臺灣博碩士論文加值系統

本論文以溶膠-凝膠法及噴霧熱解法在玻璃基板上沉積�狊T氧化鋅薄膜（aluminum-doped zinc oxide, AZO），探討此兩種不同製備法沉積之AZO薄膜特性，並分析這兩種不同製程製備之AZO薄膜的特性差異，包括表面形貌，成分，電性與穿透率分析。這二種製備法沉積的薄膜，其區域成份均有所差異。在後續的氬/氫混合氣體熱處理下，這二種薄膜的相關特性，變化不盡相同。在熱處理溫度達到600 ℃時，以溶膠-凝膠法製備之AZO薄膜，其變化較大，表面呈現遍佈許多孔隙與裂縫，且薄膜中的鋅原子含量遽減。相較起來以噴霧法製備之AZO薄膜有較完好穩定性。

In this thesis, we deposit the aluminum doped zinc oxide (AZO) thin film on glass substrates by sol–gel spin coating method and spray pyrolysis method. The surface morphologies, compositions, electrical and optical transmittance of the films were studied. The different composition variance of the films by the two methods can be found. With followed heat treatment under mixed argon/ hydrogen ambient, the film quality shows some different behaviors. As the temperature reach to 600℃, the AZO films prepared by sol-gel method were suffuse many cavities and less zinc quantity can be observed. On the contrary, the film prepared by spray pyrolysis method shows a better behavior at high temperature.

中文摘要 I
英文摘要 II
致謝 III
目錄 IV
表目錄 VI
圖目錄 VII
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目標 1
第二章 理論基礎 2
2.1 氧化鋅薄膜 2
2.1.1 氧化鋅性質與摻雜特性 2
2.1.2 ZnO薄膜之導電性質 3
2.2 溶膠-凝膠法製程概述 5
2.3 噴霧熱解法 8
第三章 實驗方法 11
3.1 實驗藥品與儀器 11
3.2 溶膠-凝膠法製備AZO薄膜之實驗 13
3.3 噴霧熱解法製備AZO薄膜之實驗 14
3.4 量測特性分析方法 15
3.4.1 穿透光吸收光譜量測分析 15
3.4.2 霍爾量測 16
3.4.3 光子激發螢光分析 18
3.4.4 掃瞄式電子顯微鏡 18
3.4.5 能量散佈光譜儀 19
3.4.6 原子力顯微鏡 20
第四章 實驗結果與討論 25
4.1 �狊T比例對溶膠-凝膠法製備AZO薄膜電性與光性的影響 25
4.1.1 �狊T比例對AZO薄膜電阻率之影響 25
4.1.2 �狊T比例對AZO薄膜光性之影響 25
4.2 沉積層數對溶膠-凝膠法製備AZO薄膜電性與光性的影響 27
4.2.1 沉積層數對AZO薄膜電性之影響 27
4.2.2 沉積層數對AZO薄膜光性之影響 29
4.3 氬氣/氫氣混合氣體熱處理對溶膠-凝膠法製備AZO薄膜的影響 30
4.3.1 氬氣/氫氣混合氣體熱處理時間參數對AZO薄膜影響 30
4.3.2 氬氣/氫氣混合氣體熱處理之氣體流量對AZO薄膜影響 31
4.3.3 氬氣/氫氣混合氣體熱處理之溫度對AZO薄膜電性影響 32
4.3.4 氬氣/氫氣混合氣體熱處理溫度參數對AZO薄膜光性之影響 34
4.4 噴霧熱解法實驗結果與討論 35
4.4.1 噴霧製程裝置方法對成膜之影響 35
4.4.2 不同沉積位置對AZO薄膜之影響 36
4.4.3 噴霧法之熱製程參數對AZO薄膜之影響 38
4.5 溶膠-凝膠法與噴霧熱解法製備AZO薄膜之討論 40
4.5.1 表面形貌與粗糙度分析 40
4.5.2 氬氣/氫氣混合氣體熱處理對AZO薄膜之影響 41
4.5.3 PL分析 42
第五章 結論與未來工作 75
參考文獻 77

[1] S. Hirose, Y. Yamamoto, and H. Niimi, Journal of Applied Physics 104, 013701 pp.1-12 (2008)
[2] Y. Chen, G. Saraf, P. I Reyes, Z. Duan, J. Zhong, Y. Lu, The Journal of Vacuum Science and Technology B 27(3), pp.1631-1634 (2009)
[3] T. Mitsuyu, S. Ono, K. Wasa, Journal of Applied Physics 51, pp.2464-2470 (1980)
[4] S.K Kim, J.Y. Son, Electrochemical and Solid-State Letters 12(2), pp.17-19 (2009)
[5] K.Y. Jung, Y.C. Kang, S.B. Park, Journal of Materials Science Letters 16, pp.1848-1849 (1997).
