Anomalous Kinetics of Diffusion-Controlled Defect Annealing in Irradiated Ionic Solids

The authors thanks A. Ch. Lushchik, M. Izerrouken, and V. Lisitsyn for stimulating discussions. This work has been carried out within the framework of the EUROfusion Consortium and has received funding from the Euroatom research and training programme 2014-2018 under Grant Agreement No. 633053. The views and opinions expressed herein do not necessarily reflect those of the European Commission. R.V. acknowledges the financial support by the MEIC (Ministerio de Economa, Industria y Competitivad; Project ENE2015-70300-C3-1-R). The calculations were performed using facilities of the Stuttgart Supercomputer Center (Project DEFTD 12939).

Hybrid DFT calculations of the atomic and electronic structure for ABO3 perovskite (001) surfaces

Abstract We present the results of first-principles calculations on two possible terminations of the (0 0 1) surfaces of SrTiO3, BaTiO3, and PbTiO3 perovskite crystals. Atomic structure and the electronic configurations were calculated for different 2D slabs, both stoichiometric and non-stoichiometric, using hybrid (B3PW) exchange-correlation technique and re-optimized basis sets of atomic (Gaussian) orbitals. Results are compared with previous calculations and available experimental data. The electronic density distribution near the surface and covalency effects are discussed in details for all three perovskites. Both SrTiO3 and BaTiO3 (0 0 1) surfaces demonstrate reduction of the optical …

Use of site symmetry in supercell models of defective crystals: Polarons in CeO2

The authors thank R. Merkle and G. W. Watson for stimulating discussions. E. K. also acknowledges partial financial support from the Russian Science Foundation for the study of charged defects under the project 14-43-00052. A. C. also acknowledges financial support from the University of Latvia Foundation (Arnis Riekstins's "MikroTik" donation). E. K. and D. G. express their gratitude to the High Performance Computer Centre in Stuttgart (HLRS, project DEFTD 12939) for the provided computer facilities whereas R. A. E. thanks the St. Petersburg State University Computer Center for assistance in high-performance calculations.

Small radius electron and hole polarons in PbX2 (X = F, Cl, Br) crystals: a computational study

First-principles hybrid density functional theory (DFT) calculations were performed for small radius polarons – self-trapped electrons (STELs) and holes (STHs) in PbX2 (X = F, Cl, Br) crystals, widely used as parent materials for inorganic halide perovskites (CsPbX3) and scintillators. The atomic and electronic structures, spin and charge distributions and formation energies for both types of polarons were predicted for orthorhombic PbF2 and STELs for cubic PbF2. The STH structure was identified in a controversial case of PbCl2. We also confirmed and analyzed in detail experimentally suggested configurations for other cases. It is shown how, due to a delicate balance of ionic and covalent c…

First-principles comparative study of perfect and defective CsPbX3 (X = Br, I) crystals

We thank R. Merkle for numerous fruitful discussions and G. Siegle for experimental assistance. This study was partly supported by the M-ERA-NET project SunToChem (EK). Calculations were performed using computational facilities of St. Petersburg State University and Max Planck Institute for Solid State Research. Open Access funding provided by the Max Planck Society.

Ab initio thermodynamic study of (Ba,Sr)(Co,Fe)O3 perovskite solid solutions for fuel cell applications

(Ba,Sr)(Co,Fe)O3 (BSCF) perovskite solid solutions are promising materials for solid oxide fuel cell cathodes and oxygen permeation membranes. Cathode performance strongly depends on the morphology of these materials remaining as a single phase or two-phase mixture. Combining ab initio calculations of the atomic and electronic structure of different supercells with thermodynamics of solid solutions, we have constructed and discussed phase diagrams of several important BSCF chemical compositions. It is demonstrated that in BSC cobaltite solid solution the spinodal decomposition may occur already at relatively low temperatures, while ferrite (BSF and SCF) solid solutions decompose at relative…

Ab initio Hartree-Fock calculations of LaMnO3 (110) surfaces

We present the results of ab initio Hartree-Fock calculations of the LaMnO3 (110) surface. Using seven-plane slabs, periodic in 2D and containing three formula units, we compare the properties of a stoichiometric surface with oxygen vacancies, and non-stoichiometric, defect-free surfaces, analyze the dispersion of the effective charges near the surface, and calculate the surface energy before and after relaxation, for both ferromagnetric and antiferromagnetic spin orderings in a slab. q 2003 Elsevier Ltd. All rights reserved.

Impact of point defects on the elastic properties of BaZrO3: Comprehensive insight from experiments and ab initio calculations

Abstract Acceptor doped BaZrO3 is the prototype of proton conducting perovskites which are of strong interest as electrolytes for intermediate temperature fuel cells. Elastic properties of both dry and hydrated Y-doped BaZrO3 (1.5–17 mol% Y) were determined using ultrasound time of flight (TOF) measurements, and complemented by ab initio calculations which allow for an analysis of the different contributions. The experimental and theoretical findings are consistent and reveal a strong decrease of the Young's, shear and bulk moduli upon increasing dopant concentration. This decrease is attributed to a combined effect of (i) macroscopic lattice chemical expansion mainly caused by differing io…

Stabilization of primary mobile radiation defects in MgF2 crystals

Abstract Non-radiative decay of the electronic excitations (excitons) into point defects ( F – H pairs of Frenkel defects) is main radiation damage mechanism in many ionic (halide) solids. Typical time scale of the relaxation of the electronic excitation into a primary, short-lived defect pair is about 1–50 ps with the quantum yield up to 0.2–0.8. However, only a small fraction of these primary defects are spatially separated and survive after transformation into stable, long-lived defects. The survival probability (or stable defect accumulation efficiency) can differ by orders of magnitude, dependent on the material type; e.g. ∼10% in alkali halides with f.c.c. or b.c.c. structure, 0.1% in…

First principles calculations of oxygen vacancy formation and migration in mixed conducting Ba0.5Sr0.5Co1−yFeyO3−δ perovskites

Abstract First-principles supercell calculations of oxygen vacancies in the Ba 0.5 Sr 0.5 Co 1− y Fe y O 3− δ (BSCF) perovskites are presented. The density of states is determined for different iron content and oxygen vacancy concentrations, and the characteristic differences for Co and Fe are discussed. We analyze the dependences of the defect (oxygen vacancy) formation and migration energies on the Fe content and compare the calculated properties with those of related LaCoO 3 and LaFeO 3 perovskites.

