CN111051560B - 生产具有钙钛矿状结构的吸光材料的膜的方法 - Google Patents
生产具有钙钛矿状结构的吸光材料的膜的方法 Download PDFInfo
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Abstract
本发明涉及一种生产具有钙钛矿状结构的有机‑无机吸光材料的方法,该方法可用于钙钛矿太阳能电池的制造中。具有式АСВ3的钙钛矿状结构的吸光材料的生产方法包括将具有指定反应化学计量的厚度的试剂AB的层涂布到试剂C的层上,然后将该多层置于包含试剂В2的液体或气体介质中,其中组分А可以是CH3NH3+、(NH2)2CH+、C(NH2)3+、Cs+或其混合物,组分В可以是Cl‑、Br‑、I‑或其混合物,且组分C可以是金属Sn、Pb或Bi、或它们的合金、氧化物或盐。通过使用要求保护的发明可以实现的技术结果是一种简单且快速的生产层的方法,由于形成中间相АВ‑В2的膜该层是均质的,该层为具有改善形态的具有钙钛矿状结构的吸光有机‑无机材料,由于在大面积表面上的快速结晶,这将使得生产的材料用于大面积太阳能电池中成为可能。
Description
发明领域
本发明涉及生产具有钙钛矿状结构的有机-无机吸光材料的方法,该材料可用于例如钙钛矿太阳能电池的制造中。
背景技术
现有技术公开了获得具有钙钛矿状结构的吸光材料的方法。
在本申请的框架内,这些结构直接指钙钛矿结构以及具有各种结构变化的结构(该术语详细描述于信息源Attfield J.P.,Lightfoot P.,Morris R.E.钙钛矿//Dalt.Trans.2015年,第44卷,第23期,第10541-10542页)。
特别地,文章[Burschka J.等人,作为通往高性能钙钛矿敏感型太阳能电池途径的顺序沉积(Sequential deposition as a route to high-performance perovskite-sensitized solar cells)//自然(Nature).–2013年.–Т.499.–第7458期.–С.316.]描述了一种分两步制造钙钛矿CH3NH3PbI3薄膜的方法,通过围绕垂直于衬底平面的轴线高速旋转PbI2溶液以所需厚度的层的形式将其沉积到衬底上(旋涂法),然后将所得的PbI2薄层浸入MAI的异丙醇溶液中。
文章[Saliba M.等人,铷阳离子掺入钙钛矿太阳能电池提高了光伏性能(Incorporation of rubidium cations into perovskite solar cells improvesphotovoltaic performance)//科学(Science)(80-.),2016年,第354卷,第6309期,第206–209页]描述了一步法制造钙钛矿CH3NH3PbI3薄层,通过围绕垂直于衬底平面的轴高速旋转多种有机溶剂混合物中的钙钛矿溶液以薄层形式沉积其在衬底上。
上述方法的缺点是不可能在大面积衬底上从溶液获得钙钛矿或初始组分(PbI2)的层,并且相应地不可能获得大面积钙钛矿太阳能电池。
专利CN104250723,2014年9月9日,郑直、程佳美、雷岩、贾会敏、何伟伟、贺盈盈,“一种基于铅单质薄膜原位大面积控制合成钙钛矿型CH3NH3PBI3薄膜材料的化学方法”描述了一种通过将容易以可控厚度大面积均匀沉积的金属铅膜浸入碘和甲基碘化铵的有机溶剂(例如乙醇)溶液中来制备钙钛矿CH3NH3PbI3的方法。通过磁控溅射将均匀层形式的金属铅沉积在电子导电层的无孔表面上。之后,使其与包含分子碘和甲基碘化铵的有机溶剂接触。结果,连续的无孔铅层转变为连续无孔钙钛矿层。
专利CN105369232,2015年2月16日,郑直、贺迎迎、雷岩、程佳美、贾会敏、何伟伟,“基于铅单质薄膜原位大面积控制合成钙钛矿型CH3NH3PbBr3薄膜材料的化学方法”描述了一种通过将容易以可控厚度大面积均匀沉积的金属铅膜浸入甲基溴化铵的有机溶剂(例如异丙醇)溶液中来制备钙钛矿CH3NH3PbBr3的方法。
