本研究利用電化學交流阻抗頻譜探討使用無機氧化鎳作為p-type選擇性接觸電極之氧化鎳/鈣鈦礦異質接合太陽能電池之工作機制，本研究團隊其他成員先前已利用光激發螢光（photoluminescence）頻譜與光致激發暫態吸收頻譜（photo-induced transient absorption spectroscopy, PIA）證實氧化鎳為一電洞傳輸材料。

　　本文欲探討此氧化鎳電洞傳輸材料層於氧化鎳/鈣鈦礦異質接合元件工作狀態下所扮演之角色，藉由量測此元件之電化學交流阻抗頻譜，並利用p-i-n等效電路作曲線擬合，得到元件不同施加偏壓下之阻抗，並計算出鈣鈦礦層與界面間之載子復合電阻與化學電容，再利用此結果與使用其他選擇性接觸材料之鈣鈦礦元件作比對分析。

　　分析結果顯示於元件工作狀態下，濺鍍之平板氧化鎳薄膜層所扮演之角色為電子阻擋層，能有效抑制載子復合，提高元件之開路電壓。同時，交流阻抗頻譜分析顯示元件工作狀態下有載子累積於多孔氧化鎳薄膜層，因此多孔氧化鎳薄膜確實為一電洞傳輸材料，在元件中同樣可見此特性表現。

In this study, we employee the electrochemical impedance spectroscopy method to analysis the mesoscopic NiO/perovskite/PCBM heterojunction photovoltaic device. The IS measurement results verified that the nanostructured nickel oxide is an p-type material, not only can be a scaffold allowing more perovskite loading but also be a hole transport material. This fact has important implication for the future optimization of perovskite solar cells. The NiO inorganic p-type hole transport material also provide extensive device architecture for further development of perovskite solar cells in the future.

1. Becquerel, E.,Compt. Rend., 1839.9: p.145.
2. Adams, W.G., R.E. Day, and P. Roy, Soc. London, 1877. A25:P. 113
3. M. Gräztel,R. A. J. Janssen, D. B. Mitzi, and E. H. Sargent, Nature, 2012, 488, 304.
4. A.J. NoZik, Annu, Rev, Phys. Chem., 1978, 29, 189.
5. M. Gräztel, Nature, 2001, 414, 338.
6. H. Gerischer and H. Tributsch, Ber. Bunsenges. Phys. Chem., 1968, 72, 437
7. H. Gerischer, Photochem. Photobiol., 1972, 16, 243.
8. R. Memming, Photochem. Photobiol., 1972, 16, 325.
9. A. Fujishima, T. Watanabe, O. Tatsuoki, and K. Honda, Chem. Lett., 1975, 4, 13.
10. H. Tsubomura, M.Matsumura, Y. Nomura, and T. Amamiya, Nature, 1976, 261, 402.
11. T. Osa and M. Fujihira, Nature, 1976, 264, 349.
12. T. Miyasaka, J. Phys. Chem. Lett., 2011, 2, 262
13. B. O’Regan and M. Gräztel, Nature, 1991, 353, 737.
14. A. Yella, H. W. Lee, H. N. Tsao, C. Yi, A. K. Chamdiran, Md. K. Nazeeruddin, E. W. G. Diau, C. Y. Yeh, S. M. Zakeeruddin, and M. Gräztel, Science, 2011, 334, 629.
15. U. Bach, Ph.D. Thesis EPFL, 2000.
16. U. Bach, D.Lupo, P. Comte, J. E. Moser, F. Weissortel, J. Salbeck, H. Spreitzer, and M. Gräztel, Nature, 1998, 395, 583.
17. Zhao J, W. A., Green M. A., Ferrazza F., Novel 19.8% efficient “honeycomb” textured multicrystalline and 24.4% monocrystalline silicon solar cells. 1998. 73: p. 1991-1993.
18. Green, M. A., et al., Solar cell efficiency tables (version 37). Progress in photovoltaics: Research and Applications, 2011. 19(1): p. 84-92.
