法，改變電解液及其濃度，沉積溫度，電流密度亦改變生長晶體之形狀及其它特性。在本論文中，先使用電化學方法將ZnO成長於n型Si基板上，利用不同的溫度，電解液濃度及電流密度研究其特性，發現於不同成長溫度下之樣品於X光繞射儀量測下會有不同的材料沉積在基板上。成長之薄膜具有原來之電解液硝酸鋅，金屬鋅，及氧化鋅之結構。在沉積出只具有氧化鋅結構的薄膜後，利用巨觀之光激光譜儀檢視其發光現象，幾乎沒有發現紫外光，經過熱處理於不同溫度及氣體下，情況依舊未見改善。文獻上，熱處理成長金屬鋅或離子佈植鋅於氧化材料中，可得到非常理想之紫外光強度，因此，利用電化學沉積方法加上適當的電流密度可於30度下成長金屬鋅-氧化鋅結構的特性，將其做熱處理，於光激光量測下可發現強度非常強之紫外光。本論文發現由金屬鋅所氧化而成之氧化鋅可發出強烈之紫外光，此一方法不僅可以快速製造出可放出紫外光之氧化鋅，也提供了一個電化學沉積之氧化鋅發光不足及無法發出紫外光的解決方法。此外，由文獻記載，金屬鋅氧化而成之氧化鋅發出的紫外光波長會隨著加熱之溫度而變化，以往文獻中皆記載是由量子侷限效應所致，由於氧化鋅大小並不在量子侷限效應之範圍中，在此，提供了此波長位移是由鋅的大小所影響之論點。傳統上，電化學沉積ZnO不易直接沉積於p型基板上，在此，以鍍鋁於p型Si基板之背電極上，可以較小電位及調整不同電流密度成長出不同形狀及品質之氧化鋅。近年來，由於金屬在奈米化時有不同之特殊性質，因此可應用在多項領域中。在此，使用電化學方法成長金及鉑之奈米顆粒增加氧化鋅之光催化能力。首先，將奈米金與鉑顆粒使用電化學沉積並觀察其特性，比較電化學沉積金與鉑，發現金比較會以顆粒而鉑會以聚合的形式生長。接著將金之奈米顆粒成長於氧化鋅藉以提高光催化能力，此種方法不僅快速亦可達到改善的效果。而由於電化學沉積之氧化鋅於膜較厚的情況下會以多孔的結構為主，因此在此將金與鉑之電解液個別加入硝酸鋅中一起成長，可觀察到金-氧化鋅及鉑-氧化鋅的結構，此結構可証明金, 鉑及氧化鋅可個別成長而其多孔的性質更可增加光催化的面積而使光催化能力提高。
雖然矽是最主要的半導體材料，但其能帶結構屬於間接型能帶，因此，無法應用於光電元件上，然而，直至1990年，發現發光能量位於可見光範圍可由電化學蝕刻之多孔矽產生，而其發光機制目前並不清楚，但可分為兩種型式:量子侷限效應及表面能態。雖然可以發出高效率之可見光，但波長易受外在環境所影響而位移，在此論文中使用蝕刻前浸泡化學溶液，蝕刻時加入化學溶液及蝕刻後浸泡化學溶液來鈍化多孔矽，使其不易受環境影響。

