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At least 163 records · Page 9

Selective Antisite Defect Formation in WS 2 Monolayers via Reactive Growth on Dilute W-Au Alloy Substrates

Defects are ubiquitous in 2D materials and can affect the structure and properties of the materials and also introduce new functionalities. Methods to adjust the structure and density of defects during bottom-up synthesis are required to control the growth of 2D materials with tailored optical and electronic properties. In this study, the authors present an Au-assisted chemical vapor deposition approach to selectively form S W and S2 W antisite defects, whereby one or two sulfur atoms substitute for a tungsten atom in WS 2 monolayers. Guided by first-principles calculations, they describe a new method that can maintain tungsten-poor growth conditions relative to sulfur via the low solubility of W atoms in a gold/W alloy, thereby significantly reducing the formation energy of the antisite defects during the growth of WS 2 . The atomic structure and composition of the antisite defects are unambiguously identified by Z-contrast scanning transmission electron microscopy and electron energy-loss spectroscopy, and their total concentration is statistically determined, with levels up to ≈5.0%. Furthermore, scanning tunneling microscopy/spectroscopy measurements and first-principles calculations also verified these antisite defects and revealed the localized defect states in the bandgap of WS 2 monolayers. This bottom-up synthesis method to form antisite defects should apply in the synthesis of other 2D materials.

2D materials↗

Atomic structures of interfacial solute gateways to θ' precipitates in Al-Cu alloys

Many materials employed in critical structural applications depend upon metastable strengthening precipitates that transform or dissolve at elevated temperatures. Herein, aberration-corrected scanning transmission electron microscopy and first-principles calculations are used to accurately determine the atomic structure of the highly mobile, semi-coherent precipitate interfaces that control this process in the classic θ' (Al 2 Cu) precipitate in the Al-Cu system. Semi-coherent {110} interfaces are found to be composed of an array of unexpected misfit dislocations that are arranged in two different structural units. Dislocations accommodate nearly all of the misfit between the Al matrix and strengthening phase. Cu is observed to segregate to the compressed edge of the dislocation cores at specific sites in this interface. First-principles calculations revealed the energetic landscape that facilitates these sites to become entry and exit gateways of Cu atoms in this semi-coherent interface. In conclusion, this investigation reveals critical features within semi-coherent interfaces that determine the thermal stability of precipitation-hardened alloys.

36 MATERIALS SCIENCE↗

High-Pressure Synthesis of Bulk Cobalt Cementite, Co 3 C

Transition metal carbides find use in a wide range of advanced high-resilience applications including high-strength steels, heat shields, and deep-earth drills. However, carbides of the mid-to-late transition metals remain difficult to isolate and characterize on account of their metastability, which precludes the preparation of high-quality bulk single crystal samples using traditional solid-state methods. Herein, we report a combined computational and experimental survey of the cobalt-carbon binary system under high pressures and demonstrate that pressure offers a route toward the bulk synthesis of the metastable cementite-type cobalt carbide, Co 3 C, which under ambient conditions can only be prepared in low-dimensional thin film or nanoparticle forms. First-principles calculations reveal two competitive low-energy stoichiometric phases under ambient pressures - Pnnm-Co 2 C (Fe 2 C-type) and Pnma-Co 3 C (Fe 3 Ctype) - consistent with the known low-dimensional phases that have been studied for their promising magnetic properties. However, the calculated formation enthalpy of Pnma-Co 3 C decreases steadily with the applied pressure, while that of Pnnm-Co 2 C increases. Here, we pursue these results using high-pressure laser-heated synthesis methods coupled with in situ X-ray diffraction and observe the formation of Pnma-Co 3 C above 4.8 GPa. We determine the experimental bulk modulus of Co 3 C to be K o = 237 GPa (K p = 4.0). First-principles calculations of the phonon modes in Co 3 C reveal dynamical instabilities at ambient pressure that are absent under compression. These results offer a promising new route for the synthesis of rare-earth-free magnets.

