CN112151677A - 一种钙钛矿薄膜的制备方法及其钙钛矿太阳能电池 - Google Patents
一种钙钛矿薄膜的制备方法及其钙钛矿太阳能电池 Download PDFInfo
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- CN112151677A CN112151677A CN201910580840.2A CN201910580840A CN112151677A CN 112151677 A CN112151677 A CN 112151677A CN 201910580840 A CN201910580840 A CN 201910580840A CN 112151677 A CN112151677 A CN 112151677A
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- perovskite
- thin film
- perovskite thin
- lead
- bis
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Abstract
本发明涉及一种钙钛矿薄膜的制备方法,包括如下步骤:步骤1、在透明导电基底上沉积疏水性半导体材料;步骤2、在疏水性半导体材料表面沉积钙钛矿薄膜牺牲层;步骤3、将钙钛矿前驱体溶液沉积在牺牲层表面;步骤4、对沉积有钙钛矿前驱体材料的基片退火,得到钙钛矿薄膜。本发明还公开使用该制备方法制备钙钛矿太阳能电池及方法。本发明通过钙钛矿薄膜牺牲层的引入,极大的改善了极性钙钛矿溶液在疏水性半导体材料表面的润湿效果,可以制备出均匀致密、缺陷少、结晶质量高的钙钛矿薄膜。
Description
技术领域
本发明属于钙钛矿太阳能电池技术领域,特别涉及一种钙钛矿薄膜的制备方法及其钙钛矿太阳能电池。
背景技术
一般地,将钙钛矿前驱体溶液均匀的铺展在基底表面成膜,然后高温退火制备钙钛矿晶体薄膜的方法被称为溶液法。采用溶液法制备的小面积器件光电转换效率已经超过23%,显示出溶液法在制备高性能钙钛矿薄膜太阳能电池方面具有超高的光电性能和极佳的优越性。溶液法作为钙钛矿薄膜沉积的重要方法,可以精确地调控钙钛矿薄膜的多元组分,简单方便,器件表现出优异的光电性能。在溶液法制备钙钛矿薄膜的方法中,基底材料的性能对钙钛矿薄膜的生长起着至关重要的作用。特别地,研究表明,使用疏水基底材料时,由于极性钙钛矿溶液在疏水材料表面的接触角较大,润湿性变差,在退火过程中,钙钛矿倾向于生长成较大的晶体。相对于细小的晶粒(<100nm),由较大的晶粒(100~600nm)组成的钙钛矿薄膜具有更少的晶界缺陷,器件可以获得更好的光电性能和稳定性。然而,在疏水材料表面沉积钙钛矿薄膜仍然存在着较大的问题。由于基底材料的表面疏水特征,制备的钙钛矿薄膜常常具有细小的针孔,导致器件短路,降低了电池的光电性能。此外,孔隙的存在加速了钙钛矿薄膜的降解,导致器件的稳定性变差。
为了提高极性钙钛矿溶液在疏水基底表面的成膜质量,比较常见的方法是在疏水基底表面预先沉积一层双亲性材料,该类型材料同时具有亲水和疏水性官能团,极大的改善了钙钛矿溶液在基底表面的润湿性,从而制备出均匀致密的薄膜。然而,额外加入的这层材料,改变了钙钛矿材料的界面接触特性,影响了载流子的传输性能,常常不利于器件获得良好的光电性能和长期稳定性。除此之外,通常采用UV/O3处理来提升材料界面的亲水性能,然而,通过这种方式获得亲水性能的提升不能持久,衰减非常快。更重要的是,在钙钛矿太阳能电池中广泛使用的有机材料并不适合UV/O3处理。因此,如何提高钙钛矿溶液在疏水基底表面的成膜质量是亟待解决的难题。
