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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

β -Technetium: An allotrope with a nonstandard volume-pressure relationship

In this work, we report the synthesis and structure of the second allotrope of technetium, β-Tc. Transformative pathways are accessed at extreme conditions using the laser-heated diamond anvil cell and confirmed with in situ synchrotron x-ray diffraction and Raman spectroscopy. βTc is fully recoverable to ambient conditions, although counter to our DFT calculations predicting a face-centered-cubic lattice, we observe a tetragonal structure (I4/mmm) that exhibits further tetragonal distortion with pressure. β-Tc has an expanded volume relative to the hcp ground state phase, that when doped with nitrogen has an unexpected volume lowering. Such anomalous behavior is possibly indicative of a rare electronic phase transition in a 4d element.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Investigation of the effect of local atomic polarization on field-enhanced ion transport in insulating binary oxides: The case of CeO 2

Over the course of more than 70 years, several theoretical models for electric field-enhanced ion diffusion in crystalline insulators have been presented. However, there is no assessment of the validity of these models despite the urge to have a correct description of field-enhanced ion diffusion in several emerging technologies. Herein, an assessment of five models was carried out by computing the field-dependent migration enthalpy ΔH mig (E) for the oxide ion in CeO 2 . The input to these models is the zero-field and zero-temperature migration pathway and/or the activation barrier obtained from an interatomic potential. ΔH mig (E) from these models was compared with reference values obtained from a set of classical molecular-dynamics simulations in the temperature range of 1000 ≤ T ≤ 1600 K and the electric field range of 0 ≤ E ≤ 30 MV/cm. It is revealed that the most successful theoretical models are those that consider local polarization effects induced in the diffusing ion itself and its vicinity. However, all the models did not account for the effect of the electric field and finite temperature on the local polarization, leading to discrepancies between the predicted and the reference ΔH mig (E), particularly at high fields. By comparing results from a rigid-ion potential and a polarizable core-shell potential, it is concluded that an intraionic polarization degree of freedom in the polarizable potential is an important factor in predicting ΔH mig (E), regardless of the field-enhanced diffusion model particularly for low to moderate field. Finally, future more accurate treatments should consider the field- and temperature-dependent interionic and intraionic local polarization effects.

36 MATERIALS SCIENCE↗
DOE OSTI2022

KCo 2 As 2 : A new portal for the physics of high-purity metals

High-quality single crystals of KCo 2 As 2 with the body-centered tetragonal ThCr 2 Si 2 structure were grown using KAs self flux. Structural, magnetic, thermal, and electrical transport properties were investigated. No clear evidence for any phase transitions was found in the temperature range 2–300 K. The in-plane electrical resistivity ρ versus temperature T is highly unusual, showing a T 4 behavior below 30 K and an anomalous positive curvature up to 300 K, which is different from the linear behavior expected from the Bloch-Grüneisen theory for electron scattering by acoustic phonons. This positive curvature has been previously observed in the in-plane resistivity of high-conductivity layered delafossites such as PdCoO 2 and PtCoO 2 . The in-plane ρ(T → 0) = 0.36μΩ cm of KCo 2 As 2 is exceptionally small for this class of compounds. The material also exhibits a magnetoresistance at low T which attains a value of about 40% at T = 2 K and magnetic field H = 80 kOe. The magnetic susceptibility χ of KCo 2 As 2 is isotropic and about an order of magnitude smaller than the values for the related compounds SrCo 2 As 2 and BaCo 2 As 2 . The χ increases above 100 K, which is found from our first-principles calculations to arise from a sharp peak in the electronic density of states just above the Fermi energy E F . Heat capacity C p (T) data at low T yield an electronic density of states N(E F ) that is about 36% larger than predicted by the first-principles theory. The C p (T) data near room temperature suggest the presence of excited optic vibration modes, which may also be the source of the positive curvature in ρ(T). Angle-resolved photoemission spectroscopy measurements are compared with the theoretical predictions of the band structure and Fermi surfaces. In conclusion, our results show that KCo 2 As 2 provides a new avenue for investigating the physics of high-purity metals.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Understanding the fundamental driver of semiconductor radiation tolerance with experiment and theory

