ABSTRACT
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 in situ 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.
ABSTRACT
Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal-air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite's catalytic activity toward this important reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.
ABSTRACT
Fast, reversible redox reactions in solids at low temperatures without thermomechanical degradation are a promising strategy for enhancing the overall performance and lifetime of many energy materials and devices. However, the robust nature of the cation's oxidation state and the high thermodynamic barrier have hindered the realization of fast catalysis and bulk diffusion at low temperatures. Here, we report a significant lowering of the redox temperature by epitaxial stabilization of strontium cobaltites (SrCoO(x)) grown directly as one of two distinct crystalline phases, either the perovskite SrCoO(3-δ) or the brownmillerite SrCoO(2.5). Importantly, these two phases can be reversibly switched at a remarkably reduced temperature (200-300 °C) in a considerably short time (< 1 min) without destroying the parent framework. The fast, low-temperature redox activity in SrCoO(3-δ) is attributed to a small Gibbs free-energy difference between two topotatic phases. Our findings thus provide useful information for developing highly sensitive electrochemical sensors and low-temperature cathode materials.
ABSTRACT
The ferroelectric (FE) control of electronic transport is one of the emerging technologies in oxide heterostructures. Many previous studies in FE tunnel junctions (FTJs) exploited solely the differences in the electrostatic potential across the FTJs that are induced by changes in the FE polarization direction. Here, we show that in practice the junction current ratios between the two polarization states can be further enhanced by the electrostatic modification in the correlated electron oxide electrodes, and that FTJs with nanometer thin layers can effectively produce a considerably large electroresistance ratio at room temperature. To understand these surprising results, we employed an additional control parameter, which is related to the crossing of electronic and magnetic phase boundaries of the correlated electron oxide. The FE-induced phase modulation at the heterointerface ultimately results in an enhanced electroresistance effect. Our study highlights that the strong coupling between degrees of freedom across heterointerfaces could yield versatile and novel applications in oxide electronics.
Subject(s)
Electric Conductivity , Iron/chemistry , Oxides/chemistry , Electrons , Nanostructures/chemistry , Phase TransitionABSTRACT
Using real-time spectroscopic ellipsometry, we directly observed a reversible lattice and electronic structure evolution in SrCoO(x) (x=2.5-3) epitaxial thin films. Drastically different electronic ground states, which are extremely susceptible to the oxygen content x, are found in the two topotactic phases: i.e., the brownmillerite SrCoO2.5 and the perovskite SrCoO3. First-principles calculations confirmed substantial differences in the electronic structure, including a metal-insulator transition, which originate from the modification in the Co valence states and crystallographic structures. More interestingly, the two phases can be reversibly controlled by changing the ambient pressure at greatly reduced temperatures. Our finding provides an important pathway to understanding the novel oxygen-content-dependent phase transition uniquely found in multivalent transition metal oxides.
ABSTRACT
Epitaxial strain imposed in complex oxide thin films by heteroepitaxy is recognized as a powerful tool for identifying new properties and exploring the vast potential of materials performance. A particular example is LaCoO(3), a zero spin, nonmagnetic material in the bulk, whose strong ferromagnetism in a thin film remains enigmatic despite a decade of intense research. Here, we use scanning transmission electron microscopy complemented by X-ray and optical spectroscopy to study LaCoO(3) epitaxial thin films under different strain states. We observed an unconventional strain relaxation behavior resulting in stripe-like, lattice modulated patterns, which did not involve uncontrolled misfit dislocations or other defects. The modulation entails the formation of ferromagnetically ordered sheets comprising intermediate or high spin Co(3+), thus offering an unambiguous description for the exotic magnetism found in epitaxially strained LaCoO(3) films. This observation provides a novel route to tailoring the electronic and magnetic properties of functional oxide heterostructures.
Subject(s)
Cobalt/chemistry , Lanthanum/chemistry , Metal Nanoparticles/chemistry , Metal Nanoparticles/ultrastructure , Oxides/chemistry , Elastic Modulus , Magnetic Fields , Materials Testing , Particle SizeABSTRACT
Thermal transistors have potential as thermal management devices because they can electrically control the thermal conductivity (κ) of the active layer. Recently, we realized solid-state electrochemical thermal transistors by utilizing the electrochemical redox reaction of SrCoOy (2 ≤ y ≤ 3). However, the guiding principle to improve the on/off κ ratio has yet to be clarified because the κ modulation mechanism is unclear. This study systematically modulates κ of SrCo1-xFexOy (0 ≤ x ≤ 1, 2 ≤ y ≤ 3) solid solutions used as the active layers in solid-state electrochemical thermal transistors. When y = 3, the lattice κ of SrCo1-xFexOy is â¼2.8 W m-1 K-1 and insensitive to x. When x = 0 and y = 3, κ increases to â¼3.8 W m-1 K-1 due to the contribution of the electron κ. When y = 2, κ slightly depends on the ordered atomic arrangement. Materials that are high electrical conductors with highly ordered lattices when the transistor is on but are electrical insulators with disordered lattices when the transistor is off should be well-suited for the active layers of solid-state electrochemical thermal transistors.
