本論文研究主要為做出全無機CsPbBr3鈣鈦礦發光二極體元件，並從中發現其與MAPbBr3在離子遷移上的不同，簡而言之，CsPbBr3較為穩定且無離子遷移的現象，我們從遲滯量測、有無偏壓的光致發光強度變化、XPS、電容量測、離子遷移啟動能種種計算環環相扣證明之，但我們不止於此，進一步的以離子添加劑氯化膽鹼去鈍化鈣鈦礦薄膜表面缺陷，達到近乎100%的覆蓋率且闡述了離子添加劑對於鈣鈦礦的影響，最後我們亦證實摻雜離子添加劑氯化膽鹼後能大幅減少離子遷移現象且使得鈣鈦礦發光二極體元件更像典型的元件，於低電流處即能擁有高電流轉換效率。

Due to the poor thermal stability and humidity stability as well as devices operating life time, organic-inorganic perovskite materials like CH3NH3PbBr3 has big problems. Therefore, all-inorganic cesium hailde perovskite materials have attracted more and more attentions. In this work, we replace common hole transporting layer, PEDOT:PSS, with smoother carriers injection materials, NiOx. As a result, we get high brightness and high efficiency all-inorganic cesium lead bromide light emmiting diodes. Next step we incorporate ionic additives Choline Chloride to further improve perovskite film coverage and suppress ion migration phenomena. We carefully characterize ion motion before and after doping Choline Chloride by capacitance measurement and hysteresis. Fianally, we summarize the function of ionic additves and set up the model.

[1] S. R. Forrest, “The road to high efficiency organic light emitting devices”, Org. Electron. 4, 45 (2003).
[2] J. Kido, M. Kimura, K. Nagai, “Multilayer white light-emitting organic electroluminescent device”, Science 267, 1332 (1995).
[3] M. Pope, H. P. Kallmann, P. Magnante, “Electroluminescence in organic crystals”, J. Chem. Phys. 38, 2042 (1963).
[4] C. -W. Tang, S. A. VanSlyke, “Organic electroluminescent diodes”, Appl. Phys. Lett. 57, 913 (1987).
[5] J. H. Burroughes, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, A. B. Holmes, “Light-emitting diodes based on conjugated polymers”, Nature 347, 539 (1990).
[6] https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20190802.pdf (National Renewable Energy Laboratory, NREL, 2019)
[7] J. C. -Frankel, “Newcomer juices up the race to harness sunlight”, Science 342, 1438 (2013).
[8] R. J. D. Tilley (2016). Perovskites Structure–Property Relationships. (1st ed.). United Kingdom: John Wiley & Sons, Ltd.
[9] H. -S. Kim, S. -H. Im, N. -G. Park, “Organolead halide perovskite: new horizons in solar cell research”, J. Phys. Chem. C 118, 5615 (2014).
[10] M. Era, S. Morimoto, T. Tsutsui, S. Saito, “Organic‐inorganic heterostructure electroluminescent device using a layered perovskite semiconductor (C6H5C2H4NH3)2PbI4”, Appl. Phys. Lett. 65, 676 (1994).
[11] K. Chondroudis, D. B. Mitzi, “Electroluminescence from an organic−inorganic perovskite incorporating a quaterthiophene dye within lead halide perovskite layers”, Chem. Mat. 11, 3028 (1999).
[12] Z. -K. Tan, R. S. Moghaddam, M. L. Lai, P. Docampo, R. Higler, F. Deschler, M. Price, A. Sadhanala, L. M. Pazos, D. Credgington, F. Hanusch, T. Bein, H. J. Snaith, R. H. Friend, “Bright light-emitting diodes based on organometal halide perovskite”, Nat. Nanotechnol. 9, 687 (2014).
[13] H. Cho, S. -H. Jeong, M. -H. Park, Y. -H. Kim, C. Wolf, C. -L. Lee, J. H. Heo, A. Sadhanala, N. Myoung, S. Yoo, S. H. Im, R. H. Friend, T. -W. Lee, “Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes”, Science 350, 1222 (2015).
