Mixing I and Br in Inorganic Perovskites: Atomistic Insights from Reactive Molecular Dynamics Simulations

Mike Pols; Adri C T van Duin; Sofía Calero; Shuxia Tao

doi:10.1021/acs.jpcc.4c00563

Mixing I and Br in Inorganic Perovskites: Atomistic Insights from Reactive Molecular Dynamics Simulations

J Phys Chem C Nanomater Interfaces. 2024 Feb 23;128(9):4111-4118. doi: 10.1021/acs.jpcc.4c00563. eCollection 2024 Mar 7.

Authors

Mike Pols^{1

2}, Adri C T van Duin³, Sofía Calero¹, Shuxia Tao^{1

2}

Affiliations

¹ Materials Simulation & Modelling, Department of Applied Physics and Science Education, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.
² Center for Computational Energy Research, Department of Applied Physics and Science Education, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.
³ Department of Mechanical Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, United States.

Abstract

All-inorganic halide perovskites have received a great deal of attention as attractive alternatives to overcome the stability issues of hybrid halide perovskites that are commonly associated with organic cations. To find a compromise between the optoelectronic properties of CsPbI₃ and CsPbBr₃, perovskites with CsPb(Br_xI_1-x)₃ mixed compositions are commonly used. An additional benefit is that without sacrificing the optoelectronic properties for applications such as solar cells or light-emitting diodes, small amounts of Br in CsPbI₃ can prevent the inorganic perovskite from degrading to a photo-inactive non-perovskite yellow phase. Despite indications that strain in the perovskite lattice plays a role in the stabilization of the material, a full understanding of such strain is lacking. Here, we develop a reactive force field (ReaxFF) for perovskites starting from our previous work for CsPbI₃, and we extend this force field to CsPbBr₃ and mixed CsPb(Br_xI_1-x)₃ compounds. This force field is used in large-scale molecular dynamics simulations to study perovskite phase transitions and the internal ion dynamics associated with the phase transitions. We find that an increase of the Br content lowers the temperature at which the perovskite reaches a cubic structure. Specifically, by substituting Br for I, the smaller ionic radius of Br induces a strain in the lattice that changes the internal dynamics of the octahedra. Importantly, this effect propagates through the perovskite lattice ranging up to distances of 2 nm, explaining why small concentrations of Br in CsPb(Br_xI_1-x)₃ (x ≤ 1/4) have a significant impact on the phase stability of mixed halide perovskites.