Feld-induced modulation of two-dimensional electron gas at LaAlO3/SrTiO3 interface by polar distortion of LaAlO3.

Since the discovery of two-dimensional electron gas at the LaAlO3/SrTiO3 interface, its intriguing physical properties have garnered significant interests for device applications. Yet, understanding its response to electrical stimuli remains incomplete. Our in-situ transmission electron microscopy analysis of a LaAlO3/SrTiO3 two-dimensional electron gas device under electrical bias reveals key insights. Inline electron holography visualized the field-induced modulation of two-dimensional electron gas at the interface, while electron energy loss spectroscopy showed negligible electromigration of oxygen vacancies. Instead, atom-resolved imaging indicated that electric fields trigger polar distortion in the LaAlO3 layer, affecting two-dimensional electron gas modulation. This study refutes the previously hypothesized role of oxygen vacancies, underscoring the lattice flexibility of LaAlO3 and its varied polar distortions under electric fields as central to two-dimensional electron gas dynamics. These findings open pathways for advanced oxide nanoelectronics, exploiting the interplay of polar and nonpolar distortions in LaAlO3.

Electronic-grade epitaxial (111) KTaO3 heterostructures.

KTaO3 heterostructures have recently attracted attention as model systems to study the interplay of quantum paraelectricity, spin-orbit coupling, and superconductivity. However, the high and low vapor pressures of potassium and tantalum present processing challenges to creating heterostructure interfaces clean enough to reveal the intrinsic quantum properties. Here, we report superconducting heterostructures based on high-quality epitaxial (111) KTaO3 thin films using an adsorption-controlled hybrid PLD to overcome the vapor pressure mismatch. Electrical and structural characterizations reveal that the higher-quality heterostructure interface between amorphous LaAlO3 and KTaO3 thin films supports a two-dimensional electron gas with substantially higher electron mobility, superconducting transition temperature, and critical current density than that in bulk single-crystal KTaO3-based heterostructures. Our hybrid approach may enable epitaxial growth of other alkali metal-based oxides that lie beyond the capabilities of conventional methods.

Surface triggered stabilization of metastable charge-ordered phase in SrTiO3.

Charge ordering (CO), characterized by a periodic modulation of electron density and lattice distortion, has been a fundamental topic in condensed matter physics, serving as a potential platform for inducing novel functional properties. The charge-ordered phase is known to occur in a doped system with high d-electron occupancy, rather than low occupancy. Here, we report the realization of the charge-ordered phase in electron-doped (100) SrTiO3 epitaxial thin films that have the lowest d-electron occupancy i.e., d1-d0. Theoretical calculation predicts the presence of a metastable CO state in the bulk state of electron-doped SrTiO3. Atomic scale analysis reveals that (100) surface distortion favors electron-lattice coupling for the charge-ordered state, and triggering the stabilization of the CO phase from a correlated metal state. This stabilization extends up to six unit cells from the top surface to the interior. Our approach offers an insight into the means of stabilizing a new phase of matter, extending CO phase to the lowest electron occupancy and encompassing a wide range of 3d transition metal oxides.

Optoelectronic Synapse Based on 2D Electron Gas in Stoichiometry-Controlled Oxide Heterostructures.

Emulating synaptic functionalities in optoelectronic devices is significant in developing artificial visual-perception systems and neuromorphic photonic computing. Persistent photoconductivity (PPC) in metal oxides provides a facile way to realize the optoelectronic synaptic devices, but the PPC performance is often limited due to the oxygen vacancy defects that release excess conduction electrons without external stimuli. Herein, a high-performance optoelectronic synapse based on the stoichiometry-controlled LaAlO3/SrTiO3 (LAO/STO) heterostructure is developed. By increasing La/Al ratio up to 1.057:1, the PPC is effectively enhanced but suppressed the background conductivity at the LAO/STO interface, achieving strong synaptic behaviors. The spectral noise analyses reveal that the synaptic behaviors are attributed to the cation-related point defects and their charge compensation mechanism near the LAO/STO interface. The short-term and long-term plasticity is demonstrated, including the paired-pulse facilitation, in the La-rich LAO/STO device upon exposure to UV light pulses. As proof of concepts, two essential synaptic functionalities, the pulse-number-dependent plasticity and the self-noise cancellation, are emulated using the 5 × 5 array of La-rich LAO/STO synapses. Beyond the typical oxygen deficiency control, the results show how harnessing the cation stoichiometry can be used to design oxide heterostructures for advanced optoelectronic synapses and neuromorphic applications.

Electron pairing and nematicity in LaAlO3/SrTiO3 nanostructures.

Strongly correlated electronic systems exhibit a wealth of unconventional behavior stemming from strong electron-electron interactions. The LaAlO3/SrTiO3 (LAO/STO) heterostructure supports rich and varied low-temperature transport characteristics including low-density superconductivity, and electron pairing without superconductivity for which the microscopic origins is still not understood. LAO/STO also exhibits inexplicable signatures of electronic nematicity via nonlinear and anomalous Hall effects. Nanoscale control over the conductivity of the LAO/STO interface enables mesoscopic experiments that can probe these effects and address their microscopic origins. Here we report a direct correlation between electron pairing without superconductivity, anomalous Hall effect and electronic nematicity in quasi-1D ballistic nanoscale LAO/STO Hall crosses. The characteristic magnetic field at which the Hall coefficient changes directly coincides with the depairing of non-superconducting pairs showing a strong correlation between the two distinct phenomena. Angle-dependent Hall measurements further reveal an onset of electronic nematicity that again coincides with the electron pairing transition, unveiling a rotational symmetry breaking due to the transition from paired to unpaired phases at the interface. The results presented here highlights the influence of preformed electron pairs on the transport properties of LAO/STO and provide evidence of the elusive pairing "glue" that gives rise to electron pairing in SrTiO3-based systems.

Geometrical Doping at the Atomic Scale in Oxide Quantum Materials.

Chemical dopants enabling a plethora of emergent physical properties have been treated as randomly and uniformly distributed in the frame of a three-dimensional doped system. However, in nanostructured architectures, the location of dopants relative to the interface or boundary can greatly influence device performance. This observation suggests that chemical dopants need to be considered as discrete defects, meaning that geometric control of chemical dopants becomes a critical aspect as the physical size of materials scales down into the nanotechnology regime. Here we show that geometrical control of dopants at the atomic scale is another fundamental parameter in chemical doping, extending beyond the kind and amount of dopants conventionally used. The geometrical control of dopants extends the class of geometrically controlled structures into an unexplored dimensionality, between 2D and 3D. It is well understood that in the middle of the progressive dimensionality change from 3D to 2D, the electronic state of doped SrTiO3 is altered from a highly symmetric charged fluid to a charge disproportionated insulating state. Our results introduce a geometrical control of dopants, namely, geometrical doping, as another axis to provide a variety of emergent electronic states via tuning of the electronic properties of the solid state.

Reversible Photomodulation of Two-Dimensional Electron Gas in LaAlO3/SrTiO3 Heterostructures.

Long-lived photoinduced conductance changes in LaAlO3/SrTiO3 (LAO/STO) heterostructures enable their use in optoelectronic memory applications. However, it remains challenging to quench the persistent photoconductivity (PPC) instantly and reproducibly, which limits the reversible optoelectronic switching. Herein, we demonstrate a reversible photomodulation of two-dimensional electron gas (2DEG) in LAO/STO heterostructures with high reproducibility. By irradiating UV pulses, the 2DEG at the LAO/STO interface is gradually transformed to the PPC state. Notably, the PPC can be completely removed by water treatment when two key requirements are met: (1) the moderate oxygen deficiency in STO and (2) the minimal band edge fluctuation at the interface. Through our X-ray photoelectron spectroscopy and electrical noise analysis, we reveal that the reproducible change in the conductivity of 2DEG is directly attributed to the surface-driven electron relaxation in the STO. Our results provide a stepping-stone toward developing optically tunable memristive devices based on oxide 2DEG systems.

Collective Control of Potential-Constrained Oxygen Vacancies in Oxide Heterostructures for Gradual Resistive Switching.

Filamentary resistive switching in oxides is one of the key strategies for developing next-generation non-volatile memory devices. However, despite numerous advantages, their practical applications in neuromorphic computing are still limited due to non-uniform and indeterministic switching behavior. Given the inherent stochasticity of point defect migration, the pursuit of reliable switching likely demands an innovative approach. Herein, a collective control of oxygen vacancies is introduced in LaAlO3 /SrTiO3 (LAO/STO) heterostructures to achieve reliable and gradual resistive switching. By exploiting an electrostatic potential constraint in ultrathin LAO/STO heterostructures, the formation of conducting filaments is suppressed, but instead precisely control the concentration of oxygen vacancies. Since the conductance of the LAO/STO device is governed by the ensemble concentration of oxygen vacancies, not their individual probabilistic migrations, the resistive switching is more uniform and deterministic compared to conventional filamentary devices. It provides direct evidence for the collective control of oxygen vacancies by spectral noise analysis and modeling by Monte-Carlo simulation. As a proof of concept, the significantly-improved analog switching performance of the filament-free LAO/STO devices is demonstrated, revealing potential for neuromorphic applications. The results establish an approach to store information by point defect concentration, akin to biological ionic channels, for enhancing switching characteristics of oxide materials.

Strong Interfacial Charge Trapping in Ultrathin SrRuO3 on SrTiO3 Probed by Noise Spectroscopy.

SrRuO3 (SRO) has emerged as a promising quantum material due to its exotic electron correlations and topological properties. In epitaxial SRO films, electron scattering against lattice phonons or defects has been considered as only a predominant mechanism accounting for electronic properties. Although the charge trapping by polar defects can also strongly influence the electronic behavior, it has often been neglected. Herein, we report strong interfacial charge trapping in ultrathin SRO films on SrTiO3 (STO) substrates probed by noise spectroscopy. We find that oxygen vacancies in the STO cause stochastic interfacial charge trapping, resulting in high electrical noise. Spectral analyses of the photoinduced noise prove that the oxygen vacancies buried deep in the STO can effectively contribute to the charge trapping process. These results unambiguously reveal that electron transport in ultrathin SRO films is dominated by the carrier number fluctuation that correlates with interfacial charge trapping.

Variance-aware weight quantization of multi-level resistive switching devices based on Pt/LaAlO3/SrTiO3 heterostructures.

Resistive switching devices have been regarded as a promising candidate of multi-bit memristors for synaptic applications. The key functionality of the memristors is to realize multiple non-volatile conductance states with high precision. However, the variation of device conductance inevitably causes the state-overlap issue, limiting the number of available states. The insufficient number of states and the resultant inaccurate weight quantization are bottlenecks in developing practical memristors. Herein, we demonstrate a resistive switching device based on Pt/LaAlO3/SrTiO3 (Pt/LAO/STO) heterostructures, which is suitable for multi-level memristive applications. By redistributing the surface oxygen vacancies, we precisely control the tunneling of two-dimensional electron gas (2DEG) through the ultrathin LAO barrier, achieving multiple and tunable conductance states (over 27) in a non-volatile way. To further improve the multi-level switching performance, we propose a variance-aware weight quantization (VAQ) method. Our simulation studies verify that the VAQ effectively reduces the state-overlap issue of the resistive switching device. We also find that the VAQ states can better represent the normal-like data distribution and, thus, significantly improve the computing accuracy of the device. Our results provide valuable insight into developing high-precision multi-bit memristors based on complex oxide heterostructures for neuromorphic applications.

Oxide Two-Dimensional Electron Gas with High Mobility at Room-Temperature.

The prospect of 2-dimensional electron gases (2DEGs) possessing high mobility at room temperature in wide-bandgap perovskite stannates is enticing for oxide electronics, particularly to realize transparent and high-electron mobility transistors. Nonetheless only a small number of studies to date report 2DEGs in BaSnO3 -based heterostructures. Here, 2DEG formation at the LaScO3 /BaSnO3 (LSO/BSO) interface with a room-temperature mobility of 60 cm2  V-1  s-1 at a carrier concentration of 1.7 × 1013  cm-2 is reported. This is an order of magnitude higher mobility at room temperature than achieved in SrTiO3 -based 2DEGs. This is achieved by combining a thick BSO buffer layer with an ex situ high-temperature treatment, which not only reduces the dislocation density but also produces a SnO2 -terminated atomically flat surface, followed by the growth of an overlying BSO/LSO interface. Using weak beam dark-field transmission electron microscopy imaging and in-line electron holography technique, a reduction of the threading dislocation density is revealed, and direct evidence for the spatial confinement of a 2DEG at the BSO/LSO interface is provided. This work opens a new pathway to explore the exciting physics of stannate-based 2DEGs at application-relevant temperatures for oxide nanoelectronics.

Low-voltage magnetoelectric coupling in membrane heterostructures.

