臺灣博碩士論文加值系統

本研究利用溶液法製備鋰摻雜氧化鎳作為電洞傳輸層，並利用固氣相反應甲胺氣體修飾法對鈣鈦礦薄膜進行改善，使整體發光二極體元件發光亮度與效率皆有效的提升。
本研究之元件結構為ITO/Metal-doped nickel oxided/Perovskite/TPBi/LiF/-Al。近年來，無機的金屬氧化物材料被廣泛應用於電洞傳輸層，其中較早期即被使用的p型材料為氧化鎳，由於氧化鎳有諸多優點，如穩定較佳、金屬導電性較佳等，但由於其電阻值相對較高，因此也有許多文獻嘗試利用摻雜不同金屬進氧化鎳，期望可以降低其電阻、改善能隙帶等效果。本研究透過簡單的溶液法製程，將鋰金屬摻雜入氧化鎳中，可以提升氧化鎳之導電性，並使鈣鈦礦層表面結晶性變佳、晶格變小，使載子傳遞更為快速；但摻雜後之薄膜會變得比較粗糙、晶界不明顯等問題，而使鈣鈦礦薄膜產生孔洞、晶界模糊等問題，此時再利用甲胺氣體對薄膜表面進行修飾，消除孔洞並使晶界鈍化消失等，將可使鋰摻雜氧化鎳電洞層的優點浮現，不致因為鈣鈦礦薄膜的表面缺陷而出現效率不佳的問題。使用鋰摻雜氧化鎳製備之元件，發光亮度可以從18377cd/m2提升至73325cd/m2，發光效率可以從3.4cd/A提升至12.4cd/A。

The issue of this research is to improved the performance of perovskite light-emitting didoes (PeLED) based on Lithium-doped nickel oxide. The cell’s performance have a brightness over 78000cd/m2 and the luminous efficiency(LE) over 12cd/A, which have four times improved from the original sample. Firstly, the Lithium was chose as the doped metal, because it can decrease the resistance of the NiOx, and have more better LUMO to confine the charge carriers in the CH3NH3PbBr3 layer, so in this work we doped the Lithium into NiOx by solution processes. But the film quality of perovskite film shows the traps and holes, and the passivation of grain boundary, all of these might hinder the brightness and the efficiency of PeLED.
To dissolved the problem ,we use the methylamine(MA) treatment to enhance the perovskite film quality, which significantly improves the crystallinity and the photoluminescence of the perovskite film. It also can modify the holes and traps caused by the Lithium doped NiOx. A Lithium-doped NiOx perovskite LED with the figuration of ITO/Lithium-doped nickel oxide/MA treated CH3NH3PbBr3 /TPBi/LiF /Al, display a max brightness of 73325cd/m2 at 7.5V and luminous efficiency of 12.3cd/A at 7.5V.

中文摘要 I
致謝 X
目錄 XI
圖目錄 XIV
表目錄 XVII
第一章、緒論 1
1-1 前言 1
1-2 有機電激發光元件發展 2
1-3 研究動機與大綱 7
1-3-1 研究動機 7
1-3-2 論文大綱 8
第二章、鈣鈦礦發光二極體發展 9
2-1 前言 9
2-2 有機電激發光元件的結構與操作原理 11
2-3 鈣鈦礦發光二極體重要的文獻回顧 14
2-4 摻雜金屬氧化鎳相關的重要的文獻回顧 19
2-5 鈣鈦礦薄膜成膜性重要的文獻回顧 22
2-6 本章結論 26
第三章、元件製作與實驗步驟 27
3-1 前言 27
3-2 鈣鈦礦發光二極體的製備過程 28
3-2-1 ITO基板圖案化及清潔 28
3-2-2 ITO基板清洗 30
3-2-3 電洞傳輸層製作 30
3-2-4 主動層製作 32
3-2-5 主動層修飾方法 32
3-2-6 電子傳輸層製作 33
3-2-7 電洞阻擋層製作 34
3-2-8 陰極製作 34
3-3元件光電特性量測 35
3-3-1 電流-亮度-電壓量測系統 35
3-3-2 掃描式電子顯微鏡(SEM) 35
3-3-3 光致發光光譜儀(PL) 36
3-3-4 X-射線繞射儀(XRD) 37
3-3-5 X-射線光電子光譜/化學分析電子光譜(XPS/ESCA) 38
