Publications

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Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Herein we report a design strategy to encode multilayer complexity in a family of heterometallic rare-earth metal–organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near-infrared, NIR) properties, with concomitant multi-emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult-to-counterfeit optical tags.

Physical vapor deposition of organic explosives enables growth of polycrystalline films with a unique microstructure and morphology compared to the bulk material. This study demonstrates the ability to control crystal orientation and porosity in pentaerythritol tetranitrate films by varying the interfacial energy between the substrate and the vapor-deposited explosive. Variation in density, porosity, surface roughness, and optical properties is achieved in the explosive film, with significant implications for initiation sensitivity and detonation performance of the explosive material. Various surface science techniques, including angle-resolved X-ray photoelectron spectroscopy and multiliquid contact angle analysis, are utilized to characterize interfacial characteristics between the substrate and explosive film. Optical microscopy and scanning electron microscopy of pentaerythritol tetranitrate surfaces and fracture cross sections illustrate the difference in morphology evolution and the microstructure achieved through surface energy modification. X-ray diffraction studies with the Tilt-A-Whirl three-dimensional pole figure rendering and texture analysis software suite reveal that high surface energy substrates result in a preferred (110) out-of-plane orientation of pentaerythritol tetranitrate crystallites and denser films. Low surface energy substrates create more randomly textured pentaerythritol tetranitrate and lead to nanoscale porosity and lower density films. This work furthers the scientific basis for interfacial engineering of polycrystalline organic explosive films through control of surface energy, enabling future study of dynamic and reactive detonative phenomena at the microscale. Results of this study also have potential applications to active pharmaceutical ingredients, stimuli-responsive polymer films, organic thin film transistors, and other areas.

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Germanium–antimony–telluride has emerged as a nonvolatile phase change memory material due to the large resistivity contrast between amorphous and crystalline states, rapid crystallization, and cyclic endurance. Improving thermal phase stability, however, has necessitated further alloying with optional addition of a quaternary species (e.g., C). In this work, the thermal transport implications of this additional species are investigated using frequency-domain thermoreflectance in combination with structural characterization derived from x-ray diffraction and Raman spectroscopy. Specifically, the room temperature thermal conductivity and heat capacity of (Ge₂Sb₂Te₅)_1–xC_x are reported as a function of carbon concentration (x ≤ 0:12) and anneal temperature (T ≤ 350 °C) with results assessed in reference to the measured phase, structure, and electronic resistivity. Phase stability imparted by the carbon comes with comparatively low thermal penalty as materials exhibiting similar levels of crystallinity have comparable thermal conductivity despite the addition of carbon. The additional thermal stability provided by the carbon does, however, necessitate higher anneal temperatures to achieve similar levels of structural order.

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High temperature operation of molten sodium batteries impacts cost, reliability, and lifetime, and has limited the widespread adoption of these grid-scale energy storage technologies. Poor charge transfer and high interfacial resistance between molten sodium and solid-state electrolytes, however, prevents the operation of molten sodium batteries at low temperatures. Here, in situ formation of tin-based chaperone phases on solid state NaSICON ion conductor surfaces is shown in this work to greatly improve charge transfer and lower interfacial resistance in sodium symmetric cells operated at 110 °C at current densities up to an aggressive 50 mA cm-2. It is shown that static wetting testing, as measured by the contact angle of molten sodium on NaSICON, does not accurately predict battery performance due to the dynamic formation of a chaperone NaSn phase during cycling. This work demonstrates the promise of sodium intermetallic-forming coatings for the advancement of low temperature molten sodium batteries by improved mating of sodium-NaSICON surfaces and reduced interfacial resistance.