36 MATERIALS SCIENCE↗

Ultrafast dynamics in the high-symmetry and in the charge density wave phase of 2 H –NbSe 2

Here we investigate carrier and collective mode dynamics in 2H-NbSe 2 using time-resolved optical pump-probe spectroscopy and compare the results with first-principles calculations. Broadband ultrafast reflectivity studies of 2H-NbSe 2 in a wide temperature interval covering the normal, charge density wave (CDW) and superconducting phase were performed. Spectral features observed in the transient reflectivity experiment were associated with specific optical transitions obtained from band structure calculations. Displacive excitation of coherent phonons showed CDW-associated coherent oscillations of the soft phonon mode across the whole spectral range. Temperature evolution of this coherent phonon mode in the low-excitation linear regime shows softening of the mode down to the CDW transition temperature T CDW with subsequent hardening below T CDW . The global fit of the broadband probe data reveals four different relaxation times associated with characteristic electron-electron, electron-phonon, and phonon-phonon relaxation processes. From first-principles calculations of electron-phonon coupling we associate the few picosecond electron-phonon relaxation time $\tau_2$ with a specific group of phonons with frequencies around 20 meV. On the other hand, the anomalously long relaxation time of $\tau_3 \sim$ to 100 ps is associated with anharmonicity-driven phonon-phonon scattering. All relaxation processes result from anomalies near the second order CDW phase transition that are reflected in the temperature dependencies of the characteristic relaxation times and amplitudes of coherent oscillations. At the highest fluences we observe electronic melting of the CDW and disappearance of the mode hardening below T CDW .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Machine learning of 27Al NMR electric field gradient tensors for crystalline structures from DFT

NMR crystallography has emerged as a promising technique for the determination and refinement of atomic coordinates in crystal structures. The crystal structure of compounds containing quadrupolar nuclei, such as 27Al, can be improved by directly comparing solid-state NMR measurements to DFT computations of the electric field gradient (EFG) tensor. The non-negligible computational cost of these first-principles calculations limits the applicability of this method to all but the most well-defined structures. We developed a fast, low-cost machine learning model to predict EFG parameters based on local structural motifs and elemental parameters. We computed 8081 EFG tensors from 1681 27Al crystalline solids using DFT and benchmarked them against 105 experimentally measured 27Al sites. Surprisingly, simple local geometric features dominate the predictive performance of the resulting random-forest model, yielding an R2 value of 0.98 and an RMSE of 0.61 MHz for CQ, the quadrupolar coupling constant. This model accuracy should enable pre-refining future structural assignments before finally validating with first-principles calculations. Such a catalogue of 27Al NMR tensors can serve as a tool for researchers assigning complex NMR spectra influenced by the nuclear electric quadrupole interaction.

Sun, He↗

Effects of cluster expansion on the locations of phase transition boundary as a first step to quantify uncertainty in first principles statistical mechanics framework

Predicting phase diagrams from first principle calculations eliminates the need of tedious experimental trials and errors. Fully automating first principle phase diagram calculations without any sort of human intervention has been a long daunting task and troubling scientific communities for decades. This grand problem remains not fully resolved, largely due to the vastly high-dimensional parameter space associated with density functional theory, cluster expansion, lattice Monte Carlo, and the substantial uncertainty propagating through a set of complex simulations. As a first step to tackle this grand problem, we reported a first demonstration of how sensitive phase boundary locations can be to various cluster expansion fittings and input DFT training data. To the best knowledge of the authors, this study reported the first ever attempt to quantify uncertainty in first principles statistical mechanics framework. In addition, a semi-automated phase transition detection algorithm has been devised in this paper to deal with the associated statistical errors and uncertainties from Monte Carlo method and its predecessor DFT calculations and cluster expansions. This algorithm has been applied in a classical cluster expansion Mg-Cd binary alloy system to detect phase transitions at various locations of phase diagram using different cluster expansions to demonstrate its predictive power and quantify uncertainties. The results suggested that using Chebyshev basis function shifted the transition locations toward the dilute solid solution phase and expanded the phase stability of concentrated ordered phases to wider composition range. The addition of perturbed defect configurations into training data set lowered the order-disorder transition temperature to be away from true transition temperature, suggesting the transition nature is indeed configurational disorder dominated rather than defect assisted. Finally, we found that the weighting has negligible effect on the transition locations, except for the case of using Chebyshev basis function to fit all non-weighted configurations that can be susceptible to Monte Carlo sampling hysteresis.

