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We report the formation of neutral nitrogen molecules in the cages of [Ca12Al14O32]2+ (C12A7) framework compensated by extra-framework anions. NH3 treatment of C12A7 electride (C12A7:e-) at 800 °C leads to the formation of N2 and NH2- species in the C12A7 cages. N2 and NHx species in the cages are identified using the Raman spectroscopy of 14NH3 and 15NH3-treated C12A7:e-. The concentration of H and N in the C12A7 cages after NH3 treatment is ∼1021 cm-3. We propose a two-step mechanism, supported by density functional theory (DFT) modeling, of N2 incorporation into the C12A7 cages, i.e., incorporation of NH2- formed from decomposition of NH3 at C12A7:e- surface followed by the NH2- species reacting to form N2 molecules. Encapsulation of neutral molecules, as opposed to negatively charged species reported in C12A7 previously, offers new opportunities for trapping and storing gaseous substances in nanoporous materials.

Internal electric fields that underpin functioning of multi-component materials systems and devices are coupled to structural and compositional inhomogeneities associated with interfaces in these systems. Hard-x-ray photoelectron spectroscopy is a valuable source of information on band-edge profiles, governed by the distribution of internal fields, deep inside semiconductor thin films and heterojunctions. However, extracting this information requires robust and physically meaningful decomposition of spectra into contributions from individual atomic planes. We present an approach that utilizes the physical requirements of a monotonic dependence of the built-in electrostatic potential on depth and continuity of the potential function and its derivatives. These constraints enable efficient extraction of band-edge profiles and allow one to capture details of the electronic structure, including determination of the signs and magnitudes of the band bending as well as the valence band offsets. The utility of this approach to generate quantitative insight into the electronic structure of complex materials is illustrated for epitaxial $$\hbox {SrTiO}_3$$SrTiO3 on intrinsic Si(001).

We investigate the structure, thermodynamic stability, and electronic properties of (001), (110), and (111) surfaces of mayenite (12CaO·7Al2O3 or C12A7) in its oxygen-deficient phase known as mayenite-derived electride Ca12Al14O32 using simulations based on the density functional theory. Seven types of surface terminations were identified, depending on the orientation of the lattice nanosize cages with respect to the surface plane. We find that the surface termination has a strong effect on the distribution of electron anions in the near-surface region, as demonstrated by the range of the ionic charges and binding energies of adsorbed Au atoms and dimers. Notably, in all cases, Au species acquire a negative charge and preferentially adsorb as isolated ions rather than aggregate into clusters. These results show that C12A7 electride can provide a simple, yet versatile substrate to achieve high adsorption capacity and steric selectivity for single atom catalysts.

Since the advent of the first computers, chemists have been at the forefront of using computers to understand and solve complex chemical problems. As the hardware and software have evolved, so have the theoretical and computational chemistry methods and algorithms. Parallel computers clearly changed the common computing paradigm in the late 1970s and 80s, and the field has again seen a paradigm shift with the advent of graphical processing units. This review explores the challenges and some of the solutions in transforming software from the terascale to the petascale and now to the upcoming exascale computers. While discussing the field in general, NWChem and its redesign, NWChemEx, will be highlighted as one of the early codesign projects to take advantage of massively parallel computers and emerging software standards to enable large scientific challenges to be tackled.

Understanding and controlling heat transfer across interfaces has become an important issue for the performance of micro- and nanoscale electronics, as well as achieving a high figure of merit for thermoelectrics. Intrinsic and extrinsic defects can have a significant impact on thermal transport in bulk materials and across interfaces, but the mechanism is not well understood. In this work, nonequilibrium molecular dynamics simulations are used to determine the impact of interfacial atomic vacancies on thermal transport across a Cu/Si junction. In contrast to the reduction in thermal transport typically seen with bulk defects, we find that by introducing atomic vacancies at a concentration of 6.3% near the interface in either or both materials, the interfacial thermal conductance can be increased by up to 76%. By controlling the initial positions of the vacancies and keeping track of their movements and population, we find that interfacial thermal transport is dependent on temperature, vacancy concentration, and distribution, and a positive correlation between the conductance and point defect activities (extent of vacancy migration, rate of Frenkel defect creation and annihilation) is observed. Further calculations based on the phonon density of states and normal mode decomposition reveal that the increase in interfacial thermal conductance originates primarily from high-frequency phonons, supported by enhanced inelastic phonon transport which contributes to more than 60% of the increase. Our findings suggest a practical way to manipulate inelastic phonon conversion through the presence of defects, which provides an alternative perspective on improving thermal transport between materials with a large lattice mismatch.

Two-dimensional stacking fault defects embedded in a bulk crystal can provide a homogeneous trapping potential for carriers and excitons. Here we utilize state-of-the-art structural imaging coupled with density-functional and effective-mass theory to build a microscopic model of the stacking-fault exciton. The diamagnetic shift and exciton dipole moment at different magnetic fields are calculated and compared with the experimental photoluminescence of excitons bound to a single stacking fault in GaAs. The model is used to further provide insight into the properties of excitons bound to the double-well potential formed by stacking fault pairs. This microscopic exciton model can be used as an input into models which include exciton-exciton interactions to determine the excitonic phases accessible in this system.

Interfaces and their misfit defects determine the material properties of a wide range of applications, such as electronic devices, photocatalysts, and structural materials. However, current atomic-level understanding of interfacial structures is limited. Here we reveal that a special interfacial structure, a mismatched but oriented interface formed by two differently structured facets, gives rise to Ag3PO4 polypods at room temperature in aqueous solution. Transmission and scanning electron microscopy results suggest that interfaces of {1 0 0} and {1 1 0}({1 0 0}/(1 1 0}), {1 0 0}/{1 1 1}, {1 1 0}/{1 1 1}, and {1 0 0}/{1 0 0} have certain orientation relationships, corresponding to the structural energy minima and coincident site lattices of interfacial atoms, as demonstrated by molecular dynamics simulations. Density functional theory calculations indicate that the formation of pyrophosphates and/or phosphates rotation across the interface, as well as deformation of Ag-O bonds, compensate for the lattice mismatch at the interfaces. Our work opens a new avenue for a much wider range of interfacial structures, allow for a higher diversity of structures, and shines light on tailoring crystal structures, morphologies, and their resulting properties.

The starting alloy microstructure can be tailored to achieve varying degrees of grain refinement and enhance mechanical properties through severe plastic shear deformation during solid-phase processing. Crystal plasticity-based grain misorientation modeling, coupled with systematic pin-on-disk tribometry-based subsurface shear deformation experiments on as-cast Al-xSi alloys (x = 0, 1, 4 at%), was conducted. The post-deformation microstructural analysis, through a combined computational and experimental approach, conclusively shows that the initial volume fraction of the hard Si phase enhances the evolution of local lattice misorientation, leading to efficient grain refinement during severe plastic shear deformation. The shear-deformation–induced nanostructure resulted in more than double the nanoindentation hardness in the processed alloy.

The epitaxial growth of multifunctional oxides on semiconductors has opened a pathway to introduce new functionalities to semiconductor device technologies. In particular, the integration of gate materials that enable non-volatile or hysteretic functionality in field-effect transistors could lead to device technologies that consume less power, or allow for novel modalities in computing. Here we present electrical characterization of ultrathin single crystalline SrZrxTi1-xO3 (x = 0.7) films epitaxially grown on a high mobility semiconductor, Ge. Epitaxial films of SrZrxTi1-xO3 exhibit relaxor behavior, characterized by a hysteretic polarization that can modulate the surface potential of Ge. We find that gate layers as thin as 5 nm corresponding to an equivalent-oxide-thickness of just 1.0 nm exhibit a ~ 2 V hysteretic window in the capacitance-voltage characteristics. The development of hysteretic metal-oxide-semiconductor capacitors with nanoscale gate thicknesses opens new vistas for nanoelectronic devices.

We investigate the formation mechanisms of vacancy-ordered phase and collective mass transport in epitaxial SrCrO3−δ films using ab initio simulations within the density functional theory formalism. We show that as the concentration of oxygen vacancies (VO) increases, they form 1D chains that feature Cr-centered tetrahedra. Aggregation of these 1D VO chains results in the formation of (111)-oriented oxygen-deficient planes and an extended vacancy-ordered phase observed in recent experiments. We discuss atomic-scale mechanisms enabling the quasi-2D VO aggregates to expand along and translate across (111) planes. The corresponding lowest activation energy pathways necessarily involve rotation of Cr-centered tetrahedra, which emerges as a universal feature of fast ionic conduction in complex oxides. These findings explain reversible oxidation and reduction in SrCrO3−δ at low temperatures and provide insights into transient behavior necessary to harness ionic conductive oxides for high-performance and low-tem...

We explore how the structure and composition of the terminal layer of $n\text{\ensuremath{-}}\mathrm{SrTi}{\mathrm{O}}_{3}(001)$ determine key surface electronic properties. We have measured and calculated from first principles the absolute work functions and electron affinities of bulk $\mathrm{SrN}{\mathrm{b}}_{0.01}\mathrm{T}{\mathrm{i}}_{0.99}{\mathrm{O}}_{3}(001)$ terminated along the $\mathrm{Ti}{\mathrm{O}}_{2}$ and SrO planes. The match between theory and experiment is quite satisfactory for the $\mathrm{Ti}{\mathrm{O}}_{2}$ termination if an ideal, bulk-truncated surface structure is assumed. In contrast, the ideal SrO termination leads to a calculated work function considerably lower than the experimental value. We show that this discrepancy can be associated with defects on the SrO surface that act as electron scavengers. These defects deplete the concentration of itinerant electrons in the subsurface region and increase the negative charge density on the surface, thus increasing the work function. Several different surface defect configurations were modeled; the ones that yield the best agreement with experiment involve Sr vacancies in the terminal layer along with ${\mathrm{O}}^{2\ensuremath{-}}$, $\mathrm{O}{\mathrm{H}}^{\ensuremath{-}}/{\mathrm{H}}^{\ensuremath{-}}$ pairs or ${{\mathrm{O}}_{2}}^{2\ensuremath{-}}$ occupying anion sites adjacent to the Sr vacancies.

We report charge transfer and built-in electric fields across the epitaxial SrNb_{x}Ti_{1-x}O_{3-δ}/Si(001) interface. Electrical transport measurements indicate the formation of a hole gas in the Si and the presence of built-in fields. Hard x-ray photoelectron measurements reveal pronounced asymmetries in core-level spectra that arise from these built-in fields. Theoretical analysis of core-level spectra enables built-in fields and the resulting band bending to be spatially mapped across the heterojunction. The demonstration of tunable charge transfer, built-in fields, and the spatial mapping of the latter, lays the groundwork for the development of electrically coupled, functional heterojunctions.

We have investigated the electronic and optical properties of epitaxial $\mathrm{L}{\mathrm{a}}_{1\ensuremath{-}x}\mathrm{S}{\mathrm{r}}_{x}\mathrm{Fe}{\mathrm{O}}_{3}$ for $0\ensuremath{\le}x\ensuremath{\le}1$ prepared by molecular-beam epitaxy. Core-level and valence-band x-ray photoemission features monotonically shift to lower binding energy with increasing $x$, indicating downward movement of the Fermi level toward the valence-band maximum. Combining valence-band photoemission and O $K$-edge x-ray absorption data, we map the evolution of the occupied and unoccupied bands and observe a narrowing of the gap, along with a transfer of state density from just below to just above the Fermi level as a result of hole doping. In-plane transport measurements confirm that the material becomes a $p$-type semiconductor at lower doping levels and exhibits a conversion from semiconducting to metallic behavior at $x=1$. Low-energy optical transitions revealed by spectroscopic ellipsometry are explained based on insight from theoretical densities of states and first-principles calculations of optical absorption spectra.

Metastable orientation relationships (ORs) between Cu and Cr are stabilized via epitaxial thin film deposition, with the initial layer of Cu(001) or Cr(001) grown epitaxially on MgO(001). The Bain OR is observed by x-ray diffraction and scanning/transmission electron microscopy for Cu(001) / Cr(001). In contrast, three Cr/Cu ORs are found for Cr deposition on Cu(001): the Pitsch OR, and two previously unreported ORs related to the Bain and Pitsch ORs, respectively. Ab initio calculations predict the energetics of these metastable ORs, and reveal that the deformation resistance of Cr makes the Bain OR energetically unfavorable when Cr films are deposited on Cu(001). These results show that kinetic constraints imposed by controlling the substrate surface and deposition conditions can lead to metastable interfacial structures.

Emergent phenomena at complex oxide interfaces could provide the basis for a wide variety of next-generation devices, including photovoltaics and spintronics. To date, detailed characterization and computational modeling of interfacial defects, cation intermixing, and film stoichiometry have helped to explain many of the novel behaviors observed at a single heterojunction. Unfortunately, many of the techniques employed to characterize a single heterojunction are less effective for a superlattice made up of a repeating series of interfaces that induce collective interfacial phenomena throughout a film. These repeating interfaces present an untapped opportunity to introduce an additional degree of complexity, such as confined electric fields, that cannot be realized in a single heterojunction. In this work, we explore the properties of SrTiO3–LaCrO3 superlattices to understand the role of defects, including variations in cation stoichiometry of individual layers of the superlattice, intermixing across inter...

The electronic and optical properties of α-(Fe1-xVx)2O3 at low (x = 0.04) and high (x = 0.5) doping levels are investigated using a combination of periodic and embedded cluster approaches, and time-dependent density functional theory. At low V concentrations the onset of the optical absorption is ∼0.5 eV (i.e., nearly 1.6 eV lower than that in pure α-Fe2O3) and corresponds to the electron transitions from V 3d to Fe 3d* orbitals. At high V concentrations, optical absorption energies and intensities are sensitive to specific arrangements of Fe and V atoms and their spin configuration that determine Fe-V hybridization. The onset of the lowest inter-vanadium absorption band in the case of Fe2O3/V2O3 hetero-structures is as low as ∼0.3 eV and the corresponding peak is at ∼0.7 eV. In contrast, in the case of solid solutions this peak has lower intensity and is shifted to higher energy (∼1.2 eV). Analysis of the orbital character of electronic excitation suggests that Fe2O3/V2O3 hetero-structures absorb light much more effectively than random alloys, thus promoting efficient photo-induced carrier generation. These predictions can be tested in α-(Fe1-xVx)2O3 thin films synthesized with well-controlled spatial distribution of Fe and V species.

Structure, thermodynamic stability, and electronic properties of CaH2 surfaces in (001), (110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (∼5.2 eV) is in agreement with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ∼2.7 eV. Surface VH are predicted to aggregate into dimers and form electron-rich centers (e−)Ca2+(e−) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.

Double perovskites of the form R2BB′O6 (where R is a rare earth cation and B and B′ are chemically distinct transition metal cations with half-filled and empty eg orbitals, respectively) are of significant interest for their magnetoelectric properties. La2MnNiO6 is particularly attractive because of its large expected ferromagnetic moment per formula unit (5 μB f.u.–1) and its semiconducting character. If the ideal structure nucleates, superexchange coupling can take place via the B—O—B′ bonds that form, and the moment per formula unit can attain its maximum theoretical value. However, we show that even in the case of layer-by-layer deposition via molecular beam epitaxy, the system can follow multiple reaction pathways that lead to deviations from the double perovskite structure. In particular, we observe a spatially extended phase in which B-site cation disorder occurs, resulting in Mn—O—Mn and Ni—O—Ni antiferromagnetic domains, as well as the formation of quasi-epitaxial, antiferromagnetic NiO nanoscale...

Creating new functionality in materials containing transition metals is predicated on the ability to control the associated charge states. For a given transition metal, there is an upper limit on valence that is not exceeded under normal conditions. Here, it is demonstrated that this limit of 3+ for Ni and Fe can be exceeded via synthesis of (SrNiO3 )m /(LaFeO3 )n superlattices by tuning n and m. The Goldschmidt tolerance constraints are lifted, and SrNi4+ O3 with holes on adjacent O anions is stabilized as a perovskite at the single-unit-cell level (m = 1). Holding m = 1, spectroscopy reveals that the n = 1 superlattice contains Ni3+ and Fe4+ , whereas Ni4+ and Fe3+ are observed in the n = 5 superlattice. It is revealed that the B-site cation valences can be tuned by controlling the magnitude of the FeO6 octahedral rotations, which, in turn, determine the energy balance between Ni3+ /Fe4+ and Ni4+ /Fe3+ , thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. This approach can be extended to other systems for synthesizing novel, metastable layered structures with new functionalities.

Photoemission features associated with states deep in the band gap of n−SrTiO₃ (001) are found to be ubiquitous in bulk crystals and epitaxial films. These features are present even when there is little signal near the Fermi level. Analysis reveals that these states are deep-level traps associated with defects. The commonly investigated defects—O vacancies, Sr vacancies, and aliovalent impurity cations on the Ti sites—cannot account for these features. Rather, ab initio modeling points to these states resulting from interstitial oxygen and its interaction with donor electrons.

Identification of kinetic and thermodynamic factors that control crystal nucleation and growth represents a central challenge in materials synthesis. Here we report that apparently defect-free growth of ${\mathrm{La}}_{2}{\mathrm{MnNiO}}_{6}$ (LMNO) thin films supported on ${\mathrm{SrTiO}}_{3}$ (STO) proceeds up to 1--5 nm, after which it is disrupted by precipitation of NiO phases. Local geometric phase analysis and ensemble-averaged x-ray reciprocal space mapping show no change in the film strain away from the interface, indicating that mechanisms other than strain relaxation induce the formation of the NiO phases. Ab initio simulations suggest that the electrostatic potential build-up associated with the polarity mismatch at the film-substrate interface promotes the formation of oxygen vacancies with increasing thickness. In turn, oxygen deficiency promotes the formation of Ni-rich regions, which points to the built-in potential as an additional factor that contributes to the NiO precipitation mechanisms. These results suggest that the precipitate-free region could be extended further by either incorporating dopants that suppress the built-in potential or by increasing the oxygen fugacity in order to suppress the formation of oxygen vacancies.

Significance Electrides are ionic materials in which electrons act as anions. Solvated electrons in ammonia are one of the early known examples of such anions in liquids. Electron anions in crystalline materials have previously been shown to dramatically alter their electronic properties, for example, to turn an insulator into a superconductor with minimal changes in the structure and stoichiometry. We show that electron anions modify the disordered glass network by creating highly mobile weak links, thus fundamentally altering the thermodynamic and electronic properties of the network and enabling a new design paradigm for amorphous materials.

A multi-scale simulation study of Ni/InAs nano-scale contact aimed for the sub-14 nm technology is carried out to understand material and transport properties at a metal-semiconductor interface. The deposited Ni metal contact on an 11 nm thick InAs channel forms an 8.5 nm thick InAs leaving a 2.5 nm thick InAs channel on a p-type doped (1 × 1016 cm−3) AlAs0.47Sb0.53 buffer. The density functional theory (DFT) calculations reveal a band gap narrowing in the InAs at the metal-semiconductor interface. The one-dimensional (1D) self-consistent Poisson-Schrodinger transport simulations using real-space material parameters extracted from the DFT calculations at the metal-semiconductor interface, exhibiting band gap narrowing, give a specific sheet resistance of Rsh = 90.9 Ω/sq which is in a good agreement with an experimental value of 97 Ω/sq.

Thin-film synthesis methods that have developed over the past decades have unlocked emergent interface properties ranging from conductivity to ferroelectricity. However, our attempts to exercise precise control over interfaces are constrained by a limited understanding of growth pathways and kinetics. Here we demonstrate that shuttered molecular beam epitaxy induces rearrangements of atomic planes at a polar/nonpolar junction of ${\mathrm{LaFeO}}_{3}$ (LFO)/$n\text{\ensuremath{-}}{\mathrm{SrTiO}}_{3}$ (STO) depending on the substrate termination. Surface characterization confirms that substrates with two different $({\mathrm{TiO}}_{2}$ and SrO) terminations were prepared prior to LFO deposition; however, local electron-energy-loss spectroscopy measurements of the final heterojunctions show a predominantly LaO/${\mathrm{TiO}}_{2}$ interfacial junction in both cases. Ab initio simulations suggest that the interfaces can be stabilized by trapping extra oxygen (in LaO/${\mathrm{TiO}}_{2})$ and forming oxygen vacancies (in ${\mathrm{FeO}}_{2}$/SrO), which points to different growth kinetics in each case and may explain the apparent disappearance of the ${\mathrm{FeO}}_{2}$/SrO interface. We conclude that judicious control of deposition time scales can be used to modify growth pathways, opening new avenues to control the structure and properties of interfacial systems.

A simple and robust approach to visualization of continuous wave terahertz (CW-THz) light would open up opportunities to couple physical phenomena that occur at fundamentally different energy scales. Here we demonstrate how nanoscale cages of Ca12Al14O33 crystal enable conversion of CW-THz radiation to visible light. These crystallographic cages are partially occupied with weakly bonded oxygen ions and give rise to a narrow conduction band that can be populated with localized, yet mobile electrons. CW-THz light excites a nearly stand-alone rattling motion of the encaged oxygen species, which promotes electron transfer from them to the neighboring vacant cages. When the power of CW-THz light reaches tens of watts, the coupling between forced rattling in the confined space, electronic excitation and ionization of oxygen species, and corresponding recombination processes result in emission of bright visible light.

A novel pathway of increasing the surface density of catalytically active oxygen radical sites on a MoVTeNb oxide (M1 phase) catalyst during alkane oxidative dehydrogenation is reported. The novel sites form when a fraction of Te4+ is reduced and emitted from the M1 crystals under catalytic operating conditions, without compromising structural integrity of the catalyst framework. Density functional theory calculations show this Te reduction induces multiple inter-related electron transfers, and the associated cooperative effects lead to the formation of O- radicals. The in situ observations identify complex dynamic changes in the catalyst on an atomistic level, highlighting a new way to tailor structure and dynamics for highly active catalysts.

Quantitative characterization of energy landscapes at buried interfaces is essential for assessing their functionality. This perspective highlights recent developments in reconstructing internal potential profiles based on hard x-ray photoemission experiments that have proved to be a rich source of information. We show that band-edge profiles can be reconstructed from core-level photoelectron spectra by performing a comprehensive search for the best-fit set of associated layer-resolved spectra. The use of hard x-rays allows heterostructures to be probed over length scales comparable to relevant electronic screening lengths. Significantly, this information takes our understanding of such systems to a new level that is not currently achievable using any other experimental technique.

Epitaxial thin films of $\mathrm{C}{\mathrm{r}}_{2\ensuremath{-}x}\mathrm{T}{\mathrm{i}}_{x}{\mathrm{O}}_{3}$ were deposited by oxygen-plasma-assisted molecular beam epitaxy for $0.04\ensuremath{\le}x\ensuremath{\le}0.26$. Ti valence is verified by both x-ray photoelectron spectroscopy (XPS) and Ti $K$-edge x-ray absorption near-edge spectroscopy (XANES) to be $\mathrm{T}{\mathrm{i}}^{4+}$. Substitution of Ti for Cr in the corundum lattice is verified by fitting the Ti $K$-edge extended x-ray absorption fine structure (EXAFS) data. Room temperature electrical transport measurements confirm the highly resistive nature of Ti-doped $\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{3}$, despite the presence of aliovalent $\mathrm{T}{\mathrm{i}}^{4+}$. For comparison, the resistivity of very pure, undoped $\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{3}$ was measured to be four orders of magnitude higher than for Ti-doped $\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{3}$. Analysis of the XPS and EXAFS data reveal the presence of Cr vacancies at intermediate and high Ti concentrations. This conclusion is corroborated by the results of density functional modeling. At low Ti concentrations, a strong increase of the XPS $\mathrm{Ti}\phantom{\rule{0.16em}{0ex}}2p$ core level peak width is observed as the Ti concentration decreases. In this limit, the formation of Cr vacancies becomes less favorable due to the increased distance between Ti dopants, and compensation by O interstitials contributes to broadening of the $\mathrm{Ti}\phantom{\rule{0.16em}{0ex}}2p$ XPS peak. The differences in electronic structure which render $\mathrm{T}{\mathrm{i}}^{4+}$-doped $\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{3}$ resistive due to the formation of compensating defects, but $\mathrm{T}{\mathrm{i}}^{4+}$-doped $\mathrm{F}{\mathrm{e}}_{2}{\mathrm{O}}_{3}$ conductive, are discussed. The defect compensation model developed here provides insight into previous, conflicting reports of $n$-type versus $p$-type conductivity in Ti-doped $\mathrm{C}{\mathrm{r}}_{2}{\mathrm{O}}_{3}$ at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum structure oxides.

Through systematic control of the Nd concentration, we show that the carrier density of the two-dimensional electron gas (2DEG) in ${\mathrm{SrTiO}}_{3}/{\mathrm{NdTiO}}_{3}/{\mathrm{SrTiO}}_{3}(001)$ can be modulated over a wide range. We also demonstrate that the ${\mathrm{NdTiO}}_{3}$ in heterojunctions without a ${\mathrm{SrTiO}}_{3}$ cap is degraded by oxygen absorption from air, resulting in the immobilization of donor electrons that could otherwise contribute to the 2DEG. This system is, thus, an ideal model to understand and control the insulator-to-metal transition in a 2DEG based on both environmental conditions and film-growth processing parameters.

Oxygen vacancies in LaAlO3 (LAO) play an important role in the formation of the two-dimensional electron gas observed at the LaAlO3/SrTiO3 interface and affect the performance of MOSFETs using LAO as a gate dielectric. However, their spectroscopic properties are still poorly understood, which hampers their experimental identification. Here we predict the absorption spectra and ESR parameters of oxygen vacancies in LAO using periodic and embedded cluster methods and density functional theory (DFT). The structure, charge distribution, and spectroscopic properties of the neutral and charged (1+ and 2+) oxygen vacancies in cubic and rhombohedral LaAlO3 are investigated. The highest intensity optical transitions [calculated using time-dependent DFT (TDDFT)], from the oxygen vacancy states to the conduction-band states have onsets at 3.5 and 4.2 eV for the neutral vacancy and 3.6 eV for the 1+ charged vacancy in rhombohedral LAO and 3.3 and 4.0 eV for the neutral vacancy and 3.4 eV for the 1+ charged vacancy in cubic LAO, respectively. Also reported are the isotropic g value (2.004026) and hyperfine coupling constants of the 1+ charged oxygen vacancy, which are compared to the experimental data obtained using electron spin resonance (ESR) spectroscopy, and accurately predict both the position and the width (3 mT) of its ESR signature. These results may further facilitate the experimental identification of oxygen vacancies in LAO and help to establish their role at the LAO/STO interfaces and in nanodevices using LAO.

Epitaxial interfaces and superlattices comprised of polar and non-polar perovskite oxides have generated considerable interest because they possess a range of desirable properties for functional devices. In this work, emergent polarization in superlattices of SrTiO$_3$ (STO) and LaCrO$_3$ (LCO) is demonstrated. By controlling the interfaces between polar LCO and non-polar STO, polarization is induced throughout the STO layers of the superlattice. Using x-ray absorption near-edge spectroscopy and aberration-corrected scanning transmission electron microscopy displacements of the Ti cations off-center within TiO6 octahedra along the superlattice growth direction are measured. This distortion gives rise to built-in potential gradients within the STO and LCO layers, as measured by in situ x-ray photoelectron spectroscopy. Density functional theory models explain the mechanisms underlying this behavior, revealing the existence of both an intrinsic polar distortion and a built-in electric field, which are due to alternately positively and negatively charged interfaces in the superlattice. This study paves the way for controllable polarization for carrier separation in multilayer materials and highlights the crucial role that interface structure plays in governing such behavior., 19 pages, 3 figures, supplement: 13 pages, 7 figures, Advanced Materials Interfaces, Early View, 2016

Author(s): Kaspar, TC; Sushko, PV; Spurgeon, SR; Bowden, ME; Keavney, DJ; Comes, RB; Saremi, S; Martin, L; Chambers, SA | Abstract: The behavior of polar LaMnO3 (LMO) thin films deposited epitaxially on nonpolar SrTiO3(001) (STO) is dictated by both the LMO/STO band alignment and the chemistry of the Mn cation. Using in situ X-ray photoelectron spectroscopy, the valence band offset (VBO) of LMO/STO heterojunctions is directly measured as a function of thickness, and found that the VBO is 2.5 eV for thicker (≥3 u.c.) films. No evidence of a built-in electric field in LMO films of any thickness is found. Measurements of the Mn valence by Mn L-edge X-ray absorption spectroscopy and by spatially resolved electron energy loss spectra in scanning transmission electron microscopy images reveal that Mn2+ is present at the LMO surface, but not at the LMO/STO interface. These results are corroborated by density functional theory simulations that confirm a VBO of ≈2.5 eV for both ideal and intermixed interfaces. A model is proposed for the behavior of polar/nonpolar LMO/STO heterojunctions in which the polar catastrophe is alleviated by the formation of oxygen vacancies at the LMO surface.

Nonuniform and highly localized Li dendrites are known to cause deleterious and, in many cases, catastrophic effects on the performance of rechargeable Li batteries. However, the mechanisms of cathode failures upon contact with Li metal are far from clear. In this study, using in situ transmission electron microscopy, the interaction of Li metal with well-defined, epitaxial thin films of LiCoO2 , the most widely used cathode material, is directly visualized at an atomic scale. It is shown that a spontaneous and prompt chemical reaction is triggered once Li contact is made, leading to expansion and pulverization of LiCoO2 and ending with the final reaction products of Li2 O and Co metal. A topotactic phase transition is identified close to the reaction front, resulting in the formation of CoO as a metastable intermediate. Dynamic structural and chemical imaging, in combination with ab initio simulations, reveal that a high density of grain and antiphase boundaries is formed at the reaction front, which are critical for enabling the short-range topotactic reactions and long-range Li propagation. The fundamental insights are of general importance in mitigating Li dendrites related issues and guiding the design principle for more robust energy materials.

Chemical effects at the surface and interface can broaden core-level spectra in X-ray photoemission for thin-film heterojunctions, as can electronic charge redistributions. We explore these effects and their influence on the measurement of valence and conduction band offsets at the epitaxial SrTiO3(001)/p-Ge(001) heterojunction. We observe a clear broadening in Ge 3d and Sr 3d core-level X-ray photoelectron spectra relative to those of clean, bulk Ge(001), and homoepitaxial SrTiO3(001), respectively. Angle-resolved measurements indicate that this broadening is driven primarily by chemical shifts associated with surface hydroxylation, with built-in potentials playing only a minor role. The impact of these two interpretations on the valence band offset is significant on the scale of transport energetics, amounting to a difference of 0.2 eV.

Epitaxial chromium ferrite (Fe2CrO4), prepared by state-of-the-art oxygen plasma assisted molecular beam epitaxy, is shown to exhibit unusual electronic transport properties driven by the crystallographic structure and composition of the material. Replacing 1/3 of the Fe cations with Cr converts the host ferrimagnet from a metal into a semiconductor by virtue of its fixed valence (3+); Cr substitutes for Fe at B sites in the spinel lattice. By contrast, replacing 2/3 of the Fe cations with Cr results in an insulator. Three candidate conductive paths, all involving electron hopping between Fe2+ and Fe3+, are identified in Fe2CrO4. Moreover, Fe2CrO4 is shown to be photoconductive across the visible portion of the electromagnetic spectrum. As a result, this material is of potential interest for important photo-electrochemical processes such as water splitting.

