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At least 433 records · Page 24

Molecular dynamics studies of lattice defect effects on tritium diffusion in zirconium

Tritium diffusion in α-Zr containing point defects such as vacancies or self-interstitial atoms (SIAs) is simulated using molecular dynamics. Point defects rapidly aggregate to form extended defects, such as 3D nanoclusters and Frank loops. The geometry of extended defects is affected by the presence of tritium. At low temperature and in the absence of tritium, vacancies aggregate to form stacking fault pyramids. Addition of tritium at these temperatures promotes aggregation of vacancies to form 3D nanoclusters, within which the tritium concentration can be sufficiently high to suggest that these defects may serve as nucleation sites for hydride precipitation. Trapping of tritium in vacancy nanocluster reduces the calculated bulk diffusivity by an amount proportional to the vacancy concentration. At high temperature, vacancy clusters change shape to form planar basal dislocation loops, which bind tritium less strongly, leading to a sharp reduction in the fraction of trapped tritium and a corresponding increase in tritium diffusivity at high temperature. In contrast, SIAs increase tritium diffusion through α-Zr. Analysis of atomic trajectories shows that tritium does not interact directly with SIAs. In conclusion, diffusion enhancement is instead related to expansion of the lattice.

36 MATERIALS SCIENCE↗

Development of the Local (Site) Symmetry Method in the Supercell Model for a Crystal with an Impurity

Symmetry aspects of the periodic model of a crystal with a point defect (a supercell model or a extended unit cell (EUC) model) are considered; splitting of the Wyckoff positions in a primitive crystal cell with the introduction of supercell and the change of the one-electron states classification over k-vector (Brillouin zone folding) are discussed. When considering a point defect in a crystal in the supercell model, it is necessary to take into account the symmetry of the one-electron states of the original crystal at the top of the valence band and at the bottom of the conduction band. The selected supercell should reproduce these states. Each specific selection of a supercell corresponds to a specific splitting of the Wyckoff positions of the original crystal and, as a result, the possibility to place a defect in positions with different point symmetry and to perform a calculation without taking into account the point symmetry of the crystal with a defect at all (site symmetry method). By the results of the calculation of a crystal with a defect in the supercell model, taking into account site symmetry, it is possible to determine the real symmetry of the crystal with a defect, which is essential for the interpretation of experimental data. A copper impurity in a lithium node in a LiCl crystal retains the cubic symmetry of the atom being replaced; the impurity of an iron atom in a titanium site with cubic local symmetry in a SrTiO{sub 3} crystal lowers the symmetry to tetragonal; and the H site in the CsPbI{sub 3} crystal is characterized by the complete removal of point symmetry with the formation of an I{sub 2}{sup −} ion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Computational design of quantum defects in two-dimensional materials

We report missing atoms or atom substitutions (point defects) in crystal lattices in two-dimensional (2D) materials are potential hosts for emerging quantum technologies, such as single-photon emitters and spin quantum bits (qubits). First-principles-guided design of quantum defects in 2D materials is paving the way for rational spin qubit discovery. Here we discuss the frontier of first-principles theory development and the challenges in predicting the critical physical properties of point defects in 2D materials for quantum information technology, in particular for optoelectronic and spin-optotronic properties. Strong many-body interactions at reduced dimensionality require advanced electronic structure methods beyond mean-field theory. The great challenges for developing theoretical methods that are appropriate for strongly correlated defect states, as well as general approaches for predicting spin relaxation and the decoherence time of spin defects, are yet to be addressed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Neutron irradiation effects on gallium nitride-based Schottky diodes

Depth-resolved cathodoluminescence spectroscopy (DRCLS), time-resolved surface photovoltage spectroscopy, X-ray photoemission spectroscopy (XPS), and current-voltage measurements together show that fast versus thermal neutrons differ strongly in their electronic and morphological effects on metal-GaN Schottky diodes. Fast and thermal neutrons introduce GaN displacement damage and native point defects, while thermal neutrons also drive metallurgical reactions at metal/GaN interfaces. Defect densities exhibit a threshold neutron fluence below which thermal neutrons preferentially heal versus create new native point defects. Scanning XPS and DRCLS reveal strong fluence- and metal-dependent electronic and chemical changes near the free surface and metal interfaces that impact diode properties.

