Schleusener Alexander, Faraji Mehrdad, Borreani Martina, Lauciello Simone, Pasquale Lea, Khabbaz Abkenar Sirous, Divitini Giorgio, Krahne Roman
Istituto Italiano di Tecnologia, Via Morego 30, Genova, 16163, Italy.
Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, Via Dodecaneso 31, Genova, 16146, Italy.
Adv Mater. 2024 Aug;36(31):e2402924. doi: 10.1002/adma.202402924. Epub 2024 Jun 19.
Layered perovskites consist of stacks of inorganic semiconducting metal-halide octahedra lattices sandwiched between organic layers with typically dielectric behavior. The in-plane confinement of electrical carriers in such two-dimensional metal halide perovskites drives a large range of appealing electronic properties, such as strong exciton binding, anisotropic charge diffusion, and polarization-directionality. Heterostructures provide additional control on carrier diffusion and localization, and in-plane heterojunctions are interesting because of the associated high charge mobility. Here, this work demonstrates a versatile solution-based approach to fabricate in-plane heterostructures with different halide composition in two-dimensional lead-halide perovskite microcrystals. This leads to spatially separated halide phases with different band gap and light emission. Interestingly, the composition of the exchanged phase and the morphology of the phase boundary depends on the exchange route, which can be related to the preferred localization of the halides at the equatorial or axial octahedra positions that either leads to dissolution and recrystallization of the octahedra lattice (for bromide to iodide), or allows for ion diffusion within the lattice (for iodide to bromide). These detailed insights on the ion exchange processes in layered perovskites will stimulate the development of heterostructures that can be tailored for different applications such as photocatalysis, energy storage, and light emission.
层状钙钛矿由无机半导体金属卤化物八面体晶格堆叠组成,夹在通常具有介电行为的有机层之间。在这种二维金属卤化物钙钛矿中,载流子的面内限制驱动了一系列吸引人的电子特性,如强激子结合、各向异性电荷扩散和极化方向性。异质结构为载流子扩散和定位提供了额外的控制,面内异质结因其相关的高电荷迁移率而备受关注。在此,这项工作展示了一种通用的基于溶液的方法,用于在二维卤化铅钙钛矿微晶中制备具有不同卤化物组成的面内异质结构。这导致了具有不同带隙和发光的空间分离卤化物相。有趣的是,交换相的组成和相界的形态取决于交换途径,这可能与卤化物在赤道或轴向八面体位置的优先定位有关,这要么导致八面体晶格的溶解和重结晶(对于溴化物到碘化物),要么允许离子在晶格内扩散(对于碘化物到溴化物)。这些关于层状钙钛矿中离子交换过程的详细见解将推动可针对光催化、能量存储和发光等不同应用进行定制的异质结构的发展。