Clustering of transmutation elements tantalum, rhenium and osmium in tungsten in a fusion environment

NASA Astrophysics Data System (ADS)

You, Yu-Wei; Kong, Xiang-Shan; Wu, Xuebang; Liu, C. S.; Fang, Q. F.; Chen, J. L.; Luo, G.-N.

2017-08-01

The formation of transmutation solute-rich precipitates has been reported to seriously degrade the mechanical properties of tungsten in a fusion environment. However, the underlying mechanisms controlling the formation of the precipitates are still unknown. In this study, first-principles calculations are therefore performed to systemically determine the stable structures and binding energies of solute clusters in tungsten consisting of tantalum, rhenium and osmium atoms as well as irradiation-induced vacancies. These clusters are known to act as precursors for the formation of precipitates. We find that osmium can easily segregate to form clusters even in defect-free tungsten alloys, whereas extremely high tantalum and rhenium concentrations are required for the formation of clusters. Vacancies greatly facilitate the clustering of rhenium and osmium, while tantalum is an exception. The binding energies of vacancy-osmium clusters are found to be much higher than those of vacancy-tantalum and vacancy-rhenium clusters. Osmium is observed to strongly promote the formation of vacancy-rhenium clusters, while tantalum can suppress the formation of vacancy-rhenium and vacancy-osmium clusters. The local strain and electronic structure are analyzed to reveal the underlying mechanisms governing the cluster formation. Employing the law of mass action, we predict the evolution of the relative concentration of vacancy-rhenium clusters. This work presents a microscopic picture describing the nucleation and growth of solute clusters in tungsten alloys in a fusion reactor environment, and thereby explains recent experimental phenomena.

Nitrogen vacancy complexes in nitrogen irradiated metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veen, A. van; Westerduin, K.T.; Schut, H.

1996-12-31

Gas desorption and positron annihilation techniques have been employed to study the evolution of nitrogen associated defects in nitrogen irradiated metals: Fe, Ni, Mo and W. Nitrogen in these metals has a rather high affinity to vacancy type defects. The results obtained for low irradiation dose show that substitutional nitrogen (NV; with V = vacancy) is formed. The nitrogen vacancy complex dissociates at temperatures ranging from 350 K for Ni to 900 K for Mo and 1,100 K for W. At high doses defects are formed which can be characterized as nitrogen saturated vacancy clusters. These defect, as observed bymore » helium probing, disappear during annealing for nickel at 800 K, and for Mo at 1,100 K. The direct observation of the desorbing nitrogen for nickel and molybdenum reveals a very fast desorption transient at the dissociation temperature of the clusters. This is the characteristic desorption transient of a small nitride cluster, e.g., by shrinkage with constant rate. For iron the nitrogen desorption is more complicated because of a general background that continuously rises with temperature. With the positron beam technique depth information was obtained for defects in iron and the defect character could be established with the help of the information provided on annihilation with conduction and core electrons of the defect trapped positrons.« less

Off-stoichiometric defect clustering in irradiated oxides

NASA Astrophysics Data System (ADS)

Khalil, Sarah; Allen, Todd; EL-Azab, Anter

2017-04-01

A cluster dynamics model describing the formation of vacancy and interstitial clusters in irradiated oxides has been developed. The model, which tracks the composition of the oxide matrix and the defect clusters, was applied to the early stage formation of voids and dislocation loops in UO2, and the effects of irradiation temperature and dose rate on the evolution of their densities and composition was investigated. The results show that Frenkel defects dominate the nucleation process in irradiated UO2. The results also show that oxygen vacancies drive vacancy clustering while the migration energy of uranium vacancies is a rate-limiting factor for the nucleation and growth of voids. In a stoichiometric UO2 under irradiation, off-stoichiometric vacancy clusters exist with a higher concentration of hyper-stoichiometric clusters. Similarly, off-stoichiometric interstitial clusters form with a higher concentration of hyper-stoichiometric clusters. The UO2 matrix was found to be hyper-stoichiometric due to the accumulation of uranium vacancies.

A computational microscopy study of nanostructural evolution in irradiated pressure vessel steels

NASA Astrophysics Data System (ADS)

Odette, G. R.; Wirth, B. D.

1997-11-01

Nanostructural features that form in reactor pressure vessel steels under neutron irradiation at around 300°C lead to significant hardening and embrittlement. Continuum thermodynamic-kinetic based rate theories have been very successful in modeling the general characteristics of the copper and manganese nickel rich precipitate evolution, often the dominant source of embrittlement. However, a more detailed atomic scale understanding of these features is needed to interpret experimental measurements and better underpin predictive embrittlement models. Further, other embrittling features, believed to be subnanometer defect (vacancy)-solute complexes and small regions of modest enrichment of solutes are not well understood. A general approach to modeling embrittlement nanostructures, based on the concept of a computational microscope, is described. The objective of the computational microscope is to self-consistently integrate atomic scale simulations with other sources of information, including a wide range of experiments. In this work, lattice Monte Carlo (LMC) simulations are used to resolve the chemically and structurally complex nature of CuMnNiSi precipitates. The LMC simulations unify various nanoscale analytical characterization methods and basic thermodynamics. The LMC simulations also reveal that significant coupled vacancy and solute clustering takes place during cascade aging. The cascade clustering produces the metastable vacancy-cluster solute complexes that mediate flux effects. Cascade solute clustering may also play a role in the formation of dilute atmospheres of solute enrichment and enhance the nucleation of manganese-nickel rich precipitates at low Cu levels. Further, the simulations suggest that complex, highly correlated processes (e.g. cluster diffusion, formation of favored vacancy diffusion paths and solute scavenging vacancy cluster complexes) may lead to anomalous fast thermal aging kinetics at temperatures below about 450°C. The potential technical significance of these phenomena is described.

Oxygen vacancy chain and conductive filament formation in hafnia

NASA Astrophysics Data System (ADS)

Xue, Kan-Hao; Miao, Xiang-Shui

2018-04-01

The stability and aggregation mechanisms of oxygen vacancy chains are studied for hafnia using self-energy corrected density functional theory. While oxygen vacancies tend not to align along the c-axis of monoclinic HfO2, oxygen vacancy chains along a-axis and b-axis are energetically favorable, with cohesive energies of 0.05 eV and 0.03 eV per vacancy, respectively. Nevertheless, with an increase of the cross section area, intensive oxygen vacancy chains become much more stable in hafnia, which yields phase separation into Hf-clusters and HfO2. Compared with disperse single vacancy chains, intensive oxygen vacancy chains made of 4, 6, and 8 single vacancy chains are energetically more favorable by 0.17, 0.20, and 0.30 eV per oxygen vacancy, respectively. On the other hand, while a single oxygen vacancy chain exhibits a tiny electronic energy gap of around 0.5 eV, metallic conduction emerges for the intensive vacancy chain made of 8 single vacancy chains, which possesses a filament cross section area of ˜0.4 nm2. This sets a lower area limit for Hf-cluster filaments from metallic conduction point of view, but in real hafnia resistive RAM devices the cross section area of the filaments can generally be much larger (>5 nm2) for the sake of energy minimization. Our work sets up a bridge between oxygen vacancy ordering and phase separation in hafnia, and shows a clear trend of filament stabilization with larger dimensions. The results could explain the threshold switching phenomenon in hafnia when a small AFM tip was used as the top electrode, as well as the undesired multimode operation in resistive RAM cells with 3 nm-thick hafnia.

Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

NASA Astrophysics Data System (ADS)

Bang, Junhyeok; Kim, Youg-Sung; Park, C. H.; Gao, F.; Zhang, S. B.

2014-06-01

Vacancy clusters have been observed in ZnO by positron-annihilation spectroscopy (PAS), but detailed mechanisms are unclear. This is because the clustering happens in non-equilibrium conditions, for which theoretical method has not been well established. Combining first-principles calculation and kinetic Monte Carlo simulation, we determine the roles of non-equilibrium kinetics on the vacancies clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (VZn - Vo), which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of VZn compared to VO, more VZn-abundant clusters are formed than VO-abundant clusters. The large dissociation energy barriers, e.g., over 2.5 eV for (VZn - Vo), suggest that, once formed, it is difficult for the clusters to dissociate. By promoting mono-vacancy diffusion, thermal annealing will increase the size of the clusters. As the PAS is insensitive to VO donor defects, our results suggest an interpretation of the experimental data that could not have been made without the in-depth calculations.

Point defect induced segregation of alloying solutes in α-Fe

NASA Astrophysics Data System (ADS)

You, Yu-Wei; Zhang, Yange; Li, Xiangyan; Xu, Yichun; Liu, C. S.; Chen, J. L.; Luo, G.-N.

2016-10-01

Segregation of alloying solute toward clusters and precipitates can result in hardening and embrittlement of ferritic and ferritic/martensitic steels in aging nuclear power plants. Thus, it is essential to study the segregation of solute in α-Fe. In this study, the segregation of eight kinds of alloying solutes (Al, Si, P, S, Ga, Ge, As, Se) in defect-free system and at vacancy, divacancy, and self-interstitial atom in α-Fe has been systematically studied by first-principles calculations. We find that it is energetically favorable for multiple solute S or Se atoms to segregate in defect-free system to form solute clusters, whereas it is very difficult for the other solute atoms to form the similar clusters. With the presence of vacancy and divacancy, the segregation of all the solutes are significantly promoted to form vacancy-solute and divacancy-solute clusters. The divacancy-solute cluster is more stable than the vacancy-solute cluster. The most-stable self-interstitial atom 〈110〉 dumbbell is also found to tightly bind with multiple solute atoms. The 〈110〉-S is even more stable than divacancy-S cluster. Meanwhile, the law of mass action is employed to predict the concentration evolution of vacancy-Si, vacancy-P, and vacancy-S clusters versus temperature and vacancy concentration.

Vacancy defect and defect cluster energetics in ion-implanted ZnO

NASA Astrophysics Data System (ADS)

Dong, Yufeng; Tuomisto, F.; Svensson, B. G.; Kuznetsov, A. Yu.; Brillson, Leonard J.

2010-02-01

We have used depth-resolved cathodoluminescence, positron annihilation, and surface photovoltage spectroscopies to determine the energy levels of Zn vacancies and vacancy clusters in bulk ZnO crystals. Doppler broadening-measured transformation of Zn vacancies to vacancy clusters with annealing shifts defect energies significantly lower in the ZnO band gap. Zn and corresponding O vacancy-related depth distributions provide a consistent explanation of depth-dependent resistivity and carrier-concentration changes induced by ion implantation.

Two-component density functional theory calculations of positron lifetimes for small vacancy clusters in silicon

NASA Astrophysics Data System (ADS)

Makhov, D. V.; Lewis, Laurent J.

2005-05-01

The positron lifetimes for various vacancy clusters in silicon are calculated within the framework of the two-component electron-positron density functional theory. The effect of the trapped positron on the electron density and on the relaxation of the structure is investigated. Our calculations show that, contrary to the usual assumption, the positron-induced forces do not compensate in general for electronic inward forces. Thus, geometry optimization is required in order to determine positron lifetime accurately. For the monovacancy and the divacancy, the results of our calculations are in good agreement with the experimental positron lifetimes, suggesting that this approach gives good estimates of positron lifetimes for larger vacancy clusters, required for their correct identification with positron annihilation spectroscopy. As an application, our calculations show that fourfold trivacancies and symmetric fourfold tetravacancies have positron lifetimes similar to monovacancies and divacancies, respectively, and can thus be confused in the interpretation of positron annihilation experiments.

The interaction between atomic displacement cascades and tilt symmetrical grain boundaries in α-zirconium

NASA Astrophysics Data System (ADS)

Kapustin, P.; Svetukhin, V.; Tikhonchev, M.

2017-06-01

The atomic displacement cascade simulations near symmetric tilt grain boundaries (GBs) in hexagonal close packed-Zirconium were considered in this paper. Further defect structure analysis was conducted. Four symmetrical tilt GBs -∑14?, ∑14? with the axis of rotation [0 0 0 1] and ∑32?, ∑32? with the axis of rotation ? - were considered. The molecular dynamics method was used for atomic displacement cascades' simulation. A tendency of the point defects produced in the cascade to accumulate near the GB plane, which was an obstacle to the spread of the cascade, was discovered. The results of the point defects' clustering produced in the cascade were obtained. The clusters of both types were represented mainly by single point defects. At the same time, vacancies formed clusters of a large size (more than 20 vacancies per cluster), while self-interstitial atom clusters were small-sized.

Oxygen Vacancy Linear Clustering in a Perovskite Oxide

DOE PAGES

Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

2017-07-14

Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

Oxygen Vacancy Linear Clustering in a Perovskite Oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eom, Kitae; Choi, Euiyoung; Choi, Minsu

Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

Vacancy-controlled ultrastable nanoclusters in nanostructured ferritic alloys

PubMed Central

Zhang, Z. W.; Yao, L.; Wang, X.-L.; Miller, M. K.

2015-01-01

A new class of advanced structural materials, based on the Fe-O-vacancy system, has exceptional resistance to high-temperature creep and excellent tolerance to extremely high-dose radiation. Although these remarkable improvements in properties compared to steels are known to be associated with the Y-Ti-O-enriched nanoclusters, the roles of vacancies in facilitating the nucleation of nanoclusters are a long-standing puzzle, due to the experimental difficulties in characterizing vacancies, particularly in-situ while the nanoclusters are forming. Here we report an experiment study that provides the compelling evidence for the presence of significant concentrations of vacancies in Y-Ti-O-enriched nanoclusters in a nanostructured ferritic alloy using a combination of state-of-the-art atom-probe tomography and in situ small angle neutron scattering. The nucleation of nanoclusters starts from the O-enriched solute clustering with vacancy mediation. The nanoclusters grow with an extremely low growth rate through attraction of vacancies and O:vacancy pairs, leading to the unusual stability of the nanoclusters. PMID:26023747

Vacancy-controlled ultrastable nanoclusters in nanostructured ferritic alloys

DOE PAGES

Zhang, Z. W.; Yao, L.; Wang, X. -L.; ...

2015-05-29

A new class of advanced structural materials, based on the Fe-O-vacancy system, has exceptional resistance to high-temperature creep and excellent tolerance to extremely high-dose radiation. Although these remarkable improvements in properties compared to steels are known to be associated with the Y-Ti-O-enriched nanoclusters, the roles of vacancies in facilitating the nucleation of nanoclusters are a long-standing puzzle, due to the experimental difficulties in characterizing vacancies, particularly in-situ while the nanoclusters are forming. We report an experiment study that provides the compelling evidence for the presence of significant concentrations of vacancies in Y-Ti-O-enriched nanoclusters in a nanostructured ferritic alloy using amore » combination of state-of-the-art atom-probe tomography and in situ small angle neutron scattering. The nucleation of nanoclusters starts from the O-enriched solute clustering with vacancy mediation. The nanoclusters grow with an extremely low growth rate through attraction of vacancies and O:vacancy pairs, leading to the unusual stability of the nanoclusters.« less

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

PubMed

Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

2007-10-31

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.

Investigation of point and extended defects in electron irradiated silicon—Dependence on the particle energy

NASA Astrophysics Data System (ADS)

Radu, R.; Pintilie, I.; Nistor, L. C.; Fretwurst, E.; Lindstroem, G.; Makarenko, L. F.

2015-04-01

This work is focusing on generation, time evolution, and impact on the electrical performance of silicon diodes impaired by radiation induced active defects. n-type silicon diodes had been irradiated with electrons ranging from 1.5 MeV to 27 MeV. It is shown that the formation of small clusters starts already after irradiation with high fluence of 1.5 MeV electrons. An increase of the introduction rates of both point defects and small clusters with increasing energy is seen, showing saturation for electron energies above ˜15 MeV. The changes in the leakage current at low irradiation fluence-values proved to be determined by the change in the configuration of the tri-vacancy (V3). Similar to V3, other cluster related defects are showing bistability indicating that they might be associated with larger vacancy clusters. The change of the space charge density with irradiation and with annealing time after irradiation is fully described by accounting for the radiation induced trapping centers. High resolution electron microscopy investigations correlated with the annealing experiments revealed changes in the spatial structure of the defects. Furthermore, it is shown that while the generation of point defects is well described by the classical Non Ionizing Energy Loss (NIEL), the formation of small defect clusters is better described by the "effective NIEL" using results from molecular dynamics simulations.

Unraveling the oxygen vacancy structures at the reduced Ce O2(111 ) surface

NASA Astrophysics Data System (ADS)

Han, Zhong-Kang; Yang, Yi-Zhou; Zhu, Beien; Ganduglia-Pirovano, M. Verónica; Gao, Yi

2018-03-01

Oxygen vacancies at ceria (Ce O2 ) surfaces play an essential role in catalytic applications. However, during the past decade, the near-surface vacancy structures at Ce O2(111 ) have been questioned due to the contradictory results from experiments and theoretical simulations. Whether surface vacancies agglomerate, and which is the most stable vacancy structure for varying vacancy concentration and temperature, are being heatedly debated. By combining density functional theory calculations and Monte Carlo simulations, we proposed a unified model to explain all conflicting experimental observations and theoretical results. We find a novel trimeric vacancy structure which is more stable than any other one previously reported, which perfectly reproduces the characteristics of the double linear surface oxygen vacancy clusters observed by STM. Monte Carlo simulations show that at low temperature and low vacancy concentrations, vacancies prefer subsurface sites with a local (2 × 2) ordering, whereas mostly linear surface vacancy clusters do form with increased temperature and degree of reduction. These results well explain the disputes about the stable vacancy structure and surface vacancy clustering at Ce O2(111 ) , and provide a foundation for the understanding of the redox and catalytic chemistry of metal oxides.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uedono, Akira; Yoshihara, Nakaaki; Mizushima, Yoriko

2014-10-07

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 ofmore » 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.« less

Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2015-07-01

Object kinetic Monte Carlo (OKMC) simulations have been performed to investigate various aspects of cascade aging in bulk tungsten and to determine the sensitivity of the results to the kinetic parameters. The primary focus is on how the kinetic parameters affect the initial recombination of defects in the first few ns of a simulation. The simulations were carried out using the object kinetic Monte Carlo (OKMC) code KSOME (kinetic simulations of microstructure evolution), using a database of cascades obtained from results of molecular dynamics (MD) simulations at various primary knock-on atom (PKA) energies and directions at temperatures of 300, 1025more » and 2050 K. The OKMC model was parameterized using defect migration barriers and binding energies from ab initio calculations. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters in tungsten, annealing is dominated by SIA migration even at temperatures as high as 2050 K. For 100 keV cascades initiated at 300 K recombination is dominated by annihilation of large defect clusters. But for all other PKA energies and temperatures most of the recombination is due to the migration and rotation of small SIA clusters, while all the large SIA clusters escape the cubic simulation cell. The inverse U-shape behavior exhibited by the annealing efficiency as a function of temperature curve, especially for cascades of large PKA energies, is due to asymmetry in SIA and vacancy clustering assisted by the large difference in mobilities of SIAs and vacancies. This annealing behavior is unaffected by the dimensionality of SIA migration persists over a broad range of relative mobilities of SIAs and vacancies.« less

On the interplay of point defects and Cd in non-polar ZnCdO films

NASA Astrophysics Data System (ADS)

Zubiaga, A.; Reurings, F.; Tuomisto, F.; Plazaola, F.; García, J. A.; Kuznetsov, A. Yu.; Egger, W.; Zúñiga-Pérez, J.; Muñoz-Sanjosé, V.

2013-01-01

Non-polar ZnCdO films, grown over m- and r-sapphire with a Cd concentration ranging between 0.8% and 5%, have been studied by means of slow positron annihilation spectroscopy (PAS) combined with chemical depth profiling by secondary ion mass spectroscopy and Rutherford back-scattering. Vacancy clusters and Zn vacancies with concentrations up to 1017 cm-3 and 1018 cm-3, respectively, have been measured inside the films. Secondary ion mass spectroscopy results show that most Cd stays inside the ZnCdO film but the diffused atoms can penetrate up to 1.3 μm inside the ZnO buffer. PAS results give an insight to the structure of the meta-stable ZnCdO above the thermodynamical solubility limit of 2%. A correlation between the concentration of vacancy clusters and Cd has been measured. The concentration of Zn vacancies is one order of magnitude larger than in as-grown non-polar ZnO films and the vacancy cluster are, at least partly, created by the aggregation of smaller Zn vacancy related defects. The Zn vacancy related defects and the vacancy clusters accumulate around the Cd atoms as a way to release the strain induced by the substitutional CdZn in the ZnO crystal.

Hydrogen-vacancy-dislocation interactions in α-Fe

NASA Astrophysics Data System (ADS)

Tehranchi, A.; Zhang, X.; Lu, G.; Curtin, W. A.

2017-02-01

Atomistic simulations of the interactions between dislocations, hydrogen atoms, and vacancies are studied to assess the viability of a recently proposed mechanism for the formation of nanoscale voids in Fe-based steels in the presence of hydrogen. Quantum-mechanics/molecular-mechanics method calculations confirm molecular statics simulations based on embedded atom method (EAM) potential showing that individual vacancies on the compressive side of an edge dislocation can be transported with the dislocation as it glides. Molecular dynamics simulations based on EAM potential then show, however, that vacancy clusters in the glide plane of an approaching dislocation are annihilated or reduced in size by the creation of a double-jog/climb process that is driven by the huge reduction in energy accompanying vacancy annihilation. The effectiveness of annihilation/reduction processes is not reduced by the presence of hydrogen in the vacancy clusters because typical V-H cluster binding energies are much lower than the vacancy formation energy, except at very high hydrogen content in the cluster. Analysis of a range of configurations indicates that hydrogen plays no special role in stabilizing nanovoids against jog formation processes that shrink voids. Experimental observations of nanovoids on the fracture surfaces of steels must be due to as-yet undetermined processes.

Direct Observation of Defect Range and Evolution in Ion-Irradiated Single Crystalline Ni and Ni Binary Alloys.

PubMed

Lu, Chenyang; Jin, Ke; Béland, Laurent K; Zhang, Feifei; Yang, Taini; Qiao, Liang; Zhang, Yanwen; Bei, Hongbin; Christen, Hans M; Stoller, Roger E; Wang, Lumin

2016-02-01

Energetic ions have been widely used to evaluate the irradiation tolerance of structural materials for nuclear power applications and to modify material properties. It is important to understand the defect production, annihilation and migration mechanisms during and after collision cascades. In this study, single crystalline pure nickel metal and single-phase concentrated solid solution alloys of 50%Ni50%Co (NiCo) and 50%Ni50%Fe (NiFe) without apparent preexisting defect sinks were employed to study defect dynamics under ion irradiation. Both cross-sectional transmission electron microscopy characterization (TEM) and Rutherford backscattering spectrometry channeling (RBS-C) spectra show that the range of radiation-induced defect clusters far exceed the theoretically predicted depth in all materials after high-dose irradiation. Defects in nickel migrate faster than in NiCo and NiFe. Both vacancy-type stacking fault tetrahedra (SFT) and interstitial loops coexist in the same region, which is consistent with molecular dynamics simulations. Kinetic activation relaxation technique (k-ART) simulations for nickel showed that small vacancy clusters, such as di-vacancies and tri-vacancies, created by collision cascades are highly mobile, even at room temperature. The slower migration of defects in the alloy along with more localized energy dissipation of the displacement cascade may lead to enhanced radiation tolerance.

Direct Observation of Defect Range and Evolution in Ion-Irradiated Single Crystalline Ni and Ni Binary Alloys

PubMed Central

Lu, Chenyang; Jin, Ke; Béland, Laurent K.; Zhang, Feifei; Yang, Taini; Qiao, Liang; Zhang, Yanwen; Bei, Hongbin; Christen, Hans M.; Stoller, Roger E.; Wang, Lumin

2016-01-01

Energetic ions have been widely used to evaluate the irradiation tolerance of structural materials for nuclear power applications and to modify material properties. It is important to understand the defect production, annihilation and migration mechanisms during and after collision cascades. In this study, single crystalline pure nickel metal and single-phase concentrated solid solution alloys of 50%Ni50%Co (NiCo) and 50%Ni50%Fe (NiFe) without apparent preexisting defect sinks were employed to study defect dynamics under ion irradiation. Both cross-sectional transmission electron microscopy characterization (TEM) and Rutherford backscattering spectrometry channeling (RBS-C) spectra show that the range of radiation-induced defect clusters far exceed the theoretically predicted depth in all materials after high-dose irradiation. Defects in nickel migrate faster than in NiCo and NiFe. Both vacancy-type stacking fault tetrahedra (SFT) and interstitial loops coexist in the same region, which is consistent with molecular dynamics simulations. Kinetic activation relaxation technique (k-ART) simulations for nickel showed that small vacancy clusters, such as di-vacancies and tri-vacancies, created by collision cascades are highly mobile, even at room temperature. The slower migration of defects in the alloy along with more localized energy dissipation of the displacement cascade may lead to enhanced radiation tolerance. PMID:26829570

Full-potential KKR calculations for vacancies in Al : Screening effect and many-body interactions

NASA Astrophysics Data System (ADS)

Hoshino, T.; Asato, M.; Zeller, R.; Dederichs, P. H.

2004-09-01

We give ab initio calculations for vacancies in Al . The calculations are based on the generalized-gradient approximation in the density-functional theory and employ the all-electron full-potential Korringa-Kohn-Rostoker Green’s function method for point defects, which guarantees the correct embedding of the cluster of point defects in an otherwise perfect crystal. First, we confirm the recent calculated results of Carling [Phys. Rev. Lett. 85, 3862 (2000)], i.e., repulsion of the first-nearest-neighbor (1NN) divacancy in Al , and elucidate quantitatively the micromechanism of repulsion. Using the calculated results for vacancy formation energies and divacancy binding energies in Na , Mg , Al , and Si of face-centered-cubic, we show that the single vacancy in nearly free-electron systems becomes very stable with increasing free-electron density, due to the screening effect, and that the formation of divacancy destroys the stable electron distribution around the single vacancy, resulting in a repulsion of two vacancies on 1NN sites, so that the 1NN divacancy is unstable. Second, we show that the cluster expansion converges rapidly for the binding energies of vacancy agglomerates in Al . The binding energy of 13 vacancies consisting of a central vacancy and its 12 nearest neighbors, is reproduced within the error of 0.002eV per vacancy, if many-body interaction energies up to the four-body terms are taken into account in the cluster expansion, being compared with the average error (>0.1eV) of the glue models which are very often used to provide interatomic potentials for computer simulations. For the cluster expansion of the binding energies of impurities, we get the same convergence as that obtained for vacancies. Thus, the present cluster-expansion approach for the binding energies of agglomerates of vacancies and impurities in Al may provide accurate data to construct the interaction-parameter model for computer simulations which are strongly requested to study the dynamical process in the initial stage of the formation of the so-called Guinier-Preston zones of low-concentrated Al -based alloys such as Al1-cXc ( X=Cu , Zn ; c<0.05 ).

Simulation of defects in fusion plasma first wall materials

NASA Astrophysics Data System (ADS)

T, Troev; N, Nankov; T, Yoshiie

2014-06-01

Numerical calculations of radiation damages in beryllium, alpha-iron and tungsten irradiated by fusion neutrons were performed using molecular dynamics (MD) simulations. The displacement cascades efficiency has been calculated using the Norgett-Robinson-Torrens (NRT) formula, the universal pair-potential of Ziegler-Biersack-Littmark (ZBL) and the EAM inter-atomic potential. The pair potential overestimates the defects production by a factor of 2. The ZBL pair potential results and the EAM are comparable at higher primary knock-on atom (PKA) energies (E > 100 keV). We found that the most common types of defects are single vacancies, di-vacancies, interstitials and small number of interstitial clusters. On the bases of calculated results, the behavior of vacancies, empty nano-voids and nano-voids with hydrogen and helium were discussed.

Energetics of halogen impurities in thorium dioxide

NASA Astrophysics Data System (ADS)

Kuganathan, Navaratnarajah; Ghosh, Partha S.; Arya, Ashok K.; Dey, Gautam K.; Grimes, Robin W.

2017-11-01

Defect energies for halogen impurity atoms (Cl, Br and I) in thoria are calculated using the generalized gradient approximation and projector augmented plane wave potentials under the framework of density functional theory. The energy to place a halogen atom at a pre-existing lattice site is the incorporation energy. Seven sites are considered: octahedral interstitial, O vacancy, Th vacancy, Th-O di-vacancy cluster (DV) and the three O-Th-O tri-vacancy cluster (NTV) configurations. For point defects and vacancy clusters, neutral and all possible defect charge states up to full formal charge are considered. The most favourable incorporation site for Cl is the singly charged positive oxygen vacancy while for Br and I it is the NTV1 cluster. By considering the energy to form the defect sites, solution energies are generated. These show that in both ThO2-x and ThO2 the most favourable solution equilibrium site for halides is the single positively charged oxygen vacancy (although in ThO2, I demonstrates the same solubility in the NTV1 and DV clusters). Solution energies are much lower in ThO2-x than in ThO2 indicating that stoichiometry is a significant factor in determining solubility. In ThO2, all three halogens are highly insoluble and in ThO2-x Br and I remain insoluble. Although ½Cl2 is soluble in ThO2-x alternative phases such as ZrCl4 exist which are of lower energy.

Effect of W self-implantation and He plasma exposure on early-stage defect and bubble formation in tungsten

NASA Astrophysics Data System (ADS)

Thompson, M.; Drummond, D.; Sullivan, J.; Elliman, R.; Kluth, P.; Kirby, N.; Riley, D.; Corr, C. S.

2018-06-01

To determine the effect of pre-existing defects on helium-vacancy cluster nucleation and growth, tungsten samples were self-implanted with 1 MeV tungsten ions at varying fluences to induce radiation damage, then subsequently exposed to helium plasma in the MAGPIE linear plasma device. Positron annihilation lifetime spectroscopy was performed both immediately after self-implantation, and again after plasma exposure. After self-implantation vacancies clusters were not observed near the sample surface (<30 nm). At greater depths (30–150 nm) vacancy clusters formed, and were found to increase in size with increasing W-ion fluence. After helium plasma exposure in the MAGPIE linear plasma device at ~300 K with a fluence of 1023 He-m‑2, deep (30–150 nm) vacancy clusters showed similar positron lifetimes, while shallow (<30 nm) clusters were not observed. The intensity of positron lifetime signals fell for most samples after plasma exposure, indicating that defects were filling with helium. The absence of shallow clusters indicates that helium requires pre-existing defects in order to drive vacancy cluster growth at 300 K. Further samples that had not been pre-damaged with W-ions were also exposed to helium plasma in MAGPIE across fluences from 1  ×  1022 to 1.2  ×  1024 He-m‑2. Samples exposed to fluences up to 1  ×  1023 He-m‑2 showed no signs of damage. Fluences of 5  ×  1023 He-m‑2 and higher showed significant helium-cluster formation within the first 30 nm, with positron lifetimes in the vicinity 0.5–0.6 ns. The sample temperature was significantly higher for these higher fluence exposures (~400 K) due to plasma heating. This higher temperature likely enhanced bubble formation by significantly increasing the rate interstitial helium clusters generate vacancies, which is we suspect is the rate-limiting step for helium-vacancy cluster/bubble nucleation in the absence of pre-existing defects.

Vacancy defects and defect clusters in alkali metal ion-doped MgO nanocrystallites studied by positron annihilation and photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Sellaiyan, S.; Uedono, A.; Sivaji, K.; Janet Priscilla, S.; Sivasankari, J.; Selvalakshmi, T.

2016-10-01

Pure and alkali metal ion (Li, Na, and K)-doped MgO nanocrystallites synthesized by solution combustion technique have been studied by positron lifetime and Doppler broadening spectroscopy methods. Positron lifetime analysis exhibits four characteristic lifetime components for all the samples. Doping reduces the Mg vacancy after annealing to 800 °C. It was observed that Li ion migrates to the vacancy site to recover Mg vacancy-type defects, reducing cluster vacancies and micropores. For Na- and K-doped MgO, the aforementioned defects are reduced and immobile at 800 °C. Coincidence Doppler broadening studies show the positron trapping sites as vacancy clusters. The decrease in the S parameter is due to the particle growth and reduction in the defect concentration at 800 °C. Photoluminescence study shows an emission peak at 445 nm and 498 nm, associated with F2 2+ and recombination of higher-order vacancy complexes. Further, annealing process is likely to dissociate F2 2+ to F+ and this F+ is converted into F centers at 416 nm.

Proton-irradiation induced defects in modified 310S steels characterized with positron annihilation spectroscopy and transmission electron microscopy

NASA Astrophysics Data System (ADS)

Zhang, Weiping; Shen, Zhenyu; Tang, Rui; Jin, Suoxue; Song, Yaoxiang; Long, Yunxiang; Wei, Yaxia; Zhou, Xiong; Chen, Cheng; Guo, Liping

2018-07-01

An effective method to improve the irradiation resistance of austenitic stainless steels is adding oversized solutes into steels. In this work, the irradiation resistances of two type of modified 310S steels, in one of which Zr was added and in another Nb, Ta, and W were added, were investigated by proton irradiations at 563 K. Irradiation induced vacancy-type defects was characterized with positron annihilation spectroscopy (PAS), while dislocation loops and bubbles whose size are greater than 1 nm are characterized with transmission electron microscopy (TEM). It is found that the relative S parameter ΔS/S extracted from PAS is more effective than S parameter in evaluating the quantity of vacancy-type defects. It was revealed from ΔS/S that more vacancy-type defects produced in (Nb, Ta, W)-added steels than that in Zr-added steels, and this trend became more obvious with the dose increasing. S-W curves reveal that proton irradiation induced two kinds of vacancy-type defects, i.e. vacancy clusters and proton-vacancy clusters. TEM observation shows that the density of small bubbles induced by proton in (Nb, Ta, W)-added steels is much higher than that in Zr-added steels. Both 1/3 <1 1 1> and 1/2 <1 1 0> dislocation loops were observed with TEM in all of the specimens. The mean size and number density of dislocation loops in (Nb, Ta, W)-added steels are slightly larger than that in Zr-added steels, and increased with increasing irradiation dose. Both PAS and TEM observations shows that irradiation damage in Zr-added steels is less serious than that (Nb, Ta, W)-added steels, and the possible mechanisms are discussed through the enhancement of point defect recombination by oversized solute atoms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valles, G.; Martin-Bragado, I.; Nordlund, K.

Recently, tungsten has been found to form a highly underdense nanostructured morphology (“W fuzz”) when bombarded by an intense flux of He ions, but only in the temperature window 900–2000 K. Furthermore, using object kinetic Monte Carlo simulations (pseudo-3D simulations) parameterized from first principles, we show that this temperature dependence can be understood based on He and point defect clustering, cluster growth, and detrapping reactions. At low temperatures (<900 K), fuzz does not grow because almost all He is trapped in very small He-vacancy clusters. At high temperatures (>2300 K), all He is detrapped from clusters, preventing the formation ofmore » the large clusters that lead to fuzz growth in the intermediate temperature range.« less

Stability of vacancy-type defect clusters in Ni based on first-principles and molecular dynamics simulations

DOE PAGES

Zhao, Shijun; Zhang, Yanwen; Weber, William J.

2017-10-17

Using first-principles calculations based on density-functional theory, the energetics of different vacancy-type defects, including voids, stacking fault tetrahedra (SFT) and vacancy loops, in Ni are investigated. It is found that voids are more stable than SFT at 0 K, which is also the case after taking into account the volumetric strains. By carrying out ab initio molecular dynamics simulations at temperatures up to 1000 K, direct transformations from vacancy loops and voids into SFT are observed. Our results suggest the importance of temperature effects in determining thermodynamic stability of vacancy clusters in face-centered cubic metals.

OBJECT KINETIC MONTE CARLO SIMULATIONS OF RADIATION DAMAGE IN TUNGSTEN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2015-04-16

We used our recently developed lattice-based object kinetic Monte Carlo code; KSOME [1] to carryout simulations of radiation damage in bulk tungsten at temperatures of 300, and 2050 K for various dose rates. Displacement cascades generated from molecular dynamics (MD) simulations for PKA energies at 60, 75 and 100 keV provided residual point defect distributions. It was found that the number density of vacancies in the simulation box does not change with dose rate while the number density of vacancy clusters slightly decreases with dose rate indicating that bigger clusters are formed at larger dose rates. At 300 K, althoughmore » the average vacancy cluster size increases slightly, the vast majority of vacancies exist as mono-vacancies. At 2050 K no accumulation of defects was observed during irradiation over a wide range of dose rates for all PKA energies studied in this work.« less

Vacancy clustering and its dissociation process in electroless deposited copper films studied by monoenergetic positron beams

NASA Astrophysics Data System (ADS)

Uedono, A.; Yamashita, Y.; Tsutsui, T.; Dordi, Y.; Li, S.; Oshima, N.; Suzuki, R.

2012-05-01

Positron annihilation was used to probe vacancy-type defects in electroless deposited copper films. For as-deposited films, two different types of vacancy-type defects were found to coexist; these were identified as vacancy aggregates (V3-V4) and larger vacancy clusters (˜V10). After annealing at about 200 °C, the defects started to diffuse toward the surface and aggregate. The same tendency has been observed for sulfur only, suggesting the formation of complexes between sulfur and vacancies. The defect concentration near the Cu/barrier-metal interface was high even after annealing above 600 °C, and this was attributed to an accumulation of vacancy-impurity complexes. The observed defect reactions were attributed to suppression of the vacancy diffusion to sinks through the formation of impurity-vacancy complexes. It was shown that electroless plating has a high potential to suppress the formation of voids/hillocks caused by defect migration.

Direct Observation of Defect Range and Evolution in Ion-Irradiated Single Crystalline Ni and Ni Binary Alloys

DOE PAGES

Lu, Chenyang; Jin, Ke; Béland, Laurent K.; ...

2016-02-01

We report that energetic ions have been widely used to evaluate the irradiation tolerance of structural materials for nuclear power applications and to modify material properties. It is important to understand the defect production, annihilation and migration mechanisms during and after collision cascades. In this study, single crystalline pure nickel metal and single-phase concentrated solid solution alloys of 50%Ni50%Co (NiCo) and 50%Ni50%Fe (NiFe) without apparent preexisting defect sinks were employed to study defect dynamics under ion irradiation. Both cross-sectional transmission electron microscopy characterization (TEM) and Rutherford backscattering spectrometry channeling (RBS-C) spectra show that the range of radiation-induced defect clusters farmore » exceed the theoretically predicted depth in all materials after high-dose irradiation. Defects in nickel migrate faster than in NiCo and NiFe. Both vacancy-type stacking fault tetrahedra (SFT) and interstitial loops coexist in the same region, which is consistent with molecular dynamics simulations. Kinetic activation relaxation technique (k-ART) simulations for nickel showed that small vacancy clusters, such as di-vacancies and tri-vacancies, created by collision cascades are highly mobile, even at room temperature. The slower migration of defects in the alloy along with more localized energy dissipation of the displacement cascade may lead to enhanced radiation tolerance.« less

Object Kinetic Monte Carlo Simulations of Radiation Damage In Bulk Tungsten

NASA Astrophysics Data System (ADS)

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard; Roche, Kenneth; Kurtz, Richard; Wirth, Brian

2015-11-01

Results are presented for the evolution of radiation damage in bulk tungsten investigated using the object KMC simulation tool, KSOME, as a function of dose, dose rate and primary knock-on atom (PKA) energies in the range of 10 to 100 keV, at temperatures of 300, 1025 and 2050 K. At 300 K, the number density of vacancies changes minimally with dose rate while the number density of vacancy clusters slightly decreases with dose rate indicating that larger clusters are formed at higher dose rates. Although the average vacancy cluster size increases slightly, the vast majority exists as mono-vacancies. At 1025 K void lattice formation was observed at all dose rates for cascades below 60 keV and at lower dose rates for higher PKA energies. After the appearance of initial features of the void lattice, vacancy cluster density increased minimally while the average vacancy cluster size increases rapidly with dose. At 2050 K, no accumulation of defects was observed over a broad range of dose rates for all PKA energies studied in this work. Further comparisons of results of irradiation simulations at various dose rates and PKA spectra, representative of the High Flux Isotope Reactor and future fusion relevant irradiation facilities will be discussed. The U.S. Department of Energy, Office of Fusion Energy Sciences (FES) and Office of Advanced Scientific Computing Research (ASCR) has supported this study through the SciDAC-3 program.

Temperature dependence of underdense nanostructure formation in tungsten under helium irradiation

DOE PAGES

Valles, G.; Martin-Bragado, I.; Nordlund, K.; ...

2017-04-19

Recently, tungsten has been found to form a highly underdense nanostructured morphology (“W fuzz”) when bombarded by an intense flux of He ions, but only in the temperature window 900–2000 K. Furthermore, using object kinetic Monte Carlo simulations (pseudo-3D simulations) parameterized from first principles, we show that this temperature dependence can be understood based on He and point defect clustering, cluster growth, and detrapping reactions. At low temperatures (<900 K), fuzz does not grow because almost all He is trapped in very small He-vacancy clusters. At high temperatures (>2300 K), all He is detrapped from clusters, preventing the formation ofmore » the large clusters that lead to fuzz growth in the intermediate temperature range.« less

Formation of vacancy clusters and cavities in He-implanted silicon studied by slow-positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Brusa, Roberto S.; Karwasz, Grzegorz P.; Tiengo, Nadia; Zecca, Antonio; Corni, Federico; Tonini, Rita; Ottaviani, Gianpiero

2000-04-01

The depth profile of open volume defects has been measured in Si implanted with He at an energy of 20 keV, by means of a slow-positron beam and the Doppler broadening technique. The evolution of defect distributions has been studied as a function of isochronal annealing in two series of samples implanted at the fluence of 5×1015 and 2×1016 He cm-2. A fitting procedure has been applied to the experimental data to extract a positron parameter characterizing each open volume defect. The defects have been identified by comparing this parameter with recent theoretical calculations. In as-implanted samples the major part of vacancies and divacancies produced by implantation is passivated by the presence of He. The mean depth of defects as seen by the positron annihilation technique is about five times less than the helium projected range. During the successive isochronal annealing the number of positron traps decreases, then increases and finally, at the highest annealing temperatures, disappears only in the samples implanted at the lowest fluence. A minimum of open volume defects is reached at the annealing temperature of 250 °C in both series. The increase of open volume defects at temperatures higher than 250 °C is due to the appearance of vacancy clusters of increasing size, with a mean depth distribution that moves towards the He projected range. The appearance of vacancy clusters is strictly related to the out diffusion of He. In the samples implanted at 5×1015 cm-2 the vacancy clusters are mainly four vacancy agglomerates stabilized by He related defects. They disappear starting from an annealing temperature of 700 °C. In the samples implanted at 2×1016 cm-2 and annealed at 850-900 °C the vacancy clusters disappear and only a distribution of cavities centered around the He projected range remains. The role of vacancies in the formation of He clusters, which evolve in bubble and then in cavities, is discussed.

Characterization of helium-vacancy complexes in He-ions implanted Fe9Cr by using positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Zhu, Te; Jin, Shuoxue; Zhang, Peng; Song, Ligang; Lian, Xiangyu; Fan, Ping; Zhang, Qiaoli; Yuan, Daqing; Wu, Haibiao; Yu, Runsheng; Cao, Xingzhong; Xu, Qiu; Wang, Baoyi

2018-07-01

The formation of helium bubble precursors, i.e., helium-vacancy complexes, was investigated for Fe9Cr alloy, which was uniformly irradiated by using 100 keV helium ions with fluences up to 5 × 1016 ions/cm2 at RT, 523, 623, 723, and 873 K. Helium-irradiation-induced microstructures in the alloy were probed by positron annihilation technique. The results show that the ratio of helium atom to vacancy (m/n) in the irradiation induced HemVn clusters is affected by the irradiation temperature. Irradiated at room temperature, there is a coexistence of large amounts of HemV1 and mono-vacancies in the sample. However, the overpressured HemVn (m > n) clusters or helium bubbles are easily formed by the helium-filled vacancy clusters (HemV1 and HemVn (m ≈ n)) absorbing helium atoms when irradiated at 523 K and 823 K. The results also show that void swelling of the alloy is the largest under 723 K irradiation.

Characterization of an F-center in an alkali halide cluster

NASA Astrophysics Data System (ADS)

Bader, R. F. W.; Platts, J. A.

1997-11-01

The removal of a fluorine atom from its central position in a cubiclike Li14F13+ cluster creates an F-center vacancy that may or may not be occupied by the remaining odd electron. The topology exhibited by the electron density in Li14F12+, the F-center cluster, enables one to make a clear distinction between the two possible forms that the odd electron can assume. If it possesses a separate identity, then a local maximum in the electron density will be found within the vacancy and the F-center will behave quantum mechanically as an open system, bounded by a surface of local zero flux in the gradient vector field of the electron density. If, however, the density of the odd electron is primarily delocalized onto the neighboring ions, then a cage critical point, a local minimum in the density, will be found at the center of the vacancy. Without an associated local maximum, the vacancy has no boundary and is undefined. Self-consistent field (SCF) calculations with geometry optimization of the Li14F13+ cluster and of the doublet state of Li14F12+ show that the creation of the central vacancy has only a minor effect upon the geometry of the cluster, the result of a local maximum in the electron density being formed within the vacancy. Thus the F-center is the physical manifestation of a non-nuclear attractor in the electron density. It is consequently a proper open system with a definable set of properties, the most characteristic being its low kinetic energy per electron. In addition to determining the properties of the F-center, the effect of its formation on the energies, volumes, populations, both electron and spin, and electron localizations of the ions in the cluster are determined.

Positron annihilation study of the vacancy clusters in ODS Fe-14Cr alloys

NASA Astrophysics Data System (ADS)

Domínguez-Reyes, R.; Auger, M. A.; Monge, M. A.; Pareja, R.

2017-04-01

Oxide dispersion strengthened Fe14Cr and Fe14CrWTi alloys produced by mechanical alloying and hot isostatic pressing were subjected to isochronal annealing up to 1400 °C, and the evolution and thermal stability of the vacancy-type defects were investigated by positron annihilation spectroscopy (PAS). The results were compared to those from a non-oxide dispersion strengthened Fe14Cr alloy produced by following the same powder metallurgy route. The long lifetime component of the PAS revealed the existence of tridimensional vacancy clusters, or nanovoids, in all these alloys. Two recovery stages are found in the oxide dispersion strengthened alloys irrespective of the starting conditions of the samples. The first one starting at T > 750 °C is attributed to thermal shrinkage of large vacancy clusters, or voids. A strong increase in the intensity of the long lifetime after annealing at temperatures in the 800-1050 °C range indicates the development of new vacancy clusters. These defects appear to be unstable above 1050 °C, but some of them remain at temperatures as high as 1400 °C, at least for 90 min.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Shao-Gang; Liao, Ji-Hai; Zhao, Yu-Jun

The unique electronic property induced diversified structure of boron (B) cluster has attracted much interest from experimentalists and theorists. B{sub 30–40} were reported to be planar fragments of triangular lattice with proper concentrations of vacancies recently. Here, we have performed high-throughput screening for possible B clusters through the first-principles calculations, including various shapes and distributions of vacancies. As a result, we have determined the structures of B{sub n} clusters with n = 30–51 and found a stable planar cluster of B{sub 49} with a double-hexagon vacancy. Considering the 8-electron rule and the electron delocalization, a concise model for the distributionmore » of the 2c–2e and 3c–2e bonds has been proposed to explain the stability of B planar clusters, as well as the reported B cages.« less

An empirical potential for simulating vacancy clusters in tungsten.

PubMed

Mason, D R; Nguyen-Manh, D; Becquart, C S

2017-12-20

We present an empirical interatomic potential for tungsten, particularly well suited for simulations of vacancy-type defects. We compare energies and structures of vacancy clusters generated with the empirical potential with an extensive new database of values computed using density functional theory, and show that the new potential predicts low-energy defect structures and formation energies with high accuracy. A significant difference to other popular embedded-atom empirical potentials for tungsten is the correct prediction of surface energies. Interstitial properties and short-range pairwise behaviour remain similar to the Ackford-Thetford potential on which it is based, making this potential well-suited to simulations of microstructural evolution following irradiation damage cascades. Using atomistic kinetic Monte Carlo simulations, we predict vacancy cluster dissociation in the range 1100-1300 K, the temperature range generally associated with stage IV recovery.

Mechanisms of electrical isolation in O+ -irradiated ZnO

NASA Astrophysics Data System (ADS)

Zubiaga, A.; Tuomisto, F.; Coleman, V. A.; Tan, H. H.; Jagadish, C.; Koike, K.; Sasa, S.; Inoue, M.; Yano, M.

2008-07-01

We have applied positron annihilation spectroscopy combined with sheet resistance measurements to study the electrical isolation of thin ZnO layers irradiated with 2 MeV O+ ions at various fluences. Our results indicate that Zn vacancies, the dominant defects detected by positrons, are produced in the irradiation at a relatively low rate of about 2000cm-1 when the ion fluence is at most 1015cm-2 and that vacancy clusters are created at higher fluences. The Zn vacancies introduced in the irradiation act as dominant compensating centers and cause the electrical isolation, while the results suggest that the vacancy clusters are electrically inactive.

Plentiful magnetic moments in oxygen deficient SrTiO 3

DOE PAGES

Ganesh, Panchapakesan; Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

2015-10-06

In this research, correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO 3. Hole and electron doping of oxygen deficient SrTiO 3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO 3–δ is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments inmore » the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.« less

Mechanical and microstructural changes in tungsten due to irradiation damage

NASA Astrophysics Data System (ADS)

Uytdenhouwen, I.; Schwarz-Selinger, T.; Coenen, J. W.; Wirtz, M.

2016-02-01

Stress-relieved pure tungsten received three damage levels (0.10, 0.25 and 0.50 dpa) by self-tungsten ion beam irradiation at room temperature. Positron annihilation spectroscopy showed the formation of mono-vacancies and vacancy clusters after ion beam exposure. In the first irradiation step (0-0.10 dpa) some splitting up of large vacancy clusters occurred which became more numerous. For increasing dose to 0.25 dpa, growth of the vacancy clusters was seen. At 0.50 dpa a change in the defect formation seems to occur leading to a saturation in the lifetime signal obtained from the positrons. Nano-indentation on the cross-sections showed a flat damage depth distribution profile. The nano-indentation hardness increased for increasing damage dose without any saturation up to 0.50 dpa. This means that other defects such as dislocation loops and large sized voids seem to contribute.

Rhodium clustering process on defective (8,0) SWCNT: Analysis of chemical and physical properties using density functional theory

NASA Astrophysics Data System (ADS)

Ambrusi, Ruben E.; Luna, C. Romina; Sandoval, Mario G.; Bechthold, Pablo; Pronsato, M. Estela; Juan, Alfredo

2017-12-01

The Spin-polarized density functional theory is used to study the effect of a single vacancy in a (8,0) single-walled carbon nanotube (SWCNT) on the Rh clustering process. The vacancy is considered oxygenated and non-oxygenated and, in each case, different Rhn cluster sizes (n = 1-4) are taken into account. For the analysis of these systems some physical and chemical properties are calculated, such as binding energy (Eb), work function (WF), magnetic moment, charge transfer, bond length, band gap (Eg), and density of state (DOS). From this analysis it can be concluded that: a single Rh atom and Rh2 dimer are adsorbed on vacancy without oxygen, whereas Rh3 and Rh4 clusters prefer to be adsorbed on oxygenated vacancy. In all cases, Rh adsorption induces a magnetic moment. When the Rh atom and Rh2 dimer are bonded to the defective SWCNT, it has been found that they show a semiconductor behavior that could be interesting to use in the spintronic area. In the case of Rh3 and Rh4 clusters our results show a metallic behavior suggesting that these systems are good candidates for nanotube contact.

Statistical model and first-principles simulation on concentration of HenV cluster and He bubble formation in α-Fe and W

NASA Astrophysics Data System (ADS)

Liu, Yue-Lin; Yu, Yang; Dai, Zhen-Hong

2015-01-01

Using first-principles calculations, we investigate the stabilities of He and Hen-vacancy (HenV) clusters in α-Fe and W. Vacancy formation energies are 2.08 eV in α-Fe and 3.11 eV in W, respectively. Single He in both α-Fe and W prefers to occupy the tetrahedral interstitial site. We recalculated the He solution energy considering the effect of zero-point energy (ZPE). The ZPEs of He in α-Fe and W at the tetrahedral (octahedral) interstitial site are 0.072 eV (0.031 eV) and 0.078 eV (0.034 eV), respectively. The trapping energies of single He at vacancy in α-Fe and W are -2.39 eV and -4.55 eV, respectively. By sequentially adding He into vacancy, a monovacancy trap up to 10 He atoms distributing in the vacancy vicinity. Based on the above results combined with statistical model, we evaluate the concentrations of all relevant HenV clusters as a function of He chemical potential. The critical HenV concentration is found to be ∼10-40 (atomic) at the critical temperature T = 600 K in α-Fe and T = 1600 K in W, respectively. Beyond the critical HenV concentrations, considerable HenV aggregate to form HenVm clusters. By further growing of HenVm, the HenVm clusters grow bigger resulting in the larger He bubble formation.

Investigation of defect clusters in ion-irradiated Ni and NiCo using diffuse X-ray scattering and electron microscopy

DOE PAGES

Olsen, Raina J.; Jin, Ke; Lu, Chenyang; ...

2015-11-23

The nature of defect clusters in Ni and Nimore » $$_{50}$$Co$$_{50}$$ (NiCo) irradiated at room temperature with 2–16 MeV Ni ions is studied using asymptotic diffuse X-ray scattering and transmission electron microscopy (TEM). Analysis of the scattering data provides separate size distributions for vacancy and interstitial type defect clusters, showing that both types of defect clusters have a smaller size and higher density in NiCo than in Ni. Diffuse scattering results show good quantitative agreement with TEM results for cluster sizes greater than 4 nm diameter, but find that the majority of vacancy clusters are under 2 nm in NiCo, which, if not detected, would lead to the conclusion that defect density was actually lower in the alloy. Interstitial dislocation loops and stacking fault tetrahedra are identified by TEM. Lastly comparison of diffuse scattering lineshapes to those calculated for dislocation loops and SFTs indicates that most of the vacancy clusters are SFTs.« less

MARMOT simulations of Xe segregation to grain boundaries in UO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Tonks, Michael; Casillas, Luis

2012-06-20

Diffusion of Xe and U in UO{sub 2} is controlled by vacancy mechanisms and under irradiation the formation of mobile vacancy clusters is important. We derive continuum thermodynamic and diffusion models for Xe and U in UO{sub 2} based on the vacancy and cluster diffusion mechanisms established from recent density functional theory (DFT) calculations. Segregation of defects to grain boundaries in UO{sub 2} is described by combining the diffusion model with models of the interaction between Xe atoms and vacancies with grain boundaries derived from separate atomistic calculations. The diffusion and segregation models are implemented in the MOOSE/MARMOT (MBM) finitemore » element (FEM) framework and we simulate Xe redistribution for a few simple microstructures. In this report we focus on segregation to grain boundaries. The U or vacancy diffusion model as well as the coupled diffusion of vacancies and Xe have also been implemented, but results are not included in this report.« less

Positronic probe of vacancy defects on surfaces of Au nanoparticles embedded in MgO

NASA Astrophysics Data System (ADS)

Xu, Jun; Moxom, J.; Somieski, B.; White, C. W.; Mills, A. P., Jr.; Suzuki, R.; Ishibashi, S.

2001-09-01

Clusters of four atomic vacancies were found in Au nanoparticle-embedded MgO by positron lifetime spectroscopy [Phys. Rev. Lett. 83, 4586 (1999)]. These clusters were also suggested to locate at the surface of Au nanoparticles by one-detector measurements of Doppler broadening of annihilation radiation. In this work we provide evidence, using two-detector coincidence experiments of Doppler broadening (2D-DBAR), to clarify that these vacancy clusters reside on the surfaces of Au nanoparticles. This work also demonstrates a method for identifying defects at nanomaterials interfaces: a combination of both positron lifetime spectroscopy, which tells the type of the defects, and 2D-DBAR measurements, which reveals chemical environment of the defects.

Simulations of Xe and U diffusion in UO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders D.; Vyas, Shyam; Tonks, Michael R.

2012-09-10

Diffusion of xenon (Xe) and uranium (U) in UO{sub 2} is controlled by vacancy mechanisms and under irradiation the formation of mobile vacancy clusters is important. Based on the vacancy and cluster diffusion mechanisms established from density functional theory (DFT) calculations, we derive continuum thermodynamic and diffusion models for Xe and U in UO{sub 2}. In order to capture the effects of irradiation, vacancies (Va) are explicitly coupled to the Xe and U dynamics. Segregation of defects to grain boundaries in UO{sub 2} is described by combining the bulk diffusion model with models of the interaction between Xe atoms andmore » vacancies with grain boundaries, which were derived from atomistic calculations. The diffusion and segregation models were implemented in the MOOSE-Bison-Marmot (MBM) finite element (FEM) framework and the Xe/U redistribution was simulated for a few simple microstructures.« less

DISPLACEMENT CASCADE SIMULATION IN TUNGSTEN UP TO 200 KEV OF DAMAGE ENERGY AT 300, 1025, AND 2050 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Setyawan, Wahyu; Nandipati, Giridhar; Roche, Kenneth J.

2015-09-22

We generated molecular dynamics database of primary defects that adequately covers the range of tungsten recoil energy imparted by 14-MeV neutrons. During this semi annual period, cascades at 150 and 200 keV at 300 and 1025 K were simulated. Overall, we included damage energy up to 200 keV at 300 and 1025 K, and up to 100 keV at 2050 K. We report the number of surviving Frenkel pairs (NF) and the size distribution of defect clusters. The slope of the NF curve versus cascade damage energy (EMD), on a log-log scale, changes at a transition energy (μ). For EMDmore » > μ, the cascade forms interconnected damage regions that facilitate the formation of large clusters of defects. At 300 K and EMD = 200 keV, the largest size of interstitial cluster and vacancy cluster is 266 and 335, respectively. Similarly, at 1025 K and EMD = 200 keV, the largest size of interstitial cluster and vacancy cluster is 296 and 338, respectively. At 2050 K, large interstitial clusters also routinely form, but practically no large vacancy clusters do« less

Recombination radius of a Frenkel pair and capture radius of a self-interstitial atom by vacancy clusters in bcc Fe

NASA Astrophysics Data System (ADS)

Nakashima, Kenichi; Stoller, Roger E.; Xu, Haixuan

2015-08-01

The recombination radius of a Frenkel pair is a fundamental parameter for the object kinetic Monte Carlo (OKMC) and mean field rate theory (RT) methods that are used to investigate irradiation damage accumulation in irradiated materials. The recombination radius in bcc Fe has been studied both experimentally and numerically, however there is no general consensus about its value. The detailed atomistic processes of recombination also remain uncertain. Values from 1.0a0 to 3.3a0 have been employed as a recombination radius in previous studies using OKMC and RT. The recombination process of a Frenkel pair is investigated at the atomic level using the self-evolved atomistic kinetic Monte Carlo (SEAKMC) method in this paper. SEAKMC calculations reveal that a self-interstitial atom recombines with a vacancy in a spontaneous reaction from several nearby sites following characteristic pathways. The recombination radius of a Frenkel pair is estimated to be 2.26a0 by taking the average of the recombination distances from 80 simulation cases. In addition, we apply these procedures to the capture radius of a self-interstitial atom by a vacancy cluster. The capture radius is found to gradually increase with the size of the vacancy cluster. The fitting curve for the capture radius is obtained as a function of the number of vacancies in the cluster.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Studies of Point Defects and Defect Interactions in Metals Using Perturbed Gamma Gamma Angular Correlations

NASA Astrophysics Data System (ADS)

Shropshire, Steven Leslie

Point defects in plastically deformed Au, Pt, and Ni were studied with atomic-scale sensitivity using the perturbed gamma-gamma angular correlations (PAC) technique by monitoring formation and transformation of complexes of vacancy defects with very dilute ^{111}In/ ^{111}Cd solute probes. Three topics were investigated: (1) Production of vacancy defects during plastic deformation of Au was investigated to differentiate models of defect production. Concentrations of mono-, di-, and tri-vacancy species were measured in Au, and the ratio of mono- to di-vacancies was found to be independent of the amount of deformation. Results indicate that point defects are produced in correlated lattice locations, such as in "strings", as a consequence of dislocation interactions and not at random locations. (2) Hydrogen interactions with vacancy-solute complexes were studied in Pt. From thermal detrapping experiments, binding of hydrogen in complexes with mono-, di- and tri-vacancies was determined using a model for hydrogen diffusing in a medium with traps, with enthalpies all measured in the narrow range 0.23-0.28 eV, proving that the binding is insensitive to the precise structure of small vacancy clusters. Nuclear relaxation of the probe in a trivacancy complex in Pt was studied as a function of temperature, from which an activation energy of 0.34 eV was measured. This value is inconsistent with relaxation caused by diffusion or trapping of hydrogen, but explainable by dynamical hopping of the PAC probe atom in a cage of vacancies. (3) By observing transformations between vacancy-solute complexes induced by annihilation reactions, it was demonstrated that interstitials are produced during plastic deformation. The evolution of concentrations of the different vacancy complexes under an interstitial flux was measured and analyzed using a kinetic-rate model, from which interstitial capture cross-sections for the different vacancy complexes and the relative quantities of interstitial species in the flux were determined. Deformation of Au was found to produce only mono- and di-interstitial fluxes in a 1:2 ratio. Cross-sections increased rapidly with the number of vacancies, which is attributed to the amount of relaxation of lattice strains around solute-vacancy complexes.

Positron annihilation spectroscopy investigation of vacancy defects in neutron-irradiated 3 C -SiC

DOE PAGES

Hu, Xunxiang; Koyanagi, Takaaki; Katoh, Yutai; ...

2017-03-10

We described positron annihilation spectroscopy characterization results for neutron-irradiated 3 C -SiC, with a specific focus on explaining the size and character of vacancy clusters as a complement to the current understanding of the neutron irradiation response of 3 C -SiC. Positron annihilation lifetime spectroscopy was used to capture the irradiation temperature and dose dependence of vacancy defects in 3 C -SiC following neutron irradiation from 0.01 to 31 dpa in the temperature range from 380C °to 790C .° The neutral and negatively charged vacancy clusters were identified and quantified. The results suggest that the vacancy defects that were measuredmore » by positron annihilation spectroscopy technique contribute very little to the transient swelling of SiC. Additionally, we used coincidence Doppler broadening measurement to investigate the chemical identity surrounding the positron trapping sites.Finally, we found that silicon vacancy-related defects dominate in the studied materials and the production of the antisite defect C Si may result in an increase in the probability of positron annihilation with silicon core electrons.« less

Recombination radius of a Frenkel pair and capture radius of a self-interstitial atom by vacancy clusters in bcc Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakashima, Kenichi; Stoller, Roger E.; Xu, Haixuan

The recombination radius of a Frenkel pair is a fundamental parameter for the object kinetic Monte Carlo (OKMC) and mean field rate theory (RT) methods that are used to investigate irradiation damage accumulation in neutron irradiated nuclear materials. The recombination radius in bcc Fe has been studied both experimentally and numerically, however there is no general consensus about its value. The detailed atomistic processes of recombination also remain uncertain. Values from 1:0a₀ to 3:3a₀ have been employed as a recombination radius in previous studies using OKMC and RT. The recombination process of a Frenkel pair is investigated at the atomicmore » level using the self-evolved atomistic kinetic Monte Carlo (SEAKMC) method in this paper. SEAKMC calculations reveal that a self-interstitial atom recombines with a vacancy in a spontaneous reaction from several nearby sites following characteristic pathways. The recombination radius of a Frenkel pair is estimated to be 2.26a₀ by taking the average of the recombination distances from 80 simulation cases. This value agrees well with the experimental estimate. In addition, we apply these procedures to the capture radius of a self-interstitial atom by a vacancy cluster. The capture radius is found to gradually increase with the size of the vacancy cluster. The fitting curve for the capture radius is obtained as a function of the number of vacancies in the cluster.« less

Recombination radius of a Frenkel pair and capture radius of a self-interstitial atom by vacancy clusters in bcc Fe

DOE PAGES

Nakashima, Kenichi; Stoller, Roger E.; Xu, Haixuan

2015-08-04

The recombination radius of a Frenkel pair is a fundamental parameter for the object kinetic Monte Carlo (OKMC) and mean field rate theory (RT) methods that are used to investigate irradiation damage accumulation in neutron irradiated nuclear materials. The recombination radius in bcc Fe has been studied both experimentally and numerically, however there is no general consensus about its value. The detailed atomistic processes of recombination also remain uncertain. Values from 1:0a₀ to 3:3a₀ have been employed as a recombination radius in previous studies using OKMC and RT. The recombination process of a Frenkel pair is investigated at the atomicmore » level using the self-evolved atomistic kinetic Monte Carlo (SEAKMC) method in this paper. SEAKMC calculations reveal that a self-interstitial atom recombines with a vacancy in a spontaneous reaction from several nearby sites following characteristic pathways. The recombination radius of a Frenkel pair is estimated to be 2.26a₀ by taking the average of the recombination distances from 80 simulation cases. This value agrees well with the experimental estimate. In addition, we apply these procedures to the capture radius of a self-interstitial atom by a vacancy cluster. The capture radius is found to gradually increase with the size of the vacancy cluster. The fitting curve for the capture radius is obtained as a function of the number of vacancies in the cluster.« less

Transport properties of dilute α -Fe (X ) solid solutions (X = C, N, O)

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Nastar, Maylise

2016-06-01

We extend the self-consistent mean field (SCMF) method to the calculation of the Onsager matrix of Fe-based interstitial solid solutions. Both interstitial jumps and substitutional atom-vacancy exchanges are accounted for. A general procedure is introduced to split the Onsager matrix of a dilute solid solution into intrinsic cluster Onsager matrices, and extract from them flux-coupling ratios, mobilities, and association-dissociation rates for each cluster. The formalism is applied to vacancy-interstitial solute pairs in α -Fe (V X pairs, X = C, N, O), with ab initio based thermodynamic and kinetic parameters. Convergence of the cluster mobility contribution gives a controlled estimation of the cluster definition distance, taking into account both its thermodynamic and kinetic properties. Then, the flux-coupling behavior of each V X pair is discussed, and qualitative understanding is achieved from the comparison between various contributions to the Onsager matrix. Also, the effect of low-activation energy second-nearest-neighbor interstitial solute jumps around a vacancy on these results is addressed.