36 MATERIALS SCIENCE↗

Time-resolved photoluminescence from defects in n-type GaN

Point defects in GaN were studied with time-resolved photoluminescence (PL). The effects of temperature and excitation intensity on defect-related PL have been investigated theoretically and experimentally. A phenomenological model, based on rate equations, explains the dependence of the PL intensity on excitation intensity, as well as the PL lifetime and its temperature dependence. We demonstrate that time-resolved PL measurements can be used to find the concentrations of free electrons and acceptors contributing to PL in n-type semiconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molecular dynamics simulations of swift heavy ion induced defect recovery in SiC

Swift heavy ions induce a high density of electronic excitations that can cause the formation of amorphous ion tracks in insulators. No ion tracks have been observed in the semiconductor SiC, but recent experimental work suggests that irradiation damaged SiC can undergo defect recovery under swift heavy ion irradiation. It is believed that local heating of the lattice due to the electronic energy deposition can anneal, and thereby recover, some of the disordered structure. We simulate the local heating due to the ions by the inelastic thermal spike model and perform molecular dynamics simulations of dierent model damage states to study the defect recovery on an atomistic level. We find significant recovery of point defects and a disordered layer, as well as recrystallization at the amorphous-to-crystalline interface of an amorphous layer. The simulation results support the swift heavy ion annealing hypothesis.Swift heavy ions induce a high density of electronic excitations that can cause the formation of amorphous ion tracks in insulators. No ion tracks have been observed in the semiconductor SiC, but recent experimental work suggests that irradiation damaged SiC can undergo defect recovery under swift heavy ion irradiation. It is believed that local heating of the lattice due to the electronic energy deposition can anneal, and thereby recover, some of the disordered structure. We simulate the local heating due to the ions by the inelastic thermal spike model and perform molecular dynamics simulations of dierent model damage states to study the defect recovery on an atomistic level. We find significant recovery of point defects and a disordered layer, as well as recrystallization at the amorphous-to-crystalline interface of an amorphous layer. The simulation results support the swift heavy ion annealing hypothesis.

Defect recovery↗

Semi insulating CdTe:Cl after elimination of inclusions and precipitates by post grown annealing

We present in this contribution results of two-step annealing, when the CdTe:Cl doped samples are at first annealed under Cd overpressure to remove inclusions and the re-annealed under Te overpressure to restore the high resistivity state. Investigation of samples after Cd rich annealing by infrared microscope has proven, that all inclusions are removed. Also Te nano precipitates were strongly influenced by the annealing process. The resistivity of the samples after Te-rich annealing was restored to values ( ~ 108-109Ωcm). We observed, however, decrease of mobility-lifetime product of electrons from 10-3cm2/Vs to 10-4cm2/Vs. In order to understand the reason of this decrease we performed a study of point defects before and after annealing by thermoelectric effect spectroscopy. It shows a decrease of concentrations of most deep levels after two-step annealing. This behavior is completely different compared to past annealing studies, where concentration of deep levels strongly increased after annealing. The only level with an increased concentration in the current study is the midgap level (E ~ 0.8 eV). At the same time we observed increase of micro-twins in the samples investigated by transmission electron microscopy. The decrease of charge collection efficiency after two-step annealing may be therefore connected with re-arrangement of near midgap levels due to increase of concentrations of structure defects (micro twins, dislocations) that accumulate in their surroundings point defects with energy ~ 0.75 eV.

36 MATERIALS SCIENCE↗

Signatures of distinct impurity configurations in atomic-resolution valence electron-energy-loss spectroscopy: Application to graphene

The detection and identification of impurities and other point defects in materials is a challenging task. Signatures for point defects are typically obtained using spectroscopies without spatial resolution. Here in this paper, we demonstrate the power of valence electron-energy-loss spectroscopy (VEELS) in an aberration-corrected scanning transmission-electron microscope (STEM) to provide energy-resolved and atomically resolved maps of electronic excitations of individual impurities which, combined with theoretical simulations, yield unique signatures of distinct bonding configurations of impurities. We report VEELS maps for isolated Si impurities in graphene, which are known to exist in two distinct configurations. We also report simulations of the maps, based on density functional theory and dynamical scattering theory, which agree with and provide direct interpretation of observed features. We show that theoretical VEELS maps exhibit distinct and unambiguous signatures for the threefold- and fourfold-coordinated configurations of Si impurities in different energy-loss windows, corresponding to impurity-induced bound states, resonances, and antiresonances. With the advent of new monochromators and detectors with high energy resolution and low signal-to-noise ratio, the present work ushers an atomically resolved STEM-based spectroscopy of individual impurities as an alternative to conventional spectroscopies for probing impurities and defects.

