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At least 559 records · Page 31

Critical current density and mechanism of vortex pinning in K x Fe 2-y Se₂ doped with S

We report the critical current density J c in K x Fe 2-y Se 2-z S z crystals. The J c can be enhanced significantly with optimal S doping (z=0.99). For K 0.70(7) Fe 1.55(7) Se 1.01(2) S 0.99(2) , the weak fishtail effect is found for H II c. The normalized vortex pinning forces follow the scaling law with a maximum position at 0.41 of the reduced magnetic field. These results demonstrate that the small size normal point defects dominate the vortex pinning mechanism.

Lei, Hechang↗

Computational design of thermoelectric alloys through optimization of transport and dopability

Alloying is a common technique to optimize the functional properties of materials for thermoelectrics, photovoltaics, energy storage etc. Designing thermoelectric (TE) alloys is especially challenging because it is a multi-property optimization problem, where the properties that contribute to high TE performance are interdependent. In this work, we develop a computational framework that combines first-principles calculations with alloy and point defect modeling to identify alloy compositions that optimize the electronic, thermal, and defect properties. We apply this framework to design n-type Ba 2(1–x) Sr 2x CdP 2 Zintl thermoelectric alloys. Our predictions of the crystallographic properties such as lattice parameters and site disorder are validated with experiments. To optimize the conduction band electronic structure, we perform band unfolding to sketch the effective band structures of alloys and find a range of compositions that facilitate band convergence and minimize alloy scattering of electrons. Here, we assess the n-type dopability of the alloys by extending the standard approach for computing point defect energetics in ordered structures. Through the application of this framework, we identify an optimal alloy composition range with the desired electronic and thermal transport properties, and n-type dopability. Such a computational framework can also be used to design alloys for other functional applications beyond TE.

36 MATERIALS SCIENCE↗

A General and Modular Approach to Solid-State Integration of Zero-Dimensional Quantum Systems

Here, we present an all-electrical readout mechanism for quasi-0D quantum states (0D-QS), such as point defects, adatoms, and molecules, that is modular and general, providing an approach that is amenable to scaling and integration with other solid-state quantum technologies. Our approach relies on the creation of high-quality tunnel junctions via the mechanical exfoliation and stacking of multilayer graphene (MLG) and hexagonal boron nitride (hBN) to encapsulate the target system in an MLG/hBN/0D-QS/hBN/MLG heterostructure. This structure allows for all-electronic spectroscopy and readout of candidate systems through a combination of coulomb and spin-blockade. As a proof of principle, we demonstrate electronic tunneling spectroscopy of point defects in hBN and the molecular qubit vanadyl phthalocyanine. Our approach demonstrates a new pathway for the incorporation of molecules and atomic defects into solid-state quantum devices and circuits along with a readout scheme that does not rely on highly constrained optical processes for photonic readout.

defects in hexagonal boron nitride↗

Evolution of microstructures in radiation fields using a coupled binary-collision Monte Carlo phase field approach

The simulation of radiation effects in materials broadly falls into two categories. At short time and length scales lies the modeling of primary radiation damage, such as point defect creation, energy deposition, and ballistic mixing. This is followed by the modeling at longer time scales of thermally activated microstructure evolution and defect reactions, such as recombination, clustering, and coarsening. The binary collision Monte Carlo method is an established, numerically efficient method for the computation of primary radiation damage. Conversely, the phase field method is a state of the art method for microstructure evolution on longer time and length scales. Here we present a concurrent coupling of these two methods, overcoming the difference between the discrete object Monte Carlo paradigm for primary radiation damage and the continuum field variable approach for microstructure evolution. The coupling is bidirectional, in which the microstructure evolution in the MOOSE finite element frame- work provides the spatial scattering data set for the charged particle trans- port and receives point defect, mass transport, and heat source terms from the simulated collision cascades that contribute to the field variable evolution. The concurrent coupling scheme is implemented in the code Magpie and demonstrated by investigating patterning for a model irradiated immiscible binary alloy. The results from the coupled binary collision Monte Carlo/phase field simulations reproduce the results of analytical models for phase separation, phase mixing, and patterning, supporting the approach and indicating its utility for modeling real materials systems.

