本實驗工作利用離子束濺鍍系統(Ion-beam sputter system)在室溫下製備[氧化亞銅(Cu2O)/ 氧化鎵(Ga2O3)]20週期之多層膜於c-plane氧化鋁基板上，進一步將[Cu2O/Ga2O3]20多層膜利用快速熱退火(Rapid Thermal Annealing, RTA)處理來製備具有銅鐵礦(delafossite)結構之p型透明導電氧化物薄膜。首先，固定Cu2O之單層厚度為32Å，改變氧化鎵Ga2O3單層厚度(26 ~ 83 Å)，在1100°C下進行退火60分鐘，其結果發現[Cu2O(32 Å) / Ga2O3(53 Å)]20為最佳厚度比，該薄膜具有銅鐵礦結構且具有最少之雜相存在。利用同步輻射吸收光譜可以得知該薄膜中Cu及Ga分別為+1及+3價。此外，由於使用單晶氧化鋁作為基板，由穿透式電子顯微鏡之元素分析結果得知，高溫RTA會使得Al擴散至薄膜中，且在靠近基板處高達14%，因此所形成之銅鐵礦結構為Cu(GaxAl1-x)O2。該薄膜為電洞型傳導，其載子濃度為6.37 x 1017 cm-3；其透光率在可見光區可達80 %，且其直接及間接能隙分別為3.5及3.24電子伏特。
另外，針對比例最佳化之[Cu2O(32 Å) / Ga2O3(53 Å)]20多層膜進一步改變RTA時間(5、15、30、45以及60分鐘)，我們發現30分鐘RTA之[Cu2O(32 Å) / Ga2O3(53 Å)]20多層膜可以得到單相且具有c軸紋理之銅鎵鋁氧薄膜，其晶粒大小約350 nm，且該薄膜之載子濃度僅具有3.6 x 1016 cm-3，藉由元素成分分析得知，Cu : (Ga+Al) = 1.14 : 0.72，其+3價離子(MIII)減少可能導致MIIIO2之O無法有效與MIII原子鍵結形成偽四面體結構，進而形成額外結構缺陷，亦即捕捉態(trap states)，因此造成電洞濃度下降。此外，將多層膜各層厚度減半以及降低快速熱退火溫度至1050°C也可以製備單相且c軸紋理之銅鎵鋁氧薄膜，其晶粒大小約為225 nm，電洞載子濃度則為2.32 x 1016 cm-3。藉由元素成分分析得知，Cu : (Ga+Al) = 0.98 : 0.73，其結果與30分鐘1100°C快速熱退火結果類似。

We demonstrate the p-type transparent conducting oxides of Cu-based delafossite structure materials using an ion-beam sputter system. Multilayers of Cu2O and Ga2O3 with 20 cycles were deposited on c-plane sapphire substrates at room-temperature, and then annealed at 1100°C for 60 minutes by a rapid thermal annealing (RTA) system. The layer thickness of Cu2O and Ga2O3 were respectively fixed at 32 Å and varied from 26 ~ 83 Å. Optimized Ga2O3 thickness, 53 Å, can form the delafossite structure, but exists some weak secondary phase. X-ray absorption spectroscopy analysis indicates the valence of Cu and Ga in [Cu2O(32 Å) / Ga2O3(53 Å)]20 multilayers are +1 and +3. The absorption spectroscopy is also similar to CuGaO2 bulk materials. Transmission Electron Microscopy (TEM) is also used to investigate the microstructure and elements specifics. The results show a grain size of ~350 nm in diameter, the Al diffusion from substrates into multilayers as well as 1 : 0.9 ratio of Cu versus (Ga and Al). The results indicate the RTA [Cu2O(32 Å) / Ga2O3(53 Å)]20 on sapphire form Cu(GaxAl1-x)O2 delafossite structure. Besides, the films show a hole concentration of 6.37 x 1017 cm-3 and 80 % transparency in visible region. The bandgap of films respectively shows a direct and an indirect bandgap of 3.5 and 3.24 eV for n = 0.5 and 2 in Tauc-Sunds formula.
To suppress the secondary phase and improved structure, we include two methods: (i) changing the annealing time of [Cu2O(32 Å) / Ga2O3(53 Å)]20 multilayers from 5 to 60 minutes as well as (ii) decreasing the layer thickness of Cu2O and Ga2O3 and annealing temperature. 30min RTA multilayers show a single-phase and highly c-axis textured delafossite structure and the corresponding hole concentration (nc) is 3.6 x 1016 cm-3. 1050°C annealing [Cu2O(16 Å) / Ga2O3(26 Å)]20 also show similar results, a single-phase and highly c-axis textured delafossite structure, with 30 min RTA films and the nc is 2.32 x 1016 cm-3. The decreasing nc of these films is associated with the lower ratio of (Ga and Al) from 0.9 to 0.7. Decreasing (Ga and Al) ratio could impede the formation of MIIIO2 to pesudo-tetrahedral coordination, which creates additional structure defects, i.e. trap states, and result in a decrease of hole carrier concentration.