19. Schultz, O., S. W. Glunz, and G. P. Willeke, SHORT COMMUNICATION : ACCELERATED PUBLICATION: Multicrystalline silicon solar cells exceeding 20% efficiency. Progress in Photovoltaics: Research and Applications, 2004. 12(7): p. 553-558
20. Peumans, P. and S. R. Forrest, Applied Physics Letters, 2001. 79(1) : p. 126
21. Wanli Ma, C. Y., Xiong Gong, Kwanghee Lee, and Alan J. Hegger, Adv. Funct. Mater., 2005. 15: p. 1617-1622
22. M. Gräztel., Solar Energy Conversion by Dte-Sensitized Photovoltaic Cells. Inorganic Chemistry, 2005. 44(20): p. 6841-6851.
23. Zhong Sheng Wang, M. Y., Kazuhiro Sayama, and Hideki Sugihara, Chem. Mater., 2006. 18: p.2912-2916.
24. Burschka, J., et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature, 2013. 499(7458): p.316-9
25. J. Burschka, A. Dualeh, F. Kessler, E. Baranoff, N. –L. Cevey-Ha, C. Yi, M. K. Nazeeruddin, and M. Gräztel, J. Am. Chem. Soc, 2011, 133,18402.
26. I.-K Ding, T. Nicolas, J. Brillet, B. E. Hardin, E. H. Smith, S. J. Rosenthal, F. Sauvage, M. Gräztel, and M. D. McGehee, Adv. Funct. Mater., 2009, 19, 2431.
27. J. -H Yum, P. Chem, M. Gräztel, and M. K. Nazeeruddin, ChemSusChem, 2008, 1, 699.
28. H.-S. Kim, C.-R Lee, J.-H Im, K.-B Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H Yum, J. E. Moser, M, Gräztel, and N.-G. Park, Sci. Rep., 2013,2, 591.
29. M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, and H. J. Snaith, Science, 2012, 338, 643.
30. 陳頤辰, 郭昭顯, 陳俊亨, 工研院太陽光電研究中心, 工業材料雜誌258期。
31. http://www.oe-chemicals.com/, Organic Electronic Chemicals, LLC.]
32. J. G. Bednorz and K. A. Muller, Z. Phys. B-Condensed Matter, 1984, 64, 189.
33. R. J Cava, B, Batlogg, J. J. Krajewski, R. Farrow, L. W. Rupp, A. E. White, K. Short, W. F. Peck, and T. Komentani, Nature, 1988, 332, 814.
34. R. J. Cave, B. Batlogg, J. J. Krajewski, R. Farrow, L. W. Rupp, A. E. White, K. Short, W. F. Peck, and T, Komentani, Nature, 1988, 332, 814.
35. D. B. Mitzi, S. Wang, C. A. Field, C. A. Chess, and A. M. Guloy, Science, 1995, 267, 1473.
36. D. B. Mitzi, S. Wang, C. A. Field, Z. Schlesinger, and R. B. Laibowitz, J. of Solid State Chemistry, 1995, 114, 159-163
37. V. Chakravarthy and A. M. Guloy Chem. Commun., 1997, 0, 697.
38. G. C.Papavassillou, Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, 1996, 286, 231.
39. D. B. Mitzi, K. Chondroudis, and C.R. Kagan, Inorg. Chem,., 1999, 38, 6246-6256.
40. D. B. Mitzi, Chem. Mater., 1996, 8, 791.
41. T. Ishilara, J. Takahashi, and T. Goto, Solid State Commun., 1989, 69, 933.
42. T. Ishilara, J. Takahashi, and T. Goto, Solid State Commun., 1990, 42, 11099.
43. T. Kondo, S. Iwamoto, S. Hayase, K. Tanaka, J. Ishi, M. Mizunno, K. Ema, and R. Ito, Solid State Commun., 1998, 105, 503.
