We report investigation of phonons and oxygen diffusion in Bi2O3 and (Bi0.7Y0.3)2O3. The phonon spectra have been measured in Bi2O3 at high temperatures up to 1083 K using inelastic neutron scattering. Ab-initio calculations have been used to compute the individual contributions of the constituent atoms in Bi2O3 and (Bi0.7Y0.3)2O3 to the total phonon density of states. Our computed results indicate that as temperature is increased, there is a complete loss of sharp peak structure in the vibrational density of states. Ab-initio molecular dynamics simulations show that even at 1000 K in δ-phase Bi2O3, Bi-Bi correlations remain ordered in the crystalline lattice while the correlations between O-O show liquid like disordered behavior. In the case of (Bi0.7Y0.3)2O3, the O-O correlations broadened at around 500 K indicating that oxygen conductivity is possible at such low temperatures in (Bi0.7Y0.3)2O3 although the conductivity is much less than that observed in the undoped high temperature δ-phase of Bi2O3. This result is consistent with the calculated diffusion coefficients of oxygen and observation by QENS experiments. Our ab-initio molecular dynamics calculations predict that macroscopic diffusion is attainable in (Bi0.7Y0.3)2O3 at much lower temperatures, which is more suited for technological applications. Our studies elucidate the easy directions of diffusion in δ-Bi2O3 and (Bi0.7Y0.3)2O3.
We investigated SrFeO$_{3-x}$ thin films on a SrTiO$_3$ (001) substrate prepared via pulsed laser epitaxy using an optical spectroscopy technique. The oxygen vacancy level ($x$) was controlled by post-annealing processes at different oxygen partial pressures. We achieved a brownmillerite(BM) structure at $x =$ 0.5 and observed the evolution of the crystal structure from BM into perovskite(PV) as the oxygen concentration increased. We observed the evolution of infrared-active phonons with respect to the oxygen concentration, which was closely related to the structural evolution observed via X-r…
La1-xSrxCo0.25Fe0.75O3-delta 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, controlled by their formation energies. Ab initio calculations were employed in order to study the formation of oxygen vacancies in La1-xSrxCo0.25Fe0.75O3-delta 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 press…
How impurity atoms move through a crystal is a fundamental and recurrent question in materials. The previous understanding of oxygen diffusion in titanium relied on interstitial lattice sites that were recently found to be unstable, making the diffusion pathways for oxygen unknown. Using first-principles quantum-mechanical methods, we find three oxygen interstitial sites in titanium, and quantify the multiple interpenetrating networks for oxygen diffusion. Surprisingly, no single transition dominates, but all contribute to diffusion.
A high-frequency optical phonon mode of SrTiO3 (STO) was found to assist the high-temperature superconductivity observed recently at the interface between monolayer FeSe and STO substrate. However, the origin of this mode is not clear. Through first-principles calculations, we find that there is a novel polar phonon mode on the surface layers of the STO substrate, which does not exist in the STO crystals. The oxygen vacancies near the FeSe/STO interface drives the dispersion of this phonon mode to be flat and lowers its energy, whereas the charge transfer between STO substrate and FeSe monolay…
In this letter, we study enhanced-retarded diffusion of oxygen in doped silicon by means of first principle calculations. We found that the migration of oxygen dimers can not be significantly affected by strain, doping type or rate. We attribute the enhanced oxygen diffusion in p-doped silicon to reduced monomer migration energy, and the retarded oxygen diffusion in Sb-doped to oxygen trapping close to a dopant site. The two proposed kinetic and thermodynamic mechanisms can appear at the same time and might lead to contradictory experimental results. Such mechanisms can be involved in the ligh…
The development of Ruddlesden-Popper (RP) oxides as oxygen exchange and transport materials will benefit from mechanistic understanding of how oxygen transports through these materials. Using Density Functional Theory, we found there are two distinct oxygen interstitial diffusion mechanisms involving two different oxygen interstitial species that can be active in La2-xSrxNiO4+delta, and, we believe, in hyperstoichiometric RP oxides in general. The first mechanism is the previously proposed interstitialcy-mediated mechanism, which consists of diffusing oxide interstitials. The second mechanism …