36 MATERIALS SCIENCE↗

Crystal structure, chemical expansion and phase stability of HoMnO{sub 3} at high temperature

Anisotropic thermal and chemical expansion of hexagonal HoMnO{sub 3} was investigated by high temperature X-ray diffraction in inert (N{sub 2}) and oxidizing (air) atmospheres up to 1623 K. A second order structural phase transition directly from P6{sub 3}cm to P6{sub 3}/mmc was found at 1298{+-}4 K in N{sub 2} atmosphere, and 1318{+-}4 K in air. For the low temperature polymorph P6{sub 3}cm the contraction of the c-axis was more rapid in inert than in oxidizing atmosphere. The c-axis of the P6{sub 3}/mmc polymorph of HoMnO{sub 3} displayed anomalously high expansion above 1400 K, which is discussed in relation to chemical expansion caused by point defects. The a-axis expanded stronger in inert than oxidizing atmosphere. Anisotropic chemical and thermal expansion of the P6{sub 3}cm phase of YMnO{sub 3} in N{sub 2}, air and O{sub 2} atmospheres was found to be qualitatively similar to that of HoMnO{sub 3}. Decomposition of hexagonal HoMnO{sub 3} by two different processes occurs in oxidizing atmosphere above {approx}1200 K followed by nucleation and growth of the perovskite polymorph of HoMnO{sub 3}. A rapid, reconstructive transition from the perovskite back to the hexagonal polymorph was observed in situ at 1623 K upon reduction of the partial pressure of oxygen. A phase stability diagram of the hexagonal and orthorhombic polymorphs is proposed. Finally, distinctly non-linear electrical conductivity was observed for both HoMnO{sub 3} and YMnO{sub 3} in oxidizing atmosphere between 555 and 630 K, and shown to be associated with excess oxygen. - Graphical abstract: Chemical expansion of hexagonal HoMnO{sub 3} is observed during HTXRD in different pO{sub 2}. Oxidizing atmosphere favors the competing perovskite polymorph. Electrical conductivity anomalies related to excess oxygen are found at 550-630 K. Highlights: Black-Right-Pointing-Pointer Thermal evolution of crystal structure of HoMnO{sub 3} studied up to 1623 K in air and N{sub 2}. Black-Right-Pointing-Pointer Anisotropic chemical expansion of HoMnO{sub 3} and YMnO{sub 3} in N{sub 2}, air and O{sub 2}. Black-Right-Pointing-Pointer Hexagonal phase destabilized with respect to perovskite in oxidizing atmosphere. Black-Right-Pointing-Pointer Crystal structure and phase stability discussed in terms of point defect chemistry. Black-Right-Pointing-Pointer Electrical conductivity anomalies associated with excess oxygen at 550-630 K.

36 MATERIALS SCIENCE↗

Time constant of defect relaxation in ion-irradiated 3 C -SiC

Above room temperature, the buildup of radiation damage in SiC is a dynamic process governed by the mobility and interaction of ballistically generated point defects. Here in this work, we study the dynamics of radiation defects in 3C-SiC bombarded at 100 °C with 500 keV Ar ions, with the total ion dose split into a train of equal pulses. Damage–depth profiles are measured by ion channeling for a series of samples irradiated under identical conditions except for different durations of the passive part of the beam cycle. Results reveal an effective defect relaxation time constant of ~3 ms (for second order kinetics) and a dynamic annealing efficiency of ~40% for defects in both Si and C sublattices. Finally, this demonstrates a crucial role of dynamic annealing at elevated temperatures and provides evidence of the strong coupling of defect accumulation processes in the two sublattices of 3C-SiC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Vacancy-type defects induced by grinding of Si wafers studied by monoenergetic positron beams

Vacancy-type defects introduced by the grinding of Czochralski-grown Si wafers were studied using monoenergetic positron beams. Measurements of Doppler broadening spectra of the annihilation radiation and the lifetime spectra of positrons showed that vacancy-type defects were introduced in the surface region (<98 nm), and the major defect species were identified as (i) relatively small vacancies incorporated in dislocations and (ii) large vacancy clusters. Annealing experiments showed that the defect concentration decreased with increasing annealing temperature in the range between 100 and 500°C. After 600–700°C annealing, the defect-rich region expanded up to about 170 nm, which was attributed to rearrangements of dislocation networks, and a resultant emission of point defects toward the inside of the sample. Above 800°C, the stability limit of those vacancies was reached and they started to disappear. After the vacancies were annealed out (900°C), oxygen-related defects were the major point defects and they were located at <25 nm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molecular dynamics study of grain boundary and radiation effects on tritium population and diffusion in zirconium

