Spatially Controlled Octahedral Rotations and Metal-Insulator Transitions in Nickelate Superlattices.

The properties of correlated oxides can be manipulated by forming short-period superlattices since the layer thicknesses are comparable with the typical length scales of the involved correlations and interface effects. Herein, we studied the metal-insulator transitions (MITs) in tetragonal NdNiO3/SrTiO3 superlattices by controlling the NdNiO3 layer thickness, n in the unit cell, spanning the length scale of the interfacial octahedral coupling. Scanning transmission electron microscopy reveals a crossover from a modulated octahedral superstructure at n = 8 to a uniform nontilt pattern at n = 4, accompanied by a drastically weakened insulating ground state. Upon further reducing n the predominant dimensionality effect continuously raises the MIT temperature, while leaving the antiferromagnetic transition temperature unaltered down to n = 2. Remarkably, the MIT can be enhanced by imposing a sufficiently large strain even with strongly suppressed octahedral rotations. Our results demonstrate the relevance for the control of oxide functionalities at reduced dimensions.

Metal-insulator-transition engineering by modulation tilt-control in perovskite nickelates for room temperature optical switching.

In transition metal perovskites ABO3, the physical properties are largely driven by the rotations of the BO6 octahedra, which can be tuned in thin films through strain and dimensionality control. However, both approaches have fundamental and practical limitations due to discrete and indirect variations in bond angles, bond lengths, and film symmetry by using commercially available substrates. Here, we introduce modulation tilt control as an approach to tune the ground state of perovskite oxide thin films by acting explicitly on the oxygen octahedra rotation modes-that is, directly on the bond angles. By intercalating the prototype SmNiO3 target material with a tilt-control layer, we cause the system to change the natural amplitude of a given rotation mode without affecting the interactions. In contrast to strain and dimensionality engineering, our method enables a continuous fine-tuning of the materials' properties. This is achieved through two independent adjustable parameters: the nature of the tilt-control material (through its symmetry, elastic constants, and oxygen rotation angles), and the relative thicknesses of the target and tilt-control materials. As a result, a magnetic and electronic phase diagram can be obtained, normally only accessible by A-site element substitution, within the single SmNiO3 compound. With this unique approach, we successfully adjusted the metal-insulator transition (MIT) to room temperature to fulfill the desired conditions for optical switching applications.

Saturation and self-absorption effects in the angle-dependent 2p3d resonant inelastic X-ray scattering spectra of Co3.

Angle-dependent 2p3d resonant inelastic X-ray scattering spectra of a LaCoO3 single crystal and a 55 nm LaCoO3 film on a SrTiO3 substrate are presented. Theoretical calculation shows that, with ∼20 meV resolved Co 2p3d resonant inelastic X-ray scattering (RIXS), the excited states of the isotropic 1A1g(Oh) ground state are split by 3d spin-orbit coupling, which can be distinguished via their angular dependence. However, strong self-absorption and saturation effects distort the spectra of the LaCoO3 single crystal and limit the observation of small angular dependence. In contrast, the RIXS on 55 nm LaCoO3 shows less self-absorption effects and preserves the angular dependence of the excited states.

Spin chirality fluctuation in two-dimensional ferromagnets with perpendicular magnetic anisotropy.

Non-coplanar spin textures with scalar spin chirality can generate an effective magnetic field that deflects the motion of charge carriers, resulting in a topological Hall effect (THE)1-3. However, spin chirality fluctuations in two-dimensional ferromagnets with perpendicular magnetic anisotropy have not been considered so far. Here, we report evidence of spin chirality fluctuations by probing the THE above the Curie temperature in two different ferromagnetic ultra-thin films, SrRuO3 and V-doped Sb2Te3. The temperature, magnetic field, thickness and carrier-type dependence of the THE signal, along with Monte Carlo simulations, suggest that spin chirality fluctuations are a common phenomenon in two-dimensional ferromagnets with perpendicular magnetic anisotropy. Our results open a path for exploring spin chirality with topological Hall transport in two-dimensional magnets and beyond4-7.

