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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Effect of single atom Platinum (Pt) doping and facet dependent on the electronic structure and light absorption of Lanthanum Titanium Oxide (La 2 Ti 2 O 7 ): A Density Functional Theory study

Charge generation and separation are two key processes for semiconductor photocatalysis. Here, we use Pt as a single atom catalyst to systematically examine the facet-dependent electronic band structure and light absorption of the layered perovskite-type wide-gap semiconductor, lanthanum titanium oxide (La 2 Ti 2 O 7 , LTO) by means of density functional theory simulations. In this study, it is found that single Pt atom doping of different LTO surfaces (here, (100), (101) and (001)) can not only create states in the bandgap that would promote the formation of recombination centers, but also shift the optical absorption edge to the visible region. Interestingly, the Pt doping forms a heterojunction, with the valence band maximum consisting of Pt states and the conduction band minimum consisting of LTO states, respectively. To study the facet dependent surface activity, acetic acid (CH 3 COOH) was used as a model molecule to investigate the adsorption and charge transfer on the (101), (100) and (001) Pt-LTO surface facets. The results show that the (101) facet could enable stronger adsorption of CH 3 COOH by promoting more electron transfer during the interfacial interaction. Our theoretical findings aim to promote the design and optimization of the single atom catalysts (SACs) for photocatalytic applications and other broad catalysis systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Physical properties of metallic antiferromagneticCaCo1.86As2 single crystals

X-ray powder diffraction (XRD), magnetic susceptibility χ, isothermal magnetization M, heat capacity Cp, and in-plane electrical resistivity ρ measurements as a function of temperature T and magnetic field H are presented for CaCo1.86As2 single crystals. The electronic structure is probed by angle-resolved photoemission spectroscopy (ARPES) measurements of CaCo1.86As2 and by full-potential linearized augmented-plane-wave calculations for the supercell Ca8Co15As16 (CaCo1.88As2). Our XRD crystal structure refinement is consistent with the previous combined refinement of x-ray and neutron powder diffraction data showing a collapsed-tetragonal ThCr2Si2-type structure with 7(1)% vacancies on the Co sites corresponding to the composition CaCo1.86As2 [D. G. Quirinale et al., Phys. Rev. B 88, 174420 (2013)]. The anisotropic χ(T) data are consistent with the magnetic neutron diffraction data of Quirianale et al. that demonstrate the presence of A-type collinear antiferromagnetic order below the Néel temperature TN=52(1) K with the easy axis being the tetragonal c axis. However, no clear evidence from the ρ(T) and Cp(T) data for a magnetic transition at TN is observed. A metallic ground state is demonstrated from the band calculations and the ρ(T), Cp(T), and ARPES data, and spin-polarized calculations indicate a competition between the A-type AFM and FM ground states. The Cp(T) data exhibit a large Sommerfield electronic coefficient reflecting a large density of states at the Fermi energy D(EF) that is enhanced compared with the band structure calculation where the bare D(EF) arises from Co 3d bands. At 1.8 K, the M(H) data for H∥c exhibit a well-defined first-order spin-flop transition at an applied field of 3.5 T. The small ordered moment of ≈0.3μB/Co obtained from the M(H) data at low T, the large exchange enhancement of χ and the lack of a self-consistent interpretation of the χ(T) and M(H,T) data in terms of a local moment Heisenberg model together indicate that the magnetism of CaCo1.86As2 is itinerant.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cubic Crystal Structure Formation and Optical Properties within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) Family of Semiconductors

Quaternary chalcogenide semiconductors are promising materials for energy conversion and nonlinear optical applications, with properties tunable primarily by varying the elemental composition and crystal structure. Here, we first analyze the connections among several cubic crystal structure types, as well as the orthorhombic Ag 2 PbGeS 4 -type structure, reported for select members within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) compositional space. Focusing on the Ag–Pb–Si–S and Ag–Sr–Sn–S systems, we show that one structure type, with the formulas Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , is favored. We have prepared powder and single-crystal samples of Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , showing that each takes on the noncentrosymmetric cubic space group I$\bar{43}$d and is isostructural to the previously reported compound Ag 2 Sr 3 Ge 2 Se 8 . Through hybrid density functional theory calculations, these cubic compounds are demonstrated to be (quasi-)direct band gap semiconductors with high densities of states at the band maxima. Furthermore, the band-gap energies are measured by reflectance spectroscopy as 1.95(3) and 2.66(4) eV for Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , respectively. We further measure the optical properties and show the electronic band structures of three other isostructural A I –B II –M IV –X-type materials, i.e., Ag 2 Sr 3 Si 2 S 8 , Ag 2 Sr 3 Ge 2 S 8 , and Ag 2 Sr 3 Ge 2 Se 8 , showing that the band gaps can be predictably tuned by element substitution. Detailed visual analyses of the different structures and of their relationships with other members of the Ag–B II –M IV –X compositional family provide a basis for a broader understanding of the structure formation and optoelectronic properties within the quaternary chalcogenide semiconductor family.