ABSTRACT
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 electrochemical applications.
ABSTRACT
Controlling the oxide ion (O2-) concentration in oxides is essential to develop advanced ionic devices, i.e. solid oxide fuel cells, smart windows, memory devices, energy storage devices, and so on. Among many oxides several transition metal (TM)-based perovskite oxides show high oxide ion conductivity, and their physical properties show high sensitivity to the change of the oxide ion concentration. Here, the change in the oxide ion concentration is shown through the overlayer deposition on the SrFe0.5Co0.5O2.5 (SFCO) oxygen sponge film. We grew SFCO films followed by the deposition of two kinds of complex oxide films under exactly the same growth conditions, and observed the changes in the crystal structure, valence states, and magnetic ground states. As the NSMO overlayer grows, strong evidence of oxidation at the O K edge is shown. In addition, the Fe4+ feature is revealed, and the electron valence state of Co increased from 3 to 3.25. The oxide ion concentration of SFCO changes during layer growth due to oxidation or reduction due to differences in chemical potential. The present results might be useful to develop advanced ionic devices using TM-based perovskite oxides.
ABSTRACT
Materials having an anisotropic crystal structure often exhibit anisotropy in the electrical conductivity. Compared to complex transition-metal oxides (TMOs), simple TMOs rarely show large anisotropic electrical conductivity due to their simple crystal structure. Here, we focus on the anisotropy in the electrical conductivity of a simple TMO, oxygen-deficient tungsten oxide (WOx) with an anisotropic crystal structure. We fabricated several WOx films by the pulsed laser deposition technique on the lattice-matched (110)-oriented LaAlO3 substrate under a controlled oxygen atmosphere. The crystallographic analyses of the WOx films revealed that highly dense atomic defect tunnels were aligned one-dimensionally (1D) along [001] LaAlO3. The electrical conductivity along the 1D atomic defect tunnels was â¼5 times larger than that across the tunnels. The present approach, introduction of 1D atomic defect tunnels, might be useful to design simple TMOs exhibiting anisotropic electrical conductivity.
ABSTRACT
Nitrogen ion implantation is a useful technique to put nitrogen ions into lattices. In this work, nitrogen ion implantation into epitaxial Mo films is performed to create a buried superconducting γ-Mo2N. Atomically flat epitaxial (110) Mo films are grown on (0001) Al2O3. By impinging nitrogen ions, where the beam energy is fixed to 20 keV, we observe (111) γ-Mo2N diffraction and the formation of a γ-Mo2N layer from X-ray reflectivity. Magnetization and transport measurements clearly support a superconducting layer in the implanted film. Our strategy shows that formation of a buried superconducting layer can be achieved through ion implantation and self-annealing.
ABSTRACT
The functional perovskite La1-x Sr x MnO3 (LSMO) possesses various exotic phases owing to competing physical parameters and internal degrees of freedom. In particular, the nature of the ferromagnetic insulating phase (FMI) has not been adequately explored, resulting in a limited understanding of the relationship between crystal structure and magnetism. To investigate this structure-property relationship, epitaxial La0.88Sr0.12MnO3 thin films were grown on two different substrates, (001) SrTiO3 and (001) (LaAlO3)0.3(Sr2AlTaO6)0.7, by pulsed laser deposition. Element-specific and surface-sensitive techniques were applied in conjunction with bulk magnetometry to investigate the inextricable link between the structures and magnetic properties of the films and the effects of tuning the strain. The results unambiguously demonstrate that structure-property relationship of a FMI LSMO tuned by strain has a crucial role for manipulating the properties in the FMI regime.
ABSTRACT
The slow kinetics of the oxygen reduction and evolution reactions (ORR, OER) hinder energy conversion and storage in alkaline fuel cells and electrolyzers employing abundant transition metal oxide catalysts. Systematic studies linking material properties to catalytic activity are lacking, in part due to the heterogeneous nature of powder-based electrodes. We demonstrate, for the first time, that epitaxial strain can tune the activity of oxygen electrocatalysis in alkaline solutions, focusing on the model chemistry of LaCoO3, where moderate tensile strain can further induce changes in the electronic structure leading to increased activity. The resultant decrease in charge transfer resistance to the electrolyte reduces the overpotential in the ORR more notably than the OER and suggests a different dependence of the respective rate-limiting steps on electron transfer. This provides new insight into the reaction mechanism applicable to a range of perovskite chemistries, key to the rational design of highly active catalysts.
ABSTRACT
A strategy to enhance the catalytic activity at the surface of an oxide thin film is unveiled through epitaxial orientation control of the surface oxygen vacancy concentration. By tuning the direction of the oxygen vacancy channels (OVCs) in the brownmillerite SrCoO2.5 , a 100-fold improvement in the oxygen reduction kinetics is realized in an epitaxial thin film that has the OVCs open to the surface.