Strain-mediated magnetoelectric (ME) coupling in ferroelectric (FE)/ferromagnetic (FM) heterostructures offers a unique opportunity for both fundamental scientific research and low-power multifunctional devices. Relaxor-FEs, such as (1 − x)Pb(Mg1/3Nb2/3)O3-(x)PbTiO3 (PMN-xPT), are ideal FE layer candidates because of their giant piezoelectricity. However, thin films of PMN-PT suffer from substrate clamping, which substantially reduces piezoelectric in-plane strains. Here, we demonstrate low-voltage ME coupling in an all-thin-film heterostructure that uses the anisotropic strains induced by the (011) orientation of PMN-PT. We completely remove PMN-PT films from their substrate and couple with FM Ni overlayers to create membrane PMN-PT/Ni heterostructures showing 90° Ni magnetization rotation with 3 V PMN-PT bias, much less than the bulk PMN-PT ~100-V requirement. Scanning transmission electron microscopy and phase-field simulations clarify the membrane response. These results provide a crucial step toward understanding the microstructural behavior of PMN-PT thin films for use in piezo-driven ME heterostructures.

Hot Electron Tunneling in Pt/LaAlO3/SrTiO3 Heterostructures for Enhanced Photodetection.

LaAlO3/SrTiO3 (LAO/STO) heterostructures, in which a highly mobile two-dimensional electron gas (2DEG) is formed, have great potential for optoelectronic applications. However, the inherently high density of the 2DEG hinders the observation of photo-excitation effects in oxide heterostructures. Herein, a strong photoresponse of the 2DEG in a Pt/LAO/STO heterostructure is achieved by adopting a vertical tunneling configuration. The tunneling of the 2DEG through an ultrathin LAO layer is significantly enhanced by UV light irradiation, showing a maximum photoresponsivity of ∼1.11 × 107%. The strong and reversible photoresponse is attributed to the thermionic emission of photoexcited hot electrons from the oxygen-deficient STO. Notably, the oxygen vacancy defects play a critical role in enhancing the tunneling photocurrent. Our systematic study on the hysteresis behavior and the light power dependency of the tunneling current consistently support the fact that the photoexcited hot electrons from the oxygen vacancies strongly contribute to the tunneling conduction under the UV light. This work offers valuable insights into a novel photodetection mechanism based on the 2DEG as well as into developing ultrathin optoelectronic devices based on the oxide heterostructures.

Electronically reconfigurable complex oxide heterostructure freestanding membranes.

In recent years, lanthanum aluminate/strontium titanate (LAO/STO) heterointerfaces have been used to create a growing family of nanoelectronic devices based on nanoscale control of LAO/STO metal-to-insulator transition. The properties of these devices are wide-ranging, but they are restricted by nature of the underlying thick STO substrate. Here, single-crystal freestanding membranes based on LAO/STO heterostructures were fabricated, which can be directly integrated with other materials via van der Waals stacking. The key properties of LAO/STO are preserved when LAO/STO membranes are formed. Conductive atomic force microscope lithography is shown to successfully create reversible patterns of nanoscale conducting regions, which survive to millikelvin temperatures. The ability to form reconfigurable conducting nanostructures on LAO/STO membranes opens opportunities to integrate a variety of nanoelectronics with silicon-based architectures and flexible, magnetic, or superconducting materials.

Cooperative evolution of polar distortion and nonpolar rotation of oxygen octahedra in oxide heterostructures.

Polarity discontinuity across LaAlO3/SrTiO3 (LAO/STO) heterostructures induces electronic reconstruction involving the formation of two-dimensional electron gas (2DEG) and structural distortions characterized by antiferrodistortive (AFD) rotation and ferroelectric (FE) distortion. We show that AFD and FE modes are cooperatively coupled in LAO/STO (111) heterostructures; they coexist below the critical thickness (t c) and disappear simultaneously above t c with the formation of 2DEG. Electron energy-loss spectroscopy and density functional theory (DFT) calculations provide direct evidence of oxygen vacancy (V O) formation at the LAO (111) surface, which acts as the source of 2DEG. Tracing the AFD rotation and FE distortion of LAO reveals that their evolution is strongly correlated with V O distribution. The present study demonstrates that AFD and FE modes in oxide heterostructures emerge as a consequence of interplay between misfit strain and polar field, and further that their combination can be tuned to competitive or cooperative coupling by changing the interface orientation.