36 MATERIALS SCIENCE↗

Molecular Dynamics Simulation of Fission Fragment Damage in Nuclear Fuel and Surrogate Material

We have performed classical molecular dynamics simulations of swift heavy ion damage, typical of fission fragments, in nuclear fuel (UO2) for energy deposition per unit length of 3.9 keV/nm. We did not observe amorphization. The damage mainly consisted of isolated point defects. Only about 1% of the displacements occur on the uranium sublattice. Oxygen Frenkel pairs are an order of magnitude more numerous than uranium Frenkel pairs in the primary damage state. In contrast, previous results show that the ratio of Frenkel pairs on the two sublattices is close to the stoichiometric ratio in ceria. These differences in the primary damage state may lead to differences in radiation response of UO2 and CeO2.

Molecular dynamics, radiation damage in materials,↗

Density Functional Theory Study of the Initial Stages of Cl-Induced Degradation of α -Cr 2 O 3 Passive Film

The ion exchange and point defect models are two prominent models describing the role of anions, such as chlorides, in the degradation of passive oxide films. Here the thermodynamic feasibility of critical steps of Cl-induced degradation of a hydroxylated α-Cr 2 O 3 (0001) surface, as proposed by these two models, are studied. Both models begin with Cl substitution of surface OH and H 2 O, which becomes less favorable with increasing Cl coverage. The initial stages of Cl-induced breakdown of the α-Cr 2 O 3 depend on Cl coverage and the presence of O vacancy near the surface as follows: (1) neither Cl insertion (supporting the ion exchange model) nor Cr vacancy formation (supporting the point defect model) is feasible at low Cl coverages except in the presence of O vacancies near the surface, where Cl insertion is thermodynamically feasible even at low coverages, (2) in the absence of O vacancies, Cr vacancy formation becomes feasible from 10/12 ML onwards whereas Cl insertion by exchange with subsurface OH only becomes feasible at full coverage. This implies that at higher coverages Cl-induced degradation first initiates through a vacancy formation mechanism, but both insertion and vacancy formation would be feasible at full coverage.

36 MATERIALS SCIENCE↗

p-type conductivity and damage recovery in implanted GaN annealed by rapid gyrotron microwave annealing

We demonstrate p-type activation of GaN doped by Mg ion implantation, and in situ during metalorganic chemical vapor deposition through sequential short-duration gyrotron microwave heating cycles at temperatures of 1200–1350 °C. GaN is implanted with 1019 cm−3 Mg ions, capped with AlN, and annealed under 3 MPa N2 overpressure in 5 s heating cycles for less than 60 s total using a high-power gyrotron microwave heating source. Through I–V characterization, photoluminescence spectroscopy, and Raman spectroscopy, we study the evolution of electrical properties, optically active point defects, and material strain in response to implantation and annealing. For Mg-implanted samples, increasing annealing temperature is characterized by an increase in the PL substitutional Mg-related peak (UVL) relative to the shallow-donor vacancy-related peak (GL2). Through comparison of implanted and in situ doped samples, it is demonstrated that the origin of compensating VN lies primarily in implantation rather than degradation from the annealing process. Transmission line measurements and diode I–V measurements show a sheet resistance of 1083 kΩ/□ and a hole concentration of 1.23 × 1015 cm−3, respectively, in the Mg-implanted material annealed at 1350 °C. We conclude that temperature-cycled gyrotron annealing at 1350 °C decreases implant-induced compensating point defects and activates Mg to obtain selective p-type conduction.

Meyers, V. (ORCID:0000000176731553)↗

Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Boron suboxide (B 6 O) is a boron-rich compound derived from the α-rhombohedral boron lattice with extreme hardness and unusual semiconducting properties. In this work, density functional theory (DFT) was used to show that unit cell volume, mechanical strength, band gaps, and thermodynamic stabilities of B 6 O were influenced by the interstitial elements and point defects at the icosahedral sites. While the hexagonal unit cell volume (HUCV) varies with interstitial occupancy, it is the icosahedral defect that weakens the intrinsic bulk modulus of B 6 O. Using the hybrid HSE functional, we confirmed that the perfect B 6 O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. The formation free energies calculated over a wide range of temperatures (0–2500 K) and pressures (0–80 GPa) predict that formations of interstitial defects become favorable only at higher temperatures (ca. 1800 K) in bulk B 6 O lattices. The nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barrier of 0.16 eV. More complex B diffusion paths involving the reorganization of icosahedral boron atoms incur higher barriers (>1 eV). In contrast, the diffusion of interstitial O atoms is facile with a barrier of 0.4 eV. Lastly, successive O insertions into the α-B lattice were performed using DFT to generate a basic understanding of the oxidation process. Furthermore, these calculations provide fundamental atomistic insights into the growth of B 6 O crystals and control of their point defects.

36 MATERIALS SCIENCE↗

Donor behavior of Sb in ZnO

Electrical behavior of Sb in ZnO:Sb layers doped in a wide concentration range was studied using temperature dependent Hall effect measurements. The layers were grown by plasma-enhanced molecular beam epitaxy, and the Sb concentration was changed by varying the Sb flux, resulting in electron concentrations in the range of 10{sup 16} to nearly 10{sup 20} cm{sup -3}. Upon annealing, the electron concentration increased slightly and more notable was that the electron mobility significantly improved, reaching a room-temperature value of 110 cm{sup 2}/V s and a low-temperature value of 145 cm{sup 2}/V s, close to the maximum of {approx}155 cm{sup 2}/V s set by ionized impurity scattering. Hall data and structural data suggest that Sb predominantly occupies Zn sublattice positions and acts as a shallow donor in the whole concentration range studied. In the layers with high Sb content ({approx}1 at. %), acceptor-type compensating defects (possibly Sb on oxygen sites and/or point-defect complexes involving Sb{sub O}) are formed. The increase of electron concentration with increasing oxygen pressure and the increase in ZnO:Sb lattice parameter at high Sb concentrations suggest that acceptors involving Sb{sub O} rather than Sb{sub Zn}-2V{sub Zn} complexes are responsible for the compensation of the donors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

ARPA-E PNDIODES "PN Junctions by Ion Implantation" Project (Final Report)

Electricity accounts for nearly 40% of the energy generated in the United States, of which 65% is lost to electrical system inefficiency before reaching end-use sectors. Power electronics will play a growing role in this distribution and end-use, with up to 80% of electricity estimated to pass through power electronics from generation to consumption by 2030. This gives technical improvements in power electronics enormous potential to drive efficiency gains throughout the U.S. economy. Current Si-based power architectures including MOSFETs and IGBTs are limited by high losses, low switching frequency, and poor high-temperature performance. Given the material properties of GaN, devices can exhibit a given turn-on resistance and breakdown voltage with a minute fraction of the area of a Si device—all with higher switching speeds. While n-type doping of III-nitrides has reached a high level of maturity and integration into commercialized products, p-type doping presents distinct challenges that requires continued research. The success of the next generation of GaN-based power devices depends in large part on the ability to form selective-area p-type regions, which can be accomplished by ion implantation of the prevailing acceptor dopant, Mg. This approach is relatively inexpensive and is a fab-ready processing step for creation of current-generation power electronic devices including BJTs, IGBTs, and diode rectifiers. However, ion implantation induces lattice damage and creates point defects within the material, which negatively impacts dopant activation annealing. These forms of damage may be removed by high-temperature annealing, however short annealing time and higher pressures are required to prevent decomposition of the material. We approach this challenge through an innovative combination of approaches toward obtaining high-conductivity p-type GaN. By the novel employment of a gyrotron, a microwave source that can be shaped into a highly localized beam to dissipate very high power in a semiconductor target, a wafer of GaN can be annealed in short (<2 s) ‘pulses’ at temperatures of 1450 °C (2640 °F) to achieve p-type activation without appreciable surface degradation. The p-type activation of Mg-implanted GaN can be further aided by co-implantation with N, believed to enhance the removal of point defects that compensate the acceptors dopant. Elevation to such high temperatures for even a short time induces degradation of GaN-to overcome, we have implemented additional measures to retain high-quality crystalline GaN while removing implant damage and activating Mg dopant. A bilayer cap of AlN is deposited by a combination of chemical and physical vapor deposition to protect the GaN surface. To prevent decomposition of GaN loss of N during annealing, a custom vessel—to contain pressurized N while allowing injection of microwave energy—is employed. By detailed study of the interaction of various measures that are implemented to protect the sample surface (GaN), activate the implanted dopants, and mitigate damage of the lattice heating damage during annealing, we are able to achieve p-type GaN and observe recovery of the crystal and removal of substantial density of defects created during the implantation process.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Defects go green: using defects in nanomaterials for renewable energy and environmental sustainability

