Electrical conductivity, Hall effect and magnetoresistance of In$_2$O$_3$:Sn thin films deposited on a glass substrates at different temperatures and oxygen pressures, as well as the films treated in a hydrogen plasma, have been investigated in the temperature range 1.5-300 K. The observed temperature dependences of resistivity were typical for metallic transport of electrons except temperature dependence of resistivity of the In$_2$O$_3$:Sn film deposited in the oxygen deficient atmosphere. The electron concentration and mobility for the film deposited at 230$^\circ$C was larger than that for the film deposited nominally at room temperature. Short (5 minutes) treatment of the films in hydrogen plasma leads to the enhancement of electrical conductivity while longer (30 minute) treatment has the opposite effect. The electrical measurements were accompanied by AFM and SEM studies of structural properties, as well as by XPS analysis. Basic on structural and electrical measurements we conclude the reduction process initiated by the hydrogen plasma provides essential modification of the ITO films surface. At the same time, electrical properties of the remaining (located beneath the surface layer) parts of the ITO films remain mostly unchangeable. XPS analysis shows that grown in situ oxygen deficient ITO films have enhanced DOS between the Fermi level and the valence band edge. The extra localized states behave as acceptors leading to a compensation of $n$-type ITO. That can explain lower $n$-type conductivity in this material crossing over to a Mott-type hopping.
The magnetic stability of oxygen deficiency centers on the surface of α-quartz is investigated with first- principles calculations to understand their role in contributing to magnetic flux noise in superconducting qubits (SQs) and superconducting quantum interference devices (SQUIDs) fabricated on amorphous silica substrates. Magnetic defects on the substrate are likely responsible for some of the 1/f noise that plagues these systems. Dangling-bonds associated with three-coordinated Si atoms allow electron density transfer between spin up and down channels, resulting in low energy magnetic sta…
Oxygen vacancies in transition metal oxides facilitate catalysis critical for energy storage and generation. However, it has proven elusive to promote vacancies at the lower temperatures required for operation in devices such as metal-air batteries and portable fuel cells. Here, we use thin films of the perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool towards manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen deficient states in an environment where the cobaltite would normal…
The interrelation between the epitaxial strain and oxygen deficiency in La0.7Ca0.3MnO3-δ thin films was studied in terms of structural and functional properties. The films with a thickness of 1000Å were prepared using a PLD system equipped with a RHEED facility and a pyrometric film temperature control. The epitaxial strain and the oxygen deficiency in the samples were systematically modified using three different substrates: SrTiO3, (LaAlO3)0.3-(Sr2AlTaO6)0.7 and LaSrAlO4, and four different oxygen pressures during film growth ranging from 0.27mbar to 0.1mbar. It could be demonstrated that th…
We synthesized Sr-doped $La_{0.85}Sr_{0.15}OFeAs$ sample with single phase, and systematically studied the effect of oxygen deficiency in the Sr-doped LaOFeAs system. It is found that substitution of Sr for La indeed induces the hole carrier evidenced by positive thermoelectric power (TEP), but no bulk superconductivity is observed. The superconductivity can be realized by annealing the as-grown sample in vacuum to produce the oxygen deficiency. With increasing the oxygen deficiency, the superconducting transition temperature ($T_c$) increases and maximum $T_c$ reaches about 26 K the same as t…
Single crystalline YBa$_{\text{2}}$Cu$_{\text{3}}$O$_{\text{7}-δ}$ (YBCO) thin films were grown by pulsed laser deposition (PLD) in order to probe the oxygen deficiency $δ$ using a mono-energetic positron beam. The sample set covered a large range of $δ$ (0.191<$δ$<0.791) yielding a variation of the critical temperature $T_{\text{c}}$ between 25 and 90\,K. We found a linear correlation between the Doppler broadening of the positron electron annihilation line and $δ$ determined by X-ray diffraction (XRD). Both, the origin of the found correlation and the influence of metallic vacancies, were ex…
