Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

The rapid increase in power conversion efficiencies of photovoltaic devices incorporating lead halide perovskites has resulted in intense interest in the cause of their excellent properties. In the present paper, resonant ultrasound spectroscopy has been used to determine the elastic and anelastic properties of ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}\mathrm{Pb}{X}_{3}$ (where $X=\mathrm{Cl}$, Br, or I) and ${\mathrm{CD}}_{3}{\mathrm{ND}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$ perovskites in the 5--380 K temperature range. This is coupled with differential scanning calorimetry, variable temperature neutron powder diffraction, and variable temperature photoluminescence studies to provide insights into the underlying processes and structural instabilities in the crystal structure. By comparing measurements on ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$ with the deuterated equivalent, it has been possible to distinguish processes which are related to the hydrogen bonding between the methylammonium cation and the perovskite framework. We observe that replacing hydrogen with deuterium has a significant impact on both the elastic and photophysical properties, which shows that hydrogen bonding plays a crucial role in the material performance. Temperature-dependent photoluminescence studies show that the light emission is unaffected by the tetragonal-orthorhombic phase transition, but a blueshift in the emission and a steep increase in photoluminescence quantum yield are seen at temperatures below 150 K. Finally, observations of peaks in acoustic loss occurring in ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}\mathrm{Pb}{\mathrm{Cl}}_{3}$ have revealed freezing processes in the vicinity of $\ensuremath{\sim}150\ensuremath{-}170\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, with activation energies in the range of 300 to 650 meV. These processes are attributed to freezing of the motion of methylammonium cations, and could explain the changes in photoluminescence seen in ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}\mathrm{Pb}{\mathrm{I}}_{3}$ at the same temperature.