36 MATERIALS SCIENCE↗

Unveiling the nucleation and growth of Zr oxide precipitates in internally oxidized Nb3Sn superconductors

We report on atomic-scale analyses of nucleation and growth of Zr oxide precipitates and the microstructural evolution of internally oxidized Nb3Sn wires for high-field superconducting magnet applications, utilizing atom probe tomography (APT), transmission electron microscopy (TEM), and first-principles calculations. APT analyses reveal that oxygen and zirconium are already segregated at grain boundaries (GBs) in the unreacted Nb-1Zr-4Ta (at%) alloy prior to forming Nb3Sn through reacting the Nb alloy with Sn and SnO2. After forming Nb3Sn, Zr oxide precipitates nucleate both at the Nb3Sn/Nb heterophase interfaces and in the Nb3Sn grains, driven by the small solubilities of Zr and O in Nb3Sn compared to their value in Nb. A high number density (Nv) of Zr oxide nanoprecipitates is observed in the Nb3Sn layers, ∼10 23 m −3 , with a mean diameter <10 nm for a heat treatment at 625 °C. Quantitative APT and TEM analyses of the Zr oxide precipitates in the reacted Nb3Sn layers elucidate details of the nucleation, growth, and coarsening processes of the Zr oxide precipitates in Nb3Sn. First-principles calculations and classical nucleation theory are employed to study the nucleation of Zr oxide precipitates in Nb3Sn and to estimate the maximum energy barrier and critical radius for nucleation. Our research unveils the kinetic pathways for nucleation and growth of Zr oxide precipitates and the microstructural evolution of Nb3Sn layers, which helps to understand and improve the superconducting properties of internally oxidized Nb3Sn wires for use in high-field superconducting magnets. •We investigated the nucleation and growth of Zr oxide nanoprecipitates in Nb3Sn superconductors for magnet applications.•APT and TEM analyses reveals the nucleation and growth process of Zr oxide precipitates in Nb3Sn layers.•Classical nucleation theory with DFT is employed to describe the nucleation process of Zr oxide precipitates in Nb3Sn.•We find that the interfacial reactions at Nb/Nb3Sn interface play a critical role in the nucleation of Zr oxide precipitates.•Current study provides a pathway to improve the properties of internally oxidized Nb3Sn superconducting wires.

43 PARTICLE ACCELERATORS↗

Evidence for topological semimetallicity in a chain-compound TaSe 3

Among one-dimensional transition-metal trichalcogenides, TaSe 3 is unconventional in many respects. One is its strong topological semimetallicity as predicted by first-principles calculations. We report the experimental investigations of the electronic properties of one-dimensional-like TaSe 3 single crystals. While the b-axis electrical resistivity shows good metallicity with a high residual resistivity ratio greater than 100, an extremely large magnetoresistance is observed reaching ≈7 × 10 3 % at 1.9 K for 14 T. Interestingly, the magnetoresistance follows the Kohler’s rule with nearly quadratic magnetic field dependence, consistent with the electron–hole compensation scenario as confirmed by our Hall conductivity data. Both the longitudinal and Hall conductivities show Shubnikov-de Haas oscillations with two frequencies: F α ≈ 97 T and F β ≈ 186 T. Quantitative analysis indicates that F α results from the two-dimensional-like electron band with the non-trivial Berry phase [1.1π], and Fβ from the hole band with the trivial Berry phase [0(3D) -0.16π(2D)]. Our experimental findings are consistent with the predictions based on first-principles calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic dilution effect and topological phase transitions in (Mn 1- x Pb x )Bi 2 Te 4