We present a theoretical study of the impact of oxygen diffusion in oxide crystals on metal dopants ionic state and the conduction type under dynamic changes. The slow changes under thermal equilibrium are provided in a companion, Part I paper. Oxygen vacancy formation acting as a shallow, double-electronic donor, is assumed to result from the crystal exposure to a low ambient oxygen pressure. Critical transitions from n- to a p-type at an oxygen partial pressure Pi, and in ionization state of the metal dopant at an oxygen partial pressure PM, are usually not simultaneous, and depend on the di…
To design and discover new materials for next-generation energy materials such as solid-oxide fuel cells (SOFCs), a fundamental understanding of their ionic properties and behaviors is essential. The potential applicability of a material for SOFCs is critically determined by the activation energy barrier of oxygen along various diffusion pathways. In this work, we investigate interstitial-oxygen (Oi) diffusion in brownmillerite oxide SrCoO2.5, employing a first-principles approach. Our calculations indicate highly anisotropic ionic diffusion pathways, which result from its anisotropic crystal …
We present a theoretical study of the impact of oxygen diffusion in oxide crystals on metal dopants ionic state and the conduction type under thermal equilibrium. Oxygen vacancy formation acting as a shallow, double-electronic donor is assumed to result from the crystal exposure to a low ambient oxygen pressure. It is shown, that critical transitions from n- to a p-type at an oxygen partial pressure Pi, and in ionization state of the metal dopant at an oxygen partial pressure PM, are usually not simultaneous, and depend on the different reaction constants. Experimental study of the different s…
Understanding the diffusion of oxygen vacancies in oxides under different external stimuli is crucial for the design of ion-based electronic devices, improve catalytic performance, etc. In this manuscript, using an external electric field produced by an AFM tip, we obtain the room-temperature diffusion coefficient of oxygen-vacancies in thin-films of SrTiO$_3$ under compressive/tensile epitaxial strain. Tensile strain produces a substantial increase of the diffusion coefficient, facilitating the mobility of vacancies through the film. Additionally, the effect of tip bias, pulse time, and tempe…
To shed light on the role of magnetism on the superconducting mechanism of the oxygen-free FeAs pnictides, we investigate the effect of magnetic ordering on phonon dynamics in the low-temperature orthorhombic parent compounds, which present a spin-density wave. The study covers both the 122 (AFe2As2; A=Ca, Sr, Ba) and 1111 (AFeAsF; A=Ca, Sr) phases. We extend our recent work on the Ca (122 and 1111) and Ba (122) cases by treating computationally and experimentally the 122 and 1111 Sr compounds. The effect of magnetic ordering is investigated through detailed non-magnetic and magnetic lattice d…
Phonons are produced when an excited vacancy in cuprous oxide (Cu$_2$O) relaxes. Time resolved luminescence was used to find the excited copper vacancy (acceptor) and oxygen vacancy (donor) trap levels and lifetimes. It was also used to determine the typical energy and number of phonons in the phonon pulses emitted by vacancies. The vacancy properties of cuprous oxide are controlled by several synthesis parameters and by the temperature. We directly demonstrate the absorption of light by oxygen vacancies with transient absorption. Copper and oxygen vacancies behave differently, in part because…
Si-SiO2 multilayer nanocomposite (NCp) films, grown using pulsed laser deposition with varying Si deposition time are investigated using Raman spectroscopy/mapping for studying the variation of Si phonon frequency observed in these NCps. The lower frequency (LF) phonons (~ 495 - 510 cm-1) and higher frequency (HF) phonons (~ 515 - 519 cm-1) observed in Raman mapping data (Fig. 1A) in all samples studied are attributed to have originated from surface (Si-SiO2 interface) and core of Si nanocrystals, respectively. The consistent picture of this understanding is developed using Raman spectroscopy …
A theoretical modeling of the oxygen diffusivity in silicon and germanium crystals both at normal and high hydrostatic pressure has been carried out using molecular mechanics, semiempirical and ab initio methods. It was established that the diffusion process of an interstitial oxygen atom (Oi) is controlled by the optimum configuration of three silicon (germanium) atoms nearest to Oi. The calculated values of the activation energy Ea(Si)= 2.59 eV, Ea(Ge)= 2.05 eV and pre-exponential factor Do (Si) = 0.28 sm2 s-1, Do (Ge) = 0.39 sm2 s-1 are in a good agreement with experimental ones and for the…
The theoretical analysis of the process of diffusion of interstitial oxygen atoms and hydrogen molecules in silicon and germanium crystals has been performed. The calculated values of the activation energy and pre-exponential factor for an interstitial oxygen atom Ea(Si) = 2.59 eV, Ea(Ge) = 2.05 eV, D(Si)= 0.28 cm2s-1, D(Ge)= 0.39 cm2s-1 and interstitial hydrogen molecule Ea(Si) = 0.79-0.83 eV, Ea(Ge) = 0.58-0.62 eV, D(Si)= 7.4 10(-4) cm2s-1, D(Ge)= 6.5 10(-4) cm2s-1 are in an excellent agreement with experimental ones and for the first time describe perfectly an experimental temperature depen…
The oxygen self-diffusion coefficient in UO${_2}$ has been recently studied [Cooper et al. Solid State Ionics 282 (2015) 26-30] over a range of pressures (0-10GPa) and temperatures (300-1900K) by combining molecular dynamics calculations with a thermodynamical model, the cBΩ model. A significant reduction in oxygen self-diffusion as a function of increasing hydrostatic pressure, and the associated increase in activation energy was identified. Here, we extend this study and find that the compressibility of the corresponding activation volume exceeds significantly the compressibility of the bulk…
A Devanathan-Stachurski type diffusion cell made from a fuel cell assembly is designed to evaluate the gas transport properties of a proton exchange membrane as a function of cell temperature and gas pressure. Data obtained on this cell using the electrochemical monitoring technique (EMT) is used to estimate solubility and diffusion coefficient of oxygen (O2), carbon monoxide (CO) and hydrogen sulfide (H2S) in Nafion membranes. Membrane swelling and reverse-gas diffusion due to water flux are accounted for in the parameter estimation procedure. Permeability of all three gases was found to incr…
In oxide epitaxy, the growth temperature and background oxygen partial pressure are considered as the most critical factors that control the phase stability of an oxide thin film. Here, we report an unusual case wherein diffusion of oxygen vacancies from the substrate overpowers the growth temperature and oxygen partial pressure to deterministically influence the phase stability of $Bi_{2}WO_{6}$ thin film grown by the pulsed laser deposition technique. We show that when grown on an oxygen-deficient $SrTiO_{3}$ substrate, the $Bi_{2}WO_{6}$ film exhibits a mixture of (001) and (100)/(010)-orie…
We study a multi-orbital Hubbard--Su-Schrieffer-Heeger model for the one-dimensional (1D) corner-shared cuprates in the adiabatic and nonadiabatic limits using the exact diagonalization and determinant quantum Monte Carlo methods. Our results demonstrate that lattice dimerization can be achieved only over a narrow range of couplings slightly below a critical coupling $g_c$ at half-filling. Beyond this critical coupling, the sign of the effective hopping changes, and the lattice becomes unstable. We also examine the model's temperature-dependent uniform magnetic susceptibility and the dynamical…
Transition metal oxide memristors, or resistive random-access memory (RRAM) switches, are under intense development for storage-class memory because of their favorable operating power, endurance, speed, and density. Their commercial deployment critically depends on predictive compact models based on understanding nanoscale physico-chemical forces, which remains elusive and controversial owing to the difficulties in directly observing atomic motions during resistive switching, Here, using scanning transmission synchrotron x-ray spectromicroscopy to study in-situ switching of hafnium oxide memri…
A spin decoherence mechanism is proposed for localized electrons. The irregular phonon phase disturbances originated from phonon relaxation can influence electron spin precession with a net effect of spin phase decay. A quantitative analysis demonstrates relatively high efficiency of this mechanism in the low temperature and low magnetic field regime compared to the spin-flip processes.
