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At least 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Thermal conductivity of salvaged fused cast alumina used in the glass industry

Fused cast alumina (FCA) has been and continues to be used as a refractory material in energy intensive industries such as glass melting and chemical processing. In-service degradation due to high temperature exposure in harsh environment affects the designed furnace thermal profiles and energy consumption. Phase transformation may occur at the refractory hot face during glass melting altering the properties. Three FCA blocks recovered from industrial furnaces were investigated in this study. The as-received FCA consists primarily of a mixture of alpha (α) and beta (β) alumina that has a thermal conductivity value of 5–6 W/mK. The Hot Disk method was used to obtain thermal conductivity directly on the refractory blocks. At the hot face, a transformation from β to α alumina occurred and was confirmed by an X-ray diffraction study. Thermal conductivity measurements as a function of position also showed a clear transition from β to α alumina at both ends of a complete block with no voids. Thermal conductivity of the α alumina tripled compared to β alumina. This study provides important information of heat transfer and thermal conductivity evolution to refractory manufacturers and users.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Identifying Suitable Front Contacts for High‐Efficiency Cd(Se,Te) Solar Cells on Space‐Qualified Cover Glass

Deployment of photovoltaics in space requires devices that combine high-efficiency, low areal mass, and resilience to harsh environments. Historically, high-efficiency multijunction III–V materials have dominated space power systems; however, their high cost and limited manufacturing throughput motivate the exploration of scalable alternatives. While CdTe-based thin-film photovoltaics offer an attractive option, their performance on non-conventional substrates can suffer from front contact instability under higher-temperature processing. Here, the role of front contact chemistry in limiting cell performance is investigated using CdTe-based devices fabricated on 150 μm thick Ceria-doped space-qualified 0214 Corning glass. A matrix of four transparent conducting oxides (TCOs: CTO, AZO, ITO, IZO) combined with two n-type emitters (MZO, IGO) reveals chemical stability at the front interface—rather than absorber composition alone—governs recombination losses, voltage deficits, and device reproducibility. Chemically stable front contact combinations suppress elemental diffusion and interfacial degradation, resulting in significantly improved carrier lifetimes and junction quality. These insights are validated through record-certified Cd(Se,Te) cell efficiencies of 18.4% under AM1.5G and 16.2% under AM0 illumination on ultra-thin glass. Beyond CdTe, this work provides a general framework for the rational selection of TCO/emitter interfaces in superstrate thin-film photovoltaics, including emerging technologies like metal halide perovskites, while enabling high-efficiency, lightweight photovoltaics for space applications.

14 SOLAR ENERGY↗
DOE OSTI2022

3D printing of void-free glass monoliths: rheological and geometric considerations

Direct ink writing (DIW) is a versatile additive manufacturing technique capable of printing 3D architectures from a broad range of materials. The key advantage of DIW is the ability to spatially control both the architecture and the composition of the printed part, which enables the production of components with previously unachievable combinations of functionalities. One emergent application space for DIW has been in additively manufactured glass optics, where a “green body” is patterned layer-by-layer by extruding a silica-based slurry through a microfluidic nozzle and then thermally consolidated to transparent glass. A critical aspect of the process is ensuring that the printed part is completely free of voids that can occur in the interstitial spaces between the extruded filaments. This outcome is governed by the interplay between ink rheology and strains imposed by the printing process and geometric packing of the filaments. Here, we explore the strain- and rate-dependent deformation events in the DIW process to determine conditions that enable the printing of void-free monoliths without sacrificing shape fidelity. We focus on yield stress fluids consisting of fumed silica nanoparticles dispersed in organic solvents at varied volume fractions to control the rheological properties. We investigate the printability of these ink materials as a function of print process variables and devise the appropriate dimensionless parameters that capture the geometry-dependent and rate-dependent effects on the deformation of the extruded ink. Lastly, we use these scaling arguments to construct a phase diagram for void-free monolith printability.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A method and tool to determine the colorimetric and photobiological properties of light transmitted through glass and other optical materials