[14] Y. -K. Chih, J. -C. Wang, R. -T. Yang, C. -C. Liu, Y. -C. Chang, Y. -S. Fu, W. -C. Lai, P. Chen, T. -C. Wen, Y. -C. Huang, C. -S. Tsao, T. -F. Guo, “NiOx electrode interlayer and CH3NH2/CH3NH3PbBr3 interface treatment to markedly advance hybrid perovskite-based light-emitting diodes”, Adv. Mater. 28, 8687 (2016).
[15] M. -H. Park, S. -H. Jeong, H. -K. Seo, C. Wolf, Y. -H. Kim, H. Kim, J. Byun, J. S. Kim, H. Cho, T. -W. Lee, “Unravelling Additive-based Nanocrystal Pinning for High Efficiency Organic-Inorganic Halide Perovskite Light-Emitting Diodes”, Nano Energy 42, 157 (2017).
[16] J. Liang, C. Wang, Y. Wang, Z. Xu, Z. Lu, Y. Ma, H. Zhu, Y. Hu, C. Xiao, X. Yi, G. Zhu, H. Lv, L. Ma, T. Chen, Z. Tie, Z. Jin, J. Liu, “All-Inorganic Perovskite Solar Cells”, J. Am. Chem. Soc. 138, 15829 (2016).
[17] C. C. Stoumpos, C. D. Malliakas, J. A. Peters, Z. Liu, M. Sebastian, J. Im, T. C. Chasapis, A. C. Wibowo, D. Y. Chung, A. J. Freeman, B. W. Wessels, M. G. Kanatzidis, “Crystal growth of the perovskite semiconductor CsPbBr3: a new material for high-energy radiation detection”, Cryst. Growth Des. 7, 2722 (2013).
[18] D. Di, K. P. Musselman, G. Li, A. Sadhanala, Y. Ievskaya, Q. Song, Z. K. Tan, M. L. Lai, J. L. M. -Driscoll, N. C. Greenham, R. H. Friend, “Size-dependent photon emission from organometal halide perovskite nanocrystals embedded in an organic matrix”, J. Phys. Chem. Lett. 6, 446 (2015).
[19] M. Kulbak, D. Cahen, G. Hodes, “How important is the organic part of lead halide perovskite photovoltaic cells? efficient CsPbBr3 cells”, J. Phys. Chem. Lett. 6, 2452 (2015).
[20] F. Palazon, F. DiStasio, Q. A. Akkerman, R. Krahne, M. Prato, L. Manna, “Polymerfreefilms of inorganic halide perovskite nanocrystals as UV-to-white colorconversion layers in LEDs”, Chem. Mater. 28, 2902 (2016).
[21] H. Choi, J. Jeong, H. Kim, S. Kim, B. Walker, G. Kim, J. Kim, “Cesium-doped methylammonium lead iodide perovskite light absorber for hybrid solar cells”, Nano Energy 7, 80 (2014).
[22] Y. Rakita, N. Kedem, S. Gupta, A. Sadhanala, V. Kalchenko, M. L. Böhm, M. Kulbak, R. H. Friend, D. Cahen, G. Hodes, “Low-Temperature Solution-Grown CsPbBr3 Single Crystals and Their Characterization”, Cryst. Growth 10, 5717 (2016).
[23] M. Saliba, T. Matsui, K. Domanski, J. -Y. Seo, A. Ummadisingu, S. M. Zakeeruddin, J. -P. C. -Baena, W. R. Tress, A. Abate, A. Hagfeldt, M. Grätzel, “Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance”, Science 354, 206 (2016).
[24] J. Song , J. Li , X. Li , L. Xu , Y. Dong , H. Zeng, “Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX3)”, Adv. Mater. 27, 7162 (2015).