3-3-5 四點探針(Four-Point Probe) 38
3-4本章結論 39
第四章、改善電洞傳輸層對鈣鈦礦發光二極體之研究 40
4-1 前言 40
4-2 鋰摻雜氧化鎳之電洞傳輸層對鈣鈦礦薄膜及發光二極體之影響 41
4-2-1 鋰摻雜氧化鎳電洞傳輸層之化學元素分析 42
4-2-2 鋰摻雜氧化鎳電洞傳輸層之導電性量測分析 44
4-2-3 鋰摻雜氧化鎳電洞傳輸層之接觸角分析 45
4-2-4 鋰摻雜氧化鎳電洞傳輸層對於鈣鈦礦發光層之表面形貌分析 46
4-2-5 鋰摻雜氧化鎳電洞傳輸層之能階分析 48
4-2-6 鋰摻雜氧化鎳電洞傳輸層之元件電性量測分析 50
4-3-1 甲胺氣體修飾方式下對鋰摻雜之氧化鎳於鈣鈦礦薄膜之形貌分析 54
4-3-2 甲胺氣體修飾方式下鋰摻雜氧化鎳電洞傳輸層對鈣鈦礦薄膜之結晶程度分析 55
4-3-3 甲胺氣體修飾鋰摻雜氧化鎳電洞傳輸層之光致發光分析 57
4-3-4 甲胺氣體修飾鋰摻雜氧化鎳電洞傳輸層對鈣鈦礦發光二極體之電性量測 58
4-4 本章結論 61
第五章、總結與未來工作 62
5-1 總結 62
5-2 未來工作展望 63
參考文獻 64

[1]Forrest, S.R., The road to high efficiency organic light emitting devices. Organic Electronics, 2003. 4(2): p. 45-48.
[2]Pope, M., H. Kallmann, and P. Magnante, Electroluminescence in organic crystals. The Journal of Chemical Physics, 1963. 38(8): p. 2042-2043.
[3]Tang, C.W. and S.A. VanSlyke, Organic electroluminescent diodes. Applied physics letters, 1987. 51(12): p. 913-915.
[4]Tang, C.W., S.A. VanSlyke, and C. Chen, Electroluminescence of doped organic thin films. Journal of Applied Physics, 1989. 65(9): p. 3610-3616.
[5]Lingping Kong., Gang Liu, Jue Gong, Qingyang Hu, Richard D. Schaller, Przemyslaw Dera, Dongzhou Zhang, Zhenxian Liu, Weng Yanga, Kai Zhu, Yuzhao Tang, Chuanyi Wang, Su-Hua Wei, Tao Xu, and Ho-kwang Mao, Thin-film semiconductor perspective of organometal trihalide perovskite materials for high-efficiency solar cells. Materials Science and Engineering: R: Reports, 2016. 101: p. 1-38.
[6]Gao, P., M. Grätzel, and M.K. Nazeeruddin, Organohalide lead perovskites for photovoltaic applications. Energy ＆ Environmental Science, 2014. 7(8): p. 2448.
[7]Kim, H., K.-G. Lim, and T.-W. Lee, Planar heterojunction organometal halide perovskite solar cells: roles of interfacial layers. Energy Environ. Sci., 2016. 9(1): p. 12-30.
[8]Era, M., Morimoto, S., Tsutsui, T., ＆ Saito, S., Organic‐inorganic heterostructure electroluminescent device using a layered perovskite semiconductor (C6H5C2H4NH3) 2PbI4. Applied physics letters, 1994. 65(6): p. 676-678.
[9]Zhi-Kuang Tan, Reza Saberi Moghaddam, May Ling Lai, Pablo Docampo,Ruben Higler, Felix Deschler, Michael Price, Aditya Sadhanala, Luis M. Pazos, Dan Credgington,Fabian Hanusch,Thomas Bein, Henry J. Snaith ＆ Richard H. Friend, Bright light-emitting diodes based on organometal halide perovskite. Nat Nanotechnol, 2014. 9(9): p. 687-92.