Space is the operating environment of a multitude of systems that our society is heavily reliant on today, however, maintaining operability there necessitates special consideration of the electronic systems' tolerance of space radiation. Electronic systems are critically dependent on the electronic properties of their semiconductor components, which are modified by space radiation with an adverse impact on the space system performance. What innate property allows some semiconductors to sustain little damage while others accumulate defects rapidly with dose is poorly understood, which limits the extent to which radiation tolerance can be implemented as a design criterion. Here, to gain insight into what properties are drivers of semiconductor radiation tolerance, the first step is to generate a dataset of the relative radiation tolerance of a broad sampling of semiconductors. To accomplish this, Rutherford backscatter channeling experiments are used to compare the displaced lattice atom buildup in InAs, InP, GaP, GaN, ZnO, MgO, and Si as a function of stepwise alpha particle dose. With this experimental information on radiation-induced incorporation of interstitial defects in hand, hybrid density functional theory electron densities (and their derived quantities) are calculated and their gradient and Laplacian are evaluated to obtain key fundamental information about the interactions in each material. It is shown that simple, undifferentiated values (which are typically used to describe bond strength) are insufficient to predict radiation tolerance. Instead, the curvature of the electron density at bond critical points provides a measure of radiation tolerance consistent with the experimental results obtained. This curvature and associated forces surrounding bond critical points have the potential to disfavor the localization of displaced lattice atoms at these points, favoring their diffusion toward perfect lattice positions. With this criterion to predict radiation tolerance, simple density functional theory simulations can be conducted on potential new materials to gain insight into how they may operate in demanding high radiation environments.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Disorder-driven localization and electron interactions in Bi x ⁢ TeI thin films

Strong disorder has a crucial effect on the electronic structure in quantum materials by increasing localization, interactions, and modifying the density of states. Bi x TeI films grown at room temperature and 230 K exhibit dramatic magnetotransport effects due to disorder, localization, and electron correlation effects, including a metal-insulator transition at a composition that depends on growth temperature. The increased disorder caused by growth at 230 K causes the conductivity to decrease by several orders of magnitude for several compositions of Bi x TeI. The transition from metal to insulator with decreasing composition x is accompanied by a decrease in the dephasing length, which leads to the disappearance of the weak-antilocalization effect. Electron-electron interactions cause low temperature conductivity corrections on the metallic side and Efros-Shklovskii variable range hopping on the insulating side, effects which are absent in single crystalline Bi x TeI. Finally, the observation of a tunable metal-insulator transition and the associated strong localization and quantum effects in Bi x TeI shows the possibility of tuning spin transport in quantum materials via disorder.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Multiple Lattice Instabilities and Complex Ground State in Cs 2 Ag Bi Br 6

Metal-halide perovskites (MHPs) are attracting considerable interest for optoelectronic applications, with Cs 2 Ag Bi Br 6 one of the main contenders among lead-free systems. Cs 2 Ag Bi Br 6 crystallizes in a nominally double-perovskite structure, but exhibits a soft lattice with large atomic fluctuations characteristic of MHPs. While crucial to understand electron-phonon and phonon-phonon couplings, the spatiotemporal correlations of these fluctuations remain largely unknown. Here, we reveal these correlations using comprehensive neutron and x-ray scattering measurements on Cs 2 Ag Bi Br 6 single crystals, complemented with first-principles simulations augmented with machine-learned neural-network potentials. We report the discovery of an unexpected complex modulated ground-state structure containing several hundred atoms, arising from a soft-phonon instability of the low-temperature tetragonal phase. Further, our experiments and simulations both reveal extensive correlated two-dimensional fluctuations of Br octahedra at finite temperature, arising from soft optic phonons that are strongly broadened by anhamonicity, reflecting very shallow potential wells. These results provide new insights into the atomic structure and fluctuations in MHPs, critical to understand and control their thermal and optoelectronic properties. Published by the American Physical Society 2024

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Evaluation of Equiatomic CrMnFeCoNiCu System and Subsequent Derivation of a Non-Equiatomic MnFeCoNiCu Alloy

Investigation into non-equiatomic high-entropy alloys has grown in recent years due to questions about the role of entropy stabilization in forming single-phase solid solutions. Non-equiatomic alloys have been shown to retain the outstanding mechanical properties exhibited by their equiatomic counterparts and even improve electrical, thermal, and magnetic properties, albeit with relaxed composition bounds. However, much remains to understand the processing–structure–property relationships in all classes of so-called high-entropy alloys (HEAs). Here, we are motivated by the natural phenomena of crystal growth and equilibrium conditions to introduce a method of HEA development where controlled processing conditions determine the most probable and stable composition. This is demonstrated by cooling an equiatomic CrMnFeCoNiCu alloy from the melt steadily over 3 days (cooling rate ~4 °C/h). The result is an alloy containing large Cr-rich precipitates and an almost Cr-free matrix exhibiting compositions within the MnFeCoNiCu system (with trace amounts of Cr). From this juncture, it is argued that the most stable composition is within the CrMnFeCoNiCu system rather than the CrMnFeCoNi system. With further optimization and evaluation, a unique non-equiatomic alloy, Mn 17 Fe 21 Co 24 Ni 24 Cu 14 , is derived. The alloy solidifies and recrystallizes into a single-phase face-centered cubic (FCC) polycrystal. In addition to possible applications where Invar is currently utilized, this alloy can be used in fundamental studies that contrast its behavior with its equiatomic counterpart and shed light on the development of HEAs.

36 MATERIALS SCIENCE↗
NASA NTRS1976

Float-zone processing in a weightless environment

The results were reported of investigations to: (1) test the validity of analyses which set maximum practical diameters for Si crystals that can be processed by the float zone method in a near weightless environment, (2) determine the convective flow patterns induced in a typical float zone, Si melt under conditions perceived to be advantageous to the crystal growth process using flow visualization techniques applied to a dimensionally scaled model of the Si melt, (3) revise the estimates of the economic impact of space produced Si crystal by the float zone method on the U.S. electronics industry, and (4) devise a rational plan for future work related to crystal growth phenomena wherein low gravity conditions available in a space site can be used to maximum benefit to the U.S. electronics industry.

Fowle, A. A.↗
NASA NTRS1979

Anomalous growth of single ice crystals in solution

It is shown that major discrepancies exist between experiments and theory for ice crystal growth from solution. Accurate data, taken in a microgravity environment, approximate analytical models, and exact (probably numerical) models all are needed to advance our understanding of ice crystal growth phenomena. A new approximate semi-empirical theory is presented which predicts that a relatively sharp transition from natural convection control to diffusion control for ice growth in pure water occurs at a subcooling of about 10 C (a reduced temperature difference of about 0.125). No reliable data exist to test this prediction. The theory also predicts qualitatively the growth of ice in NaCl solution in which maxima in the growth rates are observed at various levels of subcooling.

Gill, W. N.↗
NASA NTRS1984

Hot stage and sample cell design for the solidification of transparent materials with and without forced convection

A temperature gradient stage design for optical microscopy is described. Exceptional thermal stability is the major feature. The stage is used to study crystal growth phenomena occurring at the solid-liquid interface. The apparatus is designed to use transparent organic solutions as models for the study of metal-like solidification. The stage provides a controlled thermal environment for unidirectional solidification of low melting temperature materials. Freezing rate is regulated by mechanically sliding in the stage a thin glass cell containing the materials being studied. Two cell assemblies are described. One type is used for convection-free and the other for controlled forced convection studies of the solidification interface.

Kaukler, W. F.↗
NASA NTRS1986

Vapor transport processes of Ge-chalcogenides under normal and reduced gravity conditions

Experimental and theoretical studies of the GeSe-GeI4 system revealed the multicomponent, multireaction nature of this system and the existence of a diffusion boundary layer; they also yielded equations for the prediction of diffusion limited mass transport rates. Vapor transport and crystal growth experiments of the GeSe-GeI4 and GeSe-Xe systems on earth and in a microgravity environment demonstrated the effects of convection and of microgravity on mass flux and crystal morphology. The surface and bulk morphology of GeSe crystals obtained for both systems in microgravity is considerably improved relative to ground-based specimens. Unexpected crystal growth phenomena were observed for the GeSe-Xenon system on recent Shuttle flights.