Here we describe a framework and provides a computational tool to characterize the color quality and biological potential of light that is transmitted through glass and other optical materials. The IES TM-30 framework and Excel computation tool were adapted to evaluate color quality, with measures from CIE S 026, UL 24480, and the WELL Building Standard v2 added to evaluate biological potential. The user selects a pre-transmittance spectral power distribution (SPD), such as for a CIE D-Series Illuminant, Planckian radiation, electric lamp, or measurement of daylight at a building site. The tool allows a user to populate a database with spectral data for glazing or other optical materials, comprising spectral transmission and the spectral reflectance of both sides. The user creates a unit with one, two, or three panes of glazing or other optical materials, and the tool calculates the composite spectral transmittance accounting for reflections between materials. The tool computes the transmitted SPD, then determines colorimetric and photobiological outputs using the transmitted SPD as the test source. Glass, window, and skylight manufacturers can employ the tool to optimize glazing spectral transmission to achieve intentional colorimetric and photobiological performance with transmitted light. Electric lighting manufacturers, designers, and researchers can use the tool to evaluate the impact of glazing units and other optical materials on the color quality and biological potential of transmitted light.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Synergistic foam stabilization and transport improvement in simulated fractures with polyelectrolyte complex nanoparticles: Microscale observation using laser etched glass micromodels

Inaccessibility to direct pore scale observation in hydrocarbon recovery of tight shale formations poses a great challenge to water-energy nexus initiatives and necessitates the use of high throughput technologies to emulate environmentally friendly processes. Herein, we employ a precise glass micromodel fabrication and visualization method to isolate the supercritical CO 2 bubbles surrounded by CO 2 -water lamella prepared in saline produced water stabilized with molecular complexation of zwitterionic surfactants (ZS) and polyelectrolyte complex nanoparticles (PECNP). The Selective Laser Enhanced Etching (SLE) technique was selected for micromodel simulation of high-pressure flow. Two representative designs, (1) fracture/micro-crack network 28 and (2) fracture/matrix were etched on fused silica glass with a laser printing machine and scCO 2 foam was injected to study the foamability, propagation, stability, and fluid loss properties. The highly monodispersed and uniformly distributed array of scCO 2 bubbles were detected in flow of scCO 2 foam in highly saline brine containing ionic complexes of positively charged PECNPs and ZS, whereas foam flow with the lamella containing ZS in fractures offered a noticeably large and polydisperse array of scCO 2 bubbles. scCO 2 bubble motion and deformation were traced, and local description of foam flow was visually examined. The confined array of scCO 2 bubbles stabilized by ZS in microcracks was affected by bubble growth and coalescence, whereas the super-populated array of monodispersed scC O2 bubbles with lamella containing complexes of PECNP and ZS were able to fill the channels with stable configurations within the timeframe of comparative stability measurements. The ability of complex fluid to prevent the formation damage was evaluated through fluid loss visualization in micromodels. Probing scCO 2 foam transport in homogenous porous media revealed smaller volume leak-off for scCO 2 foam containing PECNP-ZS ionic complexes.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2025

Equilibrium Fe isotope fractionation between olivine, pyroxene, spinel and MORB glass: Implications for mantle partial melting to generate MORBs

Primitive mid-ocean ridge basalts (MORBs) exhibit Fe isotopic compositions heavier than the upper mantle by +0.074 ± 0.028 ‰ for δ 56 Fe. The processes responsible for this isotopic difference remain unclear. Modeling of Fe isotope fractionation during mantle partial melting requires reliable equilibrium Fe isotope fractionation factors between minerals and melts, for which consistent data are still lacking. Here, in this study, we used Nuclear Resonant Inelastic X-ray Scattering (NRIXS) technique to measure Fe force constants for a MORB glass (ALV 519-4-1) and natural mantle minerals (olivine, orthopyroxene, clinopyroxene, and spinel) to determine the equilibrium Fe isotope fractionation factors between them. The force constants determined in this study, in increasing order, are 167 ± 26 N/m for spinel, 175 ± 17 N/m for olivine, 176 ± 20 N/m for MORB glass, 205 ± 26 N/m for clinopyroxene, and 219 ± 36 N/m for orthopyroxene. We evaluated the previously proposed mechanisms for the heavy Fe isotopic composition of MORBs, including (i) mantle partial melting, (ii) mantle lithological heterogeneity, with pyroxenite in the source, (iii) mantle metasomatism by low-degree melts, and (iv) fractional crystallization of olivine from melts. For (i), we used the pMELTS program to simulate adiabatic decompression melting of mantle peridotites, and calculated Fe isotope fractionation based on Fe 3+ –Fe 2+ equilibrium-controlled fractionation, where Fe 3+ forms stronger bonds and is more incompatible than Fe 2+ . At 10 wt% peridotite melting, corresponding to MORB generation, only +0.03 ‰ Fe isotope fractionation between the melt and the original bulk composition (Δ 56 Fe = δ 56 Fe melt - δ 56 Fe 0 ) was produced, insufficient to account for the observed MORB-upper mantle difference. For (ii), melting of pyroxenites yields smaller Fe isotope fractionation than melting of peridotites, making it unlikely the cause for the MORB-upper mantle isotopic difference. For (iii), both the Fe 3+ /ΣFe ratio and the δ 56 Fe of melts increase with the degree of partial melting, indicating that low-degree melts are not isotopically heavy enough to significantly alter the isotopic composition of lithospheric mantle through metasomatism. For (iv), equilibrium isotope fractionation between olivine and melt is near zero. These results suggest that equilibrium Fe isotope fractionation alone cannot explain the MORB isotopic signature, highlighting the potential role of kinetic isotope fractionation. Using a diffusion model, we calculated kinetic Fe and Mg isotope fractionations associated with (iv) olivine crystallization from a melt, and found that the predicted Fe and Mg isotope fractionations were inconsistent with observations in MORBs. Qualitatively, two processes could have induced kinetic Fe isotope fractionation during MORB generation: (a) Fe-Mg interdiffusion between melt and solid during melt migration and (b) reactive melt-rock interactions during melt focusing. However, a quantitative understanding of their role in modifying the melt isotopic composition remains limited and requires further investigation.

