臺灣博碩士論文加值系統

本論文利用射頻磁控濺鍍法沉積氧化鋅摻氟(ZnO:F，FZO)於玻璃與p型矽基板上，首先研究不同基板溫度(室溫到300oC)對FZO薄膜的光電特性影響。其結果顯示基板溫度為150 oC時薄膜有著最大晶粒(17.3 nm)、最低的電阻率(6x10-2 Ω-cm)和在可見光區(400-800 nm)的透光率約為90%以上。由於不同基板溫度製作成太陽能電池均呈現較差的效率，推測其原因為FZO薄膜的電阻率都較高(9x10-1 Ω-cm到6 x10-2 Ω-cm)的關係，因此第二部份我們以最佳基板溫度沉積之FZO薄膜(初鍍膜)進行快速熱退火(RTA)處理(300oC至500oC)，探討退火溫度對矽基異質太陽能電池轉換效率的影響。由結果可得知，FZO薄膜於熱處理溫度在500℃時有著最低之電阻率(3.76x10-3 Ω-cm)、最高的移動率(35.2cm²/V-s)和最低載子濃度(4.71x1019cm-3)，對應於太陽能電池上顯示出最高的轉換效率6.45% ( Voc：0.48 V、Jsc：31.03 mA/cm2、FF：0.43)，此轉換效率的改善主要可歸因於FZO薄膜電阻率的下降使得太陽能電池串聯電阻(RS)下降，進而提高效率。最後，我們亦將FZO薄膜作為抗反射層用，並設計其厚度變化分別為70 nm、150 nm、200 nm，探討薄膜厚度對矽基太陽能電池轉換效率的影響。其結果顯示，FZO薄膜厚度為150 nm時有著最高的效率。而當薄膜厚度過薄(70 nm)時，儘管其有著最高JSC＝37.05 mA/cm2，但較小的晶粒(受限於較薄厚度)使得VOC(0.44V)和FF(0.37)都下降，轉換效率因而降為6.02%。而薄膜厚度過厚(200 nm)則會造成RS過大亦造成FF下降，其轉換效率為3.51%。

In this study, fluorine doped zinc oxide (FZO) films have been prepared by RF reactive magnetron sputtering on glass and p-Si substrates. The effects of substrate temperature (from RT to 300°C) on optical and electrical properties of FZO thin films were first studied. The results show that FZO thin film deposited at substrate temperatures of 150°C has largest grain size of 17.3 nm, the lowest resistivity of 6x10-2 Ω-cm, and visible range(400-800 nm) transmittance about 90%. However the cell fabricated at various substrate temperatures shows very poor conversion efficiency due to the high resistivity of FZO thin films in the range of 9x10-1-6 x10-2 Ω-cm. In the second part, the optimal FZO thin films (as-deposited) will be annealed by rapid thermal annealing (RTA) process (from 300oC to 500oC) to improve the conductivity of films, and its influence on conversion efficiency of FZO/p-Si heterojunction solar cell were also investigated. According to the experimental results, the FZO thin film annealed at 500°C shows the lowest resistivity of 3.76x10-3 Ω-cm, the highest mobility of 35.2cm²/V-s and the lowest carrier concentration 4.71x1019cm-3, corresponding to highest conversion efficiency of 6.45% ( Voc：0.48 V、Jsc：31.03 mA/cm2、FF：0.43). The improvement of conversion efficiency can be mainly attributed to the decrease of resistivity of FZO thin film causes decrease of series resistance (RS) of solar cell, thus improving the efficiency. Finally, the thickness of FZO film will be designed as 70 nm, 150 nm, and 200 nm to act an anti-reflective coating layer. From the results, FZO thin film with thickness of 150 nm has highest efficiency. When the film is too thin (70nm), the smaller grain size of film (limited by the thinner thickness) causes decrease of VOC (0.44V), FF (0.37) and conversion efficiency (6.02%) despite the cell shows the highest JSC (37.05 mA/cm2). If the film too thick (200nm), it will cause increase of RS and also decrease of FF, the conversion efficiency of 3.51%.

