本研究主要以流動氮氣環境輔助改善溶液製程製備高品質鈣鈦礦薄膜，利用X光繞射頻譜、可見光-紫外光吸收光譜、掃描式電子顯微鏡與原子力顯微鏡分析薄膜特性，其結果顯示流動氮氣環境輔助可製備良好結晶性、高覆蓋率、高粗糙度與高光吸收特性之鈣鈦礦薄膜，以此條件製備之鈣鈦礦太陽能電池元件特性如下：電流密度為25.64 mA/cm2、開路電壓為0.84 V、填充因子為0.67與光電轉換效率為14.48 %。
輔以電子傳輸材料PC71BM薄膜進行慢成長製程，藉由原子力顯微鏡分析薄膜特性，可得知電子傳輸材料薄膜覆蓋率明顯提升，有效降低元件介面阻抗，其元件填充因子從0.66提升至0.73，而光電轉換效率亦從14.08 %提升至17.84 %。

In this thesis, we have successfully fabricated high quality perovskite film by solution-process assisted with flowing nitrogen. The perovskite films exhibit good crystallinity, high coverage, smooth surface morphology, and efficient light absorption, characterized by X-Ray diffraction (XRD), UV-VIS spectrophotometry (UV-VIS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The current density, open circuit voltage, fill factor and photoelectric conversion efficiency of the solar cell realized by the perovskite film were 25.64 mA/cm2, 0.84 V, 0.67, and 14.48 %, respectively.
The slow growing technique is also implemented in the electron transporting materials to enhance the efficiency of solar cell. The coverage of the electron transporting material has been increased by the slow growing process which analysis by atomic force microscopy. The fill factor and photoelectric conversion efficiency of the device was enhanced from 0.66 to 0.73 and 14.08 % to 17.84 %, respectively.

摘要 i
Abstract ii
目錄 iii
圖目錄 v
表目錄 vii
第一章 緒論 1
1-1前言 1
1-2鈣鈦礦太陽能電池發展 1
1-3研究動機與目的 3
1-4各章提要 3
第二章 基礎理論 4
2-1鈣鈦礦材料 4
2-2鈣鈦礦太陽能電池之原理與機制 6
2-2-1自由載子與激子產生(Free carriers and Exciton formation) 6
2-2-2激子擴散(Exciton Diffusion) 6
2-2-3激子分離(Exction Dissociation) 6
2-2-4電荷收集(Charge transport and collection) 6
2-3鈣鈦礦太陽能電池結構類型 8
2-4鈣鈦礦太陽能電池輸出特性 10
2-4-1開路電壓(Open circuit voltage, Voc) 10
2-4-2短路電流(Short circuit current density, Jsc) 10
2-4-3填充因子(Fill factor, F.F.) 10
2-4-4光電轉換效率(Power conversion efficiency, PCE) 11
2-5太陽光譜與地表上太陽輻射強度 12
第三章 實驗架構 14
3-1實驗製程儀器介紹 14
3-1-1超音波震盪機 14
3-1-2紫外光臭氧清洗機 14
3-1-3旋轉塗佈機 14
3-1-4低水氧手套箱 14
3-1-5高真空熱蒸鍍系統 14
3-2太陽能電池元件製程與實驗材料 15
3-2-1 ITO電極黃光顯影蝕刻 15
3-2-2 ITO基板清洗與前處理 16
3-2-3溶液調配 17
3-2-4元件製備 19
3-3實驗量測儀器介紹 20
3-3-1紫外光-可見光吸收頻譜儀(UV-Vis Absorption Spectrum) 20
3-3-2 X-射線繞射(X-ray Diffraction) 21
3-3-3掃描式電子顯微鏡(Scanning Electron Microscope) 22
3-3-4原子力顯微鏡(Atomic Force Microscopy) 23
3-3-5太陽光譜模擬量測系統(Solar Simulator System) 25
3-3-6表面輪廓儀 (Surface profiler) 26
第四章 結果與討論 27
4-1簡介 27
4-2鈣鈦礦薄膜晶相分析 28
4-3鈣鈦礦薄膜表面特性分析 29
4-4鈣鈦礦薄膜光學特性分析 33
4-5鈣鈦礦太陽能電池電性分析 34
4-6電子傳輸層材料與製程對鈣鈦礦太陽能電池元件效率之影響 40
第五章 結論 46
參考文獻 47

[1] 張正華等編著，有機與塑膠太陽能電池，臺北市，五南出版社，2007。
[2] 廖純敏編著，改變TiO2結構對(CH3NH3)PbI3敏化太陽能電池特性影響之研究， 碩士論文，國立交通大學電子工程學系，2007。
[3] A. Kojima, K.Teshima, Y. Shirai, T. Miyasaka,” Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells”, Journal of the American Chemical Society, vol. 17, pp 6050–6051, 2009.
