Migration Of Point Defects Research Articles

Deterministic Role of Collision Cascade Density in Radiation Defect Dynamics in Si.

The formation of stable radiation damage in solids often proceeds via complex dynamic annealing (DA) processes, involving point defect migration and interaction. The dependence of DA on irradiation conditions remains poorly understood even for Si. Here, we use a pulsed ion beam method to study defect interaction dynamics in Si bombarded in the temperature range from ∼-30 °C to 210 °C with ions in a wide range of masses, from Ne to Xe, creating collision cascades with different densities. We demonstrate that the complexity of the influence of irradiation conditions on defect dynamics can be reduced to a deterministic effect of a single parameter, the average cascade density, calculated by taking into account the fractal nature of collision cascades. For each ion species, the DA rate exhibits two well-defined Arrhenius regions where different DA mechanisms dominate. These two regions intersect at a critical temperature, which depends linearly on the cascade density. The low-temperature DA regime is characterized by an activation energy of ∼0.1 eV, independent of the cascade density. The high-temperature regime, however, exhibits a change in the dominant DA process for cascade densities above ∼0.04 at.%, evidenced by an increase in the activation energy. These results clearly demonstrate a crucial role of the collision cascade density and can be used to predict radiation defect dynamics in Si.

Density Functional Theory Modeling of Cation Diffusion in Bulk Lanthanum Manganite and Tetragonal Zirconia for Solid Oxide Fuel Cell Applications

Cation diffusion in perovskites such as La1-xSrxMnO3±δ (LSM) and fluorites such as Yttria Stabilized Zirconia (YSZ) plays a key role in controlling performance and long-term stability of solid oxide fuel cells (SOFCs) and of the corresponding electrode/electrolyte interfaces. For point defects based cation migration mechanisms, discrepancies between experimental studies and atomistic modeling results are generally observed when trying to identify the apparent activation energies of the cation diffusivities. In particular, computational modeling of the simple point defect migration generally overestimates the apparent activation energies by several eVs [1-3] relative to experimental results. Despite the existence of few proposed defect cluster pathways in the SOFC literature, the corresponding energetics based on atomistic level modeling is quite limited. As a result, outstanding questions related to the influence of the local bonding environment of the material upon the activation energies of cation diffusion and upon the energetics of the defect cluster carriers are still open. In this presentation, density functional theory (DFT) calculations of the cation diffusion involving mechanisms beyond the isolated point defect migration mechanism are discussed in connection to SOFC applications. The barriers of the cations, cation vacancy clusters, and cation impurities migration as well as their corresponding saddle point configurations in bulk LaMnO3±δ (LMO) and tetragonal ZrO2 are investigated. For cation vacancy migration in both LaMnO3 and tetragonal ZrO2 systems, it was revealed that significant reduction in the barriers of 1~3 eV takes place when there exists an additional nearest neighbor vacancy or a nearest neighbor vacancy pair bound to the original cation vacancy transport carrier (i.e., partially or fully bound Schottky defects). Such a significant reduction in the migration barriers of isolated cation vacancy migration due to the presence of an additional nearest neighbor vacancy or a vacancy pair invokes the need to examine other possible defect cluster diffusion mechanisms that exhibit attractive or weakly repulsive interactions between point defects. For example, our recent studies [1,3] suggest that the presence of a nearest neighbor B-site cation vacancy in bulk LMO decreases the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition state configurations, leading to a more active A-site cation diffusion with apparent activation energies in good agreement with the experimental measurements. An analogous scenario is also observed for the Lanthanide impurity migration (via a cation vacancy related mechanism) in tetragonal ZrO2, where the migration barriers of partial and full Schottky bound defects are about 1.5 and 2.4 eV lower than those of simple cation vacancy migration (about 3 eV). By considering the attractive interactions of -1.0 and -1.4 eV for the partial (VZr-VO) and full (VO-VZr-VO) bound Schottky defects along with the separated Schottky defect formation energies of 4~5 eV (in a 288-atom ZrO2 supercells), it follows that cation impurity diffusion via partially and fully bonded Schottky defects could be more active than the cation vacancy migration of the separated Schottky defects in tetragonal ZrO2. Finally, the trends in the migration barriers of the defect cluster mechanisms among several types of cation impurities relevant for SOFC applications in LMO and tetragonal ZrO2 will be also discussed.

Mesoscale simulations of radiation damage effects in Materials: A SEAKMC perspective

Radiation damage presents a unique challenge for material simulations, with processes ranging from picoseconds to decades in time and nanometers to meters in length. Particularly, the understanding of many processes and fundamental mechanisms at the mesoscale are still lacking. In this paper, the self-evolving kinetic Monte Carlo (SEAKMC) method and its application to study mesoscale defect interaction is presented. SEAKMC is an off-lattice atomistic kinetic Monte Carlo approach which conducts ‘on-the-fly’ saddle point searches (SPS) using selective active volumes. The main components of SEAKMC are examined with focus on the comparative benefits of this method. Future areas of improvement are outlined, including suggestions for general improvements to SPS methods by reducing redundant searching and making predictive initial guesses for point defect migration events. Previous applications of SEAKMC to radiation effects in materials are briefly reviewed. Some potential applications of SEAKMC are given, including discussion of dislocation bias, and the further study of interaction between dislocation loops and point defects, which provide useful insights to understand void swelling, radiation induced segregation, and other important radiation damage processes.

Migration of Point Defects in the Field of a Temperature Gradient

The influence of the temperature gradient over the thickness of the cladding of a fuel element of a fast-neutron reactor on the migration of point defects formed in the cladding material due to neutron irradiation has been studied. It has been shown that, under the action of the temperature gradient, the flux of vacancies onto the inner surface of the cladding is higher than the flux of interstitial atoms, which leads to the formation of a specific concentration profile in the cladding with a vacancy-depleted zone near the inner surface. The experimental results on the spatial distribution of pores over the cladding thickness have been presented with which the data on the concentration profiles and vacancy fluxes have been compared.

Defect stabilization and reverse annealing in ZnO implanted with nitrogen at room and cryogenic temperature

Despite the fact that nitrogen is a potential acceptor dopant and one of the most studied elements in ZnO, lacking understanding of associated defects and their thermal evolution limits realization of reliable p-type doping of ZnO. Here, we use ion implantation to introduce N at room temperature (RT) and 15 K in ZnO samples with/without a pre-existing buried disorder layer formed by Ag ion bombardment aligned along the [0001] direction. The buried layer contains a high concentration of extended defects, which act as traps for migrating point defects. Channeling analysis shows that reverse annealing occurs in all the N implanted samples during post-implant heat treatment above 600 °C with strong non-linear additive damage accumulation in the co-implanted samples. The reverse annealing effect is less stable in the RT co-implanted sample and the data suggest that a high local concentration of intrinsic point defects, like Zn interstitials, promotes the stability of the N-defect clusters responsible for the reverse annealing. This suggestion is also corroborated by enhanced and defect-mediated Ag outdiffusion at 1100 °C in the RT co-implanted samples.

Necessary Duration of Molecular Dynamics Simulation for Calculation of Self-Diffusion Coefficient during Migration of Different Point Defects in Nickel

The evaluation of the necessary duration of molecular dynamics experiment for the calculation of the selfdiffusion coefficient during migration of different point defects in Ni (vacancy, bivacancy, self-interstitial atom, hydrogen atom) is conducted in this paper. The mentioned defects have different mobility that results in different intensities of atoms displacements caused by migration of the defect. The accuracy of diffusion coefficient calculation is related to the accuracy of estimation of rootmean-square changes of atoms coordinates. Consequently, the accuracy increases with the increase of moleculardynamic experiment duration t, the temperature T, and the mobility of the defect initiating the diffusion. To describe the interatomic interactions, the multi-particle Cleri-Rosato potential is used in the study. It is shown that the simulation duration of 100 ps is enough to calculate the diffusion coefficient when the temperature is higher than 0.6 of melting point. When calculating the diffusion coefficient of impurity in a metal crystal (for example, the hydrogen impurity), it is possible to decrease the root mean square error of displacement evaluation of impurity atoms by increasing the number of impurity atoms.DOI 10.14258/izvasu(2018)1-06

Thermodynamic mixing energy and heterogeneous diffusion uncover the mechanisms of radiation damage reduction in single-phase Ni-Fe alloys

Understanding and predicting radiation damage is of central importance to develop radiation-tolerant structural materials for current and next-generation nuclear systems. Single-phase solid solution alloys constitute attractive choices due to their promising mechanical properties and radiation tolerance. Here, by examining radiation-induced defect production and evolution in single-phase Ni-Fe alloys, we show that radiation damage resistance directly correlates with thermodynamic mixing energy and heterogeneity of defect diffusion. We found that radiation damage in materials decreases linearly with lowering mixing energy, and the relationship holds true for all studied Ni-Fe compositions. The damage reduction with varying composition is further ascribed to the increasing heterogeneity of point defect migration across a complex potential energy landscape that enhances defect recombination. This new insight into the dynamical evolution of radiation defects points to a thermodynamic criterion for designing radiation-tolerant materials.

The Necessary Duration of a Molecular Dynamics Experiment for the Diffusion Coefficient Calculation

The evaluation of the necessary duration of a molecular dynamics experiment for the calculation of the diffusion coefficient at migration of different point defects in Ni (vacancy, bivacancy, self-interstitial atom, hydrogen atom) is held in the present work. It is shown that at the temperature higher than 0.6 of melting point is usually enough the simulation during of 100 ps for this. When calculating of the diffusion coefficient of impurity in the metal crystal, for example, of hydrogen, the decrease of error of mean-square displacements of impurity atoms can be achieved by introducing of a large number of the impurities.

Proton irradiation effects on minority carrier diffusion length and defect introduction in homoepitaxial and heteroepitaxial n-GaN

Inherent advantages of wide bandgap materials make GaN-based devices attractive for power electronics and applications in radiation environments. Recent advances in the availability of wafer-scale, bulk GaN substrates have enabled the production of high quality, low defect density GaN devices, but fundamental studies of carrier transport and radiation hardness in such devices are lacking. Here, we report measurements of the hole diffusion length in low threading dislocation density (TDD), homoepitaxial n-GaN, and high TDD heteroepitaxial n-GaN Schottky diodes before and after irradiation with 2.5 MeV protons at fluences of 4–6 × 1013 protons/cm2. We also characterize the specimens before and after irradiation using electron beam-induced-current (EBIC) imaging, cathodoluminescence, deep level optical spectroscopy (DLOS), steady-state photocapacitance, and lighted capacitance-voltage (LCV) techniques. We observe a substantial reduction in the hole diffusion length following irradiation (50%–55%) and the introduction of electrically active defects which could be attributed to gallium vacancies and associated complexes (VGa-related), carbon impurities (C-related), and gallium interstitials (Gai). EBIC imaging suggests long-range migration and clustering of radiation-induced point defects over distances of ∼500 nm, which suggests mobile Gai. Following irradiation, DLOS and LCV reveal the introduction of a prominent optical energy level at 1.9 eV below the conduction band edge, consistent with the introduction of Gai.

Dynamic annealing in Ge studied by pulsed ion beams

The formation of radiation damage in Ge above room temperature is dominated by complex dynamic annealing processes, involving migration and interaction of ballistically-generated point defects. Here, we study the dynamics of radiation defects in Ge in the temperature range of 100–160 °C under pulsed beam irradiation with 500 keV Ar ions when the total ion fluence is split into a train of equal square pulses. By varying the passive portion of the beam duty cycle, we measure a characteristic time constant of dynamic annealing, which rapidly decreases from ~8 to 0.3 ms with increasing temperature. By varying the active portion of the beam duty cycle, we measure an effective diffusion length of ~38 nm at 110 °C. Results reveal a major change in the dominant dynamic annealing process at a critical transition temperature of ~130 °C. The two dominant dynamic annealing processes have an order of magnitude different activation energies of 0.13 and 1.3 eV.

