Phenomenological Prediction of Halide Perovskite Phase Stability Phenomenological Prediction of Halide Perovskite Phase Stability via Dielectric-Response Analysis: Equivalence to First-Principles Thermodynamics at Five Orders of Magnitude Reduced Computational Cost

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Original abstract

Organic-inorganic hybrid halide perovskites have achieved power conversion efficiencies exceeding 26% in single-junction solar cells, yet phase stability remains the primary bottleneck for commercialization. The cubic α-phase of FAPbI3 spontaneously transforms to the hexagonal δ-phase at room temperature, and compositional engineering through mixed cations (Cs/FA/MA) and halides (I/Br) has emerged as the dominant stabilization strategy. However, the combinatorial space of the six-component system (Cs_xFA_yMA_{1-x-y}Pb(I_zBr_{1-z})3) exceeds 5000 compositions, rendering exhaustive first-principles screening computationally prohibitive—one density functional theory (DFT) calculation requires 1–7 days per composition. Here we present the ε-field domain method, a dielectric-response-based phenomenological approach that predicts phase stability through macroscopic observables (dielectric constants ε_hi, ε_lo and Curie temperature T_c) with only three input parameters. We demonstrate equivalence between this method and the established DFT-thermodynamic framework across six experimentally validated compositions, achieving a computational acceleration of 105-fold (5043 compositions screened in 0.02 seconds versus ~1700 years of CPU time for DFT). The optimal compositional window predicted by the ε-field method (Cs 2–8%, FA 78–89%, MA 3–18%, I 93–99%) agrees quantitatively with the celebrated triple-cation perovskites of Saliba et al. (Science 354, 2016) and Kim et al. (Nat. Commun. 8, 2017). We further provide temperature-dependent predictions for eight key compositions and propose five new candidate formulations awaiting experimental verification. The physical origin of this equivalence lies in the fact that both dielectric response (ε) and thermodynamic stability (ΔH_f) emerge from the same Pb-I framework electronic structuremacroscopic permittivity and microscopic formation energy are distinct expectation values of the same Hamiltonian. The ε-field method exploits this reduced parametrization by bypassing intermediate electronic-structure calculations, directly accessing stability-relevant information encoded in macroscopic observables.

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