X-ray Spectroscopy of (Ba,Sr,La)(Fe,Zn,Y)O3-δIdentifies Structural and Electronic Features Favoring Proton Uptake

Mixed protonic–electronic conducting oxides are key functional materials for protonic ceramic fuel cells. Here, (Ba,Sr,La)(Fe,Zn,Y)O3−δ perovskites are comprehensively investigated by X-ray spectroscopy (in oxidized and reduced states). Extended X-ray absorption fine structure shows that Zn,Y doping strongly increases the tendency for Fe–O–Fe buckling. X-ray absorption near-edge spectroscopy at the Fe K-edge and X-ray Raman scattering at the O K edge demonstrate that both iron and oxygen states are involved when the samples are oxidized, and for the Zn,Y doped materials, the hole transfer from iron to oxygen is less pronounced. This can be correlated with the observation that these material…

First-principles calculations of iodine-related point defects in CsPbI3

Many thanks to A. Lushchik, A. Popov and R. Merkle for numerous fruitful discussions. This study was partly supported by the Latvian Council for Science (grant LZP-2018/1-0147 to EK). R.A.E acknowledges the assistance of the University Computer Center of Saint-Petersburg State University for high-performance computations.

Interdependence of Oxygenation and Hydration in Mixed-Conducting (Ba,Sr)FeO3-δPerovskites Studied by Density Functional Theory

Financial support by the German–Israeli Foundation for Scientific Research and Development (grant I-1342-302.5/2016) and the Latvian Council of Science (grant lzp-2018/1-0147 (D.G., E.A.K.)) is gratefully acknowledged. The authors further thank Guntars Zvejnieks for help with CRYSTAL code calculations.

First-principles calculations of the atomic and electronic structure ofFcenters in the bulk and on the (001) surface ofSrTiO3

The atomic and electronic structure, formation energy, and the energy barriers for migration have been calculated for the neutral O vacancy point defect F center in cubic SrTiO3 employing various implementations of density functional theory DFT. Both bulk and TiO2-terminated 001 surface F centers have been considered. Supercells of different shapes containing up to 320 atoms have been employed. The limit of an isolated single oxygen vacancy in the bulk corresponds to a 270-atom supercell, in contrast to commonly used supercells containing 40– 80 atoms. Calculations carried out with the hybrid B3PW functional show that the F center level approaches the conduction band bottom to within 0.5 eV…

Surface termination effects on the oxygen reduction reaction rate at fuel cell cathodes

This research was partly funded by the Latvian project IMIS2 with the computer resources provided by the High Performance Computing Centre Stuttgart (HLRS) (Project DEFTD 12939). The authors thank D. Gryaznov for fruitful discussions and M. Sokolov for technical assistance. MMK is grateful to the Office of the Director of National Science Foundation for support under the Independent Research and Development program. The ndings, conclusions, and recommendations expressed in this material are those of the authors and do not necessarily reect the views of NSF and other funding agencies.

Confinement effects for ionic carriers in SrTiO3 ultrathin films: first-principles calculations of oxygen vacancies.

One-dimensional confinement effects are modelled within the hybrid HF-DFT LCAO approach considering neutral and single-charged oxygen vacancies in SrTiO(3) ultrathin films. The calculations reveal that confinement effects are surprisingly short-range in this partly covalent perovskite; already for film thickness of 2-3 nm (and we believe, similar size nanoparticles) only the surface-plane defect properties differ from those in the bulk. This includes a pronounced decrease of the defect formation energy (by ∼1 eV), a much deeper defect band level and a noticeable change in the electronic density redistribution at the near-surface vacancy site with respect to that in the bulk. The results als…

Jahn-Teller distortion aroundFe4+inSr(FexTi1−x)O3−δfrom x-ray absorption spectroscopy, x-ray diffraction, and vibrational spectroscopy

$\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ perovskites (strontium titanate ferrite solid solution) with well-defined oxygen stoichiometry have been studied as a function of iron concentration by x-ray diffraction, Fe and Ti $K$-edge x-ray absorption spectroscopy (XAS), and vibrational (Raman and infrared) spectroscopy. In reduced $\mathrm{Sr}({\mathrm{Fe}}_{x}{\mathrm{Ti}}_{1\ensuremath{-}x}){\mathrm{O}}_{3\ensuremath{-}x∕2}$ samples, the analysis of the Fe $K$-edge extended x-ray absorption fine structure indicates the expected presence of oxygen vacancies ${\mathrm{V}}_{\mathrm{O}}^{∙∙}$ in the first coordination shell…

Dopant solubility in ceria: alloy thermodynamics combined with the DFT+U calculations

This research was partly funded by the Russian Science Foundation (under the project 14-43-0005) and ERA-NET HarvEnPiez project, with the computer resources provided by Stuttgart Supercomputing Centre (Project DEFTD 12939). A. C. also acknowledges financial support from the University of Latvia Foundation (Arnis Riekstins’s ‘‘MikroTik’’ donation). Authors thank R. Merkle, A. Popov for fruitful discussions.