发明内容
本发明所要解决的技术问题在于,提供一种钙钛矿薄膜的制备方法及其钙钛矿太阳能电池,可以制备出均匀、致密、缺陷少、结晶质量高的钙钛矿薄膜。
本发明是这样实现的,提供一种钙钛矿薄膜的制备方法,包括如下步骤:
步骤1、在透明导电基底上沉积疏水性半导体材料;
步骤2、在疏水性半导体材料表面沉积钙钛矿薄膜牺牲层;
步骤3、将钙钛矿前驱体溶液沉积在牺牲层表面;
步骤4、对沉积有钙钛矿前驱体材料的基片退火,得到钙钛矿薄膜。
进一步地,在步骤1中,所述透明导电基底具有在可见光及近红外光波段高度透明的特性,同时,具备载流子传输的能力,在波长为350nm~800nm范围光透过率不低于80%;所述透明导电基底包括复合而成的支撑层与功能层,所述支撑层的材料包括玻璃、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)及聚酰亚胺(PI)中任意一种,所述功能层的材料包括氧化铟锡(ITO)、掺氟氧化锡(FTO)、掺铝氧化锌(AZO)中任意一种。
进一步地,在步骤1中,所述疏水性半导体材料包括聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚甲基丙烯酸甲酯(PMMA)、 4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)、1,4-二[4-(二甲氨苯基)苯乙烯基]苯( TPASB)、4,4'-双[4-(二对甲苯基氨基)苯乙烯基]联苯(TPASBP)、聚苯乙烯、聚[2,1,3-苯并噻二唑-4,7-二基[4,4-双(2-乙基己基)-4H-环戊并[2,1-B:3,4-B']二噻吩-2,6-二基]](PCPDTBT)、聚[[9-(1-辛基壬基)-9H-咔唑-2,7-二基]-2,5-噻吩二基-2,1,3-苯并噻二唑-4,7-二基-2,5-噻吩二基] (PCDTBT)、N4,N4'-二(4-乙烯基苯基)-N4,N4'-二-1-萘基联苯-4,4'-二胺(VNPB)、聚[[(4-丁基苯基)亚氨基][1,1'-联苯]](poly-TPD)中任意一种。
进一步地,在步骤2中,所述钙钛矿薄膜牺牲层包括金属铅化物或者钙钛矿化合物,所述金属铅化物包括乙酸铅、硫氰酸铅、氯化铅、溴化铅、碘化铅、硫化铅中至少一种;所述钙钛矿化合物是具有ABX3结构的化合物。
进一步地,在步骤3中,所述钙钛矿前驱体溶液指将钙钛矿前驱体溶解在一种或多种溶剂中配制的溶液,所述钙钛矿前驱体是指得到步骤2中的具有ABX3结构的钙钛矿化合物的反应物材料AX和BX2,所述溶剂包括酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中至少一种。具体地,所述溶剂包括N,N-二甲基甲酰胺(DMF)、己内酰胺、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)乙醇、氯苯中至少一种。
进一步地,在所述钙钛矿化合物的ABX3结构中,A为含胺基、脒基、胍基的一价有机阳离子,或者锂、钠、钾、铷、铯的一价无机阳离子中的至少一种,B为硼、硅、锗、砷、锑、铍、镁、钙、锶、钡、铝、铟、镓、锡、铊、铅、铋、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、钌、铑、钯、银、镉、铪、钽、钨、铼、锇、铱、铂、金的二价金属离子中的至少一种,X为氯离子、溴离子、碘离子、硫氰酸根、乙酸根的负一价阴离子中的至少一种。其中,二价金属铅离子的摩尔百分数不低于80%,X负一价阴离子的摩尔百分数不低于80%。