Defect-limited thermal transport in AlN using pretrained machine-learning interatomic potentials
Seoul National University（首尔大学）；Research Institute of Advanced Materials, Seoul National University（首尔大学先进材料研究所）；Center for AI and Natural Sciences, Korea Institute for Advanced Study（韩国高等研究院人工智能与自然科学中心）；Incheon National University（仁川国立大学）
We report femtosecond time-resolved reflectivity measurements of coherent phonons in tellurium performed over a wide range of temperatures (3K to 296K) and pump laser intensities. A totally symmetric A$_{1}$ coherent phonon at 3.6 THz responsible for the oscillations in the reflectivity data is observed to be strongly positively chirped (i.e, phonon time period decreases at longer pump-probe delay times) with increasing photoexcited carrier density, more so at lower temperatures. We show for the first time that the temperature dependence of the coherent phonon frequency is anomalous (i.e, incr…
Cubic yttria-stabilized zirconia is widely used in industrial electrochemical devices. While its fast oxygen ion diffusion is well understood, why cation diffusion is much slower-its activation energy (~5 eV) is 10 times that of anion diffusion-remains a mystery. Indeed, all previous computational studies predicted more than 5 eV is needed for forming a cation defect, and another 5 eV for moving one. In contrast, our ab initio calculations have correctly predicted the experimentally observed cation diffusivity. We found Schottky pairs are the dominant defects that provide cation vacancies, and…
We report on investigations of phonons and lithium diffusion in LiAlO$_2$ based on inelastic neutron scattering (INS) measurements of the phonon density of states (DOS) in γ-LiAlO$_2$ from 473 K to 1073 K, complemented with ab-initio molecular dynamics (AIMD) simulations. We find that phonon modes related to Li vibrations broaden on warming as reflected in the measured phonon DOS and reproduced in simulations. Further, the AIMD simulations probe the nature of lithium diffusion in the perfect crystalline phase (γ-LiAlO$_2$), as well as in a structure with lithium vacancies and a related amorpho…
TiO2 is a technologically important material. In particular, its anatase polymorph plays a major role in photocatalysis, which can also accommodate charged and neutral vacancies. There is, however, scant theoretical work on the vacancy charge and associated diffusion from surface to subsurface and bulk in the literature. Here, we aim to understand +2 charge and neutral vacancy diffusion on anatase (101) surface using 72 and 216 atoms surface slabs employing a semi-local density functional and the Hubbard model. The activation-relaxation technique nouveau (ARTn) coupled with Quantum Espresso is…
Electric pulse induced resistance (EPIR) switching hysteresis loops for Pr0.7Ca0.7MnO3 (PCMO) perovskite oxide films were found to exhibit an additional sharp "shuttle peak" around the negative pulse maximum for films deposited in an oxygen deficient ambient. The device resistance hysteresis loop consists of stable high resistance and low resistance states, and transition regions between them. The resistance relaxation of the "shuttle peak" and its temperature behavior as well as the resistance relaxation in the transition regions were studied, and indicate that the resistance switching relate…
In this paper we report the determination of oxygen diffusion coefficient for optimally doped manganite thin films of La0.85Na0.15MnO3 (LNMO). The study was performed by means of isothermal conductivity measurements on two different epitaxially oriented thin films grown on SrTiO3 (100) and SrTiO3 (110). The values found for the oxygen diffusion coefficients are around 10-14 cm2s-1. The diffusion seems to be faster for the c-oriented film with respect to the other one (growth on SrTiO3 (110)). The activation energy for the diffusion process is 0.35 eV for the LNMO film on SrTiO3 (100) and 0.66 …
Nonstoichiometric perovskite-related oxides (such as ferrites and cobaltites, etc.) are characterized by fast oxygen transport at ambient temperatures, which relates to the microstructural texturing of these materials, consisting wholly of nanoscale microdomains. We have developed an inhomogeneous diffusion model to describe the kinetics of oxygen incorporation into nanostructured oxides. Nanodomain boundaries are assumed to be the high diffusivity paths for oxygen transport whereas diffusion into the domains proceeds much slower. Using Laplace transform methods, an exact solution is found for…