Structure and oxide ion conductivity: local order, defect interactions and grain boundary effects in acceptor-doped ceria

The long-range and short-range structure of nanocrystalline and microcrystalline acceptor-doped ceria is investigated by a combined approach using EXAFS, XANES, Raman, and XRD, and correlated with the oxide-ion conductivity in the bulk and in grain boundaries. Compared to Yb3+ and Er3+, the positive influence of Sm3+ is attributed to the ability to repel oxygen vacancies, and to keep a localized disorder around the dopant. The long-range structural analysis shows lattice contraction for Yb- and Er-doping and lattice expansion for Sm-doping. The short-range analysis around the dopants and cerium highlights that a more complex structural rearrangement has to be assumed to explain the compleme…

Nanosession: Ionics - Redox Kinetics, Ion Transport, and Interfaces

Oxygen Incorporation Reaction into Mixed Conducting Perovskites: a Mechanistic Analysis for (La,Sr)MnO3 Based on DFT Calculations

Based on DFT calculations of intermediates and transition states, several hypothetical mechanisms for oxygen incorporation into mixed conducting La1-xSrxMnO3{plus minus}d perovskites are discussed. In the most probable mechanism, the rate-determining step comprises the encounter of a highly mobile surface oxygen vacancy and a molecular oxygen adsorbate. Starting from these results, the variation of reaction rates for different materials is explored.

First-principles calculations for SrTiO3() surface structure

As a continuation of our recent abinitio calculations of SrTiO 3(1 0 0) surface relaxation for the two different terminations (SrO and TiO2) [Phys. Rev. B 64 (2001) 23417], we analyze here their electronic structures (band structure, density of states, and the electronic density redistribution with emphasis on the covalency effects). We compare results of abinitio Hartree–Fock method with electron correlation corrections and density functional theory with different exchange-correlation functionals, including hybrid (B3PW, B3LYP) exchange techniques. Our results are also compared with previous abinitio plane-wave local density approximation calculations and experiments when availab le. Consi…

Ab initiomodeling of surface structure forSrTiO3perovskite crystals

We present and discuss the results of calculations of ${\mathrm{SrTiO}}_{3}$ (100) surface relaxation and rumpling with two different terminations (SrO and ${\mathrm{TiO}}_{2}).$ These are based on ab initio Hartree-Fock method with electron correlation corrections and density functional theory calculations with different exchange-correlation functionals, including hybrid exchange techniques. Both approaches use the localized Gaussian-type basis set. All methods agree well on surface energies and on atomic displacements, as well as on considerable increase of covalency effects nearby the surface. More detailed experiments on surface rumpling and relaxation are necessary for further testing …

Surface Segregation Entropy of Protons and Oxygen Vacancies in BaZrO3

The perovskite BaZrO3 has attracted considerable attention in the recent decade due to its high temperature proton conducting properties, and possible application as electrolyte in intermediate temperature fuel cells and electrolyzers. In this contribution, we performed, for the first time, first-principles calculations of the phonon contribution to the defect thermodynamics of the ZrO2 terminated (001) surface of BaZrO3. The approach allows us to determine both the segregation enthalpy and entropy of defects, which we apply to two fundamental defects in BaZrO3; fully charged oxygen vacancies (vO••) and protonic defects (OHO•). The calculations show that both defects exhibit favorable segre…

Enhanced lithium storage and chemical diffusion in metal-LiF nanocomposites: Experimental and theoretical results

An extra storage of Li has been observed experimentally at low potential in Me/LiF nanocomposites where Me refers to transition metals such as Cu, Co, etc., with a pseudocapacitive behavior characterized by a high rate performance. To understand the mechanistic details of the lithium storage anomaly, we have performed comparative ab initio calculations on the atomic and electronic structure of the nonpolar Cu/ LiF001 and model Li/ LiF001 interfaces. For this aim, we inserted extra Li atoms at several possible sites of the periodic two-dimensional Me/LiF Me= Cu, Li interfaces. The energetically most favorable site for extra Li atom is

First-principles phonon calculations of Fe4+impurity in SrTiO3

The results of hybrid density functional theory calculations on phonons in Sr(Fe(x)Ti(1-x))O(3) solid solution within the formalism of a linear combination of atomic orbitals are presented. The phonon density of states (DOS) calculated for 6.25% Fe(4+) impurities is reported and defect-induced phonon modes are identified. Based on our calculations and group-theoretical analysis, we suggest for the first time an interpretation of experimentally observed Raman- and IR-active modes.

Finite element simulation of diffusion into polycrystalline materials

Diffusion in polycrystalline materials is investigated by means of numerical finite element simulations for constant source conditions. The grain boundaries are assumed to provide fast diffusion paths. Main emphasis is put on situations that typically occur for nanocrystals, viz. on situations in which (i) the diffusion length is significant compared with grain size, (ii) the influence of boundaries that are parallel to the surface become important in addition to the perpendicular ones. Furthermore, we treat the influence of blocking space charge layers sandwiching the core pathways and thus channeling grain boundary diffusion.