进一步地,在步骤1~步骤3中,所述沉积方法包括热蒸发、slot die、刮涂、旋涂、喷涂中任意一种。
进一步地,在步骤2中,所述钙钛矿薄膜牺牲层多次沉积制备,其最终膜厚不超过100纳米。
进一步地,在步骤4中,所述钙钛矿薄膜的退火温度为90~150℃,退火时间为5~90分钟。
本发明是这样实现的,提供一种钙钛矿太阳能电池,所述钙钛矿太阳能电池是采用如前所述的钙钛矿薄膜的制备方法制备的。
本发明是这样实现的,提供一种钙钛矿太阳能电池的制备方法,其包括了如前所述的钙钛矿薄膜的制备方法。
与现有技术相比,本发明的钙钛矿薄膜的制备方法及其钙钛矿太阳能电池,首先在疏水材料表面制备一层钙钛矿薄膜牺牲层,然后再将钙钛矿前驱体溶液铺展其上,钙钛矿薄膜牺牲层增加了钙钛矿前驱体溶液在基底表面的覆盖,最后经过退火,从而制备出均匀、致密的钙钛矿薄膜。本发明通过钙钛矿薄膜牺牲层的引入,极大的改善了极性钙钛矿溶液在疏水性半导体材料表面的润湿效果,可以制备出均匀致密、缺陷少、结晶质量高的钙钛矿薄膜。
附图说明
图1为本发明的钙钛矿薄膜的制备方法的步骤示意图;
图2为本发明的在疏水基底表面使用牺牲层制备钙钛矿薄膜的SEM图;
图3为在疏水基底表面不使用牺牲层制备钙钛矿薄膜的SEM图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
请参照图1所示,本发明钙钛矿薄膜的制备方法的较佳实施例,包括如下步骤:
步骤1、在透明导电基底上沉积疏水性半导体材料;
步骤2、在疏水性半导体材料表面沉积钙钛矿薄膜牺牲层;
步骤3、将钙钛矿前驱体溶液沉积在牺牲层表面;
步骤4、对沉积有钙钛矿前驱体材料的基片退火,得到钙钛矿薄膜。
其中,在步骤1中,所述透明导电基底具有在可见光及近红外光波段高度透明的特性,同时,具备载流子传输的能力,在波长为350nm~800nm范围光透过率不低于80%;所述透明导电基底包括复合而成的支撑层与功能层,所述支撑层的材料包括玻璃、聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)及聚酰亚胺(PI)中任意一种,所述功能层的材料包括氧化铟锡(ITO)、掺氟氧化锡(FTO)、掺铝氧化锌(AZO)中任意一种。
其中,在步骤1中,所述疏水性半导体材料包括聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚甲基丙烯酸甲酯(PMMA)、 4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)、1,4-二[4-(二甲氨苯基)苯乙烯基]苯( TPASB)、4,4'-双[4-(二对甲苯基氨基)苯乙烯基]联苯(TPASBP)、聚苯乙烯、聚[2,1,3-苯并噻二唑-4,7-二基[4,4-双(2-乙基己基)-4H-环戊并[2,1-B:3,4-B']二噻吩-2,6-二基]](PCPDTBT)、聚[[9-(1-辛基壬基)-9H-咔唑-2,7-二基]-2,5-噻吩二基-2,1,3-苯并噻二唑-4,7-二基-2,5-噻吩二基] (PCDTBT)、N4,N4'-二(4-乙烯基苯基)-N4,N4'-二-1-萘基联苯-4,4'-二胺(VNPB)、聚[[(4-丁基苯基)亚氨基][1,1'-联苯]](poly-TPD)中任意一种。所述疏水性半导体材料可以选择性地传输电子或者空穴,极性溶剂在这些类型材料的表面具有较大的接触角,润湿性较差。
