Disentangled structural and vibrational characteristics of methylammonium halide perovskite MAPbBr3-xClx with x = 0 [formula omitted] 3 studied by X-Ray diffraction and Raman scattering

Abstract

Structural and vibrational characteristics of methylammonium(MA) halide perovskite MAPbBr3-xClx single crystals (x = 0–3) were investigated by using powder X-ray diffraction and Raman scattering experiments. The lattice constant in the cubic phase obtained from powder X-ray diffraction peaks at room temperature showed nearly a linear dependence as a function of composition. On the other hand, some of the Raman mode frequencies obtained from single crystals exhibited substantial changes in both frequency shifts and half widths over the investigated composition range. Especially, the MA torsional mode showed a significant change from 325 to 485 cm−1 and mode splitting as Cl was replaced by Br. This mode splitting was more clearly seen at low temperatures reflecting the symmetry lowering of the local structure. The contrast between the linear change in the lattice constant and the substantial change in the vibrational frequencies and half widths of the MA torsional mode in the intermediate composition range indicates the local heterogeneous environment for the MA cations caused by the substitutional disorder.