Long-Range and Short-Range Structure of Proton-Conducting Y:BaZrO3

Yttrium-doped barium zirconate (BZY) is the most promising candidate for proton-conducting ceramics and has been extensively studied in recent years. The detailed features of the crystal structure, both short-range and long-range, as well as the crystal chemistry driving the doping process, are largely unknown. We use very high resolution X-ray diffraction (HR-XRD) to resolve the crystal structure, which is very slightly tetragonally distorted in BZY, while the local environment around Zr4+ and Y3+ is probed with extended X-ray absorption fine structure (EXAFS), and the symmetry and vibrations are investigated by using Raman spectroscopy. It is found that barium zirconate shows some degree …

Thermodynamic stability of stoichiometric BiFeO3 : hybrid DFT study

The authors are greatly indebted to R. Dovesi, R. Orlando, R. Merkle, and J. Serra for many stimulating discussions. E. H. thanks also the Department of Physical Chemistry of the Max Planck Institute for Solid State Research for long-term hospitality and support. This study was partly supported by the EC GREEN-CC FP7 project 608524. E. H., E. A. K. and A. A. B. acknowledge also the Russian Science Foundation for provided financial support through funding under the project 14-43-00052 for the analysis of the experimental literature on complex perovskite formation enthalpies, and the program of National Research Nuclear University "MEPhI" on improving the scientific competitiveness (A. A. B).…

First-principles modeling of oxygen interaction with SrTiO3(001) surface: Comparative density-functional LCAO and plane-wave study

Large scale first-principles calculations based on density functional theory (DFT) employing two different methods (atomic orbitals and plane wave basis sets) were used to study the energetics, geometry, the electronic charge redistribution and migration for adsorbed atomic and molecular oxygen on defect-free SrTiO3(001) surfaces (both SrO- and TiO2-terminated), which serves as a prototype for many ABO3-type perovskites. Both methods predict substantial binding energies for atomic O adsorption at the bridge position between the oxygen surface ions and an adjacent metal ion. A strong chemisorption is caused by formation of a surface molecular peroxide ion. In contrast, the neutral molecular …

First-principles study of bulk and surface oxygen vacancies in SrTiO3 crystal

The structural and electronic properties of the neutral and positively charged oxygen vacancies (F and F + centres) in the bulk and on the (001) surfaces of SrTiO3 crystal are examined within the hybrid Hartree-Fock and density functional theory (HF-DFT) method based upon the linear combination of atomic orbital (LCAO) approach. A comparison of the formation energy for surface and bulk defects indicates a perceptible propensity for the segregation of neutral and charged vacancies to both SrO and TiO2 surface terminations with a preference in the latter case which is important for interpretation of space charge effects at ceramic interfaces. It is found that the vacancies reveal more shallow…

On the Way to Optoionics

Discussions with Michael Grätzel, Ursula Röthlisberger, Robert A. Evarestov and Bettina V. Lotsch are gratefully acknowledged.

X-ray Absorption under Operating Conditions for Solid-Oxide Fuel Cells Electrocatalysts: The Case of LSCF/YSZ

We describe a novel electrochemical cell for X-ray absorption spectroscopy (XAS) experiments during electrical polarization suitable for high-temperature materials such as those used in solid oxide fuel cells. A half-cell LSCF/YSZ was then investigated under cathodic and anodic conditions (850 &deg

Theoretical and Experimental Studies of Charge Ordering in CaFeO 3 and SrFeO 3 Crystals

Evidence for Interfacial-Storage Anomaly in Nanocomposites for Lithium Batteries from First-Principles Simulations

We present theoretical support for a mass storage anomaly proposed for nanocomposites in the context of lithium batteries which forms the transition between an electrostatic capacitive mechanism and an electrode mechanism. Ab initio atomic and electronic structure calculations, performed on the Ti(0001)/Li2O(111) model interface, indicate the validity of the phenomenological model of interfacial Li storage and provide a deeper insight into the local situation. Beyond the specific applicability to storage devices, the possibility of a two-phase effect on mass storage generally highlights the availability of novel degrees of freedom in materials research when dealing with nanocomposites.

Thermodynamics of ABO3-Type Perovskite Surfaces

The ABO3-type perovskite manganites, cobaltates, and ferrates (A= La, Sr, Ca; B=Mn, Co, Fe) are important functional materials which have numerous high-tech applications due to their outstanding magnetic and electrical properties, such as colossal magnetoresistance, half-metallic behavior, and composition-dependent metal-insulator transition (Coey et al., 1999; Haghiri-Gosnet & Renard, 2003). Owing to high electronic and ionic conductivities. these materials show also excellent electrochemical performance, thermal and chemical stability, as well as compatibility with widely used electrolyte based on yttrium-stabilized zirconia (YSZ). Therefore they are among the most promising materials as …

Ab Initio Study of BiFeO3: Thermodynamic Stability Conditions

BiFeO3 is investigated intensively, mainly as a multiferroic material. In this paper, the state-of-the-art ab initio hybrid functional approach with atomic basis sets was employed for a study of the stability range of BiFeO3 with respect to its decomposition into binary oxides and elementary metals, as a function of temperature and oxygen partial pressure. The calculated atomic and electronic structure of BiFeO3 was compared with previous LDA+U calculations using plane-wave basis sets. Based on performed calculations, the phase diagram was constructed, which allows us to predict the stability region of stoichiometric BiFeO3.

(Invited) The Effect of (La,Sr)MnO 3 Cathode Surface Termination on Its Electronic Structure

La1-xSrxMnO3 (LSM) was one of the first perovskites used as SOFC cathode material. Its (001) surface has two possible terminations, LaSrO and MnO2, with quite different properties and oxygen reduction efficiencies. To avoid effects of surface polarity and the dipole moment across the material, symmetric non-stoichiometric slabs are commonly used in theoretical calculations with identical terminating planes on its both sides. We analyzed the dependence of the electronic structure (density of states) and charge distribution (effective atomic charges and chemical bond covalency) on the slab termination and Mn ion oxidation state (controlled by the Sr content and slab nonstoichiometry).

