5-1. 結論
1. 透過穿透式電子顯微鏡(TEM)確立合成出大小均勻、尺寸約為 3～5 奈米的 氧化鎳奈米粒子。
2. X-射線繞射分析(XRD)確立了溴化銫鉛發光層為鈣鈦礦晶體結構。
3. 透過原子力顯微鏡(AFM)分析，加入 PEO 顯著提升溴化銫鉛鈣鈦礦發光層 厚度，加入 TPBi 及 FirPic 使溴化銫鉛鈣鈦礦薄膜粗糙度下降。
4. 加入 PEO、添加劑 TPBi 及 FirPic 和甲苯蒸氣處理皆能提升元件性能。
5. 以氧化鎳奈米粒子作為電洞注入層比較 PEDOT:PSS 作為電洞注入層能大幅 降低元件的啟動電壓及漏電流、提升元件的最大亮度及效率。
6. 透過紫外光臭氧處理氧化鎳奈米粒子表面提升了元件的性能。
7. 優化電洞注入層及溴化銫鉛鈣鈦礦發光層成功使元件的啟動電壓從接近 4 伏特降至低於 2.5 伏特、漏電流減少近 2 個數量級、最大亮度從 61 cd/m2 提升至 4,455 cd/m2，電流效率從 0.04 cd/A 提升至 2.9 cd/A，優化後的元件 具有再現性。
44 5-1. 未來展望
雖然已透過加入添加劑來優化溴化銫鉛鈣鈦礦發光層、表面處理優化氧化鎳 奈米粒子電洞注入層，大幅提升溴化銫鉛鈣鈦礦發光二極體的性能，但是目前的 無機溴化銫鉛鈣鈦礦的亮度及電流效率仍然遠不及 OLED、QLED 或是有機-無機 混合的甲基胺基溴化鉛(CH3NH3PbBr3)鈣鈦礦發光二極體，希望透過更深入的研究 提升溴化銫鉛鈣鈦礦發光二極體的性能：
1. 最佳化溴化銫鉛鈣鈦礦發光層：最佳化溴化銫鉛鈣鈦礦粉末及溴化銫粉末及 PEO、TPBi、FirPic 的比例並透過原子力顯微鏡(AFM)分析其表面。
2. 深入探討不同時間氧電漿處理及紫外光臭氧處理影響元件性能的原因，例如：
透過 X-射線光電子能譜(XPS)分析其組成、紫外光電子能譜(UPS)分析能階、
時間解析光激發光光譜(Time-Resolved Photoluminescence, TRPL)分析淬滅。
45
第六章 參考文獻
[1] C. -H. Gao, F. -X. Yu, Z. -Y. Xiong, Y. -J. Dong, X. -J. Ma, Y. Zhang, Y. -L. Jia, R.
Wang, P. Chen, D. -Y. Zhou, & Z. -H. Xiong (2019). 47-Fold EQE improvement in CsPbBr3 perovskite light-emitting diodes via double-additives assistance. Org.
Electron. 70, 264-271.
[2] X. Li , Y. Wu , S. Zhang , B. Cai , Y. Gu , J. Song and H. Zeng (2016). CsPbX3 Quantum Dots for Lighting and Displays: RoomTemperature Synthesis, Photoluminescence Superiorities,Underlying Origins and White Light-Emitting Diodes. Adv. Funct. Mater. 26, 2435-2445.
[3] X. Chen, L. Peng, K. Huang, Z. Shi, R. Xie, & W. Yang (2016). Non-injection gram-scale synthesis of cesium lead halide perovskite quantum dots with
controllable size and composition. Nano Res. 9(7), 1994-2006.
[4] L. Protesescu, S. Yakunin, M. I. Bodnarchuk, F. Krieg, R. Caputo, C. H. Hendon, R.
-X. Yang, A. Walsh, & M. V. Kovalenko (2015). 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(6), 3692-3696 [5] G. R. Yettapu, D. Talukdar, S. Sarkar, A. Swarnkar, A. Nag, P. Ghosh, P. Mandal,
Terahertz Conductivity within Colloidal CsPbBr3 Perovskite Nanocrystals:
Remarkably High Carrier Mobilities and Large Diffusion Lengths. Nano Lett. , 16 4838-4848.
[6] 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 and R. H. Friend (2014). Bright light-emitting diodes based on organometal halide perovskite.Nat. Nanotechnol, 9, 687-692.
[7] K. Lin, J. Xing, L. N. Quan, F. P. G. d. Arquer, X. Gong, J. Lu, L. Xie, W. Zhao, D.
Zhang, C. Yan, W. Li, X. Liu, Y. Lu, J. Kirman, E. H. Sargent, Q. Xiong and Z. Wei (2018). Perovskite light-emitting diodes with external quantum efficiency exceeding 20 percent. Nature, 562, 245-248
[8] L. Zhao and B. P. Rand (2018). Metal-Halide Perovskites: Emerging Light-Emitting Materials. Inf. Disp., 34 (6), 18-22.