[4] 林建翰編著，進化後的敏化染料電池-鈣鈦礦太陽能電池，光連雙月刊，No.114，2014。
[5] 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.Gratzel, N.-G. Park,” Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%”, Scientific Reports, vol. 2, Article number: 591, 2012.
[6] J. Burschka, N. Pellet, S. -J. Moon, R. Humphry-Baker, P. Gao, M. K. Nazeeruddin, M. Grätzel,” Sequential Deposition As A Route To High-Performance Perovskite-Sensitized Solar Cells”, Nature, vol. 499, pp. 316-319, 2013.
[7] M. M. Lee, Joël Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith,” Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites”, Science, vol. 338, pp. 643-647, 2012.
[8] D. Liu, T. L. Kelly,” Perovskite Solar Cells With A Planar Heterojunction Structure Prepared Using Room-Temperature Solution Processing Techniques”, Nature Photonics, vol. 8, pp. 133-138, 2014.
[9] H. Zhou, Q. Chen, G. Li, S. Luo, T.-B. Song, H.-S. Duan, Z. Hong, J. You, Y. Liu, Y. Yang,” Interface Engineering of Highly Efficient Perovskite Solar Cells”, Science, vol. 345, pp. 542-546, 2014.
[10] N. Ahn, D.-Y. Son, I.-H. Jang, S. M. Kang, M. Choi, N.-G. Park,” Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide” , Journal of the American Chemical Society, vol. 137, pp. 8696-8699, 2015.
[11] M. Xiao, F. Huang, W. Huang, Y. Dkhissi, Y. Zhu, J. Etheridge, A. Gray-Weale, U. Bach, Y.-B. Cheng,. L. Spiccia,” A Fast Deposition-Crystallization Procedure for Highly Efficient Lead Iodide Perovskite Thin-Film Solar Cells”, Angewandte Chemie ,vol. 53, pp.9898 -9903, 2014.
[12] N. J. Jeon, J. H. Noh, Y. C. Kim, W. S. Yang, S. Ryu, S. I. Seok,” Solvent Engineering For High-Performance Inorganic-Organic Hybrid Perovskite Solar Cells”, Nature Materials, vol. 13, pp. 897-903, 2014.
[13] C.-H. Chiang, Z.-L. Tseng, C.-G. Wu,” Planar Heterojunction Perovskite/PC71BM Solar Cells With Enhanced Open-Circuit Voltage Via A (2/1)-Step Spin-Coating Process”, Journal of Materials Chemistry A, vol. 2, pp. 15897-15903, 2014.
[14] T.-B. Song, Q. Chen, H. Zhou, S. Luo, Y. Yang, J. You, Y. Yang,” Unraveling Film Transformations And Device Performance Of Planar Perovskite Solar Cells”, Nano Energy, vol. 12, pp. 494-500, 2015.
[15] M. Liu, M. B. Johnston, H. J. Snaith,” Efficient Planar Heterojunction Perovskite Solar Cells By Vapour Deposition” , Nature, vol. 501, pp. 395-398, 2013.
[16] X. Liu, H. Yu, L. Yan, Q. Dong, Q. Wan, Y. Zhou, B. Song, Y. Li,” Triple Cathode Buffer Layers Composed of PCBM, C60, and LiF for High-Performance Planar Perovskite Solar Cells” , ACS Applied Material and Interfaces, vol. 11, pp. 6230-6237, 2015.
[17] Z. Xiao , Q. Dong , C. Bi , Y. Shao , Y. Yuan , J. Huang,” Solvent Annealing of Perovskite-Induced Crystal Growth for Photovoltaic-Device Efficiency Enhancement”, Advanced Materials, vol. 26, pp. 6503-6509, 2014.
