Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces.

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts' functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment.

Space charge governs the kinetics of metal exsolution.

Nanostructured composite electrode materials play a major role in the fields of catalysis and electrochemistry. The self-assembly of metallic nanoparticles on oxide supports via metal exsolution relies on the transport of reducible dopants towards the perovskite surface to provide accessible catalytic centres at the solid-gas interface. At surfaces and interfaces, however, strong electrostatic gradients and space charges typically control the properties of oxides.

Crystal-facet-dependent surface transformation dictates the oxygen evolution reaction activity in lanthanum nickelate.

Electrocatalysts are the cornerstone in the transition to sustainable energy technologies and chemical processes. Surface transformations under operation conditions dictate the activity and stability. However, the dependence of the surface structure and transformation on the exposed crystallographic facet remains elusive, impeding rational catalyst design.

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.

Atomistic Insights into Activation and Degradation of LaSrCoO Electrocatalysts under Oxygen Evolution Conditions.

The stability of perovskite oxide catalysts for the oxygen evolution reaction (OER) plays a critical role in their applicability in water splitting concepts. Decomposition of perovskite oxides under applied potential is typically linked to cation leaching and amorphization of the material. However, structural changes and phase transformations at the catalyst surface were also shown to govern the activity of several perovskite electrocatalysts under applied potential.

Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis.

The oxygen evolution reaction (OER) is one of the key kinetically limiting half reactions in electrochemical energy conversion. Model epitaxial catalysts have emerged as a platform to identify structure-function-relationships at the atomic level, a prerequisite to establish advanced catalyst design rules. Previous work identified an inverse relationship between activity and the stability of noble metal and oxide OER catalysts in both acidic and alkaline environments: The most active catalysts for the anodic OER are chemically unstable under reaction conditions leading to fast catalyst dissolution or amorphization, while the most stable catalysts lack sufficient activity.

Evolution of surface and sub-surface morphology and chemical state of exsolved Ni nanoparticles.

Nanoparticle formation by dopant exsolution (migration) from bulk host lattices is a promising approach to generate highly stable nanoparticles with tunable size, shape, and distribution. We investigated Ni dopant migration from strontium titanate (STO) lattices, forming metallic Ni nanoparticles at STO surfaces. scanning probe measurements confirmed the presence of nanoparticles at the H treated surface.

Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysis.

The Co-O covalency in perovskite oxide cobaltites such as LaSrCoO is believed to impact the electrocatalytic activity during electrochemical water splitting at the anode where the oxygen evolution reaction (OER) takes place. Additionally, space charge layers through band bending at the interface to the electrolyte may affect the electron transfer into the electrode, complicating the analysis and identification of true OER activity descriptors. Here, we separate the influence of covalency and band bending in hybrid epitaxial bilayer structures of highly OER-active LaSrCoO and undoped and less-active LaCoO.

Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions.

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La Sr MnO epitaxial thin films, both at the surface and throughout the bulk.

Local inhomogeneities resolved by scanning probe techniques and their impact on local 2DEG formation in oxide heterostructures.

Lateral inhomogeneities in the formation of two-dimensional electron gases (2DEG) directly influence their electronic properties. Understanding their origin is an important factor for fundamental interpretations, as well as high quality devices. Here, we studied the local formation of the buried 2DEG at LaAlO/SrTiO (LAO/STO) interfaces grown on STO (100) single crystals with partial TiO termination, utilizing conductive atomic force microscopy (c-AFM) and scattering-type scanning near-field optical microscopy (s-SNOM).

Exsolution of Embedded Nanoparticles in Defect Engineered Perovskite Layers.

Exsolution phenomena are highly debated as efficient synthesis routes for nanostructured composite electrode materials for the application in solid oxide cells (SOCs) and the development of next-generation electrochemical devices for energy conversion. Utilizing the instability of perovskite oxides, doped with electrocatalytically active elements, highly dispersed nanoparticles can be prepared at the perovskite surface under the influence of a reducing heat treatment. For the systematic study of the mechanistic processes governing metal exsolution, epitaxial SrTiNbNiO thin films of well-defined stoichiometry are synthesized and employed as model systems to investigate the interplay of defect structures and exsolution behavior.