[9] Z. Shi, S. Li, Y. Li, H. Ji, X. Li, D. Wu, T. Xu, Y. Chen, Y. Tian, Y. Zhang, C. Shan and G. Du (2018). Strategy of Solution-Processed All-Inorganic Heterostructure for Humidity/Temperature-Stable Perovskite Quantum Dot Light-Emitting Diodes.
ACS Nano, 12 (2), 1462–1472.
[10] Y. Ling, Y. Tian, X. Wang, J. C. Wang, J. M. Knox, F. Perez-Orive, Y. Du, L. Tan, K. Hanson, B. Ma and H. Gao (2016). Enhanced Optical and Electrical Properties
46
of Polymer-Assisted All-Inorganic Perovskites for Light-Emitting Diodes. Adv.
Mater., 28 (40), 8983–8989.
[11] C. W. Tang and S. A. VanSlyke (1987). Organic electroluminescent diodes. Appl.
Phys. Lett. 51 (12), 913-915.
[12] W. L, Z. Wang, F. Deschler, S. Gao, R. H. Friend and A. K. Cheetham (2017).
Chemically diverse and multifunctional hybrid organic–inorganic perovskites. Nat.
Rev. Mater. 2, 16099.
[13] J. Chen, S. Zhou, S. Jin, H. Li and T. Zhai (2016). Crystal organometal halide perovskites with promising optoelectronic applications. J. Mater. Chem. C. 4, 11-27.
[14] M. Era, S. Morimoto, T. Tsutsui and S. Saito (1994). Organic-inorganic heterostructure electroluminescent device using a layered perovskite semiconductor (C6H5C2H4NH3)Pbl4. Appl. Phys. Lett. 65 (6), 676-678.
[15] H. Cho, S. -H. Jeong, M. -H. Park, Y.-H. Kim, C. Wolf, C. -L. Lee, J. H. Heo, A.
Sadhanala, N. Myoung, Se. Yoo, S. H. Im, R. H. Friend and T. -W. Lee (2015).
Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science, 350, 1222-1225.
[16] M. Yuan, L. N. Quan, R. Comin, G. Walters, R. Sabatini, O. Voznyy, S. Hoogland, Y. Zhao, E. M. Beauregard, P. Kanjanaboos, Z.Lu, D. H. Kim and E. H.
Sargent(2016). Perovskite energy funnels for efficient light-emitting diodes. Nat.
Nanotechnol., 11 (10), 872–877.
[17] Y. -H. Li, X. Lu, R. Wang, Y. -Y. Ma, S. Duhm and M. -K. Fung (2017).
Cu-Doped nickel oxide prepared using a low-temperature combustion method as a hole-injection layer for high-performance OLEDs. J. Mater. Chem. C , 5(45), 11751–11757.
[18] C. W. Joo, M. Kim, J. H. Kim, W. Choi, J. Lee, D. Lee, H. Cho, H. Lee, S. Park, N. S. Cho, H. Cho, C. -W. Lee, D. Y. Jeon and B. -H. Kwon (2018). Conductivity Enhancement of Nickel Oxide by Copper Cation Codoping for Hybrid Organic-Inorganic Light-Emitting Diodes. ACS Photonics, 5 (8), 3389–3398.
[19] Y. Wang, Z. Shi, H. Liu, F. Wang, Y. Bai, X. Bian, B. Zhang, T. Hayat, A. Alsaedi and Z. Tan (2017). The Effect of Donor and Nonfullerene Acceptor Inhomogeneous Distribution within the Photoactive Layer on the Performance of Polymer Solar Cells with Different Device Structures. Polymers, 9 (11), 571.
[20] S. Y. Kim, J. -L. Lee, K. -B. Kim and Y. -H. Tak (2004). Effect of ultraviolet–ozone treatment of indium–tin–oxide on electrical properties of organic light emitting diodes. J. Appl. Phys., 95 (5), 2560–2563.
47
[21] E. R. Santos, J. B. d. Moraes, C. M. Takahashi, V. Sonnenberg, E. C. Burini, S.
Yoshida, H. G. Takimoto, R. K. Onmori and W. S. Hui1 (2016). Low cost UV-Ozone reactor mounted for treatment of electrode anodes used in P-OLEDs devices. Polímeros, 26 (3), 236–241.
[22] Y. Nishihara, M. Chikamatsu, S. Kazaoui, T. Miyadera and Y. Yoshida (2018).
Influence of O2 plasma treatment on NiO x layer in perovskite solar cells. Jpn. J.
Appl. Phys, 57 (4S), 04FS07.
[23] F. Jiang, W. C. H. Choy, X. Li, D. Zhang, J. Cheng (2018).
Post-treatment-FreeSolution-Processed Non-stoichiometric NiOx Nanoparticles for Efficient Hole Transport Layers of Organic Optoelectronic Devices. Adv. Mater.
27, 2930-2937.
[24] H. Liua, Y. Wub, Y. Hua (2017). Reproducible switching effect of an all-inorganic halide perovskite CsPbBr 3 for memory applications. Ceram. Int., 43 (9),
7020-7025.