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Although the structural phase transitions in single-crystal hybrid methyl-ammonium (MA) lead halide perovskites (MAPbX3, X = Cl, Br, I) are common phenomena, they have never been observed in the corresponding nanocrystals. Here we demonstrate that two-photon-excited photoluminescence (PL) spectroscopy is capable of monitoring the structural phase transitions in MAPbX3 nanocrystals because nonlinear susceptibilities govern the light absorption rates. We provide experimental evidence that the orthorhombic-to-tetragonal structural phase transition in a single layer of 20-nm-sized 3D MAPbBr3 nanocrystals is spread out within the 70 - 140 K range. This structural phase instability range arises because, unlike in single-crystal MAPbX3, free rotations of MA ions in the corresponding nanocrystals are no longer restricted by a long-range MA dipole order. The resulting configurational entropy loss can be even enhanced by the interfacial electric field arising due to charge separation at the MAPbBr3/ZnO heterointerface, extending the orthorhombic-to-tetragonal structural phase instability range from 70 to 230 K. We conclude that the weak sensitivity of conventional one-photon-excited PL spectroscopy to the structural phase transitions in 3D MAPbX3 nanocrystals results from the structural phase instability providing negligible distortions of PbX6 octahedra. In contrast, the intensity of two-photon-excited PL and electric-field-induced one-photon-excited PL still remains sensitive enough to weak structural distortions due to the higher rank tensor nature of nonlinear susceptibilities involved. We also show that room-temperature PL originates from the radiative recombination of the optical-phonon vibrationally excited polaronic quasiparticles with energies might exceed the ground-state Frohlich polaron and Rashba energies due to optical-phonon bottleneck.
The dynamical and static Rashba effects in hybrid methylammonium (MA) lead halide perovskites have recently been theoretically predicted. However, only the static effect was experimentally confirmed so far. Here we report on the dynamical Rashba effe
We study the origin of the cubic to tetragonal and tetragonal to monoclinic structural transitions in KCrF3, and the associated change in orbital order, paying particular attention to the relevance of super-exchange in both phases. We show that super
Integrated optical devices able to control light matter interactions on the nanoscale have attracted the attention of the scientific community in recent years. However, most of these devices are based on silicon waveguides, limiting their use for tel
Excitonic/electronic coupling and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a collective low energy emission peak with accelerated dynamics. Here we report that similar spectroscopic
Three different film systems have been systematically investigated to understand the effects of strain and substrate constraint on the phase transitions of perovskite films. In SrTiO$_3$ films, the phase transition temperature T$_C$ was determined by