其中,在步骤1中,在所述透明导电基底表面覆盖一层导电的半导体材料,所述半导体材料为空穴传输材料,包括氧化镍、氧化钒、氧化钼、硫化铜、硫氰酸亚铜、氧化铜、氧化亚铜、氧化钴、PTAA、PEDOT、Spiro-MeOTAD和它们的掺杂物中的至少一种,该层半导体材料的厚度为5nm~200nm;或者,所述半导体材料为电子传输材料,包括二氧化钛、氧化锌、硫化镉、二氧化锡、三氧化二铟、氧化钨、氧化铈、C60、C70、PCBM以及它们的衍生物和掺杂物中的至少一种,该层半导体材料的厚度为5nm~300nm。
其中,在步骤2中,所述钙钛矿薄膜牺牲层包括金属铅化物或者钙钛矿化合物,所述金属铅化物包括乙酸铅、硫氰酸铅、氯化铅、溴化铅、碘化铅、硫化铅中至少一种。所述钙钛矿化合物是具有ABX3结构的一类化合物。
其中,在步骤3中,所述钙钛矿前驱体溶液指将钙钛矿前驱体溶解在一种或多种溶剂中配制的溶液,所述钙钛矿前驱体是指得到步骤2中的具有ABX3结构的钙钛矿化合物的反应物材料AX和BX2。所述溶剂包括酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中至少一种。具体地,所述溶剂包括N,N-二甲基甲酰胺(DMF)、己内酰胺、二甲基亚砜(DMSO)、N-甲基吡咯烷酮(NMP)、γ-丁内酯(GBL)乙醇、氯苯中至少一种。
具体地,在所述钙钛矿化合物的ABX3结构中,A为含胺基、脒基、胍基的一价有机阳离子,或者锂、钠、钾、铷、铯的一价无机阳离子中的至少一种;B为硼、硅、锗、砷、锑、铍、镁、钙、锶、钡、铝、铟、镓、锡、铊、铅、铋、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、钌、铑、钯、银、镉、铪、钽、钨、铼、锇、铱、铂、金的二价金属离子中的至少一种;X为氯离子、溴离子、碘离子、硫氰酸根、乙酸根的负一价阴离子中的至少一种。其中,二价金属铅离子的摩尔百分数不低于80%,X负一价阴离子,例如碘离子的摩尔百分数不低于80%。
其中,在步骤1~步骤3中,所述沉积方法包括热蒸发、slot die、刮涂、旋涂、喷涂中任意一种。
其中,在步骤2中,所述钙钛矿薄膜牺牲层多次沉积制备,其最终膜厚不超过100纳米。
其中,在步骤4中,所述钙钛矿薄膜的退火温度为90~150℃,退火时间为5~90分钟。
本发明还公开一种钙钛矿太阳能电池,所述钙钛矿太阳能电池是采用如前所述的钙钛矿薄膜的制备方法制备的。
本发明还公开一种钙钛矿太阳能电池的制备方法,其包括了如前所述的钙钛矿薄膜的制备方法。
下面结合具体实施例来进一步说明本发明的方法。
实施例1
本发明的钙钛矿薄膜的制备方法实施例1,包括如下步骤:
11. 配制钙钛矿前驱体溶液:分别将159g甲胺氢碘酸盐粉末、461g碘化铅粉末溶解在1升二甲基亚砜与N,N-二甲基甲酰胺的混合溶剂中,将所得到的亮黄色溶液在磁力搅拌条件下加热到70℃,并保持2h。
12. 在透明导电基底上沉积疏水性半导体薄膜:配制2毫克/毫升的PTAA氯苯溶液,均匀铺展在ITO玻璃的表面,以4000rpm/s的速度旋涂20s,100℃退火10分钟。
13. 沉积钙钛矿薄膜牺牲层:将经步骤12得到的基片置于蒸镀腔体中,腔体内的真空度控制在10-4Pa左右,以1Å/s的蒸发速率将乙酸铅蒸镀到PTAA表面,得到20纳米厚的乙酸铅作为钙钛矿薄膜牺牲层。
14. 沉积钙钛矿前驱体溶液:将步骤13得到的基片放置在热台上,控制热台的温度为60℃,将步骤11配制的钙钛矿前驱体溶液刮涂在钙钛矿薄膜牺牲层上,然后迅速使用高温氮气吹扫,使湿膜快速固化,得到光亮平整的钙钛矿前驱体薄膜。
15. 将步骤14得到的钙钛矿前驱体薄膜放置在100℃的热台上,退火5分钟得到均匀、致密的钙钛矿薄膜。
实施例2
