Pressure-driven structural phase transition unlocks multifunctionality in KMgX (X = P, As, Sb, and Bi) compounds: A first-principles study

Abstract

The search for materials with multifunctional properties has attracted significant attention due to their potential applications in various energy-related devices. Pressure-induced phase transitions provide an effective strategy for accessing different structural phases of a material without altering its chemical composition, thereby enabling the tuning of its physical properties and expanding its functional applications. In this work, we investigate the previously unexplored orthorhombic (Pnma) phase of the KMgX (X = P, As, Sb, and Bi) family using first-principles calculations and identify a pressure-induced structural transition from a tetragonal to orthorhombic phase. Stability of the pressure-accessible orthorhombic structure is rigorously confirmed by equation of state analysis together with phonon, elastic, and formation-enthalpy calculations, establishing its viability for further investigation. Optical properties calculated within the $G_0W_0$-Bethe-Salpeter equation (BSE) framework, incorporating quasiparticle corrections and excitonic effects, exhibit direct dipole-allowed transitions at the $Γ$ point and strong visible-light absorption with coefficients approaching $10^5~\text{cm}^{-1}$. Consequently, KMgAs and KMgSb achieve spectroscopic limited maximum efficiencies (SLME) of $27.12\%$ and $26.40\%$, respectively, at a thin-film thickness of $0.6~μ\text{m}$. Furthermore, thermoelectric transport calculations predict (zT) values of 0.65 and 0.58 at $900~\text{K}$ for p-type and n-type KMgSb, respectively, demonstrating its potential for both legs of thermoelectric devices. These values are likely conservative, as the Slack model tends to overestimate thermal conductivity. Overall, the pressure-accessible orthorhombic phase of the KMgX family emerges as a stable multifunctional semiconductor with coupled photovoltaic and thermoelectric energy-conversion capabilities.