Wiedemeier, H.↗
NASA NTRS1975

The study of single crystals for space processing and the effect of zero gravity

A study was undertaken to analyze different growth techniques affected by a space environment. Literature on crystal growth from melt, vapor phase and float zone was reviewed and the physical phenomena important for crystal growth in zero-gravity environment was analyzed. Recommendations for potential areas of crystal growth feasible for space missions are presented and a bibliography of articles in the area of crystal growth in general is listed.

Lal, R. B.↗
NASA NTRS2000

Protein Crystals Grow Purer in Space: Physics of Phenomena

This presentation will summarize the quantitative experimental and theoretical results obtained by B.R. Thomas, P.G. Vekilov, D.C. Carter, A.M. Holmes, W.K. Widierow and the Author, the team with expertise in physics, biochemistry, crystallography and engineering. Impurities inhomogeneously trapped by a growing crystal - e.g., producing sectorial structure and/or striations - may induce macroscopic internal stress in it if an impurity molecule has slightly (less than 10%) different shape or volume than the regular one(s) they replace. We tested for the first time plasticity and measured Young modulus E of the triclinic, not cross-linked lysozyme by triple point bending technique. Triclinic lysozyme crystals are purely elastic with E similar or equal to 1/5 (raised dot) 10 (exp 9) partial derivative yn/sq cm. The strength limit, sigma (sub c) similar or equal to 10 (exp -3)E similar or equal to Epsilon (sub c), where sigma (sub c) and epsilon (sub c) are critical stress and strain, respectively. Scaling E and sigma (sub c) with the lattice spacing suggests similar binding stiffness in inorganic and biomolecular crystals. The inhomogeneous internal stress may be resolved in these brittle crystals either by cracking or by creation of misoriented mosaic blocks during, not after growth. If each impurity molecule induces in the lattice elementary strain epsilon (sub 0) similar or equal to 3 (raised dot) 10 (exp -2) (this is maximal elementary strain that can arise at the supersaturation DELTA mu/kT similar or equal to 2 and macroscopic molecular concentration difference between subsequent macrolayers or growth sectors is partial derivativeC similar or equal to 5 (raised dot) 10 (exp -3), the internal strain epsilon similar or equal to epsilon (sub 0) partial derivative C similar or equal to 10 (exp -4). Mosaic misorientation resolving such strain is approximately 30 arcsec. Tenfold increase of impurity concentration may cause cracking. Estimates of stress in an isometric sectorial crystal show that lysozyme crystals can tolerate the stress till the size of 0.5mm. Dissolving mosaic lysozyme crystal shows that the mosaicity, indeed, is absent below that size.

Chernov, Alex A.↗
NASA NTRS1961

Neutralization of Hydroxide Ion in Melt-Grown NaCl Crystals

Many recent studies of solid-state phenomena, particularly in the area of crystal imperfections, have involved the use of melt-grown NaCl single crystals. Quite often trace impurities in these materials have had a prominent effect on these phenomena. Trace amounts of hydroxide ion have been found in melt-grown NaCl crystals. This paper describes a nondestructive method of neutralizing the hydroxide ion in such crystals. Crystals of similar hydroxide content are maintained at an elevated temperature below the melting point of NaCl in a flowing atmosphere containing. dry hydrogen chloride. Heat treatment is continued until an analysis of the test specimens shows no excess hydroxide ion. A colorimetric method previously described4 is used for this analysis.

Otterson, Dumas A.↗
NASA NTRS1985

Simulation of the temperature distribution in crystals grown by Czochralski method

Production of perfect crystals, free of residual strain and dislocations and with prescribed dopant concentration, by the Czochralski method is possible only if the complex, interacting phenomena that affect crystal growth in a Cz-puller are fully understood and quantified. Natural and forced convection in the melt, thermocapillary effect and heat transfer in and around the crystal affect its growth rate, the shape of the crystal-melt interface and the temperature gradients in the crystal. The heat transfer problem in the crystal and between the crystal and all other surfaces present in the crystal pulling apparatus are discussed at length. A simulation and computer algorithm are used, based on the following assumptions: (1) only conduction occurs in the crystal (experimentally determined conductivity as a function of temperature is used), (2) melt temperature and the melt-crystal heat transfer coefficient are available (either as constant values or functions of radial position), (3) pseudo-steady state is achieved with respect to temperature gradients, (4) crystal radius is fixed, and (5) both direct and reflected radiation exchange occurs among all surfaces at various temperatures in the crystal puller enclosure.