目錄
中文摘要 I
Abstract III
誌謝 V
目錄 VII
表目錄 X
圖目錄 XI
第一章 前言 1
1-1研究動機 1
1-2研究目的 4
1-3論文架構 5
第二章 基礎理論 7
2-1氧化鋅之簡介 7
2-2電漿理論 8
2-3濺鍍原理 9
2-3.1二極濺鍍 9
2-3.2偏壓濺鍍 10
2-3.3磁控濺鍍 11
2-3.4射頻濺鍍 11
2-4薄膜沉積原理 12
2-5太陽能電池基本理論 13
2-5.1光伏效應 13
2-5.2太陽光譜介紹 13
2-5.3太陽能電池等效電路圖 14
2-5.4元件效率損失因子 16
第三章 實驗方法 18
3-1實驗步驟 18
3-1.1基板清洗步驟 18
3-1.2薄膜沉積步驟 19
3-2薄膜量測分析 20
3-2.1膜厚分析儀(α-step) 20
3-2.2低掠角X光繞射儀（GIXRD 20
3-2.3霍爾效應量測(Hall effect measurement) 21
3-2.4場發射型掃描式電子顯微鏡(FE-SEM)分析 22
3-2.5紫外光-可見光光譜儀(UV-VIS)分析 22
3-3太陽能電池製作與特性量測 23
3-3.1太陽能電池製作 23
3-3.2太陽光源模擬器電流-電壓(I-V)量測 24
第四章 結果與討論 25
4-1基板溫度對FZO薄膜與太陽能電池之影響 25
4-1.1 基板溫度對FZO薄膜特性的影響 25
4-1.2 基板溫度對FZO/p-Si太陽能電池特性的影響 28
4-2RTA退火溫度對FZO薄膜與太陽能電池之影響 29
4-2.1 退火溫度對FZO薄膜特性的影響 29
4-2.2 退火溫度對FZO/p-Si太陽能電池特性的影響 29
4-3FZO薄膜厚度對太陽能電池之影響 30
4-4 FZO/p-Si、ZnO/p-Si與AZO/p-Si三種異質接面太陽能電池之特性比較 31
第五章 結論 33
參考文獻 35

[1]L. E. Chaar, L.A. lamont, N. E. Zein, Renewable and Sustainable Energy
Reviews 15 (2011) 2165.
[2]B.P. Jelle, C. Breivik, H. D. Røkenes, Sol. Energy Mater. Sol. Cells, 100
(2012) 69.
[3]L. Bruk, V. Fedorov, D. Sherban, A. Simashkevich, I. Usatii, E. Bobeico,
P. Morvillo Mater. Sci. Eng. B 159 (2009) 282.
[4]D. Song et, A. G. Aberle, J. Xia, Appl. Surf. Sci. 195 (2002) 291.
[5]S. Karadeniz, N. Tug˘luog˘lu, T. Serin, N. Serin, Appl. Surf. Sci. 246
(2005) 30.
[6]W. W. Wenas, S. Riyadi, Sol. Energy Mater. Sol. Cells, 90 (2006) 3261.
[7]J.B. DuBow, D.E. Burk, Appl. Phys. Lett. 29 (1976) 494.
[8]J.C. Manifacier, L. Szepessy, Appl. Phys. Lett. 31 (1977) 459.
[9]H. Kobayashi, H. Mori, T. Ishida, Y. Nakato, J. Appl. Phys. 77 (1995) 1301.
[10]X. Jiang, F. L. Wong, M. K. Fung, S. T. Lee, Appl. Phys. Lett. 83 (2003) 1875.
[11]D. L. Raimondi, E. Kay, J. Vac. Sci. Technol. 7 (1969) 96.
[12]L. Shen, Z. Q. Ma, C. Shen, F. Li, Bo. He, F. Xu, Superlattices Miceostuuctures. 48 (2010) 426.
[13]H. N. Chem, C. L. Lee, T. F. Lei, IEEE Trans. Electron Devices 41(1994) 5.
[14]B. G. Choi, I. H. Kim, D. H. Kim, K. S. Lee, T. S. Lee, B. Cheong, Y. J. Baik , W. M. Kim, J. Eur. Ceram. Soc. 25 (2005) 2161.