Helium spin echo experiments combined with ab initio-based Langevin molecular dynamics simulations are used to quantify the adsorbate-substrate coupling during the thermal diffusion of Na atoms on Cu(111). An analysis of trajectories within the local density friction approximation allows the contribution from electron-hole pair excitations to be separated from the total energy dissipation. Despite the minimal electronic friction coefficient of Na and the relatively small mass mismatch to Cu promoting efficient phononic dissipation, about $(20\pm5)\%$ of the total energy loss is attributable to…
It is shown theoretically that the buckling of the CuO$_{2}$ planes in certain cuprate systems can be explained in terms of an electric field across the planes which originates from different valences of atoms above and below the plane. This field results also in a strong coupling of the Raman-active out-of-phase vibration of the oxygen atoms ($B_{1g}$ mode) to the electronic charge transfer between the two oxygens in the CuO$_{2}$ plane. Consequently, the electric field can be deduced from the Fano-type line shape of the $B_{1g}$ phonon. Using the electric field estimated from the electron-ph…
With an ongoing discussion on the oxygen diffusion along crystal defects remaining, it is difficult to study this phenomenon in Al containing intermetallic materials due to its rapid and passivating oxide formation. We report here the observation of enhanced oxygen diffusion along crystal defects, i.e. dislocations and twin boundaries, in the C15 Al 2 Ca Laves phase and how the presence of oxygen induces structural changes at these defects. Three main phases were identified and characterized structurally by aberration-corrected, atomic resolution scanning transmission electron microscopy, anal…
The diffusion path and diffusivity of oxygen in crystalline silicon are computed using an empirical interatomic potential which was recently developed for modelling the interactions between oxygen and silicon atoms. The diffusion path is determined by constrained energy minimization, and the diffusivity is computed using jump rate theory. The calculated diffusivity is in excellent agreement with experiemental data. The same interatomic potntial also is used to study the formation of small clusters of oxygen atoms in silicon. The structures of these clusters are found by NPT molecular dynamics …
Oxygen isotope substitution is performed in the perovskite cobalt oxide (Pr$_{0.7}$Sm$_{0.3}$)$_{0.7}$Ca$_{0.3}$CoO${_3}$ which shows a sharp spin state transition from the intermediate spin (IS) state to the low spin (LS) state at a certain temperature. The transition temperature of the spin state up-shifts with the substitution of $^{16}O$ by $^{18}$O from the resistivity and magnetic susceptibility measurements. The up-shift value is 6.8 K and an oxygen isotope exponent ($α_S$) is about -0.8. The large oxygen isotope effect indicates strong electron-phonon coupling in this material. The sub…
The oxygen-exchange behavior has been studied in half-doped manganese and cobalt perovskite oxides. We have found that the oxygen diffusivity in Gd_{0.5}Ba_{0.5}MnO_{3-δ} can be enhanced by orders of magnitude by inducing crystallographic ordering among lanthanide and alkali-earth ions in the A-site sublattice. Transformation of a simple cubic perovskite, with randomly occupied A-sites, into a layered crystal GdBaMn_2O_{5+x} (or isostructural GdBaCo_2O_{5+x} for cobalt oxide) with alternating lanthanide and alkali-earth planes reduces the oxygen bonding strength and provides disorder-free chan…
A model for ionic and electronic grain boundary transport through thin films, scales or membranes with columnar grain structure is introduced. The grain structure is idealized as a lattice of identical hexagonal cells - a honeycomb pattern. Reactions with the environment constitute the boundary conditions and drive the transport between the surfaces. Time-dependent simulations solving the Poisson equation self-consistently with the Nernst-Planck flux equations for the mobile species are performed. In the resulting Poisson-Nernst-Planck system of equations, the electrostatic potential is obtain…
In the spin 1/2 antiferromagnetic Ca2CuO3 the optical excitation along 1D a Cu-O chain showed the enrichment of forbidden peaks that could not be explained by the group theory. We present the cluster-model ab initio study of these optical phonons based on the Hartree-Fock SCF calculation with the 3-21G basic set. The obtained results showed very good agreement with the observed data. The Cu-O resonances generally showed the lower shifts in Ca2CuO3 than in pure CuO and were primarily composed of the vibrations of the oxygen in static host lattice whereas the Cu movements happened only in the co…
