Complex Oxide Heterostructures Research Articles

Novel 2DEG System at the HfO2/STO Interface.

Multifunctional integration in a single device has always been a hot research topic, especially for contradictory phenomena, one of which is the coexistence of ferroelectricity and metallicity. The complex oxide heterostructures, as symmetric breaking systems, provide a great possibility to incorporate different properties. Moreover, finding a series of oxide heterostructures to achieve this goal remains as a challenge. Here, taking the advantage of different physical phenomena, we use H2 plasma to pretreat the SrTiO3 (STO) substrate and then fabricate HfO2/STO heterostructures with it. The novel, well-repeatable metallic two-dimensional electron gas (2DEG) is directly obtained at the heterointerfaces without any further complex procedures, while the obvious ferroelectric-like behavior and Rashba spin-orbit coupling are also observed. The understanding of the mechanism, as well as the modified facile preparation procedure, would be meaningful for further development of ferroelectric metal in complex oxide heterostructures.

High-mobility spin-polarized quasi-two-dimensional electron gas and large low-field magnetoresistance at the interface of EuTiO3/SrTiO3 (110) heterostructures

High-mobility spin-polarized two-dimensional electron gas (2DEG) at the interfaces of complex oxide heterostructures provide great potential for spintronic device applications. Unfortunately, the interfacial ferromagnetism and its associated spin polarization of mobile electrons and negative magnetoresistance (MR) are too weak. As of now, obtaining enhanced interfacial ferromagnetism and MR and strong spin-polarized 2DEG is still a great challenge. In this paper, we report on the realization of strong spin-polarized 2DEG at the interface of EuTiO3/SrTiO3 (110) heterostructures, which were prepared by directly depositing 39-nm EuTiO3 films onto as-received SrTiO3 (110) substrates. Hall and Kondo effects, low-field MR, Shubnikov–de Haas (SdH) oscillation, and magnetic hysteresis loop measurements demonstrate that high mobility electrons (1.4 × 104 cm2 V−1 s−1) accumulate at the interface of the heterostructures, which are not only highly conducting and show SdH oscillations with a non-zero Berry phase but also show a large out-of-plane and in-plane butterfly-like negative low-field MR whose magnitude is unprecedentedly large (46%–59% at 500 Oe and 1.8 K), approximately one to two orders higher than those of previously reported spin-polarized 2DEG systems. The strong spin polarization of the interfacial 2DEG is attributed to the presence of interfacial Eu2+ 4f (3.6–4 μB/f.u.) and Ti3+ 3d moments. Our results may provide guidance for exploring strong spin-polarized 2DEG at the interface of rare-earth titanate–strontium titanate heterostructures.

Low-frequency noise behaviors of quasi-two-dimensional electron systems based on complex oxide heterostructures

We report the low-frequency noise behaviors in quasi-two-dimensional (quasi-2D) electron systems based on complex oxide heterostructures. First, the surface 2D electron gas (2DEG) on SrTiO3 (STO) exhibits the 1/fα-type current power spectral density (PSD) with α∼1.39. The non-unity exponent α indicates the discrepancy between the depth distributions of electrons and oxygen vacancies in the STO substrate. Second, the amorphous LaAlO3/KTaO3 (LAO/KTO) interface, another quasi-2D electron system, shows Lorentzian components of PSD at a high-frequency region around 1 kHz, implying that the amorphous overlayer can provide additional shallow charge-trapping sites to the quasi-2D electrons in the crystalline KTO substrate. Lastly, ultrathin SrRuO3 (SRO) film grown on STO substrate exhibits the Lorentzian components of PSD at a low-frequency region around 200 Hz. The slight suppression of the fast charge trapping is attributed to the intrinsic band bending at the interface between film and substrate. These results will provide a guideline for understanding the defect-induced charge trapping and the relevant electron dynamics in the quasi-2D electron systems as well as the oxide-based electronic materials in general.

