Configurational Entropy-Driven Phase Stability and Thermal Transport in Rock-Salt High-Entropy Oxides

Abstract: High-entropy oxides (HEOs) offer a unique platform for exploring the thermodynamic interaction between configurational entropy and enthalpy in stabilizing complex solid solutions. In this study, a series of rock-salt structured oxides with varying configurational entropy, ranging from binary to multi-cation systems, to elucidate the competing roles of enthalpy and entropy in phase stabilization is investigated. Compositions including (Ni${0.8}$Cu${0.2}$)O to(NiCuZnCoMg)${0.9}$A${0.1}$O (A = Li, Na, K) were synthesized and their stuctural, microstructural and thermal properties have been discussed. X-ray diffraction combined with thermal cycling confirms that even a medium configurational entropy ($\sim$ 0.95R) can induce single-phase behavior stabilized by configurational entropy ($\Delta S_{conf}$), challenging the traditional threshold of $1.5\,R$. High-resolution TEM and EDS mapping reveal nanocrytalline features and homogeneous elemental distribution respectively, while XPS analysis confirms divalent oxidation states. A strong coupling between high configurational entropy with thermal conductivity ($\kappa$) has been observed. First, a sharp decrease in $\kappa$ with increasing $\Delta S_{conf}$ is seen and then decomposed samples (while cooling) show high $\kappa$, demonstrating the role of $\Delta S_{conf}$ on $\kappa$. Furthermore, Li-doped compositions exhibit improved thermoelectric performance, with a maximum figure of merit ($zT$) of $\sim$0.15 at 1173K\, driven by low thermal conductivity and favorable carrier transport. The results highlight that configurational entropy, even at intermediate values, plays a significant role in stabilizing disordered single-phase oxides and tailoring phonon transport.