CN112647047B - 一种铯锡碘薄膜的制备方法及其应用 - Google Patents
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Abstract
本发明公开了一种铯锡碘薄膜的制备方法,属于半导体材料技术领域。包括以下步骤:S1、在真空条件下,将二碘化锡和碘化铯分别加热至440℃和210℃,并同时向基底沉积二碘化锡和碘化铯,冷却至室温,制得铯锡碘薄膜前驱体;其中,沉积的过程中,所述二碘化锡和碘化铯分别以0.5层/min的速率共沉积25~35min;所述基底温度为‑33~‑23℃;S2、将基底上沉积的铯锡碘薄膜前驱体在温度为100~120℃进行退火处理,即得铯锡碘薄膜。本发明提供的铯锡碘薄膜的制备方法工艺简单、薄膜质量高,特别适合用于开发高性能的无铅钙钛矿太阳能电池。
Description
技术领域
本发明属于半导体材料技术领域,具体涉及一种铯锡碘薄膜的制备方法及其应用。
背景技术
目前,一类有机-无机杂化钙钛矿半导体(AMX3,A为阳离子,常见为甲胺(MA)、甲眯(FA)、铯(Cs)等,X为Cl,I,Br等)因其优异的光电性能被应用于平面异质结太阳电池。推进这种有机-无机钙钛矿太阳电池走向广泛应用存在两个关键难点:(1)需要将这种有机-无机杂化钙钛矿实现无铅化,使其更加绿色、环保。(2)这种具有优异光电性能的有机金属钙钛矿材料的热稳定性需要进一步改善。一方面,锡(Sn)和锗(Ge)被期望能替代这种杂化钙钛矿中的同族元素铅(Pb),从而使得这种钙钛矿太阳能电池能走向无铅化。另一方面,碱金属元素铯(Cs)可以用来取代这种有机金属钙钛矿的有机基团(CH3NH3 +)实现无机化,可能能在一定程度上改善这种钙钛矿光电材料的热稳定性。CsSnI3是一种无毒且直接带隙约为1.3eV的半导体,理论上能量转换效率可达33%。
尽管如此,以CsSnI3作为光吸收层的的太阳能电池的能量转换效应仅约为3%,远低于含铅的有机-无机杂化钙钛矿太阳能电池。传统的制备方法(如:二步法等)制备的CsSnI3薄膜存在高密度的Sn和Cs空位缺陷,从而使得其载流子(电子和空穴)的迁移长度和寿命变得更短,严重影响了其器件性能。二步法采用的交替沉积SnI2和CsI方式容易造成CsSnI3薄膜的化学配比在空间分布上很难得到精确控制,从而形成大量的Sn和Cs空位缺陷。
发明内容
本发明的目的在于针对上述方法所存在的缺点与不足,提供一种铯锡碘薄
膜的制备方法,该制备方法工艺简单、薄膜质量高,特别适合用于开发高性能的无铅钙钛矿太阳能电池。
本发明第一个目的提供一种铯锡碘薄膜的制备方法,包括以下步骤:
S1、在真空条件下,将二碘化锡和碘化铯分别加热至440℃和210℃,并同时向基底沉积二碘化锡和碘化铯,冷却至室温,制得铯锡碘薄膜前驱体;
其中,沉积的过程中,所述二碘化锡和碘化铯分别以0.5层/min的速率共沉积25~35min;所述基底温度为-33~-23℃;
S2、将基底上沉积的铯锡碘薄膜前驱体在温度为100~120℃进行退火处理,即得铯锡碘(CsSnI3)薄膜。
优选的,所述真空≥10-6Pa。
优选的,所述基底为Au膜、Au(111)单晶或石墨烯化的SiC(0001)。
优选的,所述退火过程中,升温速率为2.0~5℃/min。
更优选的,退火时间30~60min。
本发明第二个目的是提供一种铯锡碘薄膜。
本发明第三个目的是提供一种上述所述的铯锡碘薄膜在无铅钙钛矿太阳能电池中的应用。
本发明与现有技术相比具有如下有益效果:
本发明提供的CsSnI3薄膜的制备方法,将二碘化锡和碘化铯置石英坩埚中,在高真空环境中同时往光滑基底(如:Au(111)基底)上沉积碘化铅和碘化铯,共沉积时基底温度要维持在-33~-23℃,在低温下,碘更容易吸附在基底上,有利于减少碘的空位缺陷,使CsI和SnI2能更好的发生化学当量反应,再将制备好的样品在室温环境下退火至室温,然后再将制备好的样品在高真空中退火,即可得到具有原子级平整度的铯锡碘钙钛矿薄膜;工艺简单、薄膜质量高,特别适合用于开发高性能的无铅钙钛矿太阳能电池。
本发明的提供的CsSnI3薄膜材料相比于传统的Pb钙钛矿材料,具有无毒、绿色环保无污染、价格便宜等优势。
附图说明
图1实施例1中的CsSnI3薄膜的扫描隧道显微镜照片(STM)。
图2实施例1中的CsSnI3薄膜的原子分辨图像。
图3对比例1中的CsSnI3薄膜的扫描隧道显微镜照片(STM)。
图4对比例2中的CsSnI3薄膜的扫描隧道显微镜照片(STM)。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施,下面结合具体实施例和附图对本发明作进一步说明,但所举实施例不作为对本发明的限定。
