More is different: How chemical complexity influences stability in high entropy oxides

Abstract: Tailoring the chemical composition of a high entropy oxide (HEO) is a powerful approach to enhancing desirable material properties. However, the targeted synthesis of HEO materials is often hindered by competing stabilizing and destabilizing factors, which are difficult to predict. This work examines the effects of increased configurational entropy on the phase formation and stability of four notable complex oxide families: perovskite ($AB$O$_3$}), pyrochlore ($A_2B_2$O$_7$), Ruddlesden-Popper ($A_2B$O$_4$), and zirconium tungstate ($AB_2$O$_8$). Each of these structures has a tetravalent cation site, which we attempt to substitute with an entropic mixture of four cations, benchmarked by the parallel synthesis of a non-disordered reference compound. While all four target high entropy materials can be expected to form based on ionic radii criteria, only the high entropy perovskite Ba(Ti,Zr,Hf,Sn)O$_3$ is successfully synthesized. In the case of the pyrochlore, an entropy-stabilized defect fluorite is formed instead, while the Ruddlesden-Popper phase co-exists with multiple competing phases. For the tungstate, an unexpected deep eutectic point between the precursors results in melting that precedes the formation of a high entropy phase. Our case studies therefore illustrate that the stability of HEOs cannot be straightforwardly predicted based on ionic radii, lattice geometry, and charge-balancing considerations alone due to the underlying complexity of the interactions between the many chemical constituents.