English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Plus monthly

Global: Zendy Tools annual

Global: Zendy Tools monthly

Global: Zendy Free Plan

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.

Structural phase transitions and photoluminescence mechanism in a layer of 3D hybrid perovskite nanocrystals