Induction of point defects in nanomaterials can bestow upon them entirely new physics or augment their pre-existing physical properties, thereby expanding their potential use in green energy technology. Predicting structure-property relationships for defects a priori is challenging, and developing methods for precise control of defect type, density, or structural distribution during synthesis is an even more formidable task. Hence, tuning the defect structure to tailor nanomaterials for enhanced device performance remains an underutilized tool in materials design. We review here the state of nanomaterial design through the lens of computational prediction of defect properties for green energy technology, and synthesis methods to control defect formation for optimal performance. We illustrate the efficacy of defect-focused approaches for refining nanomaterial physics by describing several specific applications where these techniques hold potential. Most notably, we focus on quantum dots for reabsorption-free solar windows and net-zero emission buildings, oxide cathodes for high energy density lithium-ion batteries and electric vehicles, and transition metal dichalcogenides for electrocatalytic green hydrogen production and carbon-free fuels.

14 SOLAR ENERGY↗

Acceptors in ZnO

Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence indicates these point defects have acceptor levels 3.2, 1.4, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO{sub 2} contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peak in ZnO nanocrystals is attributed to an acceptor, which may involve a Zn vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g{sub ⊥} = 2.0015 and g{sub //} = 2.0056, along with an isotropic center at g = 2.0035.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Relationship between lath boundary structure and radiation induced segregation in a neutron irradiated 9 wt.% Cr model ferritic/martensitic steel

Ferritic/Martensitic (F/M) steels with high Cr content posses the high temperature strength and low swelling rates required for advanced nuclear reactor designs. Radiation induced segregation (RIS) occurs in F/M steels due to solute atoms preferentially coupling to point defect fluxes which migrate to defect sinks, such as grain boundaries (GBs). The RIS response of F/M steels and austenitic steels has been shown to be dependent on the local structure of GBs where low energy structures have suppressed RIS responses. This relationship between local GB structure and RIS has been demonstrated primarily in ion-irradiated specimens. A 9 wt.% Cr model alloy steel was irradiated to 3 dpa using neutrons at the Advanced Test Reactor (ATR) to determine the effect of a neutron radiation environment on the RIS response at different GB structures. This investigation found the relationship between GB structure and RIS is also active for F/M steels irradiated using neutrons. The data generated from the neutron irradiation is also compared to RIS data generated using proton irradiations on the same heat of model alloy.

36 MATERIALS SCIENCE↗

Disorder-induced topological change of the superconducting gap structure in iron pnictides

In superconductors with unconventional pairing mechanisms, the energy gap in the excitation spectrum often has nodes, which allow quasiparticle excitations at low energies. In many cases, such as in d-wave cuprate superconductors, the position and topology of nodes are imposed by the symmetry, and thus the presence of gapless excitations is protected against disorder. Here we report on the observation of distinct changes in the gap structure of iron–pnictide superconductors with increasing impurity scattering. By the successive introduction of nonmagnetic point defects into BaFe 2 (As 1–x P x ) 2 crystals via electron irradiation, we find from the low-temperature penetration depth measurements that the nodal state changes to a nodeless state with fully gapped excitations. Moreover, under further irradiation the gapped state evolves into another gapless state, providing bulk evidence of unconventional sign-changing s-wave superconductivity. As a result, this demonstrates that the topology of the superconducting gap can be controlled by disorder, which is a strikingly unique feature of iron pnictides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Outstanding radiation resistance of tungsten-based high-entropy alloys

