Thermodynamic and Electronic Properties of Semiconducting High-Entropy Halide Perovskites Materials through First-Principles Calculations

High-entropy materials are known for forming single phase solid solution and having the potential for property designs. They have emerged as promising candidates for sustainable energy technologies. However, their high synthesis temperatures present challenges. In contrast, halide-based perovskites offer a low-temperature synthesis alternative, providing a prospective way to bring this excellent-performance material family into real-life manufacturing and usage.



In this work, we employ density functional theory (DFT) calculations to investigate the formation enthalpy and electronic band structure of high-entropy halide perovskites designed on the cubic vacancy-ordered double-perovskite structure Cs₂MCl₆ (M=Zr⁴⁺, Sn⁴⁺, Te⁴⁺, Hf⁴⁺, Re⁴⁺, Os⁴⁺, Ir⁴⁺ or Pt⁴⁺). Our goal is to provide atomistic understanding of their electronic properties and thermodynamic stability. We analyzed the eight constituent compounds, unveiling the fundamental physical mechanisms governing transport properties which further help understand the behavior of the high-entropy phases. We assessed the thermodynamic stability of the high-entropy phases by comparing the enthalpy and entropy of mixing to their constituent phases. By leveraging high-throughput calculations and interpolation calculations, our study maps the properties of the high-entropy phases across a broad composition range. Our multidisciplinary approach provide accurate insights into high-entropy perovskites that can be synthesized at low temperatures, with the potential to advance clean and affordable energy technologies.