Billion-Fold Enhancement of Room-Temperature Ionic Conductivity in h-RMnO3/YSZ Heterostructures via Electric-Field-Assisted Oxygen Deficiency Engineering
The atomic structure and composition of non-interfacial ITO and ITO-Si interfaces were studied with Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). The films were deposited by DC magnetron sputtering on mono-crystalline p-type (100) Si wafers. Both as deposited and heat treated films consisted of crystalline ITO. The ITO/Si interface showed a more complicated composition. A thin layer of SiO$_x$ was found at the ITO/Si interface together with In and Sn nanoclusters, as well as highly oxygen deficient regions, as observed by XPS. High energy electron exposure …
It is generally assumed that oxygen potential in a thin oxide electrolyte follows a linear distribution between electrodes. Jacobsen and Mogensen have shown, however, that this is not the case for thin zirconia membranes in solid oxide electrochemical cells. Here we demonstrate that there is a ubiquitous oxygen potential transition rooted in the p-type/n-type transition of electronic conductivity inside mixed conducting oxides, and that the transition is extremely sensitive to electrode potential and current density. It is also remarkably sensitive to the conductivity ratio of electrons and ho…
We study the dependence of the formation energies of oxygen and metal induced defects in Ta2O5, TaO2, TaO, TiO2 and Ti4O7 on the chemical potential of electron and atomic constitutes. In the study of single defect, metal induced defects are found to be preferable to oxygen induced defects. This is against the experimental fact of the dominant role of oxygen induced defects in the RS process. A simple multiple defects picture without correlated atomic rearrangement does not cure this problem. The problem is resolved under the correlated multiple defect picture where the multiple defects result …
We use density functional theory (DFT) calculations to show that oxygen vacancies ($v_\mathrm{O}$) and mobility induce noncentrosymmetric polar structures in SrTi$_{1-x-y}$Fe$_{x}$Co$_{y}$O$_{3-δ}$ ($x=y=0.125$) with $δ= \{0.125, 0.25\}$, enhance the saturation magnetization and give rise to large changes in the electric polarization $\vertΔP\vert$. We present an intuitive set of rules for SrTiFeCoO$_{3-δ}$ (STFC), which are based on the interplay between (Co/Fe)-$v_\mathrm{O}$ defects, magnetic cations coordination and topological vacancy disorder. STFC structures convey layered crystals with…
We report on resistive switching (RS) characteristics of W/WO3-x/Pt-based thin film memristors modulated by precisely controlled oxygen non-stoichiometry. RS properties of the devices with varied oxygen vacancy (VO) concentration have been studied by measuring their DC current voltage properties. Switchability of the resistance states in the memristors have been found to depend strongly on the VOs concentration in the WO3-x layer. Depending on x, the memristors exhibited forming-free bipolar, forming-required bipolar and non-formable characteristics. Devices with high VOs concentration (~1*102…
Sr2VO{3-delta}FeAs superconductors with different oxygen deficiencies have been successfully fabricated. It is found that the superconducting transition temperature drops down monotonically with the increase of oxygen deficiency. The diminishing of superconductivity is accompanied by the enhancement of residual resistivity, indicating an unraveled scattering effect induced by the oxygen deficiency. The highest superconducting transition temperature at about 40 K is achieved near the stoichiometrical sample Sr$_2$VO$_{3}$FeAs. Surprisingly, the X-ray photoelectron spectroscopy (XPS) shows that …
Electronic phase separation is crucial for the fascinating macroscopic properties of the LaAlO3/SrTiO3 (LAO/STO) paradigm oxide interface, including the coexistence of superconductivity and ferromagnetism. We investigate this phenomenon using angle-resolved photoelectron spectroscopy (ARPES) in the soft-X-ray energy range, where the enhanced probing depth combined with resonant photoexcitation allow access to fundamental electronic structure characteristics (momentum-resolved spectral function, dispersions and ordering of energy bands, Fermi surface) of buried interfaces. Our experiment uses X…
