Is Reduced Strontium Titanate a Semiconductor or a Metal?

In recent decades, the behavior of SrTiO3 upon annealing in reducing conditions has been under intense academic scrutiny. Classically, its conductivity can be described using point defect chemistry and predicting n-type or p-type semiconducting behavior depending on oxygen activity. In contrast, many examples of metallic behavior induced by thermal reduction have recently appeared in the literature, challenging this established understanding. In this study, we aim to resolve this contradiction by demonstrating that an initially insulating, as-received SrTiO3 single crystal can indeed be reduced to a metallic state, and is even stable against room temperature reoxidation. However, once the sample has been oxidized at a high temperature, subsequent reduction can no longer be used to induce metallic behavior, but semiconducting behavior in agreement with the predictions of point defect chemistry is observed. Our results indicate that the dislocation-rich surface layer plays a decisive role and that its local chemical composition can be changed depending on annealing conditions. This reveals that the prediction of the macroscopic electronic properties of SrTiO3 is a highly complex task, and not only the current temperature and oxygen activity but also the redox history play an important role

A physical method for investigating defect chemistry in solid metal oxides

The investigation of the defect chemistry of solid oxides is of central importance for the understanding of redox processes. This can be performed by measuring conductivity as a function of the oxygen partial pressure, which is conventionally established by using buffer gas mixtures or oxygen pumps based on zirconia. However, this approach has some limitations, such as difficulty regulating oxygen partial pressure in some intermediate-pressure regions or the possibility of influencing the redox process by gases that can also be incorporated into the oxide or react with the surface via heterogeneous catalysis. Herein, we present an alternative physical method in which the oxygen partial pressure is controlled by dosing pure oxygen inside an ultra-high vacuum chamber. To monitor the conductivity of the oxide under investigation, we employ a dedicated four-probe measurement system that relies on the application of a very small AC voltage, in combination with lock-in data acquisition using highly sensitive electrometers, minimizing the electrochemical polarization or electro-reduction and degradation effects. By analyzing the model material SrTiO3, we demonstrate that its characteristic redox behavior can be reproduced in good agreement with the theory when performing simultaneous electrical conductivity relaxation (ECR) and high-temperature equilibrium conductivity (HTEC) measurements. We show that the use of pure oxygen allows for a direct analysis of the characteristic oxygen dose, which opens up various perspectives for a detailed analysis of the surface chemistry of redox processes.Comment: 25 page

Kelvin probe force microscopy work function characterization of transition metal oxide crystals under ongoing reduction and oxidation

Controlling the work function of transition metal oxides is of key importance with regard to future energy production and storage. As the majority of applications involve the use of heterostructures, the most suitable characterization technique is Kelvin probe force microscopy (KPFM), which provides excellent energetic and lateral resolution. In this paper, we demonstrate precise characterization of the work function using the example of artificially formed crystalline titanium monoxide (TiO) nanowires on strontium titanate (SrTiO3) surfaces, providing a sharp atomic interface. The measured value of 3.31(21) eV is the first experimental work function evidence for a cubic TiO phase, where significant variations among the different crystallographic facets were also observed. Despite the remarkable height of the TiO nanowires, KPFM was implemented to achieve a high lateral resolution of 15 nm, which is close to the topographical limit. In this study, we also show the unique possibility of obtaining work function and conductivity maps on the same area by combining noncontact and contact modes of atomic force microscopy (AFM). As most of the real applications require ambient operating conditions, we have additionally checked the impact of air venting on the work function of the TiO/SrTiO3(100) heterostructure, proving that surface reoxidation occurs and results in a work function increase of 0.9 eV and 0.6 eV for SrTiO3 and TiO, respectively. Additionally, the influence of adsorbed surface species was estimated to contribute 0.4 eV and 0.2 eV to the work function of both structures. The presented method employing KPFM and local conductivity AFM for the characterization of the work function of transition metal oxides may help in understanding the impact of reduction and oxidation on electronic properties, which is of high importance in the development of effective sensing and catalytic devices

Influence of dislocations in transition metal oxides on selected physical and chemical properties

Studies on dislocations in prototypic binary and ternary oxides (here TiO2 and SrTiO3) using modern TEM and scanning probe microscopy (SPM) techniques, combined with classical etch pits methods, are reviewed. Our review focuses on the important role of dislocations in the insulator-to-metal transition and for redox processes, which can be preferentially induced along dislocations using chemical and electrical gradients. It is surprising that, independently of the growth techniques, the density of dislocations in the surface layers of both prototypical oxides is high (109/cm2 for epipolished surfaces and up to 1012/cm2 for the rough surface). The TEM and locally-conducting atomic force microscopy (LCAFM) measurements show that the dislocations create a network with the character of a hierarchical tree. The distribution of the dislocations in the plane of the surface is, in principle, inhomogeneous, namely a strong tendency for the bundling and creation of arrays or bands in the crystallographic and directions can be observed. The analysis of the core of dislocations using scanning transmission electron microscopy (STEM) techniques (such as EDX with atomic resolution, electron-energy loss spectroscopy (EELS)) shows unequivocally that the core of dislocations possesses a different crystallographic structure, electronic structure and chemical composition relative to the matrix. Because the Burgers vector of dislocations is per se invariant, the network of dislocations (with additional d1 electrons) causes an electrical short-circuit of the matrix. This behavior is confirmed by LCAFM measurements for the stoichiometric crystals, moreover a similar dominant role of dislocations in channeling of the current after thermal reduction of the crystals or during resistive switching can be observed. In our opinion, the easy transformation of the chemical composition of the surface layers of both model oxides should be associated with the high concentration of extended defects in this region. Another important insight for the analysis of the physical properties in real oxide crystals (matrix + dislocations) comes from the studies of the nucleation of dislocations via in situ STEM indentation, namely that the dislocations can be simply nucleated under mechanical stimulus and can be easily moved at room temperature

Is reduced strontium titanate a semiconductor or a metal?

In recent decades, the behavior of SrTiO3 upon annealing in reducing conditions has been under intense academic scrutiny. Classically, its conductivity can be described using point defect chemistry and predicting n-type or p-type semiconducting behavior depending on oxygen activity. In contrast, many examples of metallic behavior induced by thermal reduction have recently appeared in the literature, challenging this established understanding. In this study, we aim to resolve this contradiction by demonstrating that an initially insulating, as-received SrTiO3 single crystal can indeed be reduced to a metallic state, and is even stable against room temperature reoxidation. However, once the sample has been oxidized at a high temperature, subsequent reduction can no longer be used to induce metallic behavior, but semiconducting behavior in agreement with the predictions of point defect chemistry is observed. Our results indicate that the dislocation-rich surface layer plays a decisive role and that its local chemical composition can be changed depending on annealing conditions. This reveals that the prediction of the macroscopic electronic properties of SrTiO3 is a highly complex task, and not only the current temperature and oxygen activity but also the redox history play an important role

The Structure of the Electric Double Layer of the Protic Ionic Liquid [Dema][TfO] Analyzed by Atomic Force Spectroscopy

Protic ionic liquids are promising electrolytes for fuel cell applications. They would allow for an increase in operation temperatures to more than 100 °C, facilitating water and heat management and, thus, increasing overall efficiency. As ionic liquids consist of bulky charged molecules, the structure of the electric double layer significantly differs from that of aqueous electrolytes. In order to elucidate the nanoscale structure of the electrolyte–electrode interface, we employ atomic force spectroscopy, in conjunction with theoretical modeling using molecular dynamics. Investigations of the low-acidic protic ionic liquid diethylmethylammonium triflate, in contact with a platinum (100) single crystal, reveal a layered structure consisting of alternating anion and cation layers at the interface, as already described for aprotic ionic liquids. The structured double layer depends on the applied electrode potential and extends several nanometers into the liquid, whereby the stiffness decreases with increasing distance from the interface. The presence of water distorts the layering, which, in turn, significantly changes the system’s electrochemical performance. Our results indicate that for low-acidic ionic liquids, a careful adjustment of the water content is needed in order to enhance the proton transport to and from the catalytic electrode

Atomic Force Spectroscopy on Ionic Liquids

Ionic liquids have become of significant relevance in chemistry, as they can serve as environmentally-friendly solvents, electrolytes, and lubricants with bespoke properties. In particular for electrochemical applications, an understanding of the interface structure between the ionic liquid and an electrified interface is needed to model and optimize the reactions taking place on the solid surface. As with ionic liquids, the interplay between electrostatic forces and steric effects leads to an intrinsic heterogeneity, as the structure of the ionic liquid above an electrified interface cannot be described by the classical electrical double layer model. Instead, a layered solvation layer is present with a structure that depends on the material combination of the ionic liquid and substrate. In order to experimentally monitor this structure, atomic force spectroscopy (AFS) has become the method of choice. By measuring the force acting on a sharp microfabricated tip while approaching the surface in an ionic liquid, it has become possible to map the solvation layers with sub-nanometer resolution. In this review, we provide an overview of the AFS studies on ionic liquids published in recent years that illustrate how the interface is formed and how it can be modified by applying electrical potential or by adding impurities and solvents

