本論文主要以分成兩部分，第一部份為製備鈣鈦礦晶體薄膜表面形貌的控制。鈣鈦礦晶體薄膜的製程目前在國際上大約有四種，分別是1) Sequential Deposition, 2) One Step Deposition 3) Duel-Source Vapor Deposition and 4) Vapor-Assisted Solution Process。由於後兩項需要用到昂貴的設備和高溫製程，吾人採取前面的兩個低溫且較簡單、不須用到昂貴設備的製程來從事研發。以達到降低生產成本且維持一定轉換效率的方向研究。依實驗室環境最佳化鈣鈦礦晶體薄膜，吾人利用快速沉積法，以DMSO做為鈣鈦礦的高沸點極性溶液形成鈣鈦礦前驅溶液，利用快速沉積方法加工鈣鈦礦晶體薄膜(FDC-Fast Deposition-Crystallization Procedure)，進而獲得致密且均勻的的鈣鈦礦晶體薄膜以改善薄膜的覆蓋性，減少孔隙的形成獲得良好的薄膜以提高元件效率以及其再現性與穩定性。製備結構Glass/PEDOT:PSS/MA-Perovskite/PCBM/Ag 製備元件，利用快速沉積法，運用甲苯加工鈣鈦礦晶體表面去除多餘DMSO進而獲得緻密且均勻的晶體薄膜。
第二部分吾人則是參考快速沉積法，利用不同溶劑加工法製備FA-Perovskite薄膜，利用結構Glass/PEDOT:PSS/FA-Perovskite/PCBM/Ag 製備鈣鈦礦/富勒烯平面結構異質介面太陽能電池，由實驗結果發現利用快速沉積法對於主動層結晶性有很大的影響，更加直接反應在元件的效率表現上。接著，吾人再加以利用混和溶液之方法調配FA鈣鈦礦，將原本單一溶液DMSO加入部分比例的GBL(γ-丁內酯)，希望藉由混和溶液的方式製備出更加緻密的主動層薄膜，最後經由實驗測試發現以比例:(DMSO:GBL= 7:3 v/v)為調配之參數所製備出的元件之光電轉換效率最佳。以SEM進行表面分析，發現使用混和溶液並配合快速沉積法所製備出薄膜其單一晶格更大且以混和溶液配合快速沉積法所製備出的鈣鈦礦晶體薄膜相較於單一溶液其表面更加緻密且表面覆蓋率高，進行SEM與AFM研究與亮，暗態電流-電壓曲線測量以探討各參數之趨勢。實驗結果與分析將在本論文中加以說明與討論。最終效率達4.596%。

The cubic HC(NH2)2PbI3 (FAPbI3) perovskite has the measured band gap of 1.43 eV and its corresponding absorption edge reaches 870 nm. Therefore, the material is potentially superior than the CH3NH3PbI3 (MAPbI3) as the light harvester. The current work made FAPbI3 perovskite solar cell with structure, as shown in Fig. 1a, by depositing a thin layer of FA-perovskite film with a one-step process. This is done by spin-coating of 40 wt % PbI2 : FAI (at 1:1) mixture in DMSO to get a pure FAPbI3 perovskite phase. To adopt the solvent-induced, fast crystallization process, the spin-coated film is immediately exposed to different kinds of non-solvents, such as toluene, chlorobenzene to induce crystallization. All the spin-coated films can be annealed at relatively low temperatures such that the cell can be made on a flexible substrate. Six different kinds of non-solvents, such as toluene, chlorobenzene, dichlorobenzene, 2-isopronol, chloroform, acetonitrile, were used to test the crystallization of FA-perovskite film at 160oC. It was found that the non-solvent of 2-isopronol has the best result of crystallization and coverage of entire film. The crystallization process took only 10 mins in comparison to the traditional method of annealing for two hours at 160oC. In order to improve the cell performance, the mixed solution of DMSO and GBL was used to dissolve PbI2 : FAI (at 1:1). It is found that the mixing ratio for DMSO versus GBL at 7:3 v/v has the best crystallization and coverage of the entire film, as shown in Fig. 1, leading to significant increase in the cell performance. The Jsc of the solar cell with PbI2 and FAI dissolved in the mixture of DMSO and GBL at 7:3 can increase from 9.585 to 10.249 mA/cm2 and FF from 0.421 to 0.56 and PEC from 3.228% to 4.596%, as shown in Fig. 2 for I-V characteristic measurements. Further improvement in cell performance will be discussed in the conference.

[1] Loi, Maria Antonietta, and Jan C. Hummelen. , et al. "Hybrid solar cells: Perovskites under the Sun." Nature materials 12.12 (2013): 1087-1089.
[2] Burschka, Julian, et al. "Sequential deposition as a route to high-performance perovskite-sensitized solar cells." Nature 499.7458 (2013): 316-319.
[3] Docampo, Pablo, et al. "Efficient organometal trihalide perovskite planar-heterojunction solar cells on flexible polymer substrates." Nature communications 4 (2013).
[4] Hodes, Gary, et al. "Perovskite-based solar cells." Science 342.6156 (2013): 317-318.