需要说明的是,下述各实施例中采用试剂和材料,如无特殊说明,均可在市场上购买得到;其中,所采用的二碘化锡和碘化铯的纯度均为99.999%;所述实验方法中如无特殊说明,均为常规方法。
实施例1
一种铯锡碘薄膜的制备方法,包括以下步骤:
分别将二碘化锡和碘化铯置石英坩埚中,然后分别在超高真空环境中加热除气,维持真空室的真空不低于10-6Pa;同时,往样品台的冷却管吹入一定量的液氮,将Au(111)基底温度降至-28℃;随后将二碘化锡和碘化铯蒸发源加热至440℃和210℃后,一同往Au(111)基底上沉积二碘化锡和碘化铯,沉积的过程中,使CsI和SnI2能更好的发生化学当量反应;其中,沉积的过程中,二碘化锡和碘化铯分别以0.5层/min的速率共沉积30min;
将基底上沉积的铯锡碘薄膜前驱体以3.5℃/min的速率加热至120℃及进行退火45min,即得高质量而具有原子级平整度的铯锡碘钙钛矿薄膜(CsSnI3薄膜)。
实施例2
与实施例1相同,不同之处在于:将Au(111)基底温度控制在-23℃;退火时间为30min。
实施例3
与实施例1相同,不同之处在于:将Au(111)基底温度控制在-33℃,退火时间为60min。
对比例1
与实施例1相同,不同之处在于:将Au(111)基底温度控制在24℃。
对比例2
与实施例1相同,不同之处在于:将Au(111)基底温度控制在47℃。
为了说明本发明提供的一种铯锡碘薄膜的制备方法得到的铯锡碘薄膜相关性能,由于对实施例1~3中制备出的铯锡碘薄膜类似,仅对实施例1制备的铯锡碘薄膜(CsSnI3薄膜)相关性能进行测试,见图1~2,同时,对比例1~2作为对照组,见图3~4。
图1实施例1中的CsSnI3薄膜的扫描隧道显微镜照片(STM)看出薄膜表面非常平整且具有非常规则的边、角,反映制备样品具有很好的结晶质量。
图2实施例1中的CsSnI3薄膜的原子分辨图像,表明制备薄膜具有高质量的晶体结构。
图3对比例1中的CsSnI3薄膜的扫描隧道显微镜照片(STM),薄膜上出现大且部分不规则的团簇(cluster),薄膜的结晶质量不如实施例1。
图4对比例2中的CsSnI3薄膜的扫描隧道显微镜照片(STM),薄膜上出现许多不规则的团簇(cluster),薄膜的结晶质量进一步变差。
综上所述,本发明提供的CsSnI3薄膜的制备方法,将二碘化锡和碘化铯置石英坩埚中,在高真空环境中同时往光滑基底(如:Au(111)基底)上沉积碘化铅和碘化铯,共沉积时基底温度要维持在-33~-23℃,在低温下,碘更容易吸附在基底上,有利于减少碘的空位缺陷,使CsI和SnI2能更好的发生化学当量反应,再将制备好的样品在室温环境下退火至室温,然后再将制备好的样品在高真空中退火,即可得到具有原子级平整度的铯锡碘钙钛矿薄膜;工艺简单、薄膜质量高,特别适合用于开发高性能的无铅钙钛矿太阳能电池。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内也意图包含这些改动和变型在内。
Claims (5)
1.一种铯锡碘薄膜的制备方法,其特征在于,包括以下步骤:
S1、在真空条件下,将二碘化锡和碘化铯分别加热至440℃和210℃,并同时向基底沉积二碘化锡和碘化铯,冷却至室温,制得铯锡碘薄膜前驱体;
其中,沉积的过程中,所述二碘化锡和碘化铯分别以0.5层/min的速率共沉积25~35min;所述基底温度为-33~-23℃;
S2、将基底上沉积的铯锡碘薄膜前驱体在温度为100~120℃进行退火处理,即得铯锡碘薄膜;所述退火过程中,升温速率为2.0~5℃/min;退火时间30~60min。
2.根据权利要求1所述的铯锡碘薄膜的制备方法,其特征在于,所述真空≥10-6Pa。
3.根据权利要求1所述的铯锡碘薄膜的制备方法,其特征在于,所述基底为Au膜、Au(111)单晶或石墨烯化的SiC(0001)。
4.一种权利要求1~3任一所述的铯锡碘薄膜的制备方法制备的铯锡碘薄膜。
5.一种权利要求4所述的铯锡碘薄膜在无铅钙钛矿太阳能电池中的应用。
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US20100055350A1 (en) * | 2006-03-21 | 2010-03-04 | Ultradots, Inc | Luminescent Materials that Emit Light in the Visible Range or the Near Infrared Range |
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