Thermally Stable Capacitive Energy-Density and Colossal Electrocaloric and Pyroelectric Effects of Sm-Doped Pb(MgNb)O-PbTiO Thin Films.

Sm-doped Pb(MgNb)O-PbTiO (Sm-PMN-PT) bulk materials have revealed outstanding ferroelectric and piezoelectric properties due to enhanced local structural heterogeneity. In this study, we further explore the potential of Sm-PMN-PT by fabricating epitaxial thin films by pulsed laser deposition, revealing that Sm doping significantly improves the capacitive energy-storage, piezoelectric, electrocaloric, and pyroelectric properties of PMN-PT thin films. These Sm-PMN-PT thin films exhibit fatigue-free performance up to 10 charge-discharge cycles and maintain thermal stability across a wide temperature range from -40 to 200 °C.

Electronic and Structural Disorder of the Epitaxial LaSrMnO 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 LaSrMnO in terms of chemical composition, electronic disorder, and surface morphology.

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 BaSrTiO (BST) with relaxor-ferroelectric BaZrTiO (BZT) layers on SrTiO-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.

In Situ X-ray Absorption Spectroscopy of LaFeO and LaFeO/LaNiO 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 LaFeO and LaFeO/LaNiO thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive LaSrMnO layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer CaNbO nanosheet-buffered 100 nm SiN membranes.

Stabilizing Perovskite Pb(MgNb)O-PbTiO Thin Films by Fast Deposition and Tensile Mismatched Growth Template.

Because of its low hysteresis, high dielectric constant, and strong piezoelectric response, Pb(MgNb)O-PbTiO (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.

Thin Films of α-Quartz GeO on TiO-Buffered Quartz Substrates.

α-Quartz (SiO) 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. GeO can also crystallize into the α-quartz phase, with a higher piezoelectric response and better thermal stability than SiO.

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.

Stabilizing Crystal Framework of an Overlithiated LiMnO 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 LiMnO (0 ≤ ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g 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.

Robust SrTiO 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 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.

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.

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

Vanadium dioxide (VO) 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.

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

Hematite (α-FeO) 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 BaTiO 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 LaMnO/BaTiO/SrTiO 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 BaTiO layers with substantially enhanced tetragonality, as revealed by atomically resolved scanning transmission electron microscopy.

Growth and Crystallization of SiO/GeO 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.

Epitaxial lift-off of freestanding (011) and (111) SrRuO 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 SrRuO thin films using SrAlO water-sacrificial layer. The epitaxial SrAlO(011) and SrAlO(111) layers were realized on SrTiO(011) and SrTiO(111), respectively.

Femtosecond Charge Density Modulations in Photoexcited CuWO.

Copper tungstate (CuWO) 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 CuWO. The Cu L 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.

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

Angle-dependent 2p3d resonant inelastic X-ray scattering spectra of a LaCoO single crystal and a 55 nm LaCoO film on a SrTiO 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 A(O) 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 LaCoO single crystal and limit the observation of small angular dependence.

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 NdNiO/SrTiO superlattices by controlling the NdNiO layer thickness, 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 = 8 to a uniform nontilt pattern at = 4, accompanied by a drastically weakened insulating ground state.

Growth mode and strain effect on relaxor ferroelectric domains in epitaxial 0.67Pb(MgNb)O-0.33PbTiO/SrRuO 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.

Strain-Engineered Metal-to-Insulator Transition and Orbital Polarization in Nickelate Superlattices Integrated on Silicon.

Epitaxial growth of SrTiO (STO) on silicon greatly accelerates the monolithic integration of multifunctional oxides into the mainstream semiconductor electronics. However, oxide superlattices (SLs), the birthplace of many exciting discoveries, remain largely unexplored on silicon. In this work, LaNiO /LaFeO SLs are synthesized on STO-buffered silicon (Si/STO) and STO single-crystal substrates, and their electronic properties are compared using dc transport and X-ray absorption spectroscopy.

Integration of Single Oriented Oxide Superlattices on Silicon Using Various Template Techniques.

To benefit from the diverse functionalities of perovskite oxides in silicon-based complementary metal oxide semiconductor (CMOS) technology, integrating oxides into a silicon platform has become one of the major tasks for oxide research. Using the deposition of LaMnO/SrTiO (STO) superlattices (SLs) as a case study, we demonstrate that (001) single oriented oxide SLs can be integrated on Si using various template techniques, including a single-layer buffer of STO prepared by molecular beam epitaxy (MBE) and pulsed laser deposition, a multilayer buffer of Y-stabilized zirconia/CeO/LaNiO/STO, and STO-coated two-dimensional nanosheets of CaNbO (CNO) and reduced graphene oxide. The textured SL grown on STO-coated CNO nanosheets shows the highest crystallinity, owing to the small lattice mismatch between CNO and STO as well as less clamping from a Si substrate.

Simultaneous heteroepitaxial growth of SrO (001) and SrO (111) during strontium-assisted deoxidation of the Si (001) surface.

Epitaxial integration of transition-metal oxides with silicon brings a variety of functional properties to the well-established platform of electronic components. In this process, deoxidation and passivation of the silicon surface are one of the most important steps, which in our study were controlled by an ultra-thin layer of SrO and monitored by using transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), synchrotron X-ray diffraction (XRD) and reflection high energy electron diffraction (RHEED) methods. Results revealed that an insufficient amount of SrO leads to uneven deoxidation of the silicon surface formation of pits and islands, whereas the composition of the as-formed heterostructure gradually changes from strontium silicide at the interface with silicon, to strontium silicate and SrO in the topmost layer.

Resistive switching studies in VO thin films.

The hysteretic insulator-to-metal transition of VO is studied in detail for pulsed laser deposition grown thin films on TiO substrates, under variation of temperature and applied bias currents. This system is of interest for novel electronics based on memristive concepts, in particular as the resistive transition in these films occurs close to room temperature. Multiple, stable resistance states can be set controllably in the temperature range of the hysteretic phase transition by tailored temperature sweeps or by Joule heating induced by current pulses.