不同淬火温度下滴铸法钙钛矿晶体生长模式分析

doi:10.6023/A24070220

摘要/Abstract

大面积致密钙钛矿薄膜制备是目前钙钛矿太阳能电池研究的热门方向, 其中揭示钙钛矿薄膜晶体生长规律对于实现致密的钙钛矿薄膜具有重要意义. 本工作基于滴铸法在不同淬火温度下进行钙钛矿薄膜制备实验, 通过光学显微镜记录其针状结晶和层状结晶生长过程, 结合X射线衍射(XRD)测试和扫描电子显微镜(SEM)测试, 分析了各类型晶体生长模式以及形成温度, 总结钙钛矿晶体结构随淬火温度提高的演化规律. 研究结果表明, 随着淬火温度及结晶速率的提高, 钙钛矿薄膜晶体从枝状结晶逐渐转变成了圆球状结晶, 薄膜的均匀性逐步提升.

关键词: 滴铸法, 钙钛矿薄膜, 结晶过程, 晶核

The preparation of large-area dense perovskite thin films is currently a popular direction in the research of perovskite solar cells. Researchers use methods such as assisted liquid film ordered evaporation and adjusting the evaporation temperature and solution composition of perovskite solutions to ensure the formation of smooth, dense, and uniform crystal morphology in perovskite films.Despite detailed studies on the conditions for the formation of needle-shaped and layered crystals in perovskite thin films, there remains a gap in understanding the impact of increased evaporation rates on crystal growth morphology and the laws governing the transition from needle-shaped crystals to dense layered crystals in perovskite thin films. Therefore, revealing the crystal growth mode of perovskite films is crucial for achieving dense perovskite films. This study utilized the drop casting method to prepare perovskite thin films. A perovskite solution was dripped onto a preheated substrate to obtain a stable and spreading perovskite precursor liquid film, which was then evaporated and crystallized at different quenching temperatures to prepare perovskite thin films. Firstly, this study recorded the growth process of needle-shaped and layered crystals in perovskite thin films during liquid film quenching and evaporation using an optical microscope. During this process, adjusting the microscope to pre-focus and minimizing the influence of external light sources during video recording can enhance the reproducibility of experimental results. Conduct an additional annealing process for the experimental group at temperatures below 100 ℃ to eliminate residual solvents and disintegrate complexes, a process that will not alter the crystal morphology. Through scanning electron microscope (SEM) testing, we investigated different crystal growth modes and compared the formation temperature and crystallinity of each crystal morphology with X-ray diffraction (XRD) testing. This article summarizes how the structure of perovskite crystals evolves with increasing quenching temperature, and speculates that the driving force of crystallization plays a key role in the mechanism of crystal morphology change. The research results indicate that with the increase of quenching temperature and crystallization rate, the perovskite film crystals transform from dendritic to spherical, and the morphology of the film changes from needle-like pores to smooth and dense. In addition, the uniformity of the film increases with the increase of quenching temperature. This transformation is crucial for enhancing the efficiency and stability of perovskite solar cells, as dense and uniform films are essential for optimal performance.

Key words: drop-casting, perovskite film, crystallization process, crystal nucleus

引用此文

肖圣宗, 许雄文. 不同淬火温度下滴铸法钙钛矿晶体生长模式分析[J]. 化学学报, 2024, 82(10): 1031-1038.

Shengzong Xiao, Xiongwen Xu. Analysis of Growth Mode of Perovskite Crystals by Drop Casting Method at Different Quenching Temperatures[J]. Acta Chimica Sinica, 2024, 82(10): 1031-1038.

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图/表 16

图1. 光学显微镜记录钙钛矿结晶过程

Figure 1. Optical microscope records the crystallization process of perovskite

图2. (a) 60 ℃、(b) 80 ℃和(c) 100 ℃淬火温度下记录各组晶体生长过程

Figure 2. Record the crystal growth process of each group at quenching temperatures of (a) 60 ℃, (b) 80 ℃, and (c) 100 ℃

图3. (a) 60 ℃、(b) 80 ℃和(c) 100 ℃持续加热1 min时的图像记录

Figure 3. Image recording of continuous heating at (a) 60 ℃, (b) 80 ℃ and (c) 100 ℃ for 1 min

图4. 110 ℃淬火温度下记录钙钛矿晶体生长过程

Figure 4. Record the growth process of perovskite crystals at quenching temperature of 110 ℃

图5. 120 ℃淬火温度下记录钙钛矿晶体生长过程

Figure 5. Record the growth process of perovskite crystals at quenching temperature of 120 ℃

图6. (a) 140 ℃和(b) 160 ℃淬火温度下记录钙钛矿晶体生长过程

Figure 6. Record the growth process of perovskite crystals at quenching temperatures of (a) 140 ℃ and (b) 160 ℃

图7. 晶体成核和生长的Lar-Mer曲线

Figure 7. The Lar-Mer curves for crystal nucleation and growth

图8. 基底表面温度变化曲线及结晶出现时刻

Figure 8. Temperature variation curve of the substrate surface and the time of crystallization

图9. 不同温度下制备的MAPbI3薄膜的光学显微镜图像

Figure 9. Optical microscopy images of MAPbI3 thin films prepared at different temperatures

图10. 不同温度下制备的MAPbI3薄膜的SEM图像

Figure 10. SEM images of MAPbI3 thin films prepared at different temperatures

图11. 淬火温度为(a) 60 ℃、(b) 80 ℃、(c) 100 ℃、(d) 120 ℃、(e) 140 ℃和(f) 160 ℃下制备的钙钛矿薄膜高倍SEM图像

Figure 11. High magnification SEM images of perovskite thin films prepared at temperatures of (a) 60 ℃, (b) 80 ℃, (c) 100 ℃, (d) 120 ℃, (e) 140 ℃, and (f) 160 ℃

图12. 不同温度下制备的MAPbI3薄膜的(a) XRD图和(b) (200)峰的半峰宽

Figure 12. (a) XRD patterns and (b) half width of (200) peak of MAPbI3 thin films prepared at different temperatures

图13. 淬火温度为180 ℃下制备的钙钛矿薄膜的光学显微图像(仅上方打光)

Figure 13. Optical microscopy image of perovskite thin film prepared at quenching temperature of 180 ℃ (Only light up above)

图14. 淬火温度为160 ℃和180 ℃下制备的MAPbI3薄膜的XRD图

Figure 14. XRD patterns of MAPbI3 thin films prepared at quenching temperatures of 160 ℃ and 180 ℃

图15. 滴铸法制备钙钛矿薄膜过程

Figure 15. Process of preparing perovskite films by drop-casting

图16. 原位观测试验台

Figure 16. In-situ observation platform

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