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At least 487 records · Page 27

Microstructural and preliminary optical and microwave characterization of erbium-doped CaMoO 4 thin films

This work explores erbium-doped calcium molybdate (Er:CaMoO4) thin films grown on silicon and yttria stabilized zirconia (YSZ) substrates, as a potential solid state system for C-band (utilizing the ∼1.5 μm Er 3+ 4f–4f transition) quantum emitters for quantum network applications. Through molecular beam epitaxial growth experiments and electron microscopy, X-ray diffraction, and reflection electron diffraction studies, we identify an incorporation limited deposition regime that enables a 1:1 Ca:Mo ratio in the growing film leading to single phase CaMoO 4 formation that can be in situ doped with Er (typically 2–100 ppm). We further show that growth on silicon substrates is single phase but polycrystalline in morphology, while growth on YSZ substrates leads to high-quality epitaxial single crystalline CaMoO 4 films. We perform preliminary optical and microwave characterization on the suspected Y 1 –Z 1 transition of 2 ppm, 200 nm epitaxial Er:CaMoO 4 annealed thin films and extract an optical inhomogeneous linewidth of 9.1(1) GHz, an optical excited state lifetime of 6.7(2) ms, a spectral diffusion-limited homogeneous linewidth of 6.7(4) MHz, and an EPR linewidth of 1.10(2) GHz.

Masiulionis, Ignas [Univ. of Chicago, IL (United S↗

High-resolution characterization of ceramic-metal interface of TiN coating on ferritic-steels for nuclear application

Advanced fuel cladding is critical for fast reactors, offering sufficient thermal conductivity, mechanical and dimensional stability and radiation tolerance of the cladding base material. Additionally, it must provide corrosion resistance and high temperature coolant compatibility on the cladding outer surface, as well as chemical stability on the cladding inner wall against fuel cladding chemical interaction (FCCI). TiN ceramic coating has been considered an effective diffusion barrier for inner and outer cladding-walls for enhanced performance. The TiN-metal interface microstructure and chemistry play a critical role in coating bond strength and integrity under harsh conditions. High-resolution transmission electron microscopy characterization of ceramic-metal interface at atomic resolution in unirradiated, irradiated and thermal cycled conditions were performed. The interface remained intact after irradiation up to 200 dpa or thermal cycling five times up to 550 °C. In conclusion, this work discusses the potential impact of these results on coating performance and design for advanced claddings.

36 - MATERIALS SCIENCE↗

Active interlocking metasurfaces enabled by shape memory alloys

Interlocking metasurfaces (ILMs) are a newly developed joining technology that relies on arrays of interlocking features that transmit force and constrain motion between adjoining bodies in one or more directions. This study explores harnessing the shape memory effect (SME) in Nickel-Titanium shape memory alloys (NiTi SMAs) in structures fabricated using additive manufacturing (AM) to advance the development of active ILMs by creating unit cells that open or close at specific temperatures. The study encompasses designing and fabricating two distinct interlocking array configurations using near-equiatomic NiTi powder and the laser powder bed fusion (L-PBF) AM technique, following a previously developed AM process optimization framework to manufacture defect-free parts. To guide the design process, finite element analysis (FEA) was employed to predict strain values during engage-disengage cycles. The martensitic transformation characteristics of the ILMs were characterized. Thermomechanical testing revealed that the ILMs demonstrate high locking force once engaged, coupled with complete shape recovery and good cyclic stability. Digital image correlation (DIC) was also employed to validate the FEA predictions during the engage-disengage cycles. The results indicate that NiTi SMA-based ILMs can be designed and fabricated into complex shapes using L-PBF. By leveraging the SME, the functionality of an ILM can be improved upon. The combination of computational modeling, additive manufacturing, and thermomechanical and physical property characterization provides a framework for designing future ILMs out of active materials.

Additive manufacturing↗

Design, synthesis and characterization of fused bithiazole- and dithiophene-based low bandgap thienylenevinylene copolymers

The structural rigidity of fused units in the polymer backbone, in addition to the resulting stabilizing effect of the quinoidal structure, and tunable electronic properties have played a key role in promoting highly-ordered π-stacking moieties, exhibiting promising charge carrier mobilities. The electron-deficient thiazole moiety shows high planarity and effective π–π stacking, which leads to the reduction in the energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), and ideally enhances the electron charge mobility. Four heterocycle-based monomers BTzS, BTzSe, DTS, and DTG based on fused bithiazole and dithiophene units incorporated with sulfur, selenium, silicon, and germanium as the bridging atoms were synthesized and characterized. Here, the monomers were copolymerized with the electron-rich alkylated thienylenevinