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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Effect of point defects on the thermal conductivity of UO 2 : molecular dynamics simulations

The thermal conductivity of uranium dioxide (UO 2 ) fuel is an important materials property that affects fuel performance since it is a key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. The thermal conductivity of UO 2 nuclear fuel is also affected by fission gas, fission products, defects, and microstructural features such as grain boundaries. Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of irradiation induced point defects on the thermal conductivity of UO 2 , as a function of defect concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Periodic surface structure bifurcation induced by ultrafast laser generated point defect diffusion in GaAs

The formation of high spatial frequency laser induced periodic surface structures (HSFL) with period <0.3 λ in GaAs after irradiation with femtosecond laser pulses in air is studied. We have identified a point defect generation mechanism that operates in a specific range of fluences in semiconductors between the band-gap closure and ultrafast-melt thresholds that produces vacancy/interstitial pairs. Stress relaxation, via diffusing defects, forms the 350–400 nm tall and ∼90 nm wide structures through a bifurcation process of lower spatial frequency surface structures. The resulting HSFL are predominately epitaxial single crystals and retain the original GaAs stoichiometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Point Defects Control Guest Molecule Diffusion in the 1D Pores of Zn(tbip)

Molecular diffusion plays a critical role in metal-organic frameworks (MOFs) within the application of kinetic chemical separations. We carefully study in this work the unexpected role of point defects for short-chain alkanes diffusing in Zn(tbip), an MOF with rigid one-dimensional (1D) channels. Inside a defect-free Zn(tbip), guest molecules are expected to follow single-file diffusion along 1D channels. It has been found previously by Heinke et al. that these parallel 1D channels are connected for molecular diffusion. Our density functional theory (DFT) calculations suggest that linker vacancy defects could arise under experimentally relevant conditions by removing a pair of linkers. Further climbing-image nudged elastic band (cNEB) DFT calculations indicate that hopping of short-chain alkanes between adjacent 1D channels over defect windows can occur at moderate temperatures. In addition to providing insights into connected adjacent 1D channels in Zn(tbip), Heinke et al. also inferred that most 1D pores are blocked from a microkinetic model. Additionally, we explored the influence of hydrolyzed linker created by the formation of linker removal inside 1D pores. Our DFT calculations show that the linkers can effectively block the pores and the linker diffusion in 1D channels is slow. Our results, for the first time, offer a mechanistic explanation of the unexpected molecular diffusion behavior in this MOF with 1D channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effects of Co Doping and Point Defect on the Ferromagnetism of ZnO

The effects of different doping proportions of Co doping and oxygen vacancies (V{sub O}) on the ferromagnetism of zinc oxide (ZnO) are controversial. To solve this problem, we investigated the effects of Co doping and point defects (V{sub O}, V{sub Zn}, H{sub i}, and Zn{sub i}) on the ferromagnetism of ZnO through first-principle calculations by using generalized gradient approximation + U (GGA + U) under density functional theory. Results show that the closer the distance between Co and vacancies (V{sub O} or V{sub Zn}), the lower the formation energy and the more stable the system will be. Co-doped ZnO with V{sub O} or V{sub Zn} exhibits long-range ordered ferromagnetism and Curie temperature above the room temperature. Especially, Co-doped ZnO with V{sub Zn} shows a half-metallic behavior, resulting in 100% conduction hole polarizability, which is highly beneficial for dilute magnetic semiconductors (DMSs) as a hole injection source. The ferromagnetism of Zn{sub 14}CoO{sub 16} is caused by the double exchange effects among the electrons of the O–2p, Co–3d, and Zn–3d orbits mediated by the hole carriers after complexes were formed by the Co doping and Zn vacancy. Similarly, the origin of ferromagnetism in Zn{sub 15}CoO{sub 15} is derived from the double exchange effects among the electrons of O–2p, Co–3d, and Zn–4s states mediated by the electron carriers after complexes were formed by the Co doping and O vacancy. In addition, the result shows that Co-doped ZnO with interstitial H (H{sub i}) or Zn (Zn{sub i}) is unfavorable for ferromagnetism and should be avoided experimentally.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Adsorption and Photodesorption of CO from Charged Point Defects on TiO 2 (110)