Diffusion-Controlled growth of Ge nanocrystals in SiO2 films under conditions of ion synthesis at high pressure

The growth of Ge nanocrystals in SiO2 films is studied in relation to the dose of implanted Ge+ ions and the annealing temperature at a pressure of 12 kbar. It is established that the dependences of the nanocrystal dimensions on the content of Ge atoms and the annealing time are described by the corresponding root functions. The nanocrystal radius squared is an exponential function of the inverse temperature. The dependences correspond to the model of the diffusion-controlled mechanism of nanocrystal growth. From the temperature dependence of the nanocrystal dimensions, the diffusion coefficient of Ge in SiO2 at a pressure of 12 kbar is determined: D = 1.1 × 10–10 exp(–1.43/kT). An increase in the diffusion coefficient of Ge under pressure is attributed to the change in the activation volume of the formation and migration of point defects. Evidence in favor of the interstitial mechanism of the diffusion of Ge atoms to nanocrystal nuclei in SiO2 is reported.

Deformation-Induced Atomic Disordering and Reordering in Alloys with L12 Structure

The paper presents a mathematical model of thermal and strain hardening of alloys having L12 superstructure which allows calculating the atomic long-range order (LRO) parameter depending on the deformation degree under various temperature and loading conditions. The observed non-monotonic change in the atomic LRO parameter during plastic deformation occurs due to the two types of competitive processes. These processes are caused by the motion and accumulation of the deformation defects and their healing due to the migration of point defects of different nature. The competitiveness between these two types of processes leads to the periodical destruction and reconstruction of the atomic LRO parameter, while the equilibrium between them can stabilize it after which it continues to be stable despite the deformation.

Specific features of the ion-beam synthesis of Ge nanocrystals in SiO2 thin films

The systematic features of the formation of Ge nanocrystals in SiO2 thin films implanted with Ge+ ions and then subjected to high-temperature annealing (1130°C) are studied in relation to hydrostatic pressure. It is established that annealing at atmospheric pressure is accompanied by the diffusion of Ge atoms from the implantation region to the Si substrate and does not induce the formation of Ge nanocrystals. An increase in pressure during annealing yields a deceleration in the diffusion of germanium into silicon and is accompanied by the formation of twinned lamellae at the Si/SiO2 interface (at pressures of ~103 bar) or by the nucleation and growth of Ge nanocrystals (at pressures of ~104 bar) in the SiO2 film. The results are discussed on the basis of the concept of a change in the activation volume of the formation and migration of point defects under conditions of compression.

Room-Temperature Multiferroics and Thermal Conductivity of 0.85BiFe1-2xTixMgxO3-0.15CaTiO3 Epitaxial Thin Films (x = 0.1 and 0.2).

Thin films of 0.85BiFe1-2xTixMgxO3-0.15CaTiO3 (x = 0.1 and 0.2, abbreviated to C-1 and C-2, respectively) have been fabricated on (001) SrTiO3 substrate with and without a conductive La0.7Sr0.3MnO3 buffer layer. The X-ray θ-2θ and ϕ scans, atomic force microscopy, and cross-sectional transmission electron microscopy confirm the (001) epitaxial nature of the thin films with very high growth quality. Both the C-1 and C-2 thin films show well-shaped magnetization-magnetic field hysteresis at room temperature, with enhanced switchable magnetization values of 145.3 and 42.5 emu/cm3, respectively. The polarization-electric loops and piezoresponse force microscopy measurements confirm the room-temperature ferroelectric nature of both films. However, the C-1 films illustrate a relatively weak ferroelectric behavior and the poled states are easy to relax, whereas the C-2 films show a relatively better ferroelectric behavior with stable poled states. More interestingly, the room-temperature thermal conductivity of C-1 and C-2 films are measured to be 1.10 and 0.77 W/(m·K), respectively. These self-consistent multiferroic properties and thermal conductivities are discussed by considering the composition-dependent content and migration of Fe-induced electrons and/or charged point defects. This study not only provides multifunctional materials with excellent room-temperature magnetic, ferroelectric, and thermal conductivity properties but may also stimulate further work to develop BiFeO3-based materials with unusual multifunctional properties.

