自2009年首次应用于太阳能电池中以来,有机铅卤化物钙钛矿材料得到了极大关注.据文献报道,有机铅卤化物钙钛矿材料在不同结构的太阳能电池中都得到了应用,其中与有机太阳能电池类似的平板结构钙钛矿具有结构简单、制备容易等优点,非常适合用于柔性电池和多节电池等各种应用.在平板结构的太阳能电池中,制备高质量的钙钛矿薄膜至关重要.真空热蒸镀法虽然可以制备厚度均匀的钙钛矿薄膜,获得高的器件性能,但是设备成本较高,不利于大规模生产.而在溶液法中,早期的一步旋涂法和两步法由于没有多孔金属氧化物的支撑,很难制备均匀的钙钛矿平板薄膜;而气相辅助的两步法虽然制备的薄膜比较均匀,但反应时间却比较长.程一兵研究组采用在旋涂N,N-二甲基甲酰胺(DMF)溶液时滴加氯苯使钙钛矿快速析出结晶的方法,制备了高质量的均匀的CH3NH3PbI3薄膜.Seok研究组采用1,4-丁内酯(GBL)和二甲基亚砜(DMSO)的混和溶剂,在旋涂时滴加甲苯的方法,在多孔二氧化钛上也制得了均匀的CH3NH3Pb I3薄膜,取得了很高转化效率(16.7%),但缺少对不同溶剂比例的细致研究,另外,也没有对平板结构电池性能进行研究.本文采用DMF-DMSO和GBL-DMSO作为混合溶剂在二氧化钛致密层上旋涂制备了平板结构的钙钛矿薄膜,并且对混合溶剂的比例对器件性能的影响进行了详细的考察和优化.当纯DMF或纯GBL作为旋涂溶剂时,得到的CH3NH3PbI3钙钛矿薄膜含有大量不连续的晶粒,表面的覆盖度很差,对入射光的吸收远弱于连续均匀的薄膜.而且XRD结果表明,纯DMF或纯GBL作为旋涂溶剂的薄膜残留有前驱体的杂质,对器件性能非常不利.而采用DMSO作为旋涂溶剂时,制得的薄膜表面则比较均匀,几乎达到100%的覆盖.这主要是由于在旋涂溶液中形成了PbI2-CH3NH3I-DMSO的中间相,这样可以避免纯DMF或纯GBL溶剂?
Control of the morphology and coverage of high-quality perovskite films is the main issue affecting planar-structured perovskite solar cells fabricated by solution processing. In this work, the solvent engineering of mixed solutions for spin-coating uniform perovskite thin films was investigated in detail by adding different ratios of N,N-dimethylformamide (DMF) or γ-butyrolactone (GBL) to dimethyl sulfoxide (DMSO). The morphology and film thickness of the resulting perovskite films were found to be significantly altered. At 20%-40%(volume fraction) of N,N-dimethylformamide mixed with DMSO, micrometer scale grains and reduced grain boundaries were observed on the highly uniform perovskite thin films. The optimized planar-structured perovskite solar cells showed power conversion efficiency as high as 16.5%and a stabilized efficiency of 14.4%at a fixed forward bias of 0.88 V.