Oxygen vacancies (VOs) effects on magnetic ordering in Eu0.5Ba0.5TiO3-δ (EBTO3-δ) thin films have been investigated using a combination of experimental measurements and first-principles density-functional calculations. Two kinds of EBTO3-δthin films with different oxygen deficiency have been fabricated. A nuclear resonance backscattering spectrometry technique has been used to quantitatively measure contents of the VOs. Eu0.5Ba0.5TiO3 ceramics have been known to exhibit ferroelectric (FE) and G-type antiferromagnetic (AFM) properties. While, a ferromagnetic (FM) behavior with a Curie temperatu…
We find that layered materials composed of various oxides of cations with $s^2$ electronic configuration, $XY_2$O$_4$, $X$=In or Sc, $Y$=Ga, Zn, Al, Cd and/or Mg, exhibit isotropic electron effective mass which can be obtained via averaging over those of the corresponding single-cation oxide constituents. This effect is due to a hybrid nature of the conduction band formed from the s-states of {\it all} cations and the oxygen p-states. Moreover, the observed insensitivity of the electron effective mass to the oxygen coordination and to the distortions in the cation-oxygen chains suggests that s…
Interfaces between (110) and (111)SrTiO3 (STO) single crystalline substrates and amorphous oxide layers, LaAlO3 (a-LAO), Y:ZrO2 (a-YSZ), and SrTiO3 (a-STO) become conducting above a critical thickness tc. Here we show that tc for a-LAO is not depending on the substrate orientation, i.e. tc (a-LAO/(110)STO) ~ tc(a-LAO/(111)STO) interfaces, whereas it strongly depends on the composition of the amorphous oxide: tc(a-LAO/(110)STO) < tc(a-YSZ/(110)STO) < tc(a-STO/(110)STO). It is concluded that the formation of oxygen vacancies in amorphous-type interfaces is mainly determined by the oxygen affinit…
DC electrical degradation as a form of dielectric and resistance breakdown is a common phenomenon in thin-film devices including resistance-switching memory. To obtain design data and to probe the degradation mechanism, highly accelerated lifetime tests (HALT) are often conducted at higher temperatures with thicker samples. While the mechanism is well established in semiconducting oxides such as perovskite titanates, it is not in stabilized zirconia and other fast oxygen-ion conductors that have little electronic conductivity. Here we model the mechanism by an oxygen-driven, transport-limited,…
We use first-principles calculations to investigate the stability of bi-axially strained \textit{Pnma} perovskite CaMnO$_3$ towards the formation of oxygen vacancies. Our motivation is provided by promising indications that novel material properties can be engineered by application of strain through coherent heteroepitaxy in thin films. While it is usually assumed that such epitaxial strain is accommodated primarily by changes in intrinsic lattice constants, point defect formation is also a likely strain relaxation mechanism. This is particularly true at the large strain magnitudes ($>$4%) whi…
The electronic properties of single- and multi-cation transparent conducting oxides (TCOs) are investigated using first-principles density functional approach. A detailed comparison of the electronic band structure of stoichiometric and oxygen deficient In$_2$O$_3$, $α$- and $β$-Ga$_2$O$_3$, rock salt and wurtzite ZnO, and layered InGaZnO$_4$ reveals the role of the following factors which govern the transport and optical properties of these TCO materials: (i) the crystal symmetry of the oxides, including both the oxygen coordination and the long-range structural anisotropy; (ii) the electroni…
The impact of oxygen deficiency on physical properties of Na2/3CoO2-x has been investigated. From the combined thermogravimetric, magnetic susceptibility and synchrotron X-ray Laue diffraction studies, it is demonstrated that Na2/3CoO2 shows no superlattice ordering due to Na ions; however Na2/3CoO1.98, which has the same Co valence as that of Na0.71CoO2, shows nearly identical magnetic and transport properties and the same simple hexagonal superlattice ordering of sqrt(12)a. It is proposed that the Na ion ordering found in Na2/3CoO1.98 is identical to the ideal Na0.71CoO2 of large sqrt(12)a x…