[5] Liu, Mingzhen, Michael B. Johnston, and Henry J. Snaith. , et al. "Efficient planar heterojunction perovskite solar cells by vapour deposition." Nature 501.7467 (2013): 395-398.
[6] Stranks, Samuel D., et al. "Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber." Science 342.6156 (2013): 341-344.
[7] Xing, Guichuan, et al. "Long-range balanced electron-and hole-transport lengths in organic-inorganic CH3NH3PbI3." Science 342.6156 (2013): 344-347.
[8] Liu, Dianyi, and Timothy L. Kelly. , et al. "Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques." Nature photonics 8.2 (2014): 133-138.
[9] Malinkiewicz, Olga, et al. "Perovskite solar cells employing organic charge-transport layers." Nature Photonics 8.2 (2014): 128-132.
[10] Yella, Aswani, et al. "Nanocrystalline rutile electron extraction layer enables low-temperature solution processed perovskite photovoltaics with 13.7% efficiency." Nano letters 14.5 (2014): 2591-2596.
[11] Yella, Aswani, et al. "Porphyrin-sensitized solar cells with cobalt (II/III)–based redox electrolyte exceed 12 percent efficiency." science 334.6056 (2011): 629-634.
[12] Zhou, Huanping, et al. "Interface engineering of highly efficient perovskite solar cells." Science 345.6196 (2014): 542-546.
[13] Lee, Michael M., et al. "Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites." Science 338.6107 (2012): 643-647.
[14] Kojima, Akihiro, et al. "Organometal halide perovskites as visible-light sensitizers for photovoltaic cells." Journal of the American Chemical Society 131.17 (2009): 6050-6051.
[15] Im, Jeong-Hyeok,et al. "6.5% efficient perovskite quantum-dot-sensitized solar cell." Nanoscale 3.10 (2011): 4088-4093
[16] H.-S. Kim et al., Sci. Rep., 2012, 2, 591
[17] Lee, Michael M., et al. "Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites." Science 338.6107 (2012): 643-647.
[18] Zhou, Huanping, et al. "Interface engineering of highly efficient perovskite solar cells." Science 345.6196 (2014): 542-546.
[19] Yang, Woon Seok, et al. "High-performance photovoltaic perovskite layers fabricated through intramolecular exchange." Science (2015): aaa9272.
[20] Ball, James M., et al. "Low-temperature processed meso-superstructured to thin-film perovskite solar cells." Energy & Environmental Science 6.6 (2013): 1739-1743.
[21] Jeng, Jun‐Yuan, et al. "CH3NH3PbI3 Perovskite/Fullerene Planar‐Heterojunction Hybrid Solar Cells." Advanced Materials 25.27 (2013): 3727-3732.
[22] Docampo, Pablo, et al. "Efficient organometal trihalide perovskite planar-heterojunction solar cells on flexible polymer substrates." Nature communications 4 (2013).
[23] You, Jingbi, et al. "Low-temperature solution-processed perovskite solar cells with high efficiency and flexibility." (2014).
[24] Bing-Huang Jiang,et al. "The Progress of Planar Type Perovskite Solar Cells"CHEMISTRY (The Chinese Chemical Society, Taipei)(2014)
[25] Pellet, Norman, et al. "Mixed‐Organic‐Cation Perovskite Photovoltaics for Enhanced Solar‐Light Harvesting." Angewandte Chemie International Edition 53.12 (2014): 3151-3157.
[26] Amat, Anna, et al. "Cation-induced band-gap tuning in organohalide perovskites: Interplay of spin–orbit coupling and octahedra tilting." Nano letters 14.6 (2014): 3608-3616.
[27] Hanusch, Fabian C., et al. "Efficient planar heterojunction perovskite solar cells based on formamidinium lead bromide." The Journal of Physical Chemistry Letters 5.16 (2014): 2791-2795.
[28] Koh, Teck Ming, et al. "Formamidinium-containing metal-halide: an alternative material for near-IR absorption perovskite solar cells." The Journal of Physical Chemistry C 118.30 (2013): 16458-16462.
[29] Pang, Shuping, et al. "NH2CH=NH2PbI3: An Alternative Organolead Iodide Perovskite Sensitizer for Mesoscopic Solar Cells." Chemistry of Materials 26.3 (2014): 1485-1491.
[30] Stoumpos, Constantinos C., Christos D. Malliakas, and Mercouri G. Kanatzidis. Malinkiewicz, Olga, et al. "Perovskite solar cells employing organic charge-transport layers." Nature Photonics 8.2 (2014): 128-132. "Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties." Inorganic chemistry 52.15 (2013): 9019-9038.
[31] Eperon, Giles E., et al. "Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells." Energy & Environmental Science 7.3 (2014): 982-988.
[32] Lv, Siliu, et al. "One-step, solution-processed formamidinium lead trihalide (FAPbI (3− x) Cl x) for mesoscopic perovskite–polymer solar cells." Physical Chemistry Chemical Physics 16.36 (2014): 19206-19211.
[33] Lee, Jin‐Wook, et al. "High‐Efficiency Perovskite Solar Cells Based on the Black Polymorph of HC (NH2) 2PbI3." Advanced Materials 26.29 (2014): 4991-4998.