Fe isotopes↗
DOE OSTI2021

New interaction potentials for alkaline earth silicate and borate glasses

New interaction potentials were developed for molecular dynamics simulations to study the role of Mg and Ca in modifying the structure and properties of alkaline earth silicates and borates. Competition between the depolymerization of the silica network and the formation of new bonds between oxygen atoms and modifiers leads to the enhancement of the elastic moduli with increasing modifier content in alkaline earth silicate glasses. Compared with calcium silicate, the higher elastic moduli of magnesium silicate result from a higher connectivity of the overall glass network due to the incorporation of fourfold coordinated magnesium and a more rigid connection between oxygen atoms and modifiers. In contrast to the silicates, the effect of modifier on the elastic moduli of alkaline earth borates is dominated by the formation of fourfold coordinated boron (N 4 ). Calcium borate with higher N 4 shows a more rigid network structure and higher elastic moduli.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Achieving 5.9% elastic strain in kilograms of metallic glasses: Nanoscopic strain engineering goes macro

The ideal elastic limit is the upper bound of the achievable strength and elastic strain of solids. However, the elastic strains that bulk materials can sustain are usually below 2%, due to the localization of inelastic deformations at the lattice scale. In this study, we achieved >5% elastic strain in bulk quantity of metallic glass, by exploiting the more uniform and smaller-magnitude atomic-scale lattice strains of martensitic transformation as a loading medium in a bulk metallic nanocomposite. The self-limiting nature of martensitic transformation helps to prevent lattice strain transfer that leads to the localization of deformation and damage. This lattice strain egalitarian strategy enables bulk metallic materials in kilogram-quantity to achieve near-ideal elastic limit. This concept is verified in a model in situ bulk amorphous (TiNiFe)-nanocrystalline (TiNi(Fe)) composite, in which the TiNiFe amorphous matrix exhibits a maximum tensile elastic strain of similar to 5.9%, which approaches its theoretical elastic limit. As a result, the model bulk composite possesses a large recoverable strain of similar to 7%, a maximum tensile strength of above 2 GPa, and a large elastic resilience of similar to 79.4 MJ/m 3 . The recoverable strain and elastic resilience are unmatched by known high strength bulk metallic materials. This design concept opens new opportunities for the development of high-performance bulk materials and elastic strain engineering of the physiochemical properties of glasses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Sol-gel derived silicate-phosphate glass SiO 2 –P 2 O 5 –CaO–TiO 2 : The effect of titanium isopropoxide on porosity and thermomechanical stability