第一章
[1] K. Badekar, Ann. Phys. 22, 749 (1907).
[2] R.G. Gordon, MRS Bull. 52 (August 2000).
[3] W.R. Sinclair, F.G. Peters, D.W. Stillinger, S.E. Koonce, J. Electrochem. Soc. 112, 1096 (1965).
[4] B.H. Choi, H.B. Im, J.S. Song, K.H. Yoon, Thin Solid Films 193, 712 (1990).
[5] G. Haacke, W.E. Mealmaker, L.A. Siegel, Thin Solid Films 55, 67 (1978).
[6] T. Minami, H. Sonohara, S. Takata, H. Sato, Jpn. J. Appl. Phys., Part 2: Lett. 33, L1693 (1994).
[7] T. Otabe, K. Ueda, A. Kudoh, H. Hosono, H. Kawazoe, Appl. Phys. Lett. 72, 1036 (1998).
[8] D.D. Edwards, T.O. Mason, F. Goutenoire, K.R. Poeppelmeier, Appl. Phys. Lett. 70, 1706 (1997).
[9] T. Minami, T. Kakumu, K. Shimokawa, S. Takata, Thin Solid Films 317, 318 (1998).
[10] T. Omata, N. Ueda, K. Ueda, H. Kawazoe, Appl. Phys. Lett. 64, 1077 (1994)
[11] R.L. Cornia, J.B. Fenn, H. Memarian, R. Ringer, Proceedings of 41st Annual Technical Conference, Boston, SVC, 452 (1998).
[12] D.R. Cairns, R.P. Witte, D.K. Sparacin, S.M. Sachsman, D.C. Paine, G.P. Crawford, R. Newton, Appl. Phys. Lett. 76, 1425 (2000).
[13] C.H. Seager, D.C. McIntyre, W.L. Warren, B.A. Tuttle, Appl. Phys. Lett. 68, 2660 (1996).
[14] M.W.J. Prince, K.O. Gross-Holtz, G. Muller, J.B. Cillessen, J.B. Giesbers, R.P. Weening, R.M. Wolf, Appl. Phys. Lett. 68, 3650 (1996).
[15] H. Kawazoe, M. Yasukawa, H. Hyodo, M. Kurita, H. Yanagi, H. Hosono, Nature 389, 939 (1997).
[16] G. Thomas, Nature 389, 907 (1997).
[17] H. Sato, T. Minami, S. Takata, T. Yamada, Thin Solid Films 236, 27 (1993).
[18] A.N. Banerjee, K.K. Chattopadhyay, Progress in Crystal Growth and Charaterization of Materials 50, 52 (2005).
[19] H. Kawazoe, H. Yanagi, K. Ueda, H. Hosono, MRS Bull. 28 (August 2000).
[20] D. DeVault, J. Chem. Educ. 21, 526 (1944).
[21] J.C. Bailar Jr., H.J. Emele´us, Sir N. Ronald, A.F. Trotman-Dickenson (Eds.), Comprehensive Inorganic Chemistry, Pergamon, New York, NY, 1973.
[22] Y.K. Leung, A.K. Khan, J.F. Kos, F.P. Koffyberg, Proceedings of National Conference on Solar Energy, Montreal, Solar Energy Society of Canada, 124 (1981).
[23] J.P. Dahl, A.C. Switendick, J. Phys. Chem. Solids 27, 931 (1966).
[24] M. Hayashi, K. Katsuki, J. Phys. Soc. Jpn. 5, 380 (1950).
[25] L. Kleinman, K. Mednick, Phys. Rev. B 21, 1549 (1980).
[26] R.D. Shannon, D.B. Rogers, C.T. Prewitt, Inorg. Chem. 10, 713 (1971).
[27] C.T. Prewitt, R.D. Shannon, D.B. Rogers, Inorg. Chem. 10, 719 (1971).
[28] D.B. Rogers, R.D. Shannon, C.T. Prewitt, J.L. Gilson, Inorg. Chem. 10, 723 (1971).
[29] H. Hiramatsu, K. Ueda, H. Ohta, M. Orita, M. Hirano, H. Hosono, Appl. Phys. Lett. 81, 598 (2002).
[30] F.A. Benko, F.P. Koffyberg, J. Phys. Chem. Solids 45, 57 (1984).
[31] H. Yanagi, S. Inoue, K. Ueda, H. Kawazoe, H. Hosono, N. Hamada, J. Appl. Phys. 88, 4159 (2000).
[32] J. Robertson, P.W. Peacock, M.D. Towler, R. Needs, Thin Solid Films 411, 96 (2002).
[33] B.J. Ingram, T.O. Mason, R. Asahi, K.T. Park, A.J. Freeman, Phys. Rev. B 64, 155114 (2001).
[34] J. Tate, M.K. Jayaraj, A.D. Draeseke, T. Ulbrich, A.W. Sleight, K.A. Vanaja, R. Nagarajan, J.F. Wager, R.L. Hoffman, Thin Solid Films 411, 119 (2002).