上述方法的缺点是需要使用溶剂和对所得钙钛矿层的形态的较差控制,这复杂化并减慢了有机-无机钙钛矿制造的技术过程,从而导致生产、健康和环境风险。
文章Mater.Horiz.,2017,4,625-632,Petrov Andrey A.,Belich Nikolai A.,Grishko Aleksei Y.,Stepanov Nikita M.,Dorofeev Sergey G.,Maksimov Eugene G.,Shevelkov Andrei V.,Zakeeruddin Shaik M.,Michael Graetzel,Tarasov Alexey B.,Goodilin Eugene A.,“通过室温反应性聚碘化物熔体形成杂化钙钛矿的新策略(A newformation strategy of hybrid perovskites via room temperature reactivepolyiodide melts)”描述了一种由金属铅层与施加到其的一般组成为MAI3+x的试剂的反应而无需溶剂的钙钛矿层的制备方法。
已知方法的缺点是难以在大的衬底面积上实现粘性聚碘化物(聚卤化物)试剂的均匀分布,并且在相互作用中缺乏控制和化学计量的偏差,这尤其可能导致形成碘化铅亚层。沉积在衬底上的试剂是液体熔体,这导致在最终产品的成膜反应过程中控制前体的化学计量比时存在一定的复杂性。结果,所得膜的质量(特别是厚度均匀性和相组成)降低,因此,负面影响基于制造的膜的最终产品(例如太阳能电池)的效率。
发明内容
要求保护的发明解决的技术问题是创造一种技术方法,无需使用溶剂即可在大面积衬底上生产具有钙钛矿状结构的吸光有机-无机材料。
通过使用要求保护的发明实现的技术结果是提供获得具有高均匀度的无通孔的单相膜的可能性,这将允许该材料能用于大面积太阳能电池中。该方法还具有可制造性和易于实施的特征,这使其更易于用于工业生产。所要求保护的方法在不使用溶剂的情况下进行,由于消除了其与所生产的钙钛矿成分之间不希望的相互作用的可能性,因此有助于提高最终产品的质量,并且还潜在地实现了更环境友好的生产。
通过以下方法解决问题:在该方法中,根据如下方式的技术方案获得由具有钙钛矿状结构的、具有结构式ACB3的吸光材料制成的膜:在衬底上依次沉积试剂C的层和试剂AB的层,然后将具有沉积多层的衬底浸入包含试剂B2的液体或气体介质中一段必要且充分的时间,以进行反应С+АВ+B2=АСВ3+Х,其中组分A表示CH3NH3 +、(NH2)2CH+、C(NH2)3 +、Cs+或它们的混合物,组分B表示Cl-、Br-、I-或它们的混合物,组分C表示金属Sn、Pb、Bi、它们的熔体、氧化物或盐,组分X表示组分C以氧化物或盐形式使用时的分解产物。所述液体介质的特征在于在其中试剂AB的不溶性和B2的溶解性。试剂C和AB以化学计量的量在每单位面积上涂布,以提供具有给定厚度的膜。通过真空溅射、电化学沉积、溶液的气溶胶喷涂或旋涂来沉积组分C和AB。在反应完成后,通过在溶剂中洗涤、将溶剂滴在表面上、在高温下退火或在减压下蒸发来除去过量的组分B。在使用氧化物或盐作为组分C的情况下,在反应C+AB+B2=ACB3+X完成后,还应确保除去组分X。没有载气的干燥的空气、氩气、或含氮的碘蒸气(卤素或它们的混合物)或碘蒸气(卤素或它们的混合物)可以用作气相;CCl4、甲苯、***和其他含碘的有机溶剂(卤素或它们的混合物)可以用作液相。
除了类似物外,在要求保护的发明的框架内,可以通过在衬底上由沉积参数严格限定的比例预先控制前体膜(AB和C)的沉积来精确地控制由吸光材料制成的膜的形成的反应的化学计量。在用含有组分B2的溶液或气体进一步处理含有组分AB和C的双层膜之后,在其表面上形成由反应混合物AB-B2制成的均匀膜,该混合物的量由先前沉积的组分AB严格限定。此外,该反应混合物与组分C的层反应以形成最终产物,这使得可以在大面积上实现膜的高均质性。