We report, as the first intrinsic antiferromagnetic topological insulator, MnBi 2 Te 4 has provided a material platform to realize various emergent phenomena arising from the interplay of magnetism and band topology. Here, by investigating (Mn 1-x Pb x )Bi 2 Te 4 (0 ≤ x ≤ 0.82) single crystals via the x-ray, electrical transport, magnetometry and neutron measurements, chemical analysis, external pressure, and first-principles calculations, we reveal the magnetic dilution effect on the magnetism and band topology in MnBi 2 Te 4 . With increasing x, both lattice parameters a and c expand linearly by around 2%. All samples undergo the paramagnetic to A-type antiferromagnetic transition with the Néel temperature decreasing lineally from 24 K at x = 0 to 2 K at x = 0.82. Our neutron data refinement of the x = 0.37 sample indicates that the ordered moment is 4.3(1)μ B /Mn at 4.85 K and the amount of the Mn Bi antisites is negligible within the error bars. Isothermal magnetization data reveal a slight decrease of the interlayer plane-plane antiferromagnetic exchange interaction and a monotonic decrease of the magnetic anisotropy due to diluting magnetic ions and enlarging the unit cell. For x = 0.37, the application of external pressures enhances the interlayer antiferromagnetic coupling, boosting the Néel temperature at a rate of 1.4 K/GPa and the saturation field at a rate of 1.8 T/GPa. Furthermore, our first-principles calculations reveal that the band inversion in the two end materials, MnBi 2 Te 4 and PbBi 2 Te 4 , occurs at the Γ and Z point, respectively, while two gapless points appear at x = 0.44 and x = 0.66, suggesting possible topological phase transitions with doping.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Colossal switchable photocurrents in topological Janus transition metal dichalcogenides

Nonlinear optical properties, such as bulk photovoltaic effects, possess great potential in energy harvesting, photodetection, rectification, etc. To enable efficient light–current conversion, materials with strong photo-responsivity are highly desirable. In this work, we predict that monolayer Janus transition metal dichalcogenides (JTMDs) in the 1T' phase possess colossal nonlinear photoconductivity owing to their topological band mixing, strong inversion symmetry breaking, and small electronic bandgap. 1T'JTMDs have inverted bandgaps on the order of 10 meV and are exceptionally responsive to light in the terahertz (THz) range. By first-principles calculations, we reveal that 1T' JTMDs possess shift current (SC) conductivity as large as 2300 nm μA V -2 , equivalent to a photo-responsivity of 2800 mA/W. The circular current (CC) conductivity of 1T' JTMDs is as large as ~10 4 nm μA V -2 . These remarkable photo-responsivities indicate that the 1T' JTMDs can serve as efficient photodetectors in the THz range. We also find that external stimuli such as the in-plane strain and out-of-plane electric field can induce topological phase transitions in 1T' JTMDs and that the SC can abruptly flip their directions. The abrupt change of the nonlinear photocurrent can be used to characterize the topological transition and has potential applications in 2D optomechanics and nonlinear optoelectronics.

Chemistry↗

Anisotropic magnetism and electronic structure of trigonal EuAl 2 Ge 2 single crystals