Adsorption and photodesorption of weakly-bound carbon monoxide, CO, from reduced and hydroxylated rutile TiO2(110) (r- and h- TiO2(110)) at sub-monolayer coverages is studied with atomically-resolved scanning tunneling microscopy (STM) along with ensemble-averaged temperature-programmed desorption (TPD) and angle-resolved photon-stimulated desorption (PSD) at low temperatures ( 50 K). STM data weighted by the concentration of each kind of adsorption sites on r-TiO2(110) give an adsorption probability which is the highest for the bridging oxygen vacancies (VO) and very low for the Ti5c sites closest to VO. Occupancy of the remaining Ti5c sites with CO is significant, but smaller than for VO. The probability distribution for the different adsorption sites corresponds to a very small difference in CO adsorption energies: < 0.02 eV. We also find that UV irradiation stimulates both diffusion and desorption of CO at low temperature. CO photodesorbs primarily from the vacancies with a bi-modal angular distribution. In addition to a major, normal to the surface component, there is a broader cosine component indicating scattering from the surface which likely also leads to photo-stimulated diffusion. Hydroxylation of VO’s does not significantly change the CO PSD yield and angular distribution, indicating that not atomic but rather electronic surface defects are involved in the site-specific PSD process. We suggest that photodesorption can be initiated by recombination of photo-generated holes with excess unpaired electrons localized near the surface point-defect (either VO or bridging hydroxyl), leading to the surface atoms rearrangement and ejection of the weakly-bound CO molecules.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

Accurate point defect energy levels from non-empirical screened range-separated hybrid functionals: The case of native vacancies in ZnO

We use density functional theory (DFT) with non-empirically tuned screened range-separated hybrid (SRSH) functionals to calculate the electronic properties of native zinc and oxygen vacancy point defects in ZnO, and we predict their defect levels for thermal and optical transitions in excellent agreement with available experiments and prior calculations that use empirical hybrid functionals. Furthermore, the ability of this non-empirical first-principles framework to accurately predict quantities of relevance to both bulk- and defect-level spectroscopy enables high-accuracy DFT calculations with non-empirical hybrid functionals for defect physics, at a reduced computational cost.

Defects↗
DOE OSTI2014

First-principles study of point defects at a semicoherent interface

Most of the atomistic modeling of semicoherent metal-metal interfaces has so far been based on the use of semiempirical interatomic potentials. Here, we show that key conclusions drawn from previous studies are in contradiction with more precise ab-initio calculations. In particular we find that single point defects do not delocalize, but remain compact near the interfacial plane in Cu-Nb multilayers. Lastly, we give a simple qualitative explanation for this difference on the basis of the well known limited transferability of empirical potentials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Direct correlation and strong reduction of native point defects and microwave dielectric loss in air-annealed (Ba,Sr)TiO{sub 3}

We report on the native defect and microwave properties of 1 μm thick Ba{sub 0.50}Sr{sub 0.50}TiO{sub 3} (BST) films grown on MgO (100) substrates by molecular beam epitaxy (MBE). Depth-resolved cathodoluminescence spectroscopy (DRCLS) showed high densities of native point defects in as-deposited BST films, causing strong subgap emission between 2.0 eV and 3.0 eV due to mixed cation V{sub C} and oxygen Vo vacancies. Post growth air anneals reduce these defects with 2.2, 2.65, and 3.0 eV V{sub O} and 2.4 eV V{sub C} intensities decreasing with increasing anneal temperature and by nearly two orders of magnitude after 950 °C annealing. These low-defect annealed BST films exhibited high quality microwave properties, including room temperature interdigitated capacitor tunability of 13% under an electric bias of 40 V and tan δ of 0.002 at 10 GHz and 40 V bias. The results provide a feasible route to grow high quality BST films by MBE through post-air annealing guided by DRCLS.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Reduced photothermal heating in diamonds enriched with H3 point defects

Solid-state laser refrigeration of semiconductors remains an outstanding experimental challenge. In this work, we show that, following excitation with a laser wavelength of 532 nm, bulk diamond crystals doped with H3 centers both emit efficient up-conversion (anti-Stokes) photoluminescence and also show significantly reduced photothermal heating relative to crystals doped with nitrogen–vacancy (NV) centers. The H3 center in diamond is a highly photostable defect that avoids bleaching at high laser irradiances of 10–70 MW/cm 2 and has been shown to exhibit laser action, tunable over the visible band of 500–600 nm. Here, the observed reduction of photothermal heating arises due to a decrease in the concentration of absorbing point defects, including NV-centers. These results encourage future exploration of techniques for H3 enrichment in diamonds under high-pressure, high-temperature conditions for the simultaneous anti-Stokes fluorescence cooling and radiation balanced lasing in semiconductor materials. Reducing photothermal heating in diamond through the formation of H3 centers also opens up new possibilities in quantum sensing via optically detected magnetic resonance spectroscopy at ambient conditions.

