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Motivated by the existence of superconductivity in pyrite-structure CuS$_2$, we explore the possibility of ionic-liquid-gating-induced superconductivity in the proximal antiferromagnetic Mott insulator NiS$_2$. A clear gating-induced transition from a two-dimensional insulating state to a three-dimensional metallic state is observed at positive gate bias on single crystal surfaces. No evidence for superconductivity is observed down to the lowest measured temperature of 0.45 K, however. Based on transport, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and other techniques, we deduce an electrochemical gating mechanism involving a substantial decrease in the S:Ni ratio (over hundreds of nm), which is both non-volatile and irreversible. This is in striking contrast to the reversible, volatile, surface-limited, electrostatic gate effect in pyrite FeS$_2$. We attribute this stark difference in electrochemical vs. electrostatic gating response in NiS$_2$ and FeS$_2$ to the much larger S diffusion coefficient in NiS$_2$, analogous to the different behaviors observed among electrolyte-gated oxides with differing O-vacancy diffusivities. The gating irreversibility, on the other hand, is associated with the lack of atmospheric S; this is in contrast to the better understood oxide case, where electrolysis of atmospheric H$_2$O provides an O reservoir. This study of NiS$_2$ thus provides new insight into electrolyte gating mechanisms in functional materials, in a previously unexplored limit., Comment: 4 figures, included supplement

Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-{\delta}, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point., Comment: 35 pages, 7 figures