tuning-oxide-properties-oxygen-vacancy-control-during-growth

Tuning Oxide Properties by Oxygen Vacancy Control During Growth and Annealing

Electrical, optical, and magnetic properties of oxide materials can often be controlled by varying the oxygen content. Here we outline two approaches for ...

Technical University of Denmark

Chinese Academy of Sciences

The discovery of two-dimensional electron gases at the heterointerface between two insulating perovskite-type oxides, such as LaAlO(3) and SrTiO(3), provides opportunities for a new generation of all-oxide electronic devices. Key challenges remain for achieving interfacial electron mobilities much beyond the current value of approximately 1,000 cm(2) V(-1) s(-1) (at low temperatures). Here we create a new type of two-dimensional electron gas at the heterointerface between SrTiO(3) and a spinel γ-Al(2)O(3) epitaxial film with compatible oxygen ions sublattices. Electron mobilities more than one order of magnitude higher than those of hitherto-investigated perovskite-type interfaces are obtained. The spinel/perovskite two-dimensional electron gas, where the two-dimensional conduction character is revealed by quantum magnetoresistance oscillations, is found to result from interface-stabilized oxygen vacancies confined within a layer of 0.9 nm in proximity to the interface. Our findings pave the way for studies of mesoscopic physics with complex oxides and design of high-mobility all-oxide electronic devices.

A high-mobility two-dimensional electron gas at the spinel/perovskite interface of γ-Al2O3/SrTiO3.

A chemical redox reaction can lead to a two-dimensional electron gas at the interface between a TiO-terminated SrTiO (STO) substrate and an amorphous LaAlO capping layer. When replacing the STO substrate with rutile and anatase TiO substrates, considerable differences in the interfacial conduction are observed. On the basis of X-ray photoelectron spectroscopy (XPS) and transport measurements, we conclude that the interfacial conduction comes from redox reactions, and that the differences among the materials systems result mainly from variations in the activation energies for the diffusion of oxygen vacancies at substrate surfaces.

Tuning the Two-Dimensional Electron Gas at Oxide Interfaces with Ti-O Configurations: Evidence from X-ray Photoelectron Spectroscopy.

2D hole gas seen.

The metallic interface between two oxide insulators, such as LaAlO /SrTiO (LAO/STO), provides new opportunities for electronics and spintronics. However, due to the presence of multiple orbital populations, tailoring the interfacial properties such as the ground state and metal-insulator transitions remains challenging. Here, an unforeseen tunability of the phase diagram of LAO/STO is reported by alloying LAO with a ferromagnetic LaMnO insulator without forming lattice disorder and at the same time without changing the polarity of the system. By increasing the Mn-doping level, x, of LaAl  Mn O /STO (0 ≤ x ≤ 1), the interface undergoes a Lifshitz transition at x = 0.225 across a critical carrier density of n = 2.8 × 10 cm , where a peak T ≈255 mK of superconducting transition temperature is observed. Moreover, the LaAl  Mn O turns ferromagnetic at x ≥ 0.25. Remarkably, at x = 0.3, where the metallic interface is populated by only d electrons and just before it becomes insulating, a same device with both signatures of superconductivity and clear anomalous Hall effect (7.6 × 10 cm < n ≤ 1.1 × 10 cm ) is achieved reproducibly. This provides a unique and effective way to tailor oxide interfaces for designing on-demand electronic and spintronic devices.

Diluted Oxide Interfaces with Tunable Ground States.

A previously unknown, water-soluble polysaccharide, named DOTP-B, was isolated from the roots of the plant Dioscorea opposita Thunb, a well-known edible and medicinal plant in China. DOTP-B was found to be neutral in charge, with an average molecular weight of 5623 Da. Monosaccharide composition analysis by GC-MS revealed that DOTP-B was a hetero-polysaccharide consisting of glucose and galactose at a molar ratio of 14.6:1.0. Structural features of DOTP-B were investigated with a combination of chemical and instrumental methods, including complete acid hydrolysis, periodate oxidation, methylation, GC-MS, FTIR and several NMR spectra. Highly correlated results demonstrated that the main chain of DOTP-B consisted of →4)-α-d-glc(1 → residues, with about 6% internal →6)-β-d-gal(1 → residues. The antioxidant activity of DOTP-B was also evaluated as the EC values against DPPH and PTIO radicals were 2.1 ± 0.1 mg/mL and 1.6 ± 0.1 mg/mL, respectively. Therefore, the polysaccharide DOTP-B could be possibly developed as a promising natural antioxidant for application in medical and food industries.