[18] http://www.nrel.gov/ncpv/images/efficiency_chart.jpg
[19] 廖學中編著，太陽光電產業的新星-鈣鈦礦太陽能電池，台灣奈米資訊電子報，2014。
[20] W. Nie, H. Tsai, R. Asadpour, J.-C. Blancon, A. J. Neukirch, G. Gupta, J. J. Crochet, M. Chhowalla, S. Tretiak, M. A. Alam, H.-L. Wang, A. D. Mohite,” High-Efficiency Solution-Processed Perovskite Solar Cells With Millimeter-Scale Grains”, Science, vol. 347, pp. 522-525, 2015.
[21] W. Zhang, M. Saliba, D. T. Moore, S. K. Pathak, M. T. Hörantner,T. Stergiopoulos,S. D. Stranks, G. E. Eperon, J. A. Alexander-Webber, A. Abate, A. Sadhanala, S. Yao, Y. Chen, R. H. Friend, L. A. Estroff, U. Wiesner, Henry J. Snaith,,” Ultrasmooth Organic-Inorganic Perovskite Thin-Film Formation And Crystallization For Efficient Planar Heterojunction Solar Cells” Nature Communications, vol. 6, Article number: 6142, 2015.
[22] http://www.ritsumei.ac.jp/se/re/takakuralab/html_storage/intro_perov2015.html
[23] Q. Lin, A. Armin, R. Chandra, R. Nagiri, P. L. Burn, P. Meredith,” Electro-Optics of Perovskite Solar Cells”, Nature Photonics, vol. 9, pp. 106-112, 2015.
[24] H. S. Jung, N. -G. Park,” Perovskite Solar Cells: From Materials to Devices”, Small, vol. 11, pp. 10-25, 2015.
[25] F. Hao, C. C. Stoumpos, R. P. H. Chang, M. G. Kanatzidis,” Anomalous Band Gap Behavior In Mixed Sn And Pb Perovskites Enables Broadening Of Absorption Spectrum In Solar Cells”, Journal of the American Chemical Society, vol. 136, pp. 8094-8099, 2014.
[26] J. You, Y. Yang, Z. Hong, T. B. Song, L. Meng, Y. Liu, C. Jiang, H. Zhou, W. H. Chang, G. Li, Y. Yang,” Moisture Assisted Perovskitefilm Growth For High Performance Solar Cells”, Applied Physics Letters, vol. 105, pp.183902-1-183902-5, 2014.
[27] G. Xing, N. Mathews, S. Sun, S. S. Lim, Y. M. Lam, M. Grätzel, S. Mhaisalkar, T. C. Sum,” Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3”, Science, vol. 18, pp. 344-347, 2013.
[28] J.-Y. Jeng, Y.-F. Chiang, M.-H. Lee, S.-R. Peng, T.-F. Guo, P.r Chen, T.-C. We,” CH3NH3PbI3 Perovskite/Fullerene Planar-Heterojunction Hybrid Solar Cells”, Science, vol. 25, pp. 3727-3732, 2013.
[29] M. Liu, M. B. Johnston, H. J. Snaith,” Efficient Planar Heterojunction Perovskite Solar Cells By Vapour Deposition”, Nature, vol. 501, pp. 395-398, 2013.
[30] L. Meng, J. You, T.-F. Guo, Y. Yang,” Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells”, Accounts of Chemical Research Special Issue Lead Halide Perovskites For Solar Energy Conversion, vol. 49, pp. 155-165, 2016.
[31] 施仁親、陳震偉、吳登峻編著，太陽光模擬器要求與新型LED太陽光模擬器簡介，光連雙月刊，No.114，2011。
[32] 陳頤承、郭昭顯、陳俊亨編著，太陽電池量測技術，工業材料雜誌，No.258，2006。
[33] http://www.newport.com/Introduction-to-Solar-Radiation/411919/1033/content.aspx
[34] http://bouman.chem.georgetown.edu/S00/handout/spectrometer.htm
[35] 林麗娟編著，X光材料分析技術與應用專題，工業材料 86 期，1994.
[36] http://khvic.nsysu.edu.tw/khvic/JL/84.htm
[37] 張達欣編著，利用化學氣相沉積法生長非極性之氧化鋅薄膜在鋁酸鋰基板上，碩士論文，國立中山大學材料科學研究所，2008.
