Unveiling the interaction mechanisms of electron and X-ray radiation with halide perovskite semiconductors using scanning nano-probe diffraction

TL;DR

This study uses nano-probe diffraction to investigate how high-energy electron and X-ray radiation cause structural degradation in halide perovskite films, revealing nanoscale degradation pathways and phase transitions.

Contribution

It introduces a nanoscale analysis of radiation-induced degradation mechanisms in halide perovskites using scanning electron and synchrotron nano X-ray diffraction techniques.

Findings

Perovskite grains develop PbBr₂ crystalline phases after high fluence irradiation.

Formation of PbI₂ crystallites occurs at high-angle grain boundaries during degradation.

Both electron and X-ray irradiation induce similar phase transition pathways.

Abstract

The interaction of high-energy electrons and X-ray photons with soft semiconductors such as halide perovskites is essential for the characterisation and understanding of these optoelectronic materials. Using nano-probe diffraction techniques, which can investigate physical properties on the nanoscale, we perform studies of the interaction of electron and X-ray radiation with state-of-the-art (FA$_{0.79}$MA$_{0.16}$Cs$_{0.05}$)Pb(I$_{0.83}$Br$_{0.17}$)$_3$ hybrid halide perovskite films (FA, formamidinium; MA, methylammonium). We track the changes in the local crystal structure as a function of fluence using scanning electron diffraction and synchrotron nano X-ray diffraction techniques. We identify perovskite grains from which additional reflections, corresponding to PbBr$_2$, appear as a crystalline degradation phase after fluences of ~200 e$^-${\AA}$^{-2}$. These changes are concomitant with the formation of small PbI$_2$ crystallites at the adjacent high-angle grain boundaries, with the formation of pinholes, and with a phase transition from tetragonal to cubic. A similar degradation pathway is caused by photon irradiation in nano-X-ray diffraction, suggesting common underlying mechanisms. Our approach explores the radiation limits of these materials and provides a description of the degradation pathways on the nanoscale. Addressing high-angle grain boundaries will be critical for the further improvement of halide polycrystalline film stability, especially for applications vulnerable to high-energy radiation such as space photovoltaics.