本研究以氫化物氣相磊晶法(Hydride Vapor Phase Epitaxy, HVPE)在圖案化藍寶石基板(Pattern Sapphire Substrate, PSS)上生長(0002)氮化鎵(GaN)薄膜。採用高純度鎵金屬(Gallium)與氯化氫(HCl)反應形成氯化鎵(GaCl)，再與氨氣(NH3) 進行反應形成氮化鎵，並採用氮氣(N2)作為載流氣體。磊晶過程分三個步驟，首先將基板在高溫下進行氮化處理，接著在低溫磊晶一層氮化鎵作為緩衝層，再升至高溫進行氮化鎵的磊晶成長。
本研究以改變Ⅴ/Ⅲ比、生長時間及基板處理等參數來探討其對GaN成長的影響。採用XRD以及SEM分析氮化鎵之磊晶品質和表面形貌，並且以AFM觀察薄膜的表面粗糙度，PL分析氮化鎵的光學性質，拉曼光譜分析薄膜和基板之間應力，TEM分析觀察試片內部的顯微結構、材料缺陷及GaN薄膜與PSS基板之間的磊晶方向。
實驗結果發現，基板先酸洗過後，在Ⅴ/Ⅲ比=30，生長時間15分鐘的條件下所生長氮化鎵薄膜為最佳條件，其半高寬為0.15°(FWHM)，且形成一個平整GaN薄膜，表面粗糙度(RMS約5.164nm)且薄膜厚度約2μm。由PL測量其光學性質，分析結果酸洗過PSS所生長GaN主要放射峰值為3.46eV (FWHM=266 meV)，且由缺陷引起的黃光帶峰值極低，代表GaN發光品質好。TEM顯微分析觀察到氮化鎵和PSS基板之間磊晶關係為[0002]GaN//[0006]PSS及[112 ̅0]GaN//[33 ̅00]PSS。

In this thesis, the growth of c-plane gallium nitride (GaN) epitaxial films on a patterned sapphire substrate (PSS) by hydride vapor phase epitaxy (HVPE). Gallium chloride (GaCl) formed by the reaction of high purity gallium metal and hydrogen chloride (HCl). GaCl and ammonia (NH3) were used as Ga and N sources, respectively. Nitrogen (N2) was used as carrier gas. First, the substrate was heated at 1050°C for nitridation. Then, the substrate temperature was lowered to 600°C to grow the GaN buffer layer. Finally, the substrate was heated at 1050°C again to grow of GaN films.
We control the quality of films by optimizing the parameters of Ⅴ/Ⅲ ratio, growth time and substrate pre-processing. The properties of the GaN films were investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), photoluminescence spectra (PL), Raman spectra (Raman) and transmission electron microscopy (TEM).
The results show that the crystal quality and surface morphology of GaN films are strongly related to the Ⅴ/Ⅲ ratio, growth time and substrate pre-processing. When the substrate was used in acid treatment, Ⅴ/Ⅲ ratio was 30 and growth time was 15 minutes, the growth of GaN films has an optimal condition. The XRD signal is obviously strong and full width at half maximum (FWHM) value reach a minimum at 0.15°. The SEM images show flat with continuous film morphologies, surface roughness (RMS) is about 5.164nm and thickness of film is 2µm.
To further analysis of GaN epitaxial films, the photoluminescence spectra shows that the peak centered at 3.46 eV (FWHM=266 meV) and the yellow-green emission was caused by defect is minimum. The microstructural properties of GaN layer grown on a pattern sapphire substrate (PSS) shows that the crystallographic orientation relationship is [0002]GaN//[0006]PSS and [112 ̅0]GaN//[33 ̅00]PSS。

目錄
摘要................................................................................ iii
Abstract.......................................................................... iv
目錄................................................................................ vi
圖目錄............................................................................. ix
表目錄............................................................................. xii
第一章 概論 ............................................................. 1
1-1 前言 ......................................................................... 1
1-2 氮化鎵簡介............................................................... 2
1-3 圖案化藍寶石基板(Pattern Sapphire Substrate, PSS) .... 3
1-4 研究動機 .................................................................. 3
第二章 文獻回顧....................................................... 5
2-1 氮化鎵(GaN)生長 ...................................................... 5
2-2 PSS基板生長氮化鎵 .............................................. 7
第三章 氫化物氣相磊晶儀介紹 ........................................ 10
3-1 氫化物氣相磊晶系統(Hydride Vapor Phase Epitaxy, HVPE) ........................................................................................10
3-2 HVPE機台介紹........................................................... 11
3-2-1 控溫系統 ............................................................. 11
3-2-2 HVPE反應爐管.................................................... 12
3-2-3 氣體管線 ............................................................ 12
3-2-4 控壓系統............................................................. 12
3-2-5 冷卻系統............................................................. 13
第四章 實驗方法......................................................... 15
4-1 實驗流程.................................................................. 15
4-1-1 反應爐管清洗 ..................................................... 15
4-1-2 基板清洗 ........................................................... 16
4-1-3 氮化鎵磊晶成長.................................................. 16
4-2 量測儀器介紹 .......................................................... 18
4-2-1 X光繞射分析儀.................................................... 18
4-2-2 場發式掃描電子顯微鏡......................................... 18
4-2-3 原子力顯微鏡................................................ 18
4-2-4 光激發光譜................................................... 19
4-2-5 拉曼光譜........................................................ 19
4-2-6 穿透式電子顯微鏡分析 ........................................20
4-3 實驗參數................................................................... 22
第五章 實驗結果 ............................................................ 25
5-1 Ⅴ/Ⅲ比對氮化鎵薄膜磊晶的影響.................................... 26
5-1-1 XRD分析結果..................................................... 26
5-1-2 SEM分析結果.................................................... 29
5-1-3 PL光學性質量測 ................................................31
5-1-4 拉曼光譜分析...................................................... 33
5-2 生長時間對氮化鎵薄膜磊晶的影響................................ 35
5-2-1 XRD分析結果 ..................................................... 35
5-2-2 SEM分析結果..................................................... 37
5-2-3 PL光學性質量測.................................................. 39
5-2-4 拉曼光譜分析..................................................... 40
5-3 基板處理對氮化鎵薄膜磊晶的影響 ................................41
5-3-1 XRD分析結果 ..................................................... 42
5-3-2 SEM分析結果..................................................... 45
5-3-3 AFM表面分析..................................................... 47
5-3-4 PL光學性質量測 ................................................52
5-3-5 拉曼光譜分析..................................................... 54
5-3-6 TEM顯微分析..................................................... 54
第六章 結論 ................................................................... 61
參考文獻 ........................................................................ 63

[1] 郭守義，“InN薄膜製程研究”，儀科中心簡訊69期 (2005).
[2] S. Strite, M. E. Lin and H. Morkoc, Thin Solid Films, 231, 197 (1993).
[3] H. P. Maruska, J. J. Tietjen, Appl. Phys. Lett., 15, 327 (1969).
[4] S. Nakamura, M. Senoh, S. Nagahama, N. Iwasa, T. Yamada, T. Natsushita, Y.
Sugimoto and H. Kiyoku, Appl. Phys. Lett., 70, 1417 (1997).
[5] T. Mukai, M. Yamada and S. Nakamura, Jpn. J. Appl. Phys., 38. 3970 (1999).
[6] C. H. Kuo, C. L. Yeh, P. H. Chen, W. C. Lai, C. J. Jun, J. K. Sheu and G. C. Chi,
Electrochemical and Solid-state Lett., 11, H269 (2008).
[7] S. Porowski, I. Grzegory, J. Cryst. Growth. 178, 174 (1997).
[8] L. Liu, J. H. Edgar, Mater. Sci. Eng. R, 37, 61 (2002).
[9] H. Amano, N. Sawaki, I. Akasaki and T. Toyoda, Appl. Phys. Lett., 48, 353 (1986).
[10] X. H. Wu, L. M. Brown, D. Kapolnek, S. Keller, S. P. DenBaars and J. S. Speck, J. Appl. Phys., 80,3228 (1996).
[11] R. J. Molnar, W. Gotz, L. T. Romano and N. M. Johnson, J. Cryst. Growth. 178, 147 (1997).
[12] H. Amano, K. Hiramatsu and I. Akasaki, Jpn. J. Appl. Phys., 27, L1384 (1998).
[13] Published on LEDinside-濕式蝕刻製程提高LED光萃取效率之產能與良率。
[14] S. Strite and H. Morkocs, J. Vac. Sci. Technol. B, 10,1237 (1992).
[15] J. I. Pankove“ Gallium Nitride(GaN)Ⅰ”New York: Academic Press(1998).
[16] H. P. Maraka, D. A. Stevenson and J. I. Pankove, Appl. Phys. Lett., 22, 303 (1973).
[17] T. L. Chu, J. Eletrochem. Sco.,118, 1200 (1971).
[18] S. Yoshida, S. Gonda and S. Misawa, Appl. Phy. Lett., 42,427 (1983).
[19] H. Amano, T. Asahi, and I. Akasaki, Jpn. J. Appl. Phys., 29, L205 (1990).
[20] K. Naniwae, S. Itoh, H. Amano, K. Itoh, K. Hiramatsu and I. Akasaki, J. Crystal. Growth, 99 ,381 (1990).
[21] S. Nakamura, Jpn. J. Appl. Phys., 30, L1705 (1991).
[22] S. Nakamura, Jpn. J. Appl. Phys., 31, 139 (1992).
[23] A. Guillén-Cervantes, Z. Rivera-Álvarez, M. López-López, A. Ponce-Pedraza, C. Guarneros and V. M. Sánchez-Reséndiz, Appl. Surf. Sci., 258, 1267 (2011).
[24] H. Li, L. Zang, Y. Shao, Y. Wu, X. Hao, H. Zang, Y. Dai and Y. Tian, Int. J. Electrochem. Sci., 8,4410 (2013).
[25] P. Waltereit, O. Brandt, A. Trampert, H. T. Grahn, J. Menniger, M. Ramsteiner and K. H. Ploog, Nature, 406, 865 (2000).
[26] 李居安，國立中山大學材料科學所碩士論文，民國九八年。
[27] 盧勁維，國立中山大學材料科學所碩士論文，民國九九年。
[28] 廖帥吾，國立中山大學材料科學所碩士論文，民國一百年。
[29] 王欽輝，國立中山大學材料科學所碩士論文，民國一百零一年。
[30] S. Keller, G. Parish, J. S. Speck, S. P. Den-Baars and U. K. Mishra, App Phys.Lett.,
77, 2665 (2000).
[31] D. S. Wuu, W. K. Wang, K. S. Wen, S. C. Huang, S. H. Lin, S. Y. Huangand C. F.
Lin. Appl Phys. Lett., 89, 161105 (2006).
[32] D. H. Kang, J. C. Song, B. Y. Shim, E. Ako, D. W. Kim, S. Kannappan and C. R.
Lee, Jpn. J. Appl. Phys., Vol. 46, No. 4B, pp. 2563–2566 (2007).
[33] J. C. Song, S. H. Lee, I. H. Lee, K. W. Seol, S. Kannappan and C. R. Lee, J. Cryst. Growth., 308, 321 (2007).
[34] H. Tsuchiya, F. Hasegawa, H. Okumura, and S. Yoshida, Jpn. J. Appl, Phys., 33,
6448 (1994).
[35] 張力權，國立中央大學光電科學與工程學系，民國九八年。
[36] Published on LEDinside-濕式蝕刻製程提高LED光萃取效率之產能與良率。
[37] 徐國洲，國立中山大學物理研究所，民國八十九年。
[38] F. A. Ponce, J. W. Steeds, C. D. Dyer and G. D. Pitt, Appl. Phys., 69, 2650 (1996).
[39] D. Y. Tao, C. Liu, C. H. Yin and Y. P. Zeng, Spectroscopy and Spectral Analysis, 33, 669 (2013).
[40] 王太伸，國立成功大學物理研究所，民國九十七年。
[41] Y. H. Kim, H. Rub, Y. K. Noh, M. D. Kim, and J. E. Oh, Jpn. J. Appl, Phys., 107, 063501 (2010).