Effect of saddle point anisotropy of point defects on their absorption by dislocations and cavities

Developing predictive models for the microstructure evolution of materials requires an accurate description of the point defects fluxes to the different sinks, such as dislocations, grain boundaries and cavities. This work aims at improving the evaluation of sink strengths of dislocations and cavities using object kinetic Monte-Carlo simulations parametrized with density functional theory calculations. The present accurate description of point defects migration enables quantitative assessment of the influence of the point defects anisotropy at saddle point. The results in aluminum show that the anisotropy at saddle point has a large influence on sink strengths. In particular, this anisotropy leads to the cavity being a biased sink. These results are explained by the analysis of the point defect trajectories to the sinks, which are shown to be strongly affected by the saddle point anisotropy.

Composition and temperature dependence of self-diffusion in Si1\u2212xGex alloys

The knowledge of diffusion processes in semiconducting alloys is very important both technologically and from a theoretical point of view. Here we show that, self-diffusion in Si1−xGex alloys as a function of temperature and Ge concentration can be described by the cBΩ thermodynamic model. This model connects the activation Gibbs free energy of point defects formation and migration with the elastic and expansion properties of the bulk material. The approach allows the systematic investigation of point defect thermodynamic parameters such as activation enthalpy, activation entropy and activation volume, based on the thermo-elastic properties (bulk modulus and its derivatives, mean atomic volume and thermal expansion coefficient) of the two end-members of the Si1−xGex alloy. Considerable deviations from Vegard’s law are observed, due to the diversification of the bulk properties of Si and Ge, in complete agreement with the available experimental data.

Effect of buried extended defects on the radiation tolerance of ZnO

Interaction between defects of different types often determines their evolution in semiconductors under ion irradiation. Here, we investigate the role of buried pre-existing extended defects in the damage accumulation in ZnO single crystals implanted at room temperature and at 15 K with 80 keV N ions. For the room temperature implants but not for the 15 K ones, the defect accumulation around the projected range is strongly suppressed while a pronounced build-up occurs in the region of the pre-existing defects. This is attributed to thermally activated migration of point defects from the implanted volume and subsequent trapping/annihilation by the pre-existing defects. The obtained results imply that a defect engineering scheme involving formation of a high density of extended defects outside the active volume of a ZnO-based device could be beneficial to enhance the radiation tolerance.

Radiation defect dynamics studied by pulsed ion beams

The formation of stable radiation damage in solids often proceeds via complex dynamic annealing processes, involving migration and interaction of ballistically-generated point defects. Our current understanding of the underlying physics is still not sufficient for predicting radiation damage even for Si, which is arguably the simplest and most extensively studied material. The complexity of radiation damage is closely related to radiation defect dynamics. Here, we demonstrate how defect interaction dynamics can be studied by pulsed beam irradiation when the total ion fluence is split into a train of equal square pulses. By varying the passive portion of the beam duty cycle, we measure a characteristic time constant of dynamic annealing and, hence, the defect relaxation rate. Measurements of stable lattice disorder as a function of the active portion of the beam duty cycle give an effective defect diffusion length. We illustrate the pulsed beam method with examples for Si bombarded at 100°C with 500keV Ar ions.

Introducing ab initio based neural networks for transition-rate prediction in kinetic Monte Carlo simulations

The quality of kinetic Monte Carlo (KMC) simulations of microstructure evolution in alloys relies on the parametrization of point-defect migration rates, which are complex functions of the local ch ...

The role of Frenkel defect diffusion in dynamic annealing in ion-irradiated Si

The formation of stable radiation damage in crystalline solids often proceeds via complex dynamic annealing processes, involving migration and interaction of ballistically-generated point defects. The dominant dynamic annealing processes, however, remain unknown even for crystalline Si. Here, we use a pulsed ion beam method to study defect dynamics in Si bombarded in the temperature range from −20 to 140 °C with 500 keV Ar ions. Results reveal a defect relaxation time constant of ~10–0.2 ms, which decreases monotonically with increasing temperature. The dynamic annealing rate shows an Arrhenius dependence with two well-defined activation energies of 73 ± 5 meV and 420 ± 10 meV, below and above 60 °C, respectively. Rate theory modeling, bench-marked against this data, suggests a crucial role of both vacancy and interstitial diffusion, with the dynamic annealing rate limited by the migration and interaction of vacancies.