[35] H. Yanagi, T. Hase, S. Ibuki, K. Ueda, H. Hosono, Appl. Phys. Lett. 78, 1583 (2001).
[36] H. Yanagi, K. Ueda, H. Ohta, M. Orita, M. Hirano, H. Hosono, Solid State Commun. 121, 15 (2001).
[37] N. Duan, A.W. Sleight, M.K. Jayaraj, J. Tate, Appl. Phys. Lett. 77, 1325 (2000).
[38] R. Nagarajan, A.D. Draeseke, A.W. Sleight, J. Tate, J. Appl. Phys. 89, 8022 (2001).
[39] M.K. Jayaraj, A.D. Draeseke, J. Tate, A.W. Sleight, Thin Solid Films 397, 244 (2001).
[40] R. Nagarajan, N. Duan, M.K. Jayaraj, J. Li, K.A. Vanaja, A. Yokochi, A. Draeseke, J. Tate, A.W. Sleight, Int. J. Inorg. Mater. 3, 265 (2001).
[41] R.J. Cava, W.F. Peck Jr., J.J. Krajewski, S.W. Cheong, H.Y. Hwang, J. Mater. Res. 9, 314 (1994).
[42] R.J. Cava, H.W. Zandbergen, A.P. Ramirez, H. Tagaki, C.T. Chien, J.J. Krajewski, W.F. Peck Jr., J.V. Waszczak, G. Meigs, R.S. Roth, L.F. Schneemeyer, J. Solid State Chem. 104, 437 (1993).
[43] M.K. Jayaraj, A. Draeseke, J. Tate, N. Duan, A.W. Sleight, Proceedings of the MRS Workshop on Transparent Conductive Oxide, Denever, CO, 2000.
[44] A.N. Banerjee, C.K. Ghosh, K.K. Chattopadhyay, Sol. Energy Mater. Sol. Cells 89, 75 (2005).
[45] K. Tonooka, K. Shimokawa, O. Nishimura, Thin Solid Films 411, 129 (2002).
[46] C.H. Ong, H. Gong, Thin Solid Films 445, 299 (2003).
[47] M.V. Lalic´, J.M. Filho, A.W. Carbonari, R.N. Saxena, M. Moralles, J. Phys.: Condens. Matter 14, 5517 (2002).
[48] M.V. Lalic´, J.M. Filho, A.W. Carbonari, R.N. Saxena, Solid State Commun. 125, 175 (2003).
[49] D.Y. Shahriari, A. Barnabe`, T.O. Mason, K.R. Poeppelmeier, Inorg. Chem. 40, 5734 (2001).
[50] P. Lunkenheimer, A. Loidl, C.R. Ottermann, K. Bange, Phys. Rev. B 44, 5927 (1991).
[51] G.A. Slack, J. Appl. Phys. 31, 1571 (1960).
[52] M.R. Norman, Phys. Rev. Lett. 64, 1162 (1990).
[53] K.L. Chopra, S. Major, D.K. Pandya, Thin Solid Films 102, 1 (1983).
[54] H.L. Hartnagel, A.L. Dawar, A.K. Jain, C. Jagadish, Semiconducting Transparent Thin Films, IOP Publishing Ltd., Bristol and Philadelphia, 1995.
[55] D.G. Thomas, J. Phys. Chem. Solids 9, 31 (1959).
[56] J.J. Lander, J. Phys. Chem. Solids 15, 324 (1960).
[57] K. Hu¨mmer, Phys. Status Solidi B 56, 249 (1973).
[58] T. Yamamoto, H.K. Yoshida, Jpn. J. Appl. Phys. 38, L166 (1999).
[59] M. Joseph, H. Tabata, T. Kawai, Jpn. J. Appl. Phys. 38, L2505 (1999).

第三章
[1] G.K. Wehner et al.﹐Handbook of Thin Film Technology, McGraw-Hill﹐New York﹐1970
[2] Soshin Chikazumi and Stanley H. Charap, Physics of Magnetism, (1972)
[3] D.C. Koningsberger and R. Prins, X-ray Absorption principles, applications, techniques of EXAFS, SEXAFS and XANES (1988), 574
[4] J.J. Rehr et al., Rev. Mod. Phys., 72 (2000), 621
[5] 半導體元件物理與製作技術(第二版)，施敏、黃調元 (2006)， p.96-98

第四章
[1] J. Pellicer-Porres, A. Segura, Ch. Ferrer-Roca, D. Martı´nez-Garcı´a, J.A. Sans, and E. Martı´nez, Phys. Rev. B 69, 024109 (2004).
[2] D.Y. Shahriari, A. Barnabe`, T.O. Mason, K.R. Poeppelmeier, Inorg. Chem. 40, 5734 (2001).

附錄一
[1] S. K. MISRA and A. C. D. CHAKLADER, Journal of The American Ceramic Society - Discussions and Notes, 509 (1963).