42 ENGINEERING↗
DOE OSTI2017

Improving the Carrier Lifetime of Tin Sulfide via Prediction and Mitigation of Harmful Point Defects

Tin monosulfide (SnS) is an emerging thin-film absorber material for photovoltaics. An outstanding challenge is to improve carrier lifetimes to >1 ns, which should enable >10% device efficiencies. However, reported results to date have only demonstrated lifetimes at or below 100 ps. In this study, we employ defect modeling to identify the sulfur vacancy and defects from Fe, Co, and Mo as most recombination-active. We attempt to minimize these defects in crystalline samples through high-purity, sulfur-rich growth and experimentally improve lifetimes to >3 ns, thus achieving our 1 ns goal. This framework might prove effective for unlocking the lifetime potential in other emerging thin-film materials by rapidly identifying and mitigating lifetime-limiting point defects.

14 SOLAR ENERGY↗
DOE OSTI2022

Nanoscale interplay of native point defects near Sr-deficient SrxTiO 3 /SrTiO 3 interfaces

SrTiO 3 has many applications involving interfaces with other materials, but defects that affect the properties of SrTiO 3 films can also play a significant role at its heterointerfaces and even at junctions with nonstoichiometric SrTiO 3 . Depth-resolved cathodoluminescence spectroscopy (DRCLS) combined with systematic cation Sr content reduction in SrxTiO 3 ultrathin films grown on SrTiO 3 showed an interplay of native point defects and electronic structure within the Sr-deficient film and how interplay extends tens of nanometers into the substrate below. Understanding how defects form and affect interface electronic structure during epitaxial growth is central to improving complex oxide devices. Controlling the balance of oxygen vacancy defects with strontium vacancies and other acceptor-like defects can improve control over free carrier densities. Likewise, control over nanoscale defect charge distributions can advance new device features such as two-dimensional hole gases and the performance of existing devices such as ferroelectric tunnel junctions. This study shows how DRCLS directly measures the relative densities and spatial distributions of multiple native defects within and extending away from nanoscale SrxTiO 3 /SrTiO 3 junctions and how their interplay varies with controlled epitaxial growth. In turn, these growth-dependent defect variations can help guide SrTiO 3 epitaxial growth with other complex oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2017

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

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 addition 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.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Excited State Properties of Point Defects in Semiconductors and Insulators Investigated with Time-Dependent Density Functional Theory

Here, we present a formulation of spin-conserving and spin-flip hybrid time-dependent density functional theory (TDDFT), including the calculation of analytical forces, which allows for efficient calculations of excited state properties of solid-state systems with hundreds to thousands of atoms. We discuss an implementation on both GPU- and CPU-based architectures along with several acceleration techniques. We then apply our formulation to the study of several point defects in semiconductors and insulators, specifically the negatively charged nitrogen-vacancy and neutral silicon-vacancy centers in diamond, the neutral divacancy center in 4H silicon carbide, and the neutral oxygen-vacancy center in magnesium oxide. Our results highlight the importance of taking into account structural relaxations in excited states in order to interpret and predict optical absorption and emission mechanisms in spin defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction

Cu 2ZnSn(S,Se)4 is an interesting, earth abundant photovoltaic material, but has suffered from low open circuit voltage. To better understand the film structure, we have measured resonant x-ray diffraction across the Cu and Zn K-edges for the device quality thin films of Cu 2ZnSnS4 (8.6% efficiency) and Cu 2ZnSn(S,Se)4 (3.5% efficiency). This approach allows for the confirmation of the underlying kesterite structure and quantification of the concentration of point defects and vacancies on the Cu, Zn, and Sn sublattices. Rietveld refinement of powder diffraction data collected at multiple energies is used to determine that there exists a high level of Cu Zn and Zn Cu defects on the 2c and 2d Wyckoff positions. We observe a significantly lower concentration of Zn Sn defects and Cu or Zn vacancies.