14 SOLAR ENERGY↗
DOE OSTI2019

Fermi surface, possible unconventional fermions, and unusually robust resistive critical fields in the chiral-structured superconductor AuBe

The noncentrosymmetric superconductor (NCS) AuBe is investigated using a variety of thermodynamic and resistive probes in magnetic fields of up to 65 T and temperatures down to 0.3 K. Despite the polycrystalline nature of the samples, the observation of a complex series of de Haas–van Alphen (dHvA) oscillations has allowed the calculated band structure for AuBe to be validated. This permits a variety of BCS parameters describing the superconductivity to be estimated, despite the complexity of the measured Fermi surface. In addition, AuBe displays a nonstandard field dependence of the phase of dHvA oscillations associated with a band thought to host unconventional fermions in this chiral lattice. Overall, this result demonstrates the power of the dHvA effect to establish the properties of a single band despite the presence of other electronic bands with a larger density of states, even in polycrystalline samples. In common with several other NCSs, we find that the resistive upper critical field exceeds that measured by heat capacity and magnetization by a considerable factor. We suggest that our data exclude mechanisms for such an effect associated with disorder, implying that topologically protected superconducting surface states may be involved.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

First-principles study of the electronic structure and the Fermi surface in rare-earth filled skutterudites R Pt 4 Ge 12

Experiments on rare-earth filled skutterudites demonstrate an intriguing array of thermodynamic, transport, and superconducting properties, and bring to fore theoretical challenges posed by f-electron systems. First-principle calculations based density functional theory and its extensions for strongly correlated systems such as the Hubbard U correction, provide valuable information about electronic structure that can be used to understand experiments. We present a comprehensive study of the electronic structure and Fermi surface of a series of rare-earth filled skutterudites, RPt 4 Ge 12 (where R = La, Ce, Pr), aimed at shedding light on: consequences of progressive increase of f-orbital occupancy in the series; the effects of the Hubbard parameter U; and the Fermi surfaces, band structures, and densities of states. The calculated Fermi surfaces may be relevant to the question of multiband versus single-band superconductivity. Computed densities of states qualitatively explain the available resonant photoemission spectroscopy experiments, and (together with available specific heat measurements) provide estimates of the effective masses. We also show the existence of pseudogaps in the total density of states which may be relevant for the thermoelectric properties of these systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Role of Multiple Charge States of Ce in the Scintillation of AB O 3 Perovskites

Ce-activated A 2+ B 4+ O 3 perovskites represent a class of compounds currently under active exploration for their potential as scintillators. Depending on the chemistry and synthesis conditions, perovskites can crystallize in multiple crystal structures, and a Ce substitutional dopant in an ABO 3 perovskite can adopt different charge states (i.e., Ce 3+ or Ce 4+ ) as well as different substitutional sites (namely, the 12-fold-coordinated A site or the octahedrally coordinated B site). We use first-principles density-functional-theory- and hybrid-functional-based computations to study relative trends in the structure, energetics, and electronic structure of bulk ABO 3 perovskites, where A = Ca, Sr, or Ba and B = Hf or Zr. Subsequently, we consider the relative energetics of preferential solution sites for Ce as a function of charge states, chemical potential, and defect configurations. Our results reveal that while Ce 3+ or Ce 4+ defects can be thermodynamically stable, depending on the choice of the substitutional site and synthesis conditions (i.e., prevailing chemical potential), only Ce 3+ dopant at the A site leads to an electronic structure that can exhibit scintillation. Our comparative analysis shows that while the positions of the 5 d 1 and 4$\mathcal{f}$ levels of Ce 3+ as a dopant at the A site are favorably placed in the band structure, these levels are consistently higher for the Ce 4+ charge state and are unlikely to manifest any luminescence. The findings of this study are also discussed in relation to previously reported results and display excellent agreement with past experimental observations. In general, it is demonstrated that control of the Ce charge state and local chemical environment can be used—in addition to band-gap and band-edge engineering—to manipulate the relative position of scintillating states with respect to the valence-band maximum and conduction-band minimum. While this study specifically focuses on perovskites, the results (in particular, the relative alignment of the positions of the 5 d 1 and 4$\mathcal{f}$ levels of Ce dopant as a function of the activator’s charge state) are expected to be general and thus transferable to other chemistries.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Uranium Doped Gallium Nitride Epitaxial Thin Films

