钙钛矿薄膜的制备优化及其太阳能电池性能研究

发布时间：2018-07-09 09:11

本文选题：钙钛矿太阳能电池 + 薄膜　；参考：《华侨大学》2017年博士论文

【摘要】：自2009年CH_3NH_3PbI_3作为太阳能电池吸光材料被报道以来,钙钛矿太阳能电池已经取得了飞快的进步,理论探索和工艺制备获得了长足的发展。如何实现进一步的跨越,加快钙钛矿太阳能电池的产业化进程,还有很多科学问题需要解决,其中高质量钙钛矿薄膜的制备工艺显得尤为重要。针对目前存在的问题,本论文开展钙钛矿薄膜晶体生长、材料能级调控、薄膜结构设计以及大面积器件开发等科学问题的研究,通过材料制备、性能结构表征、器件设计组装、效能评价测试,研究薄膜制备优化条件对器件光伏性能的影响,进一步研究钙钛矿薄膜电子传输动力学、界面匹配、能级匹配和结构匹配等科学规律,获得较好的进展,主要研究内容和结果如下:(1)开发三步旋涂法制备优质钙钛矿薄膜。采用异丙醇溶剂处理PbI2液膜而非传统的加热退火处理,获得了具有可控形貌和结晶度的巨石阵结构PbI2薄膜,为CH_3NH_3I的渗透提供了足够的通道和空间,保证了PbI2向钙钛矿的完全转化,最高获得了17.84%的光电转换效率。(2)提出使用环境友好型醇类溶剂浴法制备高质量钙钛矿薄膜,解决使用不良溶剂(乙醚、氯苯、甲苯等)带来的毒性问题。探索了不同类型溶剂浴中钙钛矿薄膜的生长机理,研究溶剂浴成膜方式对器件光伏性能的影响,以及电子传输动力学的作用机制。(3)通过控制钙钛矿前驱液中强配位剂二亚甲砜(DMSO)的含量,研究一步旋涂滴加反溶剂法制备钙钛矿薄膜的成膜机理,研究了中间配合物对于薄膜结晶及器件重现性的影响。调控二亚甲砜(DMSO)含量,拓宽滴加乙醚的工作窗口时间,获得高质量的钙钛矿薄膜。(4)研究杂化钙钛矿(CH_3NH_3PbI3-xBrx)薄膜的生长机理,通过控制I-Br的掺杂比例,研究溴化甲胺(CH_3NH_3Br)对杂化钙钛矿薄膜晶体形貌的影响,研究了钙钛矿材料的能级结构以及太阳能电池中电子传输动力学的微观机理。由于Br的引入,拓宽了钙钛矿材料的能级,提升了器件的开路电压,提高TiO_2/钙钛矿层界面的电子提取能力。(5)基于功能梯度结构设计,将Spiro-OMeTAD空穴传输材料以梯度变化的形式分散于钙钛矿薄膜中。通过能量色散X射线光谱仪(EDX)和二次离子质谱(SIMS)证实了梯度结构的存在,研究载流子传输及复合动力学,分析梯度结构的作用机理,最终获得18.84%的光电转换效率。(6)通过一步旋涂滴加反溶液法和正丁醇溶剂浴法制备大面积钙钛矿太阳能电池,比较多种大面积钙钛矿太阳能电池的光电性能,研究两种制备方法在不同尺寸下的适用性。一步旋涂滴加反溶液法仅适用于制备小面积高效钙钛矿太阳能电池;正丁醇溶剂浴法可以制备大面积高质量钙钛矿薄膜,制备的10×10 cm2钙钛矿薄膜具有良好的“镜面”效果。
[Abstract]:Since the report of Ch _ 3NH _ 3PbI _ 3 as solar cell absorbent material in 2009, the perovskite solar cell has made rapid progress, theoretical exploration and process preparation have made great progress. There are still many scientific problems to be solved in order to realize further leap and accelerate the industrialization of perovskite solar cells, among which the preparation process of high quality perovskite thin films is particularly important. In order to solve the existing problems, the research of perovskite thin film crystal growth, material energy level control, thin film structure design and large area device development has been carried out in this paper, through material preparation, performance structure characterization, device design and assembly, etc. The effects of the optimal preparation conditions on the photovoltaic properties of perovskite thin films are studied, and the scientific laws of electron transport dynamics, interface matching, energy level matching and structure matching of perovskite films are further studied. The main contents and results are as follows: (1) three-step spin coating method was developed to prepare high-quality perovskite films. PbI2 films with controllable morphology and crystallinity were obtained by using isopropanol solvent to treat PBI2 liquid film instead of traditional heating annealing treatment, which provided sufficient channel and space for CH3NHS3i permeation. The conversion of PBI2 to perovskite is guaranteed, and the highest photoelectricity conversion efficiency of 17.84% is obtained. (2) it is proposed to prepare high quality perovskite films by using environment-friendly alcohols solvent bath method to solve the problem of using bad solvents (ether, chlorobenzene, chlorobenzene). The toxicity of toluene etc. The growth mechanism of perovskite films in different kinds of solvent bath was studied. (3) by controlling the content of DMSO in perovskite precursor, the film-forming mechanism of perovskite thin films prepared by one-step spin coating and anti-solvent method was studied. The effects of the intermediate complexes on the crystallization of the films and the reproducibility of the devices were investigated. The high quality perovskite thin films were obtained by adjusting the content of DMSO and widening the working window time of dimethyl ether. (4) the growth mechanism of hybrid perovskite films was studied. By controlling the doping ratio of I-Br, the growth mechanism of hybrid perovskite films was studied. The effect of Ch _ 3CH _ 3BR on the crystal morphology of hybrid perovskite films was studied. The energy level structure of perovskite and the microscopic mechanism of electron transport kinetics in solar cells were studied. Because of the introduction of Br, the energy level of perovskite material is widened, the open circuit voltage of the device is raised, and the electronic extraction ability of TiO-2 / perovskite interface is improved. (5) based on the design of functionally gradient structure, Spiro-OMeTAD hole-transport materials were dispersed in perovskite films in the form of gradient changes. The existence of gradient structure was confirmed by energy dispersive X-ray spectrometer (edX) and secondary ion mass spectrometry (Sims). The carrier transport and recombination kinetics were studied, and the mechanism of gradient structure was analyzed. Finally, 18.84% photovoltaic conversion efficiency was obtained. (6) large area perovskite solar cells were prepared by one-step spin-drop adding inverse solution method and n-butanol solvent bath method, and the optoelectronic properties of many kinds of large area perovskite solar cells were compared. The applicability of the two preparation methods in different sizes was studied. The one-step spin-coating dripping and reverse solution method is only suitable for the preparation of small area high efficiency perovskite solar cells, and n-butanol solvent bath method can be used to prepare large area and high quality perovskite films, and the 10 脳 10 cm2 perovskite thin films have good "mirror" effect.
【学位授予单位】：华侨大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TM914.4

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