Probing the Electronic Structure of Hybrid Perovskites in the Orientationally Disordered Cubic Phase

Hybrid organic–inorganic lead halide perovskites are projected as new generation photovoltaic and optoelectronic materials with improved efficiencies. However, their electronic structure so far remains poorly understood, particularly in the orientationally disordered cubic phase. We performed electronic structure investigations using angle-resolved photoemission spectroscopy on two prototypical samples (MAPbBr₃ and MAPbCl₃) in their cubic phase, and the results are compared with the calculations within two theoretical models where MA⁺ is orientationally (1) disordered (MA⁺ ion is replaced by spherically symmetric Cs⁺ ion) and (2) ordered (MA oriented along (100) direction) but keeping the symmetry of the unit cell cubic. Degeneracy of the valence bands and behavior of constant energy contours are consistent with model 1, which supports strongly the disordered nature of the orientation of the MA⁺ ions in the cubic phase. Band structure calculations also reveal that spin–orbit coupling induced Rashba splitting is suppressed by the orientational disorder.