A Comparative Ab Initio Thermodynamic Study of Oxygen Vacancies in ZnO and SrTiO3: Emphasis on Phonon Contribution

Using a hybrid Hartree–Fock (HF)-DFT method combined with LCAO basis set and periodic supercell approach, the atomic, electronic structure and phonon properties of oxygen vacancies in ZnO and SrTiO3 were calculated and compared. The important role of a ghost basis function centered at the vacant site and defect spin state for SrTiO3 is discussed. It is shown that the use of hybrid functionals is vital for correct reproduction of defects basic properties. The Gibbs free energy of formation of oxygen vacancies and their considerable temperature dependence has been compared for the two oxides. These calculations were based on the polarizability model for the soft mode temperature behavior in S…

First-principles modelling of complex perovskite (Ba1-xSrx)(Co1-yFey)O3-δ for solid oxide fuel cell and gas separation membrane applications

The results of the first principles spin-polarized DFT calculations of the atomic and electronic structure of a complex perovskite (Ba1-xSrx)(Co1-yFey)O3-δ (BSCF) used as a cathode material for solid oxide fuel cells (SOFC) and gas separation membranes are presented and discussed. The formation energies of oxygen vacancies are found to be considerably smaller than in other magnetic perovskites, e.g. (La,Sr)MnO3, which explains the experimentally observed strong deviation of this material from stoichiometry. The presence of oxygen vacancies induces a local charge redistribution, associated with the local lattice perturbation, and expansion of the equilibrium volume, in line with the experime…

Precursor-Controlled Formation of Novel Carbon/Metal and Carbon/Metal Oxide Nanocomposites

Carbonaceous materials have long been considered as a high-performance material due to their light weight, high thermal resistance, tunable porosity and strength, but also because of their exciting electronic properties. When hybridized with other metal nanoparticles to form carbon/ metal nanocomposites (CMCs), multifunctionality is achieved through the combination of carbon and metal, leading to interesting magnetic materials, catalysts, battery electrodes, or chemical sensors. Various methods for preparing CMCs have been developed. In most cases, metal cations deposited on carbonaceous materials were reduced chemically or physically to form CMCs. In these processes, heterogeneous dispersi…

Atomic, electronic and thermodynamic properties of cubic and orthorhombic LaMnO3 surfaces

We studied in detail the atomic and electronic structure of the LaMnO3 surfaces, in both cubic and orthorhombic phases, combining GGA-plane wave approach, as implemented into the VASP-4.6.19 computer code, with a slab model. These studies are complemented by a thermodynamic analysis of the surface stability at different gas pressures and temperatures. The obtained results are compared with similar studies for other ABO3-perovskites. 2008 Elsevier B.V. All rights reserved. The ABO3-type perovskite manganites and cobaltates (A = La, Sr, Ca; B = Mn, Co) are important functional materials with numerous high-tech applications [1]. Some of them require understanding and control surface properties…

Basic properties of the F-type centers in halides, oxides and perovskites

We present a short survey of the optical properties of primary radiation-induced point defects in alkali halides, simple oxides and some ABO3 perovskites. We discuss in details the optical properties of single electron F and F + centers in rock-salt (f.c.c.) alkali halides and oxides and show that the Mollwo–Ivey law well-known for the F-type centers in alkali halides may be extended for other rock-salt structure insulators. We also discuss the major differences in point defect production mechanisms in halides and oxides. We show that the Rabin–Klick diagram may be generalized for a whole family of alkali halides. The F-type center migration and aggregation into metal colloids in alkali hal…

Radiation defects in complex perovskite solid solutions

Abstract First principles density functional theory (DFT) based modeling is performed to explore formation energies of a series of point cation and oxygen defects, Frenkel and Schottky disorder, as well as structural disorder in Ba1−xSrxCo1−yFeyO3−δ (BSCF) perovskite solid solutions. The results are compared with previous studies on a prototype SrTiO3 perovskite. It is shown that BSCF permits accommodation of a high concentration of defects and cation clusters but not antisite defects.

Enhanced interfacial lithium storage in nanocomposites of transition metals with LiF and Li2O: Comparison of DFT calculations and experimental studies

Abstract Me/LiX nanocomposites (Me – transition metal and X = F or O) exhibit extra lithium storage, with pseudo-capacitive behavior and high-rate performance. While LiX surface layers or the interfacial core serves as hosts for extra Li, atoms of contacting transition metal serve as electron sinks, depending on Me electronegativity. To verify the mechanism, we have performed comparative DFT-LCAO calculations on the polar Ti|Li|Li2O(111) and non-polar Cu|Li|LiF(001) interfaces with extra Li atoms inserted inside both 2D interfaces, gradually changing their concentration. Theoretical calculations confirm validity of this interfacial model for explanation of the extra storage capacity at low …

Hydration entropy of BaZrO3 from first principles phonon calculations

The impact of phonons on the hydration and defect thermodynamics of undoped and acceptor (Sc, In, Y and Gd) doped BaZrO3 is addressed by means of first principles supercell calculations. In contrast to previous, similar investigations, we evaluate contributions from all phonon modes, and also pressure/volume effects on the phonon properties. The calculations are performed at the GGA-level with the PBE and RPBE functionals, both of which predict for BaZrO3 a stable cubic perovskite structure. For all dopants, the vibrational formation entropy of the doubly positively charged oxygen vacancy is significantly lower than that of the protonic defect , which therefore also is the dominant contribu…

Analysis of self-trapped hole mobility in alkali halides and metal halides

Support from Latvian National Research Program IMIS2 (2014–2017) and LZP Grant No. 237/2012 (2013–2016) is greatly appreciated.

Effects of Grain Boundary Decoration on the Electrical Conduction of Nanocrystalline CeO2

In this study, we investigate the effect of decorating the grain boundaries of nanocrystalline undoped ceria on the electrical transport properties. For the decoration, different acceptors (Yb, Y, Bi) were chosen. On decoration, the conduction switches from electronic to ionic. Upon sintering the grains are characterized by a core-shell configuration, in which the core remains undoped while the shell is heavily doped as a consequence of the diffusion of the acceptors toward the grain interior. The shell dominates the overall transport properties of the nanocrystalline ceria and is found to be in the mesoscopic regime.