Direct observation of the electronic states of photoexcited hematite with ultrafast 2p3d X-ray absorption spectroscopy and resonant inelastic X-ray scattering.

Hematite, α-Fe2O3, is an important semiconductor for photoelectrochemical water splitting. Its low charge carrier mobility and the presence of midgap states provide favourable conditions for electron-hole recombination, hence affecting the semiconductor's photoelectrochemical efficiency. The nature of the excited state and charge carrier transport in hematite is strongly debated. In order to further understand the fundamental properties of the hematite photoexcited state, we conducted femtosecond 2p (L3) X-ray absorption (XAS) and 2p3d resonant inelastic scattering (RIXS) measurements on hematite thin-films at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). The observed spectral changes and kinetic processes are in agreement with previous 3p XAS reports. The potential additional information that could be acquired from 2p3d RIXS experiments is also discussed.

Asymmetric response of electrical conductivity and V valence state to strain in cation-deficient Sr1-yVO3 ultrathin films based on absorption measurements at the V L2- and L3-edges.

The correlation between electronic properties and epitaxial strain in a cation-deficient system has rarely been investigated. Cation-deficient SrVO3 films are taken as a model system to investigate the strain-dependent electrical and electronic properties. Using element- and charge-sensitive soft X-ray absorption, V L-edge absorption measurements have been performed for Sr1-yVO3 films of different thicknesses capped with 4 u.c. (unit cell) SrTiO3 layers, showing the coexistence of V4+ and V5+ in thick films. A different correlation between V valence state and epitaxial strain is observed for Sr1-yVO3 ultrathin films, i.e. a variation in V valence state is only observed for tensile-strained films. Sr1-yVO3 thin films are metallic and exhibit a thickness-driven metal-insulator transition at different critical thicknesses for tensile and compressive strains. The asymmetric response of electrical conductivity to strain observed in cation-deficient Sr1-yVO3 films will be beneficial for functional oxide electronic devices.

Quantum Anomalous Hall State in Ferromagnetic SrRuO_{3} (111) Bilayers.

SrRuO_{3} heterostructures grown in the (111) direction are a rare example of thin film ferromagnets. By means of density functional theory plus dynamical mean field theory we show that the half-metallic ferromagnetic state with an ordered magnetic moment of 2 µ_{B}/Ru survives the ultimate dimensional confinement down to a bilayer, even at elevated temperatures of 500 K. In the minority channel, the spin-orbit coupling opens a gap at the linear band crossing corresponding to 3/4 filling of the t_{2g} shell. We predict that the emergent phase is Haldane's quantum anomalous Hall state with Chern number C=1, without an external magnetic field or magnetic impurities.

Properties of epitaxial, (001)- and (110)-oriented (PbMg1/3Nb2/3O3)2/3-(PbTiO3)1/3 films on silicon described by polarization rotation.

Epitaxial (PbMg1/3Nb2/3O3)2/3-(PbTiO3)1/3 (PMN-PT) films with different out-of-plane orientations were prepared using a CeO2/yttria stabilized ZrO2 bilayer buffer and symmetric SrRuO3 electrodes on silicon substrates by pulsed laser deposition. The orientation of the SrRuO3 bottom electrode, either (110) or (001), was controlled by the deposition conditions and the subsequent PMN-PT layer followed the orientation of the bottom electrode. The ferroelectric, dielectric and piezoelectric properties of the (SrRuO3/PMN-PT/SrRuO3) ferroelectric capacitors exhibit orientation dependence. The properties of the films are explained in terms of a model based on polarization rotation. At low applied fields domain switching dominates the polarization change. The model indicates that polarization rotation is easier in the (110) film, which is ascribed to a smaller effect of the clamping on the shearing of the pseudo-cubic unit cell compared to the (001) case.

Toward Design Rules for Multilayer Ferroelectric Energy Storage Capacitors - A Study Based on Lead-Free and Relaxor-Ferroelectric/Paraelectric Multilayer Devices.

Future pulsed-power electronic systems based on dielectric capacitors require the use of environment-friendly materials with high energy-storage performance that can operate efficiently and reliably in harsh environments. Here, a study of multilayer structures, combining paraelectric-like Ba0.6Sr0.4TiO3 (BST) with relaxor-ferroelectric BaZr0.4Ti0.6O3 (BZT) layers on SrTiO3-buffered Si substrates, with the goal to optimize the high energy-storage performance is presented. The energy-storage properties of various stackings are investigated and an extremely large maximum recoverable energy storage density of ≈165.6 J cm-3 (energy efficiency ≈ 93%) is achieved for unipolar charging-discharging of a 25-nm-BZT/20-nm-BST/910-nm-BZT/20-nm-BST/25-nm-BZT multilayer structure, due to the extremely large breakdown field of 7.5 MV cm-1 and the lack of polarization saturation at high fields in this device. Strong indications are found that the breakdown field of the devices is determined by the outer layers of the multilayer stack and can be increased by improving the quality of these layers. Authors are also able to deduce design optimization rules for this material combination, which can be to a large extend justify by structural analysis. These rules are expected also to be useful for optimizing other multilayer systems and are therefore very relevant for further increasing the energy storage density of capacitors.

Control of Magnetic Shape Anisotropy by Nanopillar Dimensionality in Vertically Aligned Nanocomposites.

Perpendicular magnetic anisotropy forms the foundation of the current data storage technology. However, there is an ever-increasing demand for higher density data storage, faster read-write access times, and lower power consuming storage devices, which requires new materials to reduce the switching current, improve bit-to-bit distributions, and improve reliability of writing with scalability below 10 nm. Here, vertically aligned nanocomposites (VANs) composed of self-assembled ferromagnetic La0.7Sr0.3MnO3 (LSMO) nanopillars in a surrounding ZnO matrix are investigated for controllable magnetic anisotropy. Confinement of LSMO into nanopillar dimensions down to 15 nm in such VAN films aligns the magnetic easy axis along the out-of-plane (i.e., perpendicular) direction, in strong contrast to the typical in-plane easy axis for strained, phase pure LSMO thin films. The dominant contribution to the magnetic anisotropy in these (LSMO)0.1(ZnO)0.9 VAN films comes from the shape of the nanopillars, while the epitaxial strain at the vertical LSMO:ZnO interfaces exhibits a negligible effect. These VAN films with their large, out-of-plane remnant magnetization of 2.6 µB/Mn and bit density of 0.77 Tbits/inch2 offer an interesting strategy for enhanced data storage applications.

Stabilizing Perovskite Pb(Mg0.33Nb0.67)O3-PbTiO3 Thin Films by Fast Deposition and Tensile Mismatched Growth Template.

Because of its low hysteresis, high dielectric constant, and strong piezoelectric response, Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) thin films have attracted considerable attention for the application in PiezoMEMS, field-effect transistors, and energy harvesting and storage devices. However, it remains a great challenge to fabricate phase-pure, pyrochlore-free PMN-PT thin films. In this study, we demonstrate that a high deposition rate, combined with a tensile mismatched template layer can stabilize the perovskite phase of PMN-PT films and prevent the nucleation of passive pyrochlore phases. We observed that an accelerated deposition rate promoted mixing of the B-site cation and facilitated relaxation of the compressively strained PMN-PT on the SrTiO3 (STO) substrate in the initial growth layer, which apparently suppressed the initial formation of pyrochlore phases. By employing La-doped-BaSnO3 (LBSO) as the tensile mismatched buffer layer, 750 nm thick phase-pure perovskite PMN-PT films were synthesized. The resulting PMN-PT films exhibited excellent crystalline quality close to that of the STO substrate.

Thin Films of α-Quartz GeO2 on TiO2-Buffered Quartz Substrates.