Epitaxial-orientation-controlled magnetic anisotropy in the La0.67Sr0.33MnO3/SrTiO3 heterostructures

Magnetic anisotropy has significant importance in both designing high-efficiency magnetic devices and understanding noncollinear spin textures. Here, La0.67Sr0.33MnO3 layers are epitaxially fabricated on the (001)-, (110)-, and (111)-orientated SrTiO3 substrates to manipulate magnetic anisotropy. While the [11¯0] axis is the in-plane magnetic easy axis for the (001) La0.67Sr0.33MnO3 layer, it becomes the hard axis for the (110) and (111) samples. Interestingly, the (110) samples exhibit a great enhancement in magnetic anisotropy energy, reaching at 6.1 × 105 erg/cm3 that is 1–2 orders of magnitude higher than ones in (001) and (111) films. It is also noted that such improved magnetic anisotropy of (110) samples is maintained up to 30 nm. Those observations can be interpreted in terms of the orientation-modified orbital symmetry. While the energetically favored 3dx2−y2 orbital and degenerated eg orbitals drive the two-dimensional and bulk-like ferromagnetism in (001) and (111) La0.67Sr0.33MnO3 layers, respectively, the 3d3z2−r2 orbital provides the lowest orbital symmetry and results in the highest magnetic anisotropy energy in (110) samples. Meanwhile, this model can also explain the thickness-dependent Curie temperatures with different epitaxial orientations, deepening the understanding of the complex oxide heterostructures for magnetic modulations.

Intermittent Defect Fluctuations in Oxide Heterostructures.

The heterogeneous nature, local presence, and dynamic evolution of defects typically govern the ionic and electronic properties of a wide variety of functional materials. While the last 50 years have seen considerable efforts into development of new methods to identify the nature of defects in complex materials, such as the perovskite oxides, very little is known about defect dynamics and their influence on the functionality of a material. Here, the discovery of the intermittent behavior of point defects (oxygen vacancies) in oxide heterostructures employing X-ray photon correlation spectroscopy is reported. Local fluctuations between two ordered phases in strained SrCoOx with different degrees of stability of the oxygen vacancies are observed. Ab-initio-informed phase-field modeling reveals that fluctuations between the competing ordered phases are modulated by the oxygen ion/vacancy interaction energy and epitaxial strain. The results demonstrate how defect dynamics, evidenced by measurement and modeling of their temporal fluctuations, give rise to stochastic properties that now can be fully characterized using coherent X-rays, coupled for the first time to multiscale modeling in functional complex oxide heterostructures. The study and its findings open new avenues for engineering the dynamical response of functional materials used in neuromorphic and electrochemicalapplications.

Hybrid organic/inorganic interface: in situ and ex situ characterization in terms of structure, morphology, electronic and magnetic properties

Organic conjugated molecules are promising media to host spin-polarized carriers, due to their weak spin relaxation mechanisms. Here, we fabricated a metal–hybrid organic–inorganic complex oxide heterostructure made of Fe–Phthalocyanine (FePc): Co(0.5 nm)/FePc(0; 0.5; 1 nm)/La0.67Sr0.33MnO3/SrTiO3 and investigated the interface structure and chemical bonding, and overall magnetic properties. Details about the Co/FePc and FePc/LSMO interfaces were obtained through X-ray photoelectron and absorption characterizations. The combined in-situ and ex-situ magnetic measurements of the heterostructure indicates the contribution of FePc and Co moments to the overall magnetic response. Moreover, these measurements indicate that the LSMO bulk magnetic properties were not canceled out by the surface treatment, but favored the formation of a magnetic dead layer. The hybrid heterostructure presents a modification of the saturation magnetization attributed to the contribution of the molecular layer. The present results are a step forward in the engineering of hybrid organic/inorganic interfaces.

Controlled Electronic and Magnetic Landscape in Self-Assembled Complex Oxide Heterostructures.