[6] 蔡佳銘, 國立中央大學化學工程與材料工程研究所碩士論文(2005)
[7] Y. Tang, L. Luo, Z. Chen, Y. Jiang, B. Li, Z. Jia, L. Xu, Electrochemistry Communications 9, pp. 289-292 (2007)
[8] T. Tohsophon, J. H�劮kes, S. Calnan, W. Reetz, B. Rech, W. Beyer, N. Sirikulrat, Thin Solid Films 511, pp. 673-677 (2006)
[9] Z.Z. Zhang, Z.P. Wei, Y.M. Lu, D.Z. Shen, B. Yao, B.H. Li, D.X. Zhao, J.Y. Zhang, X.W. Fan, Z.K. Tang, Journal of Crystal Growth 301, pp.362-365 (2007)
[10] S.H. Hwang, T.H. Chung, B.T. Lee, Materials Science and Engineering: B 157, pp.32-35 (2009)
[11] D. Li, H. Haneda, Chemosphere 51, pp.129-137 (2003)
[12] R. F. Silva, M E. D. Zaniquelli, Colloids and Surfaces A: Physicochemical and Engineering Aspects 198-200, pp. 551-558 (2002)
[13] Z. Dang, L. Fan, S. Zhao, C. Nan, Materials Research Bulletin 38, pp.499-507 (2003)
[14] D. Chen, X. Jiao, G..Cheng, Solid State Communications 113, pp. 363-366 (2000)
[15] Y. Liu, J. Lian, Applied Surface Science 253, pp.3727-3730 (2007)
[16] A. E. J.Gonzalez, J. A. S. Urueta, R. S. Parra, Journal of Crystal Growth 192, pp. 430-438 (1998)
[17] P. Sagar, M. Kumar, R.M. Mehra, Thin Solid Films 489, pp.94-98 (2005)
[18] V. Shelke, B.K. Sonawane, M.P. Bhole, D.S. Patil, Journal of Non-Crystalline Solids 355, pp. 840-843 (2009)
[19] X.T. Hao, L.W. Tan, K.S. Ong, F. Zhu, Journal of Crystal Growth 287, pp. 44-47 (2006)
[20] C. Major, A. Nemeth, G. Radnoczi, Z. Czigany, M. Fried, Z. Labadi, I. Barsony, Applied Surface Science 255, pp. 8907-8912 (2009)
[21] I. Volintiru, M. Creatore, B. J. Kniknie, C. I. M. A. Spee, and M. C. M. van de Sanden, Journal of Applied Physics 102, 043709, pp.1-9 (2007)
[22] C. H. Kuo, C. L. Yeh, P. H. Chen, W. C. Lai, C. J. Tun, J. K. Sheu, G. C. Chi,
Electrochemical and Solid-State Letters 11, pp.269-271 (2008)
[23] Y.Z. Zhang, J.G. Lu, Z.Z. Ye, H.P. He, L.P. Zhu, B.H. Zhao, L. Wang, Applied Surface Science 254, pp. 1993-1996 (2008)
[24] Y. Sato, K. Yanagisawa, N. Oka, S. Nakamura, Y. Shigesato, The Journal of Vacuum Science and Technology A 27, pp.1166-1171 (2009)
[25] J.P. Lin, S.W. Chen, J.M. Wu, Electrochemical and Solid-State Letters 12, pp.1-4 (2009)
[26] J.P. Lin, J.M. Wu, Applied Physics Letters 92 134103, pp.1-3 (2008)
[27] S.H. Yi, S.K.Choi, J.M. Jang, J.A.Kim, W.G. Jung, Proceedings of the SPIE 6831 68311A , pp.1-7 (2007)
[28] M. Shahjahan, M. K. R. Khan, M. F. Hossain, S. Biswas, and T. Takahashi, The Journal of Vacuum Science and Technology A 27, pp.885-888 (2009)
[29] S. P. Shrestha, P. Basnet, Proceedings of the SPIE 6793, 67930I ,pp.1-6 (2008)
[30] M. Gab�龍, N.T. Barrett, J.R. Ramos-Barrado, S. Gota, T.C. Rojas, M.C. L.Escalante, Solar Energy Materials and Solar Cells 93, pp. 1356-1365 (2009)
[31] R. O. Ndong, F. P. Delannoy, Material Science and Engineering B97,pp.68-73 (2003)