44. K. Chondroudis and D. B. Mitzi, Chem. Mater., 1999, 11, 3028.
45. C. R. Kagan, D. B. Mitzi, and C. D. Dimitrakopoulos, Science, 1999, 286, 945.
46. T. Ishihara, J. of Lumin., 1994, 60-161, 269.
47. I. B. Koutselas, L. Ducasse, and G.C. Papavassilliou, J.Phys.: Condens. Matter, 1996, 8, 1217.
48. T. Ishihara, J. of Lumin., 1994, 60-161, 269.
49. M. Hirasawa, T. Ishihara, T. Goto, K. Uchida, and N. Miura, Physica B, 1994, 201, 427.
50. M. Hurasawa, T. Ishihara, and T.Goto, J. Phys Soc. Japan, 1994, 63, 3870.
51. K. Tanaka, T. Takahashi, T. Ban, T.Kondo, K. Uchida, and N. Miura, Solid State Commun., 2003, 127, 619.
52. D. B. Mitzi, K. Chondroudis, and C.R. Kagan, IBM J. Res. And Dev., 2001, 45, 29
53. V. M. Agranovich, Yu. N. Gartstein, and M. Litinskaya, Chem. Rev., 2011, 111, 5179
54. Z. Han, H.-S. Nguyen, F. Boitier, Y, Wei, K. Abdel-BAki, J.-S. Jauret, J. Bloch, S. Bluchoule, and E. Deleporte, Opt. Lett., 2012, 37, 5061.
55. R. Vogel, P. Hoyer, and H. Weller, J. Phys. Chem. 1994, 98, 3183.
56. P.B. Kamat, J. Phys. Chem. C, 2008, 112, 18737
57. I. Mora Sero and J. Bisquert, J. Phys. Chem. Lett., 2010, 1, 3046
58. A. Zaban, O.I. Micic, B.A. Gregg, and A. J. Nozik and, Langmuir, 1998, 14, 3153.
59. R.Vogel, K. Pohl, and H. Weller, Chem. Phys. Lett., 1990, 174, 241.
60. H. J. Lee, J.-H. Tum, H. C. Leventis, S. M. Zakeeruddin, S. A. Haque, P. Chen, S. I. Seok, M. Gra tzel, and Md. K. Nazeeruddin, J. Phys. Chem. C., 2008, 112, 11600.
61. R. Plass, S. Pelet, J. Kruger, and U. Bach M. Gratzel, J. Phys. Chem. B, 2002, 106, 7578
62. J. A. Chang, J. H. Rhee, S. H. Im, Y. H. Lee, H.-J. Kim, S. I. Seok, Md. K. Nazeeruddin, and M. Gratzel, Nano Lett., 2010, 10, 2609
63. H. J. Lee, J.-H. Yum. H.C. Leventis, S. M. Zakeeruddin, S. A. Haque, P. Chen, S. I. Seok, M.Gratzel, M. K. Nazeeruddin, J. Phys. Chem. C, 2008, 112, 11600.
64. Y.-L. Lee and Y.-S. Lo, Adv. Funct. Mater., 2009, 19, 604.
65. H. J. Lee, M. Wang, P. Chen, D. R. Gamelin, S. M. Zakeeruddin, M. Gratzel, and M. K, Nazerruddin, Nano Lett., 2009, 9, 4221.
66. A. Kojima, K. Teshima, Y. Shirai, and T. Miyasaka, J. Am. Chem. Soc., 2009, 131, 6050
67. J.- H. Im, C.-R. Lee, J.-W. Lee, S.-W. Park, and N.-G. Park, Nanoscale, 2011, 3, 4088
68. L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, Md. K. Nazeeruddin, and M. Gratzel, J. Am. Chem. Soc., 2012, 134, 17396.
69. I. Chung, B. Lee, J. He, R. P. H. Chang, and M. G. Kanatzidis, Nature, 2012, 485, 486.
70. Gonzalez-Pedro, V., Juarez-Perez, E.J., Arsyad, W-S., Barea, E.M., Fabregat-Santiago, F., Mora-Sero, I., and Bisquert, J., General working principles of CH3NH3PbX3 perovskite solar cells. Nano Letter, DOI: 10.1021/nl404252e (2014)
71. H. –S. Kim, I. Mora-Sero, V. Gonzalez-Pedreo, F. Fabregat-Santiago, E. J. Juarez-Perez, N. –G. Park, J. Bisquert, Nat. Communications 2013, DOI: 10.1038/ncomms3242.