[10]Jae Choul Yu, Dae Woo Kim, Da Bin Kim,Eui Dae Jung, Jong Hyun Park, Ah-Young Lee, Bo Ram Lee, Daniele Di Nuzzo, Richard H. Friend, Myoung Hoon Song, Improving the Stability and Performance of Perovskite Light-Emitting Diodes by Thermal Annealing Treatment. Adv Mater, 2016. 28(32): p. 6906-13.
[11]Zhibin Wang, Tai Cheng, Fuzhi Wang, Songyuan Dai, Zhan'ao Tan, Morphology Engineering for High-Performance and Multicolored Perovskite Light-Emitting Diodes with Simple Device Structures. Small, 2016. 12(32): p. 4412-20.
[12]Wang, Z., Cheng, T., Wang, F., Dai, S., ＆ Tan, Z. A, Enhanced performance in fluorene-free organometal halide perovskite light-emitting diodes using tunable, low electron affinity oxide electron injectors. Adv Mater, 2015. 27(8): p. 1414-9.
[13]Robert L. Z. Hoye, Matthew R. Chua, Kevin P. Musselman,Guangru Li, May-Ling Lai, Zhi-Kuang Tan, Neil C. Greenham,Judith L. MacManus-Driscoll, Richard H. Friend, Dan Credgington, Bright Visible-Infrared Light Emitting Diodes Based on Hybrid Halide Perovskite with Spiro-OMeTAD as a Hole-Injecting Layer. J Phys Chem Lett, 2015. 6(10): p. 1883-90.
[14]Jaramillo-Quintero, O. A., Sanchez, R. S., Rincon, M., ＆ Mora-Sero, I., A facile one-step solution deposition via non-solvent/solvent mixture for efficient organometal halide perovskite light-emitting diodes. Nanoscale, 2016. 8(21): p. 11084-90.
[15]Bo Jiao, Xiaobo Zhu, Wen Wu, Hua Dong, Bin Xia, Jun Xi, Ting Lei, Xun Hou and Zhaoxin Wu , Improved performance of perovskite light-emitting diodes using a PEDOT:PSS and MoO3composite layer. J. Mater. Chem. C, 2016. 4(35): p. 8161-8165.
[16]Da Bin Kim, Jae Choul Yu, Yun Seok Nam, Dae Woo Kim, Eui Dae Jung, Sang Yun Lee, Seungjin Lee, Jong Hyun Park, Ah-Young Lee, Bo Ram Lee, Daniele Di Nuzzo, Richard H. Friend and Myoung Hoon Song, Multicolored organic/inorganic hybrid perovskite light-emitting diodes. Adv Mater, 2015. 27(7): p. 1248-54.
[17]Kim, Y. H., Cho, H., Heo, J. H., Im, S. H., ＆ Lee, T. W., Effects of thermal treatment on organic-inorganic hybrid perovskite films and luminous efficiency of light-emitting diodes. Current Applied Physics, 2016. 16(9): p. 1069-1074.
[18]Kim, Y. H., Cho, H., Heo, J. H., Im, S. H., ＆ Lee, T. W., Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix. Nano Lett, 2015. 15(4): p. 2640-4.
[19]Liang, J., Zhang, Y., Guo, X., Gan, Z., Lin, J., Fan, Y., ＆ Liu, X., Efficient perovskite light-emitting diodes by film annealing temperature control. RSC Adv., 2016. 6(75): p. 71070-71075.
[20]Liang, J., Zhang, Y., Guo, X., Gan, Z., Lin, J., Fan, Y., ＆ Liu, X, Enhanced Optical and Electrical Properties of Polymer-Assisted All-Inorganic Perovskites for Light-Emitting Diodes. Adv Mater, 2016. 28(40): p. 8983-8989.