α-Quartz (SiO2) is one of the most widely used piezoelectric materials. However, the challenges associated with the control of the crystallization and the growth process limit its production to the hydrothermal growth of bulk crystals. GeO2 can also crystallize into the α-quartz phase, with a higher piezoelectric response and better thermal stability than SiO2. In a previous study, we have found that GeO2 crystallization on nonquartz substrates shows a tendency to form spherulites with a randomized orientation; while epitaxial growth of crystalline GeO2 thin films can take place on quartz (SiO2) substrates. However, in the latter case, the α-ß phase transition that takes place in both substrates and thin films during heating deteriorates the long-range order and, thus, the piezoelectric properties. Here, we report the ousting of spherulitic growth by using a buffer layer. Using TiO2 as a buffer layer, the epitaxial strain of the substrates can be transferred to the growing films, leading to the oriented crystallization of GeO2 in the α-quartz phase. Moreover, since the TiO2 separates the substrates and the thin films, the thermal stability of the GeO2 is kept across the substrate's phase transitions. Our findings reveal the complexity of the crystallization process of quartz thin films and present a way to eliminate the tendency for spherulitic growth of quartz thin films by epitaxial strain.

Electronic and Structural Disorder of the Epitaxial La0.67Sr0.33MnO3 Surface.

Understanding and tuning epitaxial complex oxide films are crucial in controlling the behavior of devices and catalytic processes. Substrate-induced strain, doping, and layer growth are known to influence the electronic and magnetic properties of the bulk of the film. In this study, we demonstrate a clear distinction between the bulk and surface of thin films of La0.67Sr0.33MnO3 in terms of chemical composition, electronic disorder, and surface morphology. We use a combined experimental approach of X-ray-based characterization methods and scanning probe microscopy. Using X-ray diffraction and resonant X-ray reflectivity, we uncover surface nonstoichiometry in the strontium and lanthanum alongside an accumulation of oxygen vacancies. With scanning tunneling microscopy, we observed an electronic phase separation (EPS) on the surface related to this nonstoichiometry. The EPS is likely driving the temperature-dependent resistivity transition and is a cause of proposed mixed-phase ferromagnetic and paramagnetic states near room temperature in these thin films.

In Situ X-ray Absorption Spectroscopy of LaFeO3 and LaFeO3/LaNiO3 Thin Films in the Electrocatalytic Oxygen Evolution Reaction.

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO3 and LaFeO3/LaNiO3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La0.67Sr0.33MnO3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca2Nb3O10 nanosheet-buffered 100 nm SiNx membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiNx membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO3 film.

Experimental evidence for oxygen sublattice control in polar infinite layer SrCuO2.

A recent theoretical study [Phys. Rev. B 85, 121411(R) (2012)] predicted a thickness limit below which ideal polar cuprates turn nonpolar driven by the associated electrostatic instability. Here we demonstrate this possibility by inducing a structural transformation from the bulk planar to chainlike structure upon reducing the SrCuO2 repeat thickness in SrCuO2/SrTiO3 superlattices with unit-cell precision. Our results, based on structural investigation by x-ray diffraction and high resolution scanning transmission electron microscopy, demonstrate that the oxygen sublattice can essentially be built by design. In addition, the electronic structure of the chainlike structure, as studied by x-ray absorption spectroscopy, shows the signature for preferential hole occupation in the Cu 3d(3z2-r2) orbital, which is different from the planar case.

Robust SrTiO3 Passivation of Silicon Photocathode by Reduced Graphene Oxide for Solar Water Splitting.