Effect of solute atom concentration on vacancy cluster formation in neutron-irradiated Ni alloys

NASA Astrophysics Data System (ADS)

Sato, Koichi; Itoh, Daiki; Yoshiie, Toshimasa; Xu, Qiu; Taniguchi, Akihiro; Toyama, Takeshi

2011-10-01

The dependence of microstructural evolution on solute atom concentration in Ni alloys was investigated by positron annihilation lifetime measurements. The positron annihilation lifetimes in pure Ni, Ni-0.05 at.%Si, Ni-0.05 at.%Sn, Ni-Cu, and Ni-Ge alloys were about 400 ps even at a low irradiation dose of 3 × 10 -4 dpa, indicating the presence of microvoids in these alloys. The size of vacancy clusters in Ni-Si and Ni-Sn alloys decreased with an increase in the solute atom concentration at irradiation doses less than 0.1 dpa; vacancy clusters started to grow at an irradiation dose of about 0.1 dpa. In Ni-2 at.%Si, irradiation-induced segregation was detected by positron annihilation coincidence Doppler broadening measurements. This segregation suppressed one-dimensional (1-D) motion of the interstitial clusters and promoted mutual annihilation of point defects. The frequency and mean free path of the 1-D motion depended on the solute atom concentration and the amount of segregation.

Compensating vacancy defects in Sn- and Mg-doped In2O3

NASA Astrophysics Data System (ADS)

Korhonen, E.; Tuomisto, F.; Bierwagen, O.; Speck, J. S.; Galazka, Z.

2014-12-01

MBE-grown Sn- and Mg-doped epitaxial In2O3 thin-film samples with varying doping concentrations have been measured using positron Doppler spectroscopy and compared to a bulk crystal reference. Samples were subjected to oxygen or vacuum annealing and the effect on vacancy type defects was studied. Results indicate that after oxygen annealing the samples are dominated by cation vacancies, the concentration of which changes with the amount of doping. In highly Sn-doped In2O3 , however, these vacancies are not the main compensating acceptor. Vacuum annealing increases the size of vacancies in all samples, possibly by clustering them with oxygen vacancies.

Nonlinear effects in defect production by atomic and molecular ion implantation

DOE Office of Scientific and Technical Information (OSTI.GOV)

David, C., E-mail: david@igcar.gov.in; Dholakia, Manan; Chandra, Sharat

This report deals with studies concerning vacancy related defects created in silicon due to implantation of 200 keV per atom aluminium and its molecular ions up to a plurality of 4. The depth profiles of vacancy defects in samples in their as implanted condition are carried out by Doppler broadening spectroscopy using low energy positron beams. In contrast to studies in the literature reporting a progressive increase in damage with plurality, implantation of aluminium atomic and molecular ions up to Al{sub 3}, resulted in production of similar concentration of vacancy defects. However, a drastic increase in vacancy defects is observed duemore » to Al{sub 4} implantation. The observed behavioural trend with respect to plurality has even translated to the number of vacancies locked in vacancy clusters, as determined through gold labelling experiments. The impact of aluminium atomic and molecular ions simulated using MD showed a monotonic increase in production of vacancy defects for cluster sizes up to 4. The trend in damage production with plurality has been explained on the basis of a defect evolution scheme in which for medium defect concentrations, there is a saturation of the as-implanted damage and an increase for higher defect concentrations.« less

Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3.

PubMed

Schie, Marcel; Marchewka, Astrid; Müller, Thomas; De Souza, Roger A; Waser, Rainer

2012-12-05

A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO(3)). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO(3) was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

Displacement cascades and defects annealing in tungsten, Part I: Defect database from molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Setyawan, Wahyu; Nandipati, Giridhar; Roche, Kenneth J.

Molecular dynamics simulations have been used to generate a comprehensive database of surviving defects due to displacement cascades in bulk tungsten. Twenty-one data points of primary knock-on atom (PKA) energies ranging from 100 eV (sub-threshold energy) to 100 keV (~780 × Ed, where Ed = 128 eV is the average displacement threshold energy) have been completed at 300 K, 1025 K and 2050 K. Within this range of PKA energies, two regimes of power-law energy-dependence of the defect production are observed. A distinct power-law exponent characterizes the number of Frenkel pairs produced within each regime. The two regimes intersect atmore » a transition energy which occurs at approximately 250 × Ed. The transition energy also marks the onset of the formation of large self-interstitial atom (SIA) clusters (size 14 or more). The observed defect clustering behavior is asymmetric, with SIA clustering increasing with temperature, while the vacancy clustering decreases. This asymmetry increases with temperature such that at 2050 K (~0.5 Tm) practically no large vacancy clusters are formed, meanwhile large SIA clusters appear in all simulations. The implication of such asymmetry on the long-term defect survival and damage accumulation is discussed. In addition, <100> {110} SIA loops are observed to form directly in the highest energy cascades, while vacancy <100> loops are observed to form at the lowest temperature and highest PKA energies, although the appearance of both the vacancy and SIA loops with Burgers vector of <100> type is relatively rare.« less

First-Principles Study of Carbon and Vacancy Structures in Niobium

DOE PAGES

Ford, Denise C.; Zapol, Peter; Cooley, Lance D.

2015-04-03

The interstitial chemical impurities hydrogen, oxygen, nitrogen, and carbon are important for niobium metal production, and particularly for the optimization of niobium SRF technology. These atoms are present in refined sheets and can be absorbed into niobium during processing treatments, resulting in changes to the residual resistance and the performance of SRF cavities. A first-principles approach is taken to study the properties of carbon in niobium, and the results are compared and contrasted with the properties of the other interstitial impurities. The results indicate that C will likely form precipitates or atmospheres around defects rather than strongly bound complexes withmore » other impurities. Based on the analysis of carbon and hydrogen near niobium lattice vacancies and small vacancy chains and clusters, the formation of extended carbon chains and hydrocarbons is not likely to occur. Association of carbon with hydrogen atoms can, however, occur through the strain fields created by interstitial binding of the impurity atoms. In conclusion, calculated electronic densities of states indicate that interstitial C may have a similar effect as interstitial O on the superconducting transition temperature of Nb.« less

Correlation between ferromagnetism and defects in MgO nanocrystals studied by positron annihilation

NASA Astrophysics Data System (ADS)

Wang, D. D.; Chen, Z. Q.; Li, C. Y.; Li, X. F.; Cao, C. Y.; Tang, Z.

2012-07-01

High purity MgO nanopowders were pressed into pellets and annealed in air from 100 to 1400 °C. Variation of the microstructures was investigated by X-ray diffraction and positron annihilation spectroscopy. Annealing induces an increase in the MgO grain size from 27 to 60 nm with temperature increasing up to 1400 °C. Positron annihilation measurements reveal vacancy defects including Mg vacancies, vacancy clusters, microvoids and large pores in the grain boundary region. Rapid recovery of Mg monovacancies and vacancy clusters was observed after annealing above 1200 °C. Room temperature ferromagnetism was observed for MgO nanocrystals annealed at 100, 700, and 1000 °C. However, after 1400 °C annealing, MgO nanocrystals turn into diamagnetic. Our results suggest that the room temperature ferromagnetism in MgO nanocrystals might originate from the interfacial defects.

Radiation damage in cubic ZrO 2 and yttria-stabilized zirconia from molecular dynamics simulations

DOE PAGES

Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.

2014-11-20

Here, we perform molecular dynamics simulation on cubic ZrO 2 and yttria-stabilized zirconia (YSZ) to elucidate defect cluster formation resulting from radiation damage, and evaluate the impact of Y-dopants. Interstitial clusters composed of split-interstitial building blocks, i.e., Zr-Zr or Y-Zr are formed. Moreover, oxygen vacancies control cation defect migration; in their presence, Zr interstitials aggregate to form split-interstitials whereas in their absence Zr interstitials remain immobile, as isolated single-interstitials. Y-doping prevents interstitial cluster formation due to sequestration of oxygen vacancies.

First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ford, Denise C.; Cooley, Lance D.; Seidman, David N.

Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density-functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption intomore » interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest-energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium-hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities.« less

Vacancy defects and optoelectrical properties for fluorine tin oxide thin films with various SnF2 contents

NASA Astrophysics Data System (ADS)

Zhou, Yawei; Xu, Wenwu; Li, Jingjing; Yin, Chongshan; Liu, Yong; Zhao, Bin; Chen, Zhiquan; He, Chunqing; Mao, Wenfeng; Ito, Kenji

2018-01-01

Fluorine doped tin oxide (FTO) thin films were deposited on glass substrates by e-beam evaporation. Much higher carrier concentration, broader optical band gap, and average transmittance over 80% were obtained with SnF2 doped SnO2 thin films. Positron annihilation results showed that there are two kinds of vacancy clusters with different sizes existing in the annealed FTO thin films, and the concentration of the larger vacancy clusters of VSnO in the thin films increases with increasing SnF2 contents. Meanwhile, photoluminescence spectra results indicated that the better electrical and optical properties of the FTO thin films are attributed to FO substitutions and oxygen vacancies with higher concentration, which are supported by positron annihilation Doppler broadening results and confirmed by X-ray photoelectron spectroscopy. The results showed that widening of the optical band gap of the FTO thin films strongly depends on the carrier concentration, which is interpreted for the Burstein-Moss effect and is associated with the formation of FO and oxygen vacancies with increasing SnF2 content.

The effects of cation–anion clustering on defect migration in MgAl 2O 4

DOE PAGES

Zamora, Richard J.; Voter, Arthur F.; Perez, Danny; ...

2016-06-28

Magnesium aluminate spinel (MgAl 2O 4), like many other ceramic materials, offers a range of technological applications, from nuclear reactor materials to military body armor. For many of these applications, it is critical to understand both the formation and evolution of lattice defects throughout the lifetime of the material. We use the Speculatively Parallel Temperature Accelerated Dynamics (SpecTAD) method to investigate the effects of di-vacancy and di-interstitial formation on the mobility of the component defects. From long-time trajectories of the state-to-state dynamics, we characterize the migration pathways of defect clusters, and calculate their self-diffusion constants across a range of temperatures.more » We find that the clustering of Al and O vacancies drastically reduces the mobility of both defects, while the clustering of Mg and O vacancies completely immobilizes them. For interstitials, we find that the clustering of Mg and O defects greatly reduces O interstitial mobility, but has only a weak effect on Mg. Lastly, these findings illuminate important new details regarding defect kinetics relevant to the application of MgAl 2O 4 in extreme environments.« less

Clusterization Effects in III-V Nitrides: Nitrogen Vacancies, and Si and Mg Impurities in Aluminum Nitride and Gallium Nitride

NASA Astrophysics Data System (ADS)

Gubanov, V. A.; Pentaleri, E. A.; Boekema, C.; Fong, C. Y.; Klein, B. M.

1997-03-01

We have investigated clusterization of nitrogen vacancies and Si and Mg doping impurities in zinc-blende aluminum nitride (c-AlN) and gallium nitride (c-GaN) by the tight-binding LMTO technique. The calculations used 128-site supercells. Si and Mg atoms replacing ions in both the cation and anion sublattices of the host lattices of the host crystals have been considered. The Mg impurity at cation sites is found to form partially occupied states at the valence-band edge, and may result in p-type conductivity. When Si substitutes for Ga, the impurity band is formed at the conduction-band edge, resulting in n-type conductivity. Si impurities at cation sites, and Mg impurity at anion sites are able to form resonance states in the gap. The influence of impurity clusterization in the host lattice and interstitial sites on electronic properties of c-AlN and c-GaN crystals are modeled. The changes in vacancy- and impurity-state energies, bonding type, localization, density of states at the Fermi level in different host lattices, their dependence on impurity/vacancy concentration are analyzed and compared with the experimental data.

The energy and stability of helium-related cluster in nickel: A study of molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Gong, Hengfeng; Wang, Chengbin; Zhang, Wei; Xu, Jian; Huai, Ping; Deng, Huiqiu; Hu, Wangyu

2016-02-01

Using molecular dynamics simulation, we investigated the energy and stability of helium-related cluster in nickel. All the binding energies of the He-related clusters are demonstrated to be positive and increase with the cluster sizes. Due to the pre-existed self-interstitial nickel atom, the trapping capability of vacancy to defects becomes weak. Besides, the minimum energy configurations of He-related clusters exhibit the very high symmetry in the local atomistic environment. And for the HeN and HeNV1SIA1 clusters, the average length of He-He bonds shortens, but it elongates for the HeNV1 clusters with helium cluster sizes. The helium-to-vacancy ratio plays a decisive role on the binding energies of HeNVM cluster. These results can provide some excellent clues to insight the initial stage of helium bubbles nucleation and growth in the Ni-based alloys for the Generation-IV Molten Salt Reactor.

Formation and Growth of Stacking Fault Tetrahedra in Ni via Vacancy Aggregation Mechanism

DOE PAGES

Aidhy, Dilpuneet S.; Lu, Chenyang; Jin, Ke; ...

2015-12-29

Using molecular dynamics simulations, the formation and growth of stacking fault tetrahedra (SFT) are captured by vacancy cluster diffusion and aggregation mechanisms in Ni. The vacancytetrahedron acts as a nucleation point for SFT formation. Simulations show that perfect SFT can grow to the next size perfect SFT via a vacancy aggregation mechanism. The stopping and range of ions in matter (SRIM) calculations and transmission electron microscopy (TEM) observations reveal that SFT can form farther away from the initial cascade-event locations, indicating the operation of diffusion-based vacancy-aggregation mechanism.

Formation and Growth of Stacking Fault Tetrahedra in Ni via Vacancy Aggregation Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aidhy, Dilpuneet S.; Lu, Chenyang; Jin, Ke

Using molecular dynamics simulations, the formation and growth of stacking fault tetrahedra (SFT) are captured by vacancy cluster diffusion and aggregation mechanisms in Ni. The vacancytetrahedron acts as a nucleation point for SFT formation. Simulations show that perfect SFT can grow to the next size perfect SFT via a vacancy aggregation mechanism. The stopping and range of ions in matter (SRIM) calculations and transmission electron microscopy (TEM) observations reveal that SFT can form farther away from the initial cascade-event locations, indicating the operation of diffusion-based vacancy-aggregation mechanism.

Positron annihilation study of the interfacial defects in ZnO nanocrystals: Correlation with ferromagnetism

NASA Astrophysics Data System (ADS)

Wang, Dong; Chen, Z. Q.; Wang, D. D.; Qi, N.; Gong, J.; Cao, C. Y.; Tang, Z.

2010-01-01

High purity ZnO nanopowders were pressed into pellets and annealed in air between 100 and 1200 °C. The crystal quality and grain size of the ZnO nanocrystals were investigated by x-ray diffraction 2θ scans. Annealing induces an increase in the grain size from 25 to 165 nm with temperature increasing from 400 to 1200 °C. Scanning electron microscopy and high-resolution transmission electron microscopy observations also confirm the grain growth during annealing. Positron annihilation measurements reveal vacancy defects including Zn vacancies, vacancy clusters, and voids in the grain boundary region. The voids show an easy recovery after annealing at 100-700 °C. However, Zn vacancies and vacancy clusters observed by positrons remain unchanged after annealing at temperatures below 500 °C and begin to recover at higher temperatures. After annealing at temperatures higher than 1000 °C, no positron trapping by the interfacial defects can be observed. Raman spectroscopy studies confirm the recovery of lattice disorder after annealing. Hysteresis loops are observed for the 100 and 400 °C annealed samples, which indicate ferromagnetism in ZnO nanocrystals. However, the ferromagnetism disappears after annealing above 700 °C, suggesting that it might originate from the surface defects such as Zn vacancies.

Study on defect properties of nanocrystalline TiO2 during phase transition by positron annihilation lifetime

NASA Astrophysics Data System (ADS)

Zheng, F.; Liu, Y.; Liu, Z.; Dai, Y.-Q.; Fang, P.-F.; Wang, S.-J.

2012-08-01

The defect properties of nanocrystalline TiO2 were investigated by positron annihilation lifetime spectroscopy (PALS) and X-ray diffraction (XRD) as a function of annealed temperature that ranged from 300 to 850 °C. Below 500 °C, the measured positron lifetimes of τ1 (200-206 ps) and τ2 (378-402 ps) revealed the existence of mono-vacancy and vacancy-clusters at grain surface and in the micro-void of intergranular region. Between 500 and 750 °C, the phase transition from anatase to rutile was probed by the variations of positron lifetime and XRD pattern. With the increasing temperature from 500 to 850 °C, the positron lifetime τ1, τ2 and its intensity I2 sharply decreased from 200 ps, 378 ps, and 60% to 135 ps, 274 ps, and 33%, respectively. The results clearly indicate that the mono-vacancy or vacancy-clusters at grain surface and micro-voids between the grains were annealed out during the phase transition.

Combined Molecular and Spin Dynamics Simulation of Lattice Vacancies in BCC Iron

NASA Astrophysics Data System (ADS)

Mudrick, Mark; Perera, Dilina; Eisenbach, Markus; Landau, David P.

Using an atomistic model that treats translational and spin degrees of freedom equally, combined molecular and spin dynamics simulations have been performed to study dynamic properties of BCC iron at varying levels of defect impurity. Atomic interactions are described by an empirical many-body potential, and spin interactions with a Heisenberg-like Hamiltonian with a coordinate dependent exchange interaction. Equations of motion are solved numerically using the second-order Suzuki-Trotter decomposition for the time evolution operator. We analyze the spatial and temporal correlation functions for atomic displacements and magnetic order to obtain the effect of vacancy defects on the phonon and magnon excitations. We show that vacancy clusters in the material cause splitting of the characteristic transverse spin-wave excitations, indicating the production of additional excitation modes. Additionally, we investigate the coupling of the atomic and magnetic modes. These modes become more distinct with increasing vacancy cluster size. This material is based upon work supported by the U.S. Department of Energy Office of Science Graduate Student Research (SCGSR) program.

Coarsening behavior of γ' and γ″ phases in GH4169 superalloy by electric field treatment

NASA Astrophysics Data System (ADS)

Wang, Lei; Wang, Yao; Liu, Yang; Song, Xiu; Lü, Xu-dong; Zhang, Bei-jiang

2013-09-01

The coarsening behaviors of γ' and γ″ phases in GH4169 alloy aged at 1023 and 1073 K with electric field treatment (EFT) were investigated by transmission electron microscopy (TEM) and positron annihilation lifetime spectroscopy (PALS). It is demonstrated that precipitation coarsening occurs, and the growth activation energies of γ' and γ″ phases can be decreased to 115.6 and 198.1 kJ·mol-1, respectively, by applying the electric field. The formation of a large number of vacancies in the matrix is induced by EFT. Due to the occurrence of vacancy migration, the diffusion coefficients of Al and Nb atoms are increased to be 1.6-5.0 times larger than those without EFT at 1023 or 1073 K. Furthermore, the formation of vacancy clusters is promoted by EFT, and the increase in strain energy for the coarsening of γ' and γ″ phases can be counterbalanced by the formation of vacancy clusters.

Cation vacancies and electrical compensation in Sb-doped thin-film SnO2 and ZnO

NASA Astrophysics Data System (ADS)

Korhonen, E.; Prozheeva, V.; Tuomisto, F.; Bierwagen, O.; Speck, J. S.; White, M. E.; Galazka, Z.; Liu, H.; Izyumskaya, N.; Avrutin, V.; Özgür, Ü.; Morkoç, H.

2015-02-01

We present positron annihilation results on Sb-doped SnO2 and ZnO thin films. The vacancy types and the effect of vacancies on the electrical properties of these intrinsically n-type transparent semiconducting oxides are studied. We find that in both materials low and moderate Sb-doping leads to formation of vacancy clusters of variable sizes. However, at high doping levels cation vacancy defects dominate the positron annihilation signal. These defects, when at sufficient concentrations, can efficiently compensate the n-type doping produced by Sb. This is the case in ZnO, but in SnO2 the concentrations appear too low to cause significant compensation.

The evolution of vacancy-type defects in silicon-on-insulator structures studied by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Coleman, P. G.; Nash, D.; Edwardson, C. J.; Knights, A. P.; Gwilliam, R. M.

2011-07-01

Variable-energy positron annihilation spectroscopy (VEPAS) has been applied to the study of the formation and evolution of vacancy-type defect structures in silicon (Si) and the 1.5 μm thick Si top layer of silicon-on-insulator (SOI) samples. The samples were implanted with 2 MeV Si ions at fluences between 1013 and 1015 cm-2, and probed in the as-implanted state and after annealing for 30 min at temperatures between 350 and 800 °C. In the case of SOI the ions were implanted such that their profile was predominantly in the insulating buried oxide layer, and thus their ability to combine with vacancies in the top Si layer, and that of other interstitials beyond the buried oxide, was effectively negated. No measurable differences in the positron response to the evolution of small clusters of n vacancies (Vn, n ˜ 3) in the top Si layer of the Si and SOI samples were observed after annealing up to 500 °C; at higher temperatures, however, this response persisted in the SOI samples as that in Si decreased toward zero. At 700 and 800 °C the damage in Si was below detectable levels, but the VEPAS response in the top Si layer in the SOI was consistent with the development of nanovoids.

Defect engineering of the oxygen-vacancy clusters formation in electron irradiated silicon by isovalent doping: An infrared perspective

NASA Astrophysics Data System (ADS)

Londos, C. A.; Sgourou, E. N.; Chroneos, A.

2012-12-01

Infrared spectroscopy was used to study the production and evolution of oxygen-vacancy (VOn for n = 1, 2, 3 and VmO for m = 1, 2, 3) clusters, in electron-irradiated Czochralski silicon (Cz-Si) samples, doped with isovalent dopants. It was determined that the production of the VO pair is enhanced in Ge-doped Si but is suppressed in Sn and Pb-doped Si. The phenomenon is discussed in terms of the competition between isovalent dopants and oxygen atoms in capturing vacancies in the course of irradiation. In the case of Ge, only transient GeV pairs form, leading finally to an increase of the VO production. Conversely, for Sn and Pb the corresponding pairs with vacancies are stable, having an opposite impact on the formation of VO pairs. Regarding V2O and V3O clusters, our measurements indicate that Ge doping enhances their formation, although Sn and Pb dopants suppress it. Similar arguments as those for the VO pair could be put forward, based on the effect of isovalent impurities on the availability of vacancies. Additionally, it was found that the conversion ratio of VO to VO2 decreases as the covalent radius of the isovalent dopant increases. These results are discussed in terms of the local strains introduced by the isovalent dopants in the Si lattice. These local strains affect the balance of the intrinsic defects created as a result of irradiation, as well as the balance between the two main reactions (VO + Oi → VO2 and VO + SiI → Oi) participating in the VO annealing, leading finally to a decrease of the VO2 production. The larger the covalent radius of the isovalent dopant (rGe < rSn < rPb), the larger the introduced strains in the lattice and then the less the VO2 formation in accordance with our experimental results. Interestingly, an opposite trend was observed for the conversion ratio of VO2 to VO3. The phenomenon is attributed to the enhanced diffusivity of oxygen impurity as a result of the presence of isovalent dopants, leading to an enhanced formation of the VO3 cluster. The results indicate that isovalent doping of Si is an effective way to control the formation of the deleterious oxygen-vacancy clustering that can affect Si-based devices.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Fission gas in thoria

NASA Astrophysics Data System (ADS)

Kuganathan, Navaratnarajah; Ghosh, Partha S.; Galvin, Conor O. T.; Arya, Ashok K.; Dutta, Bijon K.; Dey, Gautam K.; Grimes, Robin W.

2017-03-01

The fission gases Xe and Kr, formed during normal reactor operation, are known to degrade fuel performance, particularly at high burn-up. Using first-principles density functional theory together with a dispersion correction (DFT + D), in ThO2 we calculate the energetics of neutral and charged point defects, the di-vacancy (DV), different neutral tri-vacancies (NTV), the charged tetravacancy (CTV) defect cluster geometries and their interaction with Xe and Kr. The most favourable incorporation point defect site for Xe or Kr in defective ThO2 is the fully charged thorium vacancy. The lowest energy NTV in larger supercells of ThO2 is NTV3, however, a single Xe atom is most stable when accommodated within a NTV1. The di-vacancy (DV) is a significantly less favoured incorporation site than the NTV1 but the CTV offers about the same incorporation energy. Incorporation of a second gas atom in a NTV is a high energy process and more unfavourable than accommodation within an existing Th vacancy. The bi-NTV (BNTV) cluster geometry studied will accommodate one or two gas atoms with low incorporation energies but the addition of a third gas atom incurs a high energy penalty. The tri-NTV cluster (TNTV) forms a larger space which accommodates three gas atoms but again there is a penalty to accommodate a fourth gas atom. By considering the energy to form the defect sites, solution energies were generated showing that in ThO2-x the most favourable solution equilibrium site is the NTV1 while in ThO2 it is the DV.

An ab initio-based Er–He interatomic potential in hcp Er

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Li; ye, Yeting; Fan, K. M.

2014-09-01

We have developed an empirical erbium-helium (Er-He) potential by fitting to the results calculated from ab initio method. Based on the electronic hybridization between Er and He atoms, an s-band model, along with a repulsive pair potential, has been derived to describe the Er-He interaction. The atomic configurations and the formation energies of single He defects, small He interstitial clusters (Hen) and He-vacancy (HenV ) clusters obtained by ab initio calculations are used as the fitting database. The binding energies and relative stabilities of the HnVm clusters are studied by the present potential and compared with the ab initio calculations.more » The Er-He potential is also applied to study the migration of He in hcp-Er at different temperatures, and He clustering is found to occur at 600 K in hcp Er crystal, which may be due to the anisotropic migration behavior of He interstitials.« less

From solid solution to cluster formation of Fe and Cr in α-Zr

NASA Astrophysics Data System (ADS)

Burr, P. A.; Wenman, M. R.; Gault, B.; Moody, M. P.; Ivermark, M.; Rushton, M. J. D.; Preuss, M.; Edwards, L.; Grimes, R. W.

2015-12-01

To understand the mechanisms by which the re-solution of Fe and Cr additions increase the corrosion rate of irradiated Zr alloys, the solubility and clustering of Fe and Cr in model binary Zr alloys was investigated using a combination of experimental and modelling techniques - atom probe tomography (APT), x-ray diffraction (XRD), thermoelectric power (TEP) and density functional theory (DFT). Cr occupies both interstitial and substitutional sites in the α-Zr lattice; Fe favours interstitial sites, and a low-symmetry site that was not previously modelled is found to be the most favourable for Fe. Lattice expansion as a function of Fe and Cr content in the α-Zr matrix deviates from Vegard's law and is strongly anisotropic for Fe additions, expanding the c-axis while contracting the a-axis. Matrix content of solutes cannot be reliably estimated from lattice parameter measurements, instead a combination of TEP and APT was employed. Defect clusters form at higher solution concentrations, which induce a smaller lattice strain compared to the dilute defects. In the presence of a Zr vacancy, all two-atom clusters are more soluble than individual point defects and as many as four Fe or three Cr atoms could be accommodated in a single Zr vacancy. The Zr vacancy is critical for the increased apparent solubility of defect clusters; the implications for irradiation induced microstructure changes in Zr alloys are discussed.

Impact-induced concerted mass transport on W surfaces by a voidion mechanism

NASA Astrophysics Data System (ADS)

Mazilova, T. I.; Sadanov, E. V.; Voyevodin, V. N.; Ksenofontov, V. A.; Mikhailovskij, I. M.

2018-03-01

Using low-temperature field ion microscope techniques, we studied at the atomic level morphological evolution of the W surface through bombardment by a beam of several keV He atoms. This technique allows the direct observation of the results of the high energy He atom impact on the elementary damage stages. The formation of the 〈110〉 and 〈100〉 linear vacancy chains and the high relaxation of the near-neighbors of the surface vacancy clusters were revealed. Performed molecular dynamics simulations shows that a single He atom impact triggers the relaxation process of the linear vacancy chain by a substantial decrease of the distance between atoms at both sides of the chain. The observed inward relaxations in W and Mo are an order of magnitude more than that for a single vacancy. It was revealed a novel highly cooperative impact-induced mass transport mechanism on the stepped surface: the formation and motion of a surface spatially delocalized vacancies (voidions). Surface voidions are extremely mobile: the mean velocity of atoms in voidions equals to a substantial portion of the sound velocity. Successive collective translations of the 〈111〉 lines of atoms in adjacent voidions give rise to a concerted gliding motion of great atomic clusters.

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2.

PubMed

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-06-08

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies.

Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

NASA Astrophysics Data System (ADS)

Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

2016-06-01

Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies.

Localized versus itinerant states created by multiple oxygen vacancies in SrTiO3

NASA Astrophysics Data System (ADS)

Jeschke, Harald O.; Shen, Juan; Valentí, Roser

2015-02-01

Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti {{t}2g} states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.

Production and aging of paramagnetic point defects in P-doped floating zone silicon irradiated with high fluence 27 MeV electrons

NASA Astrophysics Data System (ADS)

Joita, A. C.; Nistor, S. V.

2018-04-01

Enhancing the long term stable performance of silicon detectors used for monitoring the position and flux of the particle beams in high energy physics experiments requires a better knowledge of the nature, stability, and transformation properties of the radiation defects created over the operation time. We report the results of an electron spin resonance investigation in the nature, transformation, and long term stability of the irradiation paramagnetic point defects (IPPDs) produced by high fluence (2 × 1016 cm-2), high energy (27 MeV) electrons in n-type, P-doped standard floating zone silicon. We found out that both freshly irradiated and aged (i.e., stored after irradiation for 3.5 years at 250 K) samples mainly contain negatively charged tetravacancy and pentavacancy defects in the first case and tetravacancy defects in the second one. The fact that such small cluster vacancy defects have not been observed by irradiation with low energy (below 5 MeV) electrons, but were abundantly produced by irradiation with neutrons, strongly suggests the presence of the same mechanism of direct formation of small vacancy clusters by irradiation with neutrons and high energy, high fluence electrons, in agreement with theoretical predictions. Differences in the nature and annealing properties of the IPPDs observed between the 27 MeV electrons freshly irradiated, and irradiated and aged samples were attributed to the presence of a high concentration of divacancies in the freshly irradiated samples, defects which transform during storage at 250 K through diffusion and recombination processes.

Defect evolution in single crystalline tungsten following low temperature and low dose neutron irradiation

DOE PAGES

Hu, Xunxiang; Koyanagi, Takaaki; Fukuda, Makoto; ...

2016-01-01

The tungsten plasma-facing components of fusion reactors will experience an extreme environment including high temperature, intense particle fluxes of gas atoms, high-energy neutron irradiation, and significant cyclic stress loading. Irradiation-induced defect accumulation resulting in severe thermo-mechanical property degradation is expected. For this reason, and because of the lack of relevant fusion neutron sources, the fundamentals of tungsten radiation damage must be understood through coordinated mixed-spectrum fission reactor irradiation experiments and modeling. In this study, high-purity (110) single-crystal tungsten was examined by positron annihilation spectroscopy and transmission electron microscopy following low-temperature (~90 °C) and low-dose (0.006 and 0.03 dpa) mixed-spectrum neutronmore » irradiation and subsequent isochronal annealing at 400, 500, 650, 800, 1000, 1150, and 1300 °C. The results provide insights into microstructural and defect evolution, thus identifying the mechanisms of different annealing behavior. Following 1 h annealing, ex situ characterization of vacancy defects using positron lifetime spectroscopy and coincidence Doppler broadening was performed. The vacancy cluster size distributions indicated intense vacancy clustering at 400 °C with significant damage recovery around 1000 °C. Coincidence Doppler broadening measurements confirm the trend of the vacancy defect evolution, and the S–W plots indicate that only a single type of vacancy cluster is present. Furthermore, transmission electron microscopy observations at selected annealing conditions provide supplemental information on dislocation loop populations and visible void formation. This microstructural information is consistent with the measured irradiation-induced hardening at each annealing stage. This provides insight into tungsten hardening and embrittlement due to irradiation-induced matrix defects.« less

Molecular dynamics study of the role of symmetric tilt grain boundaries on the helium distribution in nickel

NASA Astrophysics Data System (ADS)

Torres, E.; Pencer, J.

2018-04-01

Helium impurities, from either direct implantation or transmutation reactions, have been associated with embrittlement in nickel-based alloys. Helium has very low solubility in nickel, and has been found to aggregate at lattice defects such as vacancies, dislocations, and grain boundaries. The retention and precipitation of helium in nickel-based alloys have deleterious effects on the material mechanical properties. However, the underlying mechanisms that lead to helium effects in the host metal are not fully understood. In the present work, we investigate the role of symmetric tilt grain boundary (STGB) structures on the distribution of helium in nickel using molecular dynamics simulations. We investigate the family of STGBs specific to the 〈 110 〉 tilt axis. The present results indicate that accumulation of helium at the grain boundary may be modulated by details of grain boundary geometry. A plausible correlation between the grain boundary energy and misorientation with the accumulation and mobility of helium is proposed. Small clusters with up to 6 helium atoms show significant interstitial mobility in the nickel bulk, but also become sites for nucleation and grow of more stable helium clusters. High-energy GBs are found mainly populated with small helium clusters. The high mobility of small clusters along the GBs indicates the role of these GBs as fast two-dimensional channels for diffusion. In contrast, the accumulation of helium in large helium clusters at low-energy STGB creates a favorable environment for the formation of large helium bubbles, indicating a potential role for low-energy STGB in promoting helium-induced GB embrittlement.

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

PubMed

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.

Evaluation of structural vacancies for 1/1-Al-Re-Si approximant crystals by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Yamada, K.; Suzuki, H.; Kitahata, H.; Matsushita, Y.; Nozawa, K.; Komori, F.; Yu, R. S.; Kobayashi, Y.; Ohdaira, T.; Oshima, N.; Suzuki, R.; Takagiwa, Y.; Kimura, K.; Kanazawa, I.

2018-01-01

The size of structural vacancies and structural vacancy density of 1/1-Al-Re-Si approximant crystals with different Re compositions were evaluated by positron annihilation lifetime and Doppler broadening measurements. Incident positrons were found to be trapped at the monovacancy-size open space surrounded by Al atoms. From a previous analysis using the maximum entropy method and Rietveld method, such an open space is shown to correspond to the centre of Al icosahedral clusters, which locates at the vertex and body centre. The structural vacancy density of non-metallic Al73Re17Si10 was larger than that of metallic Al73Re15Si12. The observed difference in the structural vacancy density reflects that in bonding nature and may explain that in the physical properties of the two samples.

Oxygen vacancy effects in HfO2-based resistive switching memory: First principle study

NASA Astrophysics Data System (ADS)

Dai, Yuehua; Pan, Zhiyong; Wang, Feifei; Li, Xiaofeng

2016-08-01

The work investigated the shape and orientation of oxygen vacancy clusters in HfO2-base resistive random access memory (ReRAM) by using the first-principle method based on the density functional theory. Firstly, the formation energy of different local Vo clusters was calculated in four established orientation systems. Then, the optimized orientation and charger conductor shape were identified by comparing the isosurface plots of partial charge density, formation energy, and the highest isosurface value of oxygen vacancy. The calculated results revealed that the [010] orientation was the optimal migration path of Vo, and the shape of system D4 was the best charge conductor in HfO2, which effectively influenced the SET voltage, formation voltage and the ON/OFF ratio of the device. Afterwards, the PDOS of Hf near Vo and total density of states of the system D4_010 were obtained, revealing the composition of charge conductor was oxygen vacancy instead of metal Hf. Furthermore, the migration barriers of the Vo hopping between neighboring unit cells were calculated along four different orientations. The motion was proved along [010] orientation. The optimal circulation path for Vo migration in the HfO2 super-cell was obtained.

Self-consistent calculations for the electronic structure of a vacancy in copper. A solution of the embedding problem

NASA Astrophysics Data System (ADS)

Zeller, R.; Braspenning, P. J.

1982-06-01

The charge density and the local density of states for a vacancy in Cu and for the first shell of Cu neighbours are calculated by the KKR-Green's function technique. The muffin-tin potentials for the vacancy and the neighbour shell atoms are determined self-consistently in the local density approximation of density functional theory. By the use of the proper host Green's function the embedding of this cluster of 13 perturbed muffin-tins into the infinite array of bulk Cu muffin-tin potentials is described rigorously, thus representing a solution of the embedding problem. The calculations demonstrate a rather large charge transfer of 1.1 electrons from the first neighbour shell to the vacancy.

Long-time atomistic dynamics through a new self-adaptive accelerated molecular dynamics method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, N.; Yang, L.; Gao, F.

2017-02-27

A self-adaptive accelerated molecular dynamics method is developed to model infrequent atomic- scale events, especially those events that occur on a rugged free-energy surface. Key in the new development is the use of the total displacement of the system at a given temperature to construct a boost-potential, which is slowly increased to accelerate the dynamics. The temperature is slowly increased to accelerate the dynamics. By allowing the system to evolve from one steady-state con guration to another by overcoming the transition state, this self-evolving approach makes it possible to explore the coupled motion of species that migrate on vastly differentmore » time scales. The migrations of single vacancy (V) and small He-V clusters, and the growth of nano-sized He-V clusters in Fe for times in the order of seconds are studied by this new method. An interstitial- assisted mechanism is rst explored for the migration of a helium-rich He-V cluster, while a new two-component Ostwald ripening mechanism is suggested for He-V cluster growth.« less

The defect chemistry of UO2 ± x from atomistic simulations

NASA Astrophysics Data System (ADS)

Cooper, M. W. D.; Murphy, S. T.; Andersson, D. A.

2018-06-01

Control of the defect chemistry in UO2 ± x is important for manipulating nuclear fuel properties and fuel performance. For example, the uranium vacancy concentration is critical for fission gas release and sintering, while all oxygen and uranium defects are known to strongly influence thermal conductivity. Here the point defect concentrations in thermal equilibrium are predicted using defect energies from density functional theory (DFT) and vibrational entropies calculated using empirical potentials. Electrons and holes have been treated in a similar fashion to other charged defects allowing for structural relaxation around the localized electronic defects. Predictions are made for the defect concentrations and non-stoichiometry of UO2 ± x as a function of oxygen partial pressure and temperature. If vibrational entropy is omitted, oxygen interstitials are predicted to be the dominant mechanism of excess oxygen accommodation over only a small temperature range (1265 K-1350 K), in contrast to experimental observation. Conversely, if vibrational entropy is included oxygen interstitials dominate from 1165 K to 1680 K (Busker potential) or from 1275 K to 1630 K (CRG potential). Below these temperature ranges, excess oxygen is predicted to be accommodated by uranium vacancies, while above them the system is hypo-stoichiometric with oxygen deficiency accommodated by oxygen vacancies. Our results are discussed in the context of oxygen clustering, formation of U4O9, and issues for fuel behavior. In particular, the variation of the uranium vacancy concentrations as a function of temperature and oxygen partial pressure will underpin future studies into fission gas diffusivity and broaden the understanding of UO2 ± x sintering.

Study of multiband disordered systems using the typical medium dynamical cluster approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yi; Terletska, Hanna; Moore, C.

We generalize the typical medium dynamical cluster approximation to multiband disordered systems. Using our extended formalism, we perform a systematic study of the nonlocal correlation effects induced by disorder on the density of states and the mobility edge of the three-dimensional two-band Anderson model. We include interband and intraband hopping and an intraband disorder potential. Our results are consistent with those obtained by the transfer matrix and the kernel polynomial methods. We also apply the method to K xFe 2-ySe 2 with Fe vacancies. Despite the strong vacancy disorder and anisotropy, we find the material is not an Anderson insulator.more » Moreover our results demonstrate the application of the typical medium dynamical cluster approximation method to study Anderson localization in real materials.« less

Study of multiband disordered systems using the typical medium dynamical cluster approximation

DOE PAGES

Zhang, Yi; Terletska, Hanna; Moore, C.; ...

2015-11-06

We generalize the typical medium dynamical cluster approximation to multiband disordered systems. Using our extended formalism, we perform a systematic study of the nonlocal correlation effects induced by disorder on the density of states and the mobility edge of the three-dimensional two-band Anderson model. We include interband and intraband hopping and an intraband disorder potential. Our results are consistent with those obtained by the transfer matrix and the kernel polynomial methods. We also apply the method to K xFe 2-ySe 2 with Fe vacancies. Despite the strong vacancy disorder and anisotropy, we find the material is not an Anderson insulator.more » Moreover our results demonstrate the application of the typical medium dynamical cluster approximation method to study Anderson localization in real materials.« less

Impact of interface manipulation of oxide on electrical transport properties and low-frequency noise in MgO/NiFe/MgO heterojunctions

NASA Astrophysics Data System (ADS)

Li, Jian-wei; Zhao, Chong-jun; Feng, Chun; Zhou, Zhongfu; Yu, Guang-hua

2015-08-01

Low-frequency noise and magnetoresistance in sputtered-deposited Ta(5 nm)/MgO (3 nm)/NiFe(10 nm)/MgO(3 nm)/Ta(3 nm) films have been measured as a function of different annealing times at 400°C. These measurements did not change synchronously with annealing time. A significant increase in magnetoresistance is observed for short annealing times (of the order of minutes) and is correlated with a relatively small reduction in 1/f noise. In contrast, a significant reduction in 1/f noise is observed for long annealing times (of the order of hours) accompanied by a small change in magnetoresistance. After annealing for 2 hours, the 1/f noise decreases by three orders of magnitude. Transmission electron microscopy and slow positron annihilation results implicate the cause being micro-structural changes in the MgO layers and interfaces following different annealing times. The internal vacancies in the MgO layers gather into vacancy clusters to reduce the defect density after short annealing times, whereas the MgO/NiFe and the NiFe/MgO interfaces improve significantly after long annealing times with the amorphous MgO layers gradually crystallizing following the release of interfacial stress.

Impact of interface manipulation of oxide on electrical transport properties and low-frequency noise in MgO/NiFe/MgO heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jian-wei; School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083; Zhao, Chong-jun

2015-08-15

Low-frequency noise and magnetoresistance in sputtered-deposited Ta(5 nm)/MgO (3 nm)/NiFe(10 nm)/MgO(3 nm)/Ta(3 nm) films have been measured as a function of different annealing times at 400°C. These measurements did not change synchronously with annealing time. A significant increase in magnetoresistance is observed for short annealing times (of the order of minutes) and is correlated with a relatively small reduction in 1/f noise. In contrast, a significant reduction in 1/f noise is observed for long annealing times (of the order of hours) accompanied by a small change in magnetoresistance. After annealing for 2 hours, the 1/f noise decreases by three ordersmore » of magnitude. Transmission electron microscopy and slow positron annihilation results implicate the cause being micro-structural changes in the MgO layers and interfaces following different annealing times. The internal vacancies in the MgO layers gather into vacancy clusters to reduce the defect density after short annealing times, whereas the MgO/NiFe and the NiFe/MgO interfaces improve significantly after long annealing times with the amorphous MgO layers gradually crystallizing following the release of interfacial stress.« less

Deformation-related spectroscopic features in natural Type Ib-IaA diamonds from Zimmi (West African craton)

NASA Astrophysics Data System (ADS)

Smit, Karen V.; D'Haenens-Johansson, Ulrika F. S.; Howell, Daniel; Loudin, Lorne C.; Wang, Wuyi

2018-06-01

Zimmi diamonds (Sierra Leone) have 500 million year mantle residency times whose origin is best explained by rapid tectonic exhumation to shallower depths in the mantle, associated with continental collision but prior to kimberlite eruption. Here we present spectroscopic data for a new suite of Zimmi sulphide-bearing diamonds that allow us to evaluate the link between their spectroscopic features and their unusual geological history. Cathodoluminesence (CL) imaging of these diamonds revealed irregular patterns with abundant deformation lamellae, associated with the diamonds' tectonic exhumation. Vacancies formed during deformation were subsequently naturally annealed to form vacancy clusters, NV0/- centres and H3 (NVN0). The brownish-yellow to greenish-yellow colours observed in Zimmi Ib-IaA diamonds result from visible absorption by a combination of isolated substitutional nitrogen ( {N}S^0 ) and deformation-related vacancy clusters. Colour-forming centres and other spectroscopic features can all be attributed to the unique geological history of Zimmi Ib-IaA diamonds and their rapid exhumation after formation.

Primary radiation damage characterization of α-iron under irradiation temperature for various PKA energies

NASA Astrophysics Data System (ADS)

Sahi, Qurat-ul-ain; Kim, Yong-Soo

2018-04-01

The understanding of radiation-induced microstructural defects in body-centered cubic (BCC) iron is of major interest to those using advanced steel under extreme conditions in nuclear reactors. In this study, molecular dynamics (MD) simulations were implemented to examine the primary radiation damage in BCC iron with displacement cascades of energy 1, 5, 10, 20, and 30 keV at temperatures ranging from 100 to 1000 K. Statistical analysis of eight MD simulations of collision cascades were carried out along each [110], [112], [111] and a high index [135] direction and the temperature dependence of the surviving number of point defects and the in-cascade clustering of vacancies and interstitials were studied. The peak time and the corresponding number of defects increase with increasing irradiation temperature and primary knock-on atom (PKA) energy. However, the final number of surviving point defects decreases with increasing lattice temperature. This is associated with the increase of thermal spike at high PKA energy and its long timespan at higher temperatures. Defect production efficiency (i.e., surviving MD defects, per Norgett-Robinson-Torrens displacements) also showed a continuous decrease with the increasing irradiation temperature and PKA energy. The number of interstitial clusters increases with both irradiation temperature and PKA energy. However, the increase in the number of vacancy clusters with PKA energy is minimal-to-constant and decreases as the irradiation temperature increases. Similarly, the probability and cluster size distribution for larger interstitials increase with temperature, whereas only smaller size vacancy clusters were observed at higher temperatures.

Interaction of hydrogen with palladium clusters deposited on graphene

NASA Astrophysics Data System (ADS)

Alonso, Julio A.; Granja, Alejandra; Cabria, Iván; López, María J.

2015-12-01

Hydrogen adsorption on nanoporous carbon materials is a promising technology for hydrogen storage. However, pure carbon materials do not meet the technological requirements due to the week binding of hydrogen to the pore walls. Experimental work has shown that doping with Pd atoms and clusters enhances the storage capacity of porous carbons. Therefore, we have investigated the role played by the Pd dopant on the enhancement mechanisms. By performing density functional calculations, we have found that hydrogen adsorbs on Pd clusters deposited on graphene following two channels, molecular adsorption and dissociative chemisorption. However, desorption of Pd-H complexes competes with desorption of hydrogen, and consequently desorption of Pd-H complexes would spoil the beneficial effect of the dopant. As a way to overcome this difficulty, Pd atoms and clusters can be anchored to defects of the graphene layer, like graphene vacancies. The competition between molecular adsorption and dissociative chemisorption of H2 on Pd6 anchored on a graphene vacancy has been studied in detail.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moutanabbir, O.; Scholz, R.; Goesele, U.

We present a detailed study of the thermal evolution of H ion-induced vacancy related complexes and voids in bulk GaN implanted under ion-cut conditions. By using transmission electron microscopy, we found that the damage band in as-implanted GaN is decorated with a high density of nanobubbles of approx1-2 nm in diameter. Variable energy Doppler broadening spectroscopy showed that this band contains vacancy clusters and voids. In addition to vacancy clusters, the presence of V{sub Ga}, V{sub Ga}-H{sub 2}, and V{sub Ga}V{sub N} complexes was evidenced by pulsed low-energy positron lifetime spectroscopy. Subtle changes upon annealing in these vacancy complexes weremore » also investigated. As a general trend, a growth in open-volume defects is detected in parallel to an increase in both size and density of nanobubbles. The observed vacancy complexes appear to be stable during annealing. However, for temperatures above 450 deg. C, unusually large lifetimes were measured. These lifetimes are attributed to the formation of positronium in GaN. Since the formation of positronium is not possible in a dense semiconductor, our finding demonstrates the presence of sufficiently large open-volume defects in this temperature range. Based on the Tao-Eldrup model, the average lattice opening during thermal annealing was quantified. We found that a void diameter of 0.4 nm is induced by annealing at 600 deg. C. The role of these complexes in the subsurface microcracking is discussed.« less

Tuning the properties of an MgO layer for spin-polarized electron transport

NASA Astrophysics Data System (ADS)

Zhao, Chong-Jun; Ding, Lei; Zhao, Zhi-Duo; Zhang, Peng; Cao, Xing-Zhong; Wang, Bao-Yi; Zhang, Jing-Yan; Yu, Guang-Hua

2014-08-01

The influence of substrate temperature and annealing on quality/microstructural evolution of MgO, as well as the resultant magnetoresistance (MR) ratio, has been investigated. It has been found that the crystallinity of MgO in the MgO/NiFe/MgO heterostructures gradually improves with increasing substrate temperature. This behavior facilitates the transport of spin-polarized electrons, resulting in a high MR value. After annealing, the formation of vacancy clusters in MgO layers observed through positron annihilation spectroscopy leads to an increase in MR at different levels because of the crystallinity improvement of MgO. However, these vacancy clusters as another important defect can limit further improvement in MR.

Counting vacancies and nitrogen-vacancy centers in detonation nanodiamond† †Electronic supplementary information (ESI) available: (1) DND synthesis; (2) HRTEM and EELS characterization methods; (3) EELS simulation method; (4) supporting figures of EELS simulations; (5) soft-X-ray K-edge spectra of the DND; and (6) ab initio N-V center modeling method. See DOI: 10.1039/C6NR01888B Click here for additional data file.

PubMed Central

Barnard, Amanda S.; Dwyer, Christian; Boothroyd, Chris B.; Hocking, Rosalie K.; Ōsawa, Eiji

2016-01-01

Detonation nanodiamond particles (DND) contain highly-stable nitrogen-vacancy (N-V) centers, making it important for quantum-optical and biotechnology applications. However, due to the small particle size, the N-V concentrations are believed to be intrinsically very low, spawning efforts to understand the formation of N-V centers and vacancies, and increase their concentration. Here we show that vacancies in DND can be detected and quantified using simulation-aided electron energy loss spectroscopy. Despite the small particle size, we find that vacancies exist at concentrations of about 1 at%. Based on this experimental finding, we use ab initio calculations to predict that about one fifth of vacancies in DND form N-V centers. The ability to directly detect and quantify vacancies in DND, and predict the corresponding N-V formation probability, has a significant impact to those emerging technologies where higher concentrations and better dispersion of N-V centres are critically required. PMID:27147128

Systematic study of the physical origin of ferromagnetism in CeO2 -δ nanoparticles

NASA Astrophysics Data System (ADS)

Ribeiro, A. N.; Ferreira, N. S.

2017-04-01

We have carried out a Schrieffer-Wolff transformation on a general tight-binding Hamiltonian and obtained a 4 f -one-band effective Hubbard Hamiltonian to study the physical origin of ferromagnetism in CeO2 -δ nanoparticle systems. For a low temperature regime and low concentrations of oxygen vacancies, isolated vacancies have previously been showed to form on the {100 } and {110 } surfaces and our studies indicate these will be in singlet and triplet states, respectively. This is sustained by a superexchange interaction between the 4 f electrons of the two cerium atoms, which are the nearest neighbors of the vacancy, and ferromagnetism and antiferromagnetism can coexist. Moreover, increasing the vacancy concentration we found that pairs of vacancies, which have been previously shown to form on the {111 } surfaces, produce Nagaoka ferromagnetism and isolated vacancies in the bulk produce an antiferromagnetic sign. Furthermore, further oxygen vacancy increases are previously known to favor the formation of oxygen vacancy clusters. In this case, our results showed a weakening of the magnetic correlations with respect to temperature. Thus, at a fixed temperature, the magnetic moment is reduced when the concentration of vacancies is increased, which is in agreement with experimental results reported in the literature. Interestingly, at a room-temperature regime, the antiferromagnetic order is destroyed and only the ferromagnetic couplings, produced mainly by isolated vacancies on the {110 } surfaces, survive. Finally, as temperature is increased further, the paramagnetic behavior of 4 f electrons dominates.

Sulfur-vacancy-dependent geometric and electronic structure of bismuth adsorbed on Mo S2

NASA Astrophysics Data System (ADS)

Park, Youngsin; Li, Nannan; Lee, Geunsik; Kim, Kwang S.; Kim, Ki-Jeong; Hong, Soon Cheol; Han, Sang Wook

2018-03-01

Through Bi deposition on the single-crystalline Mo S2 surface, we find that the density of the sulfur vacancy is a critical parameter for the growth of the crystalline Bi overlayer or cluster at room temperature. Also, the Mo S2 band structure is significantly modified near Γ due to the orbital hybridization with an adsorbed Bi monolayer. Our experimental observations and analysis in combination with density functional theory calculation suggest the importance of controlling the sulfur vacancy concentration in realizing an exotic quantum phase based on the van der Waals interface of Bi and Mo S2 .

The effect of primary recoil spectrum on radiation induced segregation in nickel-silicon alloys

NASA Astrophysics Data System (ADS)

Averback, R. S.; Rehn, L. E.; Wagner, W.; Ehrhart, P.

1983-08-01

Segregation of silicon to the surface of Ni-12.7 at% Si alloys during 2.0-MeV He and 3.25-MeV Kr irradiations was measured using Rutherford backscattering spectrometry. For equal calculated defect production rates the Kr irradiation was < 3 % as efficient as the He irradiation for promoting segregation in the temperature range, 450 °C-580 °C. It was further observed that Kr preirradiation of specimens dramatically reduced segregation during subsequent He irradiation. A model for cascade annealing in Ni-Si alloys is presented which qualitatively explains the segregation results. The model assumes that small interstitial-atom-clusters form in individual cascades and that these clusters become trapped at silicon solute atoms. The vacancy thereby becomes the more mobile defect. The model should also have relevance for the observation that void swelling in nickel is suppressed by the addition of silicon solute.

Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

DOE PAGES

Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; ...

2015-03-05

In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO 2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO 2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO 2-x, oxygenmore » transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO 2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.« less

Semiconductor color-center structure and excitation spectra: Equation-of-motion coupled-cluster description of vacancy and transition-metal defect photoluminescence

NASA Astrophysics Data System (ADS)

Lutz, Jesse J.; Duan, Xiaofeng F.; Burggraf, Larry W.

2018-03-01

Valence excitation spectra are computed for deep-center silicon-vacancy defects in 3C, 4H, and 6H silicon carbide (SiC), and comparisons are made with literature photoluminescence measurements. Optimizations of nuclear geometries surrounding the defect centers are performed within a Gaussian basis-set framework using many-body perturbation theory or density functional theory (DFT) methods, with computational expenses minimized by a QM/MM technique called SIMOMM. Vertical excitation energies are subsequently obtained by applying excitation-energy, electron-attached, and ionized equation-of-motion coupled-cluster (EOMCC) methods, where appropriate, as well as time-dependent (TD) DFT, to small models including only a few atoms adjacent to the defect center. We consider the relative quality of various EOMCC and TD-DFT methods for (i) energy-ordering potential ground states differing incrementally in charge and multiplicity, (ii) accurately reproducing experimentally measured photoluminescence peaks, and (iii) energy-ordering defects of different types occurring within a given polytype. The extensibility of this approach to transition-metal defects is also tested by applying it to silicon-substituted chromium defects in SiC and comparing with measurements. It is demonstrated that, when used in conjunction with SIMOMM-optimized geometries, EOMCC-based methods can provide a reliable prediction of the ground-state charge and multiplicity, while also giving a quantitative description of the photoluminescence spectra, accurate to within 0.1 eV of measurement for all cases considered.

Antiphase boundaries on low-energy-ion bombarded Ge(001)

NASA Astrophysics Data System (ADS)

Zandvliet, H. J. W.; de Groot, E.

1997-01-01

Surface vacancy and adatom clusters have been created on Ge(001) by bombarding the surface with 800 eV argon ions at various substrate temperatures ranging from room temperature to 600 K. The vacancies preferentially annihilate at the ends rather than at the sides of the dimer rows, resulting in monolayer deep vacancy islands which are elongated in a direction of the dimer rows of the upper terrace. As vacancy islands nucleate and expand, the dimer rows in neighbouring vacancy islands need not, in general, align with each other. An antiphase boundary will develop if two growing vacancy islands meet, but their internal dimer rows are not in the same registry. In contrast to Si(001), where only one type of antiphase boundary is found, we have found three different types of antiphase boundaries on Ge(001). Higher dose (> several monolayers) room temperature ion bombardment followed by annealing at temperatures in the range 400-500 K results in a surface which contains a high density of valleys. In addition to the preference for the annihilation of dimer vacancies at descending versus ascending steps we also suggest that the development of antiphase boundaries drives the roughening of this surface. Finally, several atomic rearrangement events, which might be induced by the tunneling process, are observed after low-dose ion bombardment at room temperature.

Influence of artificial cavity age on red-cockaded woodpecker translocation success

Treesearch

Daniel Saenz; Richard R. Schaefer; Richard N. Conner; D. Craig Rudolph; Dawn K. Carrie; M. Stephen Best

2004-01-01

Red-cockaded woodpecker (Picoides borealis) translocations have been used to bolster woodpecker populations and to fill breeding vacancies. Artificial, insert cavities have been used to offset cavity shortages in woodpecker clusters and are the primary cavity type used in recruitment clusters in Texas and Arkansas, but inserts may lose their...

Large bandgap narrowing in rutile TiO2 aimed towards visible light applications and its correlation with vacancy-type defects history and transformation

NASA Astrophysics Data System (ADS)

Nair, Radhika V.; Gayathri, P. K.; Siva Gummaluri, Venkata; Nambissan, P. M. G.; Vijayan, C.

2018-01-01

Extension of photoactivity of TiO2 to the visible region is achievable via effective control over the intrinsic defects such as oxygen and Ti vacancies, which has several applications in visible photocatalysis and sensing. We present here the first observation of an apparent bandgap narrowing and bandgap tuning effect due to vacancy cluster transformation in rutile TiO2 structures to 1.84 eV from the bulk bandgap of 3 eV. A gradual transformation of divacancies (V Ti-O) to tri vacancies ({{V}Ti-O-T{{i-}}} ) achieved through a controlled solvothermal scheme appears to result in an apparent narrowing bandgap and tunability, as supported by positron annihilation lifetime and electron paramagnetic resonance spectroscopy measurements. Visible photocatalytic activity of the samples is demonstrated in terms of photodegradation of rhodamine B dye molecules.

Defect characterization in Mg-doped GaN studied using a monoenergetic positron beam

NASA Astrophysics Data System (ADS)

Uedono, A.; Ishibashi, S.; Tenjinbayashi, K.; Tsutsui, T.; Nakahara, K.; Takamizu, D.; Chichibu, S. F.

2012-01-01

Vacancy-type defects in Mg-doped GaN grown by metalorganic vapor phase epitaxy were probed using a monoenergetic positron beam. For a sample fabricated with a high H2-flow rate, before post-growth annealing the major defect species detected by positrons was identified as vacancy-clusters. Evidence suggested that other donor-type defects such as nitrogen vacancies also existed. The defects increased the Fermi level position, and enhanced the diffusion of positrons toward the surface. The annihilation of positrons at the top surface was suppressed by Mg-doping. This was attributed to the introduction of a subsurface layer (<6 nm) with a low defect concentration, where the Fermi level position was considered to decrease due to partial activation of Mg. For samples after annealing, the trapping of positrons by residual vacancy-type defects was observed, and the sample crystal quality was found to depend on that before annealing.

Identification of Zn-vacancy-hydrogen complexes in ZnO single crystals: A challenge to positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Brauer, G.; Anwand, W.; Grambole, D.; Grenzer, J.; Skorupa, W.; Čížek, J.; Kuriplach, J.; Procházka, I.; Ling, C. C.; So, C. K.; Schulz, D.; Klimm, D.

2009-03-01

A systematic study of various, nominally undoped ZnO single crystals, either hydrothermally grown (HTG) or melt grown (MG), has been performed. The crystal quality has been assessed by x-ray diffraction, and a comprehensive estimation of the detailed impurity and hydrogen contents by inductively coupled plasma mass spectrometry and nuclear reaction analysis, respectively, has been made also. High precision positron lifetime experiments show that a single positron lifetime is observed in all crystals investigated, which clusters at 180-182 ps and 165-167 ps for HTG and MG crystals, respectively. Furthermore, hydrogen is detected in all crystals in a bound state with a high concentration (at least 0.3at.% ), whereas the concentrations of other impurities are very small. From ab initio calculations it is suggested that the existence of Zn-vacancy-hydrogen complexes is the most natural explanation for the given experimental facts at present. Furthermore, the distribution of H at a metal/ZnO interface of a MG crystal, and the H content of a HTG crystal upon annealing and time afterward has been monitored, as this is most probably related to the properties of electrical contacts made at ZnO and the instability in p -type conductivity observed at ZnO nanorods in literature. All experimental findings and presented theoretical considerations support the conclusion that various types of Zn-vacancy-hydrogen complexes exist in ZnO and need to be taken into account in future studies, especially for HTG materials.

Effect of post-implantation annealing on Al-N isoelectronic trap formation in silicon: Al-N pair formation and defect recovery mechanisms

NASA Astrophysics Data System (ADS)

Mori, Takahiro; Morita, Yukinori; Matsukawa, Takashi

2018-05-01

The effect of post-implantation annealing (PIA) on Al-N isoelectronic trap (IET) formation in silicon has been experimentally investigated to discuss the Al-N IET formation and implantation-induced defect recovery mechanisms. We performed a photoluminescence study, which indicated that self-interstitial clusters and accompanying vacancies are generated in the ion implantation process. It is supposed that Al and N atoms move to the vacancy sites and form stable Al-N pairs in the PIA process. Furthermore, the PIA process recovers self-interstitial clusters while transforming their atomic configuration. The critical temperature for the formation/dissociation of Al-N pairs was found to be 450 °C, with which we describe the process integration for devices utilizing Al-N IET technology.

Cation and Vacancy Disorder in U 1-yNd yO 2.00-X Alloys

DOE PAGES

Barabash, Rozaliya I.; Voit, Stewart L.; Aidhy, Dilpuneet S.; ...