Tritium population thermodynamics and transport kinetics critically define the tritium storage performance of zirconium tritides that can be used for a variety of nuclear applications including tritium-producing burnable absorber rods. Both thermodynamic and kinetic properties can be sensitive to grain sizes of materials and can be significantly altered by irradiated defects during operation under the reactor environments. A thorough experimental characterization of how these properties evolve under different reactor conditions and different initial grain structures is extremely challenging. Here molecular dynamics simulations are used to investigate tritium population and diffusion in zirconium with and without different planar symmetric and asymmetric tilt grain boundaries and irradiated defects. Here, we found that in addition to trapping tritium, the most significant effect of planar grain boundaries is to increase tritium diffusivity on the boundary plane. Furthermore, fine grain structures are found to mitigate the change of tritium diffusivity due to irradiated point defects as these point defects are likely to migrate to and sink at grain boundaries.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Control of donor-like effect in V2VI3 polycrystalline thermoelectric materials

Highlights: • Thermal control of donor-like effect for V{sub 2}VI{sub 3} polycrystalline materials is proposed. • Low-temperature sintering or hot deforming facilitates the donor-like effect. • Recovery role by high-temperature sintering/deforming enhances the Seebeck coefficient. • Temperature should be strictly selected for each V{sub 2}VI{sub 3} polycrystalline material. - Abstract: Intrinsic point defect plays a core role in improving thermoelectric performance of V{sub 2}VI{sub 3} polycrystalline materials. However, the control of intrinsic point defect is challenging during powder refinement due to the donor-like effect. This paper shows a systematic approach to thermal control the donor-like effect via engineering spark plasma sintering and hot deformation temperature. Bi{sub 2}Te{sub 2.85}Se{sub 0.15} polycrystalline alloy with high electron concentration was chosen as example to validate the method. The low Seebeck coefficient of n-type Bi{sub 2}Te{sub 2.85}Se{sub 0.15} polycrystalline, arising from strong donor-like effect after powder refinement, was enhanced by recovery role induced reduction in electron concentration through proper tuning sintering or deforming temperature. Repetitive hot deformation was applied to further improve the Seebeck coefficient via the recovery role and a maximum zT of 1.0 is obtained at 410 K. The present results give insights into developing higher performance V{sub 2}VI{sub 3} polycrystalline materials through thermal control the donor-like effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Neutron irradiation induced defects in oxides and their impact on the oxide properties

Understanding the irradiation-induced defects in oxides is of interest for a wide range of applications. ZnO is an interesting oxide with mixed ionic and covalent bonding that contains a variety of point defect structures—making it an excellent model for studying irradiation-induced defects and their impact on properties. Here, we investigate the effects of neutron irradiation on the formation of defects and on the structural, optical, and electrical properties of ZnO single crystals. We observe the formation of vacancies and voids via positron annihilation spectroscopy. Neutron irradiation led to a significant deterioration of the ZnO structure and formed a high concentration of point defects, vacancy clusters, and voids with large disparities in their structure across variable irradiation times. It also led to significant changes in the optical properties and sample color. Irradiation for 444 h induced a high concentration of Cu acceptors as well as a high concentration of Ga donors. Additionally, temperature-dependent Hall effect measurements revealed the competing production of donors and acceptors and showed an increase in the slope of the carrier freeze-out curve with increasing irradiation dose. This work demonstrates the combined effects of neutron irradiation in producing a wide range of structural defects, impurities, and dopants in oxides and their enormous impact on modifying the oxide structure and both the optical and electronic properties. It particularly emphasizes the importance of considering the production of new impurities and dopants during the neutron irradiation of oxides.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Tuned and screened range-separated hybrid density functional theory for describing electronic and optical properties of defective gallium nitride

We apply a hybrid density functional theory approach, based on a tuned and screened range-separated hybrid (SRSH) exchange-correlation functional, to describe the optoelectronic properties of defective gallium nitride (GaN). SRSH and time-dependent SRSH (TDSRSH) are tuned to produce accurate energetics for the pristine material and applied to the study of a series of point defects in bulk GaN, a blue light-emitting material that degrades in the presence of defects. We first establish the accuracy of the method by comparing the predicted quasiparticle gap and low-energy excitation spectra of (TD)SRSH and many-body perturbation theory for both pristine GaN and GaN containing a single nitrogen vacancy. Aided by the reduced computational cost of (TD)SRSH, we then report on three additional technologically relevant point defects and defect complexes in GaN: the gallium vacancy, the carbon interstitial, and the carbon-silicon complex. We compute the low-energy optical absorption spectra for these defects and show the presence of defect-centered transitions. Furthermore, by estimating the Stokes shift, we predict, in agreement with previous studies, that the carbon substitutional defect is a candidate for the detrimental yellow luminescence in GaN. Furthermore, this study indicates that TDSRSH is a promising and computationally feasible approach for quantitatively accurate, first-principles modeling of defective semiconductors.