Despite of several decades lasting extensive research of bioactive and bioresorbable glasses the systematic parametrization and determination of the key factors affecting porosity and thermomechanical characteristics still remains challenging. Here, we present silica-phosphate glasses, with the composition 70SiO 2 - 20P 2 O 5 - (10-x)CaO-xTiO 2 (mol%; x = 0, 2.5, 5, and 7.5), prepared by sol -gel method and reinforced by titanium dioxide via titanium isopropoxide (TTIP) incorporation which demonstrated tunable variation of porosity from micro-to macro -region and superb mechanical integrity during the calcination process. The presence of 7.5 mol% TiO 2 promotes dimensional stability up to 1000°C as investigated by thermomechanical analysis. The XRD showed the dominant presence of silicon phosphate [Si(P 2 O 7 )], titanium phosphate [Ti(P 2 O 7 )] and calcium phosphates [β-Ca(P 2 O 6 ) and γ- Ca 2 (P 2 O 7 )]. The effect of TiO 2 doping on the multiscale morphology and porosity was investigated by means of SEM, MIP, μCT, N 2 adsorption and USAXS/SAXS. Increasing TiO 2 content leads to the formation of open porosity up to 70vol% and drives the formation of a refined interconnected macroporosity of 2-30 μm. In contrast, mesoporosity with a dominance of 3-6nm pores decreases in all samples with increasing TiO 2 content. USAXS/SAXS revealed an increase in primary particle size with increasing TiO 2 content which is in good agreement with the nitrogen physisorption analysis showing that microporosity decreases with increasing TiO2 content.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Comparative study on the overall energy performance between photovoltaic and Low-E insulated glass units

In this report a novel semi-transparent building integrated photovoltaic (BIPV) laminate was developed and introduced in this paper. It was produced by cutting standard mono-crystalline silicon solar cells into small strips and then making electrical connections between each strip before laminating the cells between two layers of glass. The overall energy performance and energy saving potential of the BIPV insulated glass unit (IGU) under real world conditions were identified through a side by side comparative study. Compared to the reference IGU, the BIPV IGU had lower solar heat gain coefficient (SHGC) but much higher U-factor. The average HVAC electricity saving of the BIPV IGU was about 10% relative to the reference IGU. Daylighting measurement and analysis were carried out to evaluate the trade-offs associated with the BIPV IGU between daylight, glare, and lighting energy use. The results indicated that the BIPV IGU is better than the reference IGU in reducing discomfort glare. However, if the most conservative viewpoint near the window is used for the assessment, a lower transmittance BIPV IGU is required to bring the overall discomfort levels below the perceptible level. Lastly, the net energy saving potential associated with the novel BIPV IGU was identified based on the power, thermal and daylighting performance. On average, the BIPV IGU saved 16.8% of the total electricity use of the room. Further studies and improvement on the energy conversion efficiency of solar cells, the optimal transmittance as well as the thermal properties would make this technology more energy-efficient and affordable.

14 SOLAR ENERGY↗
DOE OSTI2022

Photothermal Atomic Force Microscopy Coupled with Infrared Spectroscopy (AFM-IR) Analysis of High Extinction Coefficient Materials: A Case Study with Silica and Silicate Glasses

Photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) brings significant value as a spatially resolved surface analysis technique for disordered oxide materials such as glasses, but additional development and fundamental understanding of governing principles is needed to interpret AFM-IR spectra, since the existing theory described for organic materials does not work for materials with high extinction coefficients for infrared (IR) absorption. This paper describes theoretical calculation of a transient temperature profile inside the IR-absorbing material considering IR refraction at the interface as well as IR adsorption and heat transfer inside the sample. Furthermore, this calculation explains the differences in peak positions and amplitudes of AFM-IR spectra from those of specular reflectance and extinction coefficient spectra. It also addresses the information depth of the AFM-IR characterization of bulk materials. AFM-IR applied to silica and silicate glass surfaces has demonstrated novel capability of characterizing subsurface structural changes and surface heterogeneity due to mechanical stresses from physical contacts, as well as chemical alterations manifested in surface layers through aqueous corrosion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Medium-Range Ordering in the Ionic Glass Electrolytes LiPON and LiSiPON

In this work, we provide an in-depth structural characterization of the amorphous ionic glasses LiPON and LiSiPON with high Li content. Based on ab initio molecular dynamics simulations, the structure of these materials is an inverted structure with either isolated polyanion tetrahedra or polyanion dimers in a Li+ matrix. Based on neutron scattering data, this type of inverted structure leads to a significant amount of medium-range ordering in the structure, as demonstrated by two sharp diffraction peaks and a periodic structural oscillation in the density function G(r). While this medium-range ordering is commonly observed in liquids and metallic glasses, it has not previously been observed in oxides. On a local scale, adding N and Si increases the number of anion bridges and polyanion dimer structures, leading to higher ionic conductivity. In the medium-range ordering, the addition of Si leads to more disorder in the polyanion substructure but a significant increase in the ordering of the O substructure. Finally, we demonstrate that this inverted structure with medium-range ordering results in a glassy material that is both mechanically stiff and ductile on the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spin-Glass-like State and Reversible Room-Temperature Magnetocaloric Effect in Double Distorted Perovskites Nd(Cu 3– x Mn x )Mn 4 O 12