The oxygen stoichiometry has a large influence on the physical and chemical properties of complex oxides. Most of the functionality in e.g. catalysis and electrochemistry depends in particular on control of the oxygen stoichiometry. In order to understand the fundamental properties of intrinsic surfaces of oxygen-deficient complex oxides, we report on in situ temperature dependent scanning tunnelling spectroscopy experiments on pristine oxygen deficient, epitaxial manganite films. Although these films are insulating in subsequent ex situ in-plane electronic transport experiments at all tempera…
In this paper we investigated the most important family of proton conducting oxides, i.e. cerates, by means of pair distribution function analysis (PDF) obtained from total neutron scattering data. The results clearly demonstrates that the local structure plays a fundamental role in the protonation process. Oxygen vacancy creation by acceptor doping reduces the local structure symmetry which is then restored upon water uptake. This mechanism mainly involves the Ba-O shell which flexibility seems to be at the basis of the proton conduction mechanism, thus providing a direct insight on the desig…
We investigated theoretically electronic and magnetic properties of the perovskite material SrCoO$_{3-δ}$ with $δ\leq 0.15$ using a projector-augmented plane-wave method and a Green's function method. This material is known from various experiments to be ferromagnetic with a Curie temperature of 260$\,$K to 305$\,$K and a magnetic moment of 1.5${\,μ_\text{B}}$ to 3.0${\,μ_\text{B}}$. Applying the magnetic force theorem as it is formulated within Green's function method, we calculated for SrCoO$_{3-δ}$ the magnetic exchange parameters and estimated the Curie temperature. Including correlation e…
Presently, cerium-doped LaMnO$_3$ is vividly discussed as an electron-doped counterpart prototype to the well-established hole-doped mixed-valence manganites. Here, La$_{0.7}$Ce$_{0.3}$MnO$_3$ thin films of different thicknesses, degrees of CeO$_2$ phase segregation, and oxygen deficiency, grown on SrTiO$_3$ single crystal substrates, are compared with respect to their resistance-vs.-temperature (R vs. T) behavior from 300~K down to 90~K. While the variation of the film thickness (and thus the degree of epitaxial strain) in the range between 10~nm and 100~nm has only a weak impact on the elect…
We demonstrate that room-temperature ferromagnetism in epitaxial Co-doped TiO2 anatase is driven by electron-mediated exchange interaction, and not by metallic Co clusters. Co(II) substitutes for Ti(VI) in the lattice and produces oxygen vacancies that do not contribute carriers. Free electrons originate with oxygen vacancies resulting from an oxygen deficiency during growth.
La$_{0.7}$Ce$_{0.3}$MnO$_3$ thin films of different thicknesses, degrees of CeO$_2$-phase segregation and oxygen deficiency, grown on SrTiO$_3$ single crystal substrates, were comparatively investigated with respect to both their spectral and temperature-dependent photoconductivity (PC) and their magnetoresistance (MR) behaviour under photoexcitation. While as-grown films were insensitive to optical excitation, oxygen reduction appeared to be an effective way to decrease the film resistance, but the film thickness was found to play a minor role. However, from the evaluation of the spectral beh…
We investigate the quality of structural models generated by the Reverse Monte Carlo (RMC) method in a typical application to amorphous systems. To this end we calculate surrogate diffraction data from a Li2O-SiO2 molecular dynamics (MD) simulation and use the total scattering function, in addition to minimal pair distances and coordination numbers of silicon (oxygen) to oxygen (silicon) ions, as input for the RMC modeling. Then we compare partial radial distribution functions, coordination numbers, bond angles, and ring sizes predicted by the RMC models with those of the MD system. It is foun…
Films of Hf0.5Z0.5O2 (HZO) contain a network of grain boundaries. In (111) HZO epitaxial films on (001) SrTiO3, for instance, twinned orthorhombic (o-HZO) ferroelectric crystallites coexist with grain boundaries between o-HZO and a residual paraelectric monoclinic (m-HZO) phase. These grain boundaries contribute to the resistive switching response in addition to the genuine ferroelectric polarization switching and have detrimental effects on device performance. Here, it is shown that, by using suitable nanometric capping layers deposited on HZO film, a radical improvement of the operation wind…
