Transition metal oxides (TMOs) are an important class of materials that show a wide range of functionalities involving spin, charge, and lattice degrees of freedom. The strong correlation between electrons in d-orbitals and the multivalence nature give rise to a variety of exotic electronic states ranging from insulator to superconductor and cause intriguing phase competition phenomena. Despite a burst of research on the multifarious functionalities in TMOs, little attention has been paid to the formation and integration of an electret-a type of quasi-permanent electric field generator useful for nanoscale functional devices as an electric counterpart to permanent magnets. Here, we find that an electret can be created in LaMnO 3 thin films by tip-induced electric fields, with a considerable surface height change, via solid-state electrochemical amorphization. The surface charge density of the formed electret area reaches~400 nC cm −2 and persists without significant charge reduction for more than a year. The temporal evolution of the surface height, charge density, and electric potential are systematically examined by scanning probe microscopy. The underlying mechanism is theoretically analyzed based on a drift-diffusion-reaction model, suggesting that positively charged particles, which are likely protons produced by the dissociation of water, play crucial roles as trapped charges and a catalysis to trigger amorphization. Our finding opens a new horizon for multifunctional TMOs.
Mobile oxygen vacancies offer a substantial potential to broaden the range of optical functionalities of complex transition metal oxides due to their high mobility and the interplay with correlated electrons. Here, we report a large electro-absorptive optical variation induced by a topotactic transition via oxygen vacancy fluidic motion in calcium ferrite with large-scale uniformity. The coloration efficiency reaches ~80 cm2 C−1, which means that a 300-nm-thick layer blocks 99% of transmitted visible light by the electrical switching. By tracking the color propagation, oxygen vacancy mobility can be estimated to be 10−8 cm2 s−1 V−1 near 300°C, which is a giant value attained due to the mosaic pseudomonoclinic film stabilized on LaAlO3 substrate. First-principles calculations reveal that the defect density modulation associated with hole charge injection causes a prominent change in electron correlation, resulting in the light absorption modulation. Our findings will pave the pathway for practical topotactic electrochromic applications.
The Jahn–Teller (JT) effect, through geometric deformation of molecules or local ionic lattices, lowers the overall energy of the system by removing electron degeneracy from partially occupied orbitals. Crystal symmetry lowered by JT distortion inevitably creates multiple variants of elastic and orbital-anisotropic states. Visualization and control of the domain/wall textures create a cornerstone to understand various correlated phenomena and explore wall properties. Here, we report the real-space observation of JT phonon and orbiton-related domains in a LaMnO3 thin film using confocal Raman spectromicroscopy. The characteristic symmetries of the JT-originated Raman modes allow us to detect and visualize the local population and orientation of the JT planes. Combined with a crystal structural analysis, we find that the formation of ferroelastic domains with W or W’ walls provides the basic framework for understanding JT domain textures. Furthermore, we demonstrate the JT domains can be manipulated by applying local external stress. Our findings provide a useful pathway for mechanically-tunable orbitronic applications.
Bulk LaMnO3 is an A-type antiferromagnetic material in which the Jahn–Teller (JT) planes each have a ferromagnetic arrangement, but are stacked in antiparallel. Here, we report the growth of epitaxial LaMnO3 films on (001)-oriented cubic KTaO3 substrates in such a way that the JT plane is parallel to the nonmagnetic substrate. We verify the presence of the JT distortion and confirm the orientation of the plane by symmetry analysis with angle-resolved polarized Raman spectroscopy. The temperature evolution of the Raman spectra indicates that the B1g JT phonon softens below the magnetic transition temperature of ∼145 K, where ferro- or ferri-magnetism with magnetic easy axis along the out-of-plane direction is exhibited.
Topological textures of ferroelectric polarizations have promise as alternative devices for future information technology. A polarization rotation inevitably deviates from the stable orientation in axial ferroelectrics, but local energy losses compromise the global symmetry, resulting in a distorted shape of the topological vortex or inhibiting the vortex. Easy planar isotropy helps to promote rotating structures and, accordingly, to facilitate access to nontrivial textures. Here, we investigate the domain structure of an epitaxial thin film of bismuth tungsten oxide (Bi2WO6) grown on a (001) SrTiO3 substrate. By using angle-resolved piezoresponse force microscopy and scanning transmission electron microscopy, we find the existence of a hidden phase with ⟨100⟩-oriented ferroelectric polarizations in the middle of the four variant ⟨110⟩-oriented polarization domains, which assists in the formation of flux closure domains. The results suggest that this material is one step closer to becoming an isotropic two-dimensional polar material.
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