The preparation, complex magnetic properties and room-temperature magnetocaloric effect in Nd(Cu 3–x Mn x )Mn 4 O 12 with cation distribution (Nd 3+ ) A (Cu 3–x 2+x Mn x 3+ ) A' (Mn 1+x 3+ Mn 3–x 4+ ) B O 12 2– (x = 1 and 1.5) have been reported. Both compounds show a sharp paramagnetic-ferromagnetic (FM) transition at T C of 300 and 280 K, respectively. The substitution of Cu by Mn at the A' site induces the emergence of a spin glass state below ≈63 K for x = 1 and ≈72 K for x = 1.5 compound. Another antiferromagnetic-like magnetic transition is also observed in both compounds at 23 and 28 K, respectively, which is discussed as the antiferromagnetic coupling between Nd 3+ at the A' site and (Mn 3+ /Mn 4+ ) at the B site. These two compounds exhibit room-temperature magnetocaloric effect. For a small field of 2 T, the maximum magnetic entropy changes –ΔS M are 1.5 J/kg K at 300 K and 1.4 J/kg K at 280 K, respectively. Furthermore, the –ΔS M (T) curves show an asymmetric distribution, resulting in high refrigerant capacity values for both compounds. We further demonstrate the distinct roles of the A'- and B-site spins on the magnetic properties and the origin of the spin-glass-like state in double distorted perovskites Ln(Cu 3–x Mn x )Mn 4 O 12 family of compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Scaling of Shear Rheology of Concentrated Charged Colloidal Suspensions across Glass Transition

Electrostatic interparticle interactions are a key component in controlling and designing rheological characteristics of concentrated charged colloidal suspensions. Herein, we investigate electroviscous effects on shear rheology using highly charged silica particles. By fixing the volume fraction but varying the salinity, the system undergoes a glass transition as evidenced by the evolution of the yield stress and zero-shear viscosity. We show that the steady shear viscosities obey a critical scaling relation that scales the flow curves into a super- and a sub-critical branch with glass transition salinity serving as the bifurcation point; we also demonstrate an isoviscosity scaling that collapses all isoviscosity lines into a single master curve that exhibits no singularity. Based on each scaling relation, in conjunction with common modeling equations, the quantitative relationships between the shear viscosity, stress, and salinity are established. This study demonstrates a new framework to model the steady shear rheology of concentrated charged colloids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Medium-Range Structural Order as the Driver of Activated Dynamics and Complexity Reduction in Glass-Forming Liquids

Here, we analyze in depth the Elastically Collective Nonlinear Langevin Equation theory of activated dynamics in metastable liquids to establish that the predicted inter-relationships between the alpha relaxation time, local cage and collective elastic barriers, dynamic localization length, and shear modulus are causally related within the theory to the medium range order (MRO) static correlation length. The latter grows exponentially with density for metastable hard sphere fluids and as a nonuniversal inverse power law with temperature for supercooled liquids under isobaric conditions. The physical origin of predicted connections between the alpha time and other metrics of cage order and the thermodynamic inverse dimensionless compressibility is fully established. It is discovered that although kinetic constraints from the real space first coordination shell are important for the alpha time, they are of secondary importance compared to the consequences of the more universal MRO correlations in both the modestly and deeply metastable regimes. This understanding sheds new light on the theoretical basis for, and prior successes of, the predictive mapping of chemically complex thermal liquids to effective hard sphere fluids based on matching their dimensionless compressibilities, a scheme we call “complexity reduction”. In essence, the latter is equivalent to the physical requirement that the thermal liquid MRO correlation equals that of its effective hard sphere analog. The mapping alone is shown to provide a remarkable level of quantitative predictive power for the glass transition temperature T g of 21 molecular and polymer liquids. Predictions for the chemically specific absolute magnitude and growth with cooling of the MRO correlation length are obtained and lie in the window of 2–6 nm at T g . Dynamic heterogeneity, elastic facilitation, and beyond pair structure issues are briefly discussed. Future opportunities to theoretically analyze the equilibrated deep glass regime are outlined.

cancer↗
DOE OSTI2024

Theory of Ion-Mediated Segmental Localization, Activated Structural Relaxation, and the Glass Transition in Polymerized Ionic Liquids