Engineered spin-orbit interactions in LaAlO3/SrTiO3-based 1D serpentine electron waveguides.

The quest to understand, design, and synthesize new forms of quantum matter guides much of contemporary research in condensed matter physics. One-dimensional (1D) electronic systems form the basis for some of the most interesting and exotic phases of quantum matter. Here, we describe a family of quasi-1D nanostructures, based on LaAlO3/SrTiO3 electron waveguides, in which a sinusoidal transverse spatial modulation is imposed. These devices display unique dispersive features in the subband spectra, namely, a sizeable shift (∼7 T) in the spin-dependent subband minima, and fractional conductance plateaus. The first property can be understood as an engineered spin-orbit interaction associated with the periodic acceleration of electrons as they undulate through the nanowire (ballistically), while the second property signifies the presence of enhanced electron-electron scattering in this system. The ability to engineer these interactions in quantum wires contributes to the tool set of a 1D solid-state quantum simulation platform.

Gate-Tunable Optical Nonlinearities and Extinction in Graphene/LaAlO3/SrTiO3 Nanostructures.

We explore the ultrafast optical response of graphene subjected to intense (∼106 V/cm) local (∼10 nm) electric fields. Nanoscale gating of graphene is achieved using a voltage-biased, SrTiO3-based conductive nanowire junction "written" directly under the graphene and isolated from it by an insulating ultrathin (<2 nm) LaAlO3 barrier. Upon illumination with ultrafast visible-to-near-infrared (VIS-NIR) light pulses, the local field from the nanojunction creates a strong gate-tunable second-order nonlinearity in the graphene and produces a substantial difference-frequency (DFG) and sum-frequency generation (SFG) response detected by the nanojunction. Spectrally sharp, gate-tunable extinction features (>99.9%) are observed in the VIS-NIR and SFG spectral ranges, in parameter regimes that are positively correlated with the enhanced nonlinear response. The observed graphene-light interaction and nonlinear response are of fundamental interest and open the way for future exploitation in graphene-based optical devices such as phase shifters, modulators, and nanoscale THz sources.

Electron-Lattice Coupling in Correlated Materials of Low Electron Occupancy.

In correlated materials including transition metal oxides, electronic properties and functionalities are modulated and enriched by couplings between the electron and lattice degrees of freedom. These couplings are controlled by external parameters such as chemical doping, pressure, magnetic and electric fields, and light irradiation. However, the electron-lattice coupling relies on orbital characters, i.e., symmetry and occupancy, of t2g and eg orbitals, so that a large electron-lattice coupling is limited to eg electron system, whereas t2g electron system exhibits an inherently weak coupling. Here, we design and demonstrate a strongly enhanced electron-lattice coupling in electron-doped SrTiO3, that is, the t2g electron system. In ultrathin films of electron-doped SrTiO3 [i.e., (La0.25Sr0.75)TiO3], we reveal the strong electron-lattice-orbital coupling, which is manifested by extremely increased tetragonality and the corresponding metal-to-insulator transition. Our findings open the way of an active tuning of the charge-lattice-orbital coupling to obtain new functionalities relevant to emerging nanoelectronic devices.

Oxygen Vacancy Linear Clustering in a Perovskite Oxide.

Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. Here, we report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti2+ valence state or corresponding Ti 3d2 electronic configuration along with divacancy cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO3 was verified by further X-ray diffuse scattering analysis. Because SrTiO3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.

Effect of laser fluence on electrical properties of (Sr0.75,La0.25)TiO3 thin films grown by pulsed-laser-deposition.

We have grown Sr0.75La0.25TiO3 (SLTO) thin films using pulsed laser deposition (PLD) with various laser energy fluences. We investigated the effect of energy fluence on the compositions of SLTO films. The stoichiometry of SLTO films was controlled by adjusting the laser energy density. At low energy densities below 1.0 J/cm2, SLTO films become non-stoichiometric with Ti deficiency. The Ti deficiency increases with decreasing the laser energy fluence. We have also investigated the effect of laser energy fluence on the electrical properties of the thin films. The electrical resistivity and carrier density intimately depend on the laser energy fluence as a result of the non-stoichiometry. After eliminating the effect of oxygen vacancies by post-annealing, the electrical properties are dependent on the cation stoichiometry in the oxide films.