本論文利用原子層沉積系統(atomic layer deposition, ALD)沉積摻鋁氧化鋅(Al-doped ZnO, AZO)於矽p-i-n結構上作為發光二極體主動層，其中p-i-n結構的p區與n區皆為重摻雜，以提供足夠的電子流經摻鋁氧化鋅進行復合。
摻鋁氧化鋅在矽p-i-n結構上使得原本具整流特性的矽p-i-n結構無論操作在正向或逆向偏壓下電流明顯變大，表示大部分的載子都流經摻鋁氧化鋅層。當元件操作在逆向電流於10mA的情況下，透過相機長時間曝光確實可以看見摻鋁氧化鋅的邊界處發光；通入順向電流於10mA下，亦能看見發光現象。
在電致發光(electroluminescence, EL)實驗中，元件的發光波長範圍寬廣，約在600nm到900nm之間，波峰則大致上位於700nm，推測發光的來源是由摻鋁氧化鋅內部的氧空缺所主導。此外，透過光學模擬可以發現在摻鋁氧化鋅厚度100nm的條件下，對於波長600nm到900nm範圍的穿透度超過80%，與元件在電致發光實驗中的發光波段相符。當減小摻鋁氧化鋅層厚度，元件EL能譜強度範圍確實更寬，峰值向短波長移動，同樣符合模擬結果。
最後，本論文的實驗成果提供將來想製作基於氧化鋅發光二極體的研究人員一個建議，除了考慮本身元件的發光機制以外，應當再考慮主動層厚度對於特定波長的穿透度，以發揮元件的最大效率。

In this thesis, an aluminum-doped zinc oxide (AZO) layer is deposited on silicon-based p-i-n junction as the active layer of light emitting diode by atomic layer deposition system. The p-region and n-region of the p-i-n junction are both heavily doped to provide sufficient electrons to recombine in AZO.
No matter under forward or reverse bias, the current obviously increases in the AZO active layer p-i-n junction. It shows that most of carriers flow through the AZO layer. When the device is operated under the reverse current of 10mA, the emission at the edge of AZO is observed by camera. On the other hand, under the forward current of 10 mA, the emission is observed at different position.
Electroluminescence (EL) measurement reveals that the wavelength of the emission ranges from 600nm to 900nm, and the peak of EL spectra centers at ~700nm. It is believed that the oxygen vacancies of AZO dominate the emission.
In addition, the simulation shows the transmittance of wavelength from 600nm to 900nm exceeds 80% with a 100nm-AZO layer. This result is consistent with the EL spectra of the device. When the thickness of AZO film is reduced to 50nm, the emission region is broader than 100nm ones and the peak moves to short wavelength. Similarly, the result conforms to our simulation.
Finally, we suggest that the light transmittance of active layer should be designed with appropriate thickness to get higher efficiency.

摘要 I
ABSTRACT II
誌謝辭 III
目錄 IV
圖目錄 VI
表目錄 VIII

第一章 引言 1
1.1 氧化鋅簡介 1
1.1.1 氧化鋅的基本特性 1
1.1.2 氧化鋅的摻雜 1
1.1.3 摻鋁氧化鋅 2
1.2 研究動機 3
第二章 基本原理介紹 4
2.1 發光二極體之工作原理 4
2.2 基於氧化鋅發光元件種類 6
2.2.1 同質接面 6
2.2.2 異質接面 9
2.2.3 金氧半結構 12
2.3 原子層沉積 15
2.3.1 原子層沉積原理 15
2.3.2 氣流中斷法 15
2.3.3 摻鋁氧化鋅的製作 16
2.4 橢圓儀工作原理 17
2.5 X光繞射分析 18
2.6 金半接觸 20
2.6.1 蕭特基能障 20
2.6.2 歐姆接觸 20
第三章 元件架構與製作 21
3.1 元件架構 21
3.2 元件製作 21
3.2.1 元件製作流程圖與各道光罩示意圖 21
3.2.2 前置作業：晶圓雷射刻號與第零層對準標記 22
3.2.3 連續製程：元件區隔與摻雜 22
3.2.4 連續製程：金屬電極沉積與蝕刻 23
3.2.5 原子層沉積前處理：移除金屬並去除原生氧化層 24
3.2.6 原子層沉積：100nm AZO與蝕刻 24
3.2.7 連續製程參數 25
第四章 實驗結果與討論 26
4.1 實驗量測設備與規格 26
4.2 摻鋁氧化鋅品質檢測 27
4.2.1 橢圓儀薄膜厚度擬合 27
4.2.2 X光繞射分析結果 27
4.3 元件電流-電壓特性 29
4.4 光致發光與電致發光 32
4.4.1 量測環境架設 32
4.4.2 光致發光 33
4.4.3 電致發光 34
4.5 驗證薄膜穿透度問題 39
4.5.1 50nm AZO層p-i-n結構電性量測 39
4.5.2 50nm AZO層p-i-n結構光譜儀量測 40
第五章 結論 43
參考文獻 44

