arXiv subjects

Vipul Chaturvedi

Publications and source records attributed to Vipul Chaturvedi.

4 recordsLinked to original sources

arXiv2023

Crystal-Chemical Origins of the Ultrahigh Conductivity of Metallic Delafossites

Despite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO2, PtCoO2) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 microns. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we first report a new approach to PdCoO2 crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios (>440). Nevertheless, the first detailed mass spectrometry measurements on these materials reveal that they are not ultrapure, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (~1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a previously unconsidered "sublattice purification" mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites.

cond-mat.mtrl-sci↗

arXiv2023

Wide-range continuous tuning of the thermal conductivity of $\rm La_{0.5}Sr_{0.5}CoO_{3-δ}$ films via room-temperature ion-gel gating

Solid-state control of the thermal conductivity of materials is of exceptional interest for novel devices such as thermal diodes and switches. Here, we demonstrate the ability to continuously tune the thermal conductivity of nanoscale films of $\rm La_{0.5}Sr_{0.5}CoO_{3-δ}$ (LSCO) by a factor of over 5, via a room-temperature electrolyte-gate-induced non-volatile topotactic phase transformation from perovskite (with $δ\approx 0.1$) to an oxygen-vacancy-ordered brownmillerite phase (with $δ=0.5$), accompanied by a metal-insulator transition. Combining time-domain thermoreflectance and electronic transport measurements, model analyses based on molecular dynamics and Boltzmann transport, and structural characterization by X-ray diffraction, we uncover and deconvolve the effects of these transitions on heat carriers, including electrons and lattice vibrations. The wide-range continuous tunability of LSCO thermal conductivity enabled by low-voltage (below 4 V) room-temperature electrolyte gating opens the door to non-volatile dynamic control of thermal transport in perovskite-based functional materials, for thermal regulation and management in device applications.

cond-mat.mtrl-sci↗

arXiv2022

Room-Temperature Valence Transition in a Strain-Tuned Perovskite Oxide

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-δ, 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.

cond-mat.mtrl-sci↗

arXiv2019

Soft X-ray Absorption Spectroscopy and Magnetic Circular Dichroism as Operando Probes of Complex Oxide Electrolyte Gate Transistors

Electrolyte-based transistors utilizing ionic liquids/gels have been highly successful in the study of charge-density-controlled phenomena, particularly in oxides. Experimental probes beyond transport have played a significant role, despite challenges to their application in electric double-layer transistors. Here, we demonstrate application of synchrotron soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) as operando probes of the charge state and magnetism in ion-gel-gated ferromagnetic perovskite films. Electrochemical response via oxygen vacancies at positive gate bias in LaAlO$_3$(001)/La$_{0.5}$Sr$_{0.5}$CoO$_{3-δ}$ is used as a test case. XAS/XMCD measurements of 4-25 unit-cell-thick films first probe the evolution of hole doping (from the O K-edge pre-peak) and ferromagnetism (at the Co L-edges), to establish a baseline. Operando soft XAS/XMCD of electrolyte-gated films is then demonstrated, using optimized spin-coated gels with thickness $\sim$1 $μ$m, and specific composition. Application of gate voltages up to +4 V is shown to dramatically suppress the O $K$-edge XAS pre-peak intensity and Co $L$-edge XMCD, thus enabling the Co valence and ferromagnetism to be tracked upon gate-induced reduction. Soft XAS and XMCD, with appropriate electrolyte design, are thus established as viable for the operando characterization of electrolyte-gated oxides.

cond-mat.mtrl-sci↗