Isolation, structure and activity of a novel water-soluble polysaccharide from Dioscorea opposita Thunb.

The rich functionalities of transition-metal oxides and their interfaces bear an enormous technological potential. Its realization in practical devices requires, however, a significant improvement of yet relatively low electron mobility in oxide materials. Recently, a mobility boost of about 2 orders of magnitude has been demonstrated at the spinel-perovskite γ-AlO/SrTiO interface compared to the paradigm perovskite-perovskite LaAlO/SrTiO interface. We explore the fundamental physics behind this phenomenon from direct measurements of the momentum-resolved electronic structure of this interface using resonant soft-X-ray angle-resolved photoemission. We find an anomaly in orbital ordering of the mobile electrons in γ-AlO/SrTiO which depopulates electron states in the top SrTiO layer. This rearrangement of the mobile electron system pushes the electron density away from the interface, which reduces its overlap with the interfacial defects and weakens the electron-phonon interaction, both effects contributing to the mobility boost. A crystal-field analysis shows that the band order alters owing to the symmetry breaking between the spinel γ-AlO and perovskite SrTiO. Band-order engineering, exploiting the fundamental symmetry properties, emerges as another route to boost the performance of oxide devices.

Band-Order Anomaly at the γ-AlO/SrTiO Interface Drives the Electron-Mobility Boost.

Heterostructures composed of dissimilar oxides with different properties offer opportunities to develop emergent devices with desired functionalities. A key feature of oxide heterostructures is interface electronics and orbital reconstructions. Here, we combined infinite-layered SrCuO and perovskite SrRuO into heterostructures. A rare high spin state as large as 3.0  f.u and an increase in Curie temperature by 12 K are achieved in an ultrathin SrRuO film capped by a SrCuO layer. Atomic-scale lattice imaging shows the uniform CuO-plane-to-RuO-pyramid connection at the interface, where the regularly arranged RuO pyramids were elongated along the out-of-plane direction. As revealed by theoretical calculations and spectral analysis, these features finally result in an abnormally high spin state of the interfacial Ru ions with highly polarized e orbitals. The present work demonstrates that oxygen coordination engineering at the infinite-layer/perovskite oxide interface is a promising approach towards advanced oxide electronics.

Infinite-layer/perovskite oxide heterostructure-induced high-spin states in SrCuO/SrRuO bilayer films.

The electronic structure as well as the mechanism underlying the high-mobility two-dimensional electron gases (2DEGs) at complex oxide interfaces remain elusive. Herein, using soft X-ray angle-resolved photoemission spectroscopy (ARPES), we present the band dispersion of metallic states at buffered LaAlO/SrTiO (LAO/STO) heterointerfaces where a single-unit-cell LaMnO (LMO) spacer not only enhances the electron mobility but also renders the electronic structure robust toward X-ray radiation. By tracing the evolution of band dispersion, orbital occupation, and electron-phonon interaction of the interfacial 2DEG, we find unambiguous evidence that the insertion of the LMO buffer strongly suppresses both the formation of oxygen vacancies as well as the electron-phonon interaction on the STO side. The latter effect makes the buffered sample different from any other STO-based interfaces and may explain the maximum mobility enhancement achieved at buffered oxide interfaces.

Robust Electronic Structure of Manganite-Buffered Oxide Interfaces with Extreme Mobility Enhancement.