2015-09-14

In this study, the intermixing and clustering of U/Nd, O, and vacancies were studied by both laboratory and synchrotron-based x-ray diffraction in U 1-yNd yO 2-X alloys. It was found that an increased holding time at the high experimental temperature during initial alloy preparation results in a lower disorder of the Nd distribution in the alloys. Adjustment of the oxygen concentration in the U 1-yNd yO 2-X alloys with different Nd concentrations was accompanied by the formation of vacancies on the oxygen sublattice and a nanocrystalline component. The lattice parameters in the U 1-yNd yO 2-X alloys were also foundmore » to deviate significantly from Vegard's law when the Nd concentration was high (53%) and decreased with increasing oxygen concentration. Such changes indicate the formation of large vacancy concentrations during oxygen adjustment at these high temperatures. Finally, the change in the vacancy concentration after the oxygen adjustment was estimated relative to Nd concentration and oxygen stoichiometry.« less

Effect of annealing on microstructure evolution in CoFeB/MgO/CoFeB heterostructures by positron annihilation

NASA Astrophysics Data System (ADS)

Zhao, Chong-Jun; Lu, Xiang-An; Zhao, Zhi-Duo; Li, Ming-Hua; Zhang, Peng; Wang, Bao-Yi; Cao, Xing-Zhong; Zhang, Jing-Yan; Yu, Guang-Hua

2013-09-01

As one of the most powerful tools for investigation of defects of materials, positron annihilation spectroscopy was employed to explore the thermal effects on the film microstructure evolution in CoFeB/MgO/CoFeB heterostructures. It is found that high annealing temperature can drive vacancy defects agglomeration and ordering acceleration in the MgO barrier. Meanwhile, another important type of defects, vacancy clusters, which are formed via the agglomeration of vacancy defects in the MgO barrier after annealing, still exists inside the MgO barrier. All these behaviors in the MgO barrier could potentially impact the overall performance in MgO based magnetic tunnel junctions.

Computational study of Zn-doped quantum spin chains and ladders

NASA Astrophysics Data System (ADS)

Laukamp, Markus

In this dissertation, the powerful Density Matrix Renormalization Group method is applied to examine the properties of spin models. The method allows to determine accurately the properties of low lying states of finite systems of large sizes. The results gained with this technique are compared to results generated with exact diagonalization and Monte Carlo techniques. Spin models have been proposed to describe dimerized chains, ladders, two dimensional antiferromagnets, and other compounds. Here the focus is on the case where some spins are replaced by spinless vacancies. This happens e.g. upon Zn doping, when Cusp{2+} atoms are replaced by Znsp{2+}. A small percentage of vacancies rapidly destroys the spin gap, and their presence induces enhanced antiferromagnetic correlations near those vacancies. Since the phenomenon of enhanced antiferromagnetism is found to occur in several models and cluster geometries, a common simple explanation for its presence may exist. In this thesis it is argued that the resonating-valence-bond character of the spin correlations at short distances of a large variety of models is responsible for the presence of robust staggered spin correlations near vacancies and lattice edges. The phenomenon takes place regardless of the long distance properties of the ground state, and it is caused by a "pruning" of the available spin singlets in the vicinity of the vacancies. The effect produces a broadening of the low temperature NMR signal for the compounds analyzed here. This broadening should be experimentally observable in the structurally dimerized chain systems Cu(NOsb3)sb{*}2.5Hsb2O,\\ CuWOsb4,\\ (VO)sb2Psb2Osb7, and Srsb{14}Cusb{24}Osb{41}, in ladder materials such as SrCusb2Osb3, in the spin-Peierls systems CuGeOsb3 and NaVsb2Osb5, and in several others since it is a universal effect common to a wide variety of models and compounds. In addition, it is argued that the Neel order observed in SrCusb2Osb3 upon Zn doping is induced by the local antiferromagnetic order discussed in this paper, enhanced by a favorable ratio between the actual Heisenberg couplings along chains and rungs, as reported in recent experimental literature. Based on this reasoning it is here predicted that other ladder materials such as Zn-doped Cusb2(Csb5Hsb{12}Nsb2)sb2Clsb4 will not present Neel order at small Zn concentrations.

Atomistic simulations to characterize the influence of applied strain and PKA energy on radiation damage evolution in pure aluminum

NASA Astrophysics Data System (ADS)

Sahi, Qurat-ul-ain; Kim, Yong-Soo

2018-05-01

Knowledge of defects generation, their mobility, growth rate, and spatial distribution is the cornerstone for understanding the surface and structural evolution of a material used under irradiation conditions. In this study, molecular dynamics simulations were used to investigate the coupled effect of primary knock-on atom (PKA) energy and applied strain (uniaxial and hydrostatic) fields on primary radiation damage evolution in pure aluminum. Cascade damage simulations were carried out for PKA energy ranging between 1 and 20 keV and for applied strain values ranging between -2% and 2% at the fixed temperature of 300 K. Simulation results showed that as the atomic displacement cascade proceeds under uniaxial and hydrostatic strains, the peak and surviving number of Frenkel point defects increases with increasing tension; however, these increments were more prominent under larger volume changing deformations (hydrostatic strain). The percentage fraction of point defects that aggregate into clusters increases under tension conditions; compared to the reference conditions with no strain, these increases are around 13% and 7% for interstitials and vacancies, respectively (under 2% uniaxial strain), and 19% and 11% for interstitials and vacancies, respectively (under 2% hydrostatic strain). Clusters formed of vacancies and interstitials were both larger under tensile strain conditions, with increases in both the average and maximum cluster sizes. The rate of increase/decrease in the number of Frenkel pairs, their clustering, and their size distributions under expansion/compression strain conditions were higher for higher PKA energies. Overall, the present results suggest that strain effects should be considered carefully in radiation damage environments, specifically for conditions of low temperature and high radiation energy. Compressive strain conditions could be beneficial for materials used in nuclear reactor power systems.

Formation and evolution of oxygen-vacancy clusters in lead and tin doped silicon

NASA Astrophysics Data System (ADS)

Londos, C. A.; Aliprantis, D.; Sgourou, E. N.; Chroneos, A.; Pochet, P.

2012-06-01

Infrared spectroscopy (IR) measurements were used to investigate the effect of lead (Pb), tin (Sn), and (Pb, Sn) codoping on electron radiation-induced defects in silicon (Si). The study was mainly focused on oxygen-vacancy (VOn) clusters and in particular their formation and evolution upon annealing. It was determined that Pb causes a larger reduction in the production of the VO defect than Sn. In (Pb, Sn) co-doped Si isochronal anneals revealed that the evolution of VO increases substantially at ˜170 °C. This is attributed to the release of V from the SnV pair. Interestingly, in the corresponding evolution curves of VO in the Sn- and the Pb-doped samples, this inverse annealing stage is also present for the former while it is not present for the latter. This is attributed to the formation of PbV pairs that do not dissociate below 280 °C. The partial capture of V by Sn in co-doped samples is rationalized through the higher compressive local strain around Pb atoms that leads to a retardation of vacancy diffusion. The conversion of VO to the VO2 defect is substantially reduced in the Pb-doped sample. The evolution curves of VO and VO2 clusters in the isovalent doped Si samples hint the production of VO2 from other mechanisms (i.e., besides VO + Oi → VO2). For larger VOn clusters (n = 3,4), the signals are very weak in the Pb-doped sample, whereas for n ≥ 5, they are not present in the spectra. Conversely, bands related with the VO5 and VOnCs defects are present in the spectra of the Sn-doped and (Pb, Sn) codoped Si.

Short-range order clustering in BCC Fe-Mn alloys induced by severe plastic deformation

NASA Astrophysics Data System (ADS)

Shabashov, V. A.; Kozlov, K. A.; Sagaradze, V. V.; Nikolaev, A. L.; Lyashkov, K. A.; Semyonkin, V. A.; Voronin, V. I.

2018-03-01

The effect of severe plastic deformation, namely, high-pressure torsion (HPT) at different temperatures and ball milling (BM) at different time intervals, has been investigated by means of Mössbauer spectroscopy in Fe100-xMnx (x = 4.1, 6.8, 9) alloys. Deformation affects the short-range clustering (SRC) in BCC lattice. Two processes occur: destruction of SRC by moving dislocations and enhancement of the SRC by migration of non-equilibrium defects. Destruction of SRC prevails during HPT at 80-293 K; whereas enhancement of SRC dominates at 473-573 K. BM starts enhancing the SRC formation at as low as 293 K due to local heating at impacts. The efficiency of HPT in terms of enhancing SRC increases with increasing temperature. The authors suppose that at low temperatures, a significant fraction of vacancies are excluded from enhancing SRC because of formation of mobile bi- and tri-vacancies having low efficiency of enhancing SRC as compared to that of mono vacancies. Milling of BCC Fe100-xMnx alloys stabilises the BCC phase with respect to α → γ transition at subsequent isothermal annealing because of a high degree of work hardening and formation of composition inhomogeneity.

Multi-level modeling of total ionizing dose in a-silicon dioxide: First principles to circuits

NASA Astrophysics Data System (ADS)

Nicklaw, Christopher J.

Oxygen vacancies have long been known to be the dominant intrinsic defect in amorphous SiO2. They exist, in concentrations dependent on processing conditions, as neutral defects in thermal oxides without usually causing any significant deleterious effects, with some spatial and energy distribution. During irradiation they can capture holes and become positively charged E '-centers, contributing to device degradation. Over the years, a considerable database has been amassed on the dynamics of E' -centers in bulk SiO2 films, and near the interface under different irradiation and annealing conditions. Theoretical calculations so far have revealed the basic properties of prototype oxygen vacancies, primarily as they behave in either a crystalline quartz environment, or in small clusters that serve as a substitute for a real amorphous structure. To date at least three categories of E'-centers, existing at or above room temperature, have been observed in SiO2. The unifying feature is an unpaired electron on a threefold coordinated silicon atom, having the form O3 ≡ Si·. Feigl et al. identified the E'1 -center in crystalline quartz as a trapped hole on an oxygen vacancy, which causes an asymmetrical relaxation, resulting in a paramagnetic center. The unpaired electron in the E'1 -center is localized on the three-fold coordinated Si atoms, while the hole is localized on the other Si atom. Results from an ab initio statistical simulation examination of the behaviors of oxygen vacancies, within amorphous structures, identify a new form of the E'-center, the E'g5 and help in the understanding of the underlying physical mechanisms involved in switched-bias annealing, and electron paramagnetic resonance (EPR) studies. The results also suggest a common border trap, induced by trapped holes in SiO2, is a hole trapped at an oxygen vacancy defect, which can be compensated by an electron, as originally proposed by Lelis and co-workers at Harry Diamond Laboratories. This dissertation provides new insights into the basic mechanisms of a-SiO2 defects, and provides a link between basic mechanisms and Electronic Design Automation (EDA) tools, providing an enhanced design flow for radiation-resistant electronics.

Positron annihilation spectroscopic studies of solvothermally synthesized ZnO nanobipyramids and nanoparticles

NASA Astrophysics Data System (ADS)

Ghoshal, Tandra; Biswas, Subhajit; Kar, Soumitra; Chaudhuri, Subhadra; Nambissan, P. M. G.

2008-02-01

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.

Zn-vacancy related defects in ZnO grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Ling, F. C. C.; Luo, C. Q.; Wang, Z. L.; Anwand, W.; Wagner, A.

2017-02-01

Undoped and Ga-doped ZnO (002) films were grown c-sapphire using the pulsed laser deposition (PLD) method. Znvacancy related defects in the films were studied by different positron annihilation spectroscopy (PAS). These included Doppler broadening spectroscopy (DBS) employing a continuous monenergetic positron beam, and positron lifetime spectroscopy using a pulsed monoenergetic positron beam attached to an electron linear accelerator. Two kinds of Znvacancy related defects namely a monovacancy and a divacancy were identified in the films. In as-grown undoped samples grown with relatively low oxygen pressure P(O2)≤1.3 Pa, monovacancy is the dominant Zn-vacancy related defect. Annealing these samples at 900 oC induced Zn out-diffusion into the substrate and converted the monovacancy to divacancy. For the undoped samples grown with high P(O2)=5 Pa irrespective of the annealing temperature and the as-grown degenerate Ga-doped sample (n=1020 cm-3), divacancy is the dominant Zn-vacancy related defect. The clustering of vacancy will be discussed.

Positron annihilation spectroscopic studies of solvothermally synthesized ZnO nanobipyramids and nanoparticles.

PubMed

Ghoshal, Tandra; Biswas, Subhajit; Kar, Soumitra; Chaudhuri, Subhadra; Nambissan, P M G

2008-02-21

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.

Stochastic annealing simulations of defect interactions among subcascades

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heinisch, H.L.; Singh, B.N.

1997-04-01

The effects of the subcascade structure of high energy cascades on the temperature dependencies of annihilation, clustering and free defect production are investigated. The subcascade structure is simulated by closely spaced groups of lower energy MD cascades. The simulation results illustrate the strong influence of the defect configuration existing in the primary damage state on subsequent intracascade evolution. Other significant factors affecting the evolution of the defect distribution are the large differences in mobility and stability of vacancy and interstitial defects and the rapid one-dimensional diffusion of small, glissile interstitial loops produced directly in cascades. Annealing simulations are also performedmore » on high-energy, subcascade-producing cascades generated with the binary collision approximation and calibrated to MD results.« less

Oxygen-vacancy behavior in La2-xSrxCuO4-y by positron annihilation and oxygen diffusion

NASA Astrophysics Data System (ADS)

Smedskjaer, L. C.; Routbort, J. L.; Flandermeyer, B. K.; Rothman, S. J.; Legnini, D. G.; Baker, J. E.

1987-09-01

Oxygen-diffusion and positron-annihilation results for La2-xSrxCuO4-y compounds are reported. A qualitative explanation of the observed results is given on the basis of a model in which the oxygen-vacancy concentration in La2-xSrxCuO4-y is determined by Sr2+ ion clustering on the La sublattice. This model also leads to a maximum in the Cu3+ ion concentration as a function of the Sr2+ ion concentration.

Understanding lattice defects to influence ferromagnetic order of ZnO nanoparticles by Ni, Cu, Ce ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verma, Kuldeep Chand, E-mail: dkuldeep.physics@gmail.com; Kotnala, R.K., E-mail: rkkotnala@gmail.com

Future spintronics technologies based on diluted magnetic semiconductors (DMS) will rely heavily on a sound understanding of the microscopic origins of ferromagnetism in such materials. It remains unclear, however, whether the ferromagnetism in DMS is intrinsic - a precondition for spintronics - or due to dopant clustering. For this, we include a simultaneous doping from transition metal (Ni, Cu) and rare earth (Ce) ions in ZnO nanoparticles that increase the antiferromagnetic ordering to achieve high-T{sub c} ferromagnetism. Rietveld refinement of XRD patterns indicate that the dopant ions in ZnO had a wurtzite structure and the dopants, Ni{sup 2+}, Cu{sup 2+},more » Ce{sup 3+} ions, are highly influenced the lattice constants to induce lattice defects. The Ni, Cu, Ce ions in ZnO have nanoparticles formation than nanorods was observed in pure sample. FTIR involve some organic groups to induce lattice defects and the metal-oxygen bonding of Zn, Ni, Cu, Ce and O atoms to confirm wurtzite structure. Raman analysis evaluates the crystalline quality, structural disorder and defects in ZnO lattice with doping. Photoluminescence spectra have strong near-band-edge emission and visible emission bands responsible for defects due to oxygen vacancies. The energy band gap is calculated using Tauc relation. Room temperature ferromagnetism has been described due to bound magnetic polarons formation with Ni{sup 2+}, Cu{sup 2+}, Ce{sup 3+} ions in ZnO via oxygen vacancies. The zero field and field cooling SQUID measurement confirm the strength of antiferromagnetism in ZnO. The field cooling magnetization is studied by Curie-Weiss law that include antiferromagnetic interactions up to low temperature. The XPS spectra have involve +3/+4 oxidation states of Ce ions to influence the observed ferromagnetism. - Graphical abstract: The lattice defects/vacancies attributed by Ni and Ce ions in the wurtzite ZnO structure are responsible in high T{sub c} -ferromagnetism due to long-range magnetic interactions with cluster and spin-glass type growth. - Highlights: • Lattice defects/vacancies attributed high T{sub c} –ferromagnetism. • Transition metal and rare earth ions deform the wurtzite ZnO lattice to induce defects. • Oxygen vacancies are more favorable than Zn with Ni, Cu, Ce into ZnO. • Defects assisted long-range ferromagnetism of doped ZnO include cluster and spin-glass growth.« less

Stability and mobility of Cu-vacancy clusters in Fe-Cu alloys: A computational study based on the use of artificial neural networks for energy barrier calculations

NASA Astrophysics Data System (ADS)

Pascuet, M. I.; Castin, N.; Becquart, C. S.; Malerba, L.

2011-05-01

An atomistic kinetic Monte Carlo (AKMC) method has been applied to study the stability and mobility of copper-vacancy clusters in Fe. This information, which cannot be obtained directly from experimental measurements, is needed to parameterise models describing the nanostructure evolution under irradiation of Fe alloys (e.g. model alloys for reactor pressure vessel steels). The physical reliability of the AKMC method has been improved by employing artificial intelligence techniques for the regression of the activation energies required by the model as input. These energies are calculated allowing for the effects of local chemistry and relaxation, using an interatomic potential fitted to reproduce them as accurately as possible and the nudged-elastic-band method. The model validation was based on comparison with available ab initio calculations for verification of the used cohesive model, as well as with other models and theories.

Displacement cascades and defect annealing in tungsten, Part II: Object kinetic Monte Carlo Simulation of Tungsten Cascade Aging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2015-07-01

The results of object kinetic Monte Carlo (OKMC) simulations of the annealing of primary cascade damage in bulk tungsten using a comprehensive database of cascades obtained from molecular dynamics (Setyawan et al.) are described as a function of primary knock-on atom (PKA) energy at temperatures of 300, 1025 and 2050 K. An increase in SIA clustering coupled with a decrease in vacancy clustering with increasing temperature, in addition to the disparate mobilities of SIAs versus vacancies, causes an interesting effect of temperature on cascade annealing. The annealing efficiency (the ratio of the number of defects after and before annealing) exhibitsmore » an inverse U-shape curve as a function of temperature. The capabilities of the newly developed OKMC code KSOME (kinetic simulations of microstructure evolution) used to carry out these simulations are described.« less

Observation and control of blinking nitrogen-vacancy centres in discrete nanodiamonds.

PubMed

Bradac, C; Gaebel, T; Naidoo, N; Sellars, M J; Twamley, J; Brown, L J; Barnard, A S; Plakhotnik, T; Zvyagin, A V; Rabeau, J R

2010-05-01

Nitrogen-vacancy colour centres in diamond can undergo strong, spin-sensitive optical transitions under ambient conditions, which makes them attractive for applications in quantum optics, nanoscale magnetometry and biolabelling. Although nitrogen-vacancy centres have been observed in aggregated detonation nanodiamonds and milled nanodiamonds, they have not been observed in very small isolated nanodiamonds. Here, we report the first direct observation of nitrogen-vacancy centres in discrete 5-nm nanodiamonds at room temperature, including evidence for intermittency in the luminescence (blinking) from the nanodiamonds. We also show that it is possible to control this blinking by modifying the surface of the nanodiamonds.

The study of optical property of sapphire irradiated with 73 MeV Ca ions

NASA Astrophysics Data System (ADS)

Yang, Yitao; Zhang, Chonghong; Song, Yin; Gou, Jie; Liu, Juan; Xian, Yongqiang

2015-12-01

Single crystals of sapphire were irradiated with 73 MeV Ca ions at room temperature to the fluences of 0.1, 0.5 and 1.0 × 1014 ions/cm2. Optical properties of these samples were characterized by ultraviolet-visible spectrometry (UV-VIS) and fluorescence spectrometer (PL). In UV-VIS spectra, it is observed the absorbance bands from oxygen single vacancy (F and F+ color centers) and vacancy pair (F2+ and F22+ color centers). The oxygen single vacancy initially increases rapidly and then does not increase in the fluence range from 0.1 to 0.5 × 1014 ions/cm2. When the fluence is higher than 0.5 × 1014 ions/cm2, oxygen single vacancy starts to increase again. Oxygen vacancy pair increases monotonically with fluence for all irradiated samples. The variation of oxygen single vacancy with fluence is probably associated with the recombination of oxygen vacancies with Al interstitials and complex defect formation (such as vacancy clusters). From PL spectra, two emission bands around 3.1 and 2.34 eV are observed. The PL intensity of the emission band around 3.1 eV decreases for all the irradiated samples. For the emission band around 2.34 eV, the PL intensity initially decreases, and then increases with fluence. Meanwhile, the peak position of the emission band around 2.34 eV gradually shifts to high energy direction with increase of fluence. The decrease of the intensity of the emission bands around 3.1 and 2.34 eV could be induced by stress from the damage layer in the irradiated samples. The shift of peak position for the emission band around 2.34 eV is induced by the appearance of emission band from Al interstitials.

The effect of the morphology of supported subnanometer Pt clusters on the first and key step of CO 2 photoreduction [Morphology effect of supported subnanometer Pt clusters on first and key step of CO 2 photoreduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Chi -Ta; Wood, Brandon C.; Bhethanabotla, Venkat R.

2015-09-04

In this study, using density functional theory calculations, we investigate the influence of size-dependent cluster morphology on the synergistic catalytic properties of anatase TiO 2(101) surfaces decorated with subnanometer Pt clusters. Focusing on the formation of the key precursor in the CO 2 photoreduction reaction (bent CO 2 –), we find that flatter (2D-like) Pt clusters that “wet” the TiO 2 surface offer significantly less benefit than 3D-like Pt clusters. We attribute the differences to three factors. First, the 3D clusters provide a greater number of accessible Pt–TiO 2 interfacial sites with geometries that can aid CO 2 bond bendingmore » and charge transfer processes. Second, binding competition among each Pt–CO 2 bonding interaction mitigates maximum orbital overlaps, leading to insufficient CO 2 binding. Third and also most interestingly, the 3D clusters tend to possess higher structural fluxionality than the flatter clusters, which is shown to correlate positively with CO2 binding strength. The preferred morphology adopted by the clusters depends on several factors, including the cluster size and the presence of oxygen vacancies on the TiO 2 surface; this suggests a strategy for optimizing the synergistic effect between Pt clusters and TiO 2 surfaces for CO 2 photocatalysis. Clusters of ~6–8 atoms should provide the largest benefit, since they retain the desired 3D morphology, yet are small enough to exhibit high structural fluxionality. Electronic structure analysis provides additional insight into the electronic motivations for the enhanced binding of CO 2 on TiO 2-supported 3D Pt clusters, as well as suppressed binding on flattened, 2D-like clusters.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jia, E-mail: jia-zhu@jxnu.edu.cn, E-mail: zhangyf@fzu.edu.cn; Zhang, Hui; Tong, Yawen

The structures and electronic properties of bimetallic oxide CrW{sub 2}O{sub 9} clusters supported on the perfect and defective MgO(001) surfaces with three different color centers, F{sub S}{sup 0}, F{sub S}{sup +}, and F{sub S}{sup 2+} centers, respectively, have been investigated by density functional theory calculations. Our results show that the configurations, adsorption energies, charge transfers, and bonding modes of dispersed CrW{sub 2}O{sub 9} clusters are sensitive to the charge states of the F{sub S} centers. Compared with the gas-phase configuration, the CrW{sub 2}O{sub 9} clusters supported on the defective surfaces are distorted dramatically, which exhibit different chain structures. On themore » perfect MgO surface, the depositions of clusters do not involve obvious charge transfer, while the situation is quite different on the defective MgO(001) surfaces in which significant electron transfer occurs from the surface to the cluster. Interestingly, this effect becomes more remarkable for electron-rich oxygen vacancies (F{sub S}{sup 0} center) than that for electron-poor oxygen vacancies (F{sub S}{sup +} and F{sub S}{sup 2+} centers). Furthermore, our work reveals a progressive Brønsted acid sites where spin density preferentially localized around the Cr atoms not the W atoms for all kinds of F{sub S}-centers, indicating the better catalytic activities can be expected for CrW{sub 2}O{sub 9} cluster on defective MgO(001) surfaces with respect to the W{sub 3}O{sub 9} cluster.« less

Atomic diffusion in strain fields near solutes

NASA Astrophysics Data System (ADS)

Shropshire, Steven L.; Collins, Gary S.

1993-03-01

Annihilation reactions between mobile self-interstitial defects and complexes of vacancies with111In probe solutes in Au were studied. Measurements were made using the technique of perturbed angular correlations of gamma rays (PAC). Au samples were doped with complexes and plastically deformed at a low temperature to generate fluxes of self-interstitials. Changes in the concentrations of monovacancy (1V) to tetravacancy (4V) complexes induced by annihilation reactions were measured. These are now analysed using a system of coupled first-order equations in order to obtain interstitial annihilation cross sections of the complexes and the fractional amounts of different interstitial clusters in the flux. Relative cross sections obtained for Au are 1.0(1), 3.3(3), 1.2(2) and 7.5(2.5), respectively, for 1V to 4V complexes. The large increase in the cross sections with vacancy number is attributed to a progressive relaxation of the dilatational strain surrounding the oversized In solute as more vacancies are trapped. Also obtained from the analysis are values 0.34(5), 0.66(7), 0.0(1) and 0.0(2), respectively, for the fractions of mobile 1I to 4I clusters in deformed Au, indicating that di-interstitials are produced more readily than mono-interstitials during plastic deformation.

The stability of vacancy-like defects in amorphous silicon

NASA Astrophysics Data System (ADS)

Joly, Jean-Francois; Mousseau, Normand

2013-03-01

The contribution of vacancy-like defects to the relaxation of amorphous silicon (a-Si) has been a matter of debate for a long time. Due to their disordered nature, there is a large number local environments in which such a defect can exists. Previous numerical studies the vacancy in a-Si have been limited to small systems and very short timescales. Here we use kinectic ART (k-ART), an off-lattice kinetic Monte-Carlo simulation method with on-the-fly catalog building to study the time evolution of 1000 different single vacancy configurations in a well-relaxed a-Si model. Our results show that most of the vacancies are annihlated quickly. In fact, while 16% of the 1000 isolated vacancies survive for more than 1 ns of simulated time, 0.043% remain after 1 ms and only 6 of them survive longer than 0.1 second. Diffusion of the full vacancy is only seen in 19% of the configurations and diffusion usually leads directly to the annihilation of the defect. The actual annihilation event, in which one of the defective atoms fills the vacancy, is usually similar in all the configurations but local bonding environment heavily influence its activation barrier and relaxation energy.

Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides

NASA Astrophysics Data System (ADS)

Buckeridge, J.; Catlow, C. R. A.; Farrow, M. R.; Logsdail, A. J.; Scanlon, D. O.; Keal, T. W.; Sherwood, P.; Woodley, S. M.; Sokol, A. A.; Walsh, A.

2018-05-01

The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3 ,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3 , but also in SnO2 and ZnO.

76 FR 61355 - National Drinking Water Advisory Council; Request for Nominations

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-04

... water supply and public health protection (two vacancies), and the general public (two vacancies). DATES... represent appropriate State and local agencies concerned with water hygiene and public water supply; and... water hygiene and public water supply, of which two members shall represent small, rural public water...

Vacancies and holes in bulk and at 180° domain walls in lead titanate

NASA Astrophysics Data System (ADS)

Paillard, Charles; Geneste, Grégory; Bellaiche, Laurent; Dkhil, Brahim

2017-12-01

Domain walls (DWs) in ferroic materials exhibit a plethora of unexpected properties that are different from the adjacent ferroic domains. Still, the intrinsic/extrinsic origin of these properties remains an open question. Here, density functional theory calculations are used to investigate the interaction between vacancies and 180° DWs in the prototypical ferroelectric PbTiO3, with a special emphasis on cationic vacancies and released holes. All vacancies are more easily formed within the DW than in the domains. This is interpreted, using a phenomenological model, as the partial compensation of an extra-tensile stress when the defect is created inside the DW. Oxygen vacancies are found to be always fully ionized, independently of the thermodynamic conditions, while cationic vacancies can be either neutral or partially ionized (oxygen-rich conditions), or fully ionized (oxygen-poor conditions). Therefore, in oxidizing conditions, holes are induced by neutral and partially ionized Pb vacancies. In the bulk PbTiO3, these holes are more stable as delocalized rather than small polarons, but at DWs, the two forms are found to be possible.

Controlling diffusion for a self-healing radiation tolerant nanostructured ferritic alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Michael K.; Parish, Chad M.; Bei, Hongbin

Diffusion plays a major role in the stability of microstructures to extreme conditions of high temperature and high doses of irradiation. In nanostructured ferritic alloys, first principle calculations indicate that the binding energy of vacancies is reduced by the presence of oxygen, titanium and yttrium atoms. Therefore, the number of free vacancies available for diffusion can be greatly reduced. The mechanical properties of these alloys, compared to traditional wrought alloys of similar composition and grain structure, is distinctly different, and the ultrafine grained alloy is distinguished by a high number density of Ti–Y–O-enriched nanoclusters and solute clusters, which drives themore » mechanical response. When a displacement cascade interacts with a nanocluster, the solute atoms are locally dispersed into the matrix by ballistic collisions, but immediately a new nanocluster reforms due to the local supersaturation of solutes and vacancies until the excess vacancies are consumed. Furthermore, the result of these processes is a structural material for advanced energy systems with a microstructure that is self-healing and tolerant to high doses of radiation and high temperatures.« less

Controlling diffusion for a self-healing radiation tolerant nanostructured ferritic alloy

DOE PAGES

Miller, Michael K.; Parish, Chad M.; Bei, Hongbin

2014-12-18

Diffusion plays a major role in the stability of microstructures to extreme conditions of high temperature and high doses of irradiation. In nanostructured ferritic alloys, first principle calculations indicate that the binding energy of vacancies is reduced by the presence of oxygen, titanium and yttrium atoms. Therefore, the number of free vacancies available for diffusion can be greatly reduced. The mechanical properties of these alloys, compared to traditional wrought alloys of similar composition and grain structure, is distinctly different, and the ultrafine grained alloy is distinguished by a high number density of Ti–Y–O-enriched nanoclusters and solute clusters, which drives themore » mechanical response. When a displacement cascade interacts with a nanocluster, the solute atoms are locally dispersed into the matrix by ballistic collisions, but immediately a new nanocluster reforms due to the local supersaturation of solutes and vacancies until the excess vacancies are consumed. Furthermore, the result of these processes is a structural material for advanced energy systems with a microstructure that is self-healing and tolerant to high doses of radiation and high temperatures.« less

Controlling diffusion for a self-healing radiation tolerant nanostructured ferritic alloy

NASA Astrophysics Data System (ADS)

Miller, M. K.; Parish, C. M.; Bei, H.

2015-07-01

Diffusion plays a major role in the stability of microstructures to extreme conditions of high temperature and high doses of irradiation. In nanostructured ferritic alloys, first principle calculations indicate that the binding energy of vacancies is reduced by the presence of oxygen, titanium and yttrium atoms. Therefore, the number of free vacancies available for diffusion can be greatly reduced. The mechanical properties of these alloys, compared to traditional wrought alloys of similar composition and grain structure, is distinctly different, and the ultrafine grained alloy is distinguished by a high number density of Ti-Y-O-enriched nanoclusters and solute clusters, which drives the mechanical response. When a displacement cascade interacts with a nanocluster, the solute atoms are locally dispersed into the matrix by ballistic collisions, but immediately a new nanocluster reforms due to the local supersaturation of solutes and vacancies until the excess vacancies are consumed. The result of these processes is a structural material for advanced energy systems with a microstructure that is self-healing and tolerant to high doses of radiation and high temperatures.

Radiation-induced segregation and precipitation behaviours around cascade clusters under electron irradiation.

PubMed

Sueishi, Yuichiro; Sakaguchi, Norihito; Shibayama, Tamaki; Kinoshita, Hiroshi; Takahashi, Heishichiro

2003-01-01

We have investigated the formation of cascade clusters and structural changes in them by means of electron irradiation following ion irradiation in an austenitic stainless steel. Almost all of the cascade clusters, which were introduced by the ion irradiation, grew to form interstitial-type dislocation loops or vacancy-type stacking fault tetrahedra after electron irradiation at 623 K, whereas a few of the dot-type clusters remained in the matrix. It was possible to recognize the concentration of Ni and Si by radiation-induced segregation around the dot-type clusters. After electron irradiation at 773 K, we found that some cascade clusters became precipitates (delta-Ni2Si) due to radiation-induced precipitation. This suggests that the cascade clusters could directly become precipitation sites during irradiation.

Analysis of the local structure around Cr3+ centers in perovskite KMgF3 using both ab initio (DFT) and semi-empirical (SPM) calculations

NASA Astrophysics Data System (ADS)

Emül, Y.; Erbahar, D.; Açıkgöz, M.

2014-11-01

The local structure around Cr3+ centers in perovskite KMgF3 crystal have been investigated through the applications of both an ab-initio, density functional theory (DFT), and a semi empirical, superposition model (SPM), analyses. A supercell approach is used for DFT calculations. All the tetragonal (Cr3+-VMg and Cr3+-Li+), trigonal (Cr3+-VK), and CrF5O cluster centers have been considered with various structural models based on the previously suggested experimental inferences. The significant structural changes around the Cr3+ centers induced by Mg2+ or K+ vacancies and the Li substitution at those vacancy sites have been determined and discussed by means of charge distribution. This study provides insight on both the roles of Mg2+ and K+ vacancies and Li+ ion in the local structural properties around Cr3+ centers in KMgF3.

Phononic thermal conductivity in silicene: the role of vacancy defects and boundary scattering

NASA Astrophysics Data System (ADS)

Barati, M.; Vazifehshenas, T.; Salavati-fard, T.; Farmanbar, M.

2018-04-01

We calculate the thermal conductivity of free-standing silicene using the phonon Boltzmann transport equation within the relaxation time approximation. In this calculation, we investigate the effects of sample size and different scattering mechanisms such as phonon–phonon, phonon-boundary, phonon-isotope and phonon-vacancy defect. We obtain some similar results to earlier works using a different model and provide a more detailed analysis of the phonon conduction behavior and various mode contributions. We show that the dominant contribution to the thermal conductivity of silicene, which originates from the in-plane acoustic branches, is about 70% at room temperature and this contribution becomes larger by considering vacancy defects. Our results indicate that while the thermal conductivity of silicene is significantly suppressed by the vacancy defects, the effect of isotopes on the phononic transport is small. Our calculations demonstrate that by removing only one of every 400 silicon atoms, a substantial reduction of about 58% in thermal conductivity is achieved. Furthermore, we find that the phonon-boundary scattering is important in defectless and small-size silicene samples, especially at low temperatures.

Defect studies of nanocrystalline zirconia powders and sintered ceramics

NASA Astrophysics Data System (ADS)

Čížek, Jakub; Melikhova, Oksana; Procházka, Ivan; Kuriplach, Jan; Kužel, Radomír; Brauer, Gerhard; Anwand, Wolfgang; Konstantinova, Tatyana E.; Danilenko, Igor A.

2010-01-01

The main objective of the present paper is to communicate a study of defects behavior in zirconia-based nanomaterials—pressure-compacted yttria-stabilized zirconia (YSZ) nanopowders with different contents of Y2O3 and ceramics obtained by sintering the YZS nanopowders. In addition, YZS single crystals were also investigated. Positron annihilation techniques including positron lifetime and coincidence Doppler broadening with a conventional positron source and Doppler broadening experiments on a monoenergetic positron beam were involved in this study as the principal tools. These techniques were supplemented with transmission electron microscopy and x-ray diffraction observations. In order to get better support of the experimental data interpretation, the state-of-art theoretical calculations of positron parameters were performed for the perfect ZrO2 lattice and selected defect configurations in the YSZ. Theoretical calculations have indicated that neither the oxygen vacancies nor their neutral complexes with substitutional yttrium atoms are capable of positron trapping. On the other hand, the zirconium vacancies are deep positron traps and obviously are responsible for the saturated positron trapping observed in the YSZ single crystals. In the compacted YSZ nanopowders, a majority of positrons is trapped either in the vacancylike defects situated in the negative space-charge layers along grain boundaries (τ1≈185ps) or in vacancy clusters at intersections of grain boundaries (τ2≈370ps) . The intensity ratio I2/I1 was found to be correlated with the mean grain size d as I2/I1˜d-2 . A small fraction of positrons (≈10%) form positronium in large pores (τ3≈2ns,τ4≈30ns) . A significant grain growth during sintering of the YSZ nanopowders above 1000°C was observed.

First-principles study of stability of helium-vacancy complexes below tungsten surfaces

NASA Astrophysics Data System (ADS)

Yang, L.; Bergstrom, Z. J.; Wirth, B. D.

2018-05-01

Density function theory calculations have been performed to study the stability of small helium-vacancy (He-V) complexes near tungsten (W) surfaces of different orientations. The results show that the stability of vacancies and He-V complexes near W surfaces depends on surface orientation. However, as the depth below the surface increased beyond about 0.65-0.8 nm, the stability of He-V complexes is similar to the bulk. The formation energies of single vacancies and di-vacancies at depths less than 0.2 nm below the W(110) surface are higher than for W(100) or W(111) surfaces, but have lower energies at depths between 0.2 and 0.65 nm. The formation energies of He-V complexes below W surfaces are sensitive to the geometric orientation of the He and vacancy, especially below the W(111) surface. Within about 0.2 nm of the top layer of the three W surfaces, neither a vacancy nor a di-vacancy can trap He. Because of the lower formation energy of He-V complexes and higher He binding energy to vacancies below the W(110) surface, the He desorption from the W(110) surface is less likely to occur than from the W(100) and W(111) surfaces. Our results provide fundamental insight into the differences in surface morphology changes observed in single W crystals with different surface orientations under He plasma exposure.

Development of a Scanning Microscale Fast Neutron Irradiation Platform for Examining the Correlation Between Local Neutron Damage and Graphite Microstructure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pinhero, Patrick; Windes, William

2015-03-10

The fast particle radiation damage effect of graphite, a main material in current and future nuclear reactors, has significant influence on the utilization of this material in fission and fusion plants. Atoms on graphite crystals can be easily replaced or dislocated by fast protons and result in interstitials and vacancies. The currently accepted model indicates that after most of the interstitials recombine with vacancies, surviving interstitials form clusters and furthermore gather to create loops with each other between layers. Meanwhile, surviving vacancies and interstitials form dislocation loops on the layers. The growth of these inserted layers cause the dimensional increase,more » i.e. swelling, of graphite. Interstitial and vacancy dislocation loops have been reported and they can easily been observed by electron microscope. However, observation of the intermediate atom clusters becomes is paramount in helping prove this model. We utilize fast protons generated from the University of Missouri Research Reactor (MURR) cyclotron to irradiate highly- oriented pyrolytic graphite (HOPG) as target for this research. Post-irradiation examination (PIE) of dosed targets with high-resolution transmission electron microscopy (HRTEM) has permit observation and analysis of clusters and dislocation loops to support the proposed theory. Another part of the research is to validate M.I. Heggie’s Ruck and Tuck model, which introduced graphite layers may fold under fast particle irradiation. Again, we employed microscopy to image irradiated specimens to determine how the extent of Ruck and Tuck by calculating the number of folds as a function of dose. Our most significant accomplishment is the invention of a novel class of high-intensity pure beta-emitters for long-term lightweight batteries. We have filed four invention disclosure records based on the research conducted in this project. These batteries are lightweight because they consist of carbon and tritium and can be fabricated to conform to many geometric shapes. In addition, we have published eight peer-reviewed American Nuclear Society (ANS) transactions, and presented our findings at ANS National Meetings, and several universities.« less

Fast nanoscale addressability of nitrogen-vacancy spins via coupling to a dynamic ferromagnetic vortex

PubMed Central

Wolf, M. S.; Badea, R.; Berezovsky, J.

2016-01-01

The core of a ferromagnetic vortex domain creates a strong, localized magnetic field, which can be manipulated on nanosecond timescales, providing a platform for addressing and controlling individual nitrogen-vacancy centre spins in diamond at room temperature, with nanometre-scale resolution. Here, we show that the ferromagnetic vortex can be driven into proximity with a nitrogen-vacancy defect using small applied magnetic fields, inducing significant nitrogen-vacancy spin splitting. We also find that the magnetic field gradient produced by the vortex is sufficient to address spins separated by nanometre-length scales. By applying a microwave-frequency magnetic field, we drive both the vortex and the nitrogen-vacancy spins, resulting in enhanced coherent rotation of the spin state. Finally, we demonstrate that by driving the vortex on fast timescales, sequential addressing and coherent manipulation of spins is possible on ∼100 ns timescales. PMID:27296550

Internal friction and vulnerability of mixed alkali glasses.

PubMed

Peibst, Robby; Schott, Stephan; Maass, Philipp

2005-09-09

Based on a hopping model we show how the mixed alkali effect in glasses can be understood if only a small fraction c(V) of the available sites for the mobile ions is vacant. In particular, we reproduce the peculiar behavior of the internal friction and the steep fall ("vulnerability") of the mobility of the majority ion upon small replacements by the minority ion. The single and mixed alkali internal friction peaks are caused by ion-vacancy and ion-ion exchange processes. If c(V) is small, they can become comparable in height even at small mixing ratios. The large vulnerability is explained by a trapping of vacancies induced by the minority ions. Reasonable choices of model parameters yield typical behaviors found in experiments.

Phosphorus vacancy cluster model for phosphorus diffusion gettering of metals in Si

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Renyu; Trzynadlowski, Bart; Dunham, Scott T.

2014-02-07

In this work, we develop models for the gettering of metals in silicon by high phosphorus concentration. We first performed ab initio calculations to determine favorable configurations of complexes involving phosphorus and transition metals (Fe, Cu, Cr, Ni, Ti, Mo, and W). Our ab initio calculations found that the P{sub 4}V cluster, a vacancy surrounded by 4 nearest-neighbor phosphorus atoms, which is the most favorable inactive P species in heavily doped Si, strongly binds metals such as Cu, Cr, Ni, and Fe. Based on the calculated binding energies, we build continuum models to describe the P deactivation and Fe getteringmore » processes with model parameters calibrated against experimental data. In contrast to previous models assuming metal-P{sub 1}V or metal-P{sub 2}V as the gettered species, the binding of metals to P{sub 4}V satisfactorily explains the experimentally observed strong gettering behavior at high phosphorus concentrations.« less

COI oxidation on a single Pd atom supported on magnesia.

PubMed

Abbet, S; Heiz, U; Häkkinen, H; Landman, U

2001-06-25

The oxidation of CO on single Pd atoms anchored to MgO(100) surface oxygen vacancies is studied with temperature-programmed-reaction mass spectrometry and infrared spectroscopy. In one-heating-cycle experiments, CO(2), formed from O(2) and CO preadsorbed at 90 K, is detected at 260 and 500 K. Ab-initio simulations suggest two reaction routes, with Pd(CO)(2)O(2) and PdCO(3)CO found as precursors for the low and high temperature channels, respectively. Both reactions result in annealing of the vacancy and induce migration and coalescence of the remaining Pd-CO to form larger clusters.

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

NASA Technical Reports Server (NTRS)

Good, Brian S.

2015-01-01

Ytterbium disilicate is of interest as a potential environmental barrier coating for aerospace applications, notably for use in next generation jet turbine engines. In such applications, the transport of oxygen and water vapor through these coatings to the ceramic substrate is undesirable if high temperature oxidation is to be avoided. In an effort to understand the diffusion process in these materials, we have performed kinetic Monte Carlo simulations of vacancy-mediated and interstitial oxygen diffusion in Ytterbium disilicate. Oxygen vacancy and interstitial site energies, vacancy and interstitial formation energies, and migration barrier energies were computed using Density Functional Theory. We have found that, in the case of vacancy-mediated diffusion, many potential diffusion paths involve large barrier energies, but some paths have barrier energies smaller than one electron volt. However, computed vacancy formation energies suggest that the intrinsic vacancy concentration is small. In the case of interstitial diffusion, migration barrier energies are typically around one electron volt, but the interstitial defect formation energies are positive, with the result that the disilicate is unlikely to exhibit experience significant oxygen permeability except at very high temperature.

Equilibrium and diffusion studies of metal-hydrogen systems

NASA Astrophysics Data System (ADS)

Maroevic, Petar

Several new methods and models have been developed pertaining to equilibrium properties of hydrogen in random binary substitutional alloys at room and lower temperatures, describing both statistics and kinetics of hydrogen in them. They represent a solution to the problem of the complete Fermi-Dirac description which is physically appropriate for these systems. Hydrogen diffusion which proceeds via lattice assisted quantum tunneling at room and lower temperatures requires a new and different description from the one based on the thermal hopping picture, which pertains only to relatively high temperatures. It is also shown that the analogs of the solution to the Fermi-Dirac problem of hydrogen can be successfully applied to the description of vacancies in a hydrogenated system, a phenomena known to occur due to high hydrogen-vacancy binding energies and the creation of hydrogen-vacancy clusters. The solution based on this model applies to much lower temperatures and higher concentrations than the tradition alone. This methodology has also been applied to the surface problem where very large vacancy and hydrogen concentrations occur. This is of special importance since mechanical properties are known to be greatly affected by the surface. As another consequence of hydrogen induced vacancies, hydrogen induced lattice migration (HILM) occurs. This has been demonstrated in our electrical resistivity study of palladium wires where recrystallization and annealing effects were observed upon hydrogen-heat-treatment (HHT).

A study of the effect of helium concentration and displacement damage on the microstructure of helium ion irradiated tungsten

NASA Astrophysics Data System (ADS)

Harrison, R. W.; Greaves, G.; Hinks, J. A.; Donnelly, S. E.

2017-11-01

Transmission electron microscopy (TEM) with in-situ He ion irradiation has been used to examine the damage microstructure of W when varying the helium concentration to displacement damage ratio, irradiation temperature and total dose. Irradiations employed 15, 60 or 85 keV He ions, at temperatures between 500 and 1000 °C up to doses of ∼3.0 DPA. Once nucleated and grown to an observable size in the TEM, bubble diameter as a function of irradiation dose did not measurably increase at irradiation temperatures of 500 °C between 1.0 and 3.0 DPA; this is attributed to the low mobility of vacancies and He/vacancy complexes at these temperatures. Bubble diameter increased slightly for irradiation temperatures of 750 °C and rapidly increased when irradiated at 1000 °C. Dislocation loops were observed at irradiation temperatures of 500 and 750 °C and no loops were observed at 1000 °C. Burgers vectors of the dislocations were determined to be b = ±½<111> type only and both vacancy and interstitial loops were observed. The proportion of interstitial loops increased with He-appm/DPA ratio and this is attributed to the concomitant increase in bubble areal density, which reduces the vacancy flux for both the growth of vacancy-type loops and the annihilation of interstitial clusters.

Argon-plasma-controlled optical reset in the SiO2/Cu filamentary resistive memory stack

NASA Astrophysics Data System (ADS)

Kawashima, T.; Yew, K. S.; Zhou, Y.; Ang, D. S.; Zhang, H. Z.; Kyuno, K.

2018-05-01

We show that resistive switching in the SiO2/Cu stack can be modified by a brief exposure of the oxide to an Ar plasma. The set voltage of the SiO2/Cu stack is reduced by 33%, while the breakdown voltage of the SiO2/Si stack (control) is almost unchanged. Besides, the Ar plasma treatment suppresses the negative photoconductivity or optical resistance reset effect, where the electrically formed filamentary conductive path consisting of Cu-ion and oxygen-vacancy clusters is disrupted by the recombination of the oxygen vacancies with nearby light-excited oxygen ions. From the enhanced O-H peak in the Fourier-transform infrared spectrum of the plasma-treated oxide, it is proposed that the Ar plasma has created more oxygen vacancies in the surface region of the oxide. These vacancies in turn adsorb water molecules, which act as counter anions (OH-) promoting the migration of Cu cations into the oxide and forming a more complete Cu filament that is less responsive to light. The finding points to the prospect of a control over the optical resistance reset effect by a simple surface treatment step.

Ferroelectric-ferromagnetic coupling in hexagonal YMnO3 film

NASA Astrophysics Data System (ADS)

Cheng, Shaobo; Li, Menglei; Deng, Shiqing; Bao, Shanyong; Tang, Peizhe; Duan, Wenhui; Ma, Jing; Nan, Cewen; Zhu, Jing

Simultaneously achieving ferroelectricity and ferromagnetism in a single phase material is an important research topic in recent decades. Here, we demonstrate that with the modulation of oxygen vacancies, the ferroelectric-ferromagnetic coupling can be realized in the typical hexagonal manganite: YMnO3. The first-principal calculations are used to reveal the importance of oxygen vacancies on the alterations of magnetic behaviors for YMnO3. In order to obtain net magnetic moments, the on-top oxygen vacancies of MnO5 clusters should be created, thus the initial 2D spin frustration structure of Mn ions will be broken. By growing YMnO3 film on Al2O3 substrate, large in-plane compressive strain is induced, thus we can experimentally realize the on-top oxygen vacancies. With the help of SQUID and spherical aberration corrected TEM, the magnetic moments are experimentally measured and the correlations between the crystal structures and magnetic properties can be clearly understood. Our findings may pave a way for future applications of single phase multiferroic materials. National 973 Project of China (2015CB654902, 2011CB606405) and Chinese National Natural Science Foundation (11374174, 51390471).

Self-assembly of Carbon Vacancies in Sub-stoichiometric ZrC1−x

PubMed Central

Zhang, Yanhui; Liu, Bin; Wang, Jingyang

2015-01-01

Sub-stoichiometric interstitial compounds, including binary transition metal carbides (MC1−x), maintain structural stability even if they accommodate abundant anion vacancies. This unique character endows them with variable-composition, diverse-configuration and controllable-performance through composition and structure design. Herein, the evolution of carbon vacancy (VC) configuration in sub-stoichiometric ZrC1−x is investigated by combining the cluster expansion method and first-principles calculations. We report the interesting self-assembly of VCs and the fingerprint VC configuration (VC triplet constructed by 3rd nearest neighboring vacancies) in all the low energy structures of ZrC1−x. When VC concentration is higher than the critical value of 0.5 (x > 0.5), the 2nd nearest neighboring VC configurations with strongly repulsive interaction inevitably appear, and meanwhile, the system energy (or formation enthalpy) of ZrC1−x increases sharply which suggests the material may lose phase stability. The present results clarify why ZrC1−x bears a huge amount of VCs, tends towards VC ordering, and retains stability up to a stoichiometry of x = 0.5. PMID:26667083

Patterned growth of p-type MoS 2 atomic layers using sol-gel as precursor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Wei; Lin, Junhao; Feng, Wei

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to themore » incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2, which shows strong rectifying behavior.« less

Patterned growth of p-type MoS 2 atomic layers using sol-gel as precursor

DOE PAGES

Zheng, Wei; Lin, Junhao; Feng, Wei; ...

2016-07-19

2D layered MoS 2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS 2 atomic layers grown by conventional chemical vapor deposition techniques are n-type due to the abundant sulfur vacancies. Facile production of MoS 2 atomic layers with p-type behavior, however, remains challenging. Here, a novel one-step growth has been developed to attain p-type MoS 2 layers in large scale by using Mo-containing sol–gel, including 1% tungsten (W). Atomic-resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as-grown MoS 2 film due to themore » incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p-type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS 2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft-lithography techniques, which enables patterned growth of p-type MoS 2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Lastly, an atomically thin p–n junction is fabricated by the as-prepared MoS 2, which shows strong rectifying behavior.« less

A Unifying Perspective on Oxygen Vacancies in Wide Band Gap Oxides.

PubMed

Linderälv, Christopher; Lindman, Anders; Erhart, Paul

2018-01-04

Wide band gap oxides are versatile materials with numerous applications in research and technology. Many properties of these materials are intimately related to defects, with the most important defect being the oxygen vacancy. Here, using electronic structure calculations, we show that the charge transition level (CTL) and eigenstates associated with oxygen vacancies, which to a large extent determine their electronic properties, are confined to a rather narrow energy range, even while band gap and the electronic structure of the conduction band vary substantially. Vacancies are classified according to their character (deep versus shallow), which shows that the alignment of electronic eigenenergies and CTL can be understood in terms of the transition between cavity-like localized levels in the large band gap limit and strong coupling between conduction band and vacancy states for small to medium band gaps. We consider both conventional and hybrid functionals and demonstrate that the former yields results in very good agreement with the latter provided that band edge alignment is taken into account.

Impact of homogeneous strain on uranium vacancy diffusion in uranium dioxide

DOE PAGES

Goyal, Anuj; Phillpot, Simon R.; Subramanian, Gopinath; ...

2015-03-03

We present a detailed mechanism of, and the effect of homogeneous strains on, the migration of uranium vacancies in UO 2. Vacancy migration pathways and barriers are identified using density functional theory and the effect of uniform strain fields are accounted for using the dipole tensor approach. We report complex migration pathways and noncubic symmetry associated with the uranium vacancy in UO 2 and show that these complexities need to be carefully accounted for to predict the correct diffusion behavior of uranium vacancies. We show that under homogeneous strain fields, only the dipole tensor of the saddle with respect tomore » the minimum is required to correctly predict the change in the energy barrier between the strained and the unstrained case. Diffusivities are computed using kinetic Monte Carlo simulations for both neutral and fully charged state of uranium single and divacancies. We calculate the effect of strain on migration barriers in the temperature range 800–1800 K for both vacancy types. Homogeneous strains as small as 2% have a considerable effect on diffusivity of both single and divacancies of uranium, with the effect of strain being more pronounced for single vacancies than divacancies. In contrast, the response of a given defect to strain is less sensitive to changes in the charge state of the defect. Further, strain leads to anisotropies in the mobility of the vacancy and the degree of anisotropy is very sensitive to the nature of the applied strain field for strain of equal magnitude. Our results indicate that the influence of strain on vacancy diffusivity will be significantly greater when single vacancies dominate the defect structure, such as sintering, while the effects will be much less substantial under irradiation conditions where divacancies dominate.« less

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

NASA Astrophysics Data System (ADS)

Good, Brian

2015-03-01

Ytterbium disilicate is of interest as a potential environmental barrier coating for aerospace applications, notably for use in next generation jet turbine engines. In such applications, the diffusion of oxygen and water vapor through these coatings is undesirable if high temperature corrosion is to be avoided. In an effort to understand the diffusion process in these materials, we have performed kinetic Monte Carlo simulations of vacancy-mediated oxygen diffusion in Ytterbium Disilicate. Oxygen vacancy site energies and diffusion barrier energies are computed using Density Functional Theory. We find that many potential diffusion paths involve large barrier energies, but some paths have barrier energies smaller than one electron volt. However, computed vacancy formation energies suggest that the intrinsic vacancy concentration is small in the pure material, with the result that the material is unlikely to exhibit significant oxygen permeability.

Crystallographic texture in oxide-dispersion-strengthened alloys

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1982-01-01

Crystallographic and elastic moduli data are presented which document the degree of texture in several oxide dispersion-strengthened (ODS) nickel-base alloys. The existence of strong crystallographic textures in such multicrystalline alloys is considered important, since the small angle grain boundaries may be partially responsible for creep threshold stresses. Gleiter (1979) has shown that ideal, low energy boundaries will act as vacancy sources only when the applied stress is greater than a threshold stress, while large angle grain boundaries will emit vacancies at all stress levels. The continued operation of a net vacancy in an ODS alloy must be avoided, since it will lead to a localized disruption of the microstructure.

Identification of vacancy-oxygen complexes in oxygen-implanted silicon probed with slow positrons

NASA Astrophysics Data System (ADS)

Fujinami, M.; Miyagoe, T.; Sawada, T.; Suzuki, R.; Ohdaira, T.; Akahane, T.

2004-04-01

Defects and their annealing behavior for low (2×1015/cm2) and high (1.7×1018/cm2) doses of 180 keV oxygen-implanted silicon have been investigated by the coincidence Doppler broadening (CDB) and lifetime measurements in variable-energy positron annihilation spectroscopy. In the low-dose sample, divacancies are induced throughout the entire implantation region. In the vacancy-oxygen coexisting region (300-500 nm depths), by raising the annealing temperature to 600 °C, vacancy-oxygen VxOy complexes with one vacant site are formed and, simultaneously, the migration of oxygen begins to takes place. In the vacancy-rich region (-200 nm depths), the evolution of simple vacancy clusters to V4 is mainly observed below 600 °C. From CDB and lifetime measurements, it has been proven that after annealing at 800 °C, the VxOy complexes are formed throughout the implanted region and they contain four vacant sites and a high ratio of y to x. On the other hand, high-dose implantation at 550 °C produces the VxOy complexes with a lifetime of a 430 ps in the near-surface region (less than 200 nm deep) and annealing at 1100 °C leads to the highest ratio of y to x. These complexes cannot be annealed out even by annealing at 1350 °C, and their structure is found to be very similar to that for the electron-irradiated amorphous SiO2.

Divacancy complexes induced by Cu diffusion in Zn-doped GaAs

NASA Astrophysics Data System (ADS)

Elsayed, M.; Krause-Rehberg, R.; Korff, B.; Ratschinski, I.; Leipner, H. S.

2013-08-01

Positron annihilation spectroscopy was applied to investigate the nature and thermal behavior of defects induced by Cu diffusion in Zn-doped p-type GaAs crystals. Cu atoms were intentionally introduced in the GaAs lattice through thermally activated diffusion from a thin Cu capping layer at 1100 °C under defined arsenic vapor pressure. During isochronal annealing of the obtained Cu-diffused GaAs in the temperature range of 450-850 K, vacancy clusters were found to form, grow and finally disappear. We found that annealing at 650 K triggers the formation of divacancies, whereas further increasing in the annealing temperature up to 750 K leads to the formation of divacancy-copper complexes. The observations suggest that the formation of these vacancy-like defects in GaAs is related to the out-diffusion of Cu. Two kinds of acceptors are detected with a concentration of about 1016 - 1017 cm-3, negative ions and arsenic vacancy copper complexes. Transmission electron microscopy showed the presence of voids and Cu precipitates which are not observed by positron measurements. The positron binding energy to shallow traps is estimated using the positron trapping model. Coincidence Doppler broadening spectroscopy showed the presence of Cu in the immediate vicinity of the detected vacancies. Theoretical calculations suggested that the detected defect is VGaVAs-2CuGa.

Thermal conductivity of electron-irradiated graphene

NASA Astrophysics Data System (ADS)

Weerasinghe, Asanka; Ramasubramaniam, Ashwin; Maroudas, Dimitrios

2017-10-01

We report results of a systematic analysis of thermal transport in electron-irradiated, including irradiation-induced amorphous, graphene sheets based on nonequilibrium molecular-dynamics simulations. We focus on the dependence of the thermal conductivity, k, of the irradiated graphene sheets on the inserted irradiation defect density, c, as well as the extent of defect passivation with hydrogen atoms. While the thermal conductivity of irradiated graphene decreases precipitously from that of pristine graphene, k0, upon introducing a low vacancy concentration, c < 1%, in the graphene lattice, further reduction of the thermal conductivity with the increasing vacancy concentration exhibits a weaker dependence on c until the amorphization threshold. Beyond the onset of amorphization, the dependence of thermal conductivity on the vacancy concentration becomes significantly weaker, and k practically reaches a plateau value. Throughout the range of c and at all hydrogenation levels examined, the correlation k = k0(1 + αc)-1 gives an excellent description of the simulation results. The value of the coefficient α captures the overall strength of the numerous phonon scattering centers in the irradiated graphene sheets, which include monovacancies, vacancy clusters, carbon ring reconstructions, disorder, and a rough nonplanar sheet morphology. Hydrogen passivation increases the value of α, but the effect becomes very minor beyond the amorphization threshold.

Fast nanoscale addressability of nitrogen-vacancy spins via coupling to a dynamic ferromagnetic vortex

DOE PAGES

Wolf, M. S.; Badea, R.; Berezovsky, J.

2016-06-14

The core of a ferromagnetic vortex domain creates a strong, localized magnetic field, which can be manipulated on nanosecond timescales, providing a platform for addressing and controlling individual nitrogen-vacancy centre spins in diamond at room temperature, with nanometre-scale resolution. Here, we show that the ferromagnetic vortex can be driven into proximity with a nitrogen-vacancy defect using small applied magnetic fields, inducing significant nitrogen-vacancy spin splitting. We also find that the magnetic field gradient produced by the vortex is sufficient to address spins separated by nanometre-length scales. By applying a microwave-frequency magnetic field, we drive both the vortex and the nitrogen-vacancymore » spins, resulting in enhanced coherent rotation of the spin state. Lastly, we demonstrate that by driving the vortex on fast timescales, sequential addressing and coherent manipulation of spins is possible on ~ 100 ns timescales.« less

Metal nanostructures: from clusters to nanocatalysis and sensors

NASA Astrophysics Data System (ADS)

Smirnov, B. M.

2017-12-01

The properties of metal clusters and nanostructures composed of them are reviewed. Various existing methods for the generation of intense beams of metal clusters and their subsequent conversion into nanostructures are compared. Processes of the flow of a buffer gas with active molecules through a nanostructure are analyzed as a basis of using nanostructures for catalytic applications. The propagation of an electric signal through a nanostructure is studied by analogy with a macroscopic metal. An analysis is given of how a nanostructure changes its resistance as active molecules attach to its surface and are converted into negative ions. These negative ions induce the formation of positively charged vacancies inside the metal conductor and attract the vacancies to together change the resistance of the metal nanostructure. The physical basis is considered for using metal clusters and nanostructures composed of them to create new materials in the form of a porous metal film on the surface of an object. The fundamentals of nanocatalysis are reviewed. Semiconductor conductometric sensors consisting of bound nanoscale grains or fibers acting as a conductor are compared with metal sensors conducting via a percolation cluster, a fractal fiber, or a bunch of interwoven nanofibers formed in superfluid helium. It is shown that sensors on the basis of metal nanostructures are characterized by a higher sensitivity than semiconductor ones, but are not selective. Measurements using metal sensors involve two stages, one of which measures to high precision the attachment rate of active molecules to the sensor conductor, and in the other one the surface of metal nanostructures is cleaned from the attached molecules using a gas discharge plasma (in particular, capillary discharge) with a subsequent chromatography analysis for products of cleaning.

In situ study of emerging metallicity on ion-bombarded SrTiO3 surface

NASA Astrophysics Data System (ADS)

Gross, Heiko; Bansal, Namrata; Kim, Yong-Seung; Oh, Seongshik

2011-10-01

We report how argon bombardment induces metallic states on the surface of insulating SrTiO3 at different temperatures by combining in situ conductance measurements and model calculations. At cryogenic temperatures, ionic bombardment created a thin-but much thicker than the argon-penetration depth-steady-state oxygen-vacant layer, leading to a highly-concentric metallic state. Near room temperatures, however, significant thermal diffusion occurred and the metallic state continuously diffused into the bulk, leaving only low concentration of electron carriers on the surface. Analysis of the discrepancy between the experiments and the models also provided evidence for vacancy clustering, which seems to occur during any vacancy formation process and affects the observed conductance.

High-resolution magnetic resonance spectroscopy using a solid-state spin sensor

NASA Astrophysics Data System (ADS)

Glenn, David R.; Bucher, Dominik B.; Lee, Junghyun; Lukin, Mikhail D.; Park, Hongkun; Walsworth, Ronald L.

2018-03-01

Quantum systems that consist of solid-state electronic spins can be sensitive detectors of nuclear magnetic resonance (NMR) signals, particularly from very small samples. For example, nitrogen–vacancy centres in diamond have been used to record NMR signals from nanometre-scale samples, with sensitivity sufficient to detect the magnetic field produced by a single protein. However, the best reported spectral resolution for NMR of molecules using nitrogen–vacancy centres is about 100 hertz. This is insufficient to resolve the key spectral identifiers of molecular structure that are critical to NMR applications in chemistry, structural biology and materials research, such as scalar couplings (which require a resolution of less than ten hertz) and small chemical shifts (which require a resolution of around one part per million of the nuclear Larmor frequency). Conventional, inductively detected NMR can provide the necessary high spectral resolution, but its limited sensitivity typically requires millimetre-scale samples, precluding applications that involve smaller samples, such as picolitre-volume chemical analysis or correlated optical and NMR microscopy. Here we demonstrate a measurement technique that uses a solid-state spin sensor (a magnetometer) consisting of an ensemble of nitrogen–vacancy centres in combination with a narrowband synchronized readout protocol to obtain NMR spectral resolution of about one hertz. We use this technique to observe NMR scalar couplings in a micrometre-scale sample volume of approximately ten picolitres. We also use the ensemble of nitrogen–vacancy centres to apply NMR to thermally polarized nuclear spins and resolve chemical-shift spectra from small molecules. Our technique enables analytical NMR spectroscopy at the scale of single cells.