36 MATERIALS SCIENCE↗

A kinetic model for simulating non-equilibrium mass transport in oxides applied to hematite growth under irradiation

We propose an approach to simulating the dynamic evolution and transport of charged point defects within and through the oxide scales that form during corrosion. The method follows the cluster dynamics formalism widely adopted for radiation damage in solids, which can apply in both quasi-static and far from equilibrium conditions, such as in radiation environments. By treating each charged defect as a cluster of an atomic defect and associated unit charges, the proposed model flexibly allows charge state transitions and shifts in the Fermi level by absorption and emission of charge carriers from point defects in a reaction network with rates constrained by local equilibrium. Applying this model to hematite predicts changes in self-diffusion and oxidation kinetics in irradiation environments, surprisingly showing reduced oxidation rates in many conditions, despite enhanced self-diffusion. In conclusion, the origin of this effect lies in a change in Fermi level induced by excess vacancies formed under irradiation, which in turn suppresses the transport of cation interstitials which facilitate hematite growth.

36 MATERIALS SCIENCE↗

Optical and microstructural studies of erbium-doped TiO 2 thin films on silicon, SrTiO 3 , and sapphire

Rare-earth ion doped oxide thin films integrated on silicon substrates provide a route toward scalable, chip-scale platforms for quantum coherent devices. Erbium-doped TiO 2 is an attractive candidate: the Er 3+ optical transition is compatible with C-band optical fiber communications, while TiO 2 is an insulating dielectric compatible with silicon process technology. Through structural and optical studies of Er-doped TiO 2 thin films grown via molecular beam deposition on silicon, SrTiO 3 , and sapphire substrates, we have explored the impact of polycrystallinity and microstructure on the optical properties of the Er emission. Comparing polycrystalline TiO 2 (rutile)/Si with single-crystalline TiO 2 (rutile)/r-sapphire and polycrystalline TiO 2 (anatase)/Si with single-crystalline TiO 2 (anatase)/SrTiO 3 , we observe that the inhomogeneous linewidth (Γ inh ) of the most prominent peak in the Er spectrum (the Y 1 –Z 1 transition, 1520 and 1533 nm in rutile and anatase TiO 2 ) is significantly narrower in the polycrystalline case. This implies a relative insensitivity to extended structural defects and grain boundaries in such films (as opposed to, e.g., point defects). We show that the growth of an undoped, underlying TiO 2 buffer on Si can reduce Γ inh by a factor of 4–5. Expectedly, Γ inh also reduces with decreasing Er concentrations: we observe a ∼2 order of magnitude reduction from ∼1000 ppm Er to ∼10 ppm Er. Γ inh then gets limited to a residual value of ∼5 GHz that is insensitive to further reduction in the Er concentration. Based upon the above results, we argue that the optical properties in these thin films are limited by the presence of high “grown-in” point defect concentrations.

Chemical elements↗

Electronic properties of doped and defective NiO: A quantum Monte Carlo study

NiO is a canonical Mott (or charge-transfer) insulator and as such is notoriously difficult to describe using density functional theory (DFT) based electronic structure methods. Doped Mott insulators such as NiO are of interest for various applications but rigorous theoretical descriptions are lacking. Here, we use quantum Monte Carlo methods, which very accurately include electron-electron interactions, to examine energetics, charge- and spin-structures of NiO with various point defects, such as vacancies or substitutional doping with potassium. The formation energy of a potassium dopant is significantly lower than for a Ni vacancy, making potassium an attractive monovalent dopant for NiO. We compare our results with DFT results that include an on-site Hubbard U (DFT+U) to account for correlations and find relatively large discrepancies for defect formation energies as well as for charge and spin redistributions in the presence of point defects. Finally, it is unlikely that single-parameter fixes of DFT may be able to obtain accurate accounts of anything but a single parameter, e.g., band gap; responses that, maybe in addition to the band gap, depend in subtle and complex ways on ground state properties, such as charge and spin densities, are likely to contain quantitative and qualitative errors.

36 MATERIALS SCIENCE↗