Two-dimensional electron gas (2DEG) formed at the heterointerface between two oxide insulators hosts plenty of emergent phenomena and provides new opportunities for electronics and photoelectronics. However, despite being long sought after, on-demand properties controlled through a fully optical illumination remain far from being explored. Herein, a giant tunability of the 2DEG at the interface of γ-AlO/SrTiO through a fully optical gating is discovered. Specifically, photon-generated carriers lead to a delicate tunability of the carrier density and the underlying electronic structure, which is accompanied by the remarkable Lifshitz transition. Moreover, the 2DEG can be optically tuned to possess a maximum Rashba spin-orbit coupling, particularly at the crossing region of the sub-bands with different symmetries. First-principles calculations essentially well explain the optical modulation of γ-AlO/SrTiO. Our fully optical gating opens a new pathway for manipulating emergent properties of the 2DEGs and is promising for on-demand photoelectric devices.

Fully Optical Modulation of the Two-Dimensional Electron Gas at the γ-AlO/SrTiO Interface.

Modifying the crystal structure and corresponding functional properties of complex oxides by regulating their oxygen content has promising applications in energy conversion and chemical looping, where controlling oxygen migration plays an important role. Therefore, finding an efficacious and feasible method to facilitate oxygen migration has become a critical requirement for practical applications. Here, we report a compressive-strain-facilitated oxygen migration with reversible topotactic phase transformation (RTPT) in LaSrCoO films based on all-solid-state electrolyte gating modulation. With the lattice strain changing from tensile to compressive strain, significant reductions in modulation duration (∼72%) and threshold voltage (∼70%) for the RTPT were observed, indicating great promotion of RTPT by compressive strain. Density functional theory calculations verify that such compressive-strain-facilitated efficient RTPT comes from significant reduction of the oxygen migration barrier in compressive-strained films. Further, ac-STEM, EELS, and sXAS investigations reveal that varying strain from tensile to compressive enhances the Co 3d band filling, thereby suppressing the Co-O hybrid bond in oxygen vacancy channels, elucidating the micro-origin of such compressive-strain-facilitated oxygen migration. Our work suggests that controlling electronic orbital occupation of Co ions in oxygen vacancy channels may help facilitate oxygen migration, providing valuable insights and practical guidance for achieving highly efficient oxygen-migration-related chemical looping and energy conversion with complex oxides.

Compressive-Strain-Facilitated Fast Oxygen Migration with Reversible Topotactic Transformation in LaSrCoO via All-Solid-State Electrolyte Gating.

The 2D electron system (2DES) at the KTaO surface or heterointerface with 5d orbitals hosts extraordinary physical properties, including a stronger Rashba spin-orbit coupling (RSOC), higher superconducting transition temperature, and potential of topological superconductivity. Herein, a huge enhancement of RSOC under light illumination achieved at a superconducting amorphous-Hf Zr O /KTaO (110) heterointerfaces is reported. The superconducting transition is observed with T = 0.62 K and the temperature-dependent upper critical field reveals the interaction between spin-orbit scattering and superconductivity. A strong RSOC with B = 1.9 T is revealed by weak antilocalization in the normal state, which undergoes sevenfold enhancement under light illumination. Furthermore, RSOC strength develops a dome-shaped dependence of carrier density with the maximum of B = 12.6 T achieved near the Lifshitz transition point n ≈ 4.1 × 10 cm . The highly tunable giant RSOC at KTaO (110)-based superconducting interfaces show great potential for spintronics.

Light-Induced Giant Rashba Spin-Orbit Coupling at Superconducting KTaO (110) Heterointerfaces.

Magnetic skyrmions are scarcely investigated for single-crystal quality films, for which skyrmions may have a remarkable performance. Even in the limited studies in this aspect, the skyrmions are usually probed by the topological Hall effect, missing important information on dynamic properties. Here, we present a comprehensive investigation on the generation/manipulation of magnetic skyrmions in LaBaMnO single-crystal films. Using the technique of magnetic force microscopy, the current-driven skyrmion dynamics are directly observed. Unlike isolated skyrmions produced by magnetic field alone, closely packed skyrmions can be generated by electric pulses in a magnetic background, with a high density (∼60/μm) and a small size (dozens of nanometers). The threshold current moving skyrmions is ∼2.3 × 10 A/cm, 2-3 orders of magnitude lower than that required by metallic multilayers or van der Waals ferromagnetic heterostructures. Our work demonstrates the great potential of single-crystal oxide films in developing skyrmion-based devices.