本发明的钙钛矿薄膜的制备方法实施例2,包括如下步骤:
21. 配制钙钛矿前驱体溶液:分别将碘化铯(CsI)、甲脒氢碘酸盐(FAI)、碘化铅(PbI2)、溴化锌(Znbr2)粉末溶解在N-甲基吡咯烷酮与γ-丁内酯的混合溶剂中,配制1.2摩尔每升的Cs0.05FA0.95PbI3(Znbr2)0.05钙钛矿前驱体溶液,将所得到的亮黄色溶液在磁力搅拌条件下加热到70℃,并保持2h。
22. 在透明导电基底上沉积疏水性半导体薄膜:选用表面覆盖掺铝氧化锌的聚酰亚胺作为透明导电基底,放入蒸镀腔体中,腔体内的真空度控制在10-4Pa左右,同时将基底加热至120℃,以0.5Å/s的蒸发速率蒸镀聚[[(4-丁基苯基)亚氨基][1,1'-联苯]],得到15纳米厚的疏水性半导体薄膜。
23. 沉积钙钛矿薄膜牺牲层:将步骤22得到的基片放置在热台上,控制热台的温度为100℃。取适量的步骤21配制的钙钛矿前驱体溶液,稀释至0.1摩尔每毫升,将稀释液均匀喷涂在基片表面,得到30纳米厚的钙钛矿薄膜牺牲层。
24. 沉积钙钛矿前驱体溶液:将步骤23得到的基片放置在roll-to-roll设备上,控制基片的温度为50℃,将步骤21配制的钙钛矿前驱体溶液涂布在钙钛矿薄膜牺牲层上,然后迅速使用氮气吹扫,使湿膜处于半干状态,再快速浸入对二甲苯溶液中,保持5s,然后用氮气吹干,得到光亮平整的钙钛矿前驱体薄膜。
25. 将钙钛矿前驱体薄膜在100℃的条件下退火10分钟,得到黑褐色的钙钛矿薄膜。
对比图2和图3可以看出,在图2中使用本发明的方法制备的钙钛矿薄膜晶粒致密、无孔洞、钙钛矿薄膜覆盖均匀。在图3中对比例(即在疏水基底表面沉积钙钛矿薄膜时,不预先使用牺牲层的情况下制备钙钛矿薄膜。)中,未使用本发明的方法制备的钙钛矿薄膜出现很多的孔洞,钙钛矿薄膜覆盖不完全。因此,使用本发明的方法制备的钙钛矿薄膜的形态和效果明显优于对比例的。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种钙钛矿薄膜的制备方法,其特征在于,包括如下步骤:
步骤1、在透明导电基底上沉积疏水性半导体材料;
步骤2、在疏水性半导体材料表面沉积钙钛矿薄膜牺牲层;
步骤3、将钙钛矿前驱体溶液沉积在牺牲层表面;
步骤4、对沉积有钙钛矿前驱体材料的基片退火,得到钙钛矿薄膜。
2.如权利要求1所述的钙钛矿薄膜的制备方法,其特征在于,在步骤1中,所述透明导电基底具有在可见光及近红外光波段高度透明的特性,同时,具备载流子传输的能力,在波长为350nm~800nm范围光透过率不低于80%;所述透明导电基底包括复合而成的支撑层与功能层,所述支撑层的材料包括玻璃、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯及聚酰亚胺中任意一种,所述功能层的材料包括氧化铟锡、掺氟氧化锡、掺铝氧化锌中任意一种。
3. 如权利要求2所述的钙钛矿薄膜的制备方法,其特征在于,在步骤1中,所述疏水性半导体材料包括聚[双(4-苯基)(2,4,6-三甲基苯基)胺](PTAA)、聚甲基丙烯酸甲酯(PMMA)、 4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)、1,4-二[4-(二甲氨苯基)苯乙烯基]苯(TPASB)、4,4'-双[4-(二对甲苯基氨基)苯乙烯基]联苯(TPASBP)、聚苯乙烯、聚[2,1,3-苯并噻二唑-4,7-二基[4,4-双(2-乙基己基)-4H-环戊并[2,1-B:3,4-B']二噻吩-2,6-二基]](PCPDTBT)、聚[[9-(1-辛基壬基)-9H-咔唑-2,7-二基]-2,5-噻吩二基-2,1,3-苯并噻二唑-4,7-二基-2,5-噻吩二基] (PCDTBT)、N4,N4'-二(4-乙烯基苯基)-N4,N4'-二-1-萘基联苯-4,4'-二胺(VNPB)、聚[[(4-丁基苯基)亚氨基][1,1'-联苯]](poly-TPD)中任意一种。
