Structural rigidity, thermochromism and piezochromism of layered hybrid perovskites containing an interdigitated organic bilayer

Abstract

Layered hybrid perovskites are intensively researched today as highly tunable materials for efficient light harvesting and emitting devices. In classical layered hybrid perovskites, the structural rigidity mainly stems from the crystalline inorganic sublattice, whereas the organic sublattice has a minor contribution to the rigidity of the material. Here, we report two layered hybrid perovskites, (BTa)2PbI4 and (F2BTa)2PbI4, which possess substantially more rigid organic layers due to hydrogen bonding, π–π stacking, and dipole–dipole interactions. These layered perovskites are phase stable under elevated pressures up to 5 GPa and upon temperature lowering down to 80 K. The organic layers, composed of benzotriazole-derived ammonium cations, are among the most rigid in the field of layered hybrid perovskites. We characterize structural rigidity using in situ single-crystal X-ray diffraction during compression up to 5 GPa. Interestingly, the enhanced rigidity of the organic sublattice does not seem to transfer to the inorganic sublattice, leading to an uncommon material configuration with rigid organic layers and deformable inorganic layers. The deformability of the inorganic sublattice is apparent from differences in optical properties between the crystal bulk and surface. Supported by first-principles calculations, we assign these differences to energy transfer processes from the surface to the bulk. The deformability also leads to reversible piezochromism due to shifting of the photoluminescence emission peak with increasing pressure up to 5 GPa, and thermochromism due to narrowing of the photoluminescence emission linewidth with decreasing temperature down to 80 K. This raises the possibility of applying these phase-stable layered hybrid perovskite materials in temperature and/or pressure sensors.