Development of a robust photocathode using low-cost and high-performing materials, e.g., p-Si, to produce clean fuel hydrogen has remained challenging since the semiconductor substrate is easily susceptible to (photo)corrosion under photoelectrochemical (PEC) operational conditions. A protective layer over the substrate to simultaneously provide corrosion resistance and maintain efficient charge transfer across the device is therefore needed. To this end, in the present work, we utilized pulsed laser deposition (PLD) to prepare a high-quality SrTiO3 (STO) layer to passivate the p-Si substrate using a buffer layer of reduced graphene oxide (rGO). Specifically, a very thin (3.9 nm ∼10 unit cells) STO layer epitaxially overgrown on rGO-buffered Si showed the highest onset potential (0.326 V vs RHE) in comparison to the counterparts with thicker and/or nonepitaxial STO. The photovoltage, flat-band potential, and electrochemical impedance spectroscopy measurements revealed that the epitaxial photocathode was more beneficial for charge separation, charge transfer, and targeted redox reaction than the nonepitaxial one. The STO/rGO/Si with a smooth and highly epitaxial STO layer outperforming the directly contacted STO/Si with a textured and polycrystalline STO layer showed the importance of having a well-defined passivation layer. In addition, the numerous pinholes formed in the directly contacted STO/Si led to the rapid degradation of the photocathode during the PEC measurements. The stability tests demonstrated the soundness of the epitaxial STO layer in passivating Si against corrosion. This study provided a facile approach for preparing a robust protection layer over a photoelectrode substrate in realizing an efficient and, at the same time, durable PEC device.

Tiling the Silicon for Added Functionality: PLD Growth of Highly Crystalline STO and PZT on Graphene Oxide-Buffered Silicon Surface.

The application of two-dimensional (2D) materials has alleviated a number of challenges of traditional epitaxy and pushed forward the integration of dissimilar materials. Besides acting as a seed layer for van der Waals epitaxy, the 2D materials─being atom(s) thick─have also enabled wetting transparency in which the potential field of the substrate, although partially screened, is still capable of imposing epitaxial overgrowth. One of the crucial steps in this technology is the preservation of the quality of 2D materials during and after their transfer to a substrate of interest. In the present study, we show that by honing the achievements of traditional epitaxy and wet chemistry a hybrid approach can be devised that offers a unique perspective for the integration of functional oxides with a silicon platform. It is based on SrO-assisted deoxidation and controllable coverage of silicon surface with a layer(s) of spin-coated graphene oxide, thus simultaneously allowing both direct and van der Waals epitaxy of SrTiO3 (STO). We were able to grow a high-quality STO pseudo-substrate suitable for further overgrowth of functional oxides, such as PbZr1-xTixO3 (PZT). Given that the quality of the films grown on a reduced graphene oxide-buffer layer was almost identical to that obtained on SiC-derived graphene, we believe that this approach may provide new routes for direct and "remote" epitaxy or layer-transfer techniques of dissimilar material systems.

Stabilizing Crystal Framework of an Overlithiated Li1+xMn2O4 Cathode by Heterointerfacial Epitaxial Strain for High-Performance Microbatteries.

To meet the increasing demands of high-energy and high-power-density lithium-ion microbatteries, overlithiated Li1+xMn2O4 (0 ≤ x ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g-1 and the interconnected lithium-ion diffusion pathways. However, overlithiation triggers the irreversible cubic-tetragonal phase transition due to Jahn-Teller distortion, causing rapid capacity degradation. In contrast to conventional lithium-ion batteries, microbatteries offer the opportunity to develop specific thin-film-based modification strategies. Here, heterointerfacial lattice strain is proposed to stabilize the spinel crystal framework of an overlithiated Li1+xMn2O4 (LMO) cathode by epitaxial thin film growth on an underlying SrRuO3 (SRO) electronic conductor layer. It is demonstrated that the lattice misfit at the LMO/SRO heterointerface results in an in-plane epitaxial constraint in the full LMO film. This suppresses the lattice expansion during overlithiation that typically occurs in the in-plane direction. It is proposed by density functional theory modeling that the epitaxial constraint can accommodate the internal lattice stress originating from the cubic-tetragonal transition during overlithiation. As a result, a doubling of the capacity is achieved by reversibly intercalating a second lithium ion in a LiMn2O4 epitaxial cathode with a complete reversible phase transition. An impressive cycling stability can be obtained with reversible capacity retentions of above 90.3 and 77.4% for the 4 and 3 V range, respectively. This provides an effective strategy toward a stable overlithiated Li1+xMn2O4 epitaxial cathode for high-performance microbatteries.