4.如权利要求1所述的钙钛矿薄膜的制备方法,其特征在于,在步骤2中,所述钙钛矿薄膜牺牲层包括金属铅化物或者钙钛矿化合物,所述金属铅化物包括乙酸铅、硫氰酸铅、氯化铅、溴化铅、碘化铅、硫化铅中至少一种;所述钙钛矿化合物是具有ABX3结构的化合物。
5.如权利要求1所述的钙钛矿薄膜的制备方法,其特征在于,在步骤3中,所述钙钛矿前驱体溶液指将钙钛矿前驱体溶解在一种或多种溶剂中配制的溶液,所述钙钛矿前驱体是指得到步骤2中的具有ABX3结构的钙钛矿化合物的反应物材料AX和BX2,所述溶剂包括酰胺类溶剂、砜类/亚砜类溶剂、酯类溶剂、烃类、卤代烃类溶剂、醇类溶剂、酮类溶剂、醚类溶剂、芳香烃溶剂中至少一种。
6.如权利要求4或5所述的钙钛矿薄膜的制备方法,其特征在于,在所述钙钛矿化合物的ABX3结构中,A为含胺基、脒基、胍基的一价有机阳离子中的至少一种,或者锂、钠、钾、铷、铯的一价无机阳离子中的至少一种,B为硼、硅、锗、砷、锑、铍、镁、钙、锶、钡、铝、铟、镓、锡、铊、铅、铋、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钇、锆、铌、钼、钌、铑、钯、银、镉、铪、钽、钨、铼、锇、铱、铂、金的二价金属离子中的至少一种,X为氯离子、溴离子、碘离子、硫氰酸根、乙酸根的负一价阴离子中的至少一种。
7. 如权利要求1所述的钙钛矿薄膜的制备方法,其特征在于,在步骤1~步骤3中,所述沉积方法包括热蒸发、slot die、刮涂、旋涂、喷涂中任意一种。
8.如权利要求1所述的钙钛矿薄膜的制备方法,其特征在于,在步骤2中,所述钙钛矿薄膜牺牲层多次沉积制备,其最终膜厚不超过100纳米。
9.一种钙钛矿太阳能电池,其特征在于,所述钙钛矿太阳能电池是采用如权利要求1至8中任意一项所述的钙钛矿薄膜的制备方法制备的。
10.一种钙钛矿太阳能电池的制备方法,其特征在于,其包括了如权利要求1至8中任意一项所述的钙钛矿薄膜的制备方法。
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CN108258128A (zh) * | 2018-01-17 | 2018-07-06 | 杭州纤纳光电科技有限公司 | 一种具有界面修饰层的钙钛矿太阳能电池及其制备方法 |
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CN112909175A (zh) * | 2021-01-22 | 2021-06-04 | 武汉大学 | 一种基于非卤铅源的钙钛矿太阳能电池及其制备方法 |
CN113764540A (zh) * | 2021-01-22 | 2021-12-07 | 西安电子科技大学 | 具有双层钙钛矿光活性层的太阳能电池的制备方法及结构 |
CN112909175B (zh) * | 2021-01-22 | 2023-06-20 | 武汉大学 | 一种基于非卤铅源的钙钛矿太阳能电池及其制备方法 |
CN113764540B (zh) * | 2021-01-22 | 2023-10-03 | 西安电子科技大学 | 具有双层钙钛矿光活性层的太阳能电池的制备方法及结构 |
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