当具有试剂C的层和化学计量的试剂AB沉积在其上的衬底浸入含有试剂B2的液体或气体介质中时,试剂AB与试剂B2反应并形成组合物AB-nB2(n≥1),其与试剂C反应。结果,通过以下中间反应形成钙钛矿ACB3:AB-nB2+C=ACB3+[(n-3)/2]B2。
在要求保护的方法的框架内,通过控制吸光材料成膜反应的化学计量来实现技术结果的实现,即大面积的吸光材料的单相高均质膜的生产。影响获得技术成果的主要参数是沉积在衬底上的膜C和AB的厚度和均匀性,以及所得双层膜与含有组分B2的溶液或气体进一步相互作用的条件。为了获得最均一的ACB3单相膜,建议均匀涂上组分AB和C的厚膜,其厚度应对应于单位面积上组分AB和C的量的等摩尔比。在组分比例明显不同的情况下,可能在最终产品的膜中形成附加相。
附图说明
通过以下附图和图片来解释所要求保护的发明,特别示出所要求保护的方法的实施方式对于特定组合物的结果。
图1示出了要求保护的方法的方案,该方法用于合成具有组成ACB3的吸光材料的膜。
图2示出了根据要求保护的方法获得的吸光有机-无机钙钛矿CH3NH3PbI3的膜的显微照片。
图上的位置表示如下:
1–衬底
2–试剂C的沉积
3–试剂AB的沉积
4–含B2的气态介质或溶液。
发明详述
可以使用已知的手段和方法来实施要求保护的发明,包括在工业生产条件下。
任何导电或非导电材料或其组合都可用作衬底。衬底材料的面积和选择可以受到吸光层形成的其他特定技术步骤的要求的限制,但是可能是任意的。基于衬底的面积和膜的特定厚度,确定所需的试剂C和AB的量。为了实施该方法,通过已知方法将试剂C沉积在选择的衬底上。最佳方法是使用金属铅、锡或铋作为C,例如通过真空沉积或电化学沉积来沉积金属铅、锡或铋。在使用组分C的氧化物或盐的情况下,除了上述方法之外,还可以使用其他形成膜的方法,例如旋涂、将溶液喷涂到衬底上、喷涂热解、化学气相沉积(CVD)等。通过诸如溅射(包括真空沉积)、旋涂、将溶液喷涂到衬底上的方法,将组分AB的层沉积到C的层上。因此,形成具有两个顺序沉积的层C和AB的双层膜。为了进行由具有钙钛矿状结构的吸光材料制成的膜的形成反应,将获得的具有沉积多层的衬底浸入包含B2的液体或气体介质中。不含载气的干燥空气、氩气或含氮的碘蒸气(卤素或它们的混合物)或碘蒸气(卤素或它们的混合物)可以用作气相;CCl4、甲苯、***和其他含碘的有机溶剂(卤素或它们的混合物)可以用作液相。实验结果表明,进行所述反应的最佳特征是通过碘蒸气与任何载气或不存在载气以及碘的甲苯和CCl4的溶液来实现。推荐的反应温度是0-150℃。
对于每种特定情况,该过程的持续时间由化学反应的速率决定直至完成。可以通过X射线相分析等来控制该过程的完成。在反应结束时,将衬底上的所得膜从包含具有组分B2的介质的室中取出。通过电子显微镜检查所得膜的质量,所述电子显微镜用于评估参数,例如膜的连续性(无通孔)和微晶的平均尺寸。确定通过所述方法获得的吸光化合物CH3NH3PbI3的膜具有均匀的结构,如图2所示,其特征在于没有通孔并且平均结晶尺寸为约800nm。
实施例
作为特定实施方式的示例,提供了关于所要求保护的方法的实施方式以及使用各种组分作为试剂的吸光化合物CH3NH3PbI3的膜的制造的信息。
实施例1:
通过真空热蒸发将60nm厚的铅层沉积在衬底上,该衬底由沉积在FTO(氟化氧化锡)或ITO(掺杂铟的氧化锡)的导电衬底上的TiO2阻挡层组成。然后通过真空热蒸发将MAI层沉积到铅层上,其量对应于每单位衬底面积的金属铅和MAI的量的等摩尔比。此后,将具有沉积多层的衬底浸入氩气中的饱和碘蒸气中,并在40℃下保持10至30分钟。结果,在衬底上形成钙钛矿状结构MAPbI3层。通过扫描电子显微镜(图2)和X射线相分析检查膜的形态和相组成。
实施例2:
