Phase segregation in inorganic mixed-halide perovskites: from phenomena to mechanisms

Abstract

Halide perovskites, such as methylammonium lead halide perovskites ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="m1"> <mml:mrow> <mml:msub> <mml:mrow> <mml:mi>MAPbX</mml:mi> </mml:mrow> <mml:mrow> <mml:mn>3</mml:mn> </mml:mrow> </mml:msub> </mml:mrow> </mml:math> , <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="m2"> <mml:mrow> <mml:mi mathvariant="normal">X</mml:mi> <mml:mo>=</mml:mo> <mml:mi mathvariant="normal">I</mml:mi> </mml:mrow> </mml:math> , Br, and Cl), are emerging as promising candidates for a wide range of optoelectronic applications, including solar cells, light-emitting diodes, and photodetectors, due to their superior optoelectronic properties. All-inorganic lead halide perovskites <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="m3"> <mml:mrow> <mml:msub> <mml:mrow> <mml:mi>CsPbX</mml:mi> </mml:mrow> <mml:mrow> <mml:mn>3</mml:mn> </mml:mrow> </mml:msub> </mml:mrow> </mml:math> are attracting a lot of attention because replacing the organic cations with <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="m4"> <mml:mrow> <mml:msup> <mml:mrow> <mml:mi>Cs</mml:mi> </mml:mrow> <mml:mrow> <mml:mo>+</mml:mo> </mml:mrow> </mml:msup> </mml:mrow> </mml:math> enhances the stability, and its halide-mixing derivatives offer broad bandgap tunability covering nearly the entire visible spectrum. However, there is evidence suggesting that the optical properties of mixed-halide perovskites are influenced by phase segregation under external stimuli, especially illumination, which may negatively impact the performance of optoelectronic devices. It is reported that the mixed-halide perovskites in forms of thin films and nanocrystals are segregated into a low-bandgap I-rich phase and a high-bandgap Br-rich phase. Herein, we present a critical review on the synthesis and basic properties of all-inorganic perovskites, phase-segregation phenomena, plausible mechanisms, and methods to mitigate phase segregation, providing insights on advancing mixed-halide perovskite optoelectronics with reliable performance.