在过去十余年中，钙钛矿光伏技术取得了令人瞩目的发展，其产业化进程持续加速。本论文针对大面积钙钛矿太阳能电池效率偏低及大面积薄膜制备均匀性不足的问题，围绕以蒸镀均质的铅盐模板为核心的钙钛矿薄膜制备方法展开研究。在系统优化关键参数的基础上，着眼于提升钙钛矿体相和界面质量，通过前驱体掺杂和界面修饰调控钙钛矿薄膜结晶生长过程，降低钙钛矿缺陷密度，从而提升基于可大面积制备技术的器件性能，为高效率钙钛矿太阳能电池的规模化生产提供了新思路。具体研究内容如下：首先，围绕蒸镀铅盐与溶液沉积铵盐相结合的蒸发-溶液法开展系统的参数优化和规律研究。研究发现，相较于传统两步溶液法，使用蒸发-溶液法制备的钙钛矿薄膜在不同尺度上的缺陷显著减少，钙钛矿薄膜的质量和均一性明显提升，并且蒸发-溶液法制备钙钛矿具有更加简单的反应和结晶过程。基于优化后的蒸发-溶液法制备的1.0 cm2钙钛矿太阳能电池实现了24.0%的高效率，初步验证了研究方法的可行性。为了进一步提高大面积制备的可行性并提升钙钛矿薄膜的质量，将蒸发-溶液法拓展到蒸镀铅盐与涂布铵盐溶液相结合的方法，并在铵盐溶液中添加了乙胺盐酸盐作为添加剂。乙胺盐酸盐的引入可以调控钙钛矿薄膜的结晶过程，使得钙钛矿薄膜具有改善的结晶质量、晶粒尺寸和垂直面外的晶体取向。使用该方法将0.1 cm2和1.0 cm2钙钛矿太阳能电池的效率分别提升至25.8%和25.2%，同时孔径面积为12.0 cm2的钙钛矿模组也获得了22.6%的认证效率，实现了高效率大面积器件的制备。最后，通过在底界面引入多功能聚合物材料聚氨基丙基双胍磷酸盐（PAPBP）修饰层，发展了全蒸发钙钛矿薄膜太阳能电池制备工艺。PAPBP的修饰兼具多重增益效应，不仅能促进真空蒸发碘化铅垂直面外生长，改善钙钛矿薄膜的质量，还有效地降低了界面缺陷进而减少了界面复合，同时也改善了界面的载流子传输质量。所制备的基于全蒸发钙钛矿的器件在0.1 cm2，1.0 cm2和12.1 cm2孔径面积下分别获得了26.9%，26.6%和24.3%的高效率，实现了具有优异性能的大面积器件的制备。
In the past decade, perovskite photovoltaic technology has achieved remarkable development, and its industrialization process is also accelerating. This paper focuses on the problems of low efficiency of large-area perovskite devices and poor uniformity of large-area perovskite film preparation, and studies the perovskite preparation method based on the evaporation of conformal and homogeneous lead salt templates. On the basis of systematic optimization of key parameters, focusing on improving the quality of the perovskite bulk phase and interface, the crystallization growth process of the perovskite film is regulated by precursor doping and interface modification, and the defect density of the perovskite is reduced, thereby improving the device performance based on the method of large-area perovskite film preparation, opening up new paths for the large-area high-quality preparation of perovskite. The specific components of this study are presented below.A new method for preparing high-quality perovskite films by a two-step evaporation-solution method combining the evaporation of lead salts with the solution deposition of ammonium salts has been developed. Compared with the traditional two-step solution method, the defects of perovskite films prepared by the evaporation-solution method are significantly reduced at different scales, and the microscopic quality and film uniformity of the perovskite are significantly improved. At the same time, it is found that the evaporation-solution method for preparing perovskites has a simpler phase reaction and crystallization process. The large-area (1.0 cm2) perovskite solar cell prepared based on the optimized evaporation-solution method achieved a record high efficiency of 24.0%, which preliminarily verified the feasibility of the experimental idea.To further improve the feasibility of large-area preparation and improve the quality of perovskite films, the evaporation solution method was expanded to a method combining the evaporation of lead salt homogeneous templates with the slot-die coating of ammonium salt solutions. In addition, multifunctional ethylamine hydrochloride was added to the ammonium salt solution as an additive to optimize the crystallization process and film performance. The introduction of ethylamine hydrochloride can regulate the crystallization process of the perovskite film, so that the perovskite film has improved crystallinity, grain size and crystal orientation perpendicular to the outside. Using this method, the efficiency of small-area (0.1 cm2) and large-area (1.0 cm2) cells was further improved to 25.8% and 25.2%, and the perovskite module with a single aperture area of 12.0 cm2 also obtained a certified photoelectric conversion efficiency of 22.6%, realizing the preparation of high-efficiency large-area devices.Finally, a fully evaporated perovskite thin-film solar cell preparation process was developed by introducing a multifunctional polymer material polyaminopropyl biguanide phosphate (PAPBP) modification layer at the bottom interface. The modification of PAPBP has a multi-faceted improvement effect on the device, which not only promotes the vertical growth of vacuum evaporated lead iodide and improves the quality of perovskite films, but also effectively reduces interface defects and thus reduces interface recombination. In addition, the carrier transport quality of the bottom interface was improved. The prepared fully evaporated perovskite-based devices achieved high efficiencies of 26.9%, 26.6% and 24.3% at aperture areas of 0.1 cm2, 1.0 cm2 and 12.1 cm2, respectively, and achieved large-area devices with excellent performance.
