Ferroelasticity in Two-Dimensional Hybrid Ruddlesden$-$Popper Perovskites Mediated by Cross-Plane Intermolecular Coupling and Metastable Funnel-Like Phases

Devesh R. Kripalani, Qiye Guan, Hejin Yan, Yongqing Cai, Kun Zhou
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Abstract

Ferroelasticity describes a phenomenon in which a material exhibits two or more equally stable orientation variants and can be switched from one form to another under an applied stress. Recent works have demonstrated that two-dimensional layered organic$-$inorganic hybrid Ruddlesden$-$Popper perovskites can serve as ideal platforms for realizing ferroelasticity, however, the ferroelastic (FE) behavior of structures with a single octahedra layer such as (BA)$_2$PbI$_4$ (BA = CH$_3$(CH$_2$)$_3$NH$_3$$^+$) has remained elusive. Herein, by using a combined first-principles and metadynamics approach, the FE behavior of (BA)$_2$PbI$_4$ under mechanical and thermal stresses is uncovered. FE switching is mediated by cross-plane intermolecular coupling, which could occur through multiple rotational modes, rendering the formation of FE domains and several metastable paraelastic (PE) phases. Such metastable phases are akin to wrinkled structures in other layered materials and can act as a "funnel" of hole carriers. Thermal excitation tends to flatten the kinetic barriers of the transition pathways between orientation variants, suggesting an enhanced concentration of metastable PE states at high temperatures, while halogen mixing with Br raises these barriers and conversely lowers the concentration of PE states. These findings reveal the rich structural diversity of (BA)$_2$PbI$_4$ domains, which can play a vital role in enhancing the optoelectronic properties of the perovskite and raise exciting prospects for mechanical switching, shape memory, and information processing.
由跨平面分子间耦合和可迁移漏斗状相态介导的二维混合 Ruddlesden$-$Popper Perovskites 中的铁弹性
铁弹性描述了一种现象,在这种现象中,一种材料表现出两种或两种以上同样稳定的取向变体,并能在外加应力作用下从一种形式切换到另一种形式。最近的研究表明,二维层状有机$$-无机杂化 Ruddlesden$-$Popperovskites 可以作为实现铁弹性的理想平台,然而,具有单个八面体层(如 (BA)$_2$PbI$_4$(BA = CH$_3$(CH$_2$)$_3$NH$_3$^+$ )的结构的铁弹性(FE)行为仍然是一个未知数。在这里,通过使用第一原理和元动力学相结合的方法,揭示了 (BA)$_2$PbI$_4$ 在机械和热应力下的 FE 行为。FE 开关由跨面分子间耦合介导,可能通过多种旋转模式发生,从而形成 FE 域和几种可蜕变的副弹性(PE)相。这种可变相类似于其他层状材料中的皱褶结构,可以充当空穴载流子的 "漏斗"。热激发倾向于平缓取向变体之间过渡途径的动力学势垒,这表明在高温下可蜕变的 PE 状态的浓度会增加,而卤素与 Br 的混合则会提高这些势垒,反之则会降低 PE 状态的浓度。这些发现揭示了 (BA)$_2$PbI$_4$ 结构域的丰富多样性,它们在增强包晶的光电特性方面发挥着重要作用,并为机械开关、形状记忆和信息处理带来了令人兴奋的前景。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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