[34] Burschka, Julian, et al. "Sequential deposition as a route to high-performance perovskite-sensitized solar cells." Nature 499.7458 (2013): 316-319.
[35] Chen, Qi, et al. "Planar heterojunction perovskite solar cells via vapor-assisted solution process." Journal of the American Chemical Society 136.2 (2013): 622-625.
[36] Seo, Jangwon, et al. "Benefits of very thin PCBM and LiF layers for solution-processed p–i–n perovskite solar cells." Energy & Environmental Science 7.8 (2014): 2642-2646.
[37] Conings, Bert, et al. "Perovskite‐Based Hybrid Solar Cells Exceeding 10% Efficiency with High Reproducibility Using a Thin Film Sandwich Approach." Advanced Materials 26.13 (2014): 2041-2046.
[38] Chen, Qi, et al. "Planar heterojunction perovskite solar cells via vapor-assisted solution process." Journal of the American Chemical Society 136.2 (2013): 622-625.
[39] Liu, Dianyi, and Timothy L. Kelly. Malinkiewicz, Olga, et al. "Perovskite solar cells employing organic charge-transport layers." Nature Photonics 8.2 (2014): 128-132. "Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques." Nature photonics 8.2 (2014): 133-138.
[40] Im, Jeong-Hyeok, et al. "Growth of CH3NH3PbI3 cuboids with controlled size for high-efficiency perovskite solar cells." Nature nanotechnology 9.11 (2014): 927-932.
[41] Xiao, Zhengguo, et al. "Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers." Energy & Environmental Science 7.8 (2014): 2619-2623.
[42] Xiao, Zhengguo, et al. "Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers." Energy & Environmental Science 7.8 (2014): 2619-2623.
[43] Chiang, Chien-Hung, Zong-Liang Tseng, and Chun-Guey Wu. , et al. "Planar heterojunction perovskite/PC 71 BM solar cells with enhanced open-circuit voltage via a (2/1)-step spin-coating process." Journal of Materials Chemistry A 2.38 (2014): 15897-15903.
[44] Salau, A. M. , et al. "Fundamental absorption edge in PbI2: KI alloys." Solar Energy Materials 2.3 (1980): 327-332.
[45] Mitzi, David B., M. T. Prikas, and K. Chondroudis. , et al. "Thin film deposition of organic-inorganic hybrid materials using a single source thermal ablation technique." Chemistry of materials 11.3 (1999): 542-544.
[46] Malinkiewicz, Olga, et al. "Perovskite solar cells employing organic charge-transport layers." Nature Photonics 8.2 (2014): 128-132.
[47] Roldán-Carmona, Cristina, et al. "Flexible high efficiency perovskite solar cells." Energy & Environmental Science 7.3 (2014): 994-997.
[48] Stranks, Samuel D., et al. "Formation of Thin Films of Organic–Inorganic Perovskites for High‐Efficiency Solar Cells." Angewandte Chemie International Edition 54.11 (2015): 3240-3248.
[49] Xiao, Manda, et al. "A fast deposition‐crystallization procedure for highly efficient lead iodide perovskite thin‐film solar cells." Angewandte Chemie 126.37 (2014): 10056-10061.
[50] Paek, Sanghyun, et al. "Improved External Quantum Efficiency from Solution-Processed (CH3NH3)PbI3 Perovskite/PC71BM Planar Heterojunction for High Efficiency Hybrid Solar Cells." The Journal of Physical Chemistry C 118.45 (2014): 25899-25905.
[51] Jeon, Nam Joong, et al. "Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells." Nature materials (2014).
[52] Chen, Chun-Chao, et al. "One-step, low-temperature deposited perovskite solar cell utilizing small molecule additive." Journal of Photonics for Energy5.1(2015):057405-057405.
[53] Yang, Xudong, Masatoshi Yanagida, and Liyuan Han. , et al. "Reliable evaluation of dye-sensitized solar cells." Energy & Environmental Science 6.1 (2013): 54-66.
[54] Snaith, Henry J., et al. "Anomalous hysteresis in perovskite solar cells." The Journal of Physical Chemistry Letters 5.9 (2014): 1511-1515.
[55] Unger, E. L., et al. "Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells." Energy & Environmental Science 7.11 (2014): 3690-3698.
[56] Wang, Qi, et al. "Large fill-factor bilayer iodine perovskite solar cells fabricated by a low-temperature solution-process." Energy & Environmental Science 7.7 (2014): 2359-2365.
[57] Xiao, Zhengguo, et al. "Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers." Energy & Environmental Science 7.8 (2014): 2619-2623.
[58] Shao, Yuchuan, et al. "Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells." Nature communications 5 (2014).
[59] Lee, Michael M., et al. "Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites." Science 338.6107 (2012): 643-647.
[60] Hao, Feng, et al. "Lead-free solid-state organic-inorganic halide perovskite solar cells." Nature Photonics 8.6 (2014): 489-494.
[61] Noel, Nakita K., et al. "Lead-free organic–inorganic tin halide perovskites for photovoltaic applications." Energy & Environmental Science 7.9 (2014): 3061-3068.