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Abstract 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 tocontinuouslytune the thermal conductivity of nanoscale films of La0.5Sr0.5CoO3-δ(LSCO) by a factor of over 5, via a room-temperature electrolyte-gate-induced non-volatile topotactic phase transformation from perovskite (withδ≈ 0.1) to an oxygen-vacancy-ordered brownmillerite phase (withδ= 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 equation, 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.
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Optical Properties of Electrochemically Gated La1−xSrxCoO3−δ as a Topotactic Phase-Change Material
Materials with tunable infrared refractive index changes have enabled active metasurfaces for novel control of optical circuits, thermal radiation, and more. Ion-gel-gated epitaxial films of the perovskite cobaltite La1−xSrxCoO3−δ (LSCO) with 0.00 ≤ x ≤ 0.70 offer a new route to significant, voltage-tuned, nonvolatile refractive index modulation for infrared active metasurfaces, shown here through Kramers–Kronig-consistent dispersion models, structural and electronic transport characterization, and electromagnetic simulations before and after electrochemical reduction. As-grown perovskite films are high-index insulators for x < 0.18 but lossy metals for x > 0.18, due to a percolation insulator-metal transition. Positive-voltage gating of LSCO transistors with x > 0.18 reveals a metal-insulator transition from the metallic perovskite phase to a high-index (n > 2.5), low-loss insulating phase, accompanied by a perovskite to oxygen-vacancy-ordered brownmillerite transformation at high x. At x < 0.18, despite nominally insulating character, the LSCO films undergo remarkable refractive index changes to another lower-index, lower-loss insulating perovskite state with Δn > 0.6. In simulations of plasmonic metasurfaces, these metal-insulator and insulator-insulator transitions support significant, varied mid-infrared reflectance modulation, thus framing electrochemically gated LSCO as a diverse library of room-temperature phase-change materials for applications including dynamic thermal imaging, camouflage, and optical memories.
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- Award ID(s):
- 2011401
- PAR ID:
- 10423688
- Date Published:
- Journal Name:
- Advanced Optical Materials
- ISSN:
- 2195-1071
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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ABSTRACT: Perovskite cobaltites have emerged as archetypes for electrochemical control of materials properties in electrolytegate devices. Voltage-driven redox cycling can be performed between fully oxygenated perovskite and oxygen-vacancy-ordered brownmillerite phases, enabling exceptional modulation of the crystal structure, electronic transport, thermal transport, magnetism, and optical properties. The vast majority of studies, however, have focused heavily on the perovskite and brownmillerite end points. In contrast, here we focus on hysteresis and reversibility across the entire perovskite ↔ brownmillerite topotactic transformation, combining gate-voltage hysteresis loops, minor hysteresis loops, quantitative operando synchrotron X-ray diffraction, and temperature-dependent (magneto)transport, on ion-gel-gated ultrathin (10-unit-cell) epitaxial La0.5Sr0.5CoO3−δ films. Gate-voltage hysteresis loops combined with operando diffraction reveal a wealth of new mechanistic findings, including asymmetric redox kinetics due to differing oxygen diffusivities in the two phases, nonmonotonic transformation rates due to the first-order nature of the transformation, and limits on reversibility due to first-cycle structural degradation. Minor loops additionally enable the first rational design of an optimal gate-voltage cycle. Combining this knowledge, we demonstrate state-of-the-art nonvolatile cycling of electronic and magnetic properties, encompassing >105 transport ON/OFF ratios at room temperature, and reversible metal−insulator−metal and ferromagnet−nonferromagnet−ferromagnet cycling, all at 10-unit-cell thickness with high room-temperature stability. This paves the way for future work to establish the ultimate cycling frequency and endurance of such devices. KEYWORDS: electrolyte gating, magnetoionics, complex oxides, perovskite−brownmillerite transformation, hysteresis, reversibilitymore » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/adom.202300098