Understanding the interplay between magnetic and electronic degrees of freedom is of profound recent interest in different Eu-based magnetic topological materials. Here, we studied the magnetic and electronic properties of the layered Zintl-phase compound EuAl 2 Ge 2 crystallizing in the trigonal CaAl 2 Si 2 -type structure. We report zero-field neutron diffraction, temperature T - and magnetic-field H-dependent magnetic susceptibility χ(T, H), isothermal magnetization M(T, H), heat capacity C p (T, H), and electrical resistivity ρ(T, H) measurements, together with T-dependent angle-resolved photoemission spectroscopy (ARPES) measurements complemented with first-principle calculations. EuAl 2 Ge 2 undergoes second-order A-type antiferromagnetic (AFM) ordering below T N = 27.5(5) K, with the Eu moments (Eu 2+ , S = 7/2) aligned ferromagnetically in the ab plane while these layers are stacked antiferromagnetically along the c axis. The critical fields at which all moments become parallel to the field are 37.5(5) and 52.5(5) kOe for H ∥ ab and H ∥ c, respectively. The H = 0 magnetic structure consists of trigonal AFM domains associated with ab-plane magnetic anisotropy and a field-induced reorientation of the Eu spins in the domains is also evident at T = 2 K below the critical field H c1 = 2.5(1) kOe. The ρ(T) measurements reveal metallic behavior transforming into a slight resistivity increase on cooling towards T N . A pronounced loss of spin-disorder scattering is observed below T N . The ARPES results show that EuAl 2 Ge 2 is metallic both above and below T N , and the Fermi surface is anisotropic with two hole pockets at the zone center and one small electron pocket at each M point. In the AFM phase, we directly observe folded bands in ARPES due to the doubling of the magnetic unit cell along the c axis with an enhancement of quasiparticle weight due to the complex change in the coupling between the magnetic moments and itinerant electrons on cooling below T N . The observed electronic structure is well reproduced by first-principle calculations, which also predict the presence of nontrivial electronic states near the Fermi level in the AFM phase with Z 2 topological numbers 1;(000)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Impact of Sr-Containing Secondary Phases on Oxide Conductivity in Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) based on a yttria-stabilized zirconia (YSZ) oxide electrolyte produce hydrogen from water with the assistance of excess thermal energy; however, Sr diffusion within the Gd-doped CeO 2 (GDC) barrier layer during processing or operation can lead to the formation of unwanted secondary phases such as SrO and SrZrO 3 . Here, to establish and compare the degree of impact of these phases on SOEC performance, we conduct first-principles calculations to study their bulk oxide conductivities and compare them to that of the YSZ electrolyte. We find that SrO has a low conductivity arising from the poor mobility and low concentration of mobile oxygen vacancies, and its presence in SOECs should therefore be avoided. SrZrO 3 also has a lower oxide conductivity than YSZ; however, this discrepancy is primarily due to lower vacancy concentrations rather than low mobility. We find that sufficient levels of Y-doping on the Zr site can increase oxygen vacancy concentrations in SrZrO 3 to achieve an oxide ionic conductivity on par with that of YSZ, thereby mitigating any potential deleterious effect on transport performance. Energy-dispersive X-ray spectroscopy confirms that Y is the most common minority element present in SrZrO 3 forming near the GDC–YSZ interface, alleviating concerns regarding the impact of SrZrO 3 on device performance. These results from our combined computational–experimental analysis can inform future engineering strategies designed to limit the detrimental effects of Sr-induced secondary phase formation on SOEC performance.

08 HYDROGEN↗

(NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a Vacancy-Ordered Three-Dimensional Tin(II) Perovskite-Derived Semiconductor

Ordering vacancies in hybrid Sn(II) halide semiconductors provides a strategy for preventing uncontrolled oxidation and formation of mobile holes. In this study, we report the structure and optical and electronic properties of (NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , a vacancy-ordered perovskite derivative with three-dimensional inorganic connectivity. The crystal structure resembles that of a Dion–Jacobson layered perovskite derivative, but with [SnI 5 ] square pyramids bridging the layers. UV–vis diffuse reflectance spectroscopy reveals a sharp onset of light absorption at 1.86(1) eV with the photoluminescence emission maximum at 1.90(1) eV. However, the maximum excitation occurs from 3.42 to 3.81 eV (325 to 370 nm), revealing a significant Stokes shift of 1.3 eV. The electronic properties determined from dark and time-resolved microwave conductivity measurements reveal a minimum carrier mobility of 4.3 × 10 –2 cm 2 V –1 s –1 and a maximum carrier density of 5.96 × 10 16 cm –3 , a uniquely low value for a hybrid Sn(II) halide semiconductor. The transport behavior in combination with first-principles calculations of the electronic band structure and dielectric permittivity suggest polaron-mediated electronic transport, yet the photogenerated carriers have a fast and fluence-dependent nonradiative recombination rate, suggestive of localized “defect-like” states at the band edge. The observed photoluminescence is most consistent with single-ion-like behavior of an asymmetric Sn(II) environment. Together, these results suggest that defect ordering presents a strategy for the reduction of mobile charge carriers at equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Multi-Scale Computational Platform for Predictive Modeling of Corrosion in Al-Steel Joints (Final Report)

