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Chromium iodide monolayers, which have different magnetic properties in comparison to the bulk chromium iodide, have been shown to form skyrmionic states in applied electromagnetic fields or in Janus-layer devices. In this work, we demonstrate that spin-canted solutions can be induced into monolayer chromium iodide by select substitution of iodide atoms with isovalent impurities. Several concentrations and spatial configurations of halide substitutional defects are selected to probe the coupling between the local defect-induced geometric distortions and orientation of chromium magnetic moments. This work provides atomic-level insight into how atomically precise chemical doping can be used to create and control complex magnetic patterns in chromium iodide layers and lays out the foundation for investigating the field- and geometric-dependent magnetic properties in similar two-dimensional materials.

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.

Efficient ammonia synthesis and decomposition processes under mild conditions are important to meet the expanding demand in major applications of ammonia as the energy carrier and to provide feedst...

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.

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.

A series of mixed cation silicate glasses of the composition A2O–2MO–4SiO2, with A = Li, Na, K and M = Ca, Sr, Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions, whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observed that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radius ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.

We show that despite very similar crystallographic properties and work function values in bulk Fe and Cr, epitaxial films of these metals on Nb:SrTiO3(001) exhibit completely different heterojunction electronic properties. The Cr/SrTiO3 interface is ohmic, whereas Fe/SrTiO3 forms a Schottky barrier with a barrier height of 0.50 eV. This difference arises because of variations in interface chemistry. In contrast to Cr [Chambers, S. A. , Adv. Mater. 2013, 25, 4001.], in-diffused Fe exhibits a +2 oxidation state and occupies Ti sites in the perovskite lattice, resulting in negligible charge transfer to Ti, upward band bending, and Schottky barrier formation. The differences between Cr and Fe are understood by performing first-principles calculations of the energetics of defect formation, which corroborate experimental results.

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.

Electrides, i.e. salts in which electrons serve as anions, are promising materials for lowering activation energies of chemical reactions. Ab initio simulations are used to investigate the effect of the electron anions in a prototype mayenite-based electride (C12A7:e(-)) on the mechanism of N2 dissociation. It is found that both atomic and molecular nitrogen species chemisorb on the electride surface and become negatively charged due to the electron transfer from the substrate. However, charging alone is not sufficient to promote dissociation of N2 molecules. In the presence of Ru, N2 adsorbs with the formation of a cis-Ru2N2 complex and the N-N bond weakens due to both the electron transfer from the substrate and interaction with Ru. This complex transforms into a more stable trans-Ru2N2 configuration, in which the N2 molecule is dissociated, with the calculated barrier of 116 kJ mol(-1) and the overall energy gain of 72 kJ mol(-1). In contrast, in the case of the stoichiometric mayentie, the cis-Ru2N2 is ~34 kJ mol(-1) more stable than the trans-Ru2N2, while the cis-trans transition has a barrier of 192 kJ mol(-1). Splitting of N2 is promoted by a combination of the strong electron donating power of C12A7:e(-), ability of Ru to capture N2, polarization of Ru clusters, and electrostatic interaction of negatively charged N species with the surface cations.

Heteroepitaxial growth of Cr metal on Nb-doped SrTiO₃(001) is accompanied by Cr diffusion to interstitial sites within the first few atomic planes, an anchoring of the Cr film to the substrate, charge transfer from Cr to Ti, and metallization of the near-surface region, as depicted in the figure. The contact resistance of the resulting interface is exceedingly low.

An atomistic model of the SiO2/BaTiO3 interface was constructed using ab initio molecular dynamics. Analysis of its structure and electronic properties reveals that (i) the band gap at the stoichiometric SiO2/BaTiO3 interface is significantly smaller than those of the bulk BaTiO3 and SiO2, and (ii) the interface contains ∼5.5 nm(-2) oxygen vacancies (V(2+)) in the outermost TiO2 plane of the BaTiO3 and ∼11 nm(-2) Si-O-Ti bonds resulting from breaking Si-O-Si and Ti-O-Ti bonds and subsequent rearrangement of the atoms. This structure gives rise to the interface polar region with positive and negative charges localized in the BaTiO3 and SiO2 parts of the interface, respectively. We propose that high dielectric response, observed experimentally in the SiO2-coated nanoparticles of BaTiO3, is due to the electron gas formed in oxygen-deficient BaTiO3 and localized in the vicinity of the polar interface.