Electronic devices made from organic materials have the potential to support a more ecologically friendly and affordable future. However, the ability to fabricate devices with well-defined and reproducible electrical and optical properties is hindered by the sensitivity to the presence of chemical impurities. Oxygen in particular is an impurity that can trap electrons and modify conductive properties of some organic materials. Until now the 3-dimensional profiling of oxygen species in organic semiconductors has been elusive and the effect of oxygen remains disputed. In this study we map out hi…
We use first-principles methods to investigate the effects of collective lattice excitations on the formation of oxygen vacancies in perovskite thin films. We find that phonons play a crucial role on the strain-mediated control of defect chemistry at finite temperatures. In particular, zero-temperature oxygen vacancy formation trends deduced as a function of epitaxial strain can be fully reversed near room temperature. Our first-principles calculations evidence a direct link between the lattice contribution to the oxygen vacancy free energy and the volume expansion that the system undergoes wh…
This paper offers a study of oxygen dissolution into a solid, and its consequences on the mechanical behaviour of the material. In fact, mechanical strains strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO2 compound near the internal interface i…
Oxyhydrides have drawn attention because of their fast ion conductivity and strong reducing properties. Recently, hydride ion migration in SrTiO$_{3-x}$H$_{x}$ oxyhydride crystals has been investigated, showing that hydride ion migration is blocked by slow oxygen diffusion. In this study, we investigate the hydride-ion migration mechanism using a kinetic Monte Carlo approach to understanding the relationship between the hydride and oxygen ions. The difficulties in applying the method to hydride and oxygen ion migration involve complex changes in the ionic migration barrier, which shifts dynami…
An effective spin relaxation mechanism that leads to electron spin decoherence in a quantum dot is proposed. In contrast to the common calculations of spin-flip transitions between the Kramers doublets, we take into account a process of phonon-mediated fluctuation in the electron spin precession and subsequent spin phase diffusion. Specifically, we consider modulations in the longitudinal g-factor and hyperfine interaction induced by the phonon-assisted transitions between the lowest electronic states. Prominent differences in the temperature and magnetic field dependence between the proposed …
Ion-conducting solid electrolytes are widely used for a variety of purposes. Therefore, designing highly ion-conductive materials is in strongly demand. Because of advancement in computers and enhancement of computational codes, theoretical simulations have become effective tools for investigating the performance of ion-conductive materials. However, an exhaustive search conducted by theoretical computations can be prohibitively expensive. Further, for practical applications, both dynamic conductivity as well as static stability must be satisfied at the same time. Therefore, we propose a compu…
We report on phonon properties and electronic transitions in CaCu3Ti4O12, a material which reveals a colossal dielectric constant at room temperature without any ferroelectric transition. The results of far- and mid-infrared measurements are compared to those obtained by broadband dielectric and millimeter-wave spectroscopy on the same single crystal. The unusual temperature dependence of phonon eigenfrequencies, dampings and ionic plasma frequencies of low lying phonon modes are analyzed and discussed in detail. Electronic excitations below 4 eV are identified as transitions between full and …
Photochromic oxygen$-$containing yttrium$-$hydride thin films are synthesized by argon$-$magnetron sputtering on microscope slides. Some of them are encapsulated with a thin, transparent and non$-$photochromic diffusion-barrier layer of either Al2O3 or Si3N4. Ion beam-based methods prove that these protective diffusion barriers are stable and free from pinholes, with thicknesses of only a few tens of nanometers. Optical spectrophotometry reveals that the photochromic response and relaxation time for both $-$ protected and unprotected $-$ samples are almost identical. Ageing effects in the unpr…