Tuning electrochemically driven surface transformation in atomically flat LaNiO thin films for enhanced water electrolysis.

Structure-activity relationships built on descriptors of bulk and bulk-terminated surfaces are the basis for the rational design of electrocatalysts. However, electrochemically driven surface transformations complicate the identification of such descriptors. Here we demonstrate how the as-prepared surface composition of (001)-terminated LaNiO epitaxial thin films dictates the surface transformation and the electrocatalytic activity for the oxygen evolution reaction.

Identifying Ionic and Electronic Charge Transfer at Oxide Heterointerfaces.

The ability to tailor oxide heterointerfaces has led to novel properties in low-dimensional oxide systems. A fundamental understanding of these properties is based on the concept of electronic charge transfer. However, the electronic properties of oxide heterointerfaces crucially depend on their ionic constitution and defect structure: ionic charges contribute to charge transfer and screening at oxide interfaces, triggering a thermodynamic balance of ionic and electronic structures.

Electronic Inhomogeneity Influence on the Anomalous Hall Resistivity Loops of SrRuO Epitaxially Interfaced with 5d Perovskites.

SrRuO, a 4d ferromagnet with multiple Weyl nodes at the Fermi level, offers a rich playground to design epitaxial heterostructures and superlattices with fascinating magnetic and magnetotransport properties. Interfacing ultrathin SrRuO layers with large spin-orbit coupling 5d transition-metal oxides, such as SrIrO, results in pronounced peaklike anomalies in the magnetic field dependence of the Hall resistivity. Such anomalies have been attributed either to the formation of Néel-type skyrmions or to modifications of the Berry curvature of the topologically nontrivial conduction bands near the Fermi level of SrRuO.

UV radiation enhanced oxygen vacancy formation caused by the PLD plasma plume.

Pulsed Laser Deposition is a commonly used non-equilibrium physical deposition technique for the growth of complex oxide thin films. A wide range of parameters is known to influence the properties of the used samples and thin films, especially the oxygen-vacancy concentration. One parameter has up to this point been neglected due to the challenges of separating its influence from the influence of the impinging species during growth: the UV-radiation of the plasma plume.

A SIMS study of cation and anion diffusion in tantalum oxide.

Ion transport in ceramics of the low-temperature phase of tantalum pentoxide, L-TaO, was examined by means of diffusion experiments and subsequent analysis of diffusion profiles with time-of-flight secondary ion mass spectrometry (ToF-SIMS). O/O isotope anneals were used to investigate oxygen diffusion, and oxygen tracer diffusion coefficients were obtained for the temperature range of 623 ≤ T/K ≤ 873 at an oxygen partial pressure of pO = 0.2 bar and for the oxygen partial pressure range of 10 ≤ pO/bar ≤ 10 at a temperature of T = 723 K.

Mobility Modulation and Suppression of Defect Formation in Two-Dimensional Electron Systems by Charge-Transfer Management.

Electron mobility is one of the most-debated key attributes of low-dimensional electron systems emerging at complex oxide heterointerfaces. However, a common understanding of how electron mobility can be optimized in these systems has not been achieved so far. Here, we discuss a novel approach for achieving a systematic increase in electron mobility in polar/nonpolar perovskite interfaces by suppressing the thermodynamically required defect formation at the nanoscale.

Unraveling the enhanced Oxygen Vacancy Formation in Complex Oxides during Annealing and Growth.

The reduction of oxides during annealing and growth in low pressure processes is a widely known problem. We hence investigate the influence of mere annealing and of growth in vacuum systems to shed light on the reasons behind the reduction of perovskites. When comparing the existing literature regarding the reduction of the perovskite model material SrTiO it is conspicuous that one finds different oxygen pressures required to achieve reduction for vacuum annealing and for chemically controlled reducing atmospheres.

Thermodynamic Ground States of Complex Oxide Heterointerfaces.

The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature equilibrium conductivity measurements. We unambiguously identify two distinct classes of oxide heterostructures: For epitaxial perovskite/perovskite heterointerfaces (LaAlO/SrTiO, NdGaO/SrTiO, and (La,Sr)(Al,Ta)O/SrTiO), we find the 2DEG formation being based on charge transfer into the interface, stabilized by the electric field in the space charge region.

Homogeneity and variation of donor doping in Verneuil-grown SrTiO3:Nb single crystals.

The homogeneity of Verneuil-grown SrTiO3:Nb crystals was investigated. Due to the fast crystal growth process, inhomogeneities in the donor dopant distribution and variation in the dislocation density are expected to occur. In fact, for some crystals optical studies show variations in the density of Ti(3+) states on the microscale and a cluster-like surface conductivity was reported in tip-induced resistive switching studies.

Verification of redox-processes as switching and retention failure mechanisms in Nb:SrTiO3/metal devices.

Nanoscale redox reactions in transition metal oxides are believed to be the physical foundation of memristive devices, which present a highly scalable, low-power alternative for future non-volatile memory devices. The interface between noble metal top electrodes and Nb-doped SrTiO3 single crystals may serve as a prominent but not yet well-understood example of such memristive devices. In this report, we will present experimental evidence that nanoscale redox reactions and the associated valence change mechanism are indeed responsible for the resistance change in noble metal/Nb-doped SrTiO3 junctions with dimensions ranging from the micrometer scale down to the nanometer regime.

Disentanglement of growth dynamic and thermodynamic effects in LaAlO3/SrTiO3 heterostructures.

The influence of non-equilibrium and equilibrium processes during growth of LaAlO3/SrTiO3 (LAO/STO) heterostructures is analyzed. We investigate the electronic properties of LAO/STO heterostructures obtained at constant growth conditions after annealing in different oxygen atmospheres within the typical growth window (1 × 10(-4) mbar -1 × 10(-2) mbar). The variation of annealing conditions is found to cause a similar change of electronic properties as observed for samples grown in different oxygen pressure.

The influence of the local oxygen vacancy concentration on the piezoresponse of strontium titanate thin films.

In this study, the influence of the local oxygen vacancy concentration on piezoresponse force microscopy (PFM) measurements was investigated. Ultra-thin single-crystalline SrTiO3 thin films were deposited on niobium doped SrTiO3 substrates and analyzed using a combined PFM and local conductive atomic force microscopy (LC-AFM) measurement setup. After applying different polarization voltages between ±2 V and ±5 V to the thin films, we simultaneously observed an anomalous contrast in the piezoresponse amplitude and phase signal as well as a changed local conductivity in the exact same region.

Surface Termination Conversion during SrTiO3 Thin Film Growth Revealed by X-ray Photoelectron Spectroscopy.

Emerging electrical and magnetic properties of oxide interfaces are often dominated by the termination and stoichiometry of substrates and thin films, which depend critically on the growth conditions. Currently, these quantities have to be measured separately with different sophisticated techniques. This report will demonstrate that the analysis of angle dependent X-ray photoelectron intensity ratios provides a unique tool to determine both termination and stoichiometry simultaneously in a straightforward experiment.

Transport limits in defect-engineered LaAlO3/SrTiO3 bilayers.

The electrical properties of the metallic interface in LaAlO3/SrTiO3 (LAO/STO) bilayers are investigated with focus on the role of cationic defects in thin film STO. Systematic growth-control of the STO thin film cation stoichiometry (defect-engineering) yields a relation between cationic defects in the STO layer and electronic properties of the bilayer-interface. Hall measurements reveal a stoichiometry-effect primarily on the electron mobility.