We report on the observation of metallic behavior in thin films of oxygen-deficient SrTiO$_3$ - down to 9 unit cells - when coherently strained on (001) SrTiO$_3$ or DyScO$_3$-buffered (001) SrTiO$_3$ substrates. These films have carrier concentrations of up to 2$\times10^{22}$ cm$^{-3}$ and mobilities of up to 19,000 cm$^2$/V-s at 2 K. There exists a non-conducting layer in our SrTiO$_{3-δ}$ films that is larger in films with lower carrier concentrations. This non-conducting layer can be attributed to a surface depletion layer due to a Fermi level pinning potential. The depletion width, trans…
High perpendicular magnetic anisotropy (PMA), a property needed for nanoscale spintronic applications, is rare in oxide conductors. We report the observation of a PMA up to 0.23 MJ/m3 in modestly strained epitaxial NiCo2O4 (NCO) films which are room-temperature ferrimagnetic conductors. Spin-lattice coupling manifested as magnetoelastic effect was found as the origin of the PMA. The in-plane xx-yy states of Co on tetrahedral sites play crucial role in the magnetic anisotropy and spin-lattice coupling with an energy scale of 1 meV/f.u. The elucidation of the microscopic origin paves a way for e…
Strain is known to greatly influence low temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional c…
Colossal Ion Conductivity (CIC) is the phenomenon in which large changes in oxygen conductivity are observed when a solid state oxygen electrolyte is placed in a heterolayer super lattice. Several hypotheses have been posed concerning both structural changes of the ion conducting material and of the ion conducting mechanism. The posed structural hypotheses are oxygen sub lattice melting, phase change of the ion conducting material, and that the heterolayer environment does not induce a phase change of the ion conducting material. The posed mechanistic hypotheses are disorder, mechanics, and sp…
Reversible topotactic transitions between oxygen-vacancy-ordered structures in transition metal oxides provide a promising strategy for active manipulation of material properties. While transformations between various oxygen-deficient phases have been attained in bulk ABO$_{3-δ}$ perovskites, substrate clamping restricts the formation of distinct ordering patterns in epitaxial films. Using in-situ scanning transmission electron microscopy (STEM), we image a thermally driven reversible transition in La$_{0.5}$Sr$_{0.5}$CoO$_{3-δ}$ films on SrTiO$_3$ from a multidomain brownmillerite (BM) struct…
The impact of oxygen deficiency on physical properties of Na2/3CoO2-x has been investigated. From the combined thermogravimetric, magnetic susceptibility and synchrotron X-ray Laue diffraction studies, it is demonstrated that Na2/3CoO2 shows no superlattice ordering due to Na ions; however Na2/3CoO1.98, which has the same Co valence as that of Na0.71CoO2, shows nearly identical magnetic and transport properties and the same simple hexagonal superlattice ordering of sqrt(12)a. It is proposed that the Na ion ordering found in Na2/3CoO1.98 is identical to the ideal Na0.71CoO2 of large sqrt(12)a x…
On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO$_{2-x}$) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfC$_x$) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfC$_x$ surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO$_2$ thin films prepared and measured under identical conditions, the formation of HfC$_x$ was not detectable suggesting that the enhanced …
X-ray photoemission spectroscopy has been used to investigate the depth dependent crystal structures and chemical compositions of sequentially chemical-etched YBa2Cu3O7-d (YBCO) ultrathin film superconductors. In the near-interface region the crystal structure is severely oxygen deficient and of tetragonal symmetry. We consider this a revelation of retarded oxygen diffusion into the O(1) sites during the post-deposition annealing in the presence of interface mismatch strain. Near the free surface, the oxygen-deficiency was much alleviated because of the partial strain relaxation and the crysta…
The synthesis and characterization of the pyrochlore solid solutions, Y2Ti2-xNbxO7-y, Lu2Ti2-xNbxO7-y, Y2Ti2-xTaxO7-y and Lu2TiTaO7-y (-0.4<y<0.5), is described. Synthesis at 1600 C, and 10-5 Torr yields oxygen deficiency in all systems. All compounds are found to be paramagnetic and semiconducting, with the size of the local moments being less, in some cases substantially less, than the expected value for the number of nominally unpaired electrons present. Thermogravimetric analysis (TGA) shows that all compounds can be fully oxidized while retaining the pyrochlore structure, yielding oxygen …