Resistive switching phenomena of extended defects in Nb-doped SrTiO3_{3} under influence of external gradients

Redox-based memristive materials have attracted much attention in the last decade owing to their ability to change the resistance upon application of an electric field making them promising candidates for future non-volatile memories. However, a fundamental understanding of the nature of the resistive switching effect, which is indispensable for designing future technological applications,is still lacking. As a prototype material of a memristive oxide, strontium titanate (SrTiO$_{3}$) has been investigated intensively and it was revealed that the valence change of a Ti “d” electron plays an important role during resistive switching related to insulator-to-metal transition. Such a transition can be induced by electrical gradients, by chemical gradients, by a combination of these gradients or by donor doping. Hence, SrTiO$_{3}$ doped with the donor Nb should have metallic properties and is used commonly as a conducting substrate for the growth of functional oxide thin films. Nevertheless, the resistive switching effect has also be observed in Nb-doped SrTiO$_{3}$. This paradoxical situation offers a unique opportunity to gain an insight into the processes during the insulator-to metal transition. In this thesis, a comprehensive study of the influence of external gradients on SrTiO$_{3}$:Nb single crystals is presented. The focus is especially set on the investigation of the crystallographic structure, the chemical composition, the electronic structure, the lattice dynamics and the electronic transport phenomena using surface-sensitive methods on the macro- and nanoscale. On the as-received epi-polished single crystals, the evolution of a surface layer having a slight excess of strontium and – in contrast to the bulk of the material – semiconducting properties are observed. Hence, the key for understanding of the resistive switching effect is the knowledge of the nature of the surface layer. On the basis of systematic studies of the influence of external gradients on the physical and chemical properties of the surface layer it is demonstrated that a transformation between a Sr-rich and a Ti-rich surface layer can be induced easily illustrating the relevance of ionic movements and phase transformations for the resistive switching effect. On the nanoscale, the switching mechanism is investigated through the use of local conductivity atomic force microscopy with atomic resolution revealing the presence of conducting clusters with a size of 20-60 nm that can be switched independently between ON and OFF states. Since distinct inhomogeneities of the donor distribution are detected by various methods, it is assumed that the conducting clusters, which can be regarded as three-dimensional extended defects, are related to Nb segregation on the nanoscale, which already evolved during the crystal growth by the Verneuil method. In order to gain an insight into the processes taking place when switching the clusters, an emulation of switching is performed on the macroscale by applying extremal electrical gradients, resulting in an evolution of a phase transformation from strontium titanate to titanium oxide in the surface layer. At the end of the thesis, a potential phenomenological model for resistive switching of SrTiO$_{3}$:Nb based on the experimental results as well as on ab initio and finite element simulations is presented. This is done after taking into account the formation of substoichiometric titanium oxide phases, which build up a switchable bridge between the conducting clusters, thereby illustrating that the resistive switching effect in oxides is a very complex phenomenon related to many different mechanisms that need to be considered

The Electronic Properties of Extended Defects in SrTiO3—A Case Study of a Real Bicrystal Boundary

This study investigates the impact of extended defects such as dislocations on the electronic properties of SrTiO3 by using a 36.8° bicrystal as a model system. In order to evaluate the hypothesis that dislocations can serve as preferential reduction sites, which has been proposed in the literature on the basis of ab initio simulations, as well as on experiments employing local-conductivity atomic force microscopy (LC-AFM), detailed investigations of the bicrystal boundary are conducted. In addition to LC-AFM, fluorescence lifetime imaging microscopy (FLIM) is applied herein as a complementary method for mapping the local electronic properties on the microscale. Both techniques confirm that the electronic structure and electronic transport in dislocation-rich regions significantly differ from those of undistorted SrTiO3. Upon thermal reduction, a further confinement of conductivity to the bicrystal boundary region was found, indicating that extended defects can indeed be regarded as the origin of filament formation. This leads to the evolution of inhomogeneous properties of defective SrTiO3 on the nano- and microscales