The research team proposed to develop innovative multi-scale models to predict corrosion and the resulting mechanical performances in aluminum-steel joints. The methods of joining considered are resistance spot welding, self-piercing riveting, and rivet-welding, all suitable for mass production applications. The multi-scale models integrate high throughput first-principle calculations based on density functional theory (DFT), high throughput calculation of phase diagrams (CALPHAD) modeling, and finite element method (FEM) simulations. These models are to be validated through laboratory experiments. Furthermore, the models are available as open source so as to enable scientists and engineers in the community to adapt and contribute to the development and application. The approaches rely on the research team’s extensive experience on the prediction of properties of individual phases at finite temperatures and variable compositions through DFT calculations, and our broad expertise on dissimilar material joining and their corrosion. The proposed computational framework enables high throughput computations for improved predictions of corrosion and the associated mechanical performance in dissimilar material joints, resulting in significant reduction in computational time needed by the current state-of-the-art methods. With the participation of researchers from three universities, an auto manufacturer, two manufacturing technology/equipment suppliers, and a software developer/vendor, the interdisciplinary research team applies the technical development on both phase-based modeling and laboratory experiments into the automobile body joining processes for validation and technology demonstration. The global cost of corrosion was estimated at about 3.4% of the global GDP in 2013. By using available corrosion control practices, it is estimated a saving between 15-35% of the cost of corrosion. In the U.S., more than $276 billion is spent repairing corrosion damage. Prediction of the corrosion and its impact on performance of the dissimilar material joints is critical for reducing the massive number of the current corrosion-based recalls for automobiles. Thus, the project goal is to develop models to enable predictive maintenance and end-of-life planning of multi-metal joints with risk of corrosion under different conditions such as exposure to high temperatures in summer and salt solutions in winter, quantified through its pH. An academia-industry consortium led by the University of Michigan and including Pennsylvania State University, University of Illinois Urbana-Champaign, University of Georgia, General Motors Company, Livermore Software Technology Corporation, and Optimal Process Technologies, LLC. created multi-scale models for prediction of corrosion in aluminum-steel joint structures such of them used in vehicle subassemblies – chassis and transmission systems. Starting from the first principle calculations, the team developed mathematical and data-driven models to predict the metallic components, which are formed during joining of two metals, for example aluminum and steel - a lightweight multilateral system which is currently used in more than 60% car bodies. These models were used for simulating chemical reactions that are happening when the joining metallic components are exposed to high temperatures and different pH values. The team was able to predict how the corrosion installs on the metallic components and how they lead to a sudden failure of components in cars. Newly developed machine learning algorithms combining Science, Technology, Engineering and Math disciplines, advanced finite element simulation and experimental validations have been integrated in a platform for prediction of the corrosion evolution and prediction the failure of joints under mechanical loadings and fatigue. Moreover, based on machine learning and inverse analysis, the team proposed solutions for designing new metallic alloys less susceptible to corrosion when joining multi-material assembles. An average of 4% error compared with experiments was achieved for the most common joints that are used in vehicle subassemblies.

36 MATERIALS SCIENCE↗

Realizing Two-Electron Transfer in Ni(OH) 2 Nanosheets for Energy Storage

The theoretical capacity of a given electrode material is ultimately determined by the number of electrons transferred in each redox center. The design of multi-electron transfer processes could break through the limitation of one–electron transfer and multiply the total capacity, but is difficult to achieve because multiple electron transfer processes are generally thermodynamically and kinetically more complex. In this work, we report the discovery of two-electron transfer in monolayer Ni(OH) 2 nanosheets, which contrasts with the traditional one-electron transfer found in multilayer materials. The first-principles calculations predict that the first oxidation process from Ni 2+ →Ni 3+ occurs easily, whereas the second electron transfer from Ni 3+ →Ni 4+ is strongly hindered in multilayer materials by both the interlayer hydrogen bonds and the domain H structure induced by the Jahn-Teller distortion of the Ni 3+ (t 2g 6 e g 1 ) centered octahedra. In contrast, the second electron transfer can easily occur in monolayers because all H’s are fully exposed. Experimentally, the as-prepared monolayer is found to deliver an exceptional redox capacity of ~ 576 mAh/g, nearly two times the theoretical capacity of one-electron processes. In-situ experiments demonstrate that monolayer Ni(OH) 2 can transfer two electrons and mostly transform to Ni 4+ in the charging process, while bulk Ni(OH) 2 can be partially transformed . Our work reveals a new redox reaction mechanism in atomically thin Ni(OH) 2 nanosheets, and suggests a promising path towards tuning the electron transfer numbers to multiply the capacity of the relevant energy storage materials.

