Size-Dependent Phase Transition in Perovskite Nanocrystals

The complex structure of halide and oxide perovskites strongly affects their physical properties. Here, the effect of dimensions reduced to the nanoscale has been investigated by a combination of single-dot optical experiments with a phase transition theory. Methylammonium lead bromide (CH3NH3PbBr3) nanocrystals with two average particle sizes of ∼2 and ∼4 nm with blue and green photoluminescence, respectively, were spectrally and temporally probed on a single-particle level from 5 to 295 K. The results show that the abrupt blue shift of the photoluminescence spectra and lifetimes at ∼150 K can be attributed to the cubic-to-tetragonal phase transition in the large 4 nm nanocrystals, while this phase transition is completely absent for the small 2 nm particles in the investigated temperature range. Theoretical calculations based on Landau theory reveal a strong size-dependent effect on temperature-induced phase transitions in individual CH3NH3PbBr3 nanocrystals, corroborating experimental observations. This effect should be considered in structure-property analysis of ultrasmall perovskite crystals.