Calculations of the atomic and electronic structure for SrTiO3 perovskite thin films

The results of calculations of SrTiO3 (100) surface relaxation and rumpling with two different terminations (SrO and TiO2) are presented and discussed. We have used the ab initio Hartree–Fock (HF) method with electron correlation corrections and the density functional theory (DFT) with different exchange–correlation functionals, including hybrid exchange techniques. All methods agree well on surface energies and on atomic displacements, as well as on the considerable increase of covalency effects near the surface. More detailed experiments on surface rumpling and relaxation are necessary for further testing of theoretical predictions.

Jahn-Teller effect in the phonon properties of defective SrTiO3from first principles

the Jahn–Teller effect occurs, thus reducing the cubic symmetry of a perfect crystal and leading to the appearance of both Raman- and infrared-active vibrational modes. The calculated phonon densities of states and group-theoretical analysis of defect-induced phonon frequencies were used for the interpretation of the relevant experimental data, once defect-induced local modes are identified. The temperature dependence of the Vo formation energy based on the calculated Gibbs free energy was also compared with experiments, and the phonon contribution therein estimated.

Fabrication of cobalt and cobalt oxide/graphene composites: towards high-performance anode materials for lithium ion batteries.

Ab initio simulations on AgCl(111) surface and AgCl(111)/α-Al2O3(0001) interface

The defect chemistry and ionic transport properties of the AgCl(111)/α-Al 2 O 3 (0001) interface were consid by using ab initio slab calculations. These calculations were performed in the framework of plane-wave basis combined with the density functional theory (DFT), as implemented into the VASP computer code, and Gaus basis set combined with the Hartree-Fock method (CRYSTAL-98 code). We analyze the electron density distribu on the interface and the electrostatic potential distribution near the AgCl surface. The size of the silver ion is great to enter the corundum surface layer and to create excess silver ions in this way. This is in agreement the experiments on heterogeneous doping of Ag…

First-principles calculations of perovskite thin films

Abstract The results of the electronic structure calculations for different surface terminations of SrTiO3 (1 0 0) perovskite thin films are discussed. These calculations are based on ab initio Hartree–Fock method with a posteriori electron correlation corrections and density functional theory with a number of different exchange-correlation functionals, including hybrid (B3PW, B3LYP) exchange techniques. Results are compared with previous ab initio plane-wave local density approximation and classical shell model calculations. Calculated considerable increase of the Ti–O chemical bond covalency nearby the surface is confirmed by experimental data. We predict also the band-gap reduction, espe…

Atomistic Modeling of a New Storage

It was observed that Me/Li2O and Me/LiF nanocomposites (Me is a metal that does not alloy with lithium) are able to exhibit an extra Li storage typically beyond the uptake of stoichiometric Li in the potential window 1.2 0.02 V, with pseudo-capacitive behavior and high-rate performance. Among the composites, the Ru/Li2O exhibits a high extra Li storage at this low potential. Moreover, the Li2O matrix allows one a higher storage in contact with transition metal than the LiF matrix [1,2]. To clarify the mechanism of the Li interfacial storage anomaly, we have performed comparative first principles calculations on the atomic and electronic structure of polar Ti/Li2O(111) and nonpolar Cu/LiF(00…

Ab initio modelling of silver adhesion on the corundum (0001) surface

The Ag/a-Al2O3(0001) interface was simulated using ab initio slab calculations. We have studied silver adhesion on both Al- and Oterminated corundum substrates. The latter case may be considered as silver adhesion on a defective Al-terminated corundum surface with external aluminium vacancies. The dependence of the adhesion energy on the interfacial distance has been analyzed for the two favorable Ag adsorption positions and for two metal coverages (a 1/3 monolayer of the Ag(111) crystallographic plane and a full Ag(111) monolayer, 1 ML). The two different terminations (Al- and O-) give rise to qualitatively different results. In the former case, the small adhesion energies per Ag atom are …

Semi-empirical simulations of surface relaxation for perovskite titanates

The (100) and (110) surface relaxations are calculated for SrTiO 3 and BaTiO 3 perovskite thin films. By means of a semi-empirical shell model, the positions of atoms in 16 near-surface layers placed atop a slab of rigid ions are calculated. Surface rumpling and surface-induced dipole moments are calculated for all possible surface terminations. Our results for the (100) surface structure are in good agreement with ab-initio plane-wave pseudopotential calculations and LEED experiments. The surface energy for the Ba-, Sr-, TiO-terminated (110) surfaces is found to be much larger than that for the (100) surface. In contrast, the surface energy for the asymmetric O termination, where outermost…

Ab initio modelling of oxygen vacancies and protonic defects in La1−xSrxFeO3−δ perovskite solid solutions

Using hybrid density functionals, detailed ab initio calculations were performed for oxygen vacancies and protons in La1−xSrxFeO3−δ perovskite solid solutions which may serve as a cathode material in protonic ceramic fuel cells. The atomic and electronic structures of different configurations of defects and the role of Fe oxidation state are analyzed in detail. The energetics of the reduction and hydration reactions are investigated. The hydration energy is found to be significantly smaller than for Ba(Zr1−xYx)O3−x/2 electrolyte materials, and the role of basicity as one decisive factor is discussed.