通过真空热蒸发将250nm厚的铅层沉积在衬底上,该衬底由沉积在FTO(氟化氧化锡)或ITO(掺杂铟的氧化锡)的导电衬底上的TiO2阻挡层组成。然后通过真空热蒸发将MAI层沉积到铅层上,其量对应于每单位衬底面积的金属铅和MAI的量的等摩尔比。之后,将具有沉积多层的衬底浸入I2含量为10mg/ml的碘的CCl4溶液中,并在室温下保持90秒。结果,在衬底上形成钙钛矿状结构MAPbI3层。通过扫描电子显微镜和X射线相分析检查膜的形态和相组成。
实施例3:
通过真空热蒸发将250nm厚的铅层沉积在衬底上,该衬底由沉积在FTO(氟化氧化锡)或ITO(掺杂铟的氧化锡)的导电衬底上的TiO2阻挡层组成。然后通过真空热蒸发将由摩尔比为1:1的MAI和FAI的混合物组成的层沉积到铅层上,其量对应于每单位衬底面积的金属铅和MAI的量的2:1的摩尔比。之后,将具有沉积多层的衬底浸入I2含量为10mg/ml的碘的CCl4溶液中,并在室温下保持90秒。结果,在衬底上形成钙钛矿状结构MA0.5FA0.5PbI3层。通过扫描电子显微镜和X射线相分析检查膜的形态和相组成。
下面给出了使用各种化合物作为试剂的方法的实施方式的实例。
表1.
在该方法的实施方式的上述实施例(表1)中,通过确保可以制造大面积的相应膜的方法,获得了具有钙钛矿状结构的吸光材料ACB3的高度均质的膜。
Claims (6)
1.合成由结构式为ACB3、具有钙钛矿状结构的吸光材料制成的膜的方法,其特征在于,依次沉积试剂C的层和试剂AB的层,然后将具有沉积双层膜的衬底放置在包含试剂B2的液体或气体介质中一段必要且充分的时间进行反应从而完成С+АВ+B2=АСВ3+Х,其中组分A表示CH3NH3 +、(NH2)2CH+、C(NH2)3 +、Cs+或它们的混合物,组分B表示Cl-、Br-、I-或它们的混合物,组分C表示金属Sn、Pb、Bi、它们的氧化物或盐,组分X表示组分C以氧化物或盐形式使用时的分解产物。
2.如权利要求1所述的方法,其特征在于,所述液体介质的特征在于在其中试剂AB的不溶性和B2的溶解性。
3.如权利要求1所述的方法,其特征在于,所述试剂C和AB以化学计量的量在每单位面积上涂布,以提供具有给定厚度的膜。
4.如权利要求1所述的方法,其特征在于,所述试剂C和AB通过真空沉积、旋涂或喷涂溶液到衬底上来涂布。
5.如权利要求1所述的方法,其特征在于,在所述氧化物或盐用于反应С+АВ+B2=АСВ3+Х中的情况下,除去组分X。
6.如权利要求1所述的方法,其特征在于,在反应完成后,通过在溶剂中洗涤、将溶剂滴在表面上、在高温下退火或在减压下蒸发来除去过量的组分B。
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EP3666921B1 (en) | 2021-11-17 |
RU2675610C1 (ru) | 2018-12-20 |
US11081292B2 (en) | 2021-08-03 |
CA3072159A1 (en) | 2019-02-14 |
ES2906881T3 (es) | 2022-04-20 |
EP3666921A1 (en) | 2020-06-17 |
JP7161535B2 (ja) | 2022-10-26 |
WO2019031991A1 (ru) | 2019-02-14 |
AU2018312837B2 (en) | 2021-10-14 |
CA3072159C (en) | 2022-05-31 |
AU2018312837A1 (en) | 2020-02-27 |
JP2020532882A (ja) | 2020-11-12 |
US20210020383A1 (en) | 2021-01-21 |
KR20200028989A (ko) | 2020-03-17 |
CN111051560A (zh) | 2020-04-21 |
KR102306250B1 (ko) | 2021-09-28 |
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