25 ENERGY STORAGE↗

High-frequency phonons drive large phonon-drag thermopower in semiconductors at high carrier density

It has been well established that (i) the thermopower of semiconductors can be enhanced through a phe- nomenon known as the drag effect, and (ii) the drag enhancement involves only low-frequency acoustic phonons and benefits from low electron densities and low temperatures. Using first-principles calculations we show that large drag enhancements to the thermopower are possible at high carrier density even at room temperature and arise from high-frequency acoustic phonons. A fascinating example is cubic boron arsenide (BAs) for which the calculated room temperature drag enhancement of the thermopower exceeds an order of magnitude at a high hole density of 10 21 cm –3 . This remarkable behavior stems from the simultaneously weak phonon-phonon and phonon-hole scattering of the high-frequency phonons in BAs that become drag active at high carrier densities through electron-phonon interactions. Furthermore, this work advances our understanding of coupled electron-phonon nanoscale transport and introduces an unexpected paradigm for achieving large thermopowers.

36 MATERIALS SCIENCE↗

Accelerating Multiscale Materials Modeling with Machine Learning

The focus of this project is to accelerate and transform the workflow of multiscale materials modeling by developing an integrated toolchain seamlessly combining DFT, SNAP, LAMMPS, (shown in Figure 1-1) and a machine-learning (ML) model that will more efficiently extract information from a smaller set of first-principles calculations. Our ML model enables us to accelerate first-principles data generation by interpolating existing high fidelity data, and extend the simulation scale by extrapolating high fidelity data (10 2 atoms) to the mesoscale (10 4 atoms). It encodes the underlying physics of atomic interactions on the microscopic scale by adapting a variety of ML techniques such as deep neural networks (DNNs), and graph neural networks (GNNs). We developed a new surrogate model for density functional theory using deep neural networks. The developed ML surrogate is demonstrated in a workflow to generate accurate band energies, total energies, and density of the 298K and 933K Aluminum systems. Furthermore, the models can be used to predict the quantities of interest for systems with more number of atoms than the training data set. We have demonstrated that the ML model can be used to compute the quantities of interest for systems with 100,000 Al atoms. When compared with 2000 Al system the new surrogate model is as accurate as DFT, but three orders of magnitude faster. We also explored optimal experimental design techniques to choose the training data and novel Graph Neural Networks to train on smaller data sets. These are promising methods that need to be explored in the future.

36 MATERIALS SCIENCE↗

Lattice-Distortion-Enhanced Yield Strength in a Refractory High-Entropy Alloy

Severe distortion is one of the four core effects in single-phase high-entropy alloys (HEAs) and contributes significantly to the yield strength. However, the connection between the atomic-scale lattice distortion and macro-scale mechanical properties through experimental verification has yet to be fully achieved, owing to two critical challenges: 1) the difficulty in the development of homogeneous single-phase solid-solution HEAs and 2) the ambiguity in describing the lattice distortion and related measurements and calculations. Here, a single-phase body-centered-cubic (BCC) refractory HEA, NbTaTiVZr, using thermodynamic modeling coupled with experimental verifications, is developed. Compared to the previously developed single-phase NbTaTiV HEA, the NbTaTiVZr HEA shows a higher yield strength and comparable plasticity. The increase in yield strength is systematically and quantitatively studied in terms of lattice distortion using a theoretical model, first-principles calculations, synchrotron X-ray/neutron diffraction, atom-probe tomography, and scanning transmission electron microscopy techniques. These results demonstrate that severe lattice distortion is a core factor for developing high strengths in refractory HEAs.

36 MATERIALS SCIENCE↗