[21]Yichuan Ling, Yu Tian, Xi Wang, Jamie C. Wang, Javon M. Knox,Fernando Perez-Orive, Yijun Du, Lei Tan, Kenneth Hanson, Biwu Ma, Hanwei Gao, Bright Light-Emitting Diodes Based on Organometal Halide Perovskite Nanoplatelets. Adv Mater, 2016. 28(2): p. 305-11.
[22]Fusheng Ma , Jiangwei Li , Wenzhe Li , Na Lin , Liduo Wang and Juan Qiao, J., Stable alpha/delta phase junction of formamidinium lead iodide perovskites for enhanced near-infrared emission. Chem Sci, 2017. 8(1): p. 800-805.
[23]Aditya Sadhanala, Abhishek Kumar, Sandeep Pathak, Akshay Rao, Ullrich Steiner, Neil C. Greenham, Henry J. Snaith, and Richard H. Friend, Electroluminescence from Organometallic Lead Halide Perovskite-Conjugated Polymer Diodes. Advanced Electronic Materials, 2015. 1(3): p. 1500008.
[24]Jing Su, Lin Sang, Di Wang, Di Lu, Wanfu Wang, Yan Wen, Solution growth and morphology of CH3NH3PbBr3 single crystals in different solvents. Crystal Research and Technology, 2016. 51(11): p. 650-655.
[25]Jianpu Wang, Nana Wang, Yizheng Jin, Junjie Si, Zhi Kuang Tan, Hui Du, Lu Cheng, Xingliang Dai, Sai Bai, Haiping He, Zhizhen Ye, May Ling Lai, Richard H. Friend, and Wei Huang, Interfacial control toward efficient and low-voltage perovskite light-emitting diodes. Adv Mater, 2015. 27(14): p. 2311-6.
[26]Nana Wang , Lu Cheng , Junjie Si , Xiaoyong Liang , Yizheng Jin , Jianpu Wang , Wei Huang, Morphology control of perovskite light-emitting diodes by using amino acid self-assembled monolayers. Applied Physics Letters, 2016. 108(14): p. 141102.
[27]Zhanhua Wei, Ajay Perumal, Rui Su, Shendre Sushant, Jun Xing, Qing Zhang, Swee Tiam Tan, Hilmi Volkan Demir and Qihua Xiong, Solution-processed highly bright and durable cesium lead halide perovskite light-emitting diodes. Nanoscale, 2016. 8(42): p. 18021-18026.
[28]Jun Yan, Xiaohan Ke, Yunlin Chen, , Ao Zhang, Bing Zhang, Effect of modulating the molar ratio of organic to inorganic content on morphology, optical absorption and photoluminescence of perovskite CH3NH3PbBr3 films. Applied Surface Science, 2015. 351: p. 1191-1196.
[29]Jun Yan, Bing Zhang, Yunlin Chen, Ao Zhang, and Xiaohan Ke, Improving the Photoluminescence Properties of Perovskite CH3NH3PbBr3-xClx Films by Modulating Organic Cation and Chlorine Concentrations. ACS Appl Mater Interfaces, 2016. 8(20): p. 12756-63.
[30]Jae Choul Yu, Da Bin Kim, Eui Dae Jung , Bo Ram Lee and Myoung Hoon Song, High-performance perovskite light-emitting diodes via morphological control of perovskite films. Nanoscale, 2016. 8(13): p. 7036-42.
[31]Kion Norrman, Morten V. Madsen, Suren A. Gevorgyan, and Frederik C. Krebs, Degradation patterns in water and oxygen of an inverted polymer solar cell. Journal of the American Chemical Society, 2010. 132(47): p. 16883-16892.
[32]Wei-Yi Chen, Lin-Long Deng, Si-Min Dai, Xin Wang, Cheng-Bo Tian, Xin-Xing Zhan, Su-Yuan Xie, Rong-Bin Huang and Lan-Sun Zheng, Low-cost solution-processed copper iodide as an alternative to PEDOT:PSS hole transport layer for efficient and stable inverted planar heterojunction perovskite solar cells. J. Mater. Chem. A, 2015. 3(38): p. 19353-19359.