Variety of conducting heterointerfaces have been made between SrTiO3 substrates and thin capping layers of distinctly different oxide materials that can be classified into polar band insulators (e.g. LaAlO3), polar Mott insulators (e.g. LaTiO3), apparently non-polar band insulators (e.g. γ-Al2O3), and amorphous oxides (e.g. amorphous SrTiO3). A fundamental question to ask is if there is a common mechanism that governs interfacial conductivity in all these heterointerfaces. Here, we examined the conductivity of different kinds of heterointerfaces by annealing in oxygen and surface treatment wit…
The anomalous Hall effect (AHE) has been studied systematically in the low-conductivity ferromagnetic oxide Fe$_{3-x}$Zn$_x$O$_4$ with $x = 0$, 0.1, and 0.5. We used (001), (110), and (111) oriented epitaxial Fe$_{3-x}$Zn$_x$O$_4$ films grown on MgO and sapphire substrates in different oxygen partial pressure to analyze the dependence of the AHE on crystallographic orientation, Zn content, strain state, and oxygen deficiency. Despite substantial differences in the magnetic properties and magnitudes of the anomalous Hall conductivity $σ_{xy}^{\rm AHE}$ and the longitudinal conductivity $σ_{xx}$…
Zincblende copper iodide has been attracting growing interest as p-type semiconductor for applications in transparent electronics and transparent thermoelectrics. A key step towards technological applications is the possibility to enhance copper iodide (CuI) conductivity by doping without deteriorating transparency. A recent high-throughput computational study revealed that chalcogen substitutions on iodine sites can act as shallow acceptors. Following computational predictions, doping by oxygen, sulfur and selenium substitutions on iodine sites has recently been realized in the laboratory, sh…
The impact of oxygen vacancies on local tunneling properties across rf-sputtered MgO thin films was investigated by optical absorption spectroscopy and conducting atomic force microscopy. Adding O$_2$ to the Ar plasma during MgO growth alters the oxygen defect populations, leading to improved local tunneling characteristics such as a lower density of current hotspots and a lower tunnel current amplitude. We discuss a defect-based potential landscape across ultrathin MgO barriers.
We have observed a nearly fourfold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie-law (spin susceptibility $\propto 1/T$) is seen from $\sim$4 K to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-an…
We present a study on the crystallization process of undoped and Ta doped TiO2 amorphous thin films. In particular, the effect of ultra-fast annealing treatments in environments characterized by different oxygen concentrations is investigated via in-situ resistance measurements. The accurate examination of the key parameters involved in this process allows us to reduce the time needed to obtain highly conducting and transparent polycrystalline thin films (resistivity about $6 \times 10^{-4}$ Ωcm, mean transmittance in the visible range about $81\%$) to just 5 minutes (with respect to the 180 m…
Doped SrTiO3 becomes a metal at extremely low doping concentrations n and is even superconducting with the superconducting transition temperature adopting a dome-like shape with the carrier concentration. It is shown here within the polarizability model that up to a well-defined carrier concentration transverse optic mode softening takes place together with polar nano-domain formation which evidences inhomogeneity and a two-component type behavior with metallicity coexisting with polarity. Beyond this region a conventional metal is formed where superconductivity as well as mode softening is ab…
Black TiO2 nanoparticles with a crystalline-core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO2 nanoparticles. Metallic conduction is achieved at the crystalline-amorphous homointerf…
This study of highly accelerated lifetime tests of SrTiO$_3$, a model semiconducting oxide, is motivated by the interest in reliable multilayer ceramic capacitors and resistance-switching thin-film devices. Our analytical solution to oxygen-vacancy migration under a DC voltage -- the cause of resistance degradation in SrTiO$_3$ -- agrees with previous numerical solutions. However, all solutions fail to explain why degradation kinetics feature a very strong voltage dependence, which we attribute to the nucleation and growth of cathode-initiated fast-conducting needles. While they have no color …