Primary damage formation in bcc iron

NASA Astrophysics Data System (ADS)

Stoller, R. E.; Odette, G. R.; Wirth, B. D.

1997-11-01

Primary defect formation in bee iron has been extensively investigated using the methods of molecular dynamics (MD) and Monte Carlo (MC) simulation. This research has employed a modified version of the Finnis-Sinclair interatomic potential. MD was used in the simulation of displacement cascades with energies up to 40 keV and to examine the migration of the interstitial clusters that were observed to form in the cascade simulations. Interstitial cluster binding energies and the stable cluster configurations were determined by structural relaxation and energy minimization using a MC method with simulated annealing. Clusters containing up to 19 interstitials were examined. Taken together with the previous work, these new simulations provide a reasonably complete description of primary defect formation in iron. The results of the displacement cascade simulations have been used to characterize the energy and temperature dependence of primary defect formation in terms of two parameters: (1) the number of surviving point defects and (2) the fraction of the surviving defects that are contained in clusters. The number of surviving point defects is expressed as a fraction of the atomic displacements calculated using the secondary displacement model of Norgett-Robinson-Torrens (NRT). Although the results of the high energy simulations are generally consistent with those obtained at lower energies, two notable exceptions were observed. The first is that extensive subcascade formation at 40 keV leads to a higher defect survival fraction than would be predicted from extrapolation of the results obtained for energies up to 20 keV. The stable defect fraction obtained from the MD simulations is a smoothly decreasing function up to 20 keV. Subcascade formation leads to a slight increase in this ratio at 40 keV, where the value is about the same as at 10 keV. Secondly, the potential for a significant level of in-cascade vacancy clustering was observed. Previous cascade studies employing this potential have reported extensive interstitial clustering, but little evidence of vacancy clustering. Interstitial clusters were found to be strongly bound, with binding energies in excess of 1 eV. The larger clusters exhibited a complex, 3D structure and were composed of <111> crowdions. These clusters were observed to migrate by collective <111> translations with an activation energy on the order of 0.1 eV.

Structural characterization combined with the first principles simulations of barium/strontium cobaltite/ferrite as promising material for solid oxide fuel cells cathodes and high-temperature oxygen permeation membranes.

PubMed

Gangopadhayay, Shruba; Inerbaev, Talgat; Masunov, Artëm E; Altilio, Deanna; Orlovskaya, Nina

2009-07-01

Mixed ionic-electronic conducting perovskite type oxides with a general formula ABO(3) (where A = Ba, Sr, Ca and B = Co, Fe, Mn) often have high mobility of the oxygen vacancies and exhibit strong ionic conductivity. They are key materials that find use in several energy related applications, including solid oxide fuel cell (SOFC), sensors, oxygen separation membranes, and catalysts. Barium/strontium cobaltite/ferrite (BSCF) Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta) was recently identified as a promising candidate for cathode material in intermediate temperature SOFCs. In this work, we perform experimental and theoretical study of the local atomic structure of BSFC. Micro-Raman spectroscopy was performed to characterize the vibrational properties of BSCF. The Jahn-Teller distortion of octahedral coordination around Co(4+) cations was observed experimentally and explained theoretically. Different cations and oxygen vacancies ordering are examined using plane wave pseudopotential density functional theory. We find that cations are completely disordered, whereas oxygen vacancies exhibit a strong trend for aggregation in L-shaped trimer and square tetramer structure. On the basis of our results, we suggest a new explanation for BSCF phase stability. Instead of linear vacancy ordering, which must take place before the phase transition into brownmillerite structure, the oxygen vacancies in BSCF prefer to form the finite clusters and preserve the disordered cubic structure. This structural feature could be found only in the first-principles simulations and can not be explained by the effect of the ionic radii alone.

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

Resolving phase stability in the Ti-O binary with first-principles statistical mechanics methods

NASA Astrophysics Data System (ADS)

Gunda, N. S. Harsha; Puchala, Brian; Van der Ven, Anton

2018-03-01

The Ti-O system consists of a multitude of stable and metastable oxides that are used in wide ranging applications. In this work we investigate phase stability in the Ti-O binary from first principles. We perform a systematic search for ground state structures as a function of oxygen concentration by considering oxygen-vacancy and/or titanium-vacancy orderings over four parent crystal structures: (i) hcp Ti, (ii) ω -Ti, (iii) rocksalt, and (iv) hcp oxygen containing interstitial titanium. We explore phase stability at finite temperature using cluster expansion Hamiltonians and Monte Carlo simulations. The calculations predict a high oxygen solubility in hcp Ti and the stability of suboxide phases that undergo order-disorder transitions upon heating. Vacancy ordered rocksalt phases are also predicted at low temperature that disorder to form an extended solid solution at high temperatures. Predicted stable and metastable phase diagrams are qualitatively consistent with experimental observations, however, important discrepancies are revealed between first-principles density functional theory predictions of phase stability and the current understanding of phase stability in this system.

Current-induced nonuniform enhancement of sheet resistance in A r+ -irradiated SrTi O3

NASA Astrophysics Data System (ADS)

Roy, Debangsu; Frenkel, Yiftach; Davidovitch, Sagi; Persky, Eylon; Haham, Noam; Gabay, Marc; Kalisky, Beena; Klein, Lior

2017-06-01

The sheet resistance Rs of A r+ irradiated SrTi O3 in patterns with a length scale of several microns increases significantly below ˜40 K in connection with driving currents exceeding a certain threshold. The initial lower Rs is recovered upon warming with accelerated recovery around 70 and 160 K. Scanning superconducting quantum interference device microscopy shows local irreversible changes in the spatial distribution of the current with a length scale of several microns. We attribute the observed nonuniform enhancement of Rs to the attraction of the charged single-oxygen and dioxygen vacancies by the crystallographic domain boundaries in SrTi O3 . The boundaries, which are nearly ferroelectric below 40 K, are polarized by the local electrical field associated with the driven current and the clustered vacancies which suppress conductivity in their vicinity and yield a noticeable enhancement in the device resistance when the current path width is on the order of the boundary extension. The temperatures of accelerated conductivity recovery are associated with the energy barriers for the diffusion of the two types of vacancies.

Helium bubbles aggravated defects production in self-irradiated copper

NASA Astrophysics Data System (ADS)

Wu, FengChao; Zhu, YinBo; Wu, Qiang; Li, XinZhu; Wang, Pei; Wu, HengAn

2017-12-01

Under the environment of high radiation, materials used in fission and fusion reactors will internally accumulate numerous lattice defects and bubbles. With extensive studies focused on bubble resolution under irradiation, the mutually effects between helium bubbles and displacement cascades in irradiated materials remain unaddressed. Therefore, the defects production and microstructure evolution under self-irradiation events in vicinity of helium bubbles are investigated by preforming large scale molecular dynamics simulations in single-crystal copper. When subjected to displacement cascades, distinguished bubble resolution categories dependent on bubble size are observed. With the existence of bubbles, radiation damage is aggravated with the increasing bubble size, represented as the promotion of point defects and dislocations. The atomic mechanisms of heterogeneous dislocation structures are attributed to different helium-vacancy cluster modes, transforming from the resolved gas trapped with vacancies to the biased absorption of vacancies by the over-pressured bubble. In both cases, helium impedes the recombination of point defects, leading to the accelerated formation of interstitial loops. The results and insight obtained here might contribute to understand the underlying mechanism of transmutant solute on the long-term evolution of irradiated materials.

Positron annihilation spectroscopy of vacancy-related defects in CdTe:Cl and CdZnTe:Ge at different stoichiometry deviations

PubMed Central

Šedivý, L.; Čížek, J.; Belas, E.; Grill, R.; Melikhova, O.

2016-01-01

Positron annihilation spectroscopy (PAS) was used to examine the effect of defined Cd-rich and Te-rich annealing on point defects in Cl-doped CdTe and Ge-doped CdZnTe semi-insulating single crystals. The as-grown crystals contain open-volume defects connected with Cd vacancies . It was found that the Cd vacancies agglomerate into clusters coupled with Cl in CdTe:Cl, and in CdZnTe:Ge they are coupled with Ge donors. While annealing in Cd pressure reduces of the density, subsequent annealing in Te pressure restores . The CdTe:Cl contains negatively-charged shallow traps interpreted as Rydberg states of A-centres and representing the major positron trapping sites at low temperature. Positrons confined in the shallow traps exhibit lifetime, which is shorter than the CdTe bulk lifetime. Interpretation of the PAS data was successfully combined with electrical resistivity, Hall effect measurements and chemical analysis, and allowed us to determine the principal point defect densities. PMID:26860684

First-principles analysis of phase stability in layered-layered composite cathodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Iddir, Hakim; Benedek, Roy; Voltage Fade Team

2014-03-01

The atomic order in layered-layered composites with composition xLi2MnO3 .(1-x)LiCoO2 is investigated with first-principles calculations at the GGA +U level. This material, and others in its class, are often regarded as solid solutions, however, only a minute solubility of Li2MnO3 in a LiCoO2 host is predicted. Calculations of Co-vacancy formation and migration energies in LiCoO2 are presented, to elucidate the rate of vacancy-mediated ordering in the transition-metal-layer, and thus determine whether low vacancy mobility could result in slow equilibration. The Co-vacancy formation energy can be predicted only to within a range, because of uncertainty in the chemical potentials. Predicted migration energies, however, are approximately 1 eV, small enough to be consistent with rapid ordering in the transition metal layer, and therefore separated Li2MnO3 and LiCoO2 phases. The relatively small (of the order of a few nm) Li2MnO3 domain sizes observed with TEM in some xLi2MnO3 .(1-x)LiMO2 composites may result from other factors, such as coherency strain, which perhaps block further domain coarsening in these materials. Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Effect of the introduction of oxide ion vacancies into cubic fluorite-type rare earth oxides on the NO decomposition catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masui, Toshiyuki; Nagai, Ryosuke; Imanaka, Nobuhito, E-mail: imanaka@chem.eng.osaka-u.ac.jp

2014-12-15

Cubic fluorite-type solid solutions based on Pr{sub 6}O{sub 11} and CeO{sub 2} were synthesized and oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice through the charge compensating mechanism by Mg{sup 2+} and/or Ca{sup 2+} doping into their lattices. The oxide anion vacancies bring about positive effect on NO decomposition catalysis. The reason for the increase in the catalytic activity was attributed to defect fluorite-type structures close to the C-type cubic one, because C-type cubic rare earth oxides, in which one-quarter of the oxygen atoms in the fluorite-type structure are removed, show high NO decomposition activity. In particular,more » the positive effect of the formation of oxide anion vacancies was significant for Pr{sub 6}O{sub 11} and its solid solutions, because the molar volume of Pr{sub 6}O{sub 11} is larger than that of CeO{sub 2}, and Pr{sub 6}O{sub 11} contains Pr{sup 3+} as well as Pr{sup 4+} and thereby a small amount of oxide anion vacancies exist inherently in the lattice. - Graphical abstract: Oxide anion vacancies intentionally introduced into the cubic fluorite-type lattice bring about positive effect on NO decomposition catalysis. - Highlights: • Cubic fluorite-type solid solutions were synthesized. • Oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice. • The oxide anion vacancies bring about positive effect on NO decomposition catalysis. • The activity was enhanced by making the structure close to the C-type cubic one.« less

Stress-Induced Resistive Switching in Pt/HfO2/Ti Devices

NASA Astrophysics Data System (ADS)

Zeevi, Gilad; Katsman, Alexander; Yaish, Yuval E.

2018-02-01

In the present work, we study the initial SET mechanism of resistive switching (RS) in Pt/HfO2/Ti devices under a static electrical stress and the RS mechanism under a bias sweeping mode with rates of 100 mV/s-300 mV/s. We characterize the thin HfO2 dielectric layer by x-ray photoelectron spectroscopy and x-ray diffraction. These findings show that the layer structure is stoichiometric and nanocrystalline with a crystal diameter of ˜ 14 Å. We measure the temporal dependence of the conductive filament growth at different temperatures and for various biases. Furthermore, these devices present stable bipolar resistive switching with a high-to-low resistive state (HRS/LRS) ratio of more than three orders of magnitude. Activation energy E RS ≈ 0.56 eV and drift current parameter V 0 ≈ 0.07 V were determined from the temporal dependence of the initial `SET' process, first HRS to LRS transition [for static electrical stress of V DS = (4.7-5.0 V)]. We analyze the results according to our model suggesting generation of double-charge oxygen vacancies at the anode and their diffusion across the dielectric layer. The double-charge vacancies transform to a single charge and then to neutral vacancies by capturing hot electrons, and form a conductive filament as soon as a critical neutral-vacancy cluster is formed across the dielectric layer.

Dynamics of Helium-Loaded Grain Boundaries under Shear Deformation in α-Fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Fei; Yang, Li; Heinisch, Howard L.

2014-03-30

The defects produced in collision cascades will interact with microstructural features in materials, such as GBs and dislocations. The coupled motion of GBs under stress has been widely observed in simulations and experiments. Two symmetric tilt GBs with a common <110> tilt axis (Σ3 and Σ11) in bcc iron are used to investigate the coupled motion of GBs under shear deformation. Also, we have explored the effect of self-interstitial atoms (SIAs) loading on the GB motion, with different concentrations of interstitials randomly inserted around the GB plane. The simulation results show that the interstitial loading reduces the critical stress ofmore » the GB coupled motion for the Σ3 GB. Furthermore, the interstitials and vacancies are inserted randomly at the GB plane and at a distance of 1 nm away from the GB plane, respectively, to understand the self-healing mechanism of GBs under stress. The behavior of the defect-loaded GBs depends on the GB structure. The loaded interstitials in the Σ3 GB easily form <111> interstitial clusters that do not move along with the GB. The vacancies in the Σ3 GB impede the GB motion. However, the interstitials move along with the Σ11 GB and annihilate with vacancies when the GB moves into the vacancy-rich region, leading to the self-healing and damage recovery of the Σ11 GB.« less

Theoretical investigation of microstructure evolution and deformation of zirconium under neutron irradiation

DOE PAGES

Barashev, A. V.; Golubov, S. I.; Stoller, R. E.

2015-06-01

We studied the radiation growth of zirconium using a reaction–diffusion model which takes into account intra-cascade clustering of self-interstitial atoms and one-dimensional diffusion of interstitial clusters. The observed dose dependence of strain rates is accounted for by accumulation of sessile dislocation loops during irradiation. Moreover, the computational model developed and fitted to available experimental data is applied to study deformation of Zr single crystals under irradiation up to hundred dpa. Finally, the effect of cold work and the reasons for negative prismatic strains and co-existence of vacancy and interstitial loops are elucidated.

Atomistic Simulation of Displacement Cascades in Zircon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devanathan, Ram; Weber, William J.; Corrales, Louis R.

2002-05-06

Low energy displacement cascades in zircon (ZrSiO4) initiated by a Zr primary knock-on atom have been investigated by molecular dynamics simulations using a Coulombic model for long-range interactions, Buckingham potential for short-range interactions and Ziegler-Biersack potentials for close pair interactions. Displacements were found to occur mainly in the O sublattice, and O replacements by a ring mechanism were predominant. Clusters containing Si interstitials bridged by O interstitials, vacancy clusters and anti-site defects were found to occur. This Si-O-Si bridging is considerable in quenched liquid ZrSiO4.

Positron annihilation studies in ZnO nanoparticles

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Pujari, P. K.; Sudarshan, K.; Dutta, D.; Mahapatra, M.; Godbole, S. V.; Jayakumar, O. D.; Tyagi, A. K.

2009-04-01

We report results on positron annihilation spectroscopic (PAS) studies using lifetime and coincidence Doppler broadening techniques in zinc oxide (ZnO) nanoparticles (4 to 40 nm) synthesized by solid state pyrolytic reaction followed by annealing in the temperature range of 200 ∘C to 800 ∘C. Positron lifetime in the nanoparticles are observed to be higher than bulk lifetime in all the cases. Theoretical calculation of lifetime indicates the presence of either Zn or (Zn, O) vacancy clusters which migrate and anneal out at high temperature. Comparison of ratio spectra from coincidence Doppler broadening measurement and calculated electron momentum distribution indicates the presence of either Zn or (Zn, O) vacancies. In addition, photoluminescence (PL) measurements have been carried out to examine the role of defects on the intensity of emission in the visible region.

Characterization of Oxygen Defect Clusters in UO2+ x Using Neutron Scattering and PDF Analysis.

PubMed

Ma, Yue; Garcia, Philippe; Lechelle, Jacques; Miard, Audrey; Desgranges, Lionel; Baldinozzi, Gianguido; Simeone, David; Fischer, Henry E

2018-06-18

In hyper-stoichiometric uranium oxide, both neutron diffraction work and, more recently, theoretical analyses report the existence of clusters such as the 2:2:2 cluster, comprising two anion vacancies and two types of anion interstitials. However, little is known about whether there exists a region of low deviation-from-stoichiometry in which defects remain isolated, or indeed whether at high deviation-from-stoichiometry defect clusters prevail that contain more excess oxygen atoms than the di-interstitial cluster. In this study, we report pair distribution function (PDF) analyses of UO 2 and UO 2+ x ( x ≈ 0.007 and x ≈ 0.16) samples obtained from high-temperature in situ neutron scattering experiments. PDF refinement for the lower deviation from stoichiometry sample suggests the system is too dilute to differentiate between isolated defects and di-interstitial clusters. For the UO 2.16 sample, several defect structures are tested, and it is found that the data are best represented assuming the presence of center-occupied cuboctahedra.

Acceptor Type Vacancy Complexes In As-Grown ZnO

NASA Astrophysics Data System (ADS)

Zubiaga, A.; Tuomisto, F.; Zuñiga-Pérez, J.

2010-11-01

One of the many technological areas that ZnO is interesting for is the construction of opto-electronic devices working in the blue-UV range as its large band gap (˜3.4 eV at 10 K) makes them suitable for that purpose. As-grown ZnO shows generally n-type conductivity partially due to the large concentration of unintentional shallow donors, like H, but impurities can also form complexes with acceptor type defects (Zn vacancy) leading to the creation of compensating defects. Recently, LiZn and NaZn acceptors have been measured and H could form similar type of defects. Doppler Broadening Positron Annihilation spectroscopy experimental results on the observation of Zn related vacancy complexes in ZnO thin films, as-grown, O implanted and Al doped will be presented. Results show that as-grown ZnO film show small Zn vacancy related complexed that could be related to presence of H as a unintentional doping element.

Strain control of oxygen vacancies in epitaxial strontium cobaltite films

DOE PAGES

Jeen, Hyoung Jeen; Choi, Woo Seok; Reboredo, Fernando A.; ...

2016-01-25

In this study, the ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoO x) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 °C. By applying a small biaxial tensile strain (2%), the oxygen activation energy barrier decreases by ≈30%, resultingmore » in a tunable oxygen deficient steady-state under conditions that would normally fully oxidize unstrained cobaltite. These strain-induced changes in oxygen stoichiometry drive the cobaltite from a ferromagnetic metal towards an antiferromagnetic insulator. The ability to decouple the oxygen vacancy concentration from its typical dependence on the operational environment is useful for effectively designing oxides materials with a specific oxygen stoichiometry.« less

Characterisation of irradiation-induced defects in ZnO single crystals

NASA Astrophysics Data System (ADS)

Prochazka, I.; Cizek, J.; Lukac, F.; Melikhova, O.; Valenta, J.; Havranek, V.; Anwand, W.; Skuratov, V. A.; Strukova, T. S.

2016-01-01

Positron annihilation spectroscopy (PAS) combined with optical methods was employed for characterisation of defects in the hydrothermally grown ZnO single crystals irradiated by 167 MeV Xe26+ ions to fluences ranged from 3×1012 to 1×1014 cm-2. The positron lifetime (LT), Doppler broadening as well as slow-positron implantation spectroscopy (SPIS) techniques were involved. The ab-initio theoretical calculations were utilised for interpretation of LT results. The optical transmission and photoluminescence measurements were conducted, too. The virgin ZnO crystal exhibited a single component LT spectrum with a lifetime of 182 ps which is attributed to saturated positron trapping in Zn vacancies associated with hydrogen atoms unintentionally introduced into the crystal during the crystal growth. The Xe ion irradiated ZnO crystals have shown an additional component with a longer lifetime of ≈ 360 ps which comes from irradiation-induced larger defects equivalent in size to clusters of ≈10 to 12 vacancies. The concentrations of these clusters were estimated on the basis of combined LT and SPIS data. The PAS data were correlated with irradiation induced changes seen in the optical spectroscopy experiments.

A novel method for computing effective diffusivity: Application to helium implanted α-Fe thin films

NASA Astrophysics Data System (ADS)

Dunn, Aaron; Agudo-Merida, Laura; Martin-Bragado, Ignacio; McPhie, Mathieu; Cherkaoui, Mohammed; Capolungo, Laurent

2014-05-01

The effective diffusivity of helium in thin iron films is quantified using spatially resolved stochastic cluster dynamics and object kinetic Monte Carlo simulations. The roles of total displacement dose (in DPA), damage rate, helium to DPA ratio, layer thickness, and damage type (cascade damage vs Frenkel pair implantation) on effective He diffusivity are investigated. Helium diffusivity is found to decrease with increasing total damage and decreasing damage rate. Arrhenius plots show strongly increased helium diffusivity at high temperatures, high total implantation, and low implantation rates due to decreased vacancy and vacancy cluster concentrations. At low temperatures, effective diffusivity is weakly dependent on foil thickness while at high temperatures, narrower foils prevent defect accumulation by releasing all defects at the free surfaces. Helium to DPA ratio is not shown to strongly change helium diffusivity in the range of irradiation conditions simulated. Frenkel pair implantation is shown to cause higher effective diffusivity and more complex diffusion mechanisms than cascade implantation. The results of these simulations indicate that the differences in damage rates between implantation experiments and fission or fusion environments may result in differences in the final microstructure.

Electronic Characterization of Defects in Narrow Gap Semiconductors-Comparison of Electronic Energy Levels and Formation Energies in Mercury Cadmium Telluride, Mercury Zinc Telluride, and Mercury Zinc Selenide

NASA Technical Reports Server (NTRS)

Patterson, James D.

1996-01-01

We have used a Green's function technique to calculate the energy levels and formation energy of deep defects in the narrow gap semiconductors mercury cadmium telluride (MCT), mercury zinc telluride (MZT) and mercury zinc selenide (MZS). The formation energy is calculated from the difference between the total energy with an impurity cluster and the total energy for the perfect crystal. Substitutional (including antisite), interstitial (self and foreign), and vacancy deep defects are considered. Relaxation effects are calculated (with molecular dynamics). By use of a pseudopotential, we generalize the ideal vacancy model so as to be able to consider relaxation for vacancies. Different charge states are considered and the charged state energy shift (as computed by a modified Haldane-Anderson model) can be twice that due to relaxation. Different charged states for vacancies were not calculated to have much effect on the formation energy. For all cases we find deep defects in the energy gap only for cation site s-like orbitals or anion site p-like orbitals, and for the substitutional case only the latter are appreciably effected by relaxation. For most cases for MCT, MZT, MZS, we consider x (the concentration of Cd or Zn) in the range appropriate for a band gap of 0.1 eV. For defect energy levels, the absolute accuracy of our results is limited, but the precision is good, and hence chemical trends are accurately predicted. For the same reason, defect formation energies are more accurately predicted than energy level position. We attempt, in Appendix B, to calculate vacancy formation energies using relatively simple chemical bonding ideas due to Harrison. However, these results are only marginally accurate for estimating vacancy binding energies. Appendix C lists all written reports and publications produced for the grant. We include abstracts and a complete paper that summarizes our work which is not yet available.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.

Here, we report how the superconducting phase forms in pseudo-single-crystal K xFe 2-ySe 2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition.more » It should be emphasized that the phase separation in pseudo-single-crystal K xFe 2-ySe 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

Atomistic simulation of the trapping capability of He-vacancy defects at Ni {\\sum}^{}3\\left(1\\bar{1}2\\right)[110] grain boundary

NASA Astrophysics Data System (ADS)

Gong, Hengfeng; Wang, Chengbin; Zhang, Wei; Huai, Ping; Lu, Wei; Zhu, Zhiyuan

2016-12-01

He atoms tend to cluster and precipitate into bubbles that prefer to grow in the grain boundaries, resulting in high temperature He embrittlement with significantly degraded material properties. This is a major bottleneck in employing Ni-based alloys for applications such as molten salt reactors (MSRs). This paper focuses on understanding how the local grain boundary structure interacts with He atoms and how the local atomistic environment in the grain boundary influences the binding energy of He defects. Using molecular dynamics simulations, we have investigated the trapping capability of the Ni {\\sum}3≤ft(1 \\bar{1} 2\\right)≤ft[1 1 0\\right] grain boundary to He defects (He N ) and to He-vacancy defects (He N V M ). The two defects in the Ni grain boundary exhibit geometries with high symmetry. The binding energy of an interstitial He atom to He N V M defects is found to be generally larger in pure Ni than that in the grain boundary. We compared the binding energy of He N defects to the Ni vacancy and to the Ni grain boundary, finding that the Ni vacancy possesses a higher trapping strength to He N . We also found that the binding strength of He N to the grain boundary is stronger than that of He N V M to the grain boundary. The He-vacancy ratio in He N V M defects does not significantly affect the binding energy in the grain boundary plane. The current work will provide insight in understanding the experimentally observed He bubble formation in Ni-based alloys and bridge atomic scale events and damage with macroscopic failure.

Precipitates and voids in cubic silicon carbide implanted with 25Mg+ ions

NASA Astrophysics Data System (ADS)

Jiang, Weilin; Spurgeon, Steven R.; Liu, Jia; Schreiber, Daniel K.; Jung, Hee Joon; Devaraj, Arun; Edwards, Danny J.; Henager, Charles H.; Kurtz, Richard J.; Wang, Yongqiang

2018-01-01

Single crystal cubic phase silicon carbide (3C-SiC) films on Si were implanted to 9.6 × 101625Mg+/cm2 at 673 K and annealed at 1073 and 1573 K for 2, 6, and 12 h in an Ar environment. The data from scanning transmission election microscopy (STEM) and electron energy loss spectroscopy (EELS) mapping suggest a possible formation of unidirectionally aligned tetrahedral precipitates of core (MgC2)-shell (Mg2Si) in the implanted sample annealed at 1573 K for 12 h. There are also small spherical voids near the surface and larger faceted voids around the region of maximum vacancy concentration. Atom probe tomography confirms 25Mg segregation dominated by small atomic clusters with local 25Mg concentrations up to 85 at.%. The resulting precipitate size and number density are found to decrease and increase, respectively, probably as a result of the thermal annealing that decomposes the 25Mg-bearing precipitates at the elevated temperatures and subsequent nucleation and growth below 1073 K during the cooling stage. The results from this study provide data needed to fully understand the property degradation of SiC in a high-flux fast neutron environment.

First-principles study on oxidation effects in uranium oxides and high-pressure high-temperature behavior of point defects in uranium dioxide

NASA Astrophysics Data System (ADS)

Geng, Hua Y.; Song, Hong X.; Jin, K.; Xiang, S. K.; Wu, Q.

2011-11-01

Formation Gibbs free energy of point defects and oxygen clusters in uranium dioxide at high-pressure high-temperature conditions are calculated from first principles, using the LSDA+U approach for the electronic structure and the Debye model for the lattice vibrations. The phonon contribution on Frenkel pairs is found to be notable, whereas it is negligible for the Schottky defect. Hydrostatic compression changes the formation energies drastically, making defect concentrations depend more sensitively on pressure. Calculations show that, if no oxygen clusters are considered, uranium vacancy becomes predominant in overstoichiometric UO2 with the aid of the contribution from lattice vibrations, while compression favors oxygen defects and suppresses uranium vacancy greatly. At ambient pressure, however, the experimental observation of predominant oxygen defects in this regime can be reproduced only in a form of cuboctahedral clusters, underlining the importance of defect clustering in UO2+x. Making use of the point defect model, an equation of state for nonstoichiometric oxides is established, which is then applied to describe the shock Hugoniot of UO2+x. Furthermore, the oxidization and compression behavior of uranium monoxide, triuranium octoxide, uranium trioxide, and a series of defective UO2 at 0 K are investigated. The evolution of mechanical properties and electronic structures with an increase of the oxidation degree are analyzed, revealing the transition of the ground state of uranium oxides from metallic to Mott insulator and then to charge-transfer insulator due to the interplay of strongly correlated effects of 5f orbitals and the shift of electrons from uranium to oxygen atoms.

Synthesis and characterization of Fe-Ti-Sb intermetallic compounds: Discovery of a new Slater-Pauling phase

NASA Astrophysics Data System (ADS)

Naghibolashrafi, N.; Keshavarz, S.; Hegde, Vinay I.; Gupta, A.; Butler, W. H.; Romero, J.; Munira, K.; LeClair, P.; Mazumdar, D.; Ma, J.; Ghosh, A. W.; Wolverton, C.

2016-03-01

Compounds of Fe, Ti, and Sb were prepared using arc melting and vacuum annealing. Fe2TiSb , expected to be a full Heusler compound crystallizing in the L 21 structure, was shown by XRD and SEM analyses to be composed of weakly magnetic grains of nominal composition Fe1.5TiSb with iron-rich precipitates in the grain boundaries. FeTiSb, a composition consistent with the formation of a half-Heusler compound, also decomposed into Fe1.5TiSb grains with Ti-Sb rich precipitates and was weakly magnetic. The dominant Fe1.5TiSb phase appears to crystallize in a defective L 21 -like structure with iron vacancies. Based on this finding, a first-principles DFT-based binary cluster expansion of Fe and vacancies on the Fe sublattice of the L 21 structure was performed. Using the cluster expansion, we computationally scanned >103 configurations and predict a novel, stable, nonmagnetic semiconductor phase to be the zero-temperature ground state. This new structure is an ordered arrangement of Fe and vacancies, belonging to the space group R 3 m , with composition Fe1.5TiSb , i.e., between the full- and half-Heusler compositions. This phase can be visualized as alternate layers of L 21 phase Fe2TiSb and C 1b phase FeTiSb, with layering along the [111] direction of the original cubic phases. Our experimental results on annealed samples support this predicted ground-state composition, but further work is required to confirm that the R 3 m structure is the ground state.

Defect induced ferromagnetism in MgO and its exceptional enhancement upon thermal annealing: a case of transformation of various defect states.

PubMed

Pathak, Nimai; Gupta, Santosh Kumar; Prajapat, C L; Sharma, S K; Ghosh, P S; Kanrar, Buddhadev; Pujari, P K; Kadam, R M

2017-05-17

MgO particles of few micron size are synthesized through a sol-gel method at different annealing temperatures such as 600 °C (MgO-600), 800 °C (MgO-800) and 1000 °C (MgO-1000). EDX and ICP-AES studies confirmed a near total purity of the sample with respect to paramagnetic metal ion impurities. Magnetic measurements showed a low temperature weak ferromagnetic ordering with a T C (Curie temperature) around 65 K (±5 K). Unexpectedly, the saturation magnetization (M s ) was found to be increased with increasing annealing temperature during synthesis. It was observed that with J = 1 or 3/2 or S = 1 or 3/2, the experimental points are fitted well with the Brillouin function of weak ferromagnetic ordering. A positron annihilation lifetime measurement study indicated the presence of a divacancy (2V Mg + 2V O ) cluster in the case of the low temperature annealed compound, which underwent dissociations into isolated monovacancies of Mg and O at higher annealing temperatures. An EPR study showed that both singly charged Mg vacancies and oxygen vacancies are responsible for ferromagnetic ordering. It also showed that at lower annealing temperatures the contribution from was very low while at higher annealing temperatures, it increased significantly. A PL study showed that most of the F + centers were present in their dimer form, i.e. as centers. DFT calculation implied that this dimer form has a higher magnetic moment than the monomer. After a careful consideration of all these observations, which have been reported for the first time, this thermally tunable unusual magnetism phenomenon was attributed to a transformation mechanism of one kind of cluster vacancy to another.

Impurity and defect interactions during laser thermal annealing in Ge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milazzo, R., E-mail: ruggero.milazzo@unipd.it; De Salvador, D.; Carnera, A.

2016-01-28

The microscopic mechanisms involving dopants, contaminants, and defects in Ge during pulsed melting laser thermal annealing (LTA) are investigated in detail. Samples both un-implanted and implanted with As or B are processed by LTA as well as characterized in terms of chemical (1D and 3D), electrical, and strain profiling. The clustering of As is directly measured by 3D chemical profiling and correlated with its partial electrical activation along with a reduction of the lattice strain induced by As atoms. A semi-quantitative microscopic model involving the interaction with mobile As-vacancy (AsV) complexes is proposed to describe the clustering mechanism. Boron ismore » shown to follow different clustering behavior that changes with depth and marked by completely different strain levels. Oxygen penetrates from the surface into all the samples as a result of LTA and, only in un-implanted Ge, it occupies an interstitial position inducing also positive strain in the lattice. On the contrary, data suggest that the presence of As or B forces O to assume different configurations with negligible strain, through O-V or O-B interactions for the two dopant species, respectively. These data suggest that LTA does not inject a significant amount of vacancies in Ge, at variance with Si, unless As atoms or possibly other n-type dopants are present. These results have to be carefully considered for modeling the LTA process in Ge and its implementation in technology.« less

Growth of Ni nanoclusters on irradiated graphene: a molecular dynamics study.

PubMed

Valencia, F J; Hernandez-Vazquez, E E; Bringa, E M; Moran-Lopez, J L; Rogan, J; Gonzalez, R I; Munoz, F

2018-04-23

We studied the soft landing of Ni atoms on a previously damaged graphene sheet by means of molecular dynamics simulations. We found a monotonic decrease of the cluster frequency as a function of its size, but few big clusters comprise an appreciable fraction of the total number of Ni atoms. The aggregation of Ni atoms is also modeled by means of a simple phenomenological model. The results are in clear contrast with the case of hard or energetic landing of metal atoms, where there is a tendency to form mono-disperse metal clusters. This behavior is attributed to the high diffusion of unattached Ni atoms, together with vacancies acting as capture centers. The findings of this work show that a simple study of the energetics of the system is not enough in the soft landing regime, where it is unavoidable to also consider the growth process of metal clusters.

The effect of sputter temperature on vacancy island behavior on Ni(111) measured by photoemission of adsorbed xenon

NASA Astrophysics Data System (ADS)

Malafsky, Geoffrey P.

1994-04-01

The temperature dependence of vacancy coalescence on an ion bombarded Ni(111) surface is measured by photoemission of adsorbed xenon (PAX). The Ni(111) crystal is sputtered by a low fluence (0.06 ML incident ions) Ar + ion beam with incident kinetic energies of 500-3000 eV. The Xe coverage decreases rapidly with increasing temperature between 88 and 375 K with little additional change from 375 to 775 K. The PAX spectra are acquired with a Xe chamber pressure of 8 × 10 -10 Torr and at a temperature of 88 K. Under these conditions, the Xe is selectively adsorbed at defect sites which would make the Xe coverage proportional to the surface defect density on simple defect structures but the large size of the Xe atom relative to the Ni atom prevents the direct relationship of Xe coverage to the defect density when complex and varying defect structures are present. The decrease in Xe coverage is not attributed to the loss of defect sites by adatom-vacancy recombination but the changing vacancy island shape and size with temperature which alters the ratio of adsorbed Xe atoms to surface vacancy sites. This ratio decreases with increasing temperature as the vacancy islands progress from small and irregularly shaped islands to larger and hexagonally shaped islands. This transition is seen in Monte Carlo simulations of the kinetically driven atomic diffusion on the sputtered surface.

Emergence of superconductivity and magnetic ordering tuned by Fe-vacancy in alkali-metal Fe chalcogenides RbxFe2-ySe2

NASA Astrophysics Data System (ADS)

Kobayashi, Yoshiaki; Kototani, Shouhei; Itoh, Masayuki; Sato, Masatoshi

2014-12-01

Samples of RbxFe2-ySe2 exhibiting superconductivity [superconducting (SC) samples] undergo a phase-separation into two phases, a Fe-vacancy ordered phase with antiferromagnetic (AFM) transition at TN1~500 K (AFM1 phase) and a phase with little Fe- vacancy and SC transition at Tc~30 K (SC phase). The samples of RbxFe2-ySe2 exhibiting no SC behaviour (non-SC samples) are phase-separated into three phases, the AFM1 phase, another AFM phase with TN2 ~150 K (AFM2 phase), and a paramagnetic phase with no SC transitions (paramagnetic non-SC phase). In this paper, we present the experimental results of magnetic susceptibility, electrical resistivity, and NMR measurements on single crystals of RbxFe2-ySe2 to reveal physical properties of these co-existing phases in the SC and non-SC samples. The 87Rb and 77Se NMR spectra show that the Fe vacancy concentration is very small in the Fe planes of the SC phase, whereas the AFM2 and paramagnetic non-SC phases in non-SC samples have larger amount of Fe vacancies. The randomness induced by the Fe vacancy in the non-SC samples makes the AFM2 and paramagnetic non-SC phases insulating/semiconducting and magnetically active, resulting in the absence of the superconductivity in RbxFe2-ySe2.

Effect of growth temperature on the epitaxial growth of ZnO on GaN by ALD

NASA Astrophysics Data System (ADS)

Särkijärvi, Suvi; Sintonen, Sakari; Tuomisto, Filip; Bosund, Markus; Suihkonen, Sami; Lipsanen, Harri

2014-07-01

We report on the epitaxial growth of ZnO on GaN template by atomic layer deposition (ALD). Diethylzinc (DEZn) and water vapour (H2O) were used as precursors. The structure and the quality of the grown ZnO layers were studied with scanning electron microscope (SEM), X-ray diffraction (XRD), photoluminescence (PL) measurements and positron annihilation spectroscopy. The ZnO films were confirmed epitaxial, and the film quality was found to improve with increasing deposition temperature in the vicinity of the threshold temperature of two dimensional growth. We conclude that high quality ZnO thin films can be grown by ALD. Interestingly only separate Zn-vacancies were observed in the films, although ZnO thin films typically contain fairly high density of surface pits and vacancy clusters.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Su, Mao; Yan, Pengfei

The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of bothmore » vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.« less

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

NASA Astrophysics Data System (ADS)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

Oxygen-related vacancy-type defects in ion-implanted silicon

NASA Astrophysics Data System (ADS)

Pi, X. D.; Burrows, C. P.; Coleman, P. G.; Gwilliam, R. M.; Sealy, B. J.

2003-10-01

Czochralski silicon samples implanted to a dose of 5 × 1015 cm-2 with 0.5 MeV O and to a dose of 1016 cm-2 with 1 MeV Si, respectively, have been studied by positron annihilation spectroscopy. The evolution of divacancies to vacancy (V)-O complexes is out-competed by V-interstitial (I) recombination at 400 and 500 °C in the Si- and O-implanted samples; the higher oxygen concentration makes the latter temperature higher. The defective region shrinks as the annealing temperature increases as interstitials are injected from the end of the implantation range (Rp). VmOn (m> n) are formed in the shallow region most effectively at 700 °C for both Si and O implantation. VxOy (x< y) are produced near Rp by the annealing. At 800 °C, implanted Si ions diffuse and reduce m and implanted O ions diffuse and increase n in VmOn. All oxygen-related vacancy-type defects appear to begin to dissociate at 950 °C, with the probable formation of oxygen clusters. At 1100 °C, oxygen precipitates appear to form just before Rp in O-implanted silicon.

Detection and quantification of solute clusters in a nanostructured ferritic alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Michael K.; Larson, David J.; Reinhard, D. A.

2014-12-26

A series of simulated atom probe datasets were examined with a friends-of-friends method to establish the detection efficiency required to resolve solute clusters in the ferrite phase of a 14YWT nanostructured ferritic alloy. The size and number densities of solute clusters in the ferrite of the as-milled mechanically-alloyed condition and the stir zone of a friction stir weld were estimated with a prototype high-detection-efficiency (~80%) local electrode atom probe. High number densities, 1.8 × 10 24 m –3 and 1.2 × 10 24 m –3, respectively of solute clusters containing between 2 and 9 solute atoms of Ti, Y andmore » O and were detected for these two conditions. Furthermore, these results support first principle calculations that predicted that vacancies stabilize these Ti–Y–O– clusters, which retard diffusion and contribute to the excellent high temperature stability of the microstructure and radiation tolerance of nanostructured ferritic alloys.« less

Annealing in tellurium-nitrogen co-doped ZnO films: The roles of intrinsic zinc defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Kun, E-mail: ktang@nju.edu.cn; Gu, Ran; Gu, Shulin, E-mail: slgu@nju.edu.cn

2015-04-07

In this article, the authors have conducted an extensive investigation on the roles of intrinsic zinc defects by annealing of a batch of Te-N co-doped ZnO films. The formation and annihilation of Zn interstitial (Zn{sub i}) clusters have been found in samples with different annealing temperatures. Electrical and Raman measurements have shown that the Zn{sub i} clusters are a significant compensation source to holes, and the Te co-doping has a notable effect on suppressing the Zn{sub i} clusters. Meanwhile, shallow acceptors have been identified in photoluminescence spectra. The N{sub O}-Zn-Te complex, zinc vacancy (V{sub Zn})-N{sub O} complex, and V{sub Zn}more » clusters are thought to be the candidates as the shallow acceptors. The evolution of shallow acceptors upon annealing temperature have been also studied. The clustering of V{sub Zn} at high annealing temperature is proposed to be a possible candidate as a stable acceptor in ZnO.« less

Positron annihilation lifetime study of oxide dispersion strengthened steels

NASA Astrophysics Data System (ADS)

Krsjak, V.; Szaraz, Z.; Hähner, P.

2012-09-01

A comparative positron annihilation lifetime study has been performed on various commercial ferritic and ferritic/martensitic oxide dispersion strengthened (ODS) steels. Both as-extruded and recrystallized materials were investigated. In the materials with recrystallized coarse-grained microstructures, only the positron trapping at small vacancy clusters and yttria nanofeatures was observed. Materials which had not undergone recrystallization treatment clearly showed additional positron trapping which is associated with dislocations. Dislocation densities were calculated from a two-component decomposition of the positron lifetime spectra by assuming the first component to be a superposition of the bulk controlled annihilation rate and the dislocation controlled trapping rate. The second component (which translates into lifetimes of 240-260 ps) was found to be well separated in all those ODS materials. This paper presents the potentialities and limitations of the positron annihilation lifetime spectroscopy, and discusses the results of the experimental determination of the defect concentrations and sensitivity of this technique to the material degradation due to thermally induced precipitation of chromium-rich α' phases.

Neural network potential for Al-Mg-Si alloys

NASA Astrophysics Data System (ADS)

Kobayashi, Ryo; Giofré, Daniele; Junge, Till; Ceriotti, Michele; Curtin, William A.

2017-10-01

The 6000 series Al alloys, which include a few percent of Mg and Si, are important in automotive and aviation industries because of their low weight, as compared to steels, and the fact their strength can be greatly improved through engineered precipitation. To enable atomistic-level simulations of both the processing and performance of this important alloy system, a neural network (NN) potential for the ternary Al-Mg-Si has been created. Training of the NN uses an extensive database of properties computed using first-principles density functional theory, including complex precipitate phases in this alloy. The NN potential accurately reproduces most of the pure Al properties relevant to the mechanical behavior as well as heat of solution, solute-solute, and solute-vacancy interaction energies, and formation energies of small solute clusters and precipitates that are required for modeling the early stage of precipitation and mechanical strengthening. This success not only enables future detailed studies of Al-Mg-Si but also highlights the ability of NN methods to generate useful potentials in complex alloy systems.

Formation mechanism of superconducting phase and its three-dimensional architecture in pseudo-single-crystal K xFe 2-ySe 2

DOE PAGES

Liu, Yong; Xing, Qingfeng; Straszheim, Warren E.; ...

2016-02-11

Here, we report how the superconducting phase forms in pseudo-single-crystal K xFe 2-ySe 2. In situ scanning electron microscopy (SEM) observation reveals that, as an order-disorder transition occurs, on cooling, most of the high-temperature iron-vacancy-disordered phase gradually changes into the iron-vacancy-ordered phase whereas a small quantity of the high-temperature phase retains its structure and aggregates to the stripes with more iron concentration but less potassium concentration compared to the iron-vacancy-ordered phase. The stripes that are generally recognized as the superconducting phase are actually formed as a remnant of the high-temperature phase with a compositional change after an “imperfect” order-disorder transition.more » It should be emphasized that the phase separation in pseudo-single-crystal K xFe 2-ySe 2 is caused by the iron-vacancy order-disorder transition. The shrinkage of the high-temperature phase and the expansion of the newly created iron-vacancy-ordered phase during the phase separation rule out the mechanism of spinodal decomposition proposed in an early report [Wang et al, Phys. Rev. B 91, 064513 (2015)]. Since the formation of the superconducting phase relies on the occurrence of the iron-vacancy order-disorder transition, it is impossible to synthesize a pure superconducting phase by a conventional solid state reaction or melt growth. By focused ion beam-scanning electron microscopy, we further demonstrate that the superconducting phase forms a contiguous three-dimensional architecture composed of parallelepipeds that have a coherent orientation relationship with the iron-vacancy-ordered phase.« less

Effect of sulphur vacancy and interlayer interaction on the electronic structure and spin splitting of bilayer MoS2.

PubMed

Dong, Yulan; Zeng, Bowen; Xiao, Jin; Zhang, Xiaojiao; Li, Dongde; Li, Mingjun; He, Jun; Long, Mengqiu

2018-02-27

Molybdenum disulfide (MoS 2 ) is one of the candidate materials for nanoelectronics and optoelectronics devices in the future. The electronic and magnetic properties of MoS 2 can be regulated by interlayer interaction and the vacancy effect. Nevertheless, the combined effect of these two factors on MoS 2 is not clearly understood. In this study, we have investigated the impact of a single S vacancy combined with interlayer interaction on the properties of bilayer MoS 2 . Our calculated results show that an S vacancy brings impurity states in the band structure of bilayer MoS 2 , and the energy level of the impurity states can be affected by the interlayer distance, which finally disappears in the bulk state when the layer distance is relatively small. Moreover, during the compression of bilayer MoS 2 , the bottom layer, where the S vacancy stays, gets an additional charge due to interlayer charge transfer, which first increases, and then decreases due to gradually forming the interlayer S-S covalent bond, as interlayer distance decreases. The change of the additional charge is consistent with the change of the total magnetic moment of the bottom layers, no magnetic moment has been found in the top layer. The distribution of magnetic moment mainly concentrates on the three Mo atoms around the S vacancy, for each of which the magnetic moment is very much related to the Mo-Mo length. Our conclusion is that the interlayer charge transfer and S vacancy co-determine the magnetic properties of this system, which may be a useful way to regulate the electronic and magnetic properties of MoS 2 for potential applications.

Effect of sulphur vacancy and interlayer interaction on the electronic structure and spin splitting of bilayer MoS2

NASA Astrophysics Data System (ADS)

Dong, Yulan; Zeng, Bowen; Xiao, Jin; Zhang, Xiaojiao; Li, Dongde; Li, Mingjun; He, Jun; Long, Mengqiu

2018-03-01

Molybdenum disulfide (MoS2) is one of the candidate materials for nanoelectronics and optoelectronics devices in the future. The electronic and magnetic properties of MoS2 can be regulated by interlayer interaction and the vacancy effect. Nevertheless, the combined effect of these two factors on MoS2 is not clearly understood. In this study, we have investigated the impact of a single S vacancy combined with interlayer interaction on the properties of bilayer MoS2. Our calculated results show that an S vacancy brings impurity states in the band structure of bilayer MoS2, and the energy level of the impurity states can be affected by the interlayer distance, which finally disappears in the bulk state when the layer distance is relatively small. Moreover, during the compression of bilayer MoS2, the bottom layer, where the S vacancy stays, gets an additional charge due to interlayer charge transfer, which first increases, and then decreases due to gradually forming the interlayer S-S covalent bond, as interlayer distance decreases. The change of the additional charge is consistent with the change of the total magnetic moment of the bottom layers, no magnetic moment has been found in the top layer. The distribution of magnetic moment mainly concentrates on the three Mo atoms around the S vacancy, for each of which the magnetic moment is very much related to the Mo-Mo length. Our conclusion is that the interlayer charge transfer and S vacancy co-determine the magnetic properties of this system, which may be a useful way to regulate the electronic and magnetic properties of MoS2 for potential applications.

Theoretical study of Ag doping-induced vacancies defects in armchair graphene

NASA Astrophysics Data System (ADS)

Benchallal, L.; Haffad, S.; Lamiri, L.; Boubenider, F.; Zitoune, H.; Kahouadji, B.; Samah, M.

2018-06-01

We have performed a density functional theory (DFT) study of the absorption of silver atoms (Ag,Ag2 and Ag3) in graphene using SIESTA code, in the generalized gradient approximation (GGA). The absorption energy, geometry, magnetic moments and charge transfer of Ag clusters-graphene system are calculated. The minimum energy configuration demonstrates that all structures remain planar and silver atoms fit into this plane. The charge transfer between the silver clusters and carbon atoms constituting the graphene surface is an indicative of a strong bond. The structure doped with a single silver atom has a magnetic moment and the two other are nonmagnetic.

Probing defects in chemically synthesized ZnO nanostrucures by positron annihilation and photoluminescence spectroscopy

NASA Astrophysics Data System (ADS)

Chaudhuri, S. K.; Ghosh, Manoranjan; Das, D.; Raychaudhuri, A. K.

2010-09-01

The present article describes the size induced changes in the structural arrangement of intrinsic defects present in chemically synthesized ZnO nanoparticles of various sizes. Routine x-ray diffraction and transmission electron microscopy have been performed to determine the shapes and sizes of the nanocrystalline ZnO samples. Detailed studies using positron annihilation spectroscopy reveals the presence of zinc vacancy. Whereas analysis of photoluminescence results predict the signature of charged oxygen vacancies. The size induced changes in positron parameters as well as the photoluminescence properties, has shown contrasting or nonmonotonous trends as size varies from 4 to 85 nm. Small spherical particles below a critical size (˜23 nm) receive more positive surface charge due to the higher occupancy of the doubly charge oxygen vacancy as compared to the bigger nanostructures where singly charged oxygen vacancy predominates. This electronic alteration has been seen to trigger yet another interesting phenomenon, described as positron confinement inside nanoparticles. Finally, based on all the results, a model of the structural arrangement of the intrinsic defects in the present samples has been reconciled.

Dielectric and AC conductivity studies on SrBi4Ti4O15

NASA Astrophysics Data System (ADS)

Jose, Roshan; Saravanan, K. Venkata

2018-05-01

The four layered SrBi4Ti4O15 ceramics which belong to the aurivillius family of oxide was prepared by conventional solid state reaction technique. Analysis of the dielectric data as a function of temperature and frequency revealed normal phase transition. The frequency dependent ac conductivity follows Jonscher's universal power law. Frequency exponent (n), pre-exponential factor (A), bulk dc conductivity (σdc), and hopping frequency (ωp) were determined from the fitting curves. The variation of frequency exponent with temperature indicates that large polaron hopping mechanism up to curie-temperature, then its changes to small polaron hopping. The activation energies were calculated from ac conductivity, bulk dc conductivity and hopping frequency. The activation energies revealed that conductivity had contributions from migrations of oxygen vacancies, bismuth ion vacancies and strontium ion vacancies.

Enhancement of deuterium retention in damaged tungsten by plasma-induced defect clustering

NASA Astrophysics Data System (ADS)

Jin, Younggil; Roh, Ki-Baek; Sheen, Mi-Hyang; Kim, Nam-Kyun; Song, Jaemin; Kim, Young-Woon; Kim, Gon-Ho

2017-12-01

The enhancement of deuterium retention was investigated for tungsten in the presence of both 2.8 MeV self-ion induced cascade damage and fuel hydrogen isotope plasma. Vacancy clustering in cascade damaged polycrystalline tungsten occurred due to deuterium irradiation and was observed near the grain boundary by using all-step transmission electron microscopy analysis. Analysis of the highest desorption temperature peak using thermal desorption spectroscopy supports reasonable evidence of defect clustering in the damaged polycrystalline tungsten. The defect clustering was neither observed on the damaged polycrystalline tungsten without deuterium irradiation nor on the damaged single-crystalline tungsten with deuterium irradiation. This result implies the synergetic role of deuterium and grain boundary on defect clustering. This study proposes a path for the defect transform from point defect to defect cluster, by the agglomeration between irradiated deuterium and cascade damage-induced defect. This agglomeration may induce more severe damage on the tungsten divertor at which the high fuel hydrogen ions, fast neutrons, and self-ions are irradiated simultaneously and it would increase the in-vessel tritium inventory.

Positron Annihilation Spectroscopy Characterization of Nanostructural Features in Reactor Steels

NASA Astrophysics Data System (ADS)

Glade, Stephen; Wirth, Brian; Asoka-Kumar, Palakkal; Sterne, Philip; Alinger, Matthew; Odette, George

2004-03-01

Irradiation embrittlement in nuclear reactor pressure vessel steels results from the formation of a high number density of nanometer sized copper rich precipitates and sub-nanometer defect-solute clusters. We present results of study to characterize the size and compositions of simple binary and ternary Fe-Cu-Mn model alloys and more representative Fe-Cu-Mn-Ni-Si-Mo-C reactor pressure vessel steels using positron annihilation spectroscopy (PAS). Using a recently developed spin-polarized PAS technique, we have also measured the magnetic properties of the nanometer-sized copper rich precipitates. Mn retards the precipitation kinetics and inhibits large vacancy cluster formation, suggesting a strong Mn-vacancy interaction which reduces radiation enhanced diffusion. The spin-polarized PAS measurements reveal the non-magnetic nature of the copper precipitates, discounting the notion that the precipitates contain significant quantities of Fe and providing an upper limit of at most a few percent Fe in the precipitates. PAS results on oxide dispersion-strengthened steel for use in fusion reactors will also be presented. Part of this work was performed under the auspices of the US Department of Energy by the University of California, Lawrence Livermore National Laboratory, under contract No. W-7405-ENG-48 with partial support provided from Basic Energy Sciences, Division of Materials Science.

Oxygen vacancies controlled multiple magnetic phases in epitaxial single crystal Co0.5(Mg0.55Zn0.45)0.5O1-v thin films

PubMed Central

Zhu, Dapeng; Cao, Qiang; Qiao, Ruimin; Zhu, Shimeng; Yang, Wanli; Xia, Weixing; Tian, Yufeng; Liu, Guolei; Yan, Shishen

2016-01-01

High quality single-crystal fcc-Cox(MgyZn1-y)1-xO1-v epitaxial thin films with high Co concentration up to x = 0.5 have been fabricated by molecular beam epitaxy. Systematic magnetic property characterization and soft X-ray absorption spectroscopy analysis indicate that the coexistence of ferromagnetic regions, superparamagnetic clusters, and non-magnetic boundaries in the as-prepared Cox(MgyZn1-y)1-xO1-v films is a consequence of the intrinsic inhomogeneous distribution of oxygen vacancies. Furthermore, the relative strength of multiple phases could be modulated by controlling the oxygen partial pressure during sample preparation. Armed with both controllable magnetic properties and tunable band-gap, Cox(MgyZn1-y)1-xO1-v films may have promising applications in future spintronics. PMID:27062992

Atomic origins of water-vapour-promoted alloy oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Su, Mao; Yan, Pengfei

The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of bothmore » vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.« less

Single-Crystalline Ultrathin Co 3O 4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

DOE PAGES

Cai, Zhao; Bi, Yongmin; Hu, Enyuan; ...

2017-09-18

The role of vacancy defects is demonstrated to be positive in various energy-related processes. However, introducing vacancy defects into single-crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this paper deliberately introduces oxygen defects into single-crystalline ultrathin Co 3O 4 nanosheets with O-terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As-prepared defect-rich Co 3O 4 nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec -1 for the oxygen evolution reaction (OER), which is among the best Co-based OERmore » catalysts to date and even more active than the state-of-the-art IrO 2 catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second-layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. Finally, this mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect-based electrocatalysts.« less

Single-Crystalline Ultrathin Co 3O 4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Zhao; Bi, Yongmin; Hu, Enyuan

The role of vacancy defects is demonstrated to be positive in various energy-related processes. However, introducing vacancy defects into single-crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this paper deliberately introduces oxygen defects into single-crystalline ultrathin Co 3O 4 nanosheets with O-terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As-prepared defect-rich Co 3O 4 nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec -1 for the oxygen evolution reaction (OER), which is among the best Co-based OERmore » catalysts to date and even more active than the state-of-the-art IrO 2 catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second-layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. Finally, this mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect-based electrocatalysts.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langguth, K.G.

The theory from MERKLE et al. has been applied to radiation damage in Ni single crytal caused by irradiation with 2MeV $sup 4$He$sup +$ ions. The determined dechanneling cross section sigmasub(d) of the vacancy cluster in Ni was: 4 . 10$sup -15$ cm$sup 2$<=sigmasub(d)<=1.7 . 10$sup -14$cm$sup 2$ for 2MeV $sup 4$He$sup +$. These values are found within the limits of the dechanneling cross sections determined by MERKLE for defect clusters in Au which were between 4 . 10$sup -15$ and 2.4 . 10$sup -14$cm$sup 2$ for the same particles and energies. The average cascade radius was found between 50Amore » and 90A. (FR)« less

Microdistribution of Impurities in Semiconductors and its Influence on Photovoltaic Energy Conversion.

NASA Astrophysics Data System (ADS)

Rava, Paolo

In the present investigation the interstitial oxygen distribution in silicon has been measured on a microscale and correlated to the activation of thermal donors by 450(DEGREES)C heat treatment. Scanning IR absorption was used to measure the axyal oxygen microdistribution at different distances from the edge of the crystal. The free carrier microdistribution along the same locations was measured, after a 450(DEGREES)C heat treatment, using a spreading resistance probe. A comparison of the two microprofiles revealed direct correspondence in the general features, but no correlation between oxygen and thermal donor concentration in some areas; in particular, no activation of donors took place in some areas. After a 650(DEGREES)C heat treatment, all donors were annihilated; after subsequent 450(DEGREES)C heat treament, donors were activated again, but in a different pattern: the areas which were activated the first time now exhibited smaller densities of thermal donors and the areas which were not previously activated exhibited high donor concentration. The microdefect distribution was studied as a function of heat treatment time and compared to the activated donor microprofiles. A high density of B-defects was found in areas where no donor activation took place upon the first heat treatment at 450(DEGREES)C, whereas A-defects were present in areas where donors were activated. Upon 650(DEGREES)C heat treatment B-defects became large and less dense, approaching A-defects and allowing activation of donors upon further 450(DEGREES)C heat treatment. These results are qualitatively in agreement with the vacancy-oxygen model proposed for donor activation. According to this model, an oxygen atom can slip into a silicon vacancy and be bound to this site by bonding one of its electrons with another nearest neighbor vacancy; this complex can then be easily ionized by releasing the extra electron. A neighbor vacancy diffused at 650(DEGREES)C can trap this free electron to form an electrically inert complex. The presence of unactivated areas close to the crystal periphery was attributed to a lower concentration of available vacancies due to the presence of the B-defects (vacancy clusters); a 650(DEGREES)C heat treatment changed their structure, possibly releasing vacancies which then participated in donor formation. On the other hand, the areas activated the first time at 450(DEGREES)C have fewer vacancies available the second time for donor formation and therefore are less activated. It was shown that the vacancy-oxygen complex must be the first step in the formation of multivacancy or any multioxygen donor complexes. The role of a factor other than oxygen in donor activation can be revealed only by a microscale analysis such as the one presented here. In fact, the areas in which donor formation is enhanced by 650(DEGREES)C heat treatment are completely undetected in a macroscale analysis, which therefore would lead to a proportionality between oxygen concentration and activated donors. This work shows that the accepted premise that the concentration of oxygen donors is proportional to the oxygen concentration is not generally valid. Multiple p-n junctions have been prepared in b -doped Si through overcompensation near the oxygen periodic concentration maxima by thermal donors generated during an appropriate heat treatment at 450(DEGREES)C. Application of this structure to photovoltaic energy conversion has been investigated. A new solar cell structure based on multiple p-n junctions was developed and tested. An increase in short circuit current was achieved, but at the same time a degradation in open circuit voltage occurred. An interpretation of the experimental data in the light of the results of a computer simulation showed that an overall increase in efficiency can be achieved in this structure with a small and regular junction spacing. The effect of carrier density inhomogeneities in InP and GaAs samples was then investigated. The same scanning IR absorption technique employed in the first part of this study was used to measure free carrier microprofiles in order to determine the homogeneity of the samples. It was established that the presence of inhomogeneities can lead to a significant ambiguity in the determination on a macroscale of mobility, carrier concentration and absorption coefficient.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaspar, Tiffany C.; Sushko, Peter V.; Bowden, Mark E.

Epitaxial thin films of Cr2-xTixO3 were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) for 0.04 ≤ x ≤ 0.26. Ti speciation is verified by both x-ray photoelectron spectroscopy (XPS) and Ti K-edge x-ray absorption near-edge spectroscopy (XANES) to be Ti4+. Substitution of Ti for Cr in the corundum lattice is confirmed by modeling of the Ti K-edge extended x-ray absorption fine structure (EXAFS). Room temperature electrical transport measurements confirm the highly insulating nature of Ti-doped Cr2O3, despite the presence of aliovalent Ti4+. The resistivity of highly pure, undoped Cr2O3 was measured to be three orders of magnitude higher than formore » Ti-doped Cr2O3. Although the formation of Cr vacancies in Ti-doped Cr2O3 is found by density functional theory (DFT) calculations to be the energetically preferable defect compensation mechanism to maintain charge neutrality, an analysis of the XPS and EXAFS data reveal the presence of both Cr vacancies and oxygen interstitials at intermediate and high Ti concentrations, with a weak trend towards Cr vacancies as the Ti concentration increases. At low Ti concentrations, a strong dependence of the XPS Ti 2p core level peak width on concentration is observed. This dependence is attributed to the presence of widely spaced Ti dopants, which renders compensation of two or three Ti by a single oxygen interstitial or Cr vacancy, respectively, less probable. Instead, defect clusters of unknown type occur, although they may involve Cr vacancies. The defect compensation model developed here provides insight into previous, conflicting reports of n-type versus p-type conductivity in Ti-doped Cr2O3 at high temperature, and will inform future studies to exploit the wide variety of electronic and magnetic properties of corundum-structure oxides.« less

Liquid-like cationic sub-lattice in copper selenide clusters

NASA Astrophysics Data System (ADS)

White, Sarah L.; Banerjee, Progna; Jain, Prashant K.

2017-02-01

Super-ionic solids, which exhibit ion mobilities as high as those in liquids or molten salts, have been employed as solid-state electrolytes in batteries, improved thermoelectrics and fast-ion conductors in super-capacitors and fuel cells. Fast-ion transport in many of these solids is supported by a disordered, `liquid-like' sub-lattice of cations mobile within a rigid anionic sub-lattice, often achieved at high temperatures or pressures via a phase transition. Here we show that ultrasmall clusters of copper selenide exhibit a disordered cationic sub-lattice under ambient conditions unlike larger nanocrystals, where Cu+ ions and vacancies form an ordered super-structure similar to the bulk solid. The clusters exhibit an unusual cationic sub-lattice arrangement wherein octahedral sites, which serve as bridges for cation migration, are stabilized by compressive strain. The room-temperature liquid-like nature of the Cu+ sub-lattice combined with the actively tunable plasmonic properties of the Cu2Se clusters make them suitable as fast electro-optic switches.

Space-filling, multifractal, localized thermal spikes in Si, Ge and ZnO

NASA Astrophysics Data System (ADS)

Ahmad, Shoaib; Abbas, Muhammad Sabtain; Yousuf, Muhammad; Javeed, Sumera; Zeeshan, Sumaira; Yaqub, Kashif

2018-04-01

The mechanism responsible for the emission of clusters from heavy ion irradiated solids is proposed to be thermal spikes. Collision cascade-based theories describe atomic sputtering but cannot explain the consistently observed experimental evidence for significant cluster emission. Statistical thermodynamic arguments for thermal spikes are employed here for qualitative and quantitative estimation of the thermal spike-induced cluster emission from Si, Ge and ZnO. The evolving cascades and spikes in elemental and molecular semiconducting solids are shown to have fractal characteristics. Power law potential is used to calculate the fractal dimension. With the loss of recoiling particles' energy the successive branching ratios get smaller. The fractal dimension is shown to be dependent upon the exponent of the power law interatomic potential D = 1/2m. Each irradiating ion has the probability of initiating a space-filling, multifractal thermal spike that may sublime a localized region near the surface by emitting clusters in relative ratios that depend upon the energies of formation of respective surface vacancies.

Switching Plasmons: Gold Nanorod-Copper Chalcogenide Core-Shell Nanoparticle Clusters with Selectable Metal/Semiconductor NIR Plasmon Resonances.

PubMed

Muhammed, Madathumpady Abubaker Habeeb; Döblinger, Markus; Rodríguez-Fernández, Jessica

2015-09-16

Exerting control over the near-infrared (NIR) plasmonic response of nanosized metals and semiconductors can facilitate access to unexplored phenomena and applications. Here we combine electrostatic self-assembly and Cd(2+)/Cu(+) cation exchange to obtain an anisotropic core-shell nanoparticle cluster (NPC) whose optical properties stem from two dissimilar plasmonic materials: a gold nanorod (AuNR) core and a copper selenide (Cu(2-x)Se, x ≥ 0) supraparticle shell. The spectral response of the AuNR@Cu2Se NPCs is governed by the transverse and longitudinal plasmon bands (LPB) of the anisotropic metallic core, since the Cu2Se shell is nonplasmonic. Under aerobic conditions the shell undergoes vacancy doping (x > 0), leading to the plasmon-rich NIR spectrum of the AuNR@Cu(2-x)Se NPCs. For low vacancy doping levels the NIR optical properties of the dually plasmonic NPCs are determined by the LPBs of the semiconductor shell (along its major longitudinal axis) and of the metal core. Conversely, for high vacancy doping levels their NIR optical response is dominated by the two most intense plasmon modes from the shell: the transverse (along the shortest transversal axis) and longitudinal (along the major longitudinal axis) modes. The optical properties of the NPCs can be reversibly switched back to a purely metallic plasmonic character upon reversible conversion of AuNR@Cu(2-x)Se into AuNR@Cu2Se. Such well-defined nanosized colloidal assemblies feature the unique ability of holding an all-metallic, a metallic/semiconductor, or an all-semiconductor plasmonic response in the NIR. Therefore, they can serve as an ideal platform to evaluate the crosstalk between plasmonic metals and plasmonic semiconductors at the nanoscale. Furthermore, their versatility to display plasmon modes in the first, second, or both NIR windows is particularly advantageous for bioapplications, especially considering their strong absorbing and near-field enhancing properties.

Donor defects and small polarons on the TiO2(110) surface

NASA Astrophysics Data System (ADS)

Moses, P. G.; Janotti, A.; Franchini, C.; Kresse, G.; Van de Walle, C. G.

2016-05-01

The role of defects in the chemical activity of the rutile TiO2(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend to localize in the form of small polarons, which are the factual cause of the deep states ˜1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO2 and related oxides.

Computational nano-material design of exotic luminescent materials based upon europium doped gallium nitrides

NASA Astrophysics Data System (ADS)

Masago, Akira; Fukushima, Tetsuya; Sato, Kazunori; Katayama-Yoshida, Hiroshi

2015-03-01

Eu-doped GaN has attracted much attention, because the red light luminescence ability provides us with expectations to realize monolithic full-color LEDs, which work on seamless conditions such as substrates, electrodes, and operating bias voltages. Toward implementation of multifunctional activity into the luminescent materials using the spinodal nano-structures, we investigate atomic configurations and magnetic structures of the GaN crystal codoped with Eu, Mg, Si, O, and/or the vacancies using the density functional method (DFT) calculations. Our calculations show that the impurity clusterized distributions are energetically favorable more than the homogeneous distribution. Moreover, analyses of the formation energy and binding energy suggest that the clusterized distributions are spontaneously formed by the nano-spinodal decomposition. Though the host matrix has no magnetic moments, the cluster has finite magnetic moments, where Zener's p-f exchange interaction works between the Eu f-state and the nearby N p-states.

A Low Temperature, Ultrahigh Vacuum, Microwave-Frequency-Compatible Scanning Tunneling Microscope

DTIC Science & Technology

1994-05-01

vibrationally decoupled from the chamber using a Subadmed oo -3.- 21 April 1994 Reviw of Sdent* k Immownu Low Topasom UHV ACS7M Stranick et al...molecules, two isolated clusters of benzene molecules on the upper terrace, and several vacancy defects in the Cu(111) surface on the lower terrace...fine and is easily removed and replaced. 11. National Electrostatics Corporation, Middleton, WI. 12. K . Besocke, Surf. Sci. 181, 145 (1987); J. Frohn, J

Effects of oxide distributed in grain boundaries on microstructure stability of nanocrystalline metals

NASA Astrophysics Data System (ADS)

Zhou, Kai; Li, Hui; Biao Pang, Jin; Wang, Zhu

2013-06-01

Nanocrystalline copper and zinc prepared by high-pressure compaction method have been studied by positron lifetime spectroscopy associated with X-ray diffraction. For nanocrystalline Cu, mean grain sizes of the samples decrease after being annealed at 900 °C and increase during aging at 180 °C, revealing that the atoms exchange between the two regions. The positron lifetime results indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder the grain growth during the ageing at 180 °C, and the vacancy clusters inside the disorder regions which are related to Cu2O need longer aging time to decompose. In the case of nanocrystalline Zn, the open volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ1). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τav) during the annealing, which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. For both nanocrystalline copper and zinc, the oxides in grain boundaries enhance the thermal stability of the microstucture, in spite of their different crystal structures. This effect is very important for the nanocrystalline materials using as radiation resistant materials.

Non-flipping 13C spins near an NV center in diamond: hyperfine and spatial characteristics by density functional theory simulation of the C510[NV]H252 cluster

NASA Astrophysics Data System (ADS)

Nizovtsev, A. P.; Kilin, S. Ya; Pushkarchuk, A. L.; Pushkarchuk, V. A.; Kuten, S. A.; Zhikol, O. A.; Schmitt, S.; Unden, T.; Jelezko, F.

2018-02-01

Single NV centers in diamond coupled by hyperfine interaction (hfi) to neighboring 13C nuclear spins are now widely used in emerging quantum technologies as elements of quantum memory adjusted to a nitrogen-vacancy (NV) center electron spin qubit. For nuclear spins with low flip-flop rate, single shot readout was demonstrated under ambient conditions. Here we report on a systematic search for such stable NV-13C systems using density functional theory to simulate the hfi and spatial characteristics of all possible NV-13C complexes in the H-terminated cluster C510[NV]-H252 hosting the NV center. Along with the expected stable ‘NV-axial-13C’ systems wherein the 13C nuclear spin is located on the NV axis, we found for the first time new families of positions for the 13C nuclear spin exhibiting negligible hfi-induced flipping rates due to near-symmetric local spin density distribution. Spatially, these positions are located in the diamond bilayer passing through the vacancy of the NV center and being perpendicular to the NV axis. Analysis of available publications showed that, apparently, some of the predicted non-axial near-stable NV-13C systems have already been observed experimentally. A special experiment performed on one of these systems confirmed the prediction made.

Initial aging phenomena in copper-chromium alloys

NASA Technical Reports Server (NTRS)

Suzuki, H.; Motohiro, K.

1985-01-01

The effects of quenching and aging temperatures on the initial aging curves of Cu-Cr alloy were examined mainly by means of electrical resistivity measurements. Three Cu-Cr alloy specimens having 0.24, 0.74, and 1.0% Cr were solution-treated at 950-1050 C, quenched into ice-water, and subsequently aged at 300-500 C. The results were as follows: (1) At the very early stage of aging (within about 30 sec), an abrupt decrease of resistivity with lowering aging tempratures. (T sub A) and rising solution temperatures (T sub S) was observed at (T sub A) up to about 400 C. In contrast, a transient increase of resistivity with rising T sub A and lowering T sub S was observed at T sub A from about 450 to 500 C. These phenomena seem to be caused by a rapid formation of solute clusters and the reversion of clusters formed during quenching, which are enhanced by quenched-in vacancies, respectively. (2) The amount of precipitation increased at the latter stage of aging with rising T sub S and T sub A as generally expected, where T sub S was not so high as to form secondary defects. (3) As a result, the initial aging phenomena in Cr-Cr alloy were revealed to be complicated against expectations. This was considered to be due to the migration energy of vacancies so larger in Cu-base.

Effect of defects on the small polaron formation and transport properties of hematite from first-principles calculations

NASA Astrophysics Data System (ADS)

Smart, Tyler J.; Ping, Yuan

2017-10-01

Hematite (α-Fe2O3) is a promising candidate as a photoanode material for solar-to-fuel conversion due to its favorable band gap for visible light absorption, its stability in an aqueous environment and its relatively low cost in comparison to other prospective materials. However, the small polaron transport nature in α-Fe2O3 results in low carrier mobility and conductivity, significantly lowering its efficiency from the theoretical limit. Experimentally, it has been found that the incorporation of oxygen vacancies and other dopants, such as Sn, into the material appreciably enhances its photo-to-current efficiency. Yet no quantitative explanation has been provided to understand the role of oxygen vacancy or Sn-doping in hematite. We employed density functional theory to probe the small polaron formation in oxygen deficient hematite, N-doped as well as Sn-doped hematite. We computed the charged defect formation energies, the small polaron formation energy and hopping activation energies to understand the effect of defects on carrier concentration and mobility. This work provides us with a fundamental understanding regarding the role of defects on small polaron formation and transport properties in hematite, offering key insights into the design of new dopants to further improve the efficiency of transition metal oxides for solar-to-fuel conversion.

Collective relaxation processes in atoms, molecules and clusters

NASA Astrophysics Data System (ADS)

Kolorenč, Přemysl; Averbukh, Vitali; Feifel, Raimund; Eland, John

2016-04-01

Electron correlation is an essential driver of a variety of relaxation processes in excited atomic and molecular systems. These are phenomena which often lead to autoionization typically involving two-electron transitions, such as the well-known Auger effect. However, electron correlation can give rise also to higher-order processes characterized by multi-electron transitions. Basic examples include simultaneous two-electron emission upon recombination of an inner-shell vacancy (double Auger decay) or collective decay of two holes with emission of a single electron. First reports of this class of processes date back to the 1960s, but their investigation intensified only recently with the advent of free-electron lasers. High fluxes of high-energy photons induce multiple excitation or ionization of a system on the femtosecond timescale and under such conditions the importance of multi-electron processes increases significantly. We present an overview of experimental and theoretical works on selected multi-electron relaxation phenomena in systems of different complexity, going from double Auger decay in atoms and small molecules to collective interatomic autoionization processes in nanoscale samples.

Coverage dependent molecular assembly of anthraquinone on Au(111)

NASA Astrophysics Data System (ADS)

DeLoach, Andrew S.; Conrad, Brad R.; Einstein, T. L.; Dougherty, Daniel B.

2017-11-01

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Coverage dependent molecular assembly of anthraquinone on Au(111).

PubMed

DeLoach, Andrew S; Conrad, Brad R; Einstein, T L; Dougherty, Daniel B

2017-11-14

A scanning tunneling microscopy study of anthraquinone (AQ) on the Au(111) surface shows that the molecules self-assemble into several structures depending on the local surface coverage. At high coverages, a close-packed saturated monolayer is observed, while at low coverages, mobile surface molecules coexist with stable chiral hexamer clusters. At intermediate coverages, a disordered 2D porous network interlinking close-packed islands is observed in contrast to the giant honeycomb networks observed for the same molecule on Cu(111). This difference verifies the predicted extreme sensitivity [J. Wyrick et al., Nano Lett. 11, 2944 (2011)] of the pore network to small changes in the surface electronic structure. Quantitative analysis of the 2D pore network reveals that the areas of the vacancy islands are distributed log-normally. Log-normal distributions are typically associated with the product of random variables (multiplicative noise), and we propose that the distribution of pore sizes for AQ on Au(111) originates from random linear rate constants for molecules to either desorb from the surface or detach from the region of a nucleated pore.

Diamond nitrogen vacancy electronic and nuclear spin-state anti-crossings under weak transverse magnetic fields

NASA Astrophysics Data System (ADS)

Clevenson, Hannah; Chen, Edward; Dolde, Florian; Teale, Carson; Englund, Dirk; Braje, Danielle

2016-05-01

We report on detailed studies of electronic and nuclear spin states in the diamond nitrogen vacancy (NV) center under moderate transverse magnetic fields. We numerically predict and experimentally verify a previously unobserved NV ground state hyperfine anti-crossing occurring at magnetic bias fields as low as tens of Gauss - two orders of magnitude lower than previously reported hyperfine anti-crossings at ~ 510 G and ~ 1000 G axial magnetic fields. We then discuss how this regime can be optimized for magnetometry and other sensing applications and propose a method for how the nitrogen-vacancy ground state Hamiltonian can be manipulated by small transverse magnetic fields to polarize the nuclear spin state. Acknowlegement: The Lincoln Laboratory portion of this work is sponsored by the Assistant Secretary of Defense for Research & Engineering under Air Force Contract #FA8721-05-C-0002. Opinions, interpretations, conclusions and recommendations are those of the authors and are not necessarily endorsed by the United States Government.

Solution nuclear magnetic resonance spectroscopy on a nanostructured diamond chip.

PubMed

Kehayias, P; Jarmola, A; Mosavian, N; Fescenko, I; Benito, F M; Laraoui, A; Smits, J; Bougas, L; Budker, D; Neumann, A; Brueck, S R J; Acosta, V M

2017-08-04

Sensors using nitrogen-vacancy centers in diamond are a promising tool for small-volume nuclear magnetic resonance (NMR) spectroscopy, but the limited sensitivity remains a challenge. Here we show nearly two orders of magnitude improvement in concentration sensitivity over previous nitrogen-vacancy and picoliter NMR studies. We demonstrate NMR spectroscopy of picoliter-volume solutions using a nanostructured diamond chip with dense, high-aspect-ratio nanogratings, enhancing the surface area by 15 times. The nanograting sidewalls are doped with nitrogen-vacancies located a few nanometers from the diamond surface to detect the NMR spectrum of roughly 1 pl of fluid lying within adjacent nanograting grooves. We perform 1 H and 19 F nuclear magnetic resonance spectroscopy at room temperature in magnetic fields below 50 mT. Using a solution of CsF in glycerol, we determine that 4 ± 2 × 10 12 19 F spins in a 1 pl volume can be detected with a signal-to-noise ratio of 3 in 1 s of integration.Nitrogen vacancy (NV) centres in diamond can be used for NMR spectroscopy, but increased sensitivity is needed to avoid long measurement times. Kehayias et al. present a nanostructured diamond grating with a high density of NV centres, enabling NMR spectroscopy of picoliter-volume solutions.

Oxygen vacancy doping of hematite analyzed by electrical conductivity and thermoelectric power measurements

NASA Astrophysics Data System (ADS)

Mock, Jan; Klingebiel, Benjamin; Köhler, Florian; Nuys, Maurice; Flohre, Jan; Muthmann, Stefan; Kirchartz, Thomas; Carius, Reinhard

2017-11-01

Hematite (α -F e2O3 ) is known for poor electronic transport properties, which are the main drawback of this material for optoelectronic applications. In this study, we investigate the concept of enhancing electrical conductivity by the introduction of oxygen vacancies during temperature treatment under low oxygen partial pressure. We demonstrate the possibility of tuning the conductivity continuously by more than five orders of magnitude during stepwise annealing in a moderate temperature range between 300 and 620 K. With thermoelectric power measurements, we are able to attribute the improvement of the electrical conductivity to an enhanced charge-carrier density by more than three orders of magnitude. We compare the oxygen vacancy doping of hematite thin films with hematite nanoparticle layers. Thereby we show that the dominant potential barrier that limits charge transport is either due to grain boundaries in hematite thin films or due to potential barriers that occur at the contact area between the nanoparticles, rather than the potential barrier within the small polaron hopping model, which is usually applied for hematite. Furthermore, we discuss the transition from oxygen-deficient hematite α -F e2O3 -x towards the magnetite F e3O4 phase of iron oxide at high density of vacancies.

Temporal and voltage stress stability of high performance indium-zinc-oxide thin film transistors

NASA Astrophysics Data System (ADS)

Song, Yang; Katsman, Alexander; Butcher, Amy L.; Paine, David C.; Zaslavsky, Alexander

2017-10-01

Thin film transistors (TFTs) based on transparent oxide semiconductors, such as indium zinc oxide (IZO), are of interest due to their improved characteristics compared to traditional a-Si TFTs. Previously, we reported on top-gated IZO TFTs with an in-situ formed HfO2 gate insulator and IZO active channel, showing high performance: on/off ratio of ∼107, threshold voltage VT near zero, extracted low-field mobility μ0 = 95 cm2/V·s, and near-perfect subthreshold slope at 62 mV/decade. Since device stability is essential for technological applications, in this paper we report on the temporal and voltage stress stability of IZO TFTs. Our devices exhibit a small negative VT shift as they age, consistent with an increasing carrier density resulting from an increasing oxygen vacancy concentration in the channel. Under gate bias stress, freshly annealed TFTs show a negative VT shift during negative VG gate bias stress, while aged (>1 week) TFTs show a positive VT shift during negative VG stress. This indicates two competing mechanisms, which we identify as the field-enhanced generation of oxygen vacancies and the field-assisted migration of oxygen vacancies, respectively. A simplified kinetic model of the vacancy concentration evolution in the IZO channel under electrical stress is provided.

Computation of heats of transport in crystalline solids: II

NASA Astrophysics Data System (ADS)

Grout, P. J.; Lidiard, A. B.

2008-10-01

This paper explores the application of classical molecular dynamics to the computation of the heat of transport of Au atoms in a model of solid gold at several elevated temperatures above the Debye temperature. It is assumed that the solid shows vacancy disorder. The work shows that to obtain consistent and reliable results it is necessary (a) to use very small time steps (≈1 fs) in the molecular dynamics integration routine and (b) to take averages over a very large number of vacancy displacements—a number which varies with temperature but which is of the order of 105. The results for the reduced heat of transport for the Au atoms show that: (1) it is positive in sign, i.e. that the diffusion of Au atoms in a temperature gradient is biassed towards the cold region or equivalently that the vacancies tend to migrate towards the hotter region; (2) it is predicted to fall as the average temperature increases and that the variation is closely linear in (1/T); (3) its value at high T relative to the energy of activation for vacancy movement is close to the corresponding ratio of experimental quantities. Analysis of these results indicates that the method and model may allow reliable predictions for other metals having the face centred cubic structure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Hao; Materials Science Program, University of Wisconsin, Madison, Wisconsin 53706; Stewart, Derek A., E-mail: derek.stewart@hgst.com

Metal oxide resistive memory devices based on Ta{sub 2}O{sub 5} have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta{sub 2}O{sub 5} is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta{sub 2}O{sub 5}. Identified diffusion paths are associated with collective motion of neighboringmore » atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta{sub 2}O{sub 5} is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta{sub 2}O{sub 5} based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.« less

Direct experimental observation of nonclassicality in ensembles of single-photon emitters

NASA Astrophysics Data System (ADS)

Moreva, E.; Traina, P.; Forneris, J.; Degiovanni, I. P.; Ditalia Tchernij, S.; Picollo, F.; Brida, G.; Olivero, P.; Genovese, M.

2017-11-01

In this work we experimentally demonstrate a recently proposed criterion addressed to detect nonclassical behavior in the fluorescence emission of ensembles of single-photon emitters. In particular, we apply the method to study clusters of nitrogen-vacancy centers in diamond characterized with single-photon-sensitive confocal microscopy. Theoretical considerations on the behavior of the parameter at any arbitrary order in the presence of Poissonian noise are presented and, finally, the opportunity of detecting manifold coincidences is discussed.

Electronic structure and nature of the color centers in MgF2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freidman, S.P.; Golota, A.F.; Galakhov, V.R.

1986-09-01

The electronic structure and spectroscopic properties of samples of magnesium fluoride with different numbers of defects have been investigated with the use of the methods of x-ray photoelectron, x-ray emission, ESR, and optical spectroscopy. Nonempirical self-consistent calculations of the electronic structure of clusters which simulate stoichiometric and defective MgF2 have been carried out. The color centers in the approx. 5-eV energy range are attributed to the presence of vacancies in the anionic sublattice.

Positron Annihilation in Polycrystalline Silver Samples Subjected to the Stretching Force

NASA Astrophysics Data System (ADS)

Pajak, J.; Rudzińska, W.; Pietrzak, R.; Szymański, Cz.; Smiatek, W.

Angular distributions of the positron annihilation quanta, positron lifetime and resistivity were measured for polycrystalline silver samples deformed by uniaxial tension up to different deformation degrees. The S parameter as a function of deformation degree of the sample has been determined. The data obtained for silver samples elongated up to different elongation degrees indicate the dominant role of vacancies and larger defects type clusters created during the deformation process. The positron annihilation data are corrob-orated by results obtained by resistivity measurements.

Atomic origins of water-vapour-promoted alloy oxidation

NASA Astrophysics Data System (ADS)

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K.; Baer, Donald R.; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M.; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion1-4. Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys5,6. However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Two-dimensional nanowires on homoepitaxial interfaces: Atomic-scale mechanism of breakdown and disintegration

NASA Astrophysics Data System (ADS)

Michailov, Michail; Ranguelov, Bogdan

2018-03-01

We present a model for hole-mediated spontaneous breakdown of ahomoepitaxial two-dimensional (2D) flat nanowire based exclusively on random, thermally-activated motion of atoms. The model suggests a consecutive three-step mechanism driving the rupture and complete disintegration of the nanowire on a crystalline surface. The breakdown scenario includes: (i) local narrowing of a part of the stripe to a monatomic chain, (ii) formation of a recoverable single vacancy or a 2D vacancy cluster that causes temporary nanowire rupture, (iii) formation of a non-recoverable 2D hole leading to permanent nanowire breakdown. These successive events in the temporal evolution of the nanowire morphology bring the nanowire stripe into an irreversible unstable state, leading to a dramatic change in its peculiar physical properties and conductivity. The atomistic simulations also reveal a strong increase of the nanowire lifetime with an enlargement of its width and open up a way for a fine atomic-scale control of the nanowire lifetime and structural, morphological and thermodynamic stability.

Oxygen vacancies controlled multiple magnetic phases in epitaxial single crystal Co 0.5(Mg 0.55Zn 0.45) 0.5O 1-v thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Dapeng; Cao, Qiang; Qiao, Ruimin

2016-04-11

High quality single-crystal fcc-Co x (Mg y Zn 1-y ) 1-x O 1-v epitaxial thin films with high Co concentration up to x = 0.5 have been fabricated by molecular beam epitaxy. Systematic magnetic property characterization and soft X-ray absorption spectroscopy analysis indicate that the coexistence of ferromagnetic regions, superparamagnetic clusters, and non-magnetic boundaries in the as-prepared Co x (Mg y Zn 1-y ) 1-x O 1-v films is a consequence of the intrinsic inhomogeneous distribution of oxygen vacancies. Furthermore, the relative strength of multiple phases could be modulated by controlling the oxygen partial pressure during sample preparation. Armed withmore » both controllable magnetic properties and tunable band-gap, Co x (Mg y Zn 1-y ) 1-x O 1-v films may have promising applications in future spintronics.« less

Effect of nickel on point defects diffusion in Fe – Ni alloys

DOE PAGES

Anento, Napoleon; Serra, Anna; Osetsky, Yury N.

2017-05-05

Iron-Nickel alloys are perspective alloys as nuclear energy structural materials because of their good radiation damage tolerance and mechanical properties. Understanding of experimentally observed features such as the effect of Ni content to radiation defects evolution is essential for developing predictive models of radiation. Recently an atomic-scale modelling study has revealed one particular mechanism of Ni effect related to the reduced mobility of clusters of interstitial atoms in Fe-Ni alloys. In this paper we present results of the microsecond-scale molecular dynamics study of point defects, i.e. vacancies and self-interstitial atoms, diffusion in Fe-Ni alloys. It is found that the additionmore » of Ni atoms affects diffusion processes: diffusion of vacancies is enhanced in the presence of Ni, whereas diffusion of interstitials is reduced and these effects increase at high Ni concentration and low temperature. As a result, the role of Ni solutes in radiation damage evolution in Fe-Ni alloys is discussed.« less

Atomic origins of water-vapour-promoted alloy oxidation.

PubMed

Luo, Langli; Su, Mao; Yan, Pengfei; Zou, Lianfeng; Schreiber, Daniel K; Baer, Donald R; Zhu, Zihua; Zhou, Guangwen; Wang, Yanting; Bruemmer, Stephen M; Xu, Zhijie; Wang, Chongmin

2018-06-01

The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and corrosion 1-4 . Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys 5,6 . However, the atomistic mechanisms behind such oxidation remain elusive. Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a nickel-chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction.

Effects of quench rate and natural ageing on the age hardening behaviour of aluminium alloy AA6060

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strobel, Katharina, E-mail: katharina.strobel@aol.com; Lay, Matthew D.H., E-mail: mlay@fbrice.com; Easton, Mark A., E-mail: mark.easton@rmit.edu.au

Quench sensitivity in Al–Mg–Si alloys has been largely attributed to the solute loss at the heterogeneous nucleation sites, primarily dispersoids, during slow cooling after extrusion. As such, the number density of dispersoids, the solute type and concentration are considered to be the key variables for the quench sensitivity. In this study, quench sensitivity and the influence of natural ageing in a lean Al–Mg–Si alloy, AA6060, which contains few dispersoids, have been investigated by hardness measurement, thermal analysis, transmission electron microscopy (TEM) and positron annihilation lifetime spectroscopy (PALS). It is shown that the quench sensitivity in this alloy is associated withmore » the degree of supersaturation of vacancies after cooling. Due to vacancy annihilation and clustering during natural ageing, the quench sensitivity is more pronounced after a short natural ageing time (30 min) compared to a longer natural ageing time (24 h). Therefore, prolonged natural ageing not only leads to an increase in hardness, but can also have a positive effect on the quench sensitivity of lean Al–Mg–Si alloys. - Highlights: • Significant quench sensitivity observed in AA6060 alloy after 30 min natural ageing • Prolonged natural ageing increased hardness and reduced QS. • Low dispersoid density leads to insignificant QS from non-hardening precipitates. • Vacancy supersaturation identified as a contributor to QS.« less

Electronic structure, magnetic and structural properties of Ni doped ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Shalendra, E-mail: shailuphy@gmail.com; Vats, Prashant; Gautam, S.

Highlights: • XRD, and HR-TEM results show the single phase nature of Ni doped ZnO nanoparticles. • dc magnetization results indicate the RT-FM in Ni doped ZnO nanoparticles. • Ni L{sub 3,2} edge NEXAFS spectra infer that Ni ions are in +2 valence state. • O K edge NEXAFS spectra show that O vacancy increases with Ni doping in ZnO. - Abstract: We report structural, magnetic and electronic structural properties of Ni doped ZnO nanoparticles prepared by auto-combustion method. The prepared nanoparticles were characterized by using X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), near edge X-ray absorption finemore » structure (NEXAFS) spectroscopy, and dc magnetization measurements. The XRD and HR-TEM results indicate that Ni doped ZnO nanoparticles have single phase nature with wurtzite lattice and exclude the presence of secondary phase. NEXAFS measurements performed at Ni L{sub 3,2}-edges indicates that Ni ions are in +2 valence state and exclude the presence of Ni metal clusters. O K-edge NEXAFS spectra indicate an increase in oxygen vacancies with Ni-doping, while Zn L{sub 3,2}-edge show the absence of Zn-vacancies. The magnetization measurements performed at room temperature shows that pure and Ni doped ZnO exhibits ferromagnetic behavior.« less

Compositional and Ionic-Size Controls on the Diffusion of Divalent Cations in Garnet: Insights from Atomistic Simulations

NASA Astrophysics Data System (ADS)

Carlson, W. D.

2012-12-01

Divalent cations in garnet (Mg, Fe, Mn, Ca) diffuse at rates that depend strongly on the host-crystal composition and on the ionic radius of the diffusant. Understanding of the nanoscale basis for these behaviors comes from atomistic simulations that calculate energies in the static limit for the defects and transition-state configurations associated with each diffusive step. Diffusion of divalent cations requires (a) creation of a cation-vacancy defect in a dodecahedral site and of a charge-compensating oxygen-vacancy defect that may or may not be in close spatial association; (b) except in the case of self-diffusion, creation of an impurity defect in which a foreign atom replaces the normal atom in a dodecahedral site adjacent to the vacancy; and (c) during the diffusive process, motion of the diffusing atom to a 'saddlepoint' position that represents the transition-state configuration. Comparisons of the system's energy in these various states, in structures of different composition and for ions of different ionic size, allows assessment of the nanoscale controls on diffusion kinetics. Molecular-statics calculations quantify defect energies and identify the transition-state configuration: the maximum energy along the diffusion path between two adjacent dodecahedral sites results when the diffusing ion is surrounded symmetrically by the six oxygen atoms that lie between the two sites. Across the range of end-member compositions, self-diffusion coefficients measured at identical conditions, and the tracer diffusivity of a single ion measured at identical conditions, can each vary by five orders of magnitude or more. Measured activation energies for these motions, however, are all equivalent to within ±6%. Calculated activation energies are in agreement with observations, in that they vary by only ±10%. Calculated vacancy-formation energies, on the other hand, are significantly larger in expanded structures; for example, that energy is greater for Prp than for Grs by ~ 470 kJ/mol. Thus in expanded structures, much higher vacancy concentrations can be produced at the same energetic cost, greatly enhancing rates of diffusion. The primary explanation for the more rapid diffusion of divalent cations in structures with larger cell dimensions therefore comes not from reduced saddlepoint strain energies in more compliant structures, but instead from the smaller energy required to create vacancy defects. Diffusivities of divalent cations exhibit a curious parabolic dependence on ionic size: for each structure, an optimally-sized ion exists, close in size to the dominant ion, that exhibits the fastest diffusion. Larger ions — and enigmatically, smaller ions — both diffuse more slowly. Calculated impurity-defect energies show that undersized impurity ions are bound more tightly in their sites, but the effects are too small in comparison to corresponding reductions in strain energy for the transition-state configuration to account for observed rate differences. Calculated vacancy-association energies reveal a slight tendency for vacancies to associate preferentially with larger impurity ions, but again the effect appears to be too small to provide a full explanation for observed behaviors.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

Trails of Kilovolt Ions Created by Subsurface Channeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Redinger, Alex; Standop, Sebastian; Michely, Thomas

2010-02-19

Using scanning tunneling microscopy, we observe the damage trails produced by keV noble-gas ions incident at glancing angles onto Pt(111). Surface vacancies and adatoms aligned along the ion trajectory constitute the ion trails. Atomistic simulations reveal that these straight trails are produced by nuclear (elastic) collisions with surface layer atoms during subsurface channeling of the projectiles. In a small energy window around 5 keV, Xe{sup +} ions create vacancy grooves that mark the ion trajectory with atomic precision. The asymmetry of the adatom production on the two sides of the projectile path is traced back to the asymmetry of themore » ion's subsurface channel.« less

The role of silicon, vacancies, and strain in carbon distribution for low temperature bainite

DOE PAGES

Sampath, S.; Rementeria, R.; Huang, X.; ...

2016-02-19

Here, we investigated the phenomenon of carbon supersaturation and carbon clustering in bainitic ferrite with atom probe tomography (APT) and ab-initio density functional theory (DFT) calculations. The experimental results show a homogeneous distribution of silicon in the microstructure, which contains both ferrite and retained austenite. This distribution is mimicked well by the computational approach. In addition, an accumulation of C in certain regions of the bainitic ferrite with C concentrations up to 13 at % is observed. Based on the DFT results, these clusters are explained as strained, tetragonal regions in the ferritic bainite, in which the solution enthalpy ofmore » C can reach large, negative values. It seems that Si itself only has a minor influence on this phenomenon.« less

Interfacial diffusion aided deformation during nanoindentation

DOE PAGES

Samanta, Amit; E., Weinan

2015-07-06

Nanoindentation is commonly used to quantify the mechanical response of material surfaces. Despite its widespread use, a detailed understanding of the deformation mechanisms responsible for plasticity during these experiments has remained elusive. Nanoindentation measurements often show stress values close to a material’s ideal strength which suggests that dislocation nucleation and subsequent dislocation activity dominates the deformation. However, low strain-rate exponents and small activation volumes have also been reported which indicates high temperature sensitivity of the deformation processes. Using an order parameter aided temperature accelerated sampling technique called adiabatic free energy dynamics [J. B. Abrams and M. E. Tuckerman, J. Phys.more » Chem. B, 112, 15742 (2008)], and molecular dynamics we have probed the diffusive mode of deformation during nanoindentation. Localized processes such as surface vacancy and ad-atom pair formation, vacancy diffusion are found to play an important role during indentation. Furthermore, our analysis suggests a change in the dominant deformation mode from dislocation mediated plasticity to diffusional flow at high temperatures, slow indentation rates and small indenter tip radii.« less

Donor defects and small polarons on the TiO{sub 2}(110) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moses, P. G.; Janotti, A., E-mail: janotti@udel.edu; Van de Walle, C. G.

2016-05-14

The role of defects in the chemical activity of the rutile TiO{sub 2}(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend tomore » localize in the form of small polarons, which are the factual cause of the deep states ∼1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO{sub 2} and related oxides.« less

Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chelikowsky, James R.

2014-04-14

We explored a wide variety of oxide materials and related problems, including materials at the nanoscale and generic problems associated with oxide materials such as the development of more efficient computational tools to examine these materials. We developed and implemented methods to understand the optical and structural properties of oxides. For ground state properties, our work is predominantly based on pseudopotentials and density functional theory (DFT), including new functionals and going beyond the local density approximation (LDA): LDA+U. To study excited state properties (quasiparticle and optical excitations), we use time dependent density functional theory, the GW approach, and GW plusmore » Bethe-Salpeter equation (GW-BSE) methods based on a many-body Green function approaches. Our work focused on the structural, electronic, optical and magnetic properties of defects (such as oxygen vacancies) in hafnium oxide, titanium oxide (both bulk and clusters) and related materials. We calculated the quasiparticle defect states and charge transition levels of oxygen vacancies in monoclinic hafnia. we presented a milestone G0W0 study of two of the crystalline phases of dye-sensitized TiO{sub 2} clusters. We employed hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. To identify the possible effect of epitaxial strain on stabilization of the ferromagnetic state of LaCoO{sub 3} (LCO), we compare the total energy of the magnetic and nonmagnetic states of the strained theoretical bulk structure.« less

Small polarons and point defects in LaFeO3

NASA Astrophysics Data System (ADS)

Zhu, Zhen; Peelaers, Hartwin; van de Walle, Chris G.

The proton-conductive perovskite-type LaFeO3 is a promising negative-electrode material for Ni/metal-hydride (Ni-MH) batteries. It has a discharge capacity up to 530 mAhg-1 at 333 K, which is significantly higher than commercialized AB5-type alloys. To elucidate the underlying mechanism of this performance, we have investigated the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects, using hybrid density functional methods. LaFeO3 is antiferromagnetic in the ground state with a band gap of 3.54 eV. Small hole and electron polarons can form through self- or point-defect-assisted trapping. We find that La vacancies and Sr substitutional on La sites are shallow acceptors with the induced holes trapped as small polarons, while O and Fe vacancies are deep defect centers. Hydrogen interstitials behave like shallow donors, with the donor electrons localized on nearby iron sites as electron polarons. With a large trapping energy, these polarons can act as electron or hole traps and affect the electrical performance of LaFeO3 as the negative electrode for Ni-MH batteries. We acknowledge DOE for financial support.

Fast self-diffusion of ions in CH 3 NH 3 PbI 3 : the interstiticaly mechanism versus vacancy-assisted mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang

2016-01-01

The stability of organic-inorganic halide perovskites is a major challenge for their applications and has been extensively studied. Among the possible underlying reasons, ion self-diffusion has been inferred to play important roles. While theoretical studies congruously support that iodine is more mobile, experimental studies only observe the direct diffusion of the MA ion and possible diffusion of iodine. The discrepancy may result from the incomplete understanding of ion diffusion mechanisms. With the help of first-principles calculations, we studied ion diffusion in CH3NH3PbI3 (MAPbI3) through not only the vacancy-assisted mechanisms presumed in previous theoretical studies, but also the neglected interstiticaly mechanisms.more » We found that compared to the diffusion through the vacancy-assisted mechanism, MA ion diffusion through the interstiticaly mechanism has a much smaller barrier which could explain experimental observations. For iodine diffusion, both mechanisms can yield relatively small barriers. Depending on the growth conditions, defect densities of vacancies and interstitials can vary and so do the diffusion species as well as diffusion mechanisms. Our work thus supports that both MA and iodine ion diffusion could contribute to the performance instability of MAPbI3. While being congruous with experimental results, our work fills the research gap by providing a full understanding of ion diffusion in halide perovskites.« less

Small Colleges and New Faculty Pay

ERIC Educational Resources Information Center

Marthers, Paul; Parker, Jeff

2008-01-01

Do liberal arts colleges act like research universities when they seek to appoint new faculty members? Evidence shows that research universities bid aggressively for talent, using discretionary salary policies to achieve a diverse professoriate, appoint research stars, and fill vacancies in fields where market forces require differential salaries.…

Nature of water and hydrogen reactions on transition metal surfaces studied by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Tatarkhanov, Mouslim Magomedovich

Scanning Tunneling Microscopy (STM) has already been established as a tool for the investigation of simple reaction mechanisms. In this work I present results of two parallel studies using STM: first, hydrogen on Ru(0001) surface and second, water on Ru(0001) and Pd(111). In both studies initial stages of adsorption up to saturation monolayer coverage were investigated by variable temperature scanning tunneling microscopy (VT STM). The first step of the hydrogen adsorption study was the identification and characterization of the various coverage structures on clean Ru(0001). Hydrogen was found to adsorb dissociatively forming ( 3x3 )R30°, 3 domains of (2x1), (2x2)-3H and (1x1) for increasing coverages of theta=0.3 ML, 0.5 ML, 0.75 ML and 0.1 ML respectively. Some of these structures were observed to coexist at intermediate coverage values. In addition effects of impurities such as oxygen and carbon on hydrogen adsorption has been discussed. Next, near saturation coverage the interesting mechanism of how H 2 dissociates and binds to the surface of Ru(0001) has been observed. We found that the H2 dissociation takes place only on Ru sites where the metal atom is not bound to any H atom. Such active sites are formed when at least 3 H-vacancies aggregate by thermal diffusion. Sites formed by single H-vacancies (i.e. unoccupied Ru sites) or pairs of adjoining vacancies were found to be unreactive toward H2. H-vacancies were observed as single entities diffusing on the surface at 50 K and able to form transient triangular shaped aggregations where H2 molecules dissociated. It was found that the diffusion and aggregation of the H-vacancies is essential in creation of active sites where dissociative adsorption of hydrogen occurs. The first step of water studies was the initial stages of growth of water on the hexagonal surfaces of Pd(111) and Ru(0001) in the temperature range between 40 K and 130 K. In addition, DFT calculations and STM image simulations were used to validate the models. Below 130 K water dissociation does not occur at any appreciable rate and only molecular films are formed. At these temperatures the kinetics of water growth leads to structures where the molecules bind to the metal substrate through the O-lone pair while making 3 H-bonds with neighboring molecules and form clusters of hexagonal units with a honeycomb structure. This bonding geometry imposes limitations to the size of the clusters, with unsaturated H-bonds confined to the cluster periphery. It is found that growth proceeds by attachement of water molecules to the edge of the clusters by H-bonds. These molecules bind only weakly to the metal substrate and can hop around the edges. Comparison of DFT and STM image calculations with experiments shows that on Pd the edge-attached molecules form two different structures, a metastable one where the molecule is elevated by 2.7 A with respect to the cluster molecules, and another where they are elevated by only 0.4 A. On Ru only the less elevated (0.4 A higher) edge-attached molecules are observed. In next final step, water structures on Ru(0001) were studied at temperatures above 140K. STM findings were backed by x-ray absorption spectroscopy. Additional DFT calculations and STM simulations provided validation of proposed models. It was found that while undissociated water layers are metastable below 140 K, heating above this temperature produces drastic transformations whereby a fraction of the water molecules partially dissociate and form mixed H 2O-OH structures. XPS and XAS revealed the presence of hydroxyl groups with their O-H bond essentiallymostly parallel to the surface. STM images show that the mixed H2O-OH structures consist of long narrow stripes aligned with the three crystallographic directions perpendicular to the close-packed atomic rows of the Ru(0001) substrate. The internal structure of the stripes is a honeycomb network of H-bonded water and hydroxyl species. We found that the metastable low temperature molecular phase can also be converted to a mixed H2O-OH phase through excitation by the tunneling electrons when their energy is 0.5 eV or higher above the Fermi level. Structural models based on the STM images were used for Density Functional Theory optimizations of the stripes geometry. The optimized geometry was then utilized to calculate STM images for comparison with the experiment.

Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ

DOE PAGES

Wu, Xuewang; Walter, Jeff; Feng, Tianli; ...

2017-11-02

Here, ultrafast time-domain thermoreflectance (TDTR) is utilized to extract the through-plane thermal conductivity (Λ LSCO) of epitaxial La 0.5Sr 0.5CoO 3–δ (LSCO) of varying thickness (<20 nm) on LaAlO 3 and SrTiO 3 substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room-temperature Λ LSCO of LSCO on both substrates (1.7 W m –1 K –1) are nearly a factor of four lower than that of bulk single-crystal LSCO (6.2more » W m –1 K –1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m –1 K –1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass-like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured Λ LSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution to Λ LSCO along the through-plane direction for these ultrathin LSCO films on insulating substrates.« less

Glass-Like Through-Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ [Glass-Like Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5Sr 0.5CoO 3– δ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Xuewang; Walter, Jeff; Feng, Tianli

Here, ultrafast time-domain thermoreflectance (TDTR) is utilized to extract the through-plane thermal conductivity (Λ LSCO) of epitaxial La 0.5Sr 0.5CoO 3–δ (LSCO) of varying thickness (<20 nm) on LaAlO 3 and SrTiO 3 substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room-temperature Λ LSCO of LSCO on both substrates (1.7 W m –1 K –1) are nearly a factor of four lower than that of bulk single-crystal LSCO (6.2more » W m –1 K –1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m –1 K –1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass-like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured Λ LSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution to Λ LSCO along the through-plane direction for these ultrathin LSCO films on insulating substrates.« less

Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

NASA Astrophysics Data System (ADS)

Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh

2015-12-01

Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.

Geometric and electronic structures of monolayer hexagonal boron nitride with multi-vacancy

NASA Astrophysics Data System (ADS)

Kim, Do-Hyun; Kim, Hag-Soo; Song, Min Woo; Lee, Seunghyun; Lee, Sang Yun

2017-05-01

Hexagonal boron nitride (h-BN) is an electrical insulator with a large band gap of 5 eV and a good thermal conductor of which melting point reaches about 3000 °C. Due to these properties, much attention was given to the thermal stability rather than the electrical properties of h-BN experimentally and theoretically. In this study, we report calculations that the electronic structure of monolayer h-BN can be influenced by the presence of a vacancy defect which leads to a geometric deformation in the hexagonal lattice structure. The vacancy was varied from mono- to tri-vacancy in a supercell, and different defective structures under the same vacancy density were considered in the case of an odd number of vacancies. Consequently, all cases of vacancy defects resulted in a geometric distortion in monolayer h-BN, and new energy states were created between valence and conduction band with the Fermi level shift. Notably, B atoms around vacancies attracted one another while repulsion happened between N atoms around vacancies, irrespective of vacancy density. The calculation of formation energy revealed that multi-vacancy including more B-vacancies has much lower formation energy than vacancies with more N-vacancies. This work suggests that multi-vacancy created in monolayer h-BN will have more B-vacancies and that the presence of multi-vacancy can make monolayer h-BN electrically conductive by the new energy states and the Fermi level shift.

Geometric and electronic structures of monolayer hexagonal boron nitride with multi-vacancy.

PubMed

Kim, Do-Hyun; Kim, Hag-Soo; Song, Min Woo; Lee, Seunghyun; Lee, Sang Yun

2017-01-01

Hexagonal boron nitride (h-BN) is an electrical insulator with a large band gap of 5 eV and a good thermal conductor of which melting point reaches about 3000 °C. Due to these properties, much attention was given to the thermal stability rather than the electrical properties of h-BN experimentally and theoretically. In this study, we report calculations that the electronic structure of monolayer h-BN can be influenced by the presence of a vacancy defect which leads to a geometric deformation in the hexagonal lattice structure. The vacancy was varied from mono- to tri-vacancy in a supercell, and different defective structures under the same vacancy density were considered in the case of an odd number of vacancies. Consequently, all cases of vacancy defects resulted in a geometric distortion in monolayer h-BN, and new energy states were created between valence and conduction band with the Fermi level shift. Notably, B atoms around vacancies attracted one another while repulsion happened between N atoms around vacancies, irrespective of vacancy density. The calculation of formation energy revealed that multi-vacancy including more B-vacancies has much lower formation energy than vacancies with more N-vacancies. This work suggests that multi-vacancy created in monolayer h-BN will have more B-vacancies and that the presence of multi-vacancy can make monolayer h-BN electrically conductive by the new energy states and the Fermi level shift.

Defect mediated magnetic interaction and high Tc ferromagnetism in Co doped ZnO nanoparticles.

PubMed

Pal, Bappaditya; Giri, P K

2011-10-01

Structural, optical and magnetic studies have been carried out for the Co-doped ZnO nanoparticles (NPs). ZnO NPs are doped with 3% and 5% Co using ball milling and ferromagnetism (FM) is studied at room temperature and above. A high Curie temperature (Tc) has been observed from the Co doped ZnO NPs. X-ray diffraction and high resolution transmission electron microscopy analysis confirm the absence of metallic Co clusters or any other phase different from würtzite-type ZnO. UV-visible absorption and photoluminescence studies on the doped samples show change in band structure and oxygen vacancy defects, respectively. Micro-Raman studies of doped samples shows defect related additional strong bands at 547 and 574 cm(-1) confirming the presence of oxygen vacancy defects in ZnO lattice. The field dependence of magnetization (M-H curve) measured at room temperature exhibits the clear M-H loop with saturation magnetization and coercive field of the order of 4-6 emu/g and 260 G, respectively. Temperature dependence of magnetization measurement shows sharp ferromagnetic to paramagnetic transition with a high Tc = 791 K for 3% Co doped ZnO NPs. Ferromagnetic ordering is interpreted in terms of overlapping of polarons mediated through oxygen vacancy defects based on the bound magnetic polaron (BMP) model. We show that the observed FM data fits well with the BMP model involving localised carriers and magnetic cations.

Simulations of defect spin qubits in piezoelectric semiconductors

NASA Astrophysics Data System (ADS)

Seo, Hosung

In recent years, remarkable advances have been reported in the development of defect spin qubits in semiconductors for solid-state quantum information science and quantum metrology. Promising spin qubits include the nitrogen-vacancy center in diamond, dopants in silicon, and the silicon vacancy and divacancy spins in silicon carbide. In this talk, I will highlight some of our recent efforts devoted to defect spin qubits in piezoelectric wide-gap semiconductors for potential applications in mechanical hybrid quantum systems. In particular, I will describe our recent combined theoretical and experimental study on remarkably robust quantum coherence found in the divancancy qubits in silicon carbide. We used a quantum bath model combined with a cluster expansion method to identify the microscopic mechanisms behind the unusually long coherence times of the divacancy spins in SiC. Our study indicates that developing spin qubits in complex crystals with multiple types of atom is a promising route to realize strongly coherent hybrid quantum systems. I will also discuss progress and challenges in computational design of new spin defects for use as qubits in piezoelectric crystals such as AlN and SiC, including a new defect design concept using large metal ion - vacancy complexes. Our first principles calculations include DFT computations using recently developed self-consistent hybrid density functional theory and large-scale many-body GW theory. This work was supported by the National Science Foundation (NSF) through the University of Chicago MRSEC under Award Number DMR-1420709.

Little bits of diamond: Optically detected magnetic resonance of nitrogen-vacancy centers

NASA Astrophysics Data System (ADS)

Zhang, Haimei; Belvin, Carina; Li, Wanyi; Wang, Jennifer; Wainwright, Julia; Berg, Robbie; Bridger, Joshua

2018-03-01

We give instructions for the construction and operation of a simple apparatus for performing optically detected magnetic resonance measurements on diamond samples containing high concentrations of nitrogen-vacancy (NV) centers. Each NV center has a spin degree of freedom that can be manipulated and monitored by a combination of visible and microwave radiation. We observe Zeeman shifts in the presence of small external magnetic fields and describe a simple method to optically measure magnetic field strengths with a spatial resolution of several microns. The activities described are suitable for use in an advanced undergraduate lab course, powerfully connecting core quantum concepts to cutting edge applications. An even simpler setup, appropriate for use in more introductory settings, is also presented.

Effect of γ-IRRADIATION on the Mechanical Properties of Al-Cu Alloy

NASA Astrophysics Data System (ADS)

Abo-Elsoud, M.; Ismail, H.; Sobhy, Maged S.

SEM observations and Vickers hardness tests were performed to identify the irradiation effects. γ-irradiation effect during the aging hardening process can be explained depending on the composition of the alloy and is used to derive quantitative information on the kinetics of the transformation precipitates. Increasing the Cu content of an Al-Cu alloy can improve the aging hardness. The present results of the hardness behavior, with SEM observations of surveillance specimens at different doses, suggest that the radiation-induced defects are probably complex valence-solute clusters. These clusters act as nuclei for the precipitation of θ-Al2Cu type. This can be effectively utilized to study the systematics of nucleation of precipitates at vacancy-type defects. γ-irradiation probably plays the key role in defects responsible for material strengthening and embrittlement.

The formation and structure of Fe-Mn-Ni-Si solute clusters and G-phase precipitates in steels

NASA Astrophysics Data System (ADS)

King, D. J. M.; Burr, P. A.; Middleburgh, S. C.; Whiting, T. M.; Burke, M. G.; Wenman, M. R.

2018-07-01

Solute clustering and G-phase precipitation cause hardening phenomena observed in some low alloy and stainless steels, respectively. Density functional theory was used to investigate the energetic driving force for the formation of these precipitates, capturing temperature effects through analysis of the system's configurational and magnetic entropies. It is shown that enrichment of Mn, Ni and Si is thermodynamically favourable compared to the dilute ferrite matrix of a typical A508 low alloy steel. We predict the ordered G-phase to form preferentially rather than a structure with B2-type ordering when the Fe content of the system falls below 10-18 at. %. The B2 → G-phase transformation is predicted to occur spontaneously when vacancies are introduced into the B2 structure in the absence of Fe.

Monte-Carlo simulation of defect-cluster nucleation in metals during irradiation

NASA Astrophysics Data System (ADS)

Nakasuji, Toshiki; Morishita, Kazunori; Ruan, Xiaoyong

2017-02-01

A multiscale modeling approach was applied to investigate the nucleation process of CRPs (copper rich precipitates, i.e., copper-vacancy clusters) in α-Fe containing 1 at.% Cu during irradiation. Monte-Carlo simulations were performed to investigate the nucleation process, with the rate theory equation analysis to evaluate the concentration of displacement defects, along with the molecular dynamics technique to know CRP thermal stabilities in advance. Our MC simulations showed that there is long incubation period at first, followed by a rapid growth of CRPs. The incubation period depends on irradiation conditions such as the damage rate and temperature. CRP's composition during nucleation varies with time. The copper content of CRPs shows relatively rich at first, and then becomes poorer as the precipitate size increases. A widely-accepted model of CRP nucleation process is finally proposed.

Rhombohedrally Distorted γ-Au 5–x Zn 8+y Phases in the Au–Zn System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thimmaiah, Srinivasa; Miller, Gordon J.

2013-02-04

The region of the Au–Zn phase diagram encompassing γ-brass-type phases has been studied experimentally from 45 to 85 atom % Zn. The γ phases were obtained directly from the pure elements by heating to 680 °C in evacuated silica tubes, followed by annealing at 300 °C. Powder X-ray and single-crystal diffraction studies show that γ-“Au5Zn8” phases adopt a rhombohedrally distorted Cr5Al8 structure type rather than the cubic Cu5Zn8 type. The refined compositions from two single crystals extracted from the Zn- and Au-rich loadings are Au4.27(3)Zn8.26(3)γ0.47 (I) and Au4.58(3)Zn8.12(3)γ0.3 (II), respectively (γ = vacancy). These (I and II) refinements indicated bothmore » nonstatistical mixing of Au and Zn atoms as well as partially ordered vacancy distributions. The structures of these γ phases were solved in the acentric space group R3m (No. 160, Z = 6), and the observed lattice parameters from powder patterns were found to be a = 13.1029(6) and 13.1345(8) Å and c = 8.0410(4) and 8.1103(6) Å for crystals I and II, respectively. According to single-crystal refinements, the vacancies were found on the outer tetrahedron (OT) and octahedron (OH) of the 26-atom cluster. Single-crystal structural refinement clearly showed that the vacancy content per unit cell increases with increasing Zn, or valence-electron concentration. Electronic structure calculations, using the tight-binding linear muffin-tin orbital method with the atomic-sphere approximation (TB-LMTO-ASA) method, indicated the presence of a well-pronounced pseudogap at the Fermi level for “Au5Zn8” as the representative composition, an outcome that is consistent with the Hume–Rothery interpretation of γ brass.« less

Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations

DOE PAGES

Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; ...

2015-01-21

We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO 2|ZrO 2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. Furthermore, these results couldmore » serve as guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.« less

Nitrogen-vacancy-assisted magnetometry of paramagnetic centers in an individual diamond nanocrystal.

PubMed

Laraoui, Abdelghani; Hodges, Jonathan S; Meriles, Carlos A

2012-07-11

Semiconductor nanoparticles host a number of paramagnetic point defects and impurities, many of them adjacent to the surface, whose response to external stimuli could help probe the complex dynamics of the particle and its local, nanoscale environment. Here, we use optically detected magnetic resonance in a nitrogen-vacancy (NV) center within an individual diamond nanocrystal to investigate the composition and spin dynamics of the particle-hosted spin bath. For the present sample, a ∼45 nm diamond crystal, NV-assisted dark-spin spectroscopy reveals the presence of nitrogen donors and a second, yet-unidentified class of paramagnetic centers. Both groups share a common spin lifetime considerably shorter than that observed for the NV spin, suggesting some form of spatial clustering, possibly on the nanoparticle surface. Using double spin resonance and dynamical decoupling, we also demonstrate control of the combined NV center-spin bath dynamics and attain NV coherence lifetimes comparable to those reported for bulk, Type Ib samples. Extensions based on the experiments presented herein hold promise for applications in nanoscale magnetic sensing, biomedical labeling, and imaging.

Effect of reducing atmosphere on the magnetism of Zn(1-x)Co(x)O (0≤x≤0.10) nanoparticles.

PubMed

Naeem, M; Hasanain, S K; Kobayashi, M; Ishida, Y; Fujimori, A; Buzby, Scott; Shah, S Ismat

2006-05-28

We report the crystal structure and magnetic properties of Zn(1-x)Co(x)O (0≤x≤0.10) nanoparticles synthesized by heating metal acetates in organic solvent. The nanoparticles were crystallized in the wurtzite ZnO structure after annealing in air and in a forming gas (Ar95% + H5%). The x-ray diffraction and x-ray photoemission spectroscopy (XPS) data for different Co content show clear evidence for the Co(2+) ions in tetrahedral symmetry, indicating the substitution of Co(2+) in the ZnO lattice. However, samples with x = 0.08 and higher cobalt content also indicate the presence of Co metal clusters. Only those samples annealed in the reducing atmosphere of the forming gas, that showed the presence of oxygen vacancies, exhibited ferromagnetism at room temperature. The air annealed samples remained non-magnetic down to 77 K. The essential ingredient in achieving room temperature ferromagnetism in these Zn(1-x)Co(x)O nanoparticles was found to be the presence of additional carriers generated by the presence of the oxygen vacancies.

Towards direct synthesis of alane: A predicted defect-mediated pathway confirmed experimentally

DOE PAGES

Wang, Lin -Lin; Herwadkar, Aditi; Reich, Jason M.; ...

2016-08-18

Here, alane (AlH 3) is a unique energetic material that has not found a broad practical use for over 70 years because it is difficult to synthesize directly from its elements. Using density functional theory, we examine the defect-mediated formation of alane monomers on Al(111) in a two-step process: (1) dissociative adsorption of H 2 and (2) alane formation, which are both endothermic on a clean surface. Only with Ti dopant to facilitate H 2 dissociation and vacancies to provide Al adatoms, both processes become exothermic. In agreement, in situ scanning tunneling microscopy showed that during H 2 exposure, alanemore » monomers and clusters form primarily in the vicinity of Al vacancies and Ti atoms. Moreover, ball milling of the Al samples with Ti (providing necessary defects) showed a 10 % conversion of Al into AlH 3 or closely related species at 344 bar H 2, indicating that the predicted pathway may lead to the direct synthesis of alane from elements at pressures much lower than the 104 bar expected from bulk thermodynamics.« less

Derivation of effective fission gas diffusivities in UO2 from lower length scale simulations and implementation of fission gas diffusion models in BISON

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersson, Anders David Ragnar; Pastore, Giovanni; Liu, Xiang-Yang

2014-11-07

This report summarizes the development of new fission gas diffusion models from lower length scale simulations and assessment of these models in terms of annealing experiments and fission gas release simulations using the BISON fuel performance code. Based on the mechanisms established from density functional theory (DFT) and empirical potential calculations, continuum models for diffusion of xenon (Xe) in UO 2 were derived for both intrinsic conditions and under irradiation. The importance of the large X eU3O cluster (a Xe atom in a uranium + oxygen vacancy trap site with two bound uranium vacancies) is emphasized, which is a consequencemore » of its high mobility and stability. These models were implemented in the MARMOT phase field code, which is used to calculate effective Xe diffusivities for various irradiation conditions. The effective diffusivities were used in BISON to calculate fission gas release for a number of test cases. The results are assessed against experimental data and future directions for research are outlined based on the conclusions.« less

Optical and electrical responses of magnetron-sputtered amorphous Nb-doped TiO2 thin films annealed at low temperature

NASA Astrophysics Data System (ADS)

Quynh, Luu Manh; Tien, Nguyen Thi; Thanh, Pham Van; Hieu, Nguyen Minh; Doanh, Sai Cong; Thuat, Nguyen Tran; Tuyen, Nguyen Viet; Luong, Nguyen Hoang; Hoang, Ngoc Lam Huong

2018-03-01

Nb-doped TiO2 (TNO) thin films were prepared by annealing at 300 °C for 30 min after a magnetron-sputter process. A laser-irradiated post-annealing Raman scattering analysis indirectly showed the possible formation of small size anatase TNO clusters within the thin film matrix Although the TNO thin films were not crystallized, oxygen vacancies were created by adding H2 into the sputter gas during the deposition process. This improved the conductivity and carrier concentration of the thin films. As the ratio of H2 in sputter gas is f(H2) = [H2/Ar+H2] = 10%, the carrier concentration of the amorphous TNO thin film reached 1022 (cm-3) with the resistivity being about 10-2 (Ω.cm). Even though a new methodology to decrease the fabrication temperature is not presented; this study demonstrates an efficient approach to shorten the annealing process, which ends prior to the crystallization of the thin films. Besides, in situ H2 addition into the sputter atmosphere is proven to be a good solution to enhance the electrical conductivity of semiconductor thin films like TNOs, despite the fact that they are not well crystallized.

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE PAGES

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka; ...

2018-04-04

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials.

PubMed

Németh, Károly; Chapman, Karena W; Balasubramanian, Mahalingam; Shyam, Badri; Chupas, Peter J; Heald, Steve M; Newville, Matt; Klingler, Robert J; Winans, Randall E; Almer, Jonathan D; Sandi, Giselle; Srajer, George

2012-02-21

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials. © 2012 American Institute of Physics

Crystal structure of the new A2SnTa6X18 (A = K, Rb, Cs; X = Cl, Br) cluster compounds

NASA Astrophysics Data System (ADS)

Lemoine, P.; Wilmet, M.; Malaman, B.; Paofai, S.; Dumait, N.; Cordier, S.

2018-01-01

The crystal structure of the new cluster compounds A2SnTa6X18 (with A = K, Rb, Cs, and X = Cl, Br) was determined by using single-crystal and powder X-ray diffraction, and 119Sn Mössbauer spectroscopy. Those compounds crystallize in the Cs2EuNb6Br18-type structure of space group R 3 ̅. This type of structure is built up on discrete edge-bridged [M6Xi12Xa6]4- cluster units arranged according to a pseudo face-centered cubic stacking, where the octahedral and tetrahedral vacancies are fully occupied by divalent tin cations and monovalent alkaline cations, respectively. The tin cations influence on the halogen matrix and the electronic effects on the cluster units in the Cs2EuNb6Br18-type structure are discussed by comparison with isotype compounds. From those analyses, the ionic radius of Sn2+ in coordination number VI is estimated to be 1.14(1) Å. Finally, K2SnTa6Br18 might be considered as a new example of compound containing a quite bare stannous ion (5 s2 configuration).

Edge effect on a vacancy state in semi-infinite graphene

NASA Astrophysics Data System (ADS)

Deng, Hai-Yao; Wakabayashi, Katsunori

2014-09-01

The edge effect on a single vacancy state of semi-infinite graphene (SIG) has been studied using Green's function method within the tight-binding model. In the case of infinite graphene, it is known that a vacancy induces a zero-energy resonance state, whose wave function decays inversely with distance (R) from the vacancy and is not normalizable. However, for SIG with an armchair edge, we find that the corresponding wave function decays as R-2 and hence becomes normalizable owing to the intervalley interference caused by the armchair edge. For SIG with a zigzag edge, the vacancy state depends on the sublattice of the vacancy. When the vacancy and the edge belong to different sublattices, the vacancy has no effect on the zero-energy vacancy state. In contrast, when the vacancy is located on the same sublattice as the edge, the resonance state disappears but the wave function at zero energy is strongly distorted near the vacancy. Our results reveal that the presence of edges crucially changes the vacancy state in graphene, and thus such a state can be used to probe the edge structure.

Effect of vacancy defects on generalized stacking fault energy of fcc metals.

PubMed

Asadi, Ebrahim; Zaeem, Mohsen Asle; Moitra, Amitava; Tschopp, Mark A

2014-03-19

Molecular dynamics (MD) and density functional theory (DFT) studies were performed to investigate the influence of vacancy defects on generalized stacking fault (GSF) energy of fcc metals. MEAM and EAM potentials were used for MD simulations, and DFT calculations were performed to test the accuracy of different common parameter sets for MEAM and EAM potentials in predicting GSF with different fractions of vacancy defects. Vacancy defects were placed at the stacking fault plane or at nearby atomic layers. The effect of vacancy defects at the stacking fault plane and the plane directly underneath of it was dominant compared to the effect of vacancies at other adjacent planes. The effects of vacancy fraction, the distance between vacancies, and lateral relaxation of atoms on the GSF curves with vacancy defects were investigated. A very similar variation of normalized SFEs with respect to vacancy fractions were observed for Ni and Cu. MEAM potentials qualitatively captured the effect of vacancies on GSF.

Nanocavity formation processes in MgO( 1 0 0 ) by light ion (D, He, Li) and heavy ion (Kr, Cu, Au) implantation

NASA Astrophysics Data System (ADS)

van Veen, A.; van Huis, M. A.; Fedorov, A. V.; Schut, H.; Labohm, F.; Kooi, B. J.; De Hosson, J. Th. M.

2002-05-01

In studies on the controlled growth of metallic precipitates in MgO it is attempted to use nanometer size cavities as precursors for formation of metallic precipitates. In MgO nanocavities can easily be generated by light gas ion bombardment at room temperature with typically 30 keV ion energy to a dose of 10 16 cm -2, followed by annealing to 1300 K. It has been shown earlier by transmission electron microscopy (TEM) that the cavities (thickness 2-3 nm and length/width 5-10 nm) have a perfectly rectangular shape bounded by {1 0 0} faces. The majority of the gas has been released at this temperature and the cavities are stable until annealing at 1500 K. The depth location of the cavities and the implanted ions is monitored by positron beam analysis, neutron depth profiling, RBS/channeling and energy dispersive spectroscopy. The presence of metallic nanoprecipitates is detected by optical absorption measurements and by high-resolution XTEM. Surprisingly, all the metallic implants induce, in addition to metallic precipitates in a band at the mean ion range, small rectangular and cubic nanocavities. These are most clearly observed at a depth shallower than the precipitate band. In the case of gold the cavities are produced in close proximity to the crystal surface. The results indicate that in MgO vacancy clustering dominates over Frenkel-pair recombination. Results of molecular dynamics calculations will be used to discuss the observed defect recovery and clustering processes in MgO.