[15]I. Kim, K. S. Lee, T. S. Lee, J. H. Jeong, B. K. Cheong, Y. J. Baik, W. M. Kim, J. Appl. Phys. 100 (2006) 63701.
[16]Y. Z. Tsai, N. F. Wang, C. L. Tsai, Mater. Lett. 63 (2009) 1621.
[17]Y. Z. Tsai, N. F. Wang, C. L. Tsai, Thin Solid Films 518 (2010) 4955.
[18]H. L. Hartnagel, A. K. Jain, C. Jagadish, "Semiconducting transparent thin films", Published by Institute of Physics Publication, p.17,1995.
[19]W. Water, S. Y. Chu, Mater. Lett. 55 (2002) 67.
[20]水瑞鐏，”氧化鋅薄膜特性及其在通訊元件與液體感測器上之應用”，國立成功大學電機工程學系博士論文，(2002).
[21]D. G. Baik , S. M. Cho, Thin Solid films. 354 (1999) 227.
[22]S. Y. Chu, W. Water, J. T. Liaw, J. Eur. Cera. Soc. 23 (2003) 1593.
[23]H. Hiramatsu, W. S. Seo, K. Koumoto, Chem. Mater. 10 (1998) 3033.
[24]H. Hara, T. Shiro, T. Yatabe, Jpn. J. Appl. Phys. 43 (2004) 745.
[25]T. Minami, T. Kakumu, and S. Tanaka, J. Vac. Sci. Technol. 14 (1996) 1704.
[26]Brain Campman, “Plasma”, Glow Discharge Process, (John Wiley & Sons, NewYork, U. S. A, 1980) , Chap.3.
[27]M. A. Nicolet, Thin Solid films 52 (1978) 415.
[28]J. R. Roth, "Industrial plasma engineering-Volume1:Principles
Instituteof Physics, Publishing in London,(1995).
[29]J. A. Thornton, J. Vac. Sci. Technol. 11 (1974) 666.
[30]黃惠良、曾百亨，“太陽能電池”，五南圖書出版，2008年。
[31]王藜樺，串接式太陽能電池模擬研究，國立清華大學光電工程
研究所碩士論文，2008年。
[32]林螢光，“光電子學-原理、元件與應用”，全華出版社2008。
[33]H.J. Moller, Semiconductor for Solar Cells, Artech House, Boston, 1993.
[34]黃家華、楊鈞凱，“太陽能電池之效率量測系統與元件表現參數之分析”，國立東華大學碩士論文，2005年。
[35]J. Szlufcik, S. Sivoththaman, J. F. Nlis, R. P. Mertens, R. V. Overstraeten, Proceedings of the IEEE. 85 (1997) 711.
[36]Pallab et al. Bhattacharya, Semiconductor Optoelectronic Devices, 2nd edition, prentice Hall, 1997.
[37]陳頤承、郭昭顯、陳俊亨，“太陽能電池量測技術”，《工業材料雜誌》，258 期，2008年。
[38]P.S. Nayar, Appl. Phys. Lett. 39 (1981) 105.
[39]廖士霆，“矽晶太陽能電池製作與特性分析”，國立清華大學材料科學與工程學系碩士論文，2009年。
[40]G. Sanon, R. Rup, A. Mansingh, Thin Solid Films 190 (2003) 286.
[41]S. S. Lin, J. L. Lay, P. Sajgalik, Surf. Coat. Technol. 190 (2005) 39.
[42]T. Minami, S. Ida, T. Miyata, Thin Solid Films, 416 (2002) 92.
[43]E. Fortunato, P. Barquinha, A. Pimentel, A. Goncalves, A. Marques, L. Pereira, R. Martins, Thin Solid Films 487 (2005) 205.
[44]Y. Nakanishi, S. Naito, T. Nakamura, Y. Hatanaka, G. Shimaoka, Appl. Surf. Sci. 92 (1996) 400.
[45]E. J. Lee, T. W. Bitner, J. S. Ha, M. J. Shane, M. J. Sailor, J. Am. Chem. Soc. 118 (1996) 5375.
[46]J.F. Wang, W.J. Guan, and X.Z. Zhao, J. Appl. Phys. 101 (2007) 033713.