The efficacy of the electrical conductivity relaxation (ECR) technique for investigating the oxygen transport properties of mixed conducting oxides has been evaluated. Fifteen mol% samarium doped ceria (SDC15), for which approximate values of the two principal transport properties, bulk oxygen diffusivity, $D_{Chem}$, and surface reaction rate constant, $k_S$, can be found in the literature, was chosen as the benchmark material against which to validate the methodology. Measurements were carried out at temperatures between 750 $^\circ$C and 850 $^\circ$C and over a wide range of oxygen partial…
We investigate pulsed laser deposition of LaGaO3/SrTiO3 at 10-1 mbar oxygen background pressure, demonstrating the critical effect of the target-to-substrate distance, dTS, on the interface sheet resistance, Rs. The interface turns from insulating to metallic by progressively decreasing dTS. The analysis of the LaGaO3 plume evidences the important role of the plume propagation dynamics on the interface properties. These results demonstrate the growth of conducting interfaces at an oxygen pressure of 10-1 mbar, an experimental condition where a well-oxygenated heterostructures with a reduced co…
Cerium oxide (ceria, CeO2) is one of the most promising mixed ionic and electronic conducting materials. Previous atomistic analysis has covered widely the effects of substitution on oxygen vacancy migration. However, an in-depth analysis of the role of cation substitution beyond trivalent cations has rarely been explored. Here, we investigate soluble monovalent, divalent, trivalent and tetravalent cation substituents. By combining classical simulations and quantum mechanical calculations, we provide an insight into defect association energies between substituent cations and oxygen vacancies a…
The effect of deposition oxygen pressure (P$_{O}$) on phase separation (PS) induced in epitaxial La$_{0.67}$Ca$_{0.33}$MnO$_{3}$/NdGaO$_{3}$(001) films was investigated. Fully oxygenated films grown at high P$_{O}$ are anisotropically strained. They exhibit PS over a wide temperature range, because of the large orthorhombicity of NdGaO$_{3}$ substrates. The paramagnetic insulator-to-ferromagnetic metal (FM) and FM-to-antiferromagnetic insulator (AFI) transitions gradually shift to lower temperatures with decreasing PO. The AFI state is initially weakened (P$_{O}$ >= 30 Pa), but then becomes mo…
Pulsed laser deposition of SrTiO3/LaGaO3 and SrTiO3/LaAlO3 interfaces has been analyzed with a focus on the kinetic energy of the ablated species. LaGaO3 and LaAlO3 plasma plumes were studied by fast photography and space-resolved optical emission spectroscopy. Reflection high energy electron diffraction was performed proving a layer-by-layer growth up to 10-1 mbar oxygen pressure. The role of the energetic plasma plume on the two-dimensional growth and the presence of interfacial defects at different oxygen growth pressure has been discussed in view of the conducting properties developing at …
We report that in unannealed LaAlO3/SrTiO3 (LAO/STO) heterostructures the critical thickness for the appearance of the two-dimensional electron gas can be less than 4 unit cell (uc), the interface is conducting even for STO substrates with mixed terminations and the low-temperature resistance upturn in LAO/STO heterostructures with thick LAO layers strongly depends on laser fluence. Our experimental results provide fundamental insights into the different roles played by oxygen vacancies and polarization catastrophe in the two-dimensional electron gas in crystalline LAO/STO heterostructures.
Recently, two-dimensional boron sheets have attracted a lot of attentions owing to their structural polymorphs and outstanding properties. And, due to chemical complexity and electron deficiency of B atoms, the 2D boron sheets are easy affected by the environment. So, exploring novel 2D boron oxides gets highly needed. In this study, we theoretically explored 2D boron oxides structures and their basic properties. We found 2D boron oxides are metals or semimetals, when oxygen concentration is low. More interesting, the B6O1 exhibits Dirac Loop near the Fermi level and the maximum Fermi velocity…