Influence of the K+ ions and the superstoichiometric manganese on structure defects, magneto-transport and dielectric properties of magnetoresistive La0.7Ca0.3-xKxMn1+xO3-δ ceramic

NASA Astrophysics Data System (ADS)

Liedienov, N. A.; Pashchenko, A. V.; Pashchenko, V. P.; Prokopenko, V. K.; Tatarchuk, D. D.; Revenko, Yu. F.; Turchenko, V. A.; Burchovetskii, V. V.; Sycheva, V. Ya.; Sil'cheva, A. G.; Didenko, Yu. V.; Levchenko, G. G.

2017-09-01

The structure, its defects, nanostructural clustering and functional properties of the La0.7Ca0.3-xKxMn1+xO3-δ ceramic with x = 0-0.3 have been investigated by x-ray diffraction, thermogravimetric, SEM, resistance, magnetic, magnetoresistance and dielectric spectroscopy methods. We establish that the lattice parameter of the cubic structure increases when the Ca2+ ions are substituted with ions of K+. We show that the real perovskite structure contains different valence states of manganese MnA2 +,MnB3 + and MnB4 + in A- and B-positions, as well as vacancy type point defects, in the form of anionic V(a) and cationic V(c) vacancies. The increase in the content of the superstoichiometric manganese is connected to the nanostructured clustering process. We find that K+ and superstoichiometric manganese cause the increase in relative permittivity ɛ' and dielectric loss tangent angle tg δ. The experimental phase diagram of the magnetic state has been constructed and allows determining the composition of the magnetoresistant La0.7Ca0.3-xKxMn1+xO3-δ ceramics with set magnetotransport properties. The optimal La0.7Ca0.3-xKxMn1+xO3-δ composition showing the highest magnetoresistance effect at room temperature has been determined by comparing the functional properties of lanthanum-calcium, lanthanum-strontium and lanthanum-calcium-potassium manganites.

Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

The two gap transitions in Ge1 -xSnx : Effect of non-substitutional complex defects

NASA Astrophysics Data System (ADS)

Querales-Flores, J. D.; Ventura, C. I.; Fuhr, J. D.; Barrio, R. A.

2016-09-01

The existence of non-substitutional β-Sn defects in Ge1 -xSnx alloys was confirmed by emission channeling experiments [Decoster et al., Phys. Rev. B 81, 155204 (2010)], which established that, although most Sn enters substitutionally (α-Sn) in the Ge lattice, a second significant fraction corresponds to the Sn-vacancy defect complex in the split-vacancy configuration (β-Sn), in agreement with our previous theoretical study [Ventura et al., Phys. Rev. B 79, 155202 (2009)]. Here, we present the electronic structure calculations for Ge1 -xSnx , including the substitutional α-Sn as well as the non-substitutional β-Sn defects. To include the presence of the non-substitutional complex defects in the electronic structure calculation for this multi-orbital alloy problem, we extended the approach for the purely substitutional alloy by Jenkins and Dow [Phys. Rev. B 36, 7994 (1987)]. We employed an effective substitutional two-site cluster equivalent to the real non-substitutional β-Sn defect, which was determined by a Green's functions calculation. We then calculated the electronic structure of the effective alloy purely in terms of substitutional defects, embedding the effective substitutional clusters in the lattice. Our results describe the two transitions of the fundamental gap of Ge1 -xSnx as a function of the total Sn-concentration: namely, from an indirect to a direct gap, first, and the metallization transition at a higher x. They also highlight the role of β-Sn in the reduction of the concentration range, which corresponds to the direct-gap phase of this alloy of interest for the optoelectronics applications.

Associations between the Quality of the Residential Built Environment and Pregnancy Outcomes among Women in North Carolina

PubMed Central

Messer, Lynne C.; Kroeger, Gretchen L.

2011-01-01

Background: The built environment, a key component of environmental health, may be an important contributor to health disparities, particularly for reproductive health outcomes. Objective: In this study we investigated the relationship between seven indices of residential built environment quality and adverse reproductive outcomes for the City of Durham, North Carolina (USA). Methods: We surveyed approximately 17,000 residential tax parcels in central Durham, assessing > 50 individual variables on each. These data, collected using direct observation, were combined with tax assessor, public safety, and U.S. Census data to construct seven indices representing important domains of the residential built environment: housing damage, property disorder, security measures, tenure (owner or renter occupied), vacancy, crime count, and nuisance count. Fixed-slope random-intercept multilevel models estimated the association between the residential built environment and five adverse birth outcomes. Models were adjusted for maternal characteristics and clustered at the primary adjacency community unit, defined as the index block, plus all adjacent blocks that share any portion of a line segment (block boundary) or vertex. Results: Five built environment indices (housing damage, property disorder, tenure, vacancy, and nuisance count) were associated with each of the five outcomes in the unadjusted context: preterm birth, small for gestational age (SGA), low birth weight (LBW), continuous birth weight, and birth weight percentile for gestational age (BWPGA; sex-specific birth weight distributions for infants delivered at each gestational age using National Center for Health Statistics referent births for 2000–2004). However, some estimates were attenuated after adjustment. In models adjusted for individual-level covariates, housing damage remained statistically significantly associated with SGA, birth weight, and BWPGA. Conclusion: This work suggests a real and meaningful relationship between the quality of the residential built environment and birth outcomes, which we argue are a good measure of general community health. PMID:22138639

Titanomagnetite Curie temperatures: Effects of vacancies, chemical/cation ordering and thermal history

NASA Astrophysics Data System (ADS)

Jackson, M. J.; Bowles, J. A.; Lappe, S. C. L. L.; Solheid, P.

2016-12-01

Recent experimental work [Bowles et al, 2013, Nat. Commun.; Jackson and Bowles, 2014, G-cubed] has shown that the Curie temperatures (Tc) of intermediate-composition titanomagnetites (TM30-TM50) depend strongly on thermal history, with Tc increases of ≥100°C produced by moderate-temperature (300°-400° C) annealing in the lab or in slow natural cooling. Equally large decreases are produced by rapid cooling ("quenching") from higher temperatures. The phenomenon is robustly defined and repeatable, but the underlying mechanism remains enigmatic, presumably involving rearrangement of metal cations within the spinel lattice without any change in bulk composition. Previous studies [e.g., Moskowitz and Wanamaker, 1994, GRL; Lattard et al, 2006, JGR] have shown that cation deficiency controls Tc both directly, by changing the ferrous/ferric ratio, and indirectly, by affecting the cation ordering. Our new experiments examined the effects of oxidation state and nonstoichiometry on the magnitude of Tc changes produced by quenching/annealing. In our synthetic TMs these changes are generally relatively small (ΔTc<35°), but when the samples are oxidized by heating in air (150°-250°C for 23-110 h) prior to annealing (300°-400° C for 10-1000 h in vacuum), ΔTc reaches 100°C or more, similar to the changes observed in our natural TMs. Conversely, in our natural samples annealing and quenching can cause quite large changes (ΔTc>100°), but when the samples are embedded in a reducing material (containing graphite), ΔTc becomes insignificant. These results strongly suggest that cation vacancies play an essential role in the cation rearrangements responsible for the observed changes in Tc. XMCD and low-temperature Mossbauer and magnetization measurements show no evidence of corresponding changes in ferrous/ferric site occupancy, and some form of octahedral-site chemical clustering or short-range ordering appears to be the best way to explain the large observed changes in Tc.

24 CFR 891.790 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2010 CFR

2010-04-01

... fulfilled. (b) Vacancies during rent-up. For each unit (or residential space in a group home) that is not... assisted unit (or residential space in a group home) the Borrower is entitled to vacancy payments in the... and the reasons for the vacancy immediately upon learning of the vacancy or prospective vacancy; (3...

Modifications of structural, chemical, and electrical characteristics of Er2O3/Si interface under Co-60 gamma irradiation

NASA Astrophysics Data System (ADS)

Kaya, Senol; Yilmaz, Ercan

2018-03-01

This paper reports the influences of gamma radiation on the structural, electrical, and chemical characteristics of erbium oxide (Er2O3) thin films and the possible mechanisms underlying these irradiation-induced effects. The crystallographic and morphological modifications under gamma irradiation were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively, while radiation influences on electrochemical characteristics were analyzed by X-ray photoelectron spectroscopy (XPS). Furthermore, changes in electrical characteristics were analyzed on the basis of capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements. The XRD results demonstrated that small atomic displacement was observed and that the grain size of the nanostructure slightly increased. Improvements in surface roughness were observed in AFM measurements. The observed variations in the XRD and AFM measurements can be attributed to the radiation-induced local heating and microscopic atomic mobility. In addition, the XPS analysis obviously demonstrated that the oxygen vacancies increased with irradiation dose because of the breaking of Er2O3 and ErxOy bonds. Significant influences of the generated oxygen vacancies on the electrical measurements were observed, and the radiation-induced hole traps, which caused large flat band shifts, can be attributed to the generated oxygen vacancies. The results show that radiation does not degrade the physical characteristics significantly, but the generation of oxygen vacancies considerably increases the electrical sensitivity of the Er2O3 dielectric.

Effect of Ga doping and point defect on magnetism of ZnO

NASA Astrophysics Data System (ADS)

Hou, Qingyu; Zhao, Chunwang; Jia, Xiaofang; Qu, Lingfeng

2017-02-01

The combined influence mechanism of Ga doping and Zn vacancy or O vacancy on magnetism of ZnO is studied using the first-principle calculation. The coexistence of Ga doping and Zn vacancy can achieve a Curie temperature higher than room temperature and the Ga doped ZnO system is a p-type diluted degenerate semiconductor with metalized ferromagnetism. The magnetism of the doping system of Ga doping and Zn vacancy is mainly contributed by double-exchange interaction through the holes of Zn vacancy taking carrier as medium. However, the system of Ga doping and O vacancy is non-magnetic. In the coexistence of Ga doping and Zn vacancy or O vacancy, a close relative distance between doping and vacancy will reduce the formation energy of the doping system but increase the easiness of doping and vacancy, as well as enhance the stability of the doping system.

Big Hopes for a Small Town

ERIC Educational Resources Information Center

Goldman, Jay P.

2004-01-01

Not long after Dennis Roseleip received a superintendency appointment in his native state of Montana, the district's entire administrative team departed, leaving him to fill three principalships in the opening months of his new post. The sudden vacancies were not a statement on the choice of Roseleip, then 44, to lead the Cut Bank Public Schools…

Mechanochemical formation of heterogeneous diamond structures during rapid uniaxial compression in graphite

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew P.; Goldman, Nir

2018-05-01

We predict mechanochemical formation of heterogeneous diamond structures from rapid uniaxial compression in graphite using quantum molecular dynamics simulations. Ensembles of simulations reveal the formation of different diamondlike products starting from thermal graphite crystal configurations. We identify distinct classes of final products with characteristic probabilities of formation, stress states, and electrical properties and show through simulations of rapid quenching that these products are nominally stable and can be recovered at room temperature and pressure. Some of the diamond products exhibit significant disorder and partial closure of the energy gap between the highest-occupied and lowest-unoccupied molecular orbitals (i.e., the HOMO-LUMO gap). Seeding atomic vacancies in graphite significantly biases toward forming products with small HOMO-LUMO gap. We show that a strong correlation between the HOMO-LUMO gap and disorder in tetrahedral bonding configurations informs which kinds of structural defects are associated with gap closure. The rapid diffusionless transformation of graphite is found to lock vacancy defects into the final diamond structure, resulting in configurations that prevent s p3 bonding and lead to localized HOMO and LUMO states with a small gap.

Structural, electronic and optical properties of CO adsorbed on the defective anatase TiO2 (101) surface; a DFT study

NASA Astrophysics Data System (ADS)

Rafique, Muhammad; Shuai, Yong; Hassan, Muhammad

2017-08-01

This paper illustrates the study of stable structural, electronic and optical properties of carbon mono oxide (CO) molecule adsorbed on pure anatase TiO2 (101) surface and CO molecule adsorbed on defective anatase TiO2 (101) surface containing oxygen (O) atom subsurface vacancy using first-principles study calculations based on density functional theory (DFT) method. A foreign molecule CO was added in the interstitial space of anatase TiO2 (101) surface. It was observed that, adsorption of CO molecule is not favorable on pure anatase TiO2 (101) surface, however adsorption process is improved when subsurface contains O atom vacancy defect. In case of anatase TiO2 (101) surface containing subsurface vacancy, adsorption process is exothermic, resulting in stable structures. The adsorption energies calculated for CO molecules adsorbed at O2c site, at defect site and at Ti5c site of anatase surface containing subsurface O vacancy are 0.16 eV (at O2c), 0.32 eV (at defect site) and 0.43 eV (at Ti5c) site. DOS and PDOS plots are calculated for all the structures. Results indicated that CO molecule adsorption introduces surface states at the Fermi energy level (EF) as shown in partial density of states (PDOS) plots. The dielectric matrix and absorption coefficient (α) for defective anatase TiO2 (101) surface, CO adsorbed at O2c site, at defect site and at Ti5C site of anatase TiO2 (101) surface containing O atom subsurface vacancy has been calculated within the random phase approximation (RPA) using VASP (Vienna ab-initio simulation package) code. It was observed that upon CO adsorption at defective anatase surface, real and imaginary dielectric function peaks were shifted towards lower energy level and a small absorption peak was observed at 1.1 eV energy level which is not present in case of defective anatase (101) surface. CO adsorption produces a red shift in the absorption spectrum of anatase TiO2 (101) surface containing subsurface O atom vacancy.

24 CFR 880.611 - Conditions for receipt of vacancy payments.

Code of Federal Regulations, 2014 CFR

2014-04-01

... leased as of the effective date of the Contract, the owner is entitled to vacancy payments in the amount... administrator of the vacancy or prospective vacancy and the reasons for the vacancy immediately upon learning of...

24 CFR 880.611 - Conditions for receipt of vacancy payments.

Code of Federal Regulations, 2010 CFR

2010-04-01

... leased as of the effective date of the Contract, the owner is entitled to vacancy payments in the amount... administrator of the vacancy or prospective vacancy and the reasons for the vacancy immediately upon learning of...

24 CFR 880.611 - Conditions for receipt of vacancy payments.

Code of Federal Regulations, 2011 CFR

2011-04-01

... leased as of the effective date of the Contract, the owner is entitled to vacancy payments in the amount... administrator of the vacancy or prospective vacancy and the reasons for the vacancy immediately upon learning of...

24 CFR 880.611 - Conditions for receipt of vacancy payments.

Code of Federal Regulations, 2012 CFR

2012-04-01

... leased as of the effective date of the Contract, the owner is entitled to vacancy payments in the amount... administrator of the vacancy or prospective vacancy and the reasons for the vacancy immediately upon learning of...

24 CFR 880.611 - Conditions for receipt of vacancy payments.

Code of Federal Regulations, 2013 CFR

2013-04-01

... leased as of the effective date of the Contract, the owner is entitled to vacancy payments in the amount... administrator of the vacancy or prospective vacancy and the reasons for the vacancy immediately upon learning of...

A study of vacancy defects related to gray tracks in KTiOPO{sub 4} (KTP) using positron annihilation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yang; Li, Jing; Wang, Jiyang, E-mail: hdjiang@sdu.edu.cn

For the first time to our knowledge, positron annihilation spectroscopy (PAS) was used to study vacancy defects in KTiOPO{sub 4} (KTP) single crystals. Positron annihilation lifetime spectroscopy combined with dielectric measurements identified the existence of oxygen vacancies and reflected the concentration of vacancy defects in three samples. The vacancy defects in KTP do not consist of monovacancies, but rather vacancy complexes. Doppler broadening indicates that the vacancy defects are distributed uniformly. A relationship is established where a crystal with a low oxygen vacancy concentration and a highly balanced stoichiometry has a higher resistance to gray track formation.

Dependence of Ag/Ga composition ratio in AgGaSe2 thin film

NASA Astrophysics Data System (ADS)

Matsuo, H.; Yoshino, K.; Ikari, T.

2006-09-01

AgGaSe2 thin film was deposited on glass substrates by vacuum evaporation method. The starting material was mixed Ag2Se and Ga2Se3 powders. Ag/Ga ratios of the samples were 1.5, 1.2, 1.0, 0.8, 0.7 and 0.4. The samples were annealed from 100 to 600 °C for 10 min. After these processes, single phase AgGaSe2 thin films could be obtained except Ag/Ga ratio of 0.4 at annealing temperature of 600 °C. Ag-rich samples had large grain. On the other hand, Ga-rich samples had small grain. Furthermore, Ga-rich and Ag-rich samples indicated p- and n-types because of Ag- and/or Ga-vacancy and Se-vacancy, respectively.

24 CFR 891.650 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2010 CFR

2010-04-01

...) Vacancies during rent-up. For each unit that is not leased as of the effective date of the HAP contract, the... the vacancy immediately upon learning of the vacancy or prospective vacancy; (3) Has fulfilled and...

24 CFR 891.650 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) Vacancies during rent-up. For each unit that is not leased as of the effective date of the HAP contract, the... the vacancy immediately upon learning of the vacancy or prospective vacancy; (3) Has fulfilled and...

24 CFR 891.650 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) Vacancies during rent-up. For each unit that is not leased as of the effective date of the HAP contract, the... the vacancy immediately upon learning of the vacancy or prospective vacancy; (3) Has fulfilled and...

24 CFR 891.650 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2011 CFR

2011-04-01

...) Vacancies during rent-up. For each unit that is not leased as of the effective date of the HAP contract, the... the vacancy immediately upon learning of the vacancy or prospective vacancy; (3) Has fulfilled and...

24 CFR 891.650 - Conditions for receipt of vacancy payments for assisted units.

Code of Federal Regulations, 2014 CFR

2014-04-01

...) Vacancies during rent-up. For each unit that is not leased as of the effective date of the HAP contract, the... the vacancy immediately upon learning of the vacancy or prospective vacancy; (3) Has fulfilled and...

Ordered array of CoPc-vacancies filled with single-molecule rotors

NASA Astrophysics Data System (ADS)

Xie, Zheng-Bo; Wang, Ya-Li; Tao, Min-Long; Sun, Kai; Tu, Yu-Bing; Yuan, Hong-Kuan; Wang, Jun-Zhong

2018-05-01

We report the highly ordered array of CoPc-vacancies and the single-molecule rotors inside the vacancies. When CoPc molecules are deposited on Cd(0001) at low-temperature, three types of molecular vacancies appeared randomly in the CoPc monolayer. Annealing the sample to higher temperature leads to the spontaneous phase separation and self-organized arrangement of the vacancies. Highly ordered arrays of two-molecule vacancies and single-molecule vacancies have been obtained. In particular, there is a rotating CoPc molecule inside each single-molecule vacancy, which constitutes the array of single-molecule rotors. These results provide a new routine to fabricate the nano-machines on a large scale.

Strongly Cavity-Enhanced Spontaneous Emission from Silicon-Vacancy Centers in Diamond

DOE PAGES

Zhang, Jingyuan Linda; Sun, Shuo; Burek, Michael J.; ...

2018-01-29

Quantum emitters are an integral component for a broad range of quantum technologies, including quantum communication, quantum repeaters, and linear optical quantum computation. Solid-state color centers are promising candidates for scalable quantum optics due to their long coherence time and small inhomogeneous broadening. However, once excited, color centers often decay through phonon-assisted processes, limiting the efficiency of single-photon generation and photon-mediated entanglement generation. Herein, we demonstrate strong enhancement of spontaneous emission rate of a single silicon-vacancy center in diamond embedded within a monolithic optical cavity, reaching a regime in which the excited-state lifetime is dominated by spontaneous emission into themore » cavity mode. We observe 10-fold lifetime reduction and 42-fold enhancement in emission intensity when the cavity is tuned into resonance with the optical transition of a single silicon-vacancy center, corresponding to 90% of the excited-state energy decay occurring through spontaneous emission into the cavity mode. Here, we also demonstrate the largest coupling strength ( g/2π = 4.9 ± 0.3 GHz) and cooperativity ( C = 1.4) to date for color-center-based cavity quantum electrodynamics systems, bringing the system closer to the strong coupling regime.« less

Lattice continuum and diffusional creep.

PubMed

Mesarovic, Sinisa Dj

2016-04-01

Diffusional creep is characterized by growth/disappearance of lattice planes at the crystal boundaries that serve as sources/sinks of vacancies, and by diffusion of vacancies. The lattice continuum theory developed here represents a natural and intuitive framework for the analysis of diffusion in crystals and lattice growth/loss at the boundaries. The formulation includes the definition of the Lagrangian reference configuration for the newly created lattice, the transport theorem and the definition of the creep rate tensor for a polycrystal as a piecewise uniform, discontinuous field. The values associated with each crystalline grain are related to the normal diffusional flux at grain boundaries. The governing equations for Nabarro-Herring creep are derived with coupled diffusion and elasticity with compositional eigenstrain. Both, bulk diffusional dissipation and boundary dissipation accompanying vacancy nucleation and absorption, are considered, but the latter is found to be negligible. For periodic arrangements of grains, diffusion formally decouples from elasticity but at the cost of a complicated boundary condition. The equilibrium of deviatorically stressed polycrystals is impossible without inclusion of interface energies. The secondary creep rate estimates correspond to the standard Nabarro-Herring model, and the volumetric creep is small. The initial (primary) creep rate is estimated to be much larger than the secondary creep rate.

Lattice continuum and diffusional creep

NASA Astrophysics Data System (ADS)

Mesarovic, Sinisa Dj.

2016-04-01

Diffusional creep is characterized by growth/disappearance of lattice planes at the crystal boundaries that serve as sources/sinks of vacancies, and by diffusion of vacancies. The lattice continuum theory developed here represents a natural and intuitive framework for the analysis of diffusion in crystals and lattice growth/loss at the boundaries. The formulation includes the definition of the Lagrangian reference configuration for the newly created lattice, the transport theorem and the definition of the creep rate tensor for a polycrystal as a piecewise uniform, discontinuous field. The values associated with each crystalline grain are related to the normal diffusional flux at grain boundaries. The governing equations for Nabarro-Herring creep are derived with coupled diffusion and elasticity with compositional eigenstrain. Both, bulk diffusional dissipation and boundary dissipation accompanying vacancy nucleation and absorption, are considered, but the latter is found to be negligible. For periodic arrangements of grains, diffusion formally decouples from elasticity but at the cost of a complicated boundary condition. The equilibrium of deviatorically stressed polycrystals is impossible without inclusion of interface energies. The secondary creep rate estimates correspond to the standard Nabarro-Herring model, and the volumetric creep is small. The initial (primary) creep rate is estimated to be much larger than the secondary creep rate.

SrFe12O19 based ceramics with ultra-low dielectric loss in the millimetre-wave band

NASA Astrophysics Data System (ADS)

Yu, Chuying; Zeng, Yang; Yang, Bin; Wylde, Richard; Donnan, Robert; Wu, Jiyue; Xu, Jie; Gao, Feng; Abrahams, Isaac; Reece, Mike; Yan, Haixue

2018-04-01

Non-reciprocal devices such as isolators and circulators, based mainly on ferromagnetic materials, require extremely low dielectric loss in order for strict power-link budgets to be met for millimetre (mm)-wave and terahertz (THz) systems. The dielectric loss of commercial SrFe12O19 hexaferrite was significantly reduced to below 0.002 in the 75-170 GHz band by thermal annealing. While the overall concentration of Fe2+ and oxygen vacancy defects is relatively low in the solid, their concentration at the surface is significantly higher, allowing for a surface sensitive technique such as XPS to monitor the Fe3+/Fe2+ redox reaction. Oxidation of Fe2+ and a decrease in oxygen vacancies are found at the surface on annealing, which are reflected in the bulk sample by a small change in the unit cell volume. The significant decrease in the dielectric loss property can be attributed to the decreased concentration of charged defects such as Fe2+ and oxygen vacancies through the annealing process, which demonstrated that thermal annealing could be effective in improving the dielectric performance of ferromagnetic materials for various applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Bu; Yu, Yingtian; Bauchy, Mathieu, E-mail: bauchy@ucla.edu

Although quartz (α-form) is a mineral used in numerous applications wherein radiation exposure is an issue, the nature of the atomistic defects formed during radiation-induced damage has not been fully clarified. Especially, the extent of oxygen vacancy formation is still debated, which is an issue of primary importance as optical techniques based on charged oxygen vacancies have been utilized to assess the level of radiation damage in quartz. In this paper, molecular dynamics simulations are applied to study the effects of ballistic impacts on the atomic network of quartz. We show that the defects that are formed mainly consist ofmore » over-coordinated Si and O, as well as Si–O connectivity defects, e.g., small Si–O rings and edge-sharing Si tetrahedra. Oxygen vacancies, on the contrary, are found in relatively low abundance, suggesting that characterizations based on E′ centers do not adequately capture radiation-induced structural damage in quartz. Finally, we evaluate the dependence on the incident energy, of the amount of each type of the point defects formed, and quantify unambiguously the threshold displacement energies for both O and Si atoms. These results provide a comprehensive basis to assess the nature and extent of radiation damage in quartz.« less

Strongly Cavity-Enhanced Spontaneous Emission from Silicon-Vacancy Centers in Diamond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jingyuan Linda; Sun, Shuo; Burek, Michael J.

Quantum emitters are an integral component for a broad range of quantum technologies, including quantum communication, quantum repeaters, and linear optical quantum computation. Solid-state color centers are promising candidates for scalable quantum optics due to their long coherence time and small inhomogeneous broadening. However, once excited, color centers often decay through phonon-assisted processes, limiting the efficiency of single-photon generation and photon-mediated entanglement generation. Herein, we demonstrate strong enhancement of spontaneous emission rate of a single silicon-vacancy center in diamond embedded within a monolithic optical cavity, reaching a regime in which the excited-state lifetime is dominated by spontaneous emission into themore » cavity mode. We observe 10-fold lifetime reduction and 42-fold enhancement in emission intensity when the cavity is tuned into resonance with the optical transition of a single silicon-vacancy center, corresponding to 90% of the excited-state energy decay occurring through spontaneous emission into the cavity mode. Here, we also demonstrate the largest coupling strength ( g/2π = 4.9 ± 0.3 GHz) and cooperativity ( C = 1.4) to date for color-center-based cavity quantum electrodynamics systems, bringing the system closer to the strong coupling regime.« less

The role of nitrogen doping in ALD Ta2O5 and its influence on multilevel cell switching in RRAM

NASA Astrophysics Data System (ADS)

Sedghi, N.; Li, H.; Brunell, I. F.; Dawson, K.; Potter, R. J.; Guo, Y.; Gibbon, J. T.; Dhanak, V. R.; Zhang, W. D.; Zhang, J. F.; Robertson, J.; Hall, S.; Chalker, P. R.

2017-03-01

The role of nitrogen doping on the stability and memory window of resistive state switching in N-doped Ta2O5 deposited by atomic layer deposition is elucidated. Nitrogen incorporation increases the stability of resistive memory states which is attributed to neutralization of electronic defect levels associated with oxygen vacancies. The density functional simulations with the screened exchange hybrid functional approximation show that the incorporation of nitrogen dopant atoms in the oxide network removes the O vacancy midgap defect states, thus nullifying excess defects and eliminating alternative conductive paths. By effectively reducing the density of vacancy-induced defect states through N doping, 3-bit multilevel cell switching is demonstrated, consisting of eight distinctive resistive memory states achieved by either controlling the set current compliance or the maximum voltage during reset. Nitrogen doping has a threefold effect: widening the switching memory window to accommodate the more intermediate states, improving the stability of states, and providing a gradual reset for multi-level cell switching during reset. The N-doped Ta2O5 devices have relatively small set and reset voltages (< 1 V) with reduced variability due to doping.

SBA Innovation Clusters

DTIC Science & Technology

2012-03-02

Programs and services to help you start, grow and succeed www.sba.gov U.S. Small Business Administration Your Small Business Resource 1Approved for...Public Release SBA Innovation Clusters RADM Steven G. Smith USN (Ret) Advanced Defense Technology Cluster Coordinator U.S. Small Business ...UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) U.S. Small Business Administration ,Advanced Defense Technology Cluster,409 3rd St, SW

Point defect evolution in Ni, NiFe and NiCr alloys from atomistic simulations and irradiation experiments

DOE PAGES

Aidhy, Dilpuneet S.; Lu, Chenyang; Jin, Ke; ...

2015-08-08

Using molecular dynamics simulations, we elucidate irradiation-induced point defect evolution in fcc pure Ni, Ni 0.5Fe 0.5, and Ni 0.8Cr 0.2 solid solution alloys. We find that irradiation-induced interstitials form dislocation loops that are of 1/3 <111>{111}-type, consistent with our experimental results. While the loops are formed in all the three materials, the kinetics of formation is considerably slower in NiFe and NiCr than in pure Ni, indicating that defect migration barriers and extended defect formation energies could be higher in the alloys than pure Ni. As a result, while larger size clusters are formed in pure Ni, smaller andmore » more clusters are observed in the alloys. The vacancy diffusion occurs at relatively higher temperatures than interstitials, and their clustering leads to formation of stacking fault tetrahedra, also consistent with our experiments. The results also show that the surviving Frenkel pairs are composition-dependent and are largely Ni dominated.« less

Vacancies and Vacancy-Mediated Self Diffusion in Cr 2 O 3 : A First-Principles Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medasani, Bharat; Sushko, Maria L.; Rosso, Kevin M.

Charged and neutral vacancies and vacancy mediated self diffusion in alpha-Cr2O3 were investigated using first principles density functional theory (DFT) and periodic supercell formalism. The vacancy formation energies of charged defects were calculated using the electrostatic finite-size corrections to account for electrostatic interactions between supercells and the corrections for the bandgap underestimation in DFT. Calculations predict that neutral oxygen (O) vacancies are predominant in chromium (Cr)-rich conditions and Cr vacancies with -2 charge state are the dominant defects in O-rich conditions. The charge transition levels of both O and Cr vacancies are deep within the bandgap indicating the stability ofmore » these defects. Transport calculations indicate that vacancy mediated diffusion along the basal plane has lower energy barriers for both O and Cr ions. The most favorable vacancy mediated self diffusion processes correspond to the diffusion of Cr ion in 3+ charge state and O ion in 2- state, respectively. Our calculations reveal that Cr triple defects comprised of Cr in octahedral interstitial sites with two adjacent Cr vacancies along the c-axis have a lower formation energy compared to that of charged Cr vacancies. The formation of such triple defects facilitate Cr self diffusion along the c-axis.« less

Free energy reconstruction from steered dynamics without post-processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Athenes, Manuel, E-mail: Manuel.Athenes@cea.f; Condensed Matter and Materials Division, Physics and Life Sciences Directorate, LLNL, Livermore, CA 94551; Marinica, Mihai-Cosmin

2010-09-20

Various methods achieving importance sampling in ensembles of nonequilibrium trajectories enable one to estimate free energy differences and, by maximum-likelihood post-processing, to reconstruct free energy landscapes. Here, based on Bayes theorem, we propose a more direct method in which a posterior likelihood function is used both to construct the steered dynamics and to infer the contribution to equilibrium of all the sampled states. The method is implemented with two steering schedules. First, using non-autonomous steering, we calculate the migration barrier of the vacancy in Fe-{alpha}. Second, using an autonomous scheduling related to metadynamics and equivalent to temperature-accelerated molecular dynamics, wemore » accurately reconstruct the two-dimensional free energy landscape of the 38-atom Lennard-Jones cluster as a function of an orientational bond-order parameter and energy, down to the solid-solid structural transition temperature of the cluster and without maximum-likelihood post-processing.« less

First-principles theory of cation- and intercalation-ordering in Li_xCoO_2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

1998-03-01

Using a combination of first-principles total energies, a cluster expansion technique, and Monte Carlo simulations, we present a first-principles theory which can predict both cation- and intercalation-ordering patterns at both zero and finite temperatures, and can provide first-principles predictions of battery voltages of Li_xCoO_2/Li cells. The classes of ordering problems that we study are the following: (i) The LiMO2 oxides (M=3d metal) form a series of structures based on an octahedrally-coordinated network with anions (O) on one fcc sublattice and cations (Li and M) on the other, leading to Li/Co ordering in LiCoO2 (x=1). We find the ground state is the CuPt or (111)-layered cation arrangment, in agreement with the observed structure. (ii) In battery applications, Li is (de)intercalated from the compound, creating a vacancy (denoted Box) that can be positioned in different lattice locations; Thus, Box/Co ordering in BoxCoO2 (x=0) is also of interest. We find the ground state for BoxCoO2 is also a (111)-layered structure, although a different stacking sequence (AAA) of close-packed layers is preferred. (iii) The vacancies left behind by Li extraction can form ordered vacancy compounds in partially de-lithiated Li_xCoO_2, leading to a Box/Li ordering problem (0<=x<=1). Our calculations agree with the observed voltage profiles in these systems, and predict the existence of new intercalation-ordered compounds. Supported by BES/OER/DMS under contract DE-AC36-83CH10093.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moutanabbir, O.; Scholz, R.; Senz, S.

We investigated the microstructural transformations during hydrogen ion-induced splitting of GaN thin layers. Cross-sectional transmission electron microscopy and positron annihilation spectroscopy data show that the implanted region is decorated with a high density of 1-2 nm bubbles resulting from vacancy clustering during implantation. These nanobubbles persist up to 450 deg. C. Ion channeling data show a strong dechanneling enhancement in this temperature range tentatively attributed to strain-induced lattice distortion. The dechanneling level decreases following the formation of plateletlike structures at 475 deg. C. Extended internal surfaces develop around 550 deg. C leading to the exfoliation of GaN thin layer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dholabhai, Pratik P., E-mail: pratik.dholabhai@asu.ed; Anwar, Shahriar, E-mail: anwar@asu.ed; Adams, James B., E-mail: jim.adams@asu.ed

Kinetic lattice Monte Carlo (KLMC) model is developed for investigating oxygen vacancy diffusion in praseodymium-doped ceria. The current approach uses a database of activation energies for oxygen vacancy migration, calculated using first-principles, for various migration pathways in praseodymium-doped ceria. Since the first-principles calculations revealed significant vacancy-vacancy repulsion, we investigate the importance of that effect by conducting simulations with and without a repulsive interaction. Initially, as dopant concentrations increase, vacancy concentration and thus conductivity increases. However, at higher concentrations, vacancies interfere and repel one another, and dopants trap vacancies, creating a 'traffic jam' that decreases conductivity, which is consistent with themore » experimental findings. The modeled effective activation energy for vacancy migration slightly increased with increasing dopant concentration in qualitative agreement with the experiment. The current methodology comprising a blend of first-principle calculations and KLMC model provides a very powerful fundamental tool for predicting the optimal dopant concentration in ceria related materials. -- graphical abstract: Ionic conductivity in praseodymium doped ceria as a function of dopant concentration calculated using the kinetic lattice Monte Carlo vacancy-repelling model, which predicts the optimal composition for achieving maximum conductivity. Display Omitted Research highlights: {yields} KLMC method calculates the accurate time-dependent diffusion of oxygen vacancies. {yields} KLMC-VR model predicts a dopant concentration of {approx}15-20% to be optimal in PDC. {yields} At higher dopant concentration, vacancies interfere and repel one another, and dopants trap vacancies. {yields} Activation energy for vacancy migration increases as a function of dopant content« less

Evaluating Intention to Use Remote Robotics Experimentation in Programming Courses

ERIC Educational Resources Information Center

Cheng, Pericles L.

2017-01-01

The Digital Agenda for Europe (2015) states that there will be 825,000 unfilled vacancies for Information and Communications Technology by 2020. This lack of IT professionals stems from the small number of students graduating in computer science. To retain more students in the field, teachers can use remote robotic experiments to explain difficult…

Thermodynamics of impurity-enhanced vacancy formation in metals

NASA Astrophysics Data System (ADS)

Bukonte, Laura; Ahlgren, Tommy; Heinola, Kalle

2017-01-01

Hydrogen induced vacancy formation in metals and metal alloys has been of great interest during the past couple of decades. The main reason for this phenomenon, often referred to as the superabundant vacancy formation, is the lowering of vacancy formation energy due to the trapping of hydrogen. By means of thermodynamics, we study the equilibrium vacancy formation in fcc metals (Pd, Ni, Co, and Fe) in correlation with the H amounts. The results of this study are compared and found to be in good agreement with experiments. For the accurate description of the total energy of the metal-hydrogen system, we take into account the binding energies of each trapped impurity, the vibrational entropy of defects, and the thermodynamics of divacancy formation. We demonstrate the effect of vacancy formation energy, the hydrogen binding, and the divacancy binding energy on the total equilibrium vacancy concentration. We show that the divacancy fraction gives the major contribution to the total vacancy fraction at high H fractions and cannot be neglected when studying superabundant vacancies. Our results lead to a novel conclusion that at high hydrogen fractions, superabundant vacancy formation takes place regardless of the binding energy between vacancies and hydrogen. We also propose the reason of superabundant vacancy formation mainly in the fcc phase. The equations obtained within this work can be used for any metal-impurity system, if the impurity occupies an interstitial site in the lattice.

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jianbao; Ma, Zhongjun, E-mail: mzj1234402@163.com; Chen, Guanrong

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding ormore » deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.« less

Robustness of cluster synchronous patterns in small-world networks with inter-cluster co-competition balance

NASA Astrophysics Data System (ADS)

Zhang, Jianbao; Ma, Zhongjun; Chen, Guanrong

2014-06-01

All edges in the classical Watts and Strogatz's small-world network model are unweighted and cooperative (positive). By introducing competitive (negative) inter-cluster edges and assigning edge weights to mimic more realistic networks, this paper develops a modified model which possesses co-competitive weighted couplings and cluster structures while maintaining the common small-world network properties of small average shortest path lengths and large clustering coefficients. Based on theoretical analysis, it is proved that the new model with inter-cluster co-competition balance has an important dynamical property of robust cluster synchronous pattern formation. More precisely, clusters will neither merge nor split regardless of adding or deleting nodes and edges, under the condition of inter-cluster co-competition balance. Numerical simulations demonstrate the robustness of the model against the increase of the coupling strength and several topological variations.

Factors driving stable growth of He clusters in W: first-principles study

NASA Astrophysics Data System (ADS)

Feng, Y. J.; Xin, T. Y.; Xu, Q.; Wang, Y. X.

2018-07-01

The evolution of helium (He) bubbles is responsible for the surface morphology variation and subsequent degradation of the properties of plasma-facing materials (PFMs) in nuclear fusion reactors. These severe problems unquestionably trace back to the behavior of He in PFMs, which is closely associated with the interaction between He and the matrix. In this paper, we decomposed the binding energy of the He cluster into three parts, those from W–W, W–He, and He–He interactions, using density functional theory. As a result, we clearly identified the main factors that determine a steplike decrease in the binding energy with increasing number of He atoms, which explains the process of self-trapping and athermal vacancy generation during He cluster growth in the PFM tungsten. The three interactions were found to synergetically shape the features of the steplike decrease in the binding energy. Fairly strong He–He repulsive forces at a short distance, which stem from antibonding states between He atoms, need to be released when additional He atoms are continuously bonded to the He cluster. This causes the steplike feature in the binding energy. The bonding states between W and He atoms in principle facilitate the decreasing trend of the binding energy. The decrease in binding energy with increasing number of He atoms implies that He clusters can grow stably.

Classification Order of Surface-Confined Intermixing at Epitaxial Interface

NASA Astrophysics Data System (ADS)

Michailov, M.

The self-organization phenomena at epitaxial interface hold special attention in contemporary material science. Being relevant to the fundamental physical problem of competing, long-range and short-range atomic interactions in systems with reduced dimensionality, these phenomena have found exacting academic interest. They are also of great technological importance for their ability to bring spontaneous formation of regular nanoscale surface patterns and superlattices with exotic properties. The basic phenomenon involved in this process is surface diffusion. That is the motivation behind the present study which deals with important details of diffusion scenarios that control the fine atomic structure of epitaxial interface. Consisting surface imperfections (terraces, steps, kinks, and vacancies), the interface offers variety of barriers for surface diffusion. Therefore, the adatoms and clusters need a certain critical energy to overcome the corresponding diffusion barriers. In the most general case the critical energies can be attained by variation of the system temperature. Hence, their values define temperature limits of system energy gaps associated with different diffusion scenarios. This systematization imply classification order of surface alloying: blocked, incomplete, and complete. On that background, two diffusion problems, related to the atomic-scale surface morphology, will be discussed. The first problem deals with diffusion of atomic clusters on atomically smooth interface. On flat domains, far from terraces and steps, we analyzed the impact of size, shape, and cluster/substrate lattice misfit on the diffusion behavior of atomic clusters (islands). We found that the lattice constant of small clusters depends on the number N of building atoms at 1 < N ≤ 10. In heteroepitaxy, this effect of variable lattice constant originates from the enhanced charge transfer and the strong influence of the surface potential on cluster atomic arrangement. At constant temperature, the variation of the lattice constant leads to variable misfit which affects the island migration. The cluster/substrate commensurability influences the oscillation behavior of the diffusion coefficient caused by variation in the cluster shape. We discuss the results in a physical model that implies cluster diffusion with size-dependent cluster/substrate misfit. The second problem is devoted to diffusion phenomena in the vicinity of atomic terraces on stepped or vicinal surfaces. Here, we develop a computational model that refines important details of diffusion behavior of adatoms accounting for the energy barriers at specific atomic sites (smooth domains, terraces, and steps) located on the crystal surface. The dynamic competition between energy gained by mixing and substrate strain energy results in diffusion scenario where adatoms form alloyed islands and alloyed stripes in the vicinity of terrace edges. Being in agreement with recent experimental findings, the observed effect of stripe and island alloy formation opens up a way regular surface patterns to be configured at different atomic levels on the crystal surface. The complete surface alloying of the entire interface layer is also briefly discussed with critical analysis and classification of experimental findings and simulation data.

The impacts of different expansion modes on performance of small solar energy firms: perspectives of absorptive capacity.

PubMed

Chen, Hsing Hung; Shen, Tao; Xu, Xin-Long; Ma, Chao

2013-01-01

The characteristics of firm's expansion by differentiated products and diversified products are quite different. However, the study employing absorptive capacity to examine the impacts of different modes of expansion on performance of small solar energy firms has never been discussed before. Then, a conceptual model to analyze the tension between strategies and corporate performance is proposed to filling the vacancy. After practical investigation, the results show that stronger organizational institutions help small solar energy firms expanded by differentiated products increase consistency between strategies and corporate performance; oppositely, stronger working attitudes with weak management controls help small solar energy firms expanded by diversified products reduce variance between strategies and corporate performance.

Defect-induced magnetism in two-dimensional NbSe2

NASA Astrophysics Data System (ADS)

Manchanda, P.; Skomski, R.

2017-01-01

The energetics and magnetism of perfect and vacancy-containing two-dimensional NbSe2 monolayers is investigated by first-principle calculations. It has been found the single Se vacancy has the lowest formation energy. Perfect NbSe2 monolayers, as well as monolayers containing single-selenium and double-selenium vacancies, are nonmagnetic metallic. However, Nb vacancies create a magnetic moment of 1.5 μB per vacancy. The moment is highly localized, confined nearly exclusively on the Se atoms adjacent to the vacancy, and mainly originates from the Se 4p electrons. The moment distribution indicates strongly anisotropic exchange bonds between vacancy moments.

Origin of Nanobubbles Electrochemically Formed in a Magnetic Field: Ionic Vacancy Production in Electrode Reaction

NASA Astrophysics Data System (ADS)

Aogaki, Ryoichi; Sugiyama, Atsushi; Miura, Makoto; Oshikiri, Yoshinobu; Miura, Miki; Morimoto, Ryoichi; Takagi, Satoshi; Mogi, Iwao; Yamauchi, Yusuke

2016-07-01

As a process complementing conventional electrode reactions, ionic vacancy production in electrode reaction was theoretically examined; whether reaction is anodic or cathodic, based on the momentum conservation by Newton’s second law of motion, electron transfer necessarily leads to the emission of original embryo vacancies, and dielectric polarization endows to them the same electric charge as trans- ferred in the reaction. Then, the emitted embryo vacancies immediately receive the thermal relaxation of solution particles to develop steady-state vacancies. After the vacancy production, nanobubbles are created by the collision of the vacancies in a vertical magnetic field.

Vacancy dynamic in Ni-Mn-Ga ferromagnetic shape memory alloys

NASA Astrophysics Data System (ADS)

Merida, D.; García, J. A.; Sánchez-Alarcos, V.; Pérez-Landazábal, J. I.; Recarte, V.; Plazaola, F.

2014-06-01

Vacancies control any atomic ordering process and consequently most of the order-dependent properties of the martensitic transformation in ferromagnetic shape memory alloys. Positron annihilation spectroscopy demonstrates to be a powerful technique to study vacancies in NiMnGa alloys quenched from different temperatures and subjected to post-quench isothermal annealing treatments. Considering an effective vacancy type the temperature dependence of the vacancy concentration has been evaluated. Samples quenched from 1173 K show a vacancy concentration of 1100 ± 200 ppm. The vacancy migration and formation energies have been estimated to be 0.55 ± 0.05 eV and 0.90 ± 0.07 eV, respectively.

Ferromagnetism in ferroelectric BaTiO3 induced by vacancies: Sensitive dependence on charge state, origin of magnetism, and temperature range of existence

NASA Astrophysics Data System (ADS)

Raeliarijaona, Aldo; Fu, Huaxiang

2017-10-01

Using density-functional calculations we investigate the possibility and underlying mechanism of generating ferromagnetism (FM) in ferroelectric BaTiO3 by native vacancies. For the same vacancy species but different charge states (e.g., VO0 vs VO2 +), our paper reveals a marked difference in magnetic behaviors. For instance, while VO0 is ferromagnetic, VO2 + is not. This sensitive dependence, which has often been overlooked, highlights the critical importance of taking into account different charge states. Furthermore, while oxygen vacancies have been often used in experiments to explain the vacancy-induced FM, our calculation demonstrates that Ti vacancies, in particular VTi3 - and VTi2 - with low formation energies, generate even stronger ferromagnetism in BaTiO3, with a magnetic moment which is 400% larger than that of VO0. Interestingly, this strong FM of VTi can be further enhanced by hole doping. Although both cation vacancies (VTiq) and anion vacancies (VO0) induce FM, their mechanisms differ drastically. FM of anion vacancies originates from the spin-polarized electrons at Ti sites, but FM of cation vacancies stems from the spin-polarized holes at O sites. This paper also sheds light on vacancy-induced FM by discovering that the spin densities of all three considered vacancy species are highly extended in real space, distributed far away from the vacancy. Moreover, we predict that the ferromagnetism caused by VTi3 - is able to survive at high temperatures, which is promising for room-temperature spintronic or multiferroic applications.

Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep

We conducted two sets of diffusion-reaction numerical simulations using a finite difference method (FDM) in order to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,Ga)Se 2 (CIGS) and Cu 2ZnSn(S, Se) 4 (CZTSSe or CZTS) via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases themore » equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. And according to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.« less

Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

DOE PAGES

Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep; ...

2016-05-13

We conducted two sets of diffusion-reaction numerical simulations using a finite difference method (FDM) in order to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,Ga)Se 2 (CIGS) and Cu 2ZnSn(S, Se) 4 (CZTSSe or CZTS) via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases themore » equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. And according to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.« less

Density-based clustering of small peptide conformations sampled from a molecular dynamics simulation.

PubMed

Kim, Minkyoung; Choi, Seung-Hoon; Kim, Junhyoung; Choi, Kihang; Shin, Jae-Min; Kang, Sang-Kee; Choi, Yun-Jaie; Jung, Dong Hyun

2009-11-01

This study describes the application of a density-based algorithm to clustering small peptide conformations after a molecular dynamics simulation. We propose a clustering method for small peptide conformations that enables adjacent clusters to be separated more clearly on the basis of neighbor density. Neighbor density means the number of neighboring conformations, so if a conformation has too few neighboring conformations, then it is considered as noise or an outlier and is excluded from the list of cluster members. With this approach, we can easily identify clusters in which the members are densely crowded in the conformational space, and we can safely avoid misclustering individual clusters linked by noise or outliers. Consideration of neighbor density significantly improves the efficiency of clustering of small peptide conformations sampled from molecular dynamics simulations and can be used for predicting peptide structures.

Evaluation of defect formation in helium irradiated Y2O3 doped W-Ti alloys by positron annihilation and nanoindentation

NASA Astrophysics Data System (ADS)

Richter, Asta; Anwand, Wolfgang; Chen, Chun-Liang; Böttger, Roman

2017-10-01

Helium implanted tungsten-titanium ODS alloys are investigated using positron annihilation spectroscopy and nanoindentation. Titanium reduces the brittleness of the tungsten alloy, which is manufactured by mechanical alloying. The addition of Y2O3 nanoparticles increases the mechanical properties at elevated temperature and enhances irradiation resistance. Helium ion implantation was applied to simulate irradiation effects on these materials. The irradiation was performed using a 500 kV He ion implanter at fluences around 5 × 1015 cm-2 for a series of samples both at room temperature and at 600 °C. The microstructure and mechanical properties of the pristine and irradiated W-Ti-ODS alloy are compared with respect to the titanium and Y2O3 content. Radiation damage is studied by positron annihilation spectroscopy analyzing the lifetime and the Doppler broadening. Three types of helium-vacancy defects were detected after helium irradiation in the W-Ti-ODS alloy: small defects with high helium-to-vacancy ratio (low S parameter) for room temperature irradiation, larger open volume defects with low helium-to-vacancy ratio (high S parameter) at the surface and He-vacancy complexes pinned at nanoparticles deeper in the material for implantation at 600 °C. Defect induced hardness was studied by nanoindentation. A drastic hardness increase is observed after He ion irradiation both for room temperature and elevated irradiation temperature of 600 °C. The Ti alloyed tungsten-ODS is more affected by the hardness increase after irradiation compared to the pure W-ODS alloy.

3D discrete dislocation dynamics study of creep behavior in Ni-base single crystal superalloys by a combined dislocation climb and vacancy diffusion model

NASA Astrophysics Data System (ADS)

Gao, Siwen; Fivel, Marc; Ma, Anxin; Hartmaier, Alexander

2017-05-01

A three-dimensional (3D) discrete dislocation dynamics (DDD) creep model is developed to investigate creep behavior under uniaxial tensile stress along the crystallographic [001] direction in Ni-base single crystal superalloys, which takes explicitly account of dislocation glide, climb and vacancy diffusion, but neglects phase transformation like rafting of γ‧ precipitates. The vacancy diffusion model takes internal stresses by dislocations and mismatch strains into account and it is coupled to the dislocation dynamics model in a numerically efficient way. This model is helpful for understanding the fundamental creep mechanisms in superalloys and clarifying the effects of dislocation glide and climb on creep deformation. In cases where the precipitate cutting rarely occurs, e.g. due to the high anti-phase boundary energy and the lack of superdislocations, the dislocation glide in the γ matrix and the dislocation climb along the γ/γ‧ interface dominate plastic deformation. The simulation results show that a high temperature or a high stress both promote dislocation motion and multiplication, so as to cause a large creep strain. Dislocation climb accelerated by high temperature only produces a small plastic strain, but relaxes the hardening caused by the filling γ channels and lets dislocations further glide and multiply. The strongest variation of vacancy concentration occurs in the horizontal channels, where more mixed dislocations exit and tend to climb. The increasing internal stresses due to the increasing dislocation density are easily overcome by dislocations under a high external stress that leads to a long-term dislocation glide accompanied by multiplication.

Effect of post-irradiation annealing on the irradiated microstructure of neutron-irradiated 304L stainless steel

NASA Astrophysics Data System (ADS)

Jiao, Z.; Hesterberg, J.; Was, G. S.

2018-03-01

Post-irradiation annealing was performed on a 304L SS that was irradiated to 5.9 dpa in the Barsebäck 1 BWR reactor. Evolution of dislocation loops, radiation-induced solute clusters and radiation-induced segregation at the grain boundary was investigated following thermal annealing at 500 °C and 550 °C up to 20 h. Dislocation loops, Ni-Si and Al-Cu clusters, and enrichment of Ni, Si and depletion of Cr at the grain boundary were observed in the as-irradiated condition. Dislocation loop size did not change significantly after annealing at 550 °C for 5 h but the loop number density decreased considerably and loops mostly disappeared after annealing at 550 °C for 20 h. The average size of Ni-Si and Al-Cu clusters increased while the number density decreased with annealing. The increase in cluster size was due to diffusion of solutes rather than cluster coarsening. Significant volume fractions of Ni-Si and Al-Cu clusters still remained after annealing at 550 °C for 20 h. Substantial recovery of Cr and Ni at the grain boundary was observed after annealing at 550 °C for 5 h but neither Cr nor Ni was fully recovered after 20 h. Annihilation of dislocation loops, driven by the thermal vacancy concentration gradient caused by the strain field and stacking fault associated with the loops appeared to be faster than annihilation of solute clusters and recovery of Ni and Si at the grain boundary, both of which are driven by the solute concentration gradients.

Contributed Review: Camera-limits for wide-field magnetic resonance imaging with a nitrogen-vacancy spin sensor

NASA Astrophysics Data System (ADS)

Wojciechowski, Adam M.; Karadas, Mürsel; Huck, Alexander; Osterkamp, Christian; Jankuhn, Steffen; Meijer, Jan; Jelezko, Fedor; Andersen, Ulrik L.

2018-03-01

Sensitive, real-time optical magnetometry with nitrogen-vacancy centers in diamond relies on accurate imaging of small (≪10-2), fractional fluorescence changes across the diamond sample. We discuss the limitations on magnetic field sensitivity resulting from the limited number of photoelectrons that a camera can record in a given time. Several types of camera sensors are analyzed, and the smallest measurable magnetic field change is estimated for each type. We show that most common sensors are of a limited use in such applications, while certain highly specific cameras allow achieving nanotesla-level sensitivity in 1 s of a combined exposure. Finally, we demonstrate the results obtained with a lock-in camera that paves the way for real-time, wide-field magnetometry at the nanotesla level and with a micrometer resolution.

Effect of bending and vacancies on the conductance of carbon nanotubes

NASA Astrophysics Data System (ADS)

Hansson, Anders; Paulsson, Magnus; Stafström, Sven

2000-09-01

Electron transport through nanotubes is studied theoretically using the Landauer formalism. The studies are carried out for finite metallic nanotubes that bridge two contacts pads. The current is observed to increase stepwise with the applied voltage. Each step corresponds to resonance tunneling including one single-particle eigenstate of the nanotube. Moderate bending of the nanotube results in a shift of the single-particle levels but the overall current remains essentially unaffected. For large bending, however, the π electron system becomes more disturbed, which introduces backscattering and a marked decrease in the conductivity along the tube. A single carbon vacancy in the nanotube is shown to have very small effect on the conductivity in the center of the metallic band whereas, by increasing the defect concentration the conductivity decreases in the same way as for the strongly bent tubes.

Effects of Vacancy Concentration and Temperature on Mechanical Properties of Single-Crystal γ-TiAl Based on Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Ruicheng, Feng; Hui, Cao; Haiyan, Li; Zhiyuan, Rui; Changfeng, Yan

2018-01-01

Molecular dynamics simulation is used to analyze tensile strength and elastic modulus under different temperatures and vacancy concentrations. The effects of temperature and vacancy concentration on the mechanical properties of γ-TiAl alloy are investigated. The results show that the ultimate stress, ultimate strain and elastic modulus decrease nonlinearly with increasing temperature and vacancy concentration. As the temperature increases, the plastic of material is reinforced. The influence of temperature on strength and elastic modulus is larger than that of vacancy concentration. The evolution process of vacancy could be observed clearly. Furthermore, vacancies with different concentrations develop into voids first as a function of external forces or other factors, micro cracks evolve from those voids, those micro cracks then converge to a macro crack, and fracture will finally occur. The vacancy evolution process cannot be observed clearly owing to the thermal motion of atoms at high temperature. In addition, potential energy is affected by both temperature and vacancy concentration.

NO-sensing performance of vacancy defective monolayer MoS2 predicted by density function theory

NASA Astrophysics Data System (ADS)

Li, Feifei; Shi, Changmin

2018-03-01

Using density functional theory (DFT), we predict the NO-sensing performance of monolayer MoS2 (MoS2-MLs) with and without MoS3-vacancy/S-vacancy defects. Our theoretical results demonstrate that MoS3- and S-vacancy defective MoS2-MLs show stronger chemisorption and greater electron transfer effects than pure MoS2-MLs. The charge transfer analysis showed pure and defective MoS2-MLs all act as donors. Both MoS3-vacancy and S-vacancy defects induce dramatic changes of electronic properties of MoS2-MLs, which have direct relationship with gas sensing performance. In addition, S-vacancy defect leads to more electrons transfer to NO molecule than MoS3-vacancy defect. The H2O molecule urges more electrons transfer from MoS3- or S-vacancy defective MoS2-MLs to NO molecule. We believe that this calculation results will provide some information for future experiment.

Fe-vacancy ordering in superconducting K 1–xFe 2–ySe 2: First-principles calculations and Monte Carlo simulations

DOE PAGES

Fang, Yong; Tai, Yuan -Yen; Deng, Junkai; ...

2015-07-20

Fe vacancies in the 33 K superconductor K 1–xFe 2–ySe 2 show ordering schemes that may be correlated with its superconducting properties. First-principles calculations and kinetic Monte Carlo simulations lead to a very simple model for vacancy ordering. Repulsive dipolar interactions between Fe vacancies show three ground states: amore » $$\\sqrt{8}\\times \\sqrt{10}$$ rhombus-ordered structure for 12.5% vacancies, a $$\\sqrt{5}\\times \\sqrt{5}$$ squared lattice for 20% vacancies, and a $$\\sqrt{5}\\times \\sqrt{5}$$ rhombus-ordered structure for 25% vacancies. Other structural states are derived from these three ground states and may contain additional disordered spatial regions. As a result, the repulsive interaction between Fe vacancies arises from enhanced Fe–Se covalent bonds, which differs from the well-known attractive interaction of Fe vacancies in body-centered cubic Fe.« less

Determination of atomic vacancies in InAs/GaSb strained-layer superlattices by atomic strain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Honggyu; Meng, Yifei; Kwon, Ji-Hwan

Determining vacancy in complex crystals or nanostructures represents an outstanding crystallographic problem that has a large impact on technology, especially for semiconductors, where vacancies introduce defect levels and modify the electronic structure. However, vacancy is hard to locate and its structure is difficult to probe experimentally. Reported here are atomic vacancies in the InAs/GaSb strained-layer superlattice (SLS) determined by atomic-resolution strain mapping at picometre precision. It is shown that cation and anion vacancies in the InAs/GaSb SLS give rise to local lattice relaxations, especially the nearest atoms, which can be detected using a statistical method and confirmed by simulation. Themore » ability to map vacancy defect-induced strain and identify its location represents significant progress in the study of vacancy defects in compound semiconductors.« less

Determination of atomic vacancies in InAs/GaSb strained-layer superlattices by atomic strain

DOE PAGES

Kim, Honggyu; Meng, Yifei; Kwon, Ji-Hwan; ...

2018-01-01

Determining vacancy in complex crystals or nanostructures represents an outstanding crystallographic problem that has a large impact on technology, especially for semiconductors, where vacancies introduce defect levels and modify the electronic structure. However, vacancy is hard to locate and its structure is difficult to probe experimentally. Reported here are atomic vacancies in the InAs/GaSb strained-layer superlattice (SLS) determined by atomic-resolution strain mapping at picometre precision. It is shown that cation and anion vacancies in the InAs/GaSb SLS give rise to local lattice relaxations, especially the nearest atoms, which can be detected using a statistical method and confirmed by simulation. Themore » ability to map vacancy defect-induced strain and identify its location represents significant progress in the study of vacancy defects in compound semiconductors.« less

DISPLACEMENT CASCADE SIMULATION IN TUNGSTEN AT 1025 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Setyawan, Wahyu; Nandipati, Giridhar; Roche, Kenneth J.

2013-09-30

Molecular dynamics simulation was employed to investigate the irradiation damage properties of bulk tungsten at 1025 K (0.25 melting temperature). A comprehensive data set of primary cascade damage was generated up to primary knock-on atom (PKA) energies 100 keV. The dependence of the number of surviving Frenkel pairs (NFP) on the PKA energy (E) exhibits three different characteristic domains presumably related to the different cascade morphologies that form. The low-energy regime < 0.2 keV is characterized by a hit-or-miss type of Frenkel pair (FP) production near the displacement threshold energy of 128 eV. The middle regime 0.3 – 30 keVmore » exhibits a sublinear dependence of log(NFP) vs log(E) associated with compact cascade morphology with a slope of 0.73. Above 30 keV, the cascade morphology consists of complex branches or interconnected damage regions. In this extended morphology, large interstitial clusters form from superposition of interstitials from nearby damage regions. Strong clustering above 30 keV results in a superlinear dependence of log(NFP) vs log(E) with a slope of 1.365. At 100 keV, an interstitial cluster of size 92 and a vacancy cluster of size 114 were observed.« less

Point Defects in Quenched and Mechanically-Milled Intermetallic Compounds

NASA Astrophysics Data System (ADS)

Sinha, Praveen

Investigations were made of structural and thermal point defects in the highly-ordered B2 compound PdIn and deformation-induced defects in PdIn and NiAl. The defects were detected through the quadrupole interactions they induce at nearby ^{111}In/Cd probe atoms using the technique of perturbed gamma-gamma angular correlations (PAC). Measurements on annealed PdIn on both sides of stoichiometry show structural defects that are the Pd vacancies on the Pd-poor side of the stoichiometry and Pd antisite atoms on the Pd-rich side. Signals were attributed to various defect configurations near the In/Cd probes. In addition to the first-shell Pd vacancy and second-shell Pd antisite atom configurations previously observed by Hahn and Muller, we observed two Pd-divacancy configurations in the first shell, a fourth-shell Pd vacancy, a second-shell In vacancy and the combination of a first -shell Pd vacancy and fourth-shell Pd vacancy. Vacancies on both the Pd and In sublattices were detected after quenching. Fractions of probe atoms having each type of neighboring vacancy defect were observed to increase monotonically with quenching temperature over the range 825-1500 K. For compositions very close to 50.15 at.% Pd, nearly equal site fractions were observed for Pd and In vacancies, indicating that the Schottky vacancy-pair defect is the thermal defect at high temperature. The formation enthalpy of the Schottky defect was determined from measurements of the Pd-vacancy site fraction to be 1.30(18) eV from analysis of quenching data in the range 825-1200 K, using the law of mass action and assuming a random distribution. Above 1200 K, the Pd-vacancy concentration was observed to be saturated at a value of 1.3(2) atomic percent. For more Pd-rich compositions, evidence was also obtained for a defect reaction in which a Pd antisite atom and Pd vacancy react to form an In vacancy, thereby increasing the In vacancy concentration and decreasing the Pd vacancy concentration. Analysis of defect concentrations allowed the conclusion that the In vacancy signal was due to second-shell and not third-shell defects. PAC spectroscopy was applied to study deformation -induced defects in PdIn and NiAl after mechanically milling in a SPEX 8000 vibrator mill for periods of up to four hours. For PdIn, the Pd vacancy concentration increased rapidly for short milling times and was observed to saturate at a value of 3.5(5) at.% after 10 minutes of milling when milling was carried out using a WC vial to avoid sample contamination. Such a large vacancy concentration accounts for 4.41(63) kJ mol-1 excess-stored energy in milled PdIn and implies a high density of "broken bonds" which may lead to mechanical instability of the lattice. Milling also produced In antisite atoms on the Pd sublattice. The antisite-atom concentration increased linearly with milling time, reaching a value of 4.0(7) at.% after 2 hours of milling. The Ni vacancy concentration in NiAl was also observed to increase with milling and to saturate after two hours of milling. Here, the "local" Ni vacancy concentration in the first-neighbor shell of the probe, deduced from the vacancy site fraction, was in excess of values that should occur if defects were located at random. This is attributed to binding between the Ni vacancy and the In/Cd probe, which is known from other work to be 0.22 eV.