Gallium nitride (GaN) is near ubiquitous in modern day technologies, forming the backbone of solid-state lighting and high-power electronics. Engineering the physical properties of GaN has been investigated to some degree by the incorporation or doping of most of the elements of the periodic table, but the actinides remain unexplored. Molecular beam epitaxy is used to demonstrate uranium doping of GaN single crystals. High structural quality of the host matrix is maintained despite partial elemental segregation of the uranium dopant into 1D structures at the levels presented here. Electronic transport measurements reveal relatively high conductivity, which persists down to cryogenic temperature and is characterized by the formation of narrow gaps in the electronic band structures very close to the Fermi level. Photoluminescence measurements reveal that the U-doped GaN exhibits optical behavior similar to that of the GaN substrate. The addition of actinide materials to a non-centrosymmetric, optically active, radiation-hard, and electronically tunable host matrix opens a world of possibilities for investigating and leveraging elements with high electron correlations in the pursuit of novel devices.

36 - MATERIALS SCIENCE↗
DOE OSTI2018

A DFT Study on Structural, Electronic Mechanical and Thermodynamic Properties of 5f-Electron System BaAmO{sub 3}

The structural, electronic, mechanical and thermodynamic properties of the perovskite oxide BaAmO{sub 3} have been predicted using the full-potential linearized augmented plane wave (FP-LAPW) method. The equilibrium lattice constant, bulk modulus and pressure derivative were computed using different exchange correlations. The optimization of structure was carried out in ferromagnetic, anti-ferromagnetic and non-magnetic states, and the compound was found to be stable in the ferromagnetic state. A systematic study on the band structure and density of states was accomplished using generalized gradient approximation (GGA), Hubbard approximation (GGA + U) and modified Becke–Johnson exchange potential (mBJ),and the compound was found to have a half-metallic nature in all the approximations. The calculated total spin magnetic moment was found to be 5 μ{sub B} in all the approximations used. The second-order elastic constants, Young modulus, shear modulus, Poisson ratio and anisotropic factor have also been calculated. In order to have a complete understanding of BaAmO{sub 3}, the thermodynamic properties were studied in the pressure range of 0 to 40 GPa and the temperature range extending from 0 to 600 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Influence of Cation Size on the Electronic and Magnetic Structure of M CoO{sub 3} (M = Bi, La) from Ab Initio Calculations

Using the first-principle DFT method and LSDA+ U calculations, we have performed a detailed investigation on the structural and magnetic ground states of strongly correlated M CoO{sub 3} (M= Bi, La) perovskites. Magneticphase stabilities, structural behaviors and electronic properties of both materials have been investigated. LSDA+ U calculations show that the antiferromagnetic (AFM)-C phase in the tetragonal La/BiCoO{sub 3} is energetically more favorable than the other configurations, and both rhombohedral materials are nonmagnetic. All structural data of tetragonal BiCoO{sub 3} and rhombohedral LaCoO{sub 3} compounds are found in excellent agreement with the experiment for U{sub eff}= 6 eV. We have predicted also band gaps and magnetic moments with a good accuracy via the band structure calculations. From the total and partial densities of states, we have shown the important role of O p Co d and Bi/La s-O p hybridizations in both systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Qualitative analysis of magnetic waveguides for two-dimensional Dirac fermions

We focus on the confinement of two-dimensional Dirac fermions within the waveguides created by realistic magnetic fields. Understanding of their band structure is of our main concern. We provide easily applicable criteria, mostly depending only on the asymptotic behavior of the magnetic field, that can guarantee existence or absence of the energy bands and provide valuable insight into the systems where analytical solution is impossible. The general results are employed in specific systems where the waveguide is created by the magnetic field of a set of electric wires or magnetized strips.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2012

SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6} - two new Ae-Zn-Sn polar intermetallic compounds (Ae: alkaline earth metal)

SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}, two closely related new polar intermetallic compounds, were obtained by high temperature reactions of the elements. Their crystal structures were determined with single crystal XRD methods, and their electronic structures were analyzed by means of DFT calculations. The Zn-Sn structure part of SrZn{sub 2}Sn{sub 2} comprises (anti-)PbO-like {l_brace}ZnSn{sub 4/4}{r_brace} and {l_brace}SnZn{sub 4/4}{r_brace} layers. Ca{sub 2}Zn{sub 3}Sn{sub 6} shows similar {l_brace}ZnSn{sub 4/4}{r_brace} layers and {l_brace}Sn{sub 4}Zn{r_brace} slabs constructed of a covalently bonded Sn scaffold capped by Zn atoms. For both phases, the two types of layers are alternatingly stacked and interconnected via Zn-Sn bonds. SrZn{sub 2}Sn{sub 2} adopts the SrPd{sub 2}Bi{sub 2} structure type, and Ca{sub 2}Zn{sub 3}Sn{sub 6} is isotypic to the R{sub 2}Zn{sub 3}Ge{sub 6} compounds (R=La, Ce, Pr, Nd). Band structure calculations indicate that both SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6} are metallic. Analyses of the chemical bonding with the electron localization function (ELF) show lone pair like basins at Sn atoms and Zn-Sn bonding interactions between the layers for both title phases, and covalent Sn-Sn bonding within the {l_brace}Sn{sub 4}Zn{r_brace} layers of Ca{sub 2}Zn{sub 3}Sn{sub 6}. - Graphical abstract: Crystal structures of the new Ae-Zn-Sn polar intermetallic phases SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}. Highlights: Black-Right-Pointing-Pointer New polar intermetallic phases SrZn{sub 2}Sn{sub 2} and Ca{sub 2}Zn{sub 3}Sn{sub 6}. Black-Right-Pointing-Pointer Obtained by high temperature reactions of the elements. Black-Right-Pointing-Pointer Single crystal XRD structure determination and DFT electronic structure calculations. Black-Right-Pointing-Pointer Closely related crystal and electronic structures. Black-Right-Pointing-Pointer Metallic conductivity coexisting with lone pairs and covalent bonding features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Linearity for Ca2+-Doped CeBr3 Scintillating Materials

The National Security Technologies, LLC, Remote Sensing Laboratory (RSL) developed an aliovalently calcium-doped cerium tribromide (CeBr3:Ca2+) crystal with a FWHM resolution of 3.2% at the 137Cs 662 keV gamma energy. RSL completed a crystal assessment and Sandia National Laboratories calculated the predictive performance and physical characteristics using proven density functional theory (DFT) formalism. Results are reported for the work done to map the detector performance, characteristics, calcium doping concentration, and crystal strength. Preliminary scintillation measurements for this aliovalently calcium-doped CeBr3 scintillator exhibit a slight blue shift in fluorescence emission at 371 nm excitation for CeBr3. The structural, electronic, and optical properties of CeBr3 crystals were investigated using the DFT within generalized gradient approximation. The calculated lattice parameters are in good agreement with the experimental data. The energy band structures and density of states were obtained. The optical properties of CeBr3, including the dielectric function of photons per unit energy, were calculated. Specifically, we report excellent linearity with the aliovalent CeBr3:Ca2+ crystal. Proportionality of light yield is one area of performance in which Ce-doped and Ce-based lanthanide halides excel. Maintaining proportionality is the key to producing a strong, high-performance scintillator. Relative light yield proportionality was measured for both doped and undoped samples of CeBr3 to ensure no loss in performance was incurred by doping. The light output and proportionality, however, appear to be similar to CeBr3. There was a reduced yield at low energy. Relative light yield proportionality measurements suggest that dopants do not significantly affect proportionality at higher energies. RSL completed additional testing and evaluation of the new crystal as well as the assessment of benchmarking spectroscopy. Results, which present energy resolution as a function of energy, are summarized. Typical spectroscopy results using a 137Cs radiation source are shown for our crystallites with diameters <1 cm. We obtain 3.2% before packing the crystallite in a sealed detector container and 4.5% for the packaged crystallite. More spectra were obtained for 241Am, 60Co, 228Th, and background to exemplify CeBr3:Ca2+ over a broader energy range.