Formation and migration of oxygen vacancies in La1−xSrxCo1−yFeyO3−δperovskites: insight from ab initio calculations and comparison with Ba1−xSrxCo1−yFeyO3−δ

The formation and migration of oxygen vacancies in the series of (La,Sr)(Co,Fe)O3−δ perovskites, which can be used as mixed conducting SOFC cathode materials and oxygen permeation membranes, are explored in detail by means of first principles density functional calculations. Structure distortions, charge redistributions and transition state energies during the oxygen ion migration are obtained and analyzed. Both the overall chemical composition and vacancy formation energy are found to have only a small impact on the migration barrier; it is rather the local cation configuration which affects the barrier. The electron charge transfer from the migrating O ion towards the transition metal ion…

Oxygen vacancy formation energies in Sr-doped complex perovskites: ab initio thermodynamic study

Abstract La 1 − x Sr x Co 0.25 Fe 0.75 O 3 − δ is known as one of the best cathode materials for permeation membranes and solid oxide fuel cells. Optimization of its chemical composition is a challenging problem. One of the key properties is concentration of oxygen vacancies, which is controlled by their formation energies. Ab initio calculations were employed in order to study the formation of oxygen vacancies in La 1 − x Sr x Co 0.25 Fe 0.75 O 3 − δ perovskites by varying the Sr content from x = 12.5% to 50%. The formation energies were obtained for different stoichiometries as functions of temperature and oxygen partial pressure. For this purpose we calculated the phonon frequencies in t…

Comparative density-functional LCAO and plane-wave calculations ofLaMnO3surfaces

We compare two approaches to the atomic, electronic, and magnetic structures of LaMnO3 bulk and the (001), (110) surfaces—hybrid B3PW with optimized LCAO basis set (CRYSTAL-2003 code) and GGA-PW91 with plane-wave basis set (VASP 4.6 code). Combining our calculations with those available in the literature, we demonstrate that combination of nonlocal exchange and correlation used in hybrid functionals allows to reproduce the experimental magnetic coupling constants Jab and Jc as well as the optical gap. Surface calculations performed by both methods using slab models show that the antiferromagnetic (AF) and ferromagnetic (FM) (001) surfaces have lower surface energies than the FM (110) surfac…

Theoretical modeling of antiferrodistortive phase transition forSrTiO3ultrathin films

Combining group-theoretical analysis and first-principles density functional theory calculations, we confirm theoretically the antiferrodistortive phase transition in ultrathin SrTiO${}_{3}$ (001) TiO${}_{2}$-terminated films and compare it with a similar transition in the bulk. We demonstrate phonon softening at the $M$ point of the surface Brillouin zone and analyze the change in the calculated electronic and phonon properties upon phase transition.

Atomistic Simulations of the LaMnO3 (110) Polar Surface.

The results of atomic structure calculations, with a focus on the surface relaxation and polarization, are presented for the LaMnO3 (110) O-terminated polar surface. We compare results of the classical shell model calculations for four possible terminations, including (1 × 2) (110) surface reconstruction, and demonstrate that the latter has the lowest surface energy. The surface energy is saturated only when six to eight near-surface atomic planes are relaxed which is accompanied by the considerable dipole moments perpendicular to the surface. Results are compared with those for iso-structural BaTiO3 (110) surfaces.

Energy Conversion: Solid Oxide Fuel Cells: First-Principles Modeling of Elementary Processes

Fuel cells are electrochemical devices that directly transform the chemical free energy of combustion (e.g., H2 + O2 and CHx + O2) into electrical energy. The avoidance of a thermal detour guarantees high theoretical efficiency. As far as the temperature regimes are concerned, we distinguish between high temperature ceramic fuel cells, intermediate-temperature fuel cells, and low temperature (i.e., only slightly above room temperature) fuel cells. The high temperature fuel cells are usually based on oxide components (ternary transition metal oxides as cathodes, Ni or Cu cermets as anodes, and acceptor-doped zirconia or ceria as electrolytes). The high temperature necessary for ion conductio…

Thermodynamic stability of non-stoichiometric SrFeO 3−δ : a hybrid DFT study

SrFeO3-δ is mixed ionic-electronic conductor with complex magnetic structure which reveals also colossal magnetoresistance effect. This material and its solid solutions are attractive for various spintronic, catalytic and electrochemical applications, including cathodes for solid oxide fuel cells and permeation membranes. Its properties strongly depend on oxygen non-stoichiometry. Ab initio hybrid functional approach was applied here for a study of thermodynamic stability of a series of SrFeO3-δ compositions with several non-stoichiometries δ, ranging from 0 to 0.5 (SrFeO3 - SrFeO2.875 - SrFeO2.75 - SrFeO2.5) as the function of temperature and oxygen pressure. The results obtained by consid…

First principles simulations of F centers in cubic SrTiO 3

Atomic and electronic structure of regular and O-deficient SrTiO3 have been studied. Several types of first principles atomistic simulations: Hartree-Fock method, Density Functional Theory, and hybrid HF-DFT functionals, have been applied to periodic models that consider supercells of different sizes (ranging between 40 and 240 atoms). We confirm the ionic character of the Sr-O bonds and the high covalency of the Ti-O2 substructure. For the stoichiometric cubic crystal; the lattice constant and bulk modulus correctly reproduce the experimental data whereas the band gap is only properly obtained by the B3PW functional. The relaxed geometry around the F center shows a large expansion of the t…

First Principles Calculations of Oxygen Vacancy Formation and Migration in Ba1−xSrxCo1−yFeyO3−δPerovskites

Based on first principles DFT calculations, we analyze oxygen vacancy formation and migration energies as a function of chemical composition in complex multicomponent (Ba,Sr)(Co,Fe)O3−δ perovskites which are candidate materials for SOFC cathodes and permeation membranes. The atomic relaxation, electronic charge redistribution and energies of the transition states of oxygen migration are compared for several perovskites to elucidate the atomistic reason for the exceptionally low migration barrier in Ba0.5Sr0.5Co0.8Fe0.2O3−δ that was previously determined experimentally. The critical comparison of Ba1−xSrxCo1−yFeyO3−δ perovskites with different cation compositions and arrangements shows that …

Thermodynamic properties of neutral and charged oxygen vacancies in BaZrO3 based on first principles phonon calculations.

