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CH3NH3PbI3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溶剂蒸发时PbI2和CH3NH3I的剧烈反应,因此退火后制得的CH3NH3PbI3薄膜非常均匀.然而由于纯DMSO的高粘度和低挥发速度,并不是非常适合作为旋涂溶剂,因此我们将DMF和GBL加入到DMSO中形成混合溶剂来考察对制备的钙钛矿薄膜质量和器件性能的影响.扫描电镜结果表明,加入20%~40%体积分数的DMF时,形成的薄膜表面非常均匀而且晶粒尺寸很大,达到微米级别,这样有利于减少晶界处的复合,提高电池性能.继续增加DMF比例会导致晶粒减小,晶界和孔隙增多,薄膜表面也更加粗糙.而加入GBL时得到的晶粒要远小于加入DMF时的尺寸,并且随着GBL比例的增加,薄膜的表面变得更加粗糙,孔隙明显增多,严重影响电池性能. XRD结果表明,纯DMSO和混合溶剂制得的薄膜都没有前驱体的残留.紫外可见吸收光谱表明,随着DMF比例的增加,吸收逐渐增强；而随着GBL比例的增加,吸收逐渐减弱.这主要由于不同比例溶剂制得的薄膜厚度有所差异造成的.
由相关的薄膜制备的平板结构太阳能电池I-V测试表明：当使用DMF-DMSO混合溶剂时,随着DMF比例由0%增至40%,短路电流和开路电压逐渐增加,填充因子略微减小,总体上导致光电转化效率逐渐增大.随着DMF继续增多,开路电压和填充因子的减小导致转化效率逐渐降低.而当使用GBL-DMSO混合溶剂时,主要受到短路电流的影响,电池的效率明显低于含DMF的混合溶剂的情况,而且随着GBL增多,电池效率逐渐降低.电池的最高转化效率达到了16.5%,最高功率点下固定电压扫描得到的稳态效率也达到了14.4%,高于报道中采用类似结构的电池的性能.由于在整个电池制备过程中,整个实验过程都低于100°C,该方法非常适合未来推广到柔性太阳能电池和多节太阳能电池上.
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.
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