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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, reversibility
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Direct neutron-diffraction-based measurement of magnetic order in brownmillerite SrCoO2.5 and La0.5Sr0.5CoO2.5 thin films
Epitaxial cobaltites have emerged as exemplary materials for electrochemical gating, in large part due to their topotactic perovskite (P) ↔ brownmillerite (BM) transformations. SrCoO3−δ, for example, can be cycled between metallic ferromagnetic P SrCoO3 and insulating BM SrCoO2.5, realizing exceptional modulation of electronic, thermal, and optical properties. It is often presumed that such cycling also generates ferromagnetic–antiferromagnetic (F-AF) modulation due to the G-type AF order in bulk SrCoO2.5. Little is understood about magnetism in thin-film BM SrCoO2.5, however, meaning that the true magnetic property modulation is unclear. We address this here through a neutron diffraction study of BM La1−xSrxCoO2.5 films at x = 0.5 and 1.0. Lightly compressively strained SrCoO2.5 films are shown to retain G-type AF order, albeit with suppressed Néel temperature (∼340 K). Of high interest for AF spintronics, room-temperature F–AF cycling is thus possible across the SrCoO3-δ P ↔ BM transformation. At x = 0.5, however, BM La0.5Sr0.5CoO2.5 films are found to exhibit no detectable G-type AF order but instead weak F order (Curie temperature ∼115 K), unveiling a La0.5Sr0.5CoO3−δ phase diagram with two distinct F phases. These results thus uncover new, unanticipated magnetic phase behavior in these materials, in addition to being directly relevant to cobaltite-based magnetoionics.
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- PAR ID:
- 10506578
- Publisher / Repository:
- APL Mater.
- Date Published:
- Journal Name:
- APL Materials
- Volume:
- 12
- Issue:
- 4
- ISSN:
- 2166-532X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1063/5.0196646