The structural, electronic and thermodynamic properties of neutral and positively doubly charged oxygen vacancies in BaZrO3 are addressed by first principles phonon calculations. The calculations are performed using two complementary first principles approaches and functionals; the linear combination of atomic orbitals (LCAO) within the hybrid Hartree–Fock and density functional theory formalism (HF-DFT), and the projector augmented plane wave approach (PAW) within DFT. Phonons are shown to contribute significantly to the formation energy of the charged oxygen vacancy at high temperatures (∼1 eV at 1000 K), due to both its large distortion of the local structure, and its large negative form…

Comparative study of polar perovskite surfaces

A novel model of the ‘‘zig–zag’’ (1 1 0) polar surface termination of ABO3 perovskites is suggested and analyzed. Classical shell model calculations for BaTiO3, SrTiO3 and LaMnO3 show that such the (1 · 2) (1 1 0) surface reconstruction has the lowest energy, comparable to that for the (1 0 0) surfaces. The calculated surface energy reaches the saturation only when 6–8 atomic near-surface planes are allowed to relax. Surface relaxation leads to the formation of considerable dipole moment perpendicular to the surface. The predicted surface polarization of thin perovskite films, even in the cubic phase, could affect their dielectric properties. � 2004 Elsevier B.V. All rights reserved.

Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells

Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,…

Phonon calculations in cubic and tetragonal phases of SrTiO3: A comparative LCAO and plane-wave study

The atomic, electronic structure and phonon frequencies have been calculated in cubic and low-temperature tetragonal SrTiO${}_{3}$ phases at the ab initio level. We demonstrate that the use of the hybrid exchange-correlation PBE0 functional gives the best agreement with experimental data. The results for the standard generalized gradient approximation (PBE) and hybrid PBE0 functionals are compared for the two types of approaches: a linear combination of atomic orbitals (CRYSTAL09 computer code) and plane waves (VASP5.2 code). The relation between cubic and tetragonal phases and the relevant antiferrodistortive phase transition is discussed in terms of group theory and is illustrated with an…

Thermodynamic stability of stoichiometric LaFeO 3 and BiFeO 3 : a hybrid DFT study

BiFeO3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi1−xSrxFeO3−δ and Bi1−xSrxFe1−yCoyO3−δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO3 perovskite is the end member for well-known solid solutions (La1−xSrxFe1−yCoyO3−δ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO3 and BiFeO3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing th…

Proton, Hydroxide Ion, and Oxide Ion Affinities of Closed-Shell Oxides: Importance for the Hydration Reaction and Correlation to Electronic Structure

Phenomenologically, the enthalpy of the dissociative water incorporation (hydration) of oxides is often found to be more favorable for more basic oxides. In the present work, we investigate proton,...

Adsorption of atomic and molecular oxygen on the LaMnO3(001) surface: ab initio supercell calculations and thermodynamics.

We present and discuss the results of ab initio DFT plane-wave supercell calculations of the atomic and molecular oxygen adsorption and diffusion on the LaMnO(3) (001) surface which serves as a model material for a cathode of solid oxide fuel cells. The dissociative adsorption of O(2) molecules from the gas phase is energetically favorable on surface Mn ions even on a defect-free surface. The surface migration energy for adsorbed O ions is found to be quite high, 2.0 eV. We predict that the adsorbed O atoms could penetrate the electrode first plane when much more mobile surface oxygen vacancies (migration energy of 0.69 eV) approach the O ions strongly bound to the surface Mn ions. The form…

First principles calculations of oxygen reduction reaction at fuel cell cathodes

This study was partly supported by M-ERA-NET project SunToChem (EK, YM). The computer resources were provided by Stuttgart Super-computing Center (Project DEFTD 12939). Authors thank E. Heifets, M. M. Kuklja, M. Arrigoni, D. Morgan, R. Evarestov, and D. Gryaznov for fruitful discussions.

Calculations of radiation-induced point defects, polarons and excitons in ferroelectric perovskites

Abstract We review results of our recent large-scale computer simulations of radiation-induced point defects, excitons and polarons in ABO3 perovskite crystals, focusing mostly on KNbO3 and KTaO3 as representative examples. We have calculated the atomic and electronic structure of defects, their optical absorption, defect-induced electron density redistribution, and activation energies for defect migration. The majority of our results were obtained using the quantum-chemical method of the intermediate neglect of differential overlap (INDO) based on the Hartree–Fock formalism, as well as the shell model (SM). The main findings are compared with those obtained by means of ab initio density fu…

DFT plane wave calculations of the atomic and electronic structure of LaMnO3(001) surface

We present the results of ab initio DFT plane wave periodic structure calculations of the LaMnO3 (001) surface. The effects related to three different kinds of pseudopotentials, the slab thickness, magnetic ordering, and surface relaxation are studied and discussed. The antiferromagnetic surface lowest in energy (that is, the spins on Mn ions are parallel in basal plane and antiparallel from plane to plane) has a considerable atomic relaxation up to the fourth plane from the surface. The calculated (Bader) effective charges and the electronic density maps demonstrate a considerable reduction of the Mn atom ionicity on the surface accompanied by a covalent contribution to the Mn–O bonding.

Generalised Maxwell-Garnett equation: application to electrical and chemical transport.

In this paper we discuss the implementation of different equilibrium concentrations in each of the phases into the Maxwell-Garnett effective medium formula for diffusion in heterogeneous media. We put the derivation given by Kalnin et al., J. Phys. Chem. Solids, 2002, 63, 449, on safer grounds and extend it to non-dilute carrier concentrations. The relation to Maxwell’s mixing rule is also elaborated. It is shown that the formula can not only successfully be applied to conductivity problems but also to describe steady state chemical diffusion in heterogeneous media such as polycrystalline samples. The comparison with the brick layer model corroborates these points but also shows that—in the…