We demonstrate that the electronic structure of mesoporous silicon is affected by adsorption of nitro-based explosive molecules in a compound-selective manner. This selective response is demonstrated by probing the adsorption of two nitro-based molecular explosives (trinitrotoluene and cyclotrimethylenetrinitramine) and a nonexplosive nitro-based arematic molecule (nitrotoluene) on mesoporous silicon using soft X-ray spec- troscopy. The Si atoms strongly interact with adsorbed molecules to form Si-O and Si-N bonds, as evident from the large shifts in emission energy present in the Si L2,3 X-ray emission spectroscopy (XES) measurements. Furthermore, we find that the energy gap of mesoporous silicon changes depending on the adsorbant, as estimated from the Si L2,3 XES and 2p X-ray absorption spectroscopy (XAS) measurements. Our ab initio molecular dynamics calculations of model compounds suggest that these changes are due to spontaneous breaking of the nitro groups upon contacting surface Si atoms. This compound-selective change in electronic structure may provide a powerful tool for the detection and identification of trace quantities of airborne explosive molecules., 27 pages, 9 figures

Natural 12CaO$\ifmmode\cdot\else\textperiodcentered\fi{}$7Al${}_{2}$O${}_{3}$ (C12A7) is a wide band gap insulator, but conductivity can be realized by introducing oxygen deficiency. Currently, there are two competing models explaining conductivity in oxygen-deficient C12A7, one involving the electron transfer via a ``cage conduction band'' inside the nominal band gap, the other involving electron hopping along framework lattice sites. To help resolve this debate, we probe insulating and conducting C12A7 with x-ray emission, x-ray absorption, and x-ray photoemission spectroscopy, which provide a full picture of both the valence and conduction band edges in these materials. These measurements suggest the existence of a narrow conduction band between the main conduction and valence bands common in both conducting and insulating C12A7 and support the theory that free electrons in oxygen-deficient C12A7 occupy the low-energy states of this narrow band. Our measurements are corroborated with density functional theory calculations.

International audience; Site-specific functionalization of oxide nanostructures gives rise to novel optical and chemical surface properties. In addition, it can provide deeper insights into the electronic surface structure of the associated materials. We applied chemisorption of molecular hydrogen, induced by ultraviolet (UV) light, followed by vacuum annealing to MgO nanocubes to selectively decorate three-coordinated oxygen ions (oxygen corner sites, for simplicity) with protons. Fully dehydroxylated nanocubes exhibit 3.2 +/- 0.1 eV photoluminescence induced by 4.6 eV light, where both emission and absorption are associated with three-coordinated oxygen sites. We find that partially hydroxylated nanocubes show an additional photoluminescence feature at 2.9 0.1 eV. Interestingly, the excitation spectra of the 2.9 and 3.2 eV emission bands, associated with protonated and nonprotonated oxygen corner sites, respectively, nearly coincide and show well-pronounced maxima at 4.6 eV in spite of a significant difference in their local atomic and electronic structures. These observations are explained with the help of ab initio calculations, which reveal that (i) the absorption band at 4.6 eV involves four-coordinated O and Mg ions in the immediate vicinity of the corner sites and (ii) protonation of the three-coordinated oxygen ions eliminates the optical transitions associated with them and strongly red-shifts other optical transitions associated with neighboring atoms. These results demonstrate that the optical absorption bands assigned to topological surface defects are not simply determined by the ions of lowest coordination number but involve contributions due to the neighboring atoms of higher coordination. Thus, we suggest that the absorption band at 4.6 eV should not be regarded as merely a signature of the three-coordinated O2- ions but ought to be assigned to corners as multiatomic topological features. Our results also suggest that optical absorption signatures of protonated and nonprotonated sites of oxide surfaces can be remarkably similar.

Two-dimensional (2D) ultra-high carrier densities at complex oxide interfaces are of considerable current research interest for novel plasmonic and high charge-gain devices. However, the highest 2D electron density obtained in oxide heterostructures is thus far limited to 3×1014 cm-2 (½ electron/unit cell/interface) at GdTiO3/SrTiO3 interfaces, and is typically an order of magnitude lower at LaAlO3/SrTiO3 interfaces. Here we show that carrier densities much higher than 3×1014 cm-2 can be achieved via band engineering. Transport measurements for 3 nm SrTiO3/t u.c. NdTiO3/3 nm SrTiO3/LSAT (001) show that charge transfer significantly in excess of the value expected from the polar discontinuity model occurs for higher t values. The carrier density remains unchanged, and equivalent to ½ electron/unit cell/interface for t < 6 unit cells. However, above a critical NdTiO3 thickness of 6 u.c., electrons from the valence band of NdTiO3 spill over into the SrTiO3 conduction band as a natural consequence of the band alignment. An atomistic model consistent with first-principle calculations and experimental results is proposed for the charge transfer mechanisms. These results may provide an exceptional route to the realization of the room-temperature oxide electronics.