[25] N. Yantara, S. Bhaumik, F. Yan, D. Sabba, H. Dewi, N. Mathews, P. Boix, H. Demir, S. Mhaisalkar, “Inorganic Halide Perovskites for Efficient Light-Emitting Diodes”, J.Phys.Chem.Lett 6, 4360 (2015).
[26] Y. Ling, Y. Tian, X. Wang, J. C. Wang, J. M. Knox, F. P. ‐Orive, Y. Du, L. Tan, K. Hanson, B. Ma, H. Gao, “Enhanced Optical and Electrical Properties of Polymer-Assisted All-Inorganic Perovskites for Light-Emitting Diodes”, Adv. Mater. 28, 8983 (2016).
[27] N. Yantara , S. Bhaumik , F. Yan , D. Sabba , H. A. Dewi , N. Mathews ,P. P. Boix , H. V. Demir , S. Mhaisalkar, “Inorganic Halide Perovskites for Efficient Light-Emitting Diodes”, J. Phys. Chem. Lett. 6, 4360 (2015).
[28] X. Zhang , B. Xu , J. Zhang , Y. Gao , Y. Zheng , K. Wang , X. W. Sun, “All‐Inorganic Perovskite Nanocrystals for High‐Efficiency Light Emitting Diodes: Dual‐Phase CsPbBr3‐CsPb2Br5 Composites”, Adv. Funct. Mater. 26, 4595 (2016).
[29] L. Zhang, X. Yang, Q. Jiang, P. Wang, Z. Yin, X. Zhang, H. Tan, Y.M. Yang, M. Wei, B. Sutherland, E. Sargent, J. You, “Ultra-bright and highly efficient inorganic based perovskite light-emitting diodes”, Nat. Commun. 8, 15640 (2017).
[30] H. Cho, C. Wolf, J. S. Kim, H. J. Yun, J. S. Bae, H. Kim, J.-M. Heo, S. Ahn, T.-W. Lee, “High-efficiency solution-processed inorganic metal halide perovskite light-emitting diodes”, Adv. Mater. 29, 1700579 (2017).
[31] Y. Yuan, J. Huang, “Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability”, Acc. Chem. Res. 49, 286 (2016).
[32] Y. Shao, Y.Fang, T. Li, Q. Wang, Q. Dong, Y. Deng, Y. Yuan, H. Wei, M. Wang, A. Gruverman, J. Shielda and J. Huang, “Grain boundary dominated ion migration in polycrystalline organic–inorganic halide perovskite films”, Energy Environ. Sci. 9, 1752 (2016).
[33] 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”, J. Phys. Chem. Lett. 5, 1511 (2014).
[34] E. L. Unger, E. T. Hoke, C. D. Bailie, W. H. Nguyen, A. R. Bowring, T. Heumüller, M. G. Christoforod, M. D. McGehee, “Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells”, Energy Environ. Sci. 7, 3690 (2014).
[35] J. M. Azpiroz, E. Mosconi, J. Bisquertcd, F. D. Angelis, “Defect migration in methyl-ammonium lead iodide and its role in perovskite solar cell operation”, Energy Environ. Sci. 8, 2118 (2015).
[36] S. Wang, Y. Jiang, E. J. J.-Perez, L. K. Ono, Y. Qi, “Accelerated degradation of methylammonium lead iodide perovskites induced by exposure to iodine vapour”, Nature Energy 2, 16195 (2016).
[37] A. G. Aberle, “Surface passivation of crystalline silicon solar cells: a review”, Prog. Photovoltaics 8, 473 (2000).
[38] Y. Liu, T. Lai, H. Li, Y. Wang, Z. Mei, H. Liang, Z. Li, F. Zhang, W. Wang, A. Y. Kuznetsov, X. Du, “Nanostructure formation and passivation of large-area black silicon for solar cell applications”, Small 8, 1392(2012).
[39] B. Yan, G. Yue, L. Sivec, J. Yang, S. Guha, C. -S. Jiang, “Innovative dual function nc-SiOx : H layer leading to a >16% efficient multi-junction thin-film silicon solar cell”, Appl. Phys. Lett. 99, 113512 (2011).