A body-centered cubic W-based refractory high entropy alloy with outstanding radiation resistance has been developed. The alloy was grown as thin films showing a bimodal grain size distribution in the nanocrystalline and ultrafine regimes and a unique 4-nm lamella-like structure revealed by atom probe tomography (APT). Transmission electron microscopy (TEM) and x-ray diffraction show certain black spots appearing after thermal annealing at elevated temperatures. TEM and APT analysis correlated the black spots with second-phase particles rich in Cr and V. No sign of irradiation-created dislocation loops, even after 8 dpa, was observed. Furthermore, nanomechanical testing shows a large hardness of 14 GPa in the as-deposited samples, with near negligible irradiation hardening. Theoretical modeling combining ab initio and Monte Carlo techniques predicts the formation of Cr- and V-rich second-phase particles and points at equal mobilities of point defects as the origin of the exceptional radiation tolerance.

36 MATERIALS SCIENCE↗

Competition between orthorhombic and re-entrant tetragonal phases in underdoped Ba 1–x K x Fe 2 As 2 probed by the response to controlled disorder

Low-temperature (22 K) irradiation with 2.5-MeV electrons, creating point defects affecting elastic scattering, was used to study the competition between stripe C 2 and tetragonal C 4 antiferromagnetic phases which exist in a narrow doping range around x = 0.25 in hole-doped Ba 1–x K x Fe 2 As 2 . In nearby compositions outside of this range, at x = 0.22 and x = 0.19, the temperatures of both the concomitant orthorhombic/stripe antiferromagnetic transition T C2 and the superconducting transition T c are monotonically suppressed by added disorder at similar rates of about 0.1 K/ μ Ωcm, as revealed through using resistivity variation as an intrinsic measure of scattering rate. In a stark contrast, a rapid suppression of the C 4 phase at the rate of 0.24 K/ μ Ωcm is found at x = 0.25. Moreover, this suppression of the C 4 phase is accompanied by unusual disorder-induced stabilization of the C 2 phase, determined by resistivity and specific heat measurements. Furthermore, the rate of the C 4 phase suppression is notably higher than the suppression rate of the spin-vortex phase in the Ni-doped CaKFe 4 As 4 (0.16 K/ μ Ωcm).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Local and average structure of Mn- and La-substituted BiFeO{sub 3}

The local and average structure of solid solutions of the multiferroic perovskite BiFeO{sub 3} is investigated by synchrotron X-ray diffraction (XRD) and electron density functional theory (DFT) calculations. The average experimental structure is determined by Rietveld refinement and the local structure by total scattering data analyzed in real space with the pair distribution function (PDF) method. With equal concentrations of La on the Bi site or Mn on the Fe site, La causes larger structural distortions than Mn. Structural models based on DFT relaxed geometry give an improved fit to experimental PDFs compared to models constrained by the space group symmetry. Berry phase calculations predict a higher ferroelectric polarization than the experimental literature values, reflecting that structural disorder is not captured in either average structure space group models or DFT calculations with artificial long range order imposed by periodic boundary conditions. Only by including point defects in a supercell, here Bi vacancies, can DFT calculations reproduce the literature results on the structure and ferroelectric polarization of Mn-substituted BiFeO{sub 3}. The combination of local and average structure sensitive experimental methods with DFT calculations is useful for illuminating the structure-property-composition relationships in complex functional oxides with local structural distortions. - Graphical abstract: The experimental and simulated partial pair distribution functions (PDF) for BiFeO{sub 3}, BiFe{sub 0.875}Mn{sub 0.125}O{sub 3}, BiFe{sub 0.75}Mn{sub 0.25}O{sub 3} and Bi{sub 0.9}La{sub 0.1}FeO{sub 3}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