Dudokovic, M. P.↗
NASA NTRS1993

Transport phenomena of growth-in-gel zeolite crystallization in microgravity

Secondary nucleation (SN) due to crystal sedimentation has been believed to be one of the major effects that causes smaller sizes of final zeolite crystals. The present investigation indicates that, in a reactor, this gravity-induced SN occurs only within a white opaque column termed the gel portion. Under normal gravity this portion shrinks to the bottom of the hydrothermal reactor, leaving a clear portion of solution at the top, due to depletion of the flocculated gel particles. Solution phase nucleation and crystallization is assumed and a correlation for the shrinkage is therefore derived, which shows good agreement with experimental observations. A non-dimensional parameter is suggested as a criterion for the occurrence of SN. Based on the parameter whether or not microgravity is beneficial to zeolite growth is discussed. Also, the growth mechanism and the transport phenomena in the absence of gravity are discussed.

Zhang, H.↗
NASA NTRS1993

Diffusion on Cu surfaces

Understanding surface diffusion is essential in understanding surface phenomena, such as crystal growth, thin film growth, corrosion, physisorption, and chemisorption. Because of its importance, various experimental and theoretical efforts have been directed to understand this phenomena. The Field Ion Microscope (FIM) has been the major experimental tool for studying surface diffusion. FIM have been employed by various research groups to study surface diffusion of adatoms. Because of limitations of the FIM, such studies are only limited to a few surfaces: nickel, platinum, aluminum, iridium, tungsten, and rhodium. From the theoretical standpoint, various atomistic simulations are performed to study surface diffusion. In most of these calculations the Embedded Atom Method (EAM) along with the molecular static (MS) simulation are utilized. The EAM is a semi-empirical approach for modeling the interatomic interactions. The MS simulation is a technique for minimizing the total energy of a system of particles with respect to the positions of its particles. One of the objectives of this work is to develop the EAM functions for Cu and use them in conjunction with the molecular static (MS) simulation to study diffusion of a Cu atom on a perfect as well as stepped Cu(100) surfaces. This will provide a test of the validity of the EAM functions on Cu(100) surface and near the stepped environments. In particular, we construct a terrace-ledge-kink (TLK) model and calculate the migration energies of an atom on a terrace, near a ledge site, near a kink site, and going over a descending step. We have also calculated formation energies of an atom on the bare surface, a vacancy in the surface, a stepped surface, and a stepped-kink surface. Our results are compared with the available experimental and theoretical results.

Karimi, Majid↗
NASA NTRS2003

Crystal Growth Rate Dispersion: A Predictor of Crystal Quality in Microgravity?

In theory macromolecular crystals grow through a process involving at least two transport phenomena of solute to the crystal surface: diffusion and convection. In absence of standard gravitational forces, the ratio of these two phenomena can change and explain why crystal growth in microgravity is different from that on Earth. Experimental evidence clearly shows, however, that crystal growth of various systems is not equally sensitive to reduction in gravitational forces, leading to quality improvement in microgravity for some crystals but not for others. We hypothesize that the differences in final crystal quality are related to crystal growth rate dispersion. If growth rate dispersion exists on Earth, decreases in microgravity, and coincides with crystal quality improvements then this dispersion is a predictor for crystal quality improvement. In order to test this hypothesis, we will measure growth rate dispersion both in microgravity and on Earth and will correlate the data with previously established data on crystal quality differences for the two environments. We present here the first crystal growth rate measurement data for three proteins (lysozyme, xylose isomerase and human recombinant insulin), collected on Earth, using hardware identical to the hardware to be used in microgravity and show how these data correlate with crystal quality improvements established in microgravity.

Kephart, Richard D.↗