Complex oxide heterointerfaces contain a rich playground of novel physical properties and functionalities, which give rise to emerging technologies. Among designing and controlling the functional properties of complex oxide film heterostructures, vertically aligned nanostructure (VAN) films using a self-assembling bottom-up deposition method presents great promise in terms of structural flexibility and property tunability. Here, the bottom-up self-assembly is extended to a new approach using a mixture containing a 2Dlayer-by-layer film growth, followed by a 3D VAN film growth. In this work, the two-phase nanocomposite thin films are based on LaAlO3 :LaBO3 , grown on a lattice-mismatched SrTiO3001 (001) single crystal.The 2D-to-3D transient structural assembly is primarily controlled by the composition ratio, leading to the coexistence of multiple interfacial properties, 2D electron gas, and magnetic anisotropy. This approach provides multidimensional film heterostructures which enrich the emergent phenomena for multifunctional applications.

Coexistence of surface oxygen vacancy and interface conducting states in LaAlO3/SrTiO3 revealed by grazing-angle resonant soft x-ray scattering

Oxide heterostructures have shown rich physics phenomena, particularly in the conjunction of exotic insulator–metal transition (IMT) at the interface between polar insulator LaAlO3 and non-polar insulator SrTiO3 (LaAlO3/SrTiO3). The polarization catastrophe model has suggested an electronic reconstruction, yielding to metallicity at both the interface and surface. Another scenario is the occurrence of surface oxygen vacancy at LaAlO3 (surface-Ov), which has predicted surface-to-interface charge transfer, yielding metallic interface but insulating surface. To clarify the origin of IMT, one should probe surface-Ov and the associated electronic structures at both the surface and the buried interface simultaneously. Here, using grazing-angle resonant soft x-ray scattering (GA-RSXS) supported with first-principles calculations, we reveal the co-existence of the surface-Ov state and the interface conducting state only in conducting LaAlO3/SrTiO3 (001) films. Interestingly, both the surface-Ov state and the interface conducting state are absent for the insulating film. As a function of Ov density, while the surface-Ov state is responsible for the IMT, the spatial charge distribution is found responsible for a transition from two-dimensional-like to three-dimensional-like conductivity accompanied by spectral weight transfer, revealing the importance of electronic correlation. Our results show the importance of surface-Ov in determining interface properties and provide a new strategy in utilizing GA-RSXS to directly probe the surface and buried interface electronic properties in complex oxide heterostructures.

Polar Perturbations in Functional Oxide Heterostructures

AbstractGrowth and characterization of metal‐oxide thin films foster successful development of oxide‐material‐integrated thin‐film devices represented by metal‐oxide‐semiconductor field‐effect transistors (MOSFET), drawing enormous technological and scientific interest for several decades. In recent years, functional oxide heterostructures have demonstrated remarkable achievements in modern technologies and provided deeper insights into condensed‐matter physics and materials science owing to their versatile tunability and selective amplification of the functionalities. One of the most critical aspects of their physical properties is the polar perturbation stemming from the ionic framework of an oxide. By engineering and exploiting the structural, electrical, magnetic, and optical characteristics through various routes, numerous perceptive studies have clearly shown how polar perturbations advance functionalities or drive exotic physical phenomena in complex oxide heterostructures. In this review, both intrinsic (engraved by thin‐film heteroepitaxy) and extrinsic (reversibly controllable defect‐mediated disorder and polar adsorbates) elements of polar perturbations, highlighting their abilities for the development of highly tunable functional properties are summarized. Scientifically, the recent approaches of polar perturbations render one to consolidate a prospect of atomic‐level manipulation of polar order in epitaxial oxide thin films. Technologically, this review also offers useful guidelines for rational design to heterogeneously integrated oxide‐based multi‐functional devices with high performances.