[1] Ü. Özgür et al., "A comprehensive review of ZnO materials and devices", Journal of Applied Physics 98, 041301, 2005.
[2] Y. -S. Choi et al., "Recent Advances in ZnO-Based Light-Emitting Diodes", IEEE Transactions on Electron Devices, Volume 57, Issue 1, 2010.
[3] R.K. Shukl et al., “Growth of transparent conducting nanocrystalline Al doped ZnO thin films by pulsed laser deposition”, Journal of Crystal Growth, Volume 294, Issue 2, 2006.
[4] A. Tsukazaki et al., "Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on ZnO", Nature Materials, Volume 4, 2005.
[5] J.‐H. Lim et al., "UV Electroluminescence Emission from ZnO Light‐Emitting Diodes Grown by High‐Temperature Radiofrequency Sputtering", Advanced Materials, Volume 18, Issue 20, 2006.
[6] Y. Ryu, "Next generation of oxide photonic devices: ZnO-based ultraviolet light emitting diodes", Applied Physics Letters 88, 241108, 2006.
[7] Ya. I. Alivov et al., "Observation of 430 nm electroluminescence from ZnO/GaN heterojunction light-emitting diodes", Applied Physics Letters 83, 2943, 2003.
[8] J. D. Ye et al., "Electroluminescent and transport mechanisms of n-ZnO∕p-Si heterojunctions", Applied Physics Letters 88, 182112, 2006.
[9] P. Chen et al., "Ultraviolet electroluminescence from ZnO/p‐Si heterojunctions", Journal of Applied Physics 101, 053103, 2007.
[10] P. Chen et al., "Fairly pure ultraviolet electroluminescence from ZnO-based light-emitting devices", Applied Physics Letters 89, 111112, 2006.
[11] H. Huang et al., "ZnO-Based Fairly Pure Ultraviolet Light-Emitting Diodes With a Low Operation Voltage", IEEE Electron Device Letters, Volume 30, Issue 10, 2009.
[12] H. Zhu et al., "Low-Threshold Electrically Pumped Random Lasers", Advanced Materials, Volume 22, Issue 16, 2010.
[13] 曾柏憲, "利用原子層沉積法成長出高品質摻鋁氧化鋅薄膜於矽光學元件之應用", 國立新竹教育大學, 碩士論文, 2015.
[14] P. Banerjee et al., "Structural, electrical, and optical properties of atomic layer deposition Al-doped ZnO films", Journal of Applied Physics 108, 043504, 2010.
[15] W. Muhammad et al., "Optical, morphological and biological analysis of zinc oxide nanoparticles (ZnO NPs) using Papaver somniferum L.", RSC Advances 9, 29541, 2019.
[16] 江至淳, ”基於單層石墨烯的發光元件”, 國立清華大學, 碩士論文, 2019.
[17] N. H. Alvi et al., "The origin of the red emission in n-ZnO nanotubes/p-GaN white light emitting diodes", Nanoscale Research Letters 6, Article number 130, 2011.