Surface structures of stoichiometric and oxygen-deficient complex subnanoporous oxide 12CaO·7Al 2 O 3 (C12A7) are generated by simulating lattice rupture under the influence of an external strain. Extra-framework anions are found to serve as buffers, maintaining stability of the lattice cages in both elastic and inelastic stretching regimes. Modification of the local atomic structure in the near-surface region reduces the band gap in stoichiometric insulating C12A7. On the contrary, the band gap appears in the oxygen-deficient form of C12A7, which is metallic in the bulk. This is due to formation of the surface electron traps, which differ both in the type of the local atomic structure and stability of the electronic states. The implications of this electronic structure for the surface chemical and electron emission properties are discussed.

Previous experiments have demonstrated that photoluminescence properties, both excitation and emission spectra, of powdered MgO depend strongly on the powder preparation and treatment. Similar dependencies have been found for CaO, SrO, and BaO powders. The observed broad photoemission bands have been attributed to the low-coordinated surface sites. Recent advances in nanoscale science and technology have made it possible to produce nearly monodispersed alkaline-earth oxide nanoparticles of very high surface area and investigate their optical properties in details. Here we present the results of our theoretical and experimental work in this area and present new results.

We investigate theoretically the effects of isovalent substitutional doping on the optical properties of cubic MgO nanoparticles. The Ca, Sr, and Ba impurities preferentially occupy the three-coordinated cation sites and counterbalance the lattice strain induced by the finite size of the host particles. The lowest optical absorption band shifts to the lower energies as the radius of the substitutional species increases. Two types of nearly iso-energetic triplet excitons are found: the symmetric and asymmetric configurations correspond to the hole component being delocalized over three four-coordinated anion and localized on a single anion, respectively. The photoluminescence energies strongly depend on the exciton configuration and can be controlled by the judicious choice of the dopans.

12CaO·7Al2O3 (C12A7) with a unique nano-porous structure and free O2− ions entrapped in sub-nanometer-sized cages is a fast oxygen-ion-conducting material. These free O2– may be replaced by various oxygen-related species, OH−, O2− and O−, by tuning the atmosphere during the heat treatment. We examined the conduction mechanism for stoichiometric C12A7 (C12A7:O2−), in which O2− ions exist as counter anions in sub-nanometer-sized cages, by Raman measurement of C12A7:O2− annealed in a dry 18O2 atmosphere. It was revealed that the primary ion conducting species is an O2− ion which diffuses via exchange with O2− in the cage wall. An experimental result on the sample containing O− ions implied that O− is more mobile than O2− in C12A7. Ab initio calculations on the diffusion paths of O2− and O− ions in C12A7 supported the above experimental results.

Density functional theory simulation results of the atomic structure at the Si-SiO 2 interface implies a non-abrupt transition of the band-gap within the oxide. The depth of the transition, 2-6 A, is comparable to the approximately nm oxide thickness in nano-CMOS devices, and is expected to affect their characteristics. Using hierurchical simulation approach, we combine for the first time ab-initio density functional theory simulations of the interface, with self-consistent Poisson - Schrodinger one-dimensional device simulations, and estimate the impact of interface band-gap transition on the inversion layer quantisation, capacitance, and tunnelling characteristics of a metal-oxide-semiconductor structure.

We have studied the intra- and intermolecular hydrogen transfer in a crystalline 1,1-diamino-2,2-dinitroethylene (DADNE) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) by means of an embedded cluster method and density functional theory (DFT). We found that, even though both of these materials have similar amino- and nitro- functional groups and layered crystalline structures, there are important differences in the mechanisms of hydrogen transfer. In particular, our calculations suggest that the proton migration from an amino-group to a nitro-group of the same molecule is a feasible process in TATB but not in DADNE. At the same time, we have found that no intermolecular hydrogen transfer occurs in either molecular crystal. These results imply that the activation of the decomposition reactions proceeds via different paths in these two materials.

Recently, a novel inorganic electride stable at room temperatures has been obtained by reducing a complex nanoporous oxide 12CaO.7Al2O3 (C12A7) in a Ca atmosphere (Matsuishi, S.; Toda, Y.; Miyakawa, M.; Hayashi, K.; Kamiya, T.; Hirano, M.; Tanaka, I.; Hosono, H. Science 2003, 301, 626). In this system, up to 2.3 x 1021/cm3 electrons can be accommodated in a three-dimensional network of cages formed by a positively charged oxide framework. We demonstrate theoretically that at all concentrations, ne, the electrons are neither associated with specific atoms nor fully delocalized. At low ne, the electrons are isolated from each other and resemble the color centers in insulating materials. They are well localized in some of the lattice cages and yield strong inhomogeneous lattice distortions that provide polaron-type cage-to-cage electron hopping. As ne increases, the electrons form a denser electron gas and become more evenly spread over all available lattice cages. At sufficiently high ne, the system becomes metallic but still retains partially localized character of the conducting electrons. We describe the nature of the electronic states at the Fermi level and predict the changes in the optical and magnetic properties of this system as a function of ne.

Epitaxial La1-x Srx CrO3 deposited on SrTiO3 (001) is shown to be a p-type transparent conducting oxide with competitive figures of merit and a cubic perovskite structure, facilitating integration into oxide electronics. Holes in the Cr 3d t2g bands play a critical role in enhancing p-type conductivity, while transparency to visible light is maintained because low-lying d-d transitions arising from hole doping are dipole forbidden.

Epitaxial La1-x Srx CrO3 deposited on SrTiO3 (001) is shown to be a p-type transparent conducting oxide with competitive figures of merit and a cubic perovskite structure, facilitating integration into oxide electronics. Holes in the Cr 3d t2g bands play a critical role in enhancing p-type conductivity, while transparency to visible light is maintained because low-lying d-d transitions arising from hole doping are dipole forbidden.

Novel approaches to efficient ammonia synthesis at an ambient pressure are actively sought out so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen–nitrogen triple bond, which is generally considered a rate-determining step. Here we examine kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis—ruthenium-loaded 12CaO·7Al2O3 electride (Ru/C12A7:e−)—and find that the rate controlling step of ammonia synthesis over Ru/C12A7:e− is not dissociation of the nitrogen–nitrogen triple bond but the subsequent formation of N–Hn species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:e− surface is proposed on the basis of observed hydrogen absorption/desorption kinetics., Development of catalysts that enhance dissociation of the nitrogen–nitrogen triple bond will reduce costs of ammonia production. Here, the authors study ammonia synthesis over a ruthenium loaded electride catalyst and show that the rate-determining step is shifted to nitrogen–hydrogen bond formation.

We used an ab initio embedded cluster method to study and compare three charged states of the Si-Si dimer configurations of oxygen vacancies in @a-quartz and amorphous silica. The Si-Si bond in the neutral vacancy remains largely the same in both crystalline and amorphous SiO"2. In @a-quartz the positively charged dimer E' centre exists only as a meta-stable configuration, whereas in amorphous silica stable dimer configuration can be formed at favorable precursor sites. Our results demonstrate that negatively charged dimer oxygen vacancies can be formed in @a-quartz.

We performed first-principle embedded cluster calculations of the hyperfine parameters, g-tensors and optical excitation energies for the dimer and back-projected configurations of the centre in amorphous silica. The optical transition energies of these defects are calculated for the first time. We predict a strong optical transition at about 6.3 eV for the dimer configuration and a relatively weak transition at 5.6 eV for the back-projected configuration of the centre. These predictions could be used for further experimental identification of these centres. Our results support the dimer model of the centre, and for the first time provide a full range of spectroscopic parameters for the back-projected configuration of the centre in amorphous silica.

Oxygen-vacancy dipoles and dimers in CaF2 crystals have been studied ab initio at DFT level and with the shell model using pair potentials. The calculated dipole reorientation barrier is 0.64 eV and the activation energy for diffusion of the dipoles is 1.61 eV. Optical absorption of O 2--VA dipole have been calculated with TD DFT and identified with experimental absorption bands, which appeared to have complex structure. The photodissociation mechanism of the dipole is discussed. Several configurations of the dimer (O2--VA)2 were calculated. The association energy for the most favourable one is 0.48 eV. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen vacancies are often present in complex oxides as point defects, and their effect on the electronic properties is typically uniform and isotropic. Exploiting oxygen deficiency in order to generate controllably novel structures and functional properties remains a challenging goal. Here we show that epitaxial strontium chromite films can be transformed, reversibly and at low temperature, from rhombohedral, semiconducting SrCrO(2.8) to cubic, metallic perovskite SrCrO(3-δ). Oxygen vacancies in SrCrO(2.8) aggregate and give rise to ordered arrays of {111}-oriented SrO(2) planes interleaved between layers of tetrahedrally coordinated Cr(4+) and separated by ~1 nm. First-principle calculations provide insight into the origin of the stability of such nanostructures and, consistent with the experimental data, predict that the barrier for O(2-) diffusion along these quasi-two-dimensional nanostructures is significantly lower than that in cubic SrCrO(3-δ). This property is of considerable relevance to solid oxide fuel cells in which fast O(2-) diffusion reduces the required operating temperature.

The true oxidation state of formally ‘H−’ ions incorporated in an oxide host is frequently discussed in connection with chemical shifts of 1H nuclear magnetic resonance spectroscopy, as they can exhibit values typically attributed to H+. Here we systematically investigate the link between geometrical structure and chemical shift of H− ions in an oxide host, mayenite, with a combination of experimental and ab initio approaches, in an attempt to resolve this issue. We demonstrate that the electron density near the hydrogen nucleus in an OH− ion (formally H+ state) exceeds that in an H− ion. This behaviour is the opposite to that expected from formal valences. We deduce a relationship between the chemical shift of H− and the distance from the H− ion to the coordinating electropositive cation. This relationship is pivotal for resolving H− species that are masked by various states of H+ ions., The oxidation state of hydride ions in oxide hosts is a matter of debate. Here, the authors address this question with a range of techniques and suggest that the electron density near an incorporated hydride ion is less than that at the hydrogen in a hydroxide ion, contrary to formal valence arguments.

Activation of carbon dioxide is the most important step in its conversion into valuable chemicals. Surfaces of stable oxide with a low work function may be promising for this purpose. Here we report that the surfaces of the inorganic electride [Ca24Al28O64]4+(e−)4 activate and split carbon dioxide at room temperature. This behaviour is attributed to a high concentration of localized electrons in the near-surface region and a corrugation of the surface that can trap oxygen atoms and strained carbon monoxide and carbon dioxide molecules. The [Ca24Al28O64]4+(e−)4 surface exposed to carbon dioxide is studied using temperature-programmed desorption, and spectroscopic methods. The results of these measurements, corroborated with ab initio simulations, show that both carbon monoxide and carbon dioxide adsorb on the [Ca24Al28O64]4+(e−)4 surface at RT and above and adopt unusual configurations that result in desorption of molecular carbon monoxide and atomic oxygen upon heating., Effective activation and spitting of carbon dioxide are important steps in its conversion to valuable chemicals. Here the authors report an inorganic electride material with a high concentration of near-surface electrons that is capable of adsorbing and decomposing carbon dioxide.

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.

A novel nanoporous material 12CaO.7Al2O3 (C12A7) offers a possibility of incorporating large concentrations (>1021 cm-3) of a wide range of extraframework anions inside its nanopores. We have investigated, both experimentally and theoretically, optical absorption associated with several types of such anions, including F-, OH-, O-, O2-, O2-, and O22-, and assigned their optical absorption bands. It is demonstrated that the chemical identity and concentration of extraframework anions can be controlled by an appropriate treatment of "as grown" C12A7. We also show that the position of the adsorption edge is, in turn, determined by the chemical identity of the extraframework species and can be varied in the range of approximately 4-6 eV. We suggest that C12A7 is a unique host material, which can be used as a playground for studying negatively charged species that are unstable in other environments.

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.

The structure and mechanisms of bonding and defect formation at the interfaces between amorphous silica (a-SiO2) and BaTiO3(0 0 1) were investigated using ab initio molecular dynamics. It was found that the nature of interfacial bonds crucially depends on the BaTiO3 surface termination. In particular, the interface between silica and TiO2-terminated BaTiO3 (BTO) slab is characterised by strong covalent Ti-O-Si bonds, while the interface between silica and BaO-terminated BTO demonstrates ionic character of interfacial bonds and exhibits bond instability. In both cases, the dynamics of oxygen species at oxide interfaces is a driving force of the formation of interfacial bonds and defects.

We review recent developments in controlling photoinduced desorption processes of alkali halides. We focus primarily on hyperthermal desorption of halogen atoms and show that the yield, electronic state, and velocity distributions of desorbed atoms can be selected using tunable laser excitation. We demonstrate that the observed control is due to preferential excitation of surface excitons. This approach takes advantage of energetic differences between surface and bulk exciton states and probes the surface exciton directly. We demonstrate that desorption of these materials leads to controlled modification of their surface geometric and electronic structures. We then extend the exciton mechanism of desorption, developed for alkali halides, to metal oxide surfaces, in particular magnesium oxide. In addition, these results demonstrate that laser desorption can serve as a solid-state source of halogen and oxygen atoms, in well-defined electronic and velocity states, for studying chemical processes in the gas phase and at surfaces.