Influence of O-Co-O layer thickness on the thermal conductivity of Na{sub x}Co{sub 2}O{sub 4} studied by positron annihilation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, H. Q.; Zhao, B.; Zhang, T.

2015-07-21

Nominal stoichiometric Na{sub x}Co{sub 2}O{sub 4} (x = 1.0, 1.2, 1.4, 1.6, 1.8, and 2.0) polycrystals were synthesized by a solid-state reaction method. They were further pressed into pellets by the spark plasma sintering. The crystal structure and morphology of Na{sub x}Co{sub 2}O{sub 4} samples were characterized by X-ray diffraction and scanning electron microscopy measurements. Good crystallinity and layered structures were observed for all the samples. Positron annihilation measurements were performed for Na{sub x}Co{sub 2}O{sub 4} as a function of Na content. Two lifetime components are resolved. τ{sub 1} is attributed mainly to positron annihilation in the O-Co-O layers and shifts tomore » Na layers only in the H3 phase. The second lifetime τ{sub 2} is due to positron annihilation in vacancy clusters which may exist in the Na layers or grain boundary region. The size of vacancy clusters grow larger but their concentration decreases with increasing Na content in the range of 1.0 < x < 1.8. The thickness of O-Co-O layer also shows continuous increase with increasing Na content, which is reflected by the increase of τ{sub 1}. The thermal conductivity κ, on the other hand, shows systematic decrease with increasing Na content. This suggests that the increasing spacing of O-Co-O layer could effectively reduce the thermal conductivity of Na{sub x}Co{sub 2}O{sub 4}.« less

Effects of Vacancy Cluster Defects on Electrical and Thermodynamic Properties of Silicon Crystals

PubMed Central

Huang, Pei-Hsing; Lu, Chi-Ming

2014-01-01

A first-principle plane-wave pseudopotential method based on the density function theory (DFT) was employed to investigate the effects of vacancy cluster (VC) defects on the band structure and thermoelectric properties of silicon (Si) crystals. Simulation results showed that various VC defects changed the energy band and localized electron density distribution of Si crystals and caused the band gap to decrease with increasing VC size. The results can be ascribed to the formation of a defect level produced by the dangling bonds, floating bonds, or high-strain atoms surrounding the VC defects. The appearance of imaginary frequencies in the phonon spectrum of defective Si crystals indicates that the defect-region structure is dynamically unstable and demonstrates phase changes. The phonon dispersion relation and phonon density of state were also investigated using density functional perturbation theory. The obtained Debye temperature (θ D) for a perfect Si crystal had a minimum value of 448 K at T = 42 K and a maximum value of 671 K at the high-temperature limit, which is consistent with the experimental results reported by Flubacher. Moreover, the Debye temperature decreased with increases in the VC size. VC defects had minimal effects on the heat capacity (C v) value when temperatures were below 150 K. As the temperature was higher than 150 K, the heat capacity gradually increased with increasing temperature until it achieved a constant value of 11.8 cal/cell·K. The heat capacity significantly decreased as the VC size increased. For a 2 × 2 × 2 superlattice Si crystal containing a hexagonal ring VC (HRVC10), the heat capacity decreased by approximately 17%. PMID:24526923

Generation and characterization of point defects in SrTiO3 and Y3Al5O12

NASA Astrophysics Data System (ADS)

Selim, F. A.; Winarski, D.; Varney, C. R.; Tarun, M. C.; Ji, Jianfeng; McCluskey, M. D.

Positron annihilation lifetime spectroscopy (PALS) was applied to characterize point defects in single crystals of Y3Al5O12 and SrTiO3 after populating different types of defects by relevant thermal treatments. In SrTiO3, PALS measurements identified Sr vacancy, Ti vacancy, vacancy complexes of Ti-O (vacancy) and hydrogen complex defects. In Y3Al5O12 single crystals the measurements showed the presence of Al-vacancy, (Al-O) vacancy and Al-vacancy passivated by hydrogen. These defects are shown to play the major role in defining the electronic and optical properties of these complex oxides.

New Zealand veterinarians--demography, remuneration and vacancies.

PubMed

Jackson, R; Goodwin, K A; Perkins, N R; Roddick, J

2004-08-01

To determine levels of remuneration for veterinarians in New Zealand, to examine associations between putative explanatory factors and gross annual remuneration, and to quantify the type and prevalence of vacant positions. A postal survey to 486 identifiable clinical practices and 53 identifiable organisations that employ veterinarians was used to gather data for the 2-month period of December 2001 to January 2002. Data were produced for 972 veterinarians (367 females and 605 males) working in 325 clinical practices, and 299 veterinarians (88 females and 211 males) employed by 32 organisations. Median levels of gross annual remuneration for assistants, partners/ shareholders and sole owners working >/=5 days per week in clinical practice were NZ$60,000, $90,000 and $75,000, respectively, and for veterinarians in organisations, irrespective of number of days per week worked, was $68,000. Pay rates increased linearly as the number of years since graduation increased for all clinicians and with increasing age for veterinarians in organisations. Full-time assistants were likely to be paid more if the practice was rural rather than urban in location, if they were males, and if administrative duties were part of the job. The same factors, except for sex, were significant for remuneration for owners and partners/shareholders working full-time. Their remuneration tended to be higher if the practice was involved with either dairy or deer work but decreased as the number of animal species serviced increased and if they worked >5 days per week. Part-time female veterinarians were generally paid more than male counterparts. Male veterinarians working in organisations were generally paid about 8% more than their female colleagues. Veterinarians in organisations involved with administration at a head office were generally better paid than those without administrative duties. Pay rates were, on the whole, better in private organisations than in universities, state-owned enterprises, government-operated and other types of organisations About 50% of all services provided by clinical practices were directed to small animals, 27% to dairy cattle and about 10%, 6% and 3% to horses, sheep and beef cattle, and deer, respectively. About 31% of veterinarians worked solely with small animals but most had multiple species workloads. Of the 325 respondent practices, 98 reported vacancies for 119 veterinarians, of which 79 were full-time, 27 part-time and 12 locum positions. Of the 32 respondent organisations, seven reported vacancies for 16 mostly full-time positions. Farmer owned co-operative practices were less likely than privately owned practices to have full-time vacant positions. The only factor identified as influencing part-time vacancies in clinical practices was hourly pay rate. Vacancies occurred randomly across practices, irrespective of location, and there was no indication of greater demand for services for any particular species. The odds of a vacancy in organisations was lower for state-owned enterprises and private organisations than for government organisations (odds ratios (OR)=0.14 and 0.18, respectively). Relatively more females than males worked part-time and 23% of all assistants in clinical practice worked part-time. Sex made a significant difference to gross remuneration for full-time assistants in clinical practice and for veterinarians employed by private or government organisations. In both situations, males were generally better paid than females. Female part-time assistants and partners/shareholders or sole owners in clinical practice were generally better rewarded than their male counterparts. Sex had no effect on remuneration levels for owners/ partners working full-time in clinical practices. The study confirmed a serious shortage of veterinarians in New Zealand. The probability of a vacancy occurring in farmer owned co-operative ('club') practices was lower than in private practices. Vacancies were distributed randomly among rural, urban and rural/urban practices with no evidence of rural practices being more severely affected than urban or rural/urban practices.

Investigation of the Fe{sup 3+} centers in perovskite KMgF{sub 3} through a combination of ab initio (density functional theory) and semi-empirical (superposition model) calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Emül, Y.; Department of Software Engineering, Cumhuriyet University, 58140 Sivas; Erbahar, D.

2015-08-14

Analyses of the local crystal and electronic structure in the vicinity of Fe{sup 3+} centers in perovskite KMgF{sub 3} crystal have been carried out in a comprehensive manner. A combination of density functional theory (DFT) and a semi-empirical superposition model (SPM) is used for a complete analysis of all Fe{sup 3+} centers in this study for the first time. Some quantitative information has been derived from the DFT calculations on both the electronic structure and the local geometry around Fe{sup 3+} centers. All of the trigonal (K-vacancy case, K-Li substitution case, and normal trigonal Fe{sup 3+} center case), FeF{sub 5}Omore » cluster, and tetragonal (Mg-vacancy and Mg-Li substitution cases) centers have been taken into account based on the previously suggested experimental and theoretical inferences. The collaboration between the experimental data and the results of both DFT and SPM calculations provides us to understand most probable structural model for Fe{sup 3+} centers in KMgF{sub 3}.« less

Tailoring optical properties of TiO2-Cr co-sputtered films using swift heavy ions

NASA Astrophysics Data System (ADS)

Gupta, Ratnesh; Sen, Sagar; Phase, D. M.; Avasthi, D. K.; Gupta, Ajay

2018-05-01

Effect of 100 MeV Au7+ ion irradiation on structure and optical properties of Cr-doped TiO2 films has been studied using X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, UV-Visible spectroscopy, X-ray reflectivity, and atomic force microscopy. X-ray reflectivity measurement implied that film thickness reduces as a function of ion fluence while surface roughness increases. The variation in surface roughness is well correlated with AFM results. Ion irradiation decreases the band gap energy of the film. Swift heavy ion irradiation enhances the oxygen vacancies in the film, and the extra electrons in the vacancies act as donor-like states. In valence band spectrum, there is a shift in the Ti3d peak towards lower energies and the shift is equivalent to the band gap energy obtained from UV spectrum. Evidence for band bending is also provided by the corresponding Ti XPS peak which exhibits a shift towards lower energy due to the downward band bending. X-ray absorption studies on O Kand Cr L3,2 edges clearly indicate that swift heavy ion irradiation induces formation of Cr-clusters in TiO2 matrix.

Graphene defects induced by ion beam

NASA Astrophysics Data System (ADS)

Gawlik, Grzegorz; Ciepielewski, Paweł; Baranowski, Jacek; Jagielski, Jacek

2017-10-01

The CVD graphene deposited on the glass substrate was bombarded by molecular carbon ions C3+ C6+ hydrocarbon ions C3H4+ and atomic ions He+, C+, N+, Ar+, Kr+ Yb+. Size and density of ion induced defects were estimated from evolution of relative intensities of Raman lines D (∼1350 1/cm), G (∼1600 1/cm), and D‧ (∼1620 1/cm) with ion fluence. The efficiency of defect generation by atomic ions depend on ion mass and energy similarly as vacancy generation directly by ion predicted by SRIM simulations. However, efficiency of defect generation in graphene by molecular carbon ions is essentially higher than summarized efficiency of similar group of separate atomic carbon ions of the same energy that each carbon ion in a cluster. The evolution of the D/D‧ ratio of Raman lines intensities with ion fluence was observed. This effect may indicate evolution of defect nature from sp3-like at low fluence to a vacancy-like at high fluence. Observed ion graphene interactions suggest that the molecular ion interacts with graphene as single integrated object and should not be considered as a group of atomic ions with partial energy.

Understanding Oxygen Vacancy Formation, Interaction, Transport, and Strain in SOFC Components via Combined Thermodynamics and First Principles Calculations

NASA Astrophysics Data System (ADS)

Das, Tridip

Understanding of the vacancy formation, interaction, increasing its concentration and diffusion, and controlling its chemical strain will advance the design of mixed ionic and electronic conductor (MIEC) materials via element doping and strain engineering. This is especially central to improve the performance of the solid oxide fuel cell (SOFC), an energy conversion device for sustainable future. The oxygen vacancy concentration grows exponentially with the temperature at dilute vacancy concentration but not at higher concentration, or even decreases due to oxygen vacancy interaction and vacancy ordered phase change. This limits the ionic conductivity. Using density functional theory (DFT), we provided fundamental understanding on how oxygen vacancy interaction originates in one of the typical MIEC, La1-xSrxFeO3-delta (LSF). The vacancy interaction is determined by the interplay of the charge state of multi-valence ion (Fe), aliovalent doping (La/Sr ratio), the crystal structure, and the oxygen vacancy concentration and/or nonstoichiometry (delta). It was found excess electrons left due to the formation of a neutral oxygen vacancy get distributed to Fe directly connected to the vacancy or to the second nearest neighboring Fe, based on crystal field splitting of Fe 3d orbital in different Fe-O polyhedral coordination. The progressively larger polaron size and anisotropic shape changes with increasing Sr-content resulted in increasing oxygen vacancy interactions, as indicated by an increase in the oxygen vacancy formation energy above a critical delta threshold. This was consistent with experimental results showing that Sr-rich LSF and highly oxygen deficient compositions are prone to oxygen-vacancy-ordering-induced phase transformations, while Sr-poor and oxygen-rich LSF compositions are not. Since oxygen vacancy induced phase transformations, cause a decrease in the mobile oxygen vacancy site fraction (X), both delta and X were predicted as a function of temperature and oxygen partial pressure, for multiple LSF compositions and phases using a combined thermodynamics and DFT approach. A detailed oxygen vacancy migration barrier calculation gave the oxygen ionic diffusivity and conductivity. Oxygen vacancy also causes chemical strain, which was treated as a scalar in the literature. However, in many materials, it should be a tensor, which is anisotropic. We illustrate this effect on CeO2, in which it explained a puzzling experiment, which shows significant amplification of measured strain on applied bias in non-stoichiometric Gd doped ceria. The presence of highly localized 4f valence orbital in Ce causes charge disproportionation on the formation of neutral oxygen vacancy, producing anisotropic chemical strain in ceria with cubic symmetry. Understanding of delta and X and anisotropic chemical strain in the lattice has led to the design of better MIEC via element doping and strain engineering of the lattice.

Vacancy-stabilized crystalline order in hard cubes

PubMed Central

Smallenburg, Frank; Filion, Laura; Marechal, Matthieu; Dijkstra, Marjolein

2012-01-01

We examine the effect of vacancies on the phase behavior and structure of systems consisting of hard cubes using event-driven molecular dynamics and Monte Carlo simulations. We find a first-order phase transition between a fluid and a simple cubic crystal phase that is stabilized by a surprisingly large number of vacancies, reaching a net vacancy concentration of approximately 6.4% near bulk coexistence. Remarkably, we find that vacancies increase the positional order in the system. Finally, we show that the vacancies are delocalized and therefore hard to detect. PMID:23012241

Influence of vacancy defect on surface feature and adsorption of Cs on GaN(0001) surface.

PubMed

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at B(Ga) site on N vacancy defect surface. The E(ads) of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable.

Mesoscale modeling of vacancy-mediated Si segregation near an edge dislocation in Ni under irradiation

NASA Astrophysics Data System (ADS)

Li, Zebo; Trinkle, Dallas R.

2017-04-01

We use a continuum method informed by transport coefficients computed using self-consistent mean field theory to model vacancy-mediated diffusion of substitutional Si solutes in FCC Ni near an a/2 [1 1 ¯0 ] (111 ) edge dislocation. We perform two sequential simulations: first under equilibrium boundary conditions and then under irradiation. The strain field around the dislocation induces heterogeneity and anisotropy in the defect transport properties and determines the steady-state vacancy and Si distributions. At equilibrium both vacancies and Si solutes diffuse to form Cottrell atmospheres with vacancies accumulating in the compressive region above the dislocation core while Si segregates to the tensile region below the core. Irradiation raises the bulk vacancy concentration, driving vacancies to flow into the dislocation core. The out-of-equilibrium vacancy fluxes drag Si atoms towards the core, causing segregation to the compressive region, despite Si being an oversized solute in Ni.

Dynamics of vacancies in two-dimensional Lennard-Jones crystals

NASA Astrophysics Data System (ADS)

Yao, Zhenwei; Olvera de La Cruz, Monica

2015-03-01

Vacancies represent an important class of crystallographic defects, and their behaviors can be strongly coupled with relevant material properties. We report the rich dynamics of vacancies in two-dimensional Lennard-Jones crystals in several thermodynamic states. Specifically, we numerically observe significantly faster diffusion of the 2-point vacancy with two missing particles in comparison with other types of vacancies; it opens the possibility of doping 2-point vacancies into atomic materials to enhance atomic migration. In addition, the resulting dislocations in the healing of a long vacancy suggest the intimate connection between vacancies and topological defects that may provide an extra dimension in the engineering of defects in extensive crystalline materials for desired properties. We thank the financial support from the U.S. Department of Commerce, National Institute of Standards and Technology, the Office of the Director of Defense Research and Engineering (DDR&E) and the Air Force Office of Scientific Research.

Influence of Vacancy Defect on Surface Feature and Adsorption of Cs on GaN(0001) Surface

PubMed Central

Ji, Yanjun; Du, Yujie; Wang, Meishan

2014-01-01

The effects of Ga and N vacancy defect on the change in surface feature, work function, and characteristic of Cs adsorption on a (2 × 2) GaN(0001) surface have been investigated using density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations. The covalent bonds gain strength for Ga vacancy defect, whereas they grow weak for N vacancy defect. The lower work function is achieved for Ga and N vacancy defect surfaces than intact surface. The most stable position of Cs adatom on Ga vacancy defect surface is at T1 site, whereas it is at BGa site on N vacancy defect surface. The E ads of Cs on GaN(0001) vacancy defect surface increases compared with that of intact surface; this illustrates that the adsorption of Cs on intact surface is more stable. PMID:25126599

Nanodiamonds as multi-purpose labels for microscopy.

PubMed

Hemelaar, S R; de Boer, P; Chipaux, M; Zuidema, W; Hamoh, T; Martinez, F Perona; Nagl, A; Hoogenboom, J P; Giepmans, B N G; Schirhagl, R

2017-04-07

Nanodiamonds containing fluorescent nitrogen-vacancy centers are increasingly attracting interest for use as a probe in biological microscopy. This interest stems from (i) strong resistance to photobleaching allowing prolonged fluorescence observation times; (ii) the possibility to excite fluorescence using a focused electron beam (cathodoluminescence; CL) for high-resolution localization; and (iii) the potential use for nanoscale sensing. For all these schemes, the development of versatile molecular labeling using relatively small diamonds is essential. Here, we show the direct targeting of a biological molecule with nanodiamonds as small as 70 nm using a streptavidin conjugation and standard antibody labelling approach. We also show internalization of 40 nm sized nanodiamonds. The fluorescence from the nanodiamonds survives osmium-fixation and plastic embedding making them suited for correlative light and electron microscopy. We show that CL can be observed from epon-embedded nanodiamonds, while surface-exposed nanoparticles also stand out in secondary electron (SE) signal due to the exceptionally high diamond SE yield. Finally, we demonstrate the magnetic read-out using fluorescence from diamonds prior to embedding. Thus, our results firmly establish nanodiamonds containing nitrogen-vacancy centers as unique, versatile probes for combining and correlating different types of microscopy, from fluorescence imaging and magnetometry to ultrastructural investigation using electron microscopy.

Low-power resistive random access memory by confining the formation of conducting filaments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Yi-Jen; Lee, Si-Chen, E-mail: sclee@ntu.edu.tw; Shen, Tzu-Hsien

2016-06-15

Owing to their small physical size and low power consumption, resistive random access memory (RRAM) devices are potential for future memory and logic applications in microelectronics. In this study, a new resistive switching material structure, TiO{sub x}/silver nanoparticles/TiO{sub x}/AlTiO{sub x}, fabricated between the fluorine-doped tin oxide bottom electrode and the indium tin oxide top electrode is demonstrated. The device exhibits excellent memory performances, such as low operation voltage (<±1 V), low operation power, small variation in resistance, reliable data retention, and a large memory window. The current-voltage measurement shows that the conducting mechanism in the device at the high resistancemore » state is via electron hopping between oxygen vacancies in the resistive switching material. When the device is switched to the low resistance state, conducting filaments are formed in the resistive switching material as a result of accumulation of oxygen vacancies. The bottom AlTiO{sub x} layer in the device structure limits the formation of conducting filaments; therefore, the current and power consumption of device operation are significantly reduced.« less

Vacancy dynamic in Ni-Mn-Ga ferromagnetic shape memory alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Merida, D., E-mail: david.merida@ehu.es; Elektrizitate eta Elektronika Saila, Euskal Herriko Unibertsitatea UPV/EHU, p.k. 644, 48080 Bilbao; García, J. A.

2014-06-09

Vacancies control any atomic ordering process and consequently most of the order-dependent properties of the martensitic transformation in ferromagnetic shape memory alloys. Positron annihilation spectroscopy demonstrates to be a powerful technique to study vacancies in NiMnGa alloys quenched from different temperatures and subjected to post-quench isothermal annealing treatments. Considering an effective vacancy type the temperature dependence of the vacancy concentration has been evaluated. Samples quenched from 1173 K show a vacancy concentration of 1100 ± 200 ppm. The vacancy migration and formation energies have been estimated to be 0.55 ± 0.05 eV and 0.90 ± 0.07 eV, respectively.

Dynamic behaviour of nanometre-sized defect clusters emitted from an atomic displacement cascade in Au at 50 K

NASA Astrophysics Data System (ADS)

Ono, K.; Miyamoto, M.; Arakawa, K.; Birtcher, R. C.

2017-09-01

We demonstrate the emission of nanometre-sized defect clusters from an isolated displacement cascade formed by irradiation of high-energy self-ions and their subsequent 1-D motion in Au at 50 K, using in situ electron microscopy. The small defect clusters emitted from a displacement cascade exhibited correlated back-and-forth 1-D motion along the [-1 1 0] direction and coalescence which results in their growth and reduction of their mobility. From the analysis of the random 1-D motion, the diffusivity of the small cluster was evaluated. Correlated 1-D motion and coalescence of clusters were understood via elastic interaction between small clusters. These results provide direct experimental evidence of the migration of small defect clusters and defect cascade evolution at low temperature.

Density functional study of carbon vacancies in titanium carbide

NASA Astrophysics Data System (ADS)

Råsander, Mikael; Hugosson, Håkan W.; Delin, Anna

2018-01-01

It is well established that TiC contains carbon vacancies not only in carbon-deficient environments but also in carbon-rich environments. We have performed density functional calculations of the vacancy formation energy in TiC for C- as well as Ti-rich conditions using several different approximations to the exchange-correlation functional, and also carefully considering the nature and thermodynamics of the carbon reference state, as well as the effect of varying growth conditions. We find that the formation of carbon vacancies is clearly favorable under Ti-rich conditions, whereas it is slightly energetically unfavorable under C-rich conditions. Furthermore, we find that the relaxations of the atoms close to the vacancy site are rather long-ranged, and that these relaxations contribute significantly to the stabilization of the vacancy. Since carbon vacancies in TiC are also experimentally observed in carbon-rich environments, we conclude that kinetics may play an important role. This conclusion is consistent with the experimentally observed high activation energies and sluggish diffusion of vacancies in TiC, effectively causing a freezing in of the vacancies.

Appearance of superconductivity at the vacancy order-disorder boundary in KxFe2 -ySe2

NASA Astrophysics Data System (ADS)

Duan, Chunruo; Yang, Junjie; Ren, Yang; Thomas, Sean M.; Louca, Despina

2018-05-01

The role of phase separation and the effect of Fe-vacancy ordering in the emergence of superconductivity in alkali metal doped iron selenides AxFe2 -ySe2 (A = K, Rb, Cs) is explored. High energy x-ray diffraction and Monte Carlo simulation were used to investigate the crystal structure of quenched superconducting (SC) and as-grown nonsuperconducting (NSC) KxFe2 -ySe2 single crystals. The coexistence of superlattice structures with the in-plane √{2 }×√{2 } K-vacancy ordering and the √{5 }×√{5 } Fe-vacancy ordering were observed in both the SC and NSC crystals alongside the I4/mmm Fe-vacancy-free phase. Moreover, in the SC crystals, an Fe-vacancy-disordered phase is additionally proposed to be present. Monte Carlo simulations suggest that it appears at the boundary between the I4/mmm vacancy-free phase and the I4/m vacancy-ordered phases (√{5 }×√{5 } ). The vacancy-disordered phase is nonmagnetic and is most likely the host of superconductivity.

Defect evolution and its impact on the ferromagnetism of Cu-doped ZnO nanocrystals upon thermal treatment: A positron annihilation study

NASA Astrophysics Data System (ADS)

Chen, Zhi-Yuan; Chen, Yuqian; Zhang, Q. K.; Qi, N.; Chen, Z. Q.; Wang, S. J.; Li, P. H.; Mascher, P.

2017-01-01

CuO/ZnO nanocomposites with 4 at. % CuO were annealed in air at various temperatures between 100 and 1200 °C to produce Cu-doped ZnO nanocrystals. X-ray diffraction shows that a CuO phase can be observed in the CuO/ZnO nanocomposites annealed at different temperatures, and the Cu-doped ZnO nanocrystals are identified to be of wurtzite structure. The main peak (101) appears at slightly lower diffraction angles with increasing annealing temperature from 400 up to 1200 °C, which confirms the successful doping of Cu into the ZnO lattice above 400 °C. Scanning electron microscopy indicates that most particles in the CuO/ZnO nanocomposites are isolated when annealing at 100-400 °C, but these particles have a tendency to form clusters or aggregates as the annealing temperature increases from 700 to 1000 °C. Positron annihilation measurements reveal a large number of vacancy defects in the interface region of the nanocomposites, and they are gradually recovered with increasing annealing temperature up to 1000 °C. Room-temperature ferromagnetism can be observed in the CuO/ZnO nanocomposites, and the magnetization decreases continuously with increasing annealing temperature. However, there may be several different origins of ferromagnetism in the CuO/ZnO nanocomposites. At low annealing temperatures, the ferromagnetism originates from the CuO nanograins, and the ferromagnetism of CuO nanograins decreases with an increase in the grain size after subsequent higher temperature annealing, which leads to the weakening of ferromagnetism in the CuO/ZnO nanocomposites. After annealing from 400 to 1000 °C, the ferromagnetism gradually vanishes. The ferromagnetism is probably induced by Cu substitution but is mediated by vacancy defects in the CuO/ZnO nanocomposites. The disappearance of ferromagnetism coincides well with the recovery of vacancy defects. It can be inferred that the ferromagnetism is mediated by vacancy defects that are distributed in the interface region.

Probing cation and vacancy ordering in the dry and hydrated yttrium-substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: implications for proton mobility.

PubMed

Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

2012-09-05

Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites.

Probing the effects of defects on ferroelectricity in ferroelectric thin films

NASA Astrophysics Data System (ADS)

Zhu, Lin

Ferroelectric materials have been intensively studied due to their interesting properties such as piezoelectricity, ferroelectricity including spontaneous polarization, remnant polarization, hysteresis loop, and etc. In this study, effects of defects, thickness, and temperature on ferroelectric stability, hysteresis loop, and phase transition in ferroelectric thin films have been investigated using molecular dynamics simulations with first-principles effective Hamiltonian. Various types of defects are considered including oxygen vacancy, hydrogen contamination, and dead layer. We first study the effects of oxygen vacancy on ferroelectricity in PbTiO3 (PTO) thin films. An oxygen vacancy has been modeled as a +2q charged point defect which generates local strain and electrostatic fields. Atomic displacements induced by an oxygen vacancy were obtained by first-principles calculations and the corresponding strain field was fitted with elastic continuum model of a point defect. The obtained local strain and electrostatic fields are the inputs to the molecular dynamics (MD) simulations. We limited the oxygen vacancies in the interfacial layers between the film and electrodes. Oxygen vacancies reduce the spontaneous polarization and significantly increase the critical thickness below which the spontaneous polarization disappears. With the presence of oxygen vacancy only at one interface layer, PTO film exhibits asymmetric hysteresis loop which is consistent with experimental observations about the imprint effect. In the heating-up and cooling-down processes, oxygen vacancies weaken the phase transitions, but contribute tension along the thickness direction at high temperature. First-principles calculations are performed to determine the possible position, formation energy, and mobility of the interstitial hydrogen atom, and the calculated results are used as inputs to MD simulations in a large system. The hydrogen atom is able to move within one unit cell with small energy barriers. The energy difference between a hydrogen contaminated PTO and a pure PTO is considered as an energy penalty term induced by hydrogen contamination. Then, the effective Hamiltonian with the energy penalty is employed in MD simulations to investigate the effects of hydrogen contamination on the ferroelectric responses of PTO films. The hysteresis loops are presented and analyzed for PTO films with various concentrations of hydrogen impurities and thicknesses. Hydrogen contamination reduces the remnant polarization, especially for thin films. As the concentration of hydrogen impurities increases, the critical thickness increases. By analyzing the vertical cross section snapshots, it has been found that the hydrogen impurities near interfaces affect the polarization throughout the entire PTO film. To study the effect of the dead layer (depolarization field), the soft modes in the top and bottom layers are constrained to be zero, which gives rise to the reduced polarization and increased critical thickness. Negative capacitance is a new and hot topic, which was recently observed by experiment. It is a transient effect that correlated with depolarization field. Some preliminary results and application of negative capacitance are discussed.

Defects in Amorphous Semiconductors: The Case of Amorphous Indium Gallium Zinc Oxide

NASA Astrophysics Data System (ADS)

de Jamblinne de Meux, A.; Pourtois, G.; Genoe, J.; Heremans, P.

2018-05-01

Based on a rational classification of defects in amorphous materials, we propose a simplified model to describe intrinsic defects and hydrogen impurities in amorphous indium gallium zinc oxide (a -IGZO). The proposed approach consists of organizing defects into two categories: point defects, generating structural anomalies such as metal—metal or oxygen—oxygen bonds, and defects emerging from changes in the material stoichiometry, such as vacancies and interstitial atoms. Based on first-principles simulations, it is argued that the defects originating from the second group always act as perfect donors or perfect acceptors. This classification simplifies and rationalizes the nature of defects in amorphous phases. In a -IGZO, the most important point defects are metal—metal bonds (or small metal clusters) and peroxides (O - O single bonds). Electrons are captured by metal—metal bonds and released by the formation of peroxides. The presence of hydrogen can lead to two additional types of defects: metal-hydrogen defects, acting as acceptors, and oxygen-hydrogen defects, acting as donors. The impact of these defects is linked to different instabilities observed in a -IGZO. Specifically, the diffusion of hydrogen and oxygen is connected to positive- and negative-bias stresses, while negative-bias illumination stress originates from the formation of peroxides.

High temperature magnetism and microstructure of ferromagnetic alloy Si1-x Mn x

NASA Astrophysics Data System (ADS)

Aronzon, B. A.; Davydov, A. B.; Vasiliev, A. L.; Perov, N. S.; Novodvorsky, O. A.; Parshina, L. S.; Presniakov, M. Yu; Lahderanta, E.

2017-02-01

The results of a detailed study of magnetic properties and of the microstructure of SiMn films with a small deviation from stoichiometry are presented. The aim was to reveal the origin of the high temperature ferromagnetic ordering in such compounds. Unlike SiMn single crystals with the Curie temperature ~30 K, considered Si1-x Mn x compounds with x  =  0.5  +Δx and Δx in the range of 0.01-0.02 demonstrate a ferromagnetic state above room temperature. Such a ferromagnetic state can be explained by the existence of highly defective B20 SiMn nanocrystallites. These defects are Si vacancies, which are suggested to possess magnetic moments. The nanocrystallites interact with each other through paramagnons (magnetic fluctuations) inside a weakly magnetic manganese silicide matrix giving rise to a long range ferromagnetic percolation cluster. The studied structures with a higher value of Δx  ≈  0.05 contained three different magnetic phases: (a)—the low temperature ferromagnetic phase related to SiMn; (b)—the above mentioned high temperature phase with Curie temperature in the range of 200-300 K depending on the growth history and (c)—superparamagnetic phase formed by separated noninteracting SiMn nanocrystallites.

Damage structures in fission-neutron irradiated Ni-based alloys at high temperatures

NASA Astrophysics Data System (ADS)

Yamakawa, K.; Shimomura, Y.

1999-01-01

The defects formed in Ni based (Ni-Si, Ni-Cu and Ni-Fe) alloys which were irradiated with fission-neutrons were examined by electron microscopy. Irradiations were carried out at 473 K and 573 K. In the 473 K irradiated specimens, a high density of large interstitial loops and small vacancy clusters with stacking fault tetrahedra (SFT) were observed. The number densities of these two types of defects did not strongly depend on the amount of solute atoms in each alloy. The density of the loops in Ni-Si alloys was much higher than those in Ni-Cu and Ni-Fe alloys, while the density of SFT only slightly depended on the kind of solute. Also, the size of the loops depended on the kinds and amounts of solute. In 573 K irradiated Ni-Cu specimens, a high density of dislocation lines developed during the growth of interstitial loops. In Ni-Si alloys, the number density and size of the interstitial loops changed as a function of the amount of solute. Voids were formed in Ni-Cu alloys but scarcely formed in Ni-Si alloys. The number density of voids was one hundredth of that of SFT observed in 473 K irradiated Ni-Cu alloys. Possible formation processes of interstitial loops, SFT dislocation lines and voids are discussed.

Gold fillings unravel the vacancy role in the phase transition of GeTe

NASA Astrophysics Data System (ADS)

Feng, Jinlong; Xu, Meng; Wang, Xiaojie; Lin, Qi; Cheng, Xiaomin; Xu, Ming; Tong, Hao; Miao, Xiangshui

2018-02-01

Phase change memory (PCM) is an important candidate for future memory devices. The crystalline phase of PCM materials contains abundant intrinsic vacancies, which plays an important role in the rapid phase transition upon memory switching. However, few experimental efforts have been invested to study these invisible entities. In this work, Au dopants are alloyed into the crystalline GeTe to fill the intrinsic Ge vacancies so that the role of these vacancies in the amorphization of GeTe can be indirectly studied. As a result, the reduction of Ge vacancies induced by Au dopants hampers the amorphization of GeTe as the activation energy of this process becomes higher. This is because the vacancy-interrupted lattice can be "repaired" by Au dopants with the recovery of bond connectivity. Our results demonstrate the importance of vacancies in the phase transition of chalcogenides, and we employ the percolation theory to explain the impact of these intrinsic defects on this vacancy-ridden crystal quantitatively. Specifically, the threshold of amorphization increases with the decrease in vacancies. The understanding of the vacancy effect sheds light on the long-standing puzzle of the mechanism of ultra-fast phase transition in PCMs. It also paves the way for designing low-power-consumption electronic devices by reducing the threshold of amorphization in chalcogenides.

Stiffness and strength of oxygen-functionalized graphene with vacancies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zandiatashbar, A.; Ban, E.; Picu, R. C., E-mail: picuc@rpi.edu

2014-11-14

The 2D elastic modulus (E{sup 2D}) and strength (σ{sup 2D}) of defective graphene sheets containing vacancies, epoxide, and hydroxyl functional groups are evaluated at 300 K by atomistic simulations. The fraction of vacancies is controlled in the range 0% to 5%, while the density of functional groups corresponds to O:C ratios in the range 0% to 25%. In-plane modulus and strength diagrams as functions of vacancy and functional group densities are generated using models with a single type of defect and with combinations of two types of defects (vacancies and functional groups). It is observed that in models containing only vacancies,more » the rate at which strength decreases with increasing the concentration of defects is largest, followed by models containing only epoxide groups and those with only hydroxyl groups. The effect on modulus of vacancies and epoxides present alone in the model is similar, and much stronger than that of hydroxyl groups. When the concentration of defects is large, the combined effect of the functional groups and vacancies cannot be obtained as the superposition of individual effects of the two types of defects. The elastic modulus deteriorates faster (slower) than predicted by superposition in systems containing vacancies and hydroxyl groups (vacancies and epoxide groups)« less

Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yan; Wei, Zhehao; Gao, Feng

2015-05-01

In this work, CeO2 nanocubes with controlled particle size and dominating (100) facets are synthesized as supports for VOx catalysts. Combined TEM, SEM, XRD, and Raman study reveals that the oxygen vacancy density of CeO2 supports can be tuned by tailoring the particle sizes without altering the dominating facets, where smaller particle sizes result in larger oxygen vacancy densities. At the same vanadium coverage, the VOx catalysts supported on small-sized CeO2 supports with higher oxygen defect densities exhibit promoted redox property and lower activation energy for methoxyl group decomposition, as evidenced by H2-TPR and methanol TPD study. These results furthermore » confirm that the presence of oxygen vacancies plays an important role in promoting the activity of VOx species in methanol oxidation. We gratefully acknowledge financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Part of this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.« less

Toward Deterministic Implantation of Nitrogen Vacancy Centers in Bulk Diamond Crystals

NASA Astrophysics Data System (ADS)

Brundage, T. O.; Atkins, Z.; Sangtawesin, S.; Petta, J. R.

2014-03-01

Over the last decade, research investigating the room temperature stability, coherence, and optical manipulation of spin states of the nitrogen vacancy (NV) center in diamond has made it a strong candidate for applications in magnetometry and quantum information processing. As research progresses and we begin to investigate the dynamics and scalability of multiple NV systems, the ability to place NV centers deterministically in the host material with high accuracy is critical. Here we implement a simple fabrication method for NV implantation. We expose and develop small dots in PMMA using an electron-beam lithography tool. Unexposed PMMA serves as a mask for 20 keV nitrogen-15 implantation. The implanted sample is then cleaned in a boiling mixture of nitric, sulfuric, and perchloric acid. Annealing at 850° for 2 hours allows vacancies to diffuse next to implanted nitrogen atoms, forming NV centers with an efficiency of a few percent. SRIM simulations provide nitrogen ion distribution within our diamond substrate and PMMA mask as functions of implantation energy. Thus, after balancing implantation parameters and exposure hole cross-sections, NV center placement can be achieved with accuracy limited by the precision of available electron-beam lithography equipment. Supported by the Sloan and Packard Foundations, the Army Research Office, and the National Science Foundation.

Lattice continuum and diffusional creep

PubMed Central

2016-01-01

Diffusional creep is characterized by growth/disappearance of lattice planes at the crystal boundaries that serve as sources/sinks of vacancies, and by diffusion of vacancies. The lattice continuum theory developed here represents a natural and intuitive framework for the analysis of diffusion in crystals and lattice growth/loss at the boundaries. The formulation includes the definition of the Lagrangian reference configuration for the newly created lattice, the transport theorem and the definition of the creep rate tensor for a polycrystal as a piecewise uniform, discontinuous field. The values associated with each crystalline grain are related to the normal diffusional flux at grain boundaries. The governing equations for Nabarro–Herring creep are derived with coupled diffusion and elasticity with compositional eigenstrain. Both, bulk diffusional dissipation and boundary dissipation accompanying vacancy nucleation and absorption, are considered, but the latter is found to be negligible. For periodic arrangements of grains, diffusion formally decouples from elasticity but at the cost of a complicated boundary condition. The equilibrium of deviatorically stressed polycrystals is impossible without inclusion of interface energies. The secondary creep rate estimates correspond to the standard Nabarro–Herring model, and the volumetric creep is small. The initial (primary) creep rate is estimated to be much larger than the secondary creep rate. PMID:27274696

Defects and oxidation of group-III monochalcogenide monolayers

NASA Astrophysics Data System (ADS)

Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

2017-09-01

Among various two-dimensional (2D) materials, monolayer group-III monochalcogenides (GaS, GaSe, InS, and InSe) stand out owing to their potential applications in microelectronics and optoelectronics. Devices made of these novel 2D materials are sensitive to environmental gases, especially O2 molecules. To address this critical issue, here we systematically investigate the oxidization behaviors of perfect and defective group-III monochalcogenide monolayers by first-principles calculations. The perfect monolayers show superior oxidation resistance with large barriers of 3.02-3.20 eV for the dissociation and chemisorption of O2 molecules. In contrast, the defective monolayers with single chalcogen vacancy are vulnerable to O2, showing small barriers of only 0.26-0.36 eV for the chemisorption of an O2 molecule. Interestingly, filling an O2 molecule to the chalcogen vacancy of group-III monochalcogenide monolayers could preserve the electronic band structure of the perfect system—the bandgaps are almost intact and the carrier effective masses are only moderately disturbed. On the other hand, the defective monolayers with single vacancies of group-III atoms carry local magnetic moments of 1-2 μB. These results help experimental design and synthesis of group-III monochalcogenides based 2D devices with high performance and stability.

Using the 18-Electron Rule To Understand the Nominal 19-Electron Half-Heusler NbCoSb with Nb Vacancies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeier, Wolfgang G.; Anand, Shashwat; Huang, Lihong

The 18-electron rule is a widely used criterion in the search for new half-Heusler thermoelectric materials. However, several 19-electron compounds such as NbCoSb have been found to be stable and exhibit thermoelectric properties rivaling state-of-the art materials. Using synchrotron X-ray diffraction and density functional theory calculations, we show that samples with nominal (19-electron) composition NbCoSb actually contain a half-Heusler phase with composition Nb0.84CoSb. The large amount of stable Nb vacancies reduces the overall electron count, which brings the stoichiometry of the compound close to an 18-electron count, and stabilizes the material. Excess electrons beyond 18 electrons provide heavy doping neededmore » to make these good thermoelectric materials. This work demonstrates that considering possible defect chemistry and allowing small variation of electron counting leads to extra degrees of freedom for tailoring thermoelectric properties and exploring new compounds. Here we discuss the 18-electron rule as a guide to find defect-free half-Heusler semiconductors. Other electron counts such as 19-electron NbCoSb can also be expected to be stable as n-type metals, perhaps with cation vacancy defects to reduce the electron count.« less

Density functional theory study of dopant effect on formation energy of intrinsic point defects in germanium crystals

NASA Astrophysics Data System (ADS)

Yamaoka, S.; Kobayashi, K.; Sueoka, K.; Vanhellemont, J.

2017-09-01

During the last decade the use of single crystal germanium (Ge) layers and structures in combination with silicon (Si) substrates has led to a revival of defect research on Ge. Ge is used because of the much higher carrier mobility compared to Si, allowing to design devices operating at much higher frequencies. A major issue for the use of Ge single crystal wafers is the fact that all Czochralski-grown Ge (CZ-Ge) crystals are vacancy-rich and contain vacancy clusters that are much larger than the ones in Si. In contrast to Si, control of intrinsic point defect concentrations has not yet been realized at the same level in Ge crystals due to the lack of experimental data especially on dopant effects. In this study, we have evaluated with density functional theory (DFT) calculations the dopant effect on the formation energy (Ef) of the uncharged vacancy (V) and self-interstitial (I) in Ge and compared the results with those for Si. The dependence of the total thermal equilibrium concentrations of point defects (sum of free V or I and V or I paired with dopant atoms) at melting temperature on the type and concentration of various dopants is obtained. It was found that (1) Ge crystals will be more V-rich by Tl, In, Sb, Sn, As and P doping, (2) Ge crystals will be more I-rich by Ga, C and B doping, (3) Si doping has negligible impact. The dopant impact on Ef of V and I in Ge has a narrower range and is smaller than that in Si. The obtained results are useful to control grown-in V and I concentrations, and will perhaps also allow to develop defect-free ;perfect; Ge crystals.

First-principles study of intrinsic vacancy defects in Sr2MgSi2O7 phosphorescent host material

NASA Astrophysics Data System (ADS)

Duan, H.; Dong, Y. Z.; Huang, Y.; Hu, Y. H.; Chen, X. S.

2016-01-01

Electronic structures of intrinsic vacancy defects in Sr2MgSi2O7 phosphorescent host material are investigated using first-principles calculations. Si vacancies are too high in energy to play any role in the persistent luminescence of Sr2MgSi2O7 phosphor. Mg vacancies form easier than Sr vacancies as a result of strain relief. Among all the vacancies, O1 vacancies stand out as a likely candidate because they are the most favorable in energy and introduce an empty triply degenerate state just below the CBM and a fully-occupied singlet state at ~1 eV above the VBM, constituting in this case effective hole trap level and electron trap levels, respectively. Mg vacancies are unlikely to explain the persistent luminescence because of its too shallow electron trap level but they may compensate the hole trap associated with O1 vacancies. We yield consistent evidence for the defect physics of these vacancy defects on the basis of the equilibrium properties of Sr2MgSi2O7, total-energy calculations, and electronic structures. The persistent luminescence mechanism of Sr2MgSi2O7:Eu2+, Dy3+ phosphor is also discussed based on our results for O1 vacancies trap center. Our results provide a guide to more refined experiments to control intrinsic traps, whereby probing synthetic strategies toward new improved phosphors.

The Impacts of Different Expansion Modes on Performance of Small Solar Energy Firms: Perspectives of Absorptive Capacity

PubMed Central

Chen, Hsing Hung; Shen, Tao; Xu, Xin-long; Ma, Chao

2013-01-01

The characteristics of firm's expansion by differentiated products and diversified products are quite different. However, the study employing absorptive capacity to examine the impacts of different modes of expansion on performance of small solar energy firms has never been discussed before. Then, a conceptual model to analyze the tension between strategies and corporate performance is proposed to filling the vacancy. After practical investigation, the results show that stronger organizational institutions help small solar energy firms expanded by differentiated products increase consistency between strategies and corporate performance; oppositely, stronger working attitudes with weak management controls help small solar energy firms expanded by diversified products reduce variance between strategies and corporate performance. PMID:24453837

Vacancy-hydrogen complexes in ammonothermal GaN

NASA Astrophysics Data System (ADS)

Tuomisto, F.; Kuittinen, T.; Zając, M.; Doradziński, R.; Wasik, D.

2014-10-01

We have applied positron annihilation spectroscopy to study in-grown vacancy defects in bulk GaN crystals grown by the ammonothermal method. We observe a high concentration of Ga vacancy related defects in n-type samples with varying free electron and oxygen content. The positron lifetimes found in these samples suggest that the Ga vacancies are complexed with hydrogen impurities. The number of hydrogen atoms in each vacancy decreases with increasing free electron concentration and oxygen and hydrogen content. The local vibrational modes observed in infrared absorption support this conclusion. Growth of high-quality ammonothermal GaN single crystals with varying electron concentrations. Identification of defect complexes containing a Ga vacancy and 1 or more hydrogen atoms, and possibly O. These vacancy complexes provide a likely explanation for electrical compensation in ammonothermal GaN.

Abnormal Strain Rate Sensitivity Driven by a Unit Dislocation-Obstacle Interaction in bcc Fe

NASA Astrophysics Data System (ADS)

Bai, Zhitong; Fan, Yue

2018-03-01

The interaction between an edge dislocation and a sessile vacancy cluster in bcc Fe is investigated over a wide range of strain rates from 108 down to 103 s-1 , which is enabled by employing an energy landscape-based atomistic modeling algorithm. It is observed that, at low strain rates regime less than 105 s-1 , such interaction leads to a surprising negative strain rate sensitivity behavior because of the different intermediate microstructures emerged under the complex interplays between thermal activation and applied strain rate. Implications of our findings regarding the previously established global diffusion model are also discussed.

Defect types and room-temperature ferromagnetism in undoped rutile TiO2 single crystals

NASA Astrophysics Data System (ADS)

Li, Dong-Xiang; Qin, Xiu-Bo; Zheng, Li-Rong; Li, Yu-Xiao; Cao, Xing-Zhong; Li, Zhuo-Xin; Yang, Jing; Wang, Bao-Yi

2013-03-01

Room-temperature ferromagnetism has been experimentally observed in annealed rutile TiO2 single crystals when a magnetic field is applied parallel to the sample plane. By combining X-ray absorption near the edge structure spectrum and positron annihilation lifetime spectroscopy, Ti3+—VO defect complexes (or clusters) have been identified in annealed crystals at a high vacuum. We elucidate that the unpaired 3d electrons in Ti3+ ions provide the observed room-temperature ferromagnetism. In addition, excess oxygen ions in the TiO2 lattice could induce a number of Ti vacancies which obviously increase magnetic moments.

First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

DOE PAGES

Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; ...

2011-12-15

Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn 1/3Nb 2/3)O₃ and Pb(Mg 1/3Nb 2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies canmore » have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

Oxygen Migration and Local Structural Changes with Schottky Defects in Pure Zirconium Oxide Crystals

NASA Astrophysics Data System (ADS)

Terada, Yayoi; Mohri, Tetsuo

2018-05-01

By employing the Buckingham potential, we performed classical molecular-dynamics computer simulations at constant pressure and temperature for a pure ZrO2 crystal without any vacancies and for a pure ZrO2 crystal containing zirconium vacancies and oxygen vacancies. We examined the positions of atoms and vacancies in the steady state, and we investigated the migration behavior of atoms and the local structure of vacancies of the pure ZrO2 crystal. We found that Schottky defects (aggregates consisting of one zirconium vacancy with an effective charge of -4 and two oxygen vacancies each with an effective charge of +2 to maintain charge neutrality) are the main defects formed in the steady state in cubic ZrO2, and that oxygen migration occurs through a mechanism involving vacancies on the oxygen sublattice near such defects. We also found that several oxygen atoms near each defect are displaced far from the sublattice site and induce oxygen migration.

Effect of structural defects on electronic and magnetic properties of ZrS2 monolayer

NASA Astrophysics Data System (ADS)

Wang, Haiyang; Zhao, Xu; Gao, Yonghui; Wang, Tianxing; Wei, Shuyi

2018-04-01

We aimed at ten configurations of vacancy defects and used the first-principles methods based on density functional theory to research electronic and magnetic properties of ZrS2 monolayer. Results show that the system of two-zirconium vacancy (V2zr) and one Zr atom + one S atom vacancy (V1Zr+1S) can induce to total spin magnetic moment of 0.245μB and 0.196μB, respectively. In addition, three and six S atoms vacancy can induce corresponding system to manifest spin magnetic moment of 0.728μB and 3.311μB, respectively. In S atom vacancy defects, vacancy defects can transform the system from semiconductor to metal, several of the Zr atoms and adjacent S atoms display antiferromagnetism coupling in three apart S atom vacancy defects. Vacancy defects can make the intrisic monolayer ZrS2 transform semiconductor into metal. These results are important for the achievement of spin devices based on ZrS2 semiconductor.

Vacancy–Vacancy Interaction Induced Oxygen Diffusivity Enhancement in Undoped Nonstoichiometric Ceria

DOE PAGES

Yuan, Fenglin; Zhang, Yanwen; Weber, William J.

2015-05-19

In this paper, molecular dynamics simulations and molecular static calculations have been used to systematically study oxygen vacancy transport in undoped nonstoichiometric ceria. A strong oxygen diffusivity enhancement appears in the vacancy concentration range of 2–4% over the temperature range from 1000 to 2000 K. An Arrhenius ion diffusion mechanism by vacancy hopping along the (100) direction is unambiguously identified, and an increasing trend of both the oxygen migration barrier and the prefactor with increasing vacancy concentration is observed. Within the framework of classical diffusion theory, a weak concentration dependence of the prefactor in oxygen vacancy migration is shown tomore » be crucial for explaining the unusual fast oxygen ion migration in the low concentration range and consequently the appearance of a maximum in oxygen diffusivity. Finally, a representative (100) direction interaction model is constructed to identify long-range vacancy–vacancy interaction as the structural origin of the positive correlation between oxygen migration barrier and vacancy concentration.« less

Positron Annihilation Spectroscopy and Small Angle Neutron Scattering Characterization of Nanostructural Features in Irradiated Fe-Cu-Mn Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wirth, B D; Asoka-Kumar, P; Howell, R H

2001-01-01

Radiation embrittlement of nuclear reactor pressure vessel steels results from a high number density of nanometer sized Cu-Mn-Ni rich precipitates (CRPs) and sub-nanometer matrix features, thought to be vacancy-solute cluster complexes (VSC). However, questions exist regarding both the composition of the precipitates and the defect character and composition of the matrix features. We present results of positron annihilation spectroscopy (PAS) and small angle neutron scattering (SANS) characterization of irradiated and thermally aged Fe-Cu and Fe-Cu-Mn alloys. These complementary techniques provide insight into the composition and character of both types of nanoscale features. The SANS measurements indicate populations of CRPs andmore » VSCs in both alloys. The CRPs are coarser in the Fe-Cu alloy and the number densities of CRP and VSC increase with the addition of Mn. The PAS involved measuring both the positron lifetimes and the Doppler broadened annihilation spectra in the high momentum region to provide elemental sensitivity at the annihilation site. The spectra in Fe-Cu-Mn specimens thermally aged to peak hardness at 450 C and irradiated at 288 C are nearly identical to elemental Cu. Positron lifetime and spectrum measurements in Fe-Cu specimens irradiated at 288 C clearly show the existence of long lifetime ({approx}500 ps) open volume defects, which also contain Cu. Thus the SANS and PAS provide a self-consistent picture of nanostructures composed of CRPs and VSCs and tend to discount high Fe concentrations in the CRPs.« less

Collective strong coupling with homogeneous Rabi frequencies using a 3D lumped element microwave resonator

NASA Astrophysics Data System (ADS)

Angerer, Andreas; Astner, Thomas; Wirtitsch, Daniel; Sumiya, Hitoshi; Onoda, Shinobu; Isoya, Junichi; Putz, Stefan; Majer, Johannes

2016-07-01

We design and implement 3D-lumped element microwave cavities that spatially focus magnetic fields to a small mode volume. They allow coherent and uniform coupling to electron spins hosted by nitrogen vacancy centers in diamond. We achieve large homogeneous single spin coupling rates, with an enhancement of more than one order of magnitude compared to standard 3D cavities with a fundamental resonance at 3 GHz. Finite element simulations confirm that the magnetic field distribution is homogeneous throughout the entire sample volume, with a root mean square deviation of 1.54%. With a sample containing 1017 nitrogen vacancy electron spins, we achieve a collective coupling strength of Ω = 12 MHz, a cooperativity factor C = 27, and clearly enter the strong coupling regime. This allows to interface a macroscopic spin ensemble with microwave circuits, and the homogeneous Rabi frequency paves the way to manipulate the full ensemble population in a coherent way.

Tunable cavity coupling of the zero phonon line of a nitrogen-vacancy defect in diamond

NASA Astrophysics Data System (ADS)

Johnson, S.; Dolan, P. R.; Grange, T.; Trichet, A. A. P.; Hornecker, G.; Chen, Y. C.; Weng, L.; Hughes, G. M.; Watt, A. A. R.; Auffèves, A.; Smith, J. M.

2015-12-01

We demonstrate the tunable enhancement of the zero phonon line of a single nitrogen-vacancy colour centre in diamond at cryogenic temperature. An open cavity fabricated using focused ion beam milling provides mode volumes as small as 1.24 μm3 (4.7 {λ }3) and quality factor Q≃ 3000. In situ tuning of the cavity resonance is achieved with piezoelectric actuators. At optimal coupling to a TEM00 cavity mode, the signal from individual zero phonon line transitions is enhanced by a factor of 6.25 and the overall emission rate of the NV- centre is increased by 40% compared with that measured from the same centre in the absence of cavity field confinement. This result represents a step forward in the realisation of efficient spin-photon interfaces and scalable quantum computing using optically addressable solid state spin qubits.

Efficiency of Cathodoluminescence Emission by Nitrogen-Vacancy Color Centers in Nanodiamonds.

PubMed

Zhang, Huiliang; Glenn, David R; Schalek, Richard; Lichtman, Jeff W; Walsworth, Ronald L

2017-06-01

Correlated electron microscopy and cathodoluminescence (CL) imaging using functionalized nanoparticles is a promising nanoscale probe of biological structure and function. Nanodiamonds (NDs) that contain CL-emitting color centers are particularly well suited for such applications. The intensity of CL emission from NDs is determined by a combination of factors, including particle size, density of color centers, efficiency of energy deposition by electrons passing through the particle, and conversion efficiency from deposited energy to CL emission. This paper reports experiments and numerical simulations that investigate the relative importance of each of these factors in determining CL emission intensity from NDs containing nitrogen-vacancy (NV) color centers. In particular, it is found that CL can be detected from NV-doped NDs with dimensions as small as ≈40 nm, although CL emission decreases significantly for smaller NDs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fiber-Optic Magnetometry and Thermometry Using Optically Detected Magnetic Resonance With Nitrogen-Vacancy Centers in Diamond

NASA Astrophysics Data System (ADS)

Blakley, Sean Michael

Nitrogen--vacancy diamond (NVD) quantum sensors are an emerging technology that has shown great promise in areas like high-resolution thermometry and magnetometry. Optical fibers provide attractive new application paradigms for NVD technology. A detailed description of the fabrication processes associated with the development of novel fiber-optic NVD probes are presented in this work. The demonstrated probes are tested on paradigmatic model systems designed to ascertain their suitability for use in challenging biological environments. Methods employing optically detected magnetic resonance (ODMR) are used to accurately measure and map temperature distributions of small objects and to demonstrate emergent temperature-dependent phenomena in genetically modified living organisms. These methods are also used to create detailed high resolution spatial maps of both magnetic scalar and magnetic vector field distributions of spatially localized weak field features in the presence of a noisy, high-field background.

Large-scale molecular dynamics simulations of TiN/TiN(001) epitaxial film growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edström, Daniel, E-mail: daned@ifm.liu.se; Sangiovanni, Davide G.; Hultman, Lars

2016-07-15

Large-scale classical molecular dynamics simulations of epitaxial TiN/TiN(001) thin film growth at 1200 K are carried out using incident flux ratios N/Ti = 1, 2, and 4. The films are analyzed as a function of composition, island size distribution, island edge orientation, and vacancy formation. Results show that N/Ti = 1 films are globally understoichiometric with dispersed Ti-rich surface regions which serve as traps to nucleate 111-oriented islands, leading to local epitaxial breakdown. Films grown with N/Ti = 2 are approximately stoichiometric and the growth mode is closer to layer-by-layer, while N/Ti = 4 films are stoichiometric with N-rich surfaces. As N/Ti is increased from 1 to 4, islandmore » edges are increasingly polar, i.e., 110-oriented, and N-terminated to accommodate the excess N flux, some of which is lost by reflection of incident N atoms. N vacancies are produced in the surface layer during film deposition with N/Ti = 1 due to the formation and subsequent desorption of N{sub 2} molecules composed of a N adatom and a N surface atom, as well as itinerant Ti adatoms pulling up N surface atoms. The N vacancy concentration is significantly reduced as N/Ti is increased to 2; with N/Ti = 4, Ti vacancies dominate. Overall, our results show that an insufficient N/Ti ratio leads to surface roughening via nucleation of small dispersed 111 islands, whereas high N/Ti ratios result in surface roughening due to more rapid upper-layer nucleation and mound formation. The growth mode of N/Ti = 2 films, which have smoother surfaces, is closer to layer-by-layer.« less

Theoretical studies of structure-property relations in graphene-based carbon nanostructures

NASA Astrophysics Data System (ADS)

Maroudas, Dimitrios

2014-03-01

This presentation focuses on establishing relations between atomic structure, electronic structure, and properties in graphene-based carbon nanostructures through first-principles density functional theory calculations and molecular-dynamics simulations. We have analyzed carbon nanostructure formation from twisted bilayer graphene, upon creation of interlayer covalent C-C bonds due to patterned hydrogenation or fluorination. For small twist angles and twist angles near 30 degrees, interlayer covalent bonding generates superlattices of diamond-like nanocrystals and of fullerene-like configurations, respectively, embedded within the graphene layers. The electronic band gaps of these superlattices can be tuned through selective chemical functionalization and creation of interlayer bonds, and range from a few meV to over 1.2 eV. The mechanical properties of these superstructures also can be precisely tuned by controlling the extent of chemical functionalization. Importantly, the shear modulus is shown to increase monotonically with the fraction of sp3-hybridized C-C bonds. We have also studied collective interactions of multiple defects such as random distributions of vacancies in single-layer graphene (SLG). We find that a crystalline-to-amorphous structural transition occurs at vacancy concentrations of 5-10% over a broad temperature range. The structure of our defect-induced amorphized graphene is in excellent agreement with experimental observations of SLG exposed to a high electron irradiation dose. Simulations of tensile tests on these irradiated graphene sheets identify trends for the ultimate tensile strength, failure strain, and toughness as a function of vacancy concentration. The vacancy-induced amorphization transition is accompanied by a brittle-to-ductile transition in the failure response of irradiated graphene sheets and even heavily damaged samples exhibit tensile strengths near 30 GPa, in significant excess of those typical of engineering materials.

Understanding the interface of six-shell cuboctahedral and icosahedral palladium clusters on reduced graphene oxide: experimental and theoretical study.

PubMed

Gracia-Espino, Eduardo; Hu, Guangzhi; Shchukarev, Andrey; Wågberg, Thomas

2014-05-07

Studies on noble-metal-decorated carbon nanostructures are reported almost on a daily basis, but detailed studies on the nanoscale interactions for well-defined systems are very rare. Here we report a study of reduced graphene oxide (rGOx) homogeneously decorated with palladium (Pd) nanoclusters with well-defined shape and size (2.3 ± 0.3 nm). The rGOx was modified with benzyl mercaptan (BnSH) to improve the interaction with Pd clusters, and N,N-dimethylformamide was used as solvent and capping agent during the decoration process. The resulting Pd nanoparticles anchored to the rGOx-surface exhibit high crystallinity and are fully consistent with six-shell cuboctahedral and icosahedral clusters containing ~600 Pd atoms, where 45% of these are located at the surface. According to X-ray photoelectron spectroscopy analysis, the Pd clusters exhibit an oxidized surface forming a PdO(x) shell. Given the well-defined experimental system, as verified by electron microscopy data and theoretical simulations, we performed ab initio simulations using 10 functionalized graphenes (with vacancies or pyridine, amine, hydroxyl, carboxyl, or epoxy groups) to understand the adsorption process of BnSH, their further role in the Pd cluster formation, and the electronic properties of the graphene-nanoparticle hybrid system. Both the experimental and theoretical results suggest that Pd clusters interact with functionalized graphene by a sulfur bridge while the remaining Pd surface is oxidized. Our study is of significant importance for all work related to anchoring of nanoparticles on nanocarbon-based supports, which are used in a variety of applications.

Electronic structure, stability and magnetic properties of small M1-4(M = Fe, Co, Ni) clusters encapsulated inside a (BN)48 cage

NASA Astrophysics Data System (ADS)

Liang, Wenjuan; Jia, Jianfeng; Lv, Jin; Wu, Haishun

2015-02-01

The geometrical structure and magnetic properties of M1-4(M = Fe, Co and Ni) clusters within a (BN)48 cage were calculated at the BPW91/LanL2DZ level. The small M1-4 clusters generally prefer an off-centered position near the hexagonal rings in the (BN)48 cages. The (BN)48 cages can increase the stability of these small magnetic clusters while protecting the magnetic nature of M and M2 clusters.

22 CFR 506.6 - Publicizing vacancies.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 22 Foreign Relations 2 2010-04-01 2010-04-01 true Publicizing vacancies. 506.6 Section 506.6 Foreign Relations BROADCASTING BOARD OF GOVERNORS PART-TIME CAREER EMPLOYMENT PROGRAM § 506.6 Publicizing vacancies. When applicants from outside the Federal service are desired, part-time vacancies may be...

Hydrogen-enhanced clusterization of intrinsic defects and impurities in silicon

NASA Astrophysics Data System (ADS)

Mukashev, B. N.; Abdullin, Kh. A.; Gorelkinskii, Yu. V.; Tamendarov, M. F.; Tokmoldin, S. Zh

2001-01-01

Formation of intrinsic and impurity defect complexes in hydrogenated monocrystalline silicon is studied. Hydrogen was incorporated into samples by different ways: either by proton implantation at 80 and 300 K, or by annealing at 1250°C for 30-60 min in a sealed quartz ampoule containing ∼10 -3 ml of distilled water, or by treatment in hydrogen plasma. Radiation defects were incorporated either during the hydrogen implantation or by additional irradiation with protons or α-particles. The measurements were performed by electron paramagnetic resonance (EPR), deep level transient spectroscopy (DLTS) and infrared absorption (IR) methods. Essential differences of defect formation processes in hydrogenated samples as compared with reference samples were detected. The main reasons responsible for the differences are (i) hydrogen precipitation in a supersaturated solution during thermal treatment; (ii) interaction of hydrogen with defects and impurities and hydrogen-induced formation of defects; (iii) ability of hydrogen to play the role of accelerator of impurities precipitation. These factors result in the formation of vacancy-related, interstitial-related and impurity clusters which are observed only in the presence of hydrogen. The nature of the clusters and possible models of their structure are discussed.

