||Photo and Heat Annealing on the Transformation of Perovskite Intermediate Phase in Hybrid Organic-Inorganic MAPbI3 Film
||Department of Materials Science and Engineering
甲基胺基碘化鉛（methylammonium lead iodide, MAPbI3）為近年來新興的有機金屬鹵化鈣鈦礦（organometal halide perovskite）太陽能電池材料，其能量轉換效率（power conversion efficiency, PCE%）可以達到24.2 %以上。然而，傳統的熱處理製程容易使MAPbI3薄膜表面形成大量孔洞與晶界，從而降低其光電特性與能量轉換效率；另一方面，近年發現採用某些製程參數所形成MAPbI3在退火之前會先形成中間相（intermediate phase, MAI-PbI2-DMSO），而經由中間相轉換為鈣鈦礦得到的薄膜，能夠具有更優異的性能。
Methylammonium lead iodide, MAPbI3, is an emerging organometal halide perovskite solar cell material, the energy conversion efficiency of MAPbI3 can reach 24.2 %. However, the traditional heat treatment process often forms many pores and grain boundaries on the surface of the MAPbI3 film, thereby reducing its photoelectric characteristics and energy conversion efficiency. In recent years, it has been found that before annealing, there will be an intermediate phase (MAI-PbI2-DMSO) developed instead of MAPbI3 phase. The MAPbI3 thin film transformed from MAI-PbI2-DMSO will have shown some superior performance.
In this study, the MAI-PbI2-DMSO thin film was annealed by photo or/and heat effect. The film property was investigated by atomic force microscope, ultraviolet/visible spectrometer, X-ray diffraction analysis and photoluminescence fluorescence spectrometer. The MAPbI3 obtained by the photo effect has higher crystallinity, lower defect concentration and surface roughness that by than the heat effect. It has also been found that MAPbI3 illuminated at 300 mW/cm2 and simultaneously annealed at 40 oC has better film characteristics, showing that light illumination combined with low temperature heating can lead MAPbI3 to form a high-quality and dense film. In order to further explore the mechanism of heat and photo-induced MAI-PbI2-DMSO intermediate transformation, we used quantitative nanomechanical (QNM-mode) AFM and X-ray diffraction analysis to measure the MAI-PbI2-DMSO film. It was observed that the elastic modulus of the film decreased quickly in the early stage of illumination, mainly due to the loose arrangement of the new MAPbI3 grain. The subsequent rebound of the elastic modulus is due to the rearrangement and growth of MAPbI3 grains and densification. At that time, the main body of the film is still MAI-PbI2-DMSO intermediate phase which has higher an elastic modulus. The final decrease in the elastic modulus is due to the decrease in MAI-PbI2-DMSO accompanied with the increase in MAPbI3. Finally, MAI-PbI2-DMSO gradually disappeared, and the elastic modulus kept stable, which means that the phase transformation is completed. Transformation mechanism of MAI-PbI2-DMSO by heat effect was also investigated. It was found that the elastic modulus did not decrease drastically during the initial heating period, presumably because the high temperature annealing led a high volatilization rate of DMSO, but the effect for grain rearrangement is minor. It showed that the thermal effect converted MAI-PbI2-DMSO to MAPbI3 completely in a very short time.
Our results displayed that the degradation resistance is in the order: mixing effect> photo effect> heat effect. Base on this result, it was believed that the method of photo combined with annealing can effectively improve the degradation resistance of MAPbI3. It is interesting to find that, in the atmospheric environment, the MAPbI3 transformed from MAI-PbI2-DMSO does not degrade to MAPbI3∙H2O phase, meaning it has better resistance to water degradation.
第 1 章 1
第 2 章 文獻回顧 4
2.1 MAPbI3之結構 4
2.2 MAPbI3薄膜製程 5
2.3 MAPbI3中間相薄膜 8
2.3.1 MAI-PbI2-DMSO 中間相 8
2.3.2 MAI-PbI2-DMF 中間相 18
第 3 章 實驗原理 30
3.1 AFM基本原理 30
3.1.1機械性質量測(Peak Force QNM) 30
3.3 X光繞射儀原理(X-ray Diffraction) 34
第 4 章 實驗方法 35
4.3 ITO導電玻璃清洗 36
4.3 MAI-PbI2-DMSO中間相薄膜製作方式 36
4.4 MAPbI3薄膜製備 37
4.5 AFM量測參數與環境控制 40
第 5 章 結果與討論 44
5.4.5一般大氣環境in-situ AFM 95
5.4.6高濕度環境in-situ AFM 102
第 6 章 結論 139
第 7 章 未來展望 142
第 8 章 參考文獻 143
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