Strong Impact of Halide Ordering on Structural Phase Transitions in Mixed Perovskites

Abstract

Mixed halide perovskites are highly versatile semiconductors with applications in photovoltaics, light-emitting diodes, and photodetectors. Understanding their thermodynamic phase behavior is central to guiding compositional design and improving device stability. Here, we train machine-learned interatomic potentials (MLIPs) on density functional theory reference data for CsxRb1-xPbBr3yI3-3y, CsxRb1-xPbBr3yCl3-3y, and CsxRb1-xPbCl3yI3-3y halide perovskites, enabling large-scale hybrid Monte Carlo-molecular dynamics simulations that sample both configurational and vibrational degrees of freedom. All three binary halide systems exhibit a miscibility gap, the extent of which correlates with halide ion size mismatch. The gaps in Br-Cl and Br-I close at low temperatures, while the Cl-I gap extends above room temperature. At temperatures above the miscibility gap (200 K to 500 K), all systems show a tendency toward layered halide ordering, with halide species preferentially occupying apical or equatorial octahedral sites. In CsPbBr3yI3-3y, this ordering occurs in a device-relevant temperature regime and is linked to the structural phase transitions, shifting transition temperatures by up to 100 K relative to randomly mixed structures. We attribute the strongly non-linear composition dependence of the orthorhombic-tetragonal phase boundary observed experimentally (a linear decrease followed by a plateau) to halide ordering. Introducing Rb on the A-site weakens halide ordering and eliminates the non-linear behavior, while narrowing the miscibility gap in both the Br-I and Br-Cl systems. These results establish halide ordering as a key determinant of structural phase stability in mixed-halide perovskites.