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.

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.

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.

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.

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.

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.

A broad-spectrum gas sensor based on correlated two-dimensional electron gas.

Designing a broad-spectrum gas sensor capable of identifying gas components in complex environments, such as mixed atmospheres or extreme temperatures, is a significant concern for various technologies, including energy, geological science, and planetary exploration. The main challenge lies in finding materials that exhibit high chemical stability and wide working temperature range. Materials that amplify signals through non-chemical methods could open up new sensing avenues. Here, we present the discovery of a broad-spectrum gas sensor utilizing correlated two-dimensional electron gas at a delta-doped LaAlO3/SrTiO3 interface with LaFeO3. Our study reveals that a back-gating on this two-dimensional electron gas can induce a non-volatile metal to insulator transition, which consequently can activate the two-dimensional electron gas to sensitively and quantitatively probe very broad gas species, no matter whether they are polar, non-polar, or inert gases. Different gas species cause resistance change at their sublimation or boiling temperature and a well-defined phase transition angle can quantitatively determine their partial pressures. Such unique correlated two-dimensional electron gas sensor is not affected by gas mixtures and maintains a wide operating temperature range. Furthermore, its readout is a simple measurement of electric resistance change, thus providing a very low-cost and high-efficient broad-spectrum sensing technique.

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.

A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation.

High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e., the key kinetically limiting half-reaction in several electrochemical energy conversion technologies, including green hydrogen generation. We compare the activity of the (001) facet of LaCr0.2Mn0.2Fe0.2Co0.2Ni0.2O3-δ with the parent compounds (single B-site in the ABO3 perovskite). While the single B-site perovskites roughly follow the expected volcano-type activity trends, the HEO clearly outperforms all of its parent compounds with 17 to 680 times higher currents at a fixed overpotential. As all samples were grown as an epitaxial layer, our results indicate an intrinsic composition-function relationship, avoiding the effects of complex geometries or unknown surface composition. In-depth X-ray photoemission studies reveal a synergistic effect of simultaneous oxidation and reduction of different transition metal cations during the adsorption of reaction intermediates. The surprisingly high OER activity demonstrates that HEOs are a highly attractive, earth-abundant material class for high-activity OER electrocatalysts, possibly allowing the activity to be fine-tuned beyond the scaling limits of mono- or bimetallic oxides.

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.

Hole Dynamics in Photoexcited Hematite Studied with Femtosecond Oxygen K-edge X-ray Absorption Spectroscopy.

Hematite (α-Fe2O3) is a photoelectrode for the water splitting process because of its relatively narrow bandgap and abundance in the earth's crust. In this study, the photoexcited state of a hematite thin film was investigated with femtosecond oxygen K-edge X-ray absorption spectroscopy (XAS) at the PAL-XFEL in order to follow the dynamics of its photoexcited states. The 200 fs decay time of the hole state in the valence band was observed via its corresponding XAS feature.

Signatures of enhanced out-of-plane polarization in asymmetric BaTiO3 superlattices integrated on silicon.

In order to bring the diverse functionalities of transition metal oxides into modern electronics, it is imperative to integrate oxide films with controllable properties onto the silicon platform. Here, we present asymmetric LaMnO3/BaTiO3/SrTiO3 superlattices fabricated on silicon with layer thickness control at the unit-cell level. By harnessing the coherent strain between the constituent layers, we overcome the biaxial thermal tension from silicon and stabilize c-axis oriented BaTiO3 layers with substantially enhanced tetragonality, as revealed by atomically resolved scanning transmission electron microscopy. Optical second harmonic generation measurements signify a predominant out-of-plane polarized state with strongly enhanced net polarization in the tricolor superlattices, as compared to the BaTiO3 single film and conventional BaTiO3/SrTiO3 superlattice grown on silicon. Meanwhile, this coherent strain in turn suppresses the magnetism of LaMnO3 as the thickness of BaTiO3 increases. Our study raises the prospect of designing artificial oxide superlattices on silicon with tailored functionalities.

High-Strain-Induced Local Modification of the Electronic Properties of VO2 Thin Films.

Vanadium dioxide (VO2) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long- and short-range elastic distortions, as well as the symmetry change and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue toward mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO2-metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO2. The tunneling barrier is formed by a very thin but persistently insulating surface layer of the VO2. The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics.

Growth and Crystallization of SiO2/GeO2 Thin Films on Si(100) Substrates.

The growth of α-quartz-based piezoelectric thin films opens the door to higher-frequency electromechanical devices than those available through top-down approaches. We report on the growth of SiO2/GeO2 thin films by pulsed laser deposition and their subsequent crystallization. By introducing a devitrifying agent uniformly within the film, we are able to obtain the α-quartz phase in the form of platelets with lateral sizes above 100 µm at accessible temperatures. Films containing different amounts of devitrifying agent are investigated, and their crystallinity is ascertained with X-ray diffraction and electron back-scatter diffraction. Our work highlights the difficulty in crystallization when competing phases arise that have markedly different crystalline orientation.

Epitaxial lift-off of freestanding (011) and (111) SrRuO3 thin films using a water sacrificial layer.

Two-dimensional freestanding thin films of single crystalline oxide perovskites are expected to have great potential in integration of new features to the current Si-based technology. Here, we showed the ability to create freestanding single crystalline (011)- and (111)-oriented SrRuO3 thin films using Sr3Al2O6 water-sacrificial layer. The epitaxial Sr3Al2O6(011) and Sr3Al2O6(111) layers were realized on SrTiO3(011) and SrTiO3(111), respectively. Subsequently, SrRuO3 films were epitaxially grown on these sacrificial layers. The freestanding single crystalline SrRuO3(011)pc and SrRuO3(111)pc films were successfully transferred on Si substrates, demonstrating possibilities to transfer desirable oriented oxide perovskite films on Si and arbitrary substrates.

Femtosecond Charge Density Modulations in Photoexcited CuWO4.

Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.

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.

Growth mode and strain effect on relaxor ferroelectric domains in epitaxial 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3/SrRuO3 heterostructures.

Controlling the growth of complex relaxor ferroelectric thin films and understanding the relationship between biaxial strain-structural domain characteristics are desirable for designing materials with a high electromechanical response. For this purpose, epitaxial thin films free of extended defects and secondary phases are urgently needed. Here, we used optimized growth parameters and target compositions to obtain epitaxial (40-45 nm) 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3/(20 nm) SrRuO3 (PMN-33PT/SRO) heterostructures using pulsed-laser deposition (PLD) on singly terminated SrTiO3 (STO) and ReScO3 (RSO) substrates with Re = Dy, Tb, Gd, Sm, and Nd. In situ reflection high-energy electron diffraction (RHEED) and high-resolution X-ray diffraction (HR-XRD) analysis confirmed high-quality and single-phase thin films with smooth 2D surfaces. High-resolution scanning transmission electron microscopy (HR-STEM) revealed sharp interfaces and homogeneous strain further confirming the epitaxial cube-on-cube growth mode of the PMN-33PT/SRO heterostructures. The combined XRD reciprocal space maps (RSMs) and piezoresponse force microscopy (PFM) analysis revealed that the domain structure of the PMN-33PT heterostructures is sensitive to the applied compressive strain. From the RSM patterns, an evolution from a butterfly-shaped diffraction pattern for mildly strained PMN-33PT layers, which is evidence of stabilization of relaxor domains, to disc-shaped diffraction patterns for high compressive strains with a highly distorted tetragonal structure, is observed. The PFM amplitude and phase of the PMN-33PT thin films confirmed the relaxor-like for a strain state below ∼1.13%, while for higher compressive strain (∼1.9%) the irregularly shaped and poled ferroelectric domains were observed. Interestingly, the PFM phase hysteresis loops of the PMN-33PT heterostructures grown on the SSO substrates (strain state of ∼0.8%) exhibited an enhanced coercive field which is about two times larger than that of the thin films grown on GSO and NSO substrates. The obtained results show that epitaxial strain engineering could serve as an effective approach for tailoring and enhancing the functional properties in relaxor ferroelectrics.