Here we combine polymer integral equation theory for structural correlations with a force-level theory for activated segmental relaxation to construct a microscopic theory for how ions modify the onset of segmental localization, the polymer alpha relaxation time, and glass transition temperature, T g , in dry polymerized ionic liquids (PolyILs). Our most important findings concerning the behavior of T g are (i) a weak dependence on anion–cation Coulomb attraction strength due to strong decoupling of ion and segmental dynamics, (ii) strong reduction with increasing mobile ion size due to both plasticization effects and weakening of ion-modified monomer caging, and (iii) increase with backbone rigidity and intrachain dynamic cooperativity. We quantitatively estimate T g variations as ion size and polymer static and dynamic rigidity are widely varied. The experimental data of 19 PolyILs are organized into a specific pattern consistent with the theoretical predictions with glass transition temperatures varying over a very wide range (~250 K) as observed experimentally. Based on the theoretical results, suggestions are made concerning the search for high conductivity Li- or Na-based PolyILs based on further lowering of T g via new polymer synthesis. Calculations of the alpha time as a function of packing fraction reveal the dynamic fragility increases for larger mobile ions, a more flexible backbone, and/or a smaller degree of intrachain dynamic cooperativity, as a consequence of the increasing importance of collective elasticity in determining the activation barrier. An analysis of transient segmental localization and a crossover to activated dynamics reveals similar, but not identical, trends as predicted at the laboratory vitrification timescale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterization of the Interfacial Orientation and Molecular Conformation in a Glass-Forming Organic Semiconductor

The ability to control structure in molecular glasses has enabled them to play a key role in modern technology; in particular, they are ubiquitous in organic light-emitting diodes. While the interplay between bulk structure and optoelectronic properties has been extensively investigated, few studies have examined molecular orientation near buried interfaces despite its critical role in emergent functionality. Direct, quantitative measurements of buried molecular orientation are inherently challenging, and many methods are insensitive to orientation in amorphous soft matter or lack the necessary spatial resolution. To overcome these challenges, we use polarized resonant soft X-ray reflectivity (pRSoXR) to measure nanometer-resolved, molecular orientation depth profiles of vapor-deposited thin films of an organic semiconductor Tris(4-carbazoyl-9-ylphenyl)amine (TCTA). Our depth profiling approach characterizes the vertical distribution of molecular orientation and reveals that molecules near the inorganic substrate and free surface have a different, nearly isotropic orientation compared to those of the anisotropic bulk. Comparison of pRSoXR results with near-edge X-ray absorption fine structure spectroscopy and optical spectroscopies reveals that TCTA molecules away from the interfaces are predominantly planar, which may contribute to their attractive charge transport qualities. Buried interfaces are further investigated in a TCTA bilayer (each layer deposited under separate conditions resulting in different orientations) in which we find a narrow interface between orientationally distinct layers extending across ≈1 nm. Coupling this result with molecular dynamics simulations provides additional insight into the formation of interfacial structure. This study characterizes the local molecular orientation at various types of buried interfaces in vapor-deposited glasses and provides a foundation for future studies to develop critical structure–function relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High frequency atomic tunneling yields ultralow and glass-like thermal conductivity in chalcogenide single crystals

Crystalline solids exhibiting glass-like thermal conductivity have attracted substantial attention both for fundamental interest and applications such as thermoelectrics. In most crystals, the competition of phonon scattering by anharmonic interactions and crystalline imperfections leads to a non-monotonic trend of thermal conductivity with temperature. Defect-free crystals that exhibit the glassy trend of low thermal conductivity with a monotonic increase with temperature are desirable because they are intrinsically thermally insulating while retaining useful properties of perfect crystals. However, this behavior is rare, and its microscopic origin remains unclear. Here, we report the observation of ultralow and glass-like thermal conductivity in a hexagonal perovskite chalcogenide single crystal, BaTiS 3 , despite its highly symmetric and simple primitive cell. Elastic and inelastic scattering measurements reveal the quantum mechanical origin of this unusual trend. A two-level atomic tunneling system exists in a shallow double-well potential of the Ti atom and is of sufficiently high frequency to scatter heat-carrying phonons up to room temperature. While atomic tunneling has been invoked to explain the low-temperature thermal conductivity of solids for decades, our study establishes the presence of sub-THz frequency tunneling systems even in high-quality, electrically insulating single crystals, leading to anomalous transport properties well above cryogenic temperatures.

36 MATERIALS SCIENCE↗