[38] http://www.directindustry.com/prod/carl-zeiss-microscopy/product-20796-961909.html
[39] 李其紘編著，原子力顯微鏡的基本介紹，科學研習，No. 52-5，2013.
[40] 沈政宇編著，電場可調控之液晶與聚合物複合薄膜的表面性質探討，碩士論文，國立中山大學物理學系研究所，2010.
[41] http://web1.knvs.tp.edu.tw/AFM/ch4.htm
[42] 郭泰麟編著，離子液體液晶製備擬固態電解質應用於染料敏化太陽能電池，碩士論文，國立中山大學光電工程學系，2010.
[43] 朱柏豪編著，表面輪廓儀的用途，奈米通訊，22卷 No.1，pp. 31-33，2015.
[44] www.mse.ttu.edu.tw/ezfiles/63/.../VeecoDEKTAK150Profilometer.pdf
[45] S. Bae, S. J. Han, T. J. Shin, W. H. Jo,” Two Different Mechanisms of CH3NH3PbI3 Film Formation In One-Step Deposition And Its Effect On Photovoltaic Properties of OPV-Type Perovskite Solar Cells”, Journal of Materials Chemistry A, vol. 3, pp. 23964-23972, 2015.
[46] S. M. H. Qaid, M. S. A. Sobaie, M. A. M. Khan, I. M. Bedja, F. H. Alharbi, M. K. Nazeeruddin, A. S. Aldwayyan,” Band-Gap Tuning of Lead Halide Perovskite Using A Single Step Spin-Coating Deposition Process”, Materials Letters, vol. 164, pp. 498-501, 2016.
[47] J. Seo, S. Park, Y. C. Kim, N. J. Jeon, J. H. Noh, S. C. Yoon, S. I. Seok,” Benefits of Very Thin PCBM And Lif Layers For Solution-Processed P-I-N Perovskite Solar Cells”, Energy & Environmental Science, vol. 7, pp. 2642-2646, 2014.
[48] H. J. Snaith, A. Abate, J. M. Ball, G. E. Eperon, T. Leijtens, N. K. Noel, S. D. Stranks, J. T.-W. Wang, K. Wojciechowski, W. Zhang,” Anomalous Hysteresis in Perovskite Solar Cells”, The Journal of Physical Letters, vol. 5, pp. 1511-1515, 2014.
[49] W. Tress, N. Marinova, T. Moehl, S. M. Zakeeruddin, M. K. Nazeeruddin, M. Grätzel,” Understanding The Rate-Dependent J–V Hysteresis, Slow Time Component, And Aging In CH3NH3PbI3 Perovskite Solar Cells: The Role of A Compensated Electric Field”, Energy & Environmental Science, vol. 5, pp. 995-1004, 2015.
[50] C. Motta, F. El-Mellouhi, S. Sanvito,” Charge Carrier Mobility In Hybrid Halide Perovskites”, Science Reports, vol. 5, Article number: 12746, 2015.
[51] C. Wehrenfennig, G. E. Eperon, M. B. Johnston, H. J. Snaith, L. M. Herz,” High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites”, Advanced Materials, vol. 26, pp. 1584-1589, 2014.
[52] http://www.sigmaaldrich.com/catalog/product/aldrich/684465?lang=en&region=TW
[53] http://www.sigmaaldrich.com/catalog/product/aldrich/684449?lang=en&region=TW
[54] S. Engmann, F. A. Bokel, A. A. Herzing, H. W. Ro, C. Girotto, B. Caputo, C. V. Hoven, E. Schaible, A. Hexemer, D. M. DeLongchamp, L. J. Richter,” Real-Time X-Ray Scattering Studies of Film Evolution In High Performing Small-Molecule–Fullerene Organic Solar Cells”, Journal of Materials Chemistry, vol. 3, pp. 8764-8771, 2015.
[55] D. Môn, A. M. Higgins, D. James, M. Hampton, J. E. Macdonald, M. B. Ward, P. Gutfreund, S. Lilliue, J. Rawlef,” Bimodal Crystallization At Polymer-Fullerene Interfaces”, Physical Chemistry Chemical Physics, vol. 17, pp. 2216-2227, 2014.
[56] S. Paek, N. Cho, H. Choi, H. Jeong, J. S. Lim, M. B. Ward, J.-Y. Hwang, J. K. Lee, J. Ko,” 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, vol. 118, pp. 25899-25905, 2014.