Dimensionality-driven in-plane antiferromagnetism in two-dimensional SrRuO3

Control of dimensionality is a powerful tool to unlock hidden electronic and magnetic phases. In particular, reduced dimensionality in strongly correlated oxides leads to an intriguing ``dead-layer'' behavior that a transition from (ferromagnetic) metal to (antiferromagnetic) insulator occurs as the thickness approaches the two-dimensional limit. However, the origin of such transition has been a subject of debate that both the intrinsic dimensionality effect and the extrinsic disorder effect are proposed to be the driving force. Here, we reveal a transition from ferromagnetic metal with perpendicular magnetic anisotropy to antiferromagnetic insulator with in-plane magnetic anisotropy in ${\mathrm{SrRuO}}_{3}$ epitaxial films down to the monolayer limit. Experimentally, we demonstrate that ${\mathrm{SrRuO}}_{3}$ films below 3 unit cells become magnetic insulators and the spin easy axis changes to the in-plane ⟨110⟩ directions. First-principles calculations reveal that the interplay of the orbital-selective quantum confinement on Ru $4d$ orbitals and the oxygen octahedral rotation drives the ultrathin films from ferromagnetic metal to antiferromagnetic insulator, reorienting Ru spins from the perpendicular to the ⟨110⟩ directions. Our findings demonstrate how reduced dimensionality can tailor the magnetic state and provide significant advances in one of the debated topics in complex oxide heterostructures that dimensionality effect alone can be the driving force of dead-layer phenomenon in two-dimensional systems.

Origin of the giant persistent photoconductivity in LaAlO3/SrTiO3 heterostructures probed by noise spectroscopy

• The origin of the giant persistent photoconductivity in LaAlO 3 /SrTiO 3 heterostructures is explained by the photo-induced valence change in oxygen vacancies. • The change in the ionization state distribution is successfully probed by the noise spectroscopy technique. • The noise spectra correlate the ionization state distribution and the charge trapping behavior of oxygen vacancies. • The neutralization of the ionized oxygen vacancies near the LaAlO 3 /SrTiO 3 interface hinders the fast and complete charge relaxation, resulting in the strong persistent photoconductivity. LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures have shown a strong persistent photoconductivity (PPC) at room temperature. The abnormally strong PPC has attracted immense research interest due to its possible applications in optically-tunable electronic devices. Despite its promise, the fundamental understanding of the PPC in the LAO/STO heterostructures is still elusive. Herein, we report that the giant PPC originates from the photo-induced valence change in oxygen vacancies near the LAO/STO interface. Our spectral analysis of the photocurrent and the model-fitting study consistently show that the ionized oxygen vacancies near the interface are neutralized during the electron relaxation process. They hinder the complete relaxation of the photoexcited electrons by the deeply-located oxygen vacancies and result in the strong PPC. The change in the ionization state distribution of the oxygen vacancies is probed by the persistent noise behavior at the frequency between 1 kHz and 20 kHz regime. These results provide insight into the role of oxygen vacancies in influencing the internal charge distribution and triggering the PPC phenomena in complex oxide heterostructures.

Resolving Diverse Oxygen Transport Pathways Across Sr‐Doped Lanthanum Ferrite and Metal‐Perovskite Heterostructures

AbstractPerovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g., Ni‐ and Cr‐based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real‐world environments. Here, this work uses isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal‐perovskite heterostructures, that is, (Ni‐Cr coated) Sr‐doped lanthanum ferrite (La0.5Sr0.5FeO3; LSFO). Annealing in 18O2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni‐Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. These results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.

Quasi-two-dimensional superconductivity at oxide heterostructures

Oxide interfaces manifest many fascinating phenomena with synergetic correlations among multiple degrees of freedom, including the interplay of broken symmetry, lattice mismatch, charge transfer, spatial confinement. In particular, the interface superconductivity in oxide heterostructure has attracted extensive attention due to the rich underlying physical connotations. The interfaces not only provide alternative research platforms with respect to the bulk material counterpart for exploring new superconductors and investigating superconducting mechanisms, but also create new opportunities for applying superconductors to future electronic devices. In recent years, owing to the rapid development of heteroepitaxial techniques and accurate characterization methods, researchers have found quasi-two-dimensional interface superconductivity in various oxide heterostructures and revealed numerous novel quantum phenomena associated with interface superconductivity, which not only promotes the development of condensed matter physics, but also lays important foundation for the practical application of interface superconductivity. In this brief review, we mainly focus on the quasi-two-dimensional superconductivity at oxide interface. Taking the typical quasi-two-dimensional superconductivity at the LaAlO<sub>3</sub>/SrTiO<sub>3</sub> interface and copper oxides such as La<sub>2</sub>CuO<sub>4</sub>/La<sub>1.56</sub>Sr<sub>0.44</sub>CuO<sub>4</sub> for example, we summarize and examine some novel physical phenomena with interface superconductivity in complex oxide heterostructures. Then we address the related problems that remain to be solved, and finally we prospect the possible future development of the interface superconductivity.