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The DOE R&D program under the Spent Fuel Waste Science Technology (SFWST) campaign has made key progress in modeling and experimental approaches towards the characterization of chemical and physical phenomena that could impact the long-term safety assessment of heat-generating nuclear waste disposition in deep clay/shale/argillaceous rock. International collaboration activities such as heater tests and postmortem analysis of samples recovered from these have elucidated key information regarding changes in the engineered barrier system (EBS) material exposed to years of thermal loads. Chemical and structural analyses of sampled bentonite material from such tests has as well as experiments conducted on these are key to the characterization of thermal effects affecting bentonite clay barrier performance and the extent of sacrificial zones in the EBS during the thermal period. Thermal, hydrologic, and chemical data collected from heater tests and laboratory experiments has been used in the development, validation, and calibration of THMC simulators to model near-field coupled processes. This information leads to the development of simulation approaches (e.g., continuum vs. discrete) to tackle issues related to flow and transport at various scales of the host-rock and EBS design concept. Consideration of direct disposal of large capacity dual-purpose canisters (DPCs) as part of the back-end SNF waste disposition strategy has generated interest in improving our understanding of the effects of elevated temperatures on the EBS design. This is particularly important for backfilled repository concepts where temperature plays a key role in the EBS behavior and long-term performance. This report describes multiple R&D efforts on disposal in argillaceous geologic media through development and application of coupled THMC process models, experimental studies on clay/metal/cement barrier and host-rock (argillite) material interactions, molecular dynamic (MD) simulations of water transport during (swelling) clay dehydration, first-principles studies of metaschoepite (UO₂ corrosion product) stability, and advances in thermodynamic plus surface complexation database development. Drift-scale URL experiments provides key data for testing hydrological-chemical (HC) model involving strong couplings of fluid mixing and barrier material chemical interactions. The THM modeling focuses on heater test experiments in argillite rock and gas migration in bentonite as part of international collaboration activities at underground research laboratories (URLs). In addition, field testing at an URL involves in situ analysis of fault slip behavior and fault permeability. Pore-scale modeling of gas bubble migration is also being investigated within the gas migration modeling effort. Interaction experiments on bentonite samples from heater test under ambient and elevated temperatures permit the evaluation of ion exchange, phase stability, and mineral transformation changes that could impact clay swelling. Advances in the development, testing, and implementation of a spent nuclear fuel (SNF) degradation model coupled with canister corrosion focus on the effects of hydrogen gas generation and its integration with Geologic Disposal Safety Assessment (GDSA). GDSA integration activities includes evaluation of groundwater chemistries in shale formations.

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Majorana zero modes (MZMs), fundamental building blocks for realizing topological quantum computers, can appear at the interface between a superconductor and a topological material. One of the experimental signatures that has been widely pursued to confirm the existence of MZMs is the observation of a large, quantized zero-bias conductance peak (ZBCP) in the differential conductance measurements. In this Letter, we report observation of such a large ZBCP in junction structures of normal metal (titanium/gold Ti/Au)-Dirac semimetal (cadmium-arsenide Cd3As2)-conventional superconductor (aluminum Al), with a value close to four times that of the normal state conductance. Our detailed analyses suggest that this large ZBCP is most likely not caused by MZMs. We attribute the ZBCP, instead, to the existence of a supercurrent between two far-separated superconducting Al electrodes, which shows up as a zero-bias peak because of the circuitry and thermal fluctuations of the supercurrent phase, a mechanism conceived by Ivanchenko and Zil'berman more than 50 years ago [Ivanchenko and Zil'berman, JETP 28, 1272 (1969)]. Our results thus call for extreme caution when assigning the origin of a large ZBCP to MZMs in a multiterminal semiconductor or topological insulator/semimetal setup. We thus provide criteria for identifying when the ZBCP is definitely not caused by an MZM. Furthermore, we present several remarkable experimental results of a supercurrent effect occurring over unusually long distances and clean perfect Andreev reflection features.

Residual strain in electrodeposited Li films may affect safety and performance in Li metal battery anodes, so it is important to understand how to detect residual strain in electrodeposited Li and the conditions under which it arises. To explore this Li films, electrodeposited onto Cu metal substrates, were prepared under an applied pressure of either 10 or 1000 kPa and subsequently tested for the presence or absence of residual strain via sin(ψ) analysis. X-ray diffraction (XRD) analysis of Li films required preparation and examination within an inert environment; hence, a Be-dome sample holder was employed during XRD characterization. Results show that the Li film grown under 1000 kPa displayed a detectable presence of in-plane compressive strain (-0.066%), whereas the Li film grown under 10 kPa displayed no detectable in-plane strain. The underlying Cu substrate revealed an in-plane residual strain near zero. Texture analysis via pole figure determination was also performed for both Li and Cu and revealed a mild fiber texture for Li metal and a strong bi-axial texture of the Cu substrate. Experimental details concerning sample preparation, alignment, and analysis of the particularly air-sensitive Li films have also been detailed. This work shows that Li metal exhibits residual strain when electrodeposited under compressive stress and that XRD can be used to quantify that strain.

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A novel metal-organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE-Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV-Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.