[33]Zuo, C. and L. Ding, Solution‐Processed Cu2O and CuO as Hole Transport Materials for Efficient Perovskite Solar Cells. Small, 2015. 11(41): p. 5528-5532.
[34]Senyun Ye, Weihai Sun, Yunlong Li, Weibo Yan, Haitao Peng, Zuqiang Bian, Zhiwei Liu, and Chunhui Huang, CuSCN-Based Inverted Planar Perovskite Solar Cell with an Average PCE of 15.6%. Nano Lett, 2015. 15(6): p. 3723-8.
[35]Jun-Yuan Jeng, Kuo-Cheng Chen, Tsung-Yu Chiang, Pei-Ying Lin, Tzung-Da Tsai, Yun-Chorng Chang, Tzung-Fang Guo, Peter Chen, Ten-Chin Wen, and Yao-Jane Hsu, Nickel Oxide Electrode Interlayer in CH3NH3PbI3 Perovskite/PCBM Planar‐Heterojunction Hybrid Solar Cells. Advanced materials, 2014. 26(24): p. 4107-4113.
[36]Long Hu, Jun Peng, Weiwei Wang, Zhe Xia, Jianyu Yuan, Jialing Lu, Xiaodong Huang, Wanli Ma, Huaibing Song, Wei Chen, Yi-Bing Cheng, and Jiang Tang, Sequential deposition of CH3NH3PbI3 on planar NiO film for efficient planar perovskite solar cells. Acs Photonics, 2014. 1(7): p. 547-553.
[37]Kuo-Chin Wang, Jun-Yuan Jeng, Po-Shen Shen, Yu-Cheng Chang, Eric Wei-Guang Diau, Cheng-Hung Tsai,Tzu-Yang Chao, Hsu-Cheng Hsu, Pei-Ying Lin, Peter Chen, Tzung-Fang Guo, and Ten-Chin Wen, p-type Mesoscopic nickel oxide/organometallic perovskite heterojunction solar cells. Sci Rep, 2014. 4: p. 4756.
[38]Kuo-Chin Wang, Po-Shen Shen, Ming-Hsien Li, Shi Chen, Ming-Wei Lin, Peter Chen, and Tzung-Fang Guo, Low-temperature sputtered nickel oxide compact thin film as effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite heterojunction solar cells. ACS applied materials ＆ interfaces, 2014. 6(15): p. 11851-11858.
[39]Wei-Chih Lai, Kun-Wei Lin, Yuan-Ting Wang, Tsung-Yu Chiang, Peter Chen, and Tzung-Fang Guo, Oxidized Ni/Au transparent electrode in efficient CH3NH3PbI3 perovskite/fullerene planar heterojunction hybrid solar cells. Advanced Materials, 2016.
[40]Jong H. Kim, Po-Wei Liang, Spencer T. Williams, Namchul Cho, Chu-Chen Chueh, Micah S. Glaz, David S. Ginger, and Alex K.-Y. Jen, High-performance and environmentally stable planar heterojunction perovskite solar cells based on a solution-processed copper-doped nickel oxide hole-transporting layer. Adv Mater, 2015. 27(4): p. 695-701.
[41]Wei Chen, Yongzhen Wu1, Youfeng Yue, Jian Liu, Wenjun Zhang, Xudong Yang, Han Chen, Enbing Bi, Islam Ashraful, Michael Grätzel, Liyuan Han, Efficient and stable large-area perovskite solar cells with inorganic charge extraction layers. Science, 2015. 350(6263): p. 944-948.
[42]Taiyang Zhang, Nanjie Guo, Ge Li, Xufang Qian, Liang Li and Yixin Zhao, Effect of lithium-ion doping concentration on structural and optical properties of NiO films fabricated by magnetron sputtering. Vacuum, 2017. 137: p. 56-59.
[43]Taiyang Zhang, Nanjie Guo, Ge Li,a Xufang Qian, Liang Lia and Yixin Zhao, A general non-CH3NH3X (X = I, Br) one-step deposition of CH3NH3PbX3perovskite for high performance solar cells. J. Mater. Chem. A, 2016. 4(9): p. 3245-3248.