Short-Range Order and Local Distortions in Entropy Stabilized Oxides

An idealized high entropy oxide is characterized by perfect chemical disorder and perfect positional order. In this work, we investigate the extent to which short-range order (SRO) and local structural distortions impede that idealized scenario. Working in the entropy stabilized α-PbO2 structure, we compare a two-component system, (Ti,Zr)O2, with a four-component system, (Ti,Zr,Hf,Sn)O2, using a combination of experimental and computational approaches. Special quasi-random structures are used in conjunction with density functional theory calculations to investigate the local distortions around specific elements revealing significant local distortions that are relatively insensitive to the number of chemical constituents. Using finite temperature Monte Carlo simulations, we are able to reproduce the previously experimentally observed SRO and transition temperature for the two-component system. However, the ideal configurational entropy is never reached, so some amount of SRO is expected even at synthesis temperatures. On the other hand, the order–disorder transition temperature is dramatically lower and experimentally inaccessible for the four-component system, while the configurational entropy is closer to ideal at synthesis conditions and less sensitive to temperature. Total scattering measurements and pair distribution function analysis of slow-cooled and quenched samples support this view. In summary, we demonstrate that SRO effects in high entropy materials are less prevalent as more components are added in, provided the pairwise interaction strengths remain comparable, while local distortions are less affected by the number of components.