The 12CaO.7Al2O3 (C12A7) crystal with a nanoporous lattice framework exhibits high electrical conductivity with an activation energy of approximately 1.5 eV when equilibrated in a hydrogen atmosphere above approximately 800 degrees C. The high conductivity is preserved in a quenched state below approximately 600 degrees C with a reduced activation energy of approximately 0.8 eV. Such complex behavior in electrical conductivity is associated with incorporation of hydride ions (H-) in cages of the lattice framework. Electromotive force measurements reveal that the major carrier for the conductivity is electron with a small contribution by proton (H+), ruling out the possibility of direct intercage migration of the H- ion. A combination of these observations with the ab initio calculations leads to the conclusion that the electrons are thermally generated from the H- ion by the dissociation into two electrons and an proton, which is further converted to an OH- ion via reaction with an extraframework oxide ion (O2-). The energy difference between the initial (H- + O2-) and the final (2e- + OH-) states as evaluated by the theoretical calculation is as small as approximately 1 eV, which agrees well with an experimentally obtained enthalpy change, approximately 1.4 eV. Thus, internal equilibration between the extraframework hydrogen and the oxygen species is responsible for the thermal generation of the carrier electron. It is also suggested that the same conductive (2e- + OH-) state is reached by the photoirradiation of H- -containing C12A7. In this case the photoionization of H- forms an electron and an Ho atom, which then forms an OH- ion and another electron with thermal assistance. The persistence of photoinduced conductivity is explained by the slow kinetics of the reverse process at room temperature.

The nanoporous main group oxide 12CaO.7Al(2)O(3) (C12A7) can be transformed from a wide-gap insulator to an electride where electrons substitute anions in cages constituting a positive frame. Our ab initio calculations of the electronic structure of this novel material give a consistent explanation of its high conductivity and optical properties. They show that the electrons confined in the inert positive frame are localized in cages and undergo hopping between neighboring cages. The results are useful for the understanding of behavior of confined electron gas of different topology and electron-phonon coupling, and for designing new transparent conductors, electron emitters, and electrides.

The electronic and structural properties of Mo(100)/GaAs(100) interfaces and Mo diffusion into GaAs are explored using first principle calculations. Our results show that the interface undergoes substantial atomic rearrangement with respect to the bulk structures and the bilayer of the GaAs adjacent to the interface becomes conducting. We study the n-type Schottky barrier height's dependence on Mo interdiffusion in the GaAs, with values ranging from ∼0.9 eV to ∼1.39 eV. This range is caused by the diffusants acting as additional n–type doping at the surface and their interaction with the metal-induced gap states.

Stoichiometric epitaxial LaAlO(3) grown on TiO(2)-terminated SrTiO(3)(001) by off-axis pulsed laser deposition is shown to exhibit strong cation intermixing. This result is corroborated by classical and quantum mechanical calculations of the relative stabilities of abrupt and intermixed interface configurations. The valence band offset was measured to be 0.16 ± 0.10 eV, and this value cannot be accounted for theoretically without including intermixing in the physical description of the interface.

The gradual transition of the band-gap at the Si-SiO2 interface affects quantisation and leakage characteristics of MOS inversion layer. We establish a link between first principles DFT simulations of the interface, and continuum simulations in the effective mass approximation, in order to obtain a realistic description of the band-gap transition for device modelling. The simplistic approach of obtaining real-space-dependent band-gap profile from the ab initio calculated electronic structure results in uncertainty of the simulated device characteristics. This uncertainty is small however, when compared to the magnitude of the simulated impact of the transition layer. A linear transition of the band-gap over 6 – 7 A in the oxide approximates well the effects simulated with the realistic band-gap profile from DFT.

We suggest, on the basis of detailed ab initio calculations of both ground and photoexcited states of H-doped 12CaO∙7Al2O3 (C12A7:H), that stable high-conductivity regions can be optically generated in this insulating system. Each H− ion in C12A7:H can, under photoirradiation at 3.8–4.5 eV, produce up to two electrons and a proton that binds to the lattice network and forms OH−. Mobile electrons play a role of anions in this system. They move over subnanosized cages of the C12A7 lattice via polaron hopping. The insulating state is reversibly restored upon heating to 300 °C.