aliovalent substitution↗
DOE OSTI2013

Crystallographic, electronic, thermal, and magnetic properties of single-crystal SrCo 2 As 2

In tetragonal SrCo 2 As 2 single crystals, inelastic neutron scattering measurements demonstrated that strong stripe-type antiferromagnetic (AFM) correlations occur at a temperature T = 5 K [W. Jayasekara et al., arXiv:1306.5174] that are the same as in the isostructural AFe 2 As 2 (A = Ca, Sr, Ba) parent compounds of high-T c superconductors. This surprising discovery suggests that SrCo 2 As 2 may also be a good parent compound for high-T c superconductivity. Here, structural and thermal expansion, electrical resistivity ρ, angle-resolved photoemission spectroscopy (ARPES), heat capacity C p , magnetic susceptibility χ, 75 As NMR and neutron diffraction measurements of SrCo 2 As 2 crystals are reported together with LDA band structure calculations that shed further light on this fascinating material. The c-axis thermal expansion coefficient α c is negative from 7 to 300 K, whereas α a is positive over this T range. The ρ(T) shows metallic character. The ARPES measurements and band theory confirm the metallic character and in addition show the presence of a flat band near the Fermi energy E F . The band calculations exhibit an extremely sharp peak in the density of states D(E F ) arising from a flat d x 2 -y 2 band. A comparison of the Sommerfeld coefficient of the electronic specific heat with χ(T → 0) suggests the presence of strong ferromagnetic itinerant spin correlations which on the basis of the Stoner criterion predicts that SrCo 2 As 2 should be an itinerant ferromagnet, in conflict with the magnetization data. The χ(T) does have a large magnitude, but also exhibits a broad maximum at 115 K suggestive of dynamic short-range AFM spin correlations, in agreement with the neutron scattering data. The measurements show no evidence for any type of phase transition between 1.3 and 300 K and we propose that metallic SrCo 2 As 2 has a gapless quantum spin-liquid ground state.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Electronic structure effects in spatiotemporally resolved photoemission interferograms of copper surfaces

Attosecond photoelectron spectroscopy allows the observation of electronic processes on attosecond time scales (1as=10 -18 s), as has been demonstrated in proof-of-principle experiments that probe the electronic dynamics in isolated atoms with unprecedented accuracy. Its recent expansion to solid targets is starting to allow the distinction of ultrafast collective electronic processes in matter with added spatial resolution, probing the electronic band structure and dielectric response in nanoplasmonically enhanced light-induced processes of relevance for photocatalysis, optoelectronics, and light harvesting. Furthermore, based on a quantum-mechanical model for photoelectron emission by an attosecond pulse train from the d band of a Cu(111) surface into a delayed assisting laser pulse, we calculate two-pathway two-photon interferograms as functions of the photoelectron energy and pulse delay. Our results scrutinize the dependence of observable photoelectron interferograms on the electronic structure of and electron transport in the substrate and agree well with experimental spectra and semiclassical Monte Carlo simulations of Lucchini et al. [Phys. Rev. Lett. 115, 137401 (2015)].

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1998

Doping Scheme of Semiconducting Atomic Chains

Atomic chains, precise structures of atomic scale created on an atomically regulated substrate surface, are candidates for future electronics. A doping scheme for intrinsic semiconducting Mg chains is considered. In order to suppress the unwanted Anderson localization and minimize the deformation of the original band shape, atomic modulation doping is considered, which is to place dopant atoms beside the chain periodically. Group I atoms are donors, and group VI or VII atoms are acceptors. As long as the lattice constant is long so that the s-p band crossing has not occurred, whether dopant atoms behave as donors or acceptors is closely related to the energy level alignment of isolated atomic levels. Band structures are calculated for Br-doped (p-type) and Cs-doped (n-type) Mg chains using the tight-binding theory with universal parameters, and it is shown that the band deformation is minimized and only the Fermi energy position is modified.