Zinc oxide (ZnO) has higher exiton binding energy (60 meV) and high band gap (~3.4 eV) that can provide efficient ultraviolet (UV) light at room temperature (RT). The easily etched in acids and alkalis that provides the fabrication of small-size ZnO-based devices. Electrodeposition is the growth method that can deposit high quality film and modify the characterizations of film by changing its deposition electrolyte concentration, temperature, and current density.
Firstly, the ZnO is deposited on n-type Si substrate by electrodeposition by different deposited temperature, electrolyte concentration, and current density. The deposited films contain zinc nitrate, metal Zn, and ZnO while electrodeposited at various deposition parameters. For the deposited film contains only ZnO, no UV light is found measured by macroscopic photoluminescent analysis even annealed at different ambient and temperature. According to previous papers, an ideal UV light intensity can be obtained by thermal treated metal Zn or Zn ion implantation into oxide materials after annealing. Annealing the Zn-ZnO structure formed in 30oC by electrodeposition can observe intense UV light. This method improves the disadvantages of insufficient light intensity and no UV light observation from conventionally electrodeposited ZnO. The variation of UV light wavelength of ZnO oxidized from metal Zn is associated with the quantum-confinement effect that was discussed by previous papers. It is found that the size of ZnO is not small enough to realize the quantum-confinement effect, herein, we suggest that the variation of UV light wavelength is affected by the metal Zn resides in ZnO. Otherwise, the electrodeposition of ZnO is not easily performed on p-type substrate, an aluminum film on the back side of p-type Si can deposit ZnO by smaller potential, and different ZnO nanostructures are obtained by modifying the current density. Recently, different characteristics were found in nano-size noble metal crystals. In this thesis, the porous structure of Au-ZnO and Pt-ZnO were co-deposited by electrodeposition to enhance the photocatalytic activity.
Si is the dominant material in semiconductor technology, but its indirect band gap property makes it not allowed in optoelectronics application. However, since 1990, the visible light is observed from porous Si fabricated by electrochemically etching of Si; though the light mechanism of porous Si is not clear, it can be divided into two parts, the quantum-confinement effect of Si nanocrystals and surface states on porous Si. Porous Si emits efficient visible light, but its light wavelength is readily influence by environment. We developed three methods, electrochemically etching the pre-treated Si substrate, adding chemical solution into electrolyte during etching process, and post-treatment of Si substrate after etching to prevent the emission of porous Si from being affected by environment.

Acknowledgment I
中文摘要 II
Abstract III
Contents V

Chapter 1
Introduction and Outline 1
1-1 Nanomaterials, Nanosciences, and Nanotechnologies 1
1-2 Zinc Oxide 2
1-3 Properties and Applications of ZnO 3
1-4 Outlines 7

Chapter 2
Electrodeposited ZnO Films 14
2-1 Introduction 14
2-2 Electrodeposited ZnO on N-type Si without Buffer Layer 16
2-2-1 Experiment 17
2-2-2 Electrodeposited Mechanism of ZnO Discussed by XRD Results 17
2-2-3 PL Analysis of Electrodeposited ZnO 19
2-3 Electrodeposited ZnO on P-type Si and Their
Nanostructural Microphotoluminescence 21
2-3-1 Electrodeposition of ZnO on P-type Si 22
2-3-2 Structure and Morphology of Electrodeposited ZnO 24
2-3-3 Microphotoluminescence of Electrodeposited ZnO 26
2-4 Summary 32

Chapter 3
Photoemission of Electrodeposited ZnO Improved by Thermal Treatment 51
3-1 Introduction 51
3-2 Electrodeposited ZnO with Postannealing Process 53
3-2-1 The Electrodeposited ZnO Annealed in Different Ambient (O2, N2, N2O) at Different Temperatures 53
3-2-2 PL Spectra of the Electrodeposited Zn-ZnO Annealed in O2 at Different Temperatures 54
3-2-3 The Electrodeposited Zn-ZnO Annealed in Different Ambient (O2, N2, N2O) at 500 oC 58
3-3 Ultraviolet Emission Blueshift of ZnO Related to Zn 59
3-4 Summary 63

Chapter 4
Applications of Electrodeposited ZnO (Photocatalytic and Electroluminescent Devices) 85
4-1 Introduction 85
4-2 Photocatalytic Activity of ZnO 85
4-2-1 Photocatalysis and ZnO Photocatalyst: A Brief Review 85
4-2-2 Photocatalytic Activity of Electrodeposited ZnO 88
4-2-3 One-step Preparation of Metal-Semiconductor Structure to Enhance Photocatalytic Activity 92
4-3 Electroluminescent Devices of ZnO/Si 97

Appendix
Passivation of Porous Silicon by Pre-treatment, In-situ Treatment, and Post-treatment 122
Vita 157
Publication List 158

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Chapter 4
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