[40] Y. Shao, Z. Xiao, C. Bi, Y. Yuan, J. Huang, “Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells”, Nat. Commun. 5, 5784 (2014).
[41] Z. Xiao, R. A. Kerner, L. Zhao, N. L. Tran, K. M. Lee, T.-W. Koh, G. D. Scholes, B. P. Rand, “Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites”, Nat. Photonics 11, 108 (2017).
[42] X. Zheng, B. Chen, J. Dai, Y. Fang, Y. Bai, Y. Lin, H. Wei, X. C. Zeng, J. Huang, “Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations”, Nat. Energy 2, 17102 (2017).
[43] M. A.-Jalebi, Z. A.-Garmaroudi, S. Cacovich, C. Stavrakas, B. Philippe, J. M. Richter, M. Alsari, E. P. Booker, E. M. Hutter, A. J. Pearson, S. Lilliu, T. J. Savenije, H. Rensmo, G. Divitini, C. Ducati, R. H. Friend, S. D. Stranks, “Maximizing and stabilizing luminescence from halide perovskites with potassium passivation”, Nature 555, 497 (2018).
[44] G. Kieslich, S. Suna, A. K. Cheetham, “Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog”, Chem. Sci. 5, 4712 (2014).
[45] J. Liang, C. Wang, Y. Wang, Z. Xu, Z. Lu, Y. Ma, H. Zhu, Y. Hu, C. Xiao, X. Yi, G. Zhu, H. Lv, L. Ma, T. Chen, Z. Tie, Z. Jin, J. Liu, “All-Inorganic Perovskite Solar Cells”, J. Am. Chem. Soc. 138, 15829 (2016).
[46] L. N. Quan, R. Q.‐Bermudez, O. Voznyy, G. Walters, A. Jain, J. Z. Fan, X. Zheng, Z. Yang, E. H. Sargent, “Highly Emissive Green Perovskite Nanocrystals in a Solid State Crystalline Matrix”, Adv. Mater. 29, 1605945 (2017).
[47] L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C. H. Hendon, R. X. Yang, A. Walsh, M. V. Kovalenko, “Nanocrystals of Cesium Lead Halide Perovskites (CsPbX₃, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut”, Nano Lett. 15, 3692 (2015).
[48] A. Swarnkar, R. Chulliyil, V. K. Ravi, M. Irfanullah, A. Chowdhury, A. Nag, “Colloidal CsPbBr3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots”, Angew. Chem. 54, 15424 (2015).
[49] H. Yang, Y. Zhang, J. Pan, J. Yin, O. M. Bakr, O. F. Mohammed, “Room-Temperature Engineering of All-Inorganic Perovskite Nanocrsytals with Different Dimensionalities”, Chem. Mater. 29, 8978 (2017).
[50] K. Zheng, Q. Zhu, M. Abdellah, M. E. Messing, W. Zhang, A. Generalov, Y. Niu, L. Ribaud, S. E. Canton, T. Pullerits, “Exciton Binding Energy and the Nature of Emissive States in Organometal Halide Perovskites”, J. Phys. Chem. Lett. 6, 2969 (2015).
[51] Y. Yang, M. Yang, Z. Li, R. Crisp, K. Zhu and M. C. Beard, “Comparison of Recombination Dynamics in CH3NH3PbBr3 and CH3NH3PbI3 Perovskite Films: Influence of Exciton Binding Energy”, J. Phys. Chem. Lett. 6, 4688 (2015).
[52] H. Wang, X. Zhang, Q. Wu. Cao, D. Yang, Y. Shang, Z. Ning, W. Zhang, W. Zheng, Y. Yan, S. V. Kershaw, L. Zhang, A. L. Rogach, X. Yang, “Trifluoroacetate induced small-grained CsPbBr3 perovskite films result in efficient and stable light-emitting devices”, Nat. Commun. 10, 665 (2019).