Direct Observation of Magnetic Skyrmions and Their Current-Induced Dynamics in Epitaxial Single-Crystal Oxide Films.

Tailoring the interface between organic semiconductor (OSC) and ferromagnetic (FM) electrodes, that is, the spinterface, offers a promising way to manipulate and optimize the magnetoresistance (MR) ratio of the organic spin valve (OSV) devices. However, the non-destructive in situ regulation method of spinterface is seldom reported, limiting its theoretical research and further application in organic spintronics. (La Pr ) Ca MnO (LPCMO), a recently developed FM material, exhibits a strong electronic phase separation (EPS) property, and can be employed as an effective in situ spinterface adjuster. Herein, we fabricated a LPCMO-based polymer spin valve with a vertical configuration of LPCMO/poly(3-hexylthiophene-2,5-diyl) (P3HT)/Co, and emphasized the important role of LPCMO/P3HT spinterface in MR regulation. A unique competitive spin-scattering mechanism generated by the EPS characteristics of LPCMO inside the polymer spin valve was discovered by abstracting the anomalous non-monotonic MR value as a function of pre-set magnetic field (B ) and temperature (T). Particularly, a record-high MR ratio of 93% was achieved in polymer spin valves under optimal conditions. These findings highlight the importance of interdisciplinary research between organic spintronics and EPS oxides and offer a novel scenario for multi-level storage via spinterface manipulation.

Article	Year
A high-mobility two-dimensional electron gas at the spinel/perovskite interface of γ-Al2O3/SrTiO3. Nature communications\| PubMed ID: 23340411	2013
Tuning the Two-Dimensional Electron Gas at Oxide Interfaces with Ti-O Configurations: Evidence from X-ray Photoelectron Spectroscopy. ACS applied materials & interfaces\| PubMed ID: 29226677	2018
2D hole gas seen. Nature materials\| PubMed ID: 29403055	2018
Diluted Oxide Interfaces with Tunable Ground States. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 30637817	2019
Isolation, structure and activity of a novel water-soluble polysaccharide from Dioscorea opposita Thunb. International journal of biological macromolecules\| PubMed ID: 30986466	2019
Band-Order Anomaly at the γ-AlO/SrTiO Interface Drives the Electron-Mobility Boost. ACS nano\| PubMed ID: 33661601	2021
Infinite-layer/perovskite oxide heterostructure-induced high-spin states in SrCuO/SrRuO bilayer films. Materials horizons\| PubMed ID: 34766611	2021
Robust Electronic Structure of Manganite-Buffered Oxide Interfaces with Extreme Mobility Enhancement. ACS nano\| PubMed ID: 35312282	2022
Fully Optical Modulation of the Two-Dimensional Electron Gas at the γ-AlO/SrTiO Interface. The journal of physical chemistry letters\| PubMed ID: 35343699	2022
Compressive-Strain-Facilitated Fast Oxygen Migration with Reversible Topotactic Transformation in LaSrCoO via All-Solid-State Electrolyte Gating. ACS nano\| PubMed ID: 36107149	2022
Light-Induced Giant Rashba Spin-Orbit Coupling at Superconducting KTaO (110) Heterointerfaces. Advanced materials (Deerfield Beach, Fla.)\| PubMed ID: 36972144	2023
Direct Observation of Magnetic Skyrmions and Their Current-Induced Dynamics in Epitaxial Single-Crystal Oxide Films. Nano letters\| PubMed ID: 37158610	2023
The In Situ Optimization of Spinterface in Polymer Spin Valve by Electronic Phase Separated Oxides. Small (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 37264712	2023

Yunzhong Chen

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