14 SOLAR ENERGY↗
NASA NTRS1999

Point Defect Distributions in ZnSe Crystals: Effects of Gravity Vector Orientation during Physical Vapor Transport Growth

ZnSe crystals were grown by the physical vapor transport technique under horizontal and vertical (stabilized and destabilized) configurations. Secondary ion mass spectroscopy and photoluminescence measurements were performed on the ZnSe samples to map the distributions of [Si], [Fe], [Cu], [Al] and [Li or Na] impurities as well as Zn vacancy, [V(zn)]. The annealings of ZnSe under controlled Zn pressures were studied to correlate the measured photoluminescence emission intensity to the equilibrium Zn partial pressure. In the horizontal grown crystals the segregations of [Si], [Fe], [Al] and [V(zn)] along the gravity vector direction were observed whereas in the vertically stabilized grown crystal the segregations of these point defects were radially symmetrical. No apparent pattern was observed on the measured distributions in the vertically destabilized grown crystal. The observed segregations in the three growth configurations were interpreted based on the possible buoyancy-driven convection in the vapor phase.

Su, Ching-Hua↗
NASA NTRS1999

Point Defect Distributions in ZnSe Crystals: Effects of Gravity Vector Orientation During Physical Vapor Transport Growth

ZnSe crystals were grown by the physical vapor transport technique under horizontal and vertical (stabilized and destabilized) configurations. Secondary ion mass spectroscopy and photoluminescence measurements were performed on the grown ZnSe samples to map the distributions of [Si], [Fe], [Cu], [Al] and [Li or Na] impurities as well as Zn vacancy, [V (sub Zn)]. Annealings of ZnSe under controlled Zn pressures were studied to correlate the measured photoluminescence emission intensity to the equilibrium Zn partial pressure. In the horizontal grown crystals the segregations of [Si], [Fe], [Al] and [V (sub Zn)] were observed along the gravity vector direction whereas in the vertically stabilized grown crystal the segregation of these point defects was radially symmetrical. No apparent pattern was observed on the measured distributions in the vertically destabilized grown crystal. The observed segregations in the three growth configurations were interpreted based on the possible buoyancy-driven convection in the vapor phase.

Su, Ching-Hua↗
DOE OSTI2019

Stabilization of point-defect spin qubits by quantum wells

Defect-based quantum systems in wide bandgap semiconductors are strong candidates for scalable quantum-information technologies. However, these systems are often complicated by charge-state instabilities and interference by phonons, which can diminish spin-initialization fidelities and limit room-temperature operation. Here, we identify a pathway around these drawbacks by showing that an engineered quantum well can stabilize the charge state of a qubit. Using density-functional theory and experimental synchrotron X-ray diffraction studies, we construct a model for previously unattributed point defect centers in silicon carbide as a near-stacking fault axial divacancy and show how this model explains these defects' robustness against photoionization and room temperature stability. These results provide a materials-based solution to the optical instability of color centers in semiconductors, paving the way for the development of robust single-photon sources and spin qubits.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Modeling neutral defects in III-V ternary alloys with a special quasirandom structure: Analysis of As- and III-site point defects in InGaAs

While first-principles density functional theory modeling has become a vital tool to investigate defect properties in semiconductors, the lack of crystalline periodicity in pseudobinary random composition alloys, such as In 1−𝑥 ⁢Ga 𝑥 ⁢As, complicates such analyses. We present a simulation strategy to systematically take into account the variability in the local defect environment in order to predict statistical properties of neutral intrinsic defects in In 1−𝑥⁢ Ga 𝑥 ⁢As. We use a comprehensive sampling from a modest-sized 64-atom special quasirandom structure (SQS) to define a statistically representative set of defects, and use a 512-atom hypercell, a 2 × 2 × 2 supercell of SQS supercells, to achieve cell-size convergence. We articulate an equivalent site principle and describe how it constrains atomic chemical reference energies in computation of defect formation energies in pseudobinary alloys. A simple protocol for estimating reference energies for the Ga and In atoms sharing the III site succeeds in obtaining the equivalence of defects at Ga-sites and In sites in the SQS supercell, (<30 meV differences in average formation energies). For III-site defects, such as the As antisite As III , the statistical variability in formation energies is modest, ≈ 0.1–0.2 eV. The variability in formation energy at As-site defects, such as the As vacancy 𝑣 As , can be much larger, >1 eV. The As antisite is shown to be a low-energy defect and the most likely to be present in as-grown materials, just as in GaAs. All other defects are higher-energy defects unlikely to be important in native material, but potentially important in radiation-damaged material. With a strong variability in defect energies, especially on the As-site, explicit consideration of statistical variability due to compositional randomness will be imperative for meaningful and quantitative comparisons to experiment.

Density functional theory↗