[32] R. D. Vispute, V. Talyansky , S. Choopun, R. P. Sharma, T. Venkatesan, M. He, X. Tang, J. B. Halpern, M. G. Spencer, Y.X. Li, L.G. Salamanca-Riba, A. A. Iliadis, K. A. Jones, Applied Physics Letters 73,pp.348-350 (1998)
[33] S. J. Pearton, D. P. Norton, K. IP, Y. W. Heo, T. Steiner, Superlattices and Microstructure 34, pp.3-32 (2003)
[34] K. E. Lee, M. Wang, E. J. Kim, S. H. Hahn, Current Applied Physics 9, pp. 683-687 (2009)
[35] Y. Yamamoto, K. Saito, K. Takahashi, M. Konagai, Solar Energy Materials and Solar Cells 65, pp.125-132 (2001)
[36] Y. Liu, J. Lian, Applied Surface Science 253, pp. 3727-3730 (2007)
[37] V. Khranovskyy, U. Grossner, O. Nilsen, V. Lazorenko, G.V. Lashkarev, B.G. Svensson, R. Yakimova, Thin Solid Films 515, pp. 472-476 (2006)
[38] U.Ozgur, Ya. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Dogan, V. Avrutin, S. J. Cho, H. Morkoc, Journal of Applied Physics 98, 041301, pp.1-103（2005）
[39] 溫文杰, 大同大學材料科學研究所碩士論文pp.10-35 (2007)
[40] G. D. Mahan, Journal of Applied Physics 54, pp.3825-3832 (1983).
[41] O. Hamad, G. Braunstein, H. Patil, N. Dhere, Thin Solid Films 489, pp.303-309 (2005).
[42] T. Minami, H. Sato, H. Nanto, S. Takata, Japanese Journal of Applied Physics 24,
pp.781-784 (1985)
[43] A. C. S. Sabioni, Solid State Ionic 170, pp.145-148 (2004).
[44] V. M., B. Teixeira, E. Fortunato, R. C. C. Monteiro, P. Vilarinho, Surface and Coatings Technology 180, pp.659-662 (2004)
[45] 陳秀連, 國立台灣科技大學材料科技研究所碩士論文, pp171-178 (2003)
[46] C. T. Brinker, G. W. Scherer, Sol-Gel Science：The Physics and Chemistry of Sol-Gel Processing, Academic Pres Inc,pp.1-14 (1990)
[47] K.R. Murali, Journal of Physics and Chemistry of Solids 68, pp.2293-2296 (2007)
[48] H.G.Pozos, A.Maldonado, M.L.Olvera, Materials Letters 61, pp1460-1464
(2007)
[49] C. L. Carnes, K. J. Klabunde, Journal of Molecular Catalysis A: Chemical 194, pp.227-236 (2003)
[50] 張倍榕, 國立台北科技大學光電系碩士論文,pp.45-47(2007)
[51] H. Zhou, D.Yi, Z.Yu, L.Xiao, J. Li, Thin Solid Films 515 , pp.6909–6914 (2007)
[52] X. Li, G. He, G. Xiao, H. Liu, M. Wang, Journal of Colloid and Interface Science 333, pp. 465-473 (2009)
[53] B.L.Cushing, V. L. Kolesnichenko, C. J. Connor, Chemical Reviews 104, pp. 3893-3899 (2004)
[54] H. Schmidt, M. Mennig, INM, Institut f�卣 Neue Materialien, Saarbr�佟ken, Germany November, pp1-4 (2000)
[55] G. G. Valle, P. Hammer, S. H. Pulcinelli, C. V. Santilli, Journal of the European Ceramic Society 24, pp.1009-1013 (2004)
[56] G. Srinivasan, R.T. Rajendra Kumar, J. Kumar, Optical Materials 30, pp.314-317 (2007)
[57] V. Shelke, B.K. Sonawane, M.P. Bhole, D.S. Patil, Journal of Non-Crystalline Solids 355,pp. 840-843 (2009)
[58] J.Chen,W.Lei,C.Li, X. Zhang, 2008 IEEE International Nanoelectronics Conference (2008)
[59] J.L.Zhao, X.M.Li, J.M.Bian,W.D.Yu,C.Y. Zhang, Journal of Crystal Growth 280, pp495-501 (2005)
[60] S. P. Shrestha, P. Basnet, Proceedings of SPIE 6793, pp.1-6 (2008)