Toshishige, Yamada↗
DOE OSTI2023

Crystal growth and magnetic structure of ternary silicide Eu Pd 3 Si 2

The hexagonal CaCu 5 –type structure (P6/mmm) is the prototype for more than 100 ternary borides, gallides, and silicides, with general stoichiometry of RTM 3 X 2 (R=lanthanide/alkaline earth; TM=transition metal; X=B, Ga, Si, Ge). Here we report the synthesis, crystal structure, and bulk magnetic properties of polycrystalline and single crystal samples of EuPd 3 Si 2 and its nonmagnetic analog SrPd 3 Si 2 . Both compounds crystallize in the orthorhombic space group symmetry Imma (no. 74, Z = 2, oI12) displaying pseudohexagonal symmetry. Ferromagnetic (FM) order of Eu 2+ at T C1 =78K and a spin-reorientation transition at T C2 =5K appear as distinctive features in bulk magnetization, specific heat, and resistivity/resistance measurements. Neutron powder diffraction measurements on EuPd 3 Si 2 confirm FM order of the Eu 2+ spins below T C1 , with the spins aligned along the a axis below T C2 . Electronic band structure calculations corroborate the crystal structure and the FM state for EuPd 3 Si 2 , with a Pd d–band polarization in the same direction as the Eu 4f polarization, enhancing the observed spin moment.

36 MATERIALS SCIENCE↗
DOE OSTI2012

First-principles study of the structural and elastic properties of Cr{sub 2}AlX (X=N, C) compounds

The structural, electronic and elastic properties of Cr{sub 2}AlX, with X=N, C, have been investigated at the density functional theory level by applying a plane-wave pseudopotential approach. The band structure and density of states reveal the metallic features of Cr{sub 2}AlX. The total and projected density of states indicate that the bonding is achieved through a hybridization of Cr 3d states with Al and X-atom p states. The Cr 3d-X2p bonds are lower in energy and are stiffer than Cr 3d-Al 3p bonds. The charge density distributions indicate that there exist soft Cr-Al and relatively strong Cr-X covalent bonds, which might be responsible for their hardness. The elastic constants were obtained in the pressure range 0-100 GPa, and satisfy the stability conditions for hexagonal crystal, which indicates that these two compounds are stable in the pressure regime studied. By analyzing bulk modulus to shear modulus ratio and Cauchy pressure, Cr{sub 2}AlC is predicted to be brittleness and Cr{sub 2}AlN is ductile. The Debye temperature was obtained from the average sound velocity. - Graphical abstract: The heterogeneity of chemical bonds in Cr{sub 2}AlX (X=N, C) is observed: soft Cr-Al and relatively strong Cr-X covalent bonds might be contributed to their hardness. Highlights: Black-Right-Pointing-Pointer Cr 3d-X2p (X=N, C) bonds are lower in energy and stiffer than Cr 3d-Al 3p bonds for Cr{sub 2}AlX. Black-Right-Pointing-Pointer The hardness of Cr{sub 2}AlX might be ascribed to soft Cr-Al and relatively strong Cr-X covalent bonds. Black-Right-Pointing-Pointer The predicted brittleness of Cr{sub 2}AlC and ductility of Cr{sub 2}AlN originated from their novel structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Self-equilibrated backstresses induce compensation between hardening and softening: Micromechanical and microstructural features

For crystal plasticity formulation neglecting the strain gradients at the dislocation scale, backstresses are necessary to satisfy the mesoscopic stress equilibrium and strain compatibility requirements. Backstresses in a material point and those between neighboring points are treated separately. Physically backstresses can dynamically induce either hardening or softening effects to adjust the dislocation hardening of slip systems, whereas the sum of the stresses resulting in backstresses in the representative volume element (RVE) is zero. Backstress hardening suppresses certain slip activities, while backstress softening triggers excess dislocations. A two-phase brass is studied. Backstresses make the hard phase deform smaller and the soft phase deform more than those without employing backstresses in a model. In the former, more homogeneous lattice strain and higher yield stress are obtained. Backstress has limited effects on the evolution of the critical resolved shear stress and crystallographic texture. Furthermore, it is a major cause of the banded structures featuring sharp crystallographic contrasts which are not parallel to the slip planes. Tests indicate that backstress induces a serrated behavior at the early stages of deformation and induces the geometrically necessary bands (GNBs), which are parallel to the macroscopic axes.

36 MATERIALS SCIENCE↗