Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites†,Chemical Science

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Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites†
Chemical Science ( IF 7.6 ) Pub Date : 2018-02-12 00:00:00 , DOI: 10.1039/c7sc05095j
Sofia Masi _{1,

2} , Federica Aiello ₃ , Andrea Listorti _{1,

2} , Federica Balzano ₃ , Davide Altamura ₄ , Cinzia Giannini ₄ , Rocco Caliandro ₄ , Gloria Uccello-Barretta ₃ , Aurora Rizzo ₁ , Silvia Colella _{1,

2}

Affiliation

The evolution from solvated precursors to hybrid halide perovskite films dictates most of the photophysical and optoelectronic properties of the final polycrystalline material. Specifically, the complex equilibria and the importantly different solubilities of lead iodide (PbI₂) and methylammonium iodide (MAI) induce inhomogeneous crystal growth, often leading to a defect dense film showing non-optimal optoelectronic properties and intrinsic instability. Here, we explore a supramolecular approach based on the use of cyclodextrins (CDs) to modify the underlying solution chemistry. The peculiar phenomenon demonstrated is a tunable complexation between different CDs and MA⁺ cations concurrent to an out of cage PbI₂ intercalation, representing the first report of a connection between the solvation equilibria of the two perovskite precursors. The optimal conditions in terms of CD cavity size and polarity translate to a neat enhancement of PbI₂ solubility in the reaction media, leading to an equilibration of the availability of the precursors in solution. The macroscopic result of this is an improved nucleation process, leading to a perovskite material with higher crystallinity, better optical properties and improved moisture resistance. Remarkably, the use of CDs presents a great potential for a wide range of device-related applications, as well as for the development of tailored composite materials.

中文翻译：

连接 PbI2 和 MAI 的溶液化学：基于环糊精的超分子方法形成杂化卤化物钙钛矿†

从溶剂化前体到杂化卤化物钙钛矿薄膜的演变决定了最终多晶材料的大部分光物理和光电特性。具体而言，碘化铅（PbI ₂ ）和碘化甲基铵（MAI）的复杂平衡和重要不同的溶解度会导致晶体生长不均匀，通常导致缺陷致密薄膜表现出非最佳光电性能和内在不稳定性。在这里，我们探索了一种基于使用环糊精（CD）来改变基础溶液化学性质的超分子方法。所展示的特殊现象是不同 CD 和 MA ⁺阳离子之间的可调络合，同时发生笼外 PbI ₂嵌入，代表了两种钙钛矿前体的溶剂化平衡之间的联系的第一份报告。 CD腔尺寸和极性方面的最佳条件转化为反应介质中PbI ₂溶解度的纯粹增强，导致溶液中前体的可用性的平衡。其宏观结果是改进的成核过程，导致钙钛矿材料具有更高的结晶度、更好的光学性能和改进的防潮性。值得注意的是，CD 的使用为广泛的设备相关应用以及定制复合材料的开发带来了巨大的潜力。

更新日期：2018-02-12

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