[61] D. Hidayat, T. Ogi, F. Iskandar, K. Okuyama, D. Hidayat et al, Materials Science and Engineering B, pp.1-7 (2008)
[62] G. K. Bhaumik, A. K. Nath, S. Basu, Materials Science and Engineering B 52, pp.25-31(1998)
[63] J. C. Viguie,J. Spitz, The Journal of The Electrochemical Society 722, pp.585-588
( 1975 )
[64] A. A.Ahrnadi, College of Engineering and Technology Ohio University In Partial Fulfillment of the Requirement for Degree Master of Science, pp.15-18 (2003)
[65] J. Hirunlabh, S. Suthateeranet, K. Kirtikara and Ralph D. Pynn: The Thammasat International Journal of Science and Technology 3, pp.10-20 (1998)
[66] http://www3.interscience.wiley.com/journal/119288073/abstract
[67] B. Ergin, E. Ketenci, F. Atay, The International Journal of Hydrogen Energy 34, pp. 5249–5254 (2009)
[68] X.Zhang, H. Fan, J. Sun, Y. Zhao, Thin Solid Films 515, pp. 8789–8792 (2007)
[69] J.H. Lee, B.O. Park, Materials Science and Engineering B 106, pp. 242–245 (2004)
[70] B. Sapoval and C. Hermann: Physics of Semiconductors ,Springer, New York, 2, p.44-46. (2003)
[71] D.K.Schroder:Semiconductor Material and Device Characterization, Wiley-Interscience IEEE, New York, pp.101 (2006)
[72] L.J. van der Pauw, Philips Research Reports 20, pp.220-224 (1958).
[73] http://www.eeel.nist.gov/812/effe.htm
[74] Optical Semiconductor Devices, Mitsuo Fukuda, JOHN WILEY & SONS, INC.
[75] D. A. Skoog and J. J. Leary, Principles of Instrumental Analysis 4th Ed, (1992)
[76] C.A.Parker et al, Photoluminescence of Solutions, Elsevier New York, pp.1-7 (1968)
[77] D. K. Schroder: Semiconductor Material and Device Characterization, Wiley-Interscience IEEE, New York, pp.631 (2006)
[78] H. Seiler: Journal of Applied Physics 54, pp.1-18 (1983)
[79]黃永盛, 科儀新知雙月刊, 第17卷第3期, pp.36–54 (1995)
[80] G. Binning, C.F. Quate, and C. Gerber, Physical Review Letters 56, pp. 930-933 (1986)
[81] K. E. Lee, M. Wang, E. J. Kim, S. H. Hahn, Current Applied Physics 9, pp. 683–687 (2009)
[82] K.C. Park, D.Y. Ma, K.H. Kim, Thin Solid Films 305, pp.201-209 (1997)
[83] M. J. Alam, D.C. Cameron, The Journal of Vacuum Science and Technology A 19,
pp.1642-1646 (2001).
[84] H. Gomez-Pozos, A. Maldonado, M. de la L. Olvera, Materials Letters 61, pp.
1460-1464 (2007)
[85] Z.Q. Xu, H. Deng, Y. Li, Q.H. Guo, Y.R. Li, Materials Research Bulletin 41, pp. 354-358 (2006)
[86] K. M. Lin, P. Tsai, Thin Solid Films 515, pp. 8601-8604 (2007)
[87] M.Wang, K. E. Lee, S. H. Hahn, E. J. Kim, S. Kim, J. S. Chung, E. W. Shin, C. Park, Materials Letters 61, pp. 1118–1121 (2007)
[88] X. Z. Qiang, D, Hong, L. Yan, C. Hang, Materials Science in Semiconductor Processing 9 , pp.132-135 (2006)
[89] J. P. Lin, J. M. Wu, Applied Physics Letters 92, 134103, pp.1-3 (2008)
[90] J. Wang, L. Meng, Y. Qi, M. Li, G. Shi, M. Liu, Journal of Crystal Growth 311, pp. 2305-2308 (2009)
[91] M. Balkanski, R. F. Wallis, Semiconductor Physics and Applications, Oxford Univ Pr pp.
