Bismuth-doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

We study the effects of bismuth doping on the crystal structure and phase transitions of single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr3. By measuring the temperature-dependent specific heat capacity (Cp) we find that, as the Bi doping level increases, the temperatures for the bismuth structural phase transitions shift, and the phase boundary assigned to the transition from the cubic to tetragonal phase decreases in temperature. Furthermore, after doping we only observe one phase transition between 135 and 155 K, in contrast to two transitions observed in the undoped single crystal. These results appear strikingly similar to the previously reported effects of mechanical pressure on the perovskite structure. Using X-ray diffraction, we show that, as more Bi is incorporated into the crystal, the lattice constant decreases, as predicted by density functional theory (DFT). Based on the lattice contraction and DFT, we propose that bismuth substitutional doping on the lead site is dominant, resulting in BiPb+ centers which induce compressive chemical strain that alters the crystalline phase transitions.