Correction: Selective Area Epitaxy of Complex Oxide Heterostructures on Si by Oxide Hard Mask Lift-Off

Correction: Selective Area Epitaxy of Complex Oxide Heterostructures on Si by Oxide Hard Mask Lift-Off

Phase Transition Dynamics in a Complex Oxide Heterostructure.

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO_{x} and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. The experimental and theoretical methods described here are broadly applicable to insitu measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

Selective Area Epitaxy of Complex Oxide Heterostructures on Si by Oxide Hard Mask Lift-Off

Selective Area Epitaxy of Complex Oxide Heterostructures on Si by Oxide Hard Mask Lift-Off

Defect-induced magnetism in homoepitaxial SrTiO3

Along with recent advancements in thin-film technologies, the engineering of complex transition metal oxide heterostructures offers the possibility of creating novel and tunable multifunctionalities. A representative complex oxide is the perovskite strontium titanate (STO), whose bulk form is nominally a centrosymmetric paraelectric band insulator. By tuning the electron doping, chemical stoichiometry, strain, and charge defects of STO, it is possible to control the electrical, magnetic, and thermal properties of such structures. Here, we demonstrate tunable magnetism in atomically engineered STO thin films grown on STO (001) substrates by controlling the atomic charge defects of titanium (VTi) and oxygen (VO) vacancies. Our results show that the magnetism can be tuned by altering the growth conditions. We provide deep insights into its association to the following defect types: (i) VTi, resulting in a charge rearrangement and local spin polarization, (ii) VO, leading to weak magnetization, and (iii) VTi–VO pairs, which lead to the appearance of a sizable magnetic signal. Our results suggest that controlling charged defects is critical for inducing a net magnetization in STO films. This work provides a crucial step for designing magnetic STO films via defect engineering for magnetic and spin-based electronic applications.

Probing oxygen vacancy distribution in oxide heterostructures by deep Learning-based spectral analysis of current noise

Exploiting oxygen vacancies has emerged as a versatile tool to tune the electronic and optoelectronic properties of complex oxide heterostructures. For the precise manipulation of the oxygen vacancies, the capability of directly probing the defect distribution in nanoscale is essential, but still lacking. Here we estimate the spatial distribution of oxygen vacancies in LaAlO3/SrTiO3 (LAO/STO) heterostructures by deep learning-based spectral analysis of current noise. The Monte-Carlo simulation and the specifically-designed deep learning model allow us to evaluate the defect distribution from current noise signals, measured through two-dimensional electron gas at the LAO/STO interface. We show that the oxygen vacancies are uniformly distributed over ∼ 100 nm from the interface in the as-grown LAO/STO heterostructure, while they can be migrated and confined to the interface within ∼ 14 nm by a vertical electric field at room temperature. These results introduce a powerful strategy to quantitatively probe the spatial distribution of point defects in oxide heterostructures with nm-scale precision.

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.

Origin of the 2D Electron Gas at the SrTiO3 Surface.

Bulk SrTiO3 is a well-known band insulator and the most common substrate used in the field of complex oxide heterostructures. Its surface and interface with other oxides, however, have demonstrated a variety of remarkable behaviors distinct from those expected. In this work, using a suite of in situ techniques to monitor both the atomic and electronic structures of the SrTiO3 (001) surface prior to and during growth, the disappearance and re-appearance of a 2D electron gas (2DEG) is observed after the completion of each SrO and TiO2 monolayer, respectively. The 2DEG is identified with the TiO2 double layer present at the initial SrTiO3 surface, which gives rise to a surface potential and mobile electrons due to vacancies within the TiO2-x adlayer. Much like the electronic reconstruction discovered in other systems, two atomic planes are required, here supplied by the double layer. The combined in situ scattering/spectroscopy findings resolve a number of longstanding issues associated with complex oxide interfaces, facilitating the employment of atomic-scale defect engineering in oxideelectronics.