Effect of annealing ambience on the formation of surface/bulk oxygen vacancies in TiO2 for photocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Hou, Lili; Zhang, Min; Guan, Zhongjie; Li, Qiuye; Yang, Jianjun

2018-01-01

The surface and bulk oxygen vacancy have a prominent effect on the photocatalytic performance of TiO2. In this study, TiO2 possessing different types and concentration of oxygen vacancies were prepared by annealing nanotube titanic acid (NTA) at various temperatures in air or vacuum atmosphere. TiO2 with the unitary bulk single-electron-trapped oxygen vacancies (SETOVs) formed when NTA were calcined in air. Whereas, TiO2 with both bulk and surface oxygen vacancies were obtained when NTA were annealed in vacuum. The series of TiO2 with different oxygen vacancies were systematically characterized by TEM, XRD, PL, XPS, ESR, and TGA. The PL and ESR analysis verified that surface oxygen vacancies and more bulk oxygen vacancies could form in vacuum atmosphere. Surface oxygen vacancies can trap electron and hinder the recombination of photo-generated charges, while bulk SETOVs act as the recombination center. The surface or bulk oxygen vacancies attributed different roles on the photo-absorbance and activity, leading that the sample of NTA-A400 displayed higher hydrogen evolution rate under UV light, whereas NTA-V400 displayed higher hydrogen evolution rate under visible light because bulk SETOVs can improve visible light absorption because sub-band formed by bulk SETOVs prompted the secondary transition of electron excited.

Study of point- and cluster-defects in radiation-damaged silicon

NASA Astrophysics Data System (ADS)

Donegani, Elena M.; Fretwurst, Eckhart; Garutti, Erika; Klanner, Robert; Lindstroem, Gunnar; Pintilie, Ioana; Radu, Roxana; Schwandt, Joern

2018-08-01

Non-ionising energy loss of radiation produces point defects and defect clusters in silicon, which result in a significant degradation of sensor performance. In this contribution results from TSC (Thermally Stimulated Current) defect spectroscopy for silicon pad diodes irradiated by electrons to fluences of a few 1014 cm-2 and energies between 3.5 and 27 MeV for isochronal annealing between 80 and 280∘C, are presented. A method based on SRH (Shockley-Read-Hall) statistics is introduced, which assumes that the ionisation energy of the defects in a cluster depends on the fraction of occupied traps. The difference of ionisation energy of an isolated point defect and a fully occupied cluster, ΔEa, is extracted from the TSC data. For the VOi (vacancy-oxygen interstitial) defect ΔEa = 0 is found, which confirms that it is a point defect, and validates the method for point defects. For clusters made of deep acceptors the ΔEa values for different defects are determined after annealing at 80∘C as a function of electron energy, and for the irradiation with 15 MeV electrons as a function of annealing temperature. For the irradiation with 3.5 MeV electrons the value ΔEa = 0 is found, whereas for the electron energies of 6-27 MeV ΔEa > 0. This agrees with the expected threshold of about 5 MeV for cluster formation by electrons. The ΔEa values determined as a function of annealing temperature show that the annealing rate is different for different defects. A naive diffusion model is used to estimate the temperature dependencies of the diffusion of the defects in the clusters.

Vacancy charged defects in two-dimensional GaN

NASA Astrophysics Data System (ADS)

González, Roberto; López-Pérez, William; González-García, Álvaro; Moreno-Armenta, María G.; González-Hernández, Rafael

2018-03-01

In this paper, we have studied the structural and electronic properties of vacancy charged defects in the graphene phase (honeycomb type) of gallium nitride (g-GaN) by using first-principle calculations within the framework of the Density Functional Theory. It is found that the vacancies introduce defect levels in the band gap, and these generate a total magnetization in the g-GaN system. The formation energy with different charge states for the vacancies of gallium and nitrogen were calculated, obtaining higher energies than the GaN wurtzite phase (w-GaN). Furthermore, nitrogen vacancies were found to be more stable than gallium vacancies in a whole range of electronic chemical potential. Finally, gallium and nitrogen vacancies produce a nonzero magnetic moment in g-GaN, making it a potential candidate for future spintronics applications.

Energetic, structural and electronic properties of metal vacancies in strained AlN/GaN interfaces.

PubMed

Kioseoglou, J; Pontikis, V; Komninou, Ph; Pavloudis, Th; Chen, J; Karakostas, Th

2015-04-01

AlN/GaN heterostructures have been studied using density-functional pseudopotential calculations yielding the formation energies of metal vacancies under the influence of local interfacial strains, the associated charge distribution and the energies of vacancy-induced electronic states. Interfaces are built normal to the polar <0 0 0 1> direction of the wurtzite structure by joining two single crystals of AlN and GaN that are a few atomic layers thick; thus, periodic boundary conditions generate two distinct heterophase interfaces. We show that the formation energy of vacancies is a function of their distance from the interfaces: the vacancy-interface interaction is found repulsive or attractive, depending on the type of the interface. When the interaction is attractive, the vacancy formation energy decreases with increasing the associated electric charge, and hence the equilibrium vacancy concentration at the interface is greater. This finding can reveal the well-known morphological differences existing between the two types of investigated interfaces. Moreover, we found that the electric charge is strongly localized around the Ga vacancy, while in the case of Al vacancies is almost uniformly distributed throughout the AlN/GaN heterostructure. Crucially, for the applications of heterostructures, metal vacancies introduce deep states in the calculated bandgap at energy levels from 0.5 to 1 eV above the valence band maximum (VBM). It is, therefore, predicted that vacancies could initiate 'green luminescence' i.e. light emission in the energy range of 2.5 eV stemming from electronic transitions between these extra levels, and the conduction band, or energy levels, due to shallow donors.

24 CFR 983.254 - Vacancies.

Code of Federal Regulations, 2010 CFR

2010-04-01

... vacancy (and notwithstanding the reasonable good faith efforts of the PHA to fill such vacancies), the PHA... on the PHA waiting list referred by the PHA. (3) The PHA and the owner must make reasonable good faith efforts to minimize the likelihood and length of any vacancy. (b) Reducing number of contract...

75 FR 3967 - Bank Secrecy Act Advisory Group; Solicitation of Application for Membership

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-25

... INFORMATION: The Annunzio-Wylie Anti-Money Laundering Act of 1992 required the Secretary of the Treasury to...--Banking (1 vacancy) Industry Trade Groups--Casino (1 vacancy) Industry Trade Groups--Money Services... Groups--State (1 vacancy) Industry Representatives--Banking (3 vacancies) Industry Representatives--Money...

Vacancy identification in Co+ doped rutile TiO2 crystal with positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Qin, X. B.; Zhang, P.; Liang, L. H.; Zhao, B. Z.; Yu, R. S.; Wang, B. Y.; Wu, W. M.

2011-01-01

Co-doped rutile TiO2 films were synthesized by ion implantation. Variable energy positron annihilation Doppler broadening spectroscopy and coincidence Doppler broadening measurements were performed for identification of the vacancies. A newly formed type of vacancy can be concluded by the S-W plot and the CDB results indicated that the oxygen vacancy (VO) complex Ti-Co-VO and/or Ti-VO are formed with Co ions implantation and the vacancy concentration is increased with increase of dopant dose.

Small-scale Conformity of the Virgo Cluster Galaxies

NASA Astrophysics Data System (ADS)

Lee, Hye-Ran; Lee, Joon Hyeop; Jeong, Hyunjin; Park, Byeong-Gon

2016-06-01

We investigate the small-scale conformity in color between bright galaxies and their faint companions in the Virgo Cluster. Cluster member galaxies are spectroscopically determined using the Extended Virgo Cluster Catalog and the Sloan Digital Sky Survey Data Release 12. We find that the luminosity-weighted mean color of faint galaxies depends on the color of adjacent bright galaxy as well as on the cluster-scale environment (gravitational potential index). From this result for the entire area of the Virgo Cluster, it is not distinguishable whether the small-scale conformity is genuine or if it is artificially produced due to cluster-scale variation of galaxy color. To disentangle this degeneracy, we divide the Virgo Cluster area into three sub-areas so that the cluster-scale environmental dependence is minimized: A1 (central), A2 (intermediate), and A3 (outermost). We find conformity in color between bright galaxies and their faint companions (color-color slope significance S ˜ 2.73σ and correlation coefficient {cc}˜ 0.50) in A2, where the cluster-scale environmental dependence is almost negligible. On the other hand, the conformity is not significant or very marginal (S ˜ 1.75σ and {cc}˜ 0.27) in A1. The conformity is not significant either in A3 (S ˜ 1.59σ and {cc}˜ 0.44), but the sample size is too small in this area. These results are consistent with a scenario in which the small-scale conformity in a cluster is a vestige of infallen groups and these groups lose conformity as they come closer to the cluster center.

Ab initio studies of isolated hydrogen vacancies in graphane

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Chetty, N.

2016-05-01

We present a density functional study of various hydrogen vacancies located on a single hexagonal ring of graphane (fully hydrogenated graphene) considering the effects of charge states and the position of the Fermi level. We find that uncharged vacancies that lead to a carbon sublattice balance are energetically favorable and are wide band gap systems just like pristine graphane. Vacancies that do create a sublattice imbalance introduce spin polarized states into the band gap, and exhibit a half-metallic behavior with a magnetic moment of 1.00 μB per vacancy. The results show the possibility of using vacancies in graphane for novel spin-based applications. When charging such vacancy configurations, the deep donor (+1/0) and deep acceptor (0/-1) transition levels within the band gap are noted. We also note a half-metallic to metallic transition and a significant reduction of the induced magnetic moment due to both negative and positive charge doping.

Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

2017-02-01

The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec-1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm-2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.

Vacancy-type defects in Mg-doped GaN grown by ammonia-based molecular beam epitaxy probed using a monoenergetic positron beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uedono, Akira; Malinverni, Marco; Martin, Denis

Vacancy-type defects in Mg-doped GaN were probed using a monoenergetic positron beam. GaN films with a thickness of 0.5–0.7 μm were grown on GaN/sapphire templates using ammonia-based molecular beam epitaxy and characterized by measuring Doppler broadening spectra. Although no vacancies were detected in samples with a Mg concentration [Mg] below 7 × 10{sup 19 }cm{sup −3}, vacancy-type defects were introduced starting at above [Mg] = 1 × 10{sup 20 }cm{sup −3}. The major defect species was identified as a complex between Ga vacancy (V{sub Ga}) and multiple nitrogen vacancies (V{sub N}s). The introduction of vacancy complexes was found to correlate with a decreasemore » in the net acceptor concentration, suggesting that the defect introduction is closely related to the carrier compensation. We also investigated Mg-doped GaN layers grown using In as the surfactant. The formation of vacancy complexes was suppressed in the subsurface region (≤80 nm). The observed depth distribution of defects was attributed to the thermal instability of the defects, which resulted in the introduction of vacancy complexes during the deposition process.« less

Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO 2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Kimmel, Gregory A.

2015-09-16

The formation of bridging hydroxyls (OHb) via reactions of water molecules with oxygen vacancies (VO) on reduced TiO 2(110) surfaces is studied using infrared reflection-absorption spectroscopy (IRAS), electron-stimulated desorption (ESD), and photon-stimulated desorption (PSD). Narrow IRAS peaks at 2737 cm-1 and 3711 cm -1 are observed for stretching vibrations of OD b and OH b on TiO 2(110), respectively. IRAS measurements with s- and p-polarized light demonstrate that the bridging hydroxyls are oriented normal to the (110) surface. The IR peaks disappear after the sample is exposed to O 2 or annealed in the temperature range of 400 – 600more » K (correlating with the temperature at which pairs of OHb’s reform water and then desorb), which is consistent with their identification as bridging hydroxyls. We have studied the kinetics of water reacting with the vacancies by monitoring the formation of bridging hydroxyls (using IRAS) as a function of the annealing temperature for a small amount of water initially dosed on the TiO 2(110) at low temperature. Separate experiments have also monitored the loss of water molecules (using water ESD) and vacancies (using the CO photooxidation reaction) due to the reactions of water molecules with the vacancies. All three techniques show that the reaction rate becomes appreciable for T > 150 K and that the reactions largely complete for T > 250 K. The temperature-dependent water-VO reaction kinetics are consistent with a Gaussian distribution of activation energies with E a = 0.545 eV, ΔE a(FWHM) = 0.125 eV, and a “normal” prefactor, v = 10 12 s -1. In contrast, a single activation energy with a physically reasonable prefactor does not fit the data well. Our experimental activation energy is close to theoretical estimates for the diffusion of water molecules along the Ti 5c rows on the reduced TiO 2(110) surface, which suggests that the diffusion of water controls the water – V O reaction rate.« less

All the catalytic active sites of MoS 2 for hydrogen evolution

DOE PAGES

Li, Guoqing; Zhang, Du; Qiao, Qiao; ...

2016-11-29

MoS 2 presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS 2, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. Here, the intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated tomore » be 7.5 s –1 (65–75 mV/dec), 3.2 s –1 (65–85 mV/dec), and 0.1 s –1 (120–160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7–10%, and the number of sulfur vacancies in high crystalline quality MoS 2 is higher than that in low crystalline quality MoS 2, which may be related with the proximity of different local crystalline structures to the vacancies.« less

Iron vacancy in tetragonal Fe1-xS crystals and its effect on the structure and superconductivity.

PubMed

Guo, Zhongnan; Sun, Fun; Han, Bingling; Lin, Kun; Zhou, Liang; Yuan, Wenxia

2017-03-29

Understanding the effects of non-stoichiometry on the structure and physical properties of tetragonal Fe chalcogenides is of great importance, especially for developing fascinating superconductivity in this system, which might be very sensitive to the non-stoichiometry. In this study, a series of Fe 1-x S single crystals were synthesized by a hydrothermal method, which show varying concentrations of Fe vacancies (0 ≤ x ≤ 0.1) in the structure. Based on the crystal samples, the effects of vacancies on the crystal structure and physical properties were studied. The vacancy-free sample (x = 0) showed a metallic state in resistance and superconductivity below 4.5 K, whereas for the samples with Fe vacancies (x ≥ 0.05), the SC was degraded and the sample exhibited semiconducting behavior. Structural analysis showed that the Fe vacancy decreases the lattice parameter a, but elongates c, leading to enhanced tetragonality in Fe 1-x S. Selected-area electron diffraction showed that the vacancy in Fe 1-x S was disordered, which is different from the scenario in FeSe-based materials. On combining the abovementioned results with the first-principles calculations, it was speculated that the disappearance of SC in non-stoichiometric Fe 1-x S resulted from the localization of the 3d electrons of Fe. Moreover, the accompanied metal-insulator transition induced by Fe vacancy mainly belonged to the Mott mechanism because the vacancy did not significantly alter the band structure. These results not only provide deep insight into the effect of Fe vacancy in Fe chalcogenides, but also provide a basis to effectively induce SC in Fe sulfides by decreasing the number of Fe vacancies.

Tailoring oxide properties: An impact on adsorption characteristics of molecules and metals

NASA Astrophysics Data System (ADS)

Honkala, Karoliina

2014-12-01

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster's theoretically predicted ability to activate and dissociate O2 at the Au-MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O2, CO, NO2, and H2O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O2 dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H2O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide-metal interface and their effect on the adsorption characteristics of water and Au are summarized. Finally, more limited computational literature on transition metal (TM) doped CaO(100) and MgO(100) surfaces is presented. Again, Au is used as a probe species. Similar to metal-supported MgO films, Au binds more strongly than on undoped CaO(100) and becomes negatively charged. The discussion focuses on rationalization of Au adsorption with the help of Born-Haber cycle, which reveals that the so-called redox energy including the electron transfer from the dopant to the Au atom together with the simultaneous structural relaxation of lattice atoms is responsible for enhanced binding. In addition, adsorption energy dependence on the position and type of the dopant is summarized.

A stochastic differential equations approach for the description of helium bubble size distributions in irradiated metals

NASA Astrophysics Data System (ADS)

Seif, Dariush; Ghoniem, Nasr M.

2014-12-01

A rate theory model based on the theory of nonlinear stochastic differential equations (SDEs) is developed to estimate the time-dependent size distribution of helium bubbles in metals under irradiation. Using approaches derived from Itô's calculus, rate equations for the first five moments of the size distribution in helium-vacancy space are derived, accounting for the stochastic nature of the atomic processes involved. In the first iteration of the model, the distribution is represented as a bivariate Gaussian distribution. The spread of the distribution about the mean is obtained by white-noise terms in the second-order moments, driven by fluctuations in the general absorption and emission of point defects by bubbles, and fluctuations stemming from collision cascades. This statistical model for the reconstruction of the distribution by its moments is coupled to a previously developed reduced-set, mean-field, rate theory model. As an illustrative case study, the model is applied to a tungsten plasma facing component under irradiation. Our findings highlight the important role of stochastic atomic fluctuations on the evolution of helium-vacancy cluster size distributions. It is found that when the average bubble size is small (at low dpa levels), the relative spread of the distribution is large and average bubble pressures may be very large. As bubbles begin to grow in size, average bubble pressures decrease, and stochastic fluctuations have a lessened effect. The distribution becomes tighter as it evolves in time, corresponding to a more uniform bubble population. The model is formulated in a general way, capable of including point defect drift due to internal temperature and/or stress gradients. These arise during pulsed irradiation, and also during steady irradiation as a result of externally applied or internally generated non-homogeneous stress fields. Discussion is given into how the model can be extended to include full spatial resolution and how the implementation of a path-integral approach may proceed if the distribution is known experimentally to significantly stray from a Gaussian description.

A comment on Baker et al. 'The time dependence of an atom-vacancy encounter due to the vacancy mechanism of diffusion'

NASA Astrophysics Data System (ADS)

Dasenbrock-Gammon, Nathan; Zacate, Matthew O.

2017-05-01

Baker et al. derived time-dependent expressions for calculating average number of jumps per encounter and displacement probabilities for vacancy diffusion in crystal lattice systems with infinitesimal vacancy concentrations. As shown in this work, their formulation is readily expanded to include finite vacancy concentration, which allows calculation of concentration-dependent, time-averaged quantities. This is useful because it provides a computationally efficient method to express lineshapes of nuclear spectroscopic techniques through the use of stochastic fluctuation models.

Quantifying substructures in Hubble Frontier Field clusters: comparison with ΛCDM simulations

DOE PAGES

Mohammed, Irshad; Saha, Prasenjit; Williams, Liliya L. R.; ...

2016-04-13

The Hubble Frontier Fields (HFF) are six clusters of galaxies, all showing indications of recent mergers, which have recently been observed for lensed images. As such they are the natural laboratories to study the merging history of galaxy clusters. In this work, we explore the 2D power spectrum of the mass distributionmore » $$P_{\\rm M}(k)$$ as a measure of substructure. We compare $$P_{\\rm M}(k)$$ of these clusters (obtained using strong gravitational lensing) to that of $$\\Lambda$$CDM simulated clusters of similar mass. In order to compute lensing $$P_{\\rm M}(k)$$, we produced free-form lensing mass reconstructions of HFF clusters, without any light traces mass (LTM) assumption. Moreover, the inferred power at small scales tends to be larger if (i)~the cluster is at lower redshift, and/or (ii)~there are deeper observations and hence more lensed images. In contrast, lens reconstructions assuming LTM show higher power at small scales even with fewer lensed images; it appears the small scale power in the LTM reconstructions is dominated by light information, rather than the lensing data. The average lensing derived $$P_{\\rm M}(k)$$ shows lower power at small scales as compared to that of simulated clusters at redshift zero, both dark-matter only and hydrodynamical. The possible reasons are: (i)~the available strong lensing data are limited in their effective spatial resolution on the mass distribution, (ii)~HFF clusters have yet to build the small scale power they would have at $$z\\sim 0$$, or (iii)~simulations are somehow overestimating the small scale power.« less

7 CFR 1205.327 - Vacancies.

Code of Federal Regulations, 2011 CFR

2011-01-01

... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE COTTON RESEARCH AND PROMOTION Cotton Research and Promotion Order Cotton Board § 1205.327 Vacancies. To fill any vacancy occasioned by the...

7 CFR 1205.327 - Vacancies.

Code of Federal Regulations, 2013 CFR

2013-01-01

... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE COTTON RESEARCH AND PROMOTION Cotton Research and Promotion Order Cotton Board § 1205.327 Vacancies. To fill any vacancy occasioned by the...

7 CFR 1205.327 - Vacancies.

Code of Federal Regulations, 2014 CFR

2014-01-01

... AND ORDERS; MISCELLANEOUS COMMODITIES), DEPARTMENT OF AGRICULTURE COTTON RESEARCH AND PROMOTION Cotton Research and Promotion Order Cotton Board § 1205.327 Vacancies. To fill any vacancy occasioned by the...

Synthesis of SiV-diamond particulates via the microwave plasma chemical deposition of ultrananocrystalline diamond on soda-lime glass fibers

NASA Astrophysics Data System (ADS)

Kunuku, Srinivasu; Chen, Yen-Chun; Yeh, Chien-Jui; Chang, Wen-Hao; Manoharan, Divinah; Leou, Keh-Chyang; Lin, I.-Nan

2016-10-01

We report the synthesis of silicon-vacancy (SiV) incorporated spherical shaped ultrananocrystalline diamond (SiV-UNCD) particulates (size ∼1 μm) with bright luminescence at 738 nm. For this purpose, different granular structured polycrystalline diamond films and particulates were synthesized by using three different kinds of growth plasma conditions on the three types of substrate materials in the microwave plasma enhanced CVD process. The grain size dependent photoluminescence properties of nitrogen vacancy (NV) and SiV color centers have been investigated for different granular structured diamond samples. The luminescence of NV center and the associated phonon sidebands, which are usually observed in microcrystalline diamond and nanocrystalline diamond films, were effectively suppressed in UNCD films and UNCD particulates. Micron sized SiV-UNCD particulates with bright SiV emission has been attained by transfer of SiV-UNCD clusters on soda-lime glass fibers to inverted pyramidal cavities fabricated on Si substrates by the simple crushing of UNCD/soda-lime glass fibers in deionized water and ultrasonication. Such a plasma enhanced CVD process for synthesizing SiV-UNCD particulates with suppressed NV emission is simple and robust to attain the bright SiV-UNCD particulates to employ in practical applications.

Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane

In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

Radiation tolerance of nanocrystalline ceramics: insights from Yttria Stabilized Zirconia.

PubMed

Dey, Sanchita; Drazin, John W; Wang, Yongqiang; Valdez, James A; Holesinger, Terry G; Uberuaga, Blas P; Castro, Ricardo H R

2015-01-13

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr(+), 400 keV) is inversely proportional to the grain size. HAADF images suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces.

Radiation Tolerance of Nanocrystalline Ceramics: Insights from Yttria Stabilized Zirconia

PubMed Central

Dey, Sanchita; Drazin, John W.; Wang, Yongqiang; Valdez, James A.; Holesinger, Terry G.; Uberuaga, Blas P.; Castro, Ricardo H. R.

2015-01-01

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr+, 400 keV) is inversely proportional to the grain size. HAADF images suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces. PMID:25582769

Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

DOE PAGES

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

2015-08-14

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(111) at 100 and 300 K is shown tomore » decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.« less

Radiation tolerance of nanocrystalline ceramics: Insights from yttria stabilized zirconia

DOE PAGES

Dey, Sanchita; Drazin, John W.; Wang, Yongqiang; ...

2015-01-13

Materials for applications in hostile environments, such as nuclear reactors or radioactive waste immobilization, require extremely high resistance to radiation damage, such as resistance to amorphization or volume swelling. Nanocrystalline materials have been reported to present exceptionally high radiation-tolerance to amorphization. In principle, grain boundaries that are prevalent in nanomaterials could act as sinks for point-defects, enhancing defect recombination. In this paper we present evidence for this mechanism in nanograined Yttria Stabilized Zirconia (YSZ), associated with the observation that the concentration of defects after irradiation using heavy ions (Kr⁺, 400 keV) is inversely proportional to the grain size. HAADF imagesmore » suggest the short migration distances in nanograined YSZ allow radiation induced interstitials to reach the grain boundaries on the irradiation time scale, leaving behind only vacancy clusters distributed within the grain. Because of the relatively low temperature of the irradiations and the fact that interstitials diffuse thermally more slowly than vacancies, this result indicates that the interstitials must reach the boundaries directly in the collision cascade, consistent with previous simulation results. Concomitant radiation-induced grain growth was observed which, as a consequence of the non-uniform implantation, caused cracking of the nano-samples induced by local stresses at the irradiated/non-irradiated interfaces.« less

Synthesis and characterization of magnesium oxide nanocrystallites and probing the vacancy-type defects through positron annihilation studies

NASA Astrophysics Data System (ADS)

Das, Anjan; Mandal, Atis Chandra; Roy, Soma; Prashanth, Pendem; Ahamed, Sk Izaz; Kar, Subhrasmita; Prasad, Mithun S.; Nambissan, P. M. G.

2016-09-01

Magnesium oxide nanocrystallites exhibit certain abnormal characteristics when compared to those of other wide band gap oxide semiconductors in the sense they are most prone to water absorption and formation of a hydroxide layer on the surface. The problem can be rectified by heating and pure nanocrystallites can be synthesized with controllable sizes. Inevitably the defect properties are distinctly divided between two stages, the one with the hydroxide layer (region I) and the other after the removal of the layer by annealing (region II). The lattice parameters, the optical band gap and even the positron annihilation characteristics are conspicuous by their distinct behavior in the two stages of the surface configurations of nanoparticles. While region I was specific with the formation of positronium-hydrogen complexes that drastically altered the defect-specific positron lifetimes, pick-off annihilation of orthopositronium atoms marked region II. The vacancy clusters within the nanocrystallites also trapped positrons. They agglomerated due to the effect of the higher temperatures and resulted in the growth of the nanocrystallites. The coincidence Doppler broadening spectroscopic measurements supported these findings and all the more indicated the trapping of positrons additionally into the neutral divacancies and negatively charged trivacancies. This is apart from the Mg2+ monovacancies which acted as the dominant trapping centers for positrons.

Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

DOE PAGES

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; ...

2017-10-04

In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

Resolving the problem of galaxy clustering on small scales: any new physics needed?

NASA Astrophysics Data System (ADS)

Kang, X.

2014-02-01

Galaxy clustering sets strong constraints on the physics governing galaxy formation and evolution. However, most current models fail to reproduce the clustering of low-mass galaxies on small scales (r < 1 Mpc h-1). In this paper, we study the galaxy clusterings predicted from a few semi-analytical models. We first compare two Munich versions, Guo et al. and De Lucia & Blaizot. The Guo11 model well reproduces the galaxy stellar mass function, but overpredicts the clustering of low-mass galaxies on small scales. The DLB07 model provides a better fit to the clustering on small scales, but overpredicts the stellar mass function. These seem to be puzzling. The clustering on small scales is dominated by galaxies in the same dark matter halo, and there is slightly more fraction of satellite galaxies residing in massive haloes in the Guo11 model, which is the dominant contribution to the clustering discrepancy between the two models. However, both models still overpredict the clustering at 0.1 < r < 10 Mpc h-1 for low-mass galaxies. This is because both models overpredict the number of satellites by 30 per cent in massive haloes than the data. We show that the Guo11 model could be slightly modified to simultaneously fit the stellar mass function and clusterings, but that cannot be easily achieved in the DLB07 model. The better agreement of DLB07 model with the data actually comes as a coincidence as it predicts too many low-mass central galaxies which are less clustered and thus brings down the total clustering. Finally, we show the predictions from the semi-analytical models of Kang et al. We find that this model can simultaneously fit the stellar mass function and galaxy clustering if the supernova feedback in satellite galaxies is stronger. We conclude that semi-analytical models are now able to solve the small-scales clustering problem, without invoking of any other new physics or changing the dark matter properties, such as the recent favoured warm dark matter.

Evidence for oxygen vacancy or ferroelectric polarization induced switchable diode and photovoltaic effects in BiFeO3 based thin films.

PubMed

Guo, Yiping; Guo, Bing; Dong, Wen; Li, Hua; Liu, Hezhou

2013-07-12

The diode and photovoltaic effects of BiFeO3 and Bi0.9Sr0.1FeO(3-δ) polycrystalline thin films were investigated by poling the films with increased magnitude and alternating direction. It was found that both electromigration of oxygen vacancies and polarization flipping are able to induce switchable diode and photovoltaic effects. For the Bi0.9Sr0.1FeO(3-δ) thin films with high oxygen vacancy concentration, reversibly switchable diode and photovoltaic effects can be observed due to the electromigration of oxygen vacancies under an electric field much lower than its coercive field. However, for the pure BiFeO3 thin films with lower oxygen vacancy concentration, the reversibly switchable diode and photovoltaic effect is hard to detect until the occurrence of polarization flipping. The switchable diode and photovoltaic effects can be explained well using the concepts of Schottky-like barrier-to-Ohmic contacts resulting from the combination of oxygen vacancies and polarization. The sign of photocurrent could be independent of the direction of polarization when the modulation of the energy band induced by oxygen vacancies is large enough to offset that induced by polarization. The photovoltaic effect induced by the electromigration of oxygen vacancies is unstable due to the diffusion of oxygen vacancies or the recombination of oxygen vacancies with hopping electrons. Our work provides deep insights into the nature of diode and photovoltaic effects in ferroelectric films, and will facilitate the advanced design of switchable devices combining spintronic, electronic, and optical functionalities.

Polaronic and ionic conduction in NaMnO2: influence of native point defects

NASA Astrophysics Data System (ADS)

Zhu, Zhen; Peelaers, Hartwin; van de Walle, Chris G.

Layered NaMnO2 has promising applications as a cathode material for sodium ion batteries. We will discuss strategies to improve the electrical performance of NaMnO2, including how to optimize the conditions of synthesis and how impurity doping affects the performance. Using hybrid density functional theory, we explored the structural, electronic, and defect properties of bulk NaMnO2. It is antiferromagnetic in the ground state with a band gap of 3.75 eV. Small hole and electron polarons can form in the bulk either through self-trapping or adjacent to point defects. We find that both Na and Mn vacancies are shallow acceptors with the induced holes trapped as small polarons, while O vacancies are deep defect centers. Cation antisites, especially MnNa, are found to have low formation energies. As a result, we expect that MnNa exists in as-grown NaMnO2 in moderate concentrations, rather than forming only at a later stage of the charging process, at which point it causes undesirable structural phase transitions. Both electronic conduction, via polaron hopping, and ionic conduction, through VNa migration, are significantly affected by the presence of point defects. This work was supported by DOE.

Vacancy cascades in small molecules following x-ray inner shell photoionization

NASA Astrophysics Data System (ADS)

Ray, D.; Dunford, R. W.; Southworth, S. H.; Kanter, E. P.; Doumy, G.; Gao, Y.; Ho, P. J.; Picon, A.

2014-05-01

We are investigating molecular effects in vacancy cascades of small molecules containing heavy atoms - IBr, Br2 and CH2BrI - following K-shell ionization. In addition to fundamental interest in the physics of such decay processes, there are practical applications such as medical treatments that use energetic fragmentation of iodinated compounds with high energy x-rays to selectively treat tumorous cells. Other biological applications are also promising. We utilize the tunable monochromatic x-ray beam at the Advanced Photon Source to trigger K-shell photoionization of Br and I, and measure charge distributions and the kinetic energies released to the fragment ions. A newly designed detection device allows us to do multi-fold coincidence measurements involving momentum imaging of all the ion fragments with very high detection efficiency in coincidence with x-ray fluorescence detection. By comparing the molecular fragmentation probabilities and the kinetic energies released in Br2, IBr and CH2BrI we aim to gain understanding of the fragmentation mechanism as a function of the bond distance between I and Br. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

Environmental Quality Assessment of Built Areas with High Vacancy

NASA Astrophysics Data System (ADS)

Jiang, Y.; Yuan, Y.; Neale, A. C.

2015-12-01

Around the world, many urban areas are challenged by vacant and abandoned residential and business property. High vacancy areas have often been associated with increasing public safety problems and declining property values and subsequent tax base. High vacancy can lead to visible signs of city decline and significant barriers to the revitalization of cities. Addressing the problem of vacancy requires knowledge of vacancy patterns and their possible contributing factors. In this study, we evaluated the ten year (2005-2015) urban environmental changes for some high vacancy areas. Social and economic variables derived from U.S. census data such as non-white population, employment rate, housing price, and environmental variables derived from National Land Cover Data such as land cover and impervious area, were used as the basis for analysis. Correlation analysis and principle components analysis were performed at the Census Block Group level. Three components were identified and interpreted as economic status, urbanness, and greenness. A synthetic Urban Environmental Quality (UEQ) index was developed by integrating the three principle components according to their weights. Comparisons of the UEQ indices between the 2005 and 2015 in the increasingly high vacancy area provided useful information for investigating the possible associations between social, economic, and environmental factors, and the vacancy status. This study could provide useful information for understanding the complex issues leading to vacancy and facilitating future rehabilitation of vacant urban area.

38 CFR 1.896 - Publicizing vacancies.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROVISIONS Part-Time Career Employment Program § 1.896 Publicizing vacancies. When applicants from outside the Federal service are desired, part-time vacancies may be publicized through various recruiting...

Feasibility Study of Problems in the Collection of Data on Job Vacancies.

ERIC Educational Resources Information Center

Illinois State Dept. of Labor, Chicago. Bureau of Employment Security.

Sixty-two firms within 20 industries were surveyed to determine (1) a definition for the term "job vacancy," (2) the extent of job vacancy records of employers, (3) the possibility of data collection on job vacancies, and (4) the problems expected to be encountered in such a collection. After stratification of an industry by the relative size of…

Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Wenshuai; Wu, Zili; Foo, Guo Shiou

Taming interfacial electronic effects on Pt nanoparticles modulated by their concomitants has emerged as an intriguing approach to optimize Pt catalytic performance. Here, we report Pt nanoparticles assembled on vacancy-abundant hexagonal boron nitride nanosheets and their use as a model catalyst to embrace an interfacial electronic effect on Pt induced by the nanosheets with N-vacancies and B-vacancies for superior CO oxidation catalysis. Experimental results indicate that strong interaction exists between Pt and the vacancies. Bader charge analysis shows that with Pt on B-vacancies, the nanosheets serve as a Lewis acid to accept electrons from Pt, and on the contrary, whenmore » Pt sits on N-vacancies, the nanosheets act as a Lewis base for donating electrons to Pt. The overall-electronic effect demonstrates an electron-rich feature of Pt after assembling on hexagonal boron nitride nanosheets. Such an interfacial electronic effect makes Pt favour the adsorption of O 2, alleviating CO poisoning and promoting the catalysis.« less

Taming interfacial electronic properties of platinum nanoparticles on vacancy-abundant boron nitride nanosheets for enhanced catalysis

DOE PAGES

Zhu, Wenshuai; Wu, Zili; Foo, Guo Shiou; ...

2017-06-09

Taming interfacial electronic effects on Pt nanoparticles modulated by their concomitants has emerged as an intriguing approach to optimize Pt catalytic performance. Here, we report Pt nanoparticles assembled on vacancy-abundant hexagonal boron nitride nanosheets and their use as a model catalyst to embrace an interfacial electronic effect on Pt induced by the nanosheets with N-vacancies and B-vacancies for superior CO oxidation catalysis. Experimental results indicate that strong interaction exists between Pt and the vacancies. Bader charge analysis shows that with Pt on B-vacancies, the nanosheets serve as a Lewis acid to accept electrons from Pt, and on the contrary, whenmore » Pt sits on N-vacancies, the nanosheets act as a Lewis base for donating electrons to Pt. The overall-electronic effect demonstrates an electron-rich feature of Pt after assembling on hexagonal boron nitride nanosheets. Such an interfacial electronic effect makes Pt favour the adsorption of O 2, alleviating CO poisoning and promoting the catalysis.« less

Migration mechanisms and diffusion barriers of vacancies in Ga2O3

NASA Astrophysics Data System (ADS)

Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico

2017-06-01

We employ the nudged elastic band and the dimer methods within the standard density functional theory (DFT) formalism to study the migration of the oxygen and gallium vacancies in the monoclinic structure of β -Ga2O3 . We identify all the first nearest neighbor paths and calculate the migration barriers for the diffusion of the oxygen and gallium vacancies. We also identify the metastable sites of the gallium vacancies which are critical for the diffusion of the gallium atoms. The migration barriers for the diffusion of the gallium vacancies are lower than the migration barriers for oxygen vacancies by 1 eV on average, suggesting that the gallium vacancies are mobile at lower temperatures. Using the calculated migration barriers we estimate the annealing temperature of these defects within the harmonic transition state theory formalism, finding excellent agreement with the observed experimental annealing temperatures. Finally, we suggest the existence of percolation paths which enable the migration of the species without utilizing all the migration paths of the crystal.

In-Situ TEM Visualization Of Vacancy Injection And Chemical Partition During Oxidation Of Ni-Cr Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chong M.; Genc, Arda; Cheng, Huikai

2014-01-14

Oxidation of alloy often involves chemical partition and injection of vacancies. Chemical partition is the consequence of selective oxidation, while injection of vacancies is associated with the differences of diffusivity of cations and anions. It is far from clear as how the injected vacancies behave during oxidation of metal. Using in-situ transmission electron microscopy, we captured unprecedented details on the collective behavior of injected vacancies during oxidation of metal, featuring an initial multi-site oxide nucleation, vacancy supersaturation, nucleation of a single cavity, sinking of vacancies into the cavity and accelerated oxidation of the particle. High sensitive energy dispersive x-ray spectroscopymore » mapping reveals that Cr is preferentially oxidized even at the initial oxidation, leading to a structure that Cr oxide is sandwiched near the inner wall of the hollow particle. The work provides a general guidance on tailoring of nanostructured materials involving multi-ion exchange such as core-shell structured composite nanoparticles.« less

Interactions of solute (3p, 4p, 5p and 6p) with solute, vacancy and divacancy in bcc Fe

NASA Astrophysics Data System (ADS)

You, Yu-Wei; Kong, Xiang-Shan; Wu, Xue-Bang; Liu, Wei; Liu, C. S.; Fang, Q. F.; Chen, J. L.; Luo, G.-N.; Wang, Zhiguang

2014-12-01

Solute-vacancy binding energy is a key quantity in understanding solute diffusion kinetics and phase segregation, and may help choice of alloy compositions for future material design. However, the binding energy of solute with vacancy is notoriously difficult to measure and largely unknown in bcc Fe. With first-principles method, we systemically calculate the binding energies of solute (3p, 4p, 5p and 6p alloying solutes are included) with vacancy, divacancy and solute in bcc Fe. The binding energy of Si with vacancy in the present work is in good consistent with experimental value available. All the solutes considered are able to form stable solute-vacancy, solute-divacancy complexes, and the binding strength of solute-divacancy is about two times larger than that of solute-vacancy. Most solutes could not form stable solute-solute complexes except S, Se, In and Tl. The factors controlling the binding energies are analyzed at last.

In-Situ TEM visualization of vacancy injection and chemical partition during oxidation of Ni-Cr nanoparticles

PubMed Central

Wang, Chong-Min; Genc, Arda; Cheng, Huikai; Pullan, Lee; Baer, Donald R.; Bruemmer, Stephen M.

2014-01-01

Oxidation of alloy often involves chemical partition and injection of vacancies. Chemical partition is the consequence of selective oxidation, while injection of vacancies is associated with the differences of diffusivity of cations and anions. It is far from clear as how the injected vacancies behave during oxidation of metal. Using in-situ transmission electron microscopy, we captured unprecedented details on the collective behavior of injected vacancies during oxidation of metal, featuring an initial multi-site oxide nucleation, vacancy supersaturation, nucleation of a single cavity, sinking of vacancies into the cavity and accelerated oxidation of the particle. High sensitive energy dispersive x-ray spectroscopy mapping reveals that Cr is preferentially oxidized even at the initial oxidation, leading to a structure that Cr oxide is sandwiched near the inner wall of the hollow particle. The work provides a general guidance on tailoring of nanostructured materials involving multi-ion exchange such as core-shell structured composite nanoparticles. PMID:24418778

7 CFR 981.36 - Vacancy.

Code of Federal Regulations, 2010 CFR

2010-01-01

... Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE ALMONDS GROWN IN CALIFORNIA Order Regulating Handling Almond Board of California § 981.36 Vacancy. To fill any vacancy occasioned by the death, removal...

Controlled manipulation of oxygen vacancies using nanoscale flexoelectricity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Saikat; Wang, Bo; Cao, Ye

Oxygen vacancies, especially their distribution, are directly coupled to the electromagnetic properties of oxides and related emergent functionalities that have implications for device applications. Here using a homoepitaxial strontium titanate thin film, we demonstrate a controlled manipulation of the oxygen vacancy distribution using the mechanical force from a scanning probe microscope tip. By combining Kelvin probe force microscopy imaging and phase-field simulations, we show that oxygen vacancies can move under a stress-gradient-induced depolarisation field. When tailored, this nanoscale flexoelectric effect enables a controlled spatial modulation. In motion, the scanning probe tip thereby deterministically reconfigures the spatial distribution of vacancies. Finally,more » the ability to locally manipulate oxygen vacancies on-demand provides a tool for the exploration of mesoscale quantum phenomena and engineering multifunctional oxide devices.« less

Study of irradiation induced surface pattern and structural changes in Inconel 718 alloy

NASA Astrophysics Data System (ADS)

Wan, Hao; Si, Naichao; Zhao, Zhenjiang; Wang, Jian; Zhang, Yifei

2018-05-01

Helium ions irradiation induced surface pattern and structural changes of Inconel 718 alloy were studied with the combined utilization of atomic force microscopy (AFM), x-ray diffraction (XRD) and transmission electron microscopy (TEM). In addition, SRIM-2013 software was used to calculate the sputtering yield and detailed collision events. The result shows that, irradiation dose play an important role in altering the pattern of the surface. Enhanced irradiation aggravated the surface etching and increased the surface roughness. In ion irradiated layer, large amount of interstitials, vacancies and defect sinks were produced. Moreover, in samples with increasing dose irradiation, the dependence of interplanar spacing variation due to point defects clustering on sink density was discussed.

Percolation threshold determines the optimal population density for public cooperation

NASA Astrophysics Data System (ADS)

Wang, Zhen; Szolnoki, Attila; Perc, Matjaž

2012-03-01

While worldwide census data provide statistical evidence that firmly link the population density with several indicators of social welfare, the precise mechanisms underlying these observations are largely unknown. Here we study the impact of population density on the evolution of public cooperation in structured populations and find that the optimal density is uniquely related to the percolation threshold of the host graph irrespective of its topological details. We explain our observations by showing that spatial reciprocity peaks in the vicinity of the percolation threshold, when the emergence of a giant cooperative cluster is hindered neither by vacancy nor by invading defectors, thus discovering an intuitive yet universal law that links the population density with social prosperity.

Positron annihilation spectroscopy in doped p-type ZnO

NASA Astrophysics Data System (ADS)

Majumdar, Sayanee; Sanyal, D.

2011-07-01

Positron annihilation lifetime (PAL) spectroscopy has been used to investigate the vacancy type defect of the Li and N doped ZnO. The mono-vacancies, shallow -vacancies and open volume defects have been found in both the Li and N doped ZnO. The mono-vacancies, shallow-vacancies and open volume defects increase in N-doped ZnO as the size of N is quite high compared to Li. Positron annihilation study showed that the doping above 1-3% Li and 3-4% N in ZnO are not required in order to achieve low resistivity, high hole concentration and good mobility.

Vacancy effects on the electronic and structural properties pentacene

NASA Astrophysics Data System (ADS)

Laraib, Iflah; Janotti, Anderson

Defects in organic crystals are likely to affect charge transport in organic electronic devices. Vacancies can create lattice distortions and modify electronic states associated with the molecules in its surrounding. Spectroscopy experiments indicate that molecular vacancies trap charge carriers. Experimental characterization of individual defects is challenging and unambiguous. Here we use density functional calculations including van der Waals interactions in a supercell approach to study the single vacancy in pentacene, a prototype organic semiconductor. We determine formation energies, local lattice relaxations, and discuss how vacancies locally distort the lattice and affect the electronic properties of the host organic semiconductor.

Formation of VP-Zn complexes in bulk InP(Zn) by migration of P vacancies from the (110) surface

NASA Astrophysics Data System (ADS)

Slotte, J.; Saarinen, K.; Ebert, Ph.

2006-05-01

We apply a combination of positron annihilation spectroscopy and scanning tunneling microscopy to show that thermally generated P vacancies diffuse from the InP surface toward the bulk. The defect observed in the bulk can be identified as a complex consisting of a P vacancy and a Zn impurity. We infer that this pair is formed when the diffusing positive P vacancy is trapped at the Zn dopant. A rough estimate for the migration energy of the P vacancy results in a value of 1.3eV .

Volume shift and charge instability of simple-metal clusters

NASA Astrophysics Data System (ADS)

Brajczewska, M.; Vieira, A.; Fiolhais, C.; Perdew, J. P.

1996-12-01

Experiment indicates that small clusters show changes (mostly contractions) of the bond lengths with respect to bulk values. We use the stabilized jellium model to study the self-expansion and self-compression of spherical clusters (neutral or ionized) of simple metals. Results from Kohn - Sham density functional theory are presented for small clusters of Al and Na, including negatively-charged ones. We also examine the stability of clusters with respect to charging.

Vacancy Transport and Interactions on Metal Surfaces

DTIC Science & Technology

2014-03-06

prevent obtaining systematical pictures with atomic scale resolution. Thus the experiments on adatom and mono -vacancy surface diffusion on Ag(110) were...vacuum conditions with atomic scale resolution with Scanning Tunneling Microscope (STM) and Field Ion Microscope (FIM). For each investigated material...experimental conditions for creation of surface vacancies on Au(100) has been determined and observations of surface diffusion of mono vacancies has been

First-principles study of Ga-vacancy induced magnetism in β-Ga2O3.

PubMed

Yang, Ya; Zhang, Jihua; Hu, Shunbo; Wu, Yabei; Zhang, Jincang; Ren, Wei; Cao, Shixun

2017-11-01

First principles calculations based on density functional theory were performed to study the electronic structure and magnetic properties of β-Ga 2 O 3 in the presence of cation vacancies. We investigated two kinds of Ga vacancies at different symmetry sites and the consequent structural distortion and defect states. We found that both the six-fold coordinated octahedral site and the four-fold coordinated tetrahedral site vacancies can lead to a spin polarized ground state. Furthermore, the calculation identified a relationship between the spin polarization and the charge states of the vacancies, which might be explained by a molecular orbital model consisting of uncompensated O 2- 2p dangling bonds. The calculations for the two vacancy systems also indicated a potential long-range ferromagnetic order which is beneficial for spintronics application.

Teaching Vacancies and Difficult-to-Staff Teaching Positions in Public Schools. Stats in Brief. NCES 2015-065

ERIC Educational Resources Information Center

Malkus, Nat; Hoyer, Kathleen Mulvaney; Sparks, Dinah

2015-01-01

This brief investigates teaching vacancies and difficult-to-staff teaching positions (i.e., positions for which the principals reported that it was very difficult to fill a vacancy or that they could not fill a vacancy in a specific subject area) in public schools in four school years (1999-2000, 2003-04, 2007-08, and 2011-12). This Statistics in…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Yi, Ming; Tian, Wei

Here, the complex interdigitated phases have greatly frustrated attempts to document the basic features of the superconductivity in the alkali metal intercalated iron chalcogenides. Here, using elastic neutron scattering, energy-dispersive x-ray spectroscopy, and resistivity measurements, we elucidate the relations of these phases in Rb xFe ySe 2-zS z. We find (i) the iron content is crucial in stabilizing the stripe antiferromagnetic (AF) phase with rhombic iron vacancy order (y ≈ 1.5), the block AF phase with root 5 x root 5 iron vacancy order (y ≈ 1.6), and the iron vacancy-free phase (y ≈ 2); and (ii) the iron vacancy-freemore » superconducting phase (z = 0) evolves into an iron vacancy-free metallic phase with sulfur substitution (z > 1.5) due to the progressive decrease of the electronic correlation strength. Both the stripe AF phase and the block AF phase are Mott insulators. The iron-rich compounds (y > 1.6) undergo a first order transition from an iron vacancy disordered phase at high temperatures into the √5 x √5 iron vacancy ordered phase and the iron vacancy-free phase below T s. Our data demonstrate that there are miscibility gaps between these three phases. The existence of the miscibility gaps in the iron content is a key to understanding the relationship between these complicated phases.« less

Sensitivity of thermal transport in thorium dioxide to defects

NASA Astrophysics Data System (ADS)

Park, Jungkyu; Farfán, Eduardo B.; Mitchell, Katherine; Resnick, Alex; Enriquez, Christian; Yee, Tien

2018-06-01

In this research, the reverse non-equilibrium molecular dynamics is employed to investigate the effect of vacancy and substitutional defects on the thermal transport in thorium dioxide (ThO2). Vacancy defects are shown to severely alter the thermal conductivity of ThO2. The thermal conductivity of ThO2 decreases significantly with increasing the defect concentration of oxygen vacancy; the thermal conductivity of ThO2 decreases by 20% when 0.1% oxygen vacancy defects are introduced in the 100 unit cells of ThO2. The effect of thorium vacancy defect on the thermal transport in ThO2 is even more detrimental; ThO2 with 0.1% thorium vacancy defect concentration exhibits a 38.2% reduction in its thermal conductivity and the thermal conductivity becomes only 8.2% of that of the pristine sample when the thorium vacancy defect concentration is increased to 5%. In addition, neutron activation of thorium produces uranium and this uranium substitutional defects in ThO2 are observed to affect the thermal transport in ThO2 marginally when compared to vacancy defects. This indicates that in the thorium fuel cycle, fissile products such as 233U is not likely to alter the thermal transport in ThO2 fuel.

Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying

NASA Astrophysics Data System (ADS)

Barman, Sajib K.; Huda, Muhammad N.

2018-04-01

As a potential solar absorber material, Cu2S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu2S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu2S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu2S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu2S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu2S, and proposed a possible route to stabilize Cu2S against Cu vacancy formations by alloying it with Ag.

Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying.

PubMed

Barman, Sajib K; Huda, Muhammad N

2018-04-25

As a potential solar absorber material, Cu 2 S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu 2 S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu 2 S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu 2 S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu 2 S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu 2 S, and proposed a possible route to stabilize Cu 2 S against Cu vacancy formations by alloying it with Ag.

Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scale

NASA Astrophysics Data System (ADS)

Kalinin, Sergei

2014-03-01

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive memories, to chemical sensors to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, LaxSr1-xCoO3, BiFeO3, and YxZr1-xO2. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortem STEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated. I present an approach based on the multivariate statistical analysis of the coordination spheres of individual atoms to reveal preferential structures and symmetries. The relevant statistical techniques including k-means clustering, principal component analysis, and Baesian unmixing are briefly intriduced. This approach is illustrated for several systems, including chemical phase identification, mapping ferroic variants, and probing topological and structural defects, and provides real space view on surface atomic processes. Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences (AK, SJ), a DOE-BES user facility.

Enhanced room temperature ferromagnetism in electrodeposited Co-doped ZnO nanostructured thin films by controlling the oxygen vacancy defects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simimol, A.; Department of Physics, National Institute of Technology Calicut, Calicut 673601; Anappara, Aji A.

We report the growth of un-doped and cobalt doped ZnO nanostructures fabricated on FTO coated glass substrates using electrodeposition method. A detailed study on the effects of dopant concentration on morphology, structural, optical, and magnetic properties of the ZnO nanostructures has been carried out systematically by varying the Co concentration (c.{sub Co}) from 0.01 to 1 mM. For c.{sub Co }≤ 0.2 mM, h-wurtzite phase with no secondary phases of Co were present in the ZnO nanostructures. For c.{sub Co} ≤ 0.2 mM, the photoluminescence spectra exhibited a decrease in the intensity of ultraviolet emission as well as band-gap narrowing with an increase in dopantmore » concentration. All the doped samples displayed a broad emission in the visible range and its intensity increased with an increase in Co concentration. It was found that the defect centers such as oxygen vacancies and zinc interstitials were the source of the visible emission. The X-ray photoelectron spectroscopy studies revealed, Co was primarily in the divalent state, replacing the Zn ion inside the tetrahedral crystal site of ZnO without forming any cluster or secondary phases of Co. The un-doped ZnO nanorods exhibited diamagnetic behavior and it remained up to a c.{sub Co} of 0.05 mM, while for c.{sub Co }> 0.05 mM, the ZnO nanostructures exhibited ferromagnetic behavior at room temperature. The coercivity increased to 695 G for 0.2 mM Co-doped sample and then it decreased for c.{sub Co }> 0.2 mM. Our results illustrate that up to a threshold concentration of 0.2 mM, the strong ferromagnetism is due to the oxygen vacancy defects centers, which exist in the Co-doped ZnO nanostructures. The origin of strong ferromagnetism at room temperature in Co-doped ZnO nanostructures is attributed to the s-d exchange interaction between the localized spin moments resulting from the oxygen vacancies and d electrons of Co{sup 2+} ions. Our findings provide a new insight for tuning the defect density by precisely controlling the dopant concentration in order to get the desired magnetic behavior at room temperature.« less

Method for large-scale fabrication of atomic-scale structures on material surfaces using surface vacancies

DOEpatents

Lim, Chong Wee; Ohmori, Kenji; Petrov, Ivan Georgiev; Greene, Joseph E.

2004-07-13

A method for forming atomic-scale structures on a surface of a substrate on a large-scale includes creating a predetermined amount of surface vacancies on the surface of the substrate by removing an amount of atoms on the surface of the material corresponding to the predetermined amount of the surface vacancies. Once the surface vacancies have been created, atoms of a desired structure material are deposited on the surface of the substrate to enable the surface vacancies and the atoms of the structure material to interact. The interaction causes the atoms of the structure material to form the atomic-scale structures.

An effect of Sm vacancies on the hybridization gap in topological Kondo insulator candidate SmB6

NASA Astrophysics Data System (ADS)

Valentine, Michael E.; Koohpayeh, Seyed; Phelan, W. Adam; McQueen, Tyrel M.; Rosa, Priscila F. S.; Fisk, Zachary; Drichko, Natalia

2018-05-01

A necessary element for the predicted topological state in Kondo insulator SmB6 is the hybridization gap which opens in this compound at low temperatures. In this work, we present a comparative study of the in-gap density of states due to Sm vacancies by Raman scattering spectroscopy and heat capacity for samples where the number of Sm vacancies is equal to or below 1%. We demonstrate that hybridization gap is very sensitive to the presence of Sm vacancies. At the amount of vacancies above 1% the gap fills in with impurity states and low temperature heat capacity is enhanced.

Gallium vacancies and the growth stoichiometry of GaN studied by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Saarinen, K.; Seppälä, P.; Oila, J.; Hautojärvi, P.; Corbel, C.; Briot, O.; Aulombard, R. L.

1998-11-01

We have applied positron spectroscopy to study the formation of vacancy defects in undoped n-type metal organic chemical vapor deposition grown GaN, where the stoichiometry was varied. Ga vacancies are found in all samples. Their concentration increases from 1016 to 1019cm-3 when the V/III molar ratio increases from 1000 to 10 000. In nitrogen rich conditions Ga lattice sites are thus left empty and Ga vacancies are abundantly formed. The creation of Ga vacancies is accompanied by the decrease of free electron concentration from 1020 to 1016cm-3, demonstrating their role as compensating centers.

Inhomogeneous Oxygen Vacancy Distribution in Semiconductor Gas Sensors: Formation, Migration and Determination on Gas Sensing Characteristics

PubMed Central

Liu, Jianqiao; Gao, Yinglin; Wu, Xu; Jin, Guohua; Zhai, Zhaoxia; Liu, Huan

2017-01-01

The density of oxygen vacancies in semiconductor gas sensors was often assumed to be identical throughout the grain in the numerical discussion of the gas-sensing mechanism of the devices. In contrast, the actual devices had grains with inhomogeneous distribution of oxygen vacancy under non-ideal conditions. This conflict between reality and discussion drove us to study the formation and migration of the oxygen defects in semiconductor grains. A model of the gradient-distributed oxygen vacancy was proposed based on the effects of cooling rate and re-annealing on semiconductive thin films. The model established the diffusion equations of oxygen vacancy according to the defect kinetics of diffusion and exclusion. We described that the steady-state and transient-state oxygen vacancy distributions, which were used to calculate the gas-sensing characteristics of the sensor resistance and response to reducing gases under two different conditions. The gradient-distributed oxygen vacancy model had the applications in simulating the sensor performances, such as the power law, the grain size effect and the effect of depletion layer width. PMID:28796167

Inhomogeneous Oxygen Vacancy Distribution in Semiconductor Gas Sensors: Formation, Migration and Determination on Gas Sensing Characteristics.

PubMed

Liu, Jianqiao; Gao, Yinglin; Wu, Xu; Jin, Guohua; Zhai, Zhaoxia; Liu, Huan

2017-08-10

The density of oxygen vacancies in semiconductor gas sensors was often assumed to be identical throughout the grain in the numerical discussion of the gas-sensing mechanism of the devices. In contrast, the actual devices had grains with inhomogeneous distribution of oxygen vacancy under non-ideal conditions. This conflict between reality and discussion drove us to study the formation and migration of the oxygen defects in semiconductor grains. A model of the gradient-distributed oxygen vacancy was proposed based on the effects of cooling rate and re-annealing on semiconductive thin films. The model established the diffusion equations of oxygen vacancy according to the defect kinetics of diffusion and exclusion. We described that the steady-state and transient-state oxygen vacancy distributions, which were used to calculate the gas-sensing characteristics of the sensor resistance and response to reducing gases under two different conditions. The gradient-distributed oxygen vacancy model had the applications in simulating the sensor performances, such as the power law, the grain size effect and the effect of depletion layer width.

Magnesium Vacancy Segregation and Fast Pipe Diffusion for the ½<110>{110} Edge Dislocation in MgO

NASA Astrophysics Data System (ADS)

Walker, A. M.; Zhang, F.; Wright, K.; Gale, J. D.

2009-12-01

The movement of point defects in minerals plays a key role in determining their rheological properties, both by permitting diffusional creep and by allowing recovery by dislocation climb. Point defect diffusion can also control the kinetics of phase transitions and grain growth, and can determine the rate of chemical equilibration between phases. Because of this, and the difficulties associated with experimental studies of diffusion, the simulation of point defect formation and migration has been a subject of considerable interest in computational mineral physics. So far, studies have concentrated on point defects moving through otherwise perfect crystals. In this work we examine the behavior of magnesium vacancies close to the core of an edge dislocation in MgO and find that the dislocation dramatically changes the behavior of the point defect. An atomic scale model of the ½<110>{110} edge dislocation in MgO was constructed by applying the anisotropic linear elastic displacement field to the crystal structure and subsequently minimizing the energy of the crystal close to the dislocation core using a parameterized potential model. This process yielded the structure of an isolated edge dislocation in an otherwise perfect crystal. The energy cost associated with introducing magnesium vacancies around the dislocation was then mapped and compared to the formation energy of an isolated magnesium vacancy in bulk MgO. We find that the formation energy of magnesium vacancies around the dislocation mirrors the elastic strain field. Above the dislocation line σxx and σyy are negative and the strain field is compressional. Atoms are squeezed together to make room for the extra half plane effectively increasing the pressure in this region. Below the dislocation line σxx and σyy are positive and the strain field is dilatational. Planes of atoms are pulled apart to avoid a discontinuity across the glide plane and the effective pressure is decreased. In the region with a compressional strain field the vacancies become less stable than those in perfect MgO. In contrast, the region with a dilatational strain field hosts vacancies which are stabilized compared to the perfect crystal. This is in agreement with the previously observed tendency for increasing pressure to decrease the stability of vacancies in MgO. The most stable position for a magnesium vacancy was found to be 1.7 eV more stable than the vacancy in the bulk crystal, suggesting that vacancies will strongly partition to dislocations in MgO. Finally, the energy profile traced out by a vacancy moving through the bulk crystal was compared with that experienced by a vacancy moving along the dislocation core. A low energy pathway for vacancy migration along the dislocation line was found with a migration energy of 1.6 eV compared with a migration energy in the perfect crystal of 1.9 eV. This shows that vacancies segregated to the dislocation line will be significantly more mobile than vacancies in the perfect crystal. Dislocations will act as pipes, allowing material to be rapidly transported through crystals of MgO.

Structural analysis of char by Raman spectroscopy: Improving band assignments through computational calculations from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Matthew W.; Dallmeyer, Ian; Johnson, Timothy J.

2016-04-01

Raman spectroscopy is a powerful tool for the characterization of many carbon 27 species. The complex heterogeneous nature of chars and activated carbons has confounded 28 complete analysis due to the additional shoulders observed on the D-band and high intensity 29 valley between the D and G-bands. In this paper the effects of various vacancy and substitution 30 defects have been systematically analyzed via molecular modeling using density functional 31 theory (DFT) and how this is manifested in the calculated gas-phase Raman spectra. The 32 accuracy of these calculations was validated by comparison with (solid-phase) experimental 33 spectra, with amore » small correction factor being applied to improve the accuracy of frequency 34 predictions. The spectroscopic effects on the char species are best understood in terms of a 35 reduced symmetry as compared to a “parent” coronene molecule. Based upon the simulation 36 results, the shoulder observed in chars near 1200 cm-1 has been assigned to the totally symmetric 37 A1g vibrations of various small polyaromatic hydrocarbons (PAH) as well as those containing 38 rings of seven or more carbons. Intensity between 1400 cm-1 and 1450 cm-1 is assigned to A1g 39 type vibrations present in small PAHs and especially those containing cyclopentane rings. 40 Finally, band intensity between 1500 cm-1 and 1550 cm-1 is ascribed to predominately E2g 41 vibrational modes in strained PAH systems. A total of ten potential bands have been assigned 42 between 1000 cm-1 and 1800 cm-1. These fitting parameters have been used to deconvolute a 43 thermoseries of cellulose chars produced by pyrolysis at 300-700 °C. The results of the 44 deconvolution show consistent growth of PAH clusters with temperature, development of non-45 benzyl rings as temperature increases and loss of oxygenated features between 400 °C and 46 600 °C« less

Diameter Control and Photoluminescence of ZnO Nanorods from Trialkylamines

DOE PAGES

Andelman, Tamar; Gong, Yinyan; Neumark, Gertrude; ...

2007-01-01

A novel solution method to control the diameter of ZnO nanorods is reported. Small diameter (2-3 nm) nanorods were synthesized from trihexylamine, and large diameter (50–80 nm) nanorods were synthesized by increasing the alkyl chain length to tridodecylamine. The defect (green) emission of the photoluminescence (PL) spectra of the nanorods varies with diameter, and can thus be controlled by the diameter control. The small ZnO nanorods have strong green emission, while the large diameter nanorods exhibit a remarkably suppressed green band. We show that this observation supports surface oxygen vacancies as the defect that gives rise to the green emission.

New insight into the spin-conserving excitation of the negatively charged nitrogen-vacancy center in diamond

PubMed Central

Deng, Bei; Zhang, R. Q.; Shi, X. Q.

2014-01-01

The negatively charged nitrogen-vacancy (N-V−) color center in diamond is an important solid-state single photon source for applications to quantum communication and distributed quantum computation. Its full usefulness relies on sufficient radiative emission of the optical photons which requires realizable control to enhance emission into the zero-phonon line (ZPL) but until now is still a challenge. Detailed understanding of the associated excitation process would be of essential importance for such objective. Here we report a theoretical work that probes the spin-conserving optical excitation of the N-V− center. Using density-functional-theory (DFT) calculations, we find that the ZPL and the phonon-side band (PSB) depend sensitively on the axial strain of the system. Besides, we find a relatively small PSB appearing at about 100 GPa in the emission spectrum at low temperatures, which provides a means to enhance the coherent emission of the N-V− center in quantum optical networks. PMID:24888367

The demand for veterinary services in western Canada

PubMed Central

Jelinski, Murray D.; Campbell, John R.

2009-01-01

The objective of this study was to determine the number of hours veterinarians in western Canada work per week, how they apportion their time by species, and clinics’ hiring intentions for new veterinary associates. Of 1099 clinics contacted, 706 (64%) responded to the survey, representing 80% (1774/2227) of private practitioners in western Canada. Practitioners devoted 73% of their time to small animals (SA), 11% to beef practice, and 9% to horses. Sixty-four percent of clinics and 66% of practitioners were devoted exclusively to companion animal (SA and horses) practice; only 4% of clinics and 4% of practitioners were devoted exclusively to food animal practice. A total of 230 clinics were seeking to hire another veterinarian, representing 223 full-time equivalents (FTEs). When adjusted for clinics that did not respond, the total number of vacancies in western Canada could be as high as 347 FTEs with 57% of vacancies in companion animal practice. The survey, however, did not assess how determined the clinics were in their attempts to hire another associate. PMID:19949555