241-242 (2000)
[92] H. Kwak, M. L. Tiago, J. R. Chelikowsky, Solid State Communications 145, Issues 5-6,
pp. 227-230(2008)
[93] S. W. Xue, X. T. Zu, W. G. Zheng, M. Y. Chen, X. Xiang, Physica B 382 pp. 201–204
(2006)
[94] J. P. Lin, J. M. Wu, Applied Physics Letters 92, pp. 134103-1~143103-3 (2008)
[95] T. S. Moss, Proceedings of the Physical Society of London B 67 , pp.775-782 (1954)
[96] G.G. Valle, P. Hammer, S.H. Pulcinelli, C.V. Santilli, Journal of the European Ceramic Society 24, pp. 1009–1013 (2004).
[97] K. Lin, P. Tsai, Materials Science and Engineering B 139, pp. 81–87 (2007)
[98] K. Lin, P. Tsai, Thin Solid Films 515 , pp. 8601–8604 (2007)
[99] S. Mridha, D. Basak, Chemical Physics Letters 427, pp. 62–66 (2006)
[100] S. W. Xue, X. T. Zu, W.G. Zheng, M. Y. Chen, X. Xiang, Physica B, pp. 201–204 (2006)
[101] Z. Q. Xu, H. Deng, Y. Li, Q.H. Guo, Y.R. Li, Materials Research Bulletin 41, pp. 354–358 (2006)
[102] Y.S. Kim, W.P. Tai, Applied Surface Science 253, pp. 4911–4916 (2007)
[103] H.M Zhou, D.Q Yi, Z.M Yu, L. Xiao, J. Li, Thin Solid Films 515, pp. 6909–6914(2007)
[104] B.Y. Oh, Journal of Crystal Growth 281, pp.475-480 (2005)
[105] 李孟賢, 林天財, 劉定杰, 劉時郡, 張慎周, 台灣金屬熱處理學會年會論文 (2006)
[106] H.G..Pozos, A. Maldonado, M. D. Olvera, Materials Letters 61, pp. 1460–1464
(2007)
[107] 吳坤陽,國立成功大學化學工程學系碩博士班, pp.65-103 (2005)
[108] R. Sharma, K. Sehrawat , R. M. Mehra, Current Applied Physics, pp.1-7(2009)
[109] F. K. Shan, Y. S. Yu, Journal of the European Ceramic Society 24, pp. 1869-1872.
(2004)
[110] J.H. Lee, B.O. Park, Materials Science and Engineering B 106, pp. 242–245 (2004)
[111] H. Gomez, A. Maldonado, R. Castanedo-Perez, G. Torres-Delgado, M. De la L.
Olvera, Materials Characterization 58, pp. 708–714 (2007)
[112] W. T. Seeber, M. O. Abou-Helal, S. Barth, D. Beil, T. H�丱he, H. H. Afify, S.E.Demian, Materials Science in Semiconductor Processing 2 , pp. 45-55(1999)
[113] B.Joseph, P.K. Manoj, V.K. Vaidyan, Ceramics International, Volume 32, Issue 5, pp. 487-493 (2006)
[114] M. Wang, K. E. Lee, S. H. Hahn, E. J. Kim, S. Kim, J. S. Chung, E. W. Shin, C. Park,
Materials Letters 61, pp. 1118–1121 (2007)
[115] B. Y. Oh, M. C. Jeong, J. M. Myoung, Applied Surface Science, Volume 253, Issue 17,
pp. 7157-7161(2007)
[116] S. Y. Kuo, W. C. Chen, F. I. Lai, C. P. Cheng, H. C. Kuo, S. C. Wang, W. F. Hsieh, Journal
of Crystal Growth 287, pp. 78–84 (2006)
[117] J. B. Cui, M. A. Thomas, Journal of Applied Physics 106, pp. 033518-1~033518-5 (2009)
[118] C. H. Ahn, S. K. Mohanta, N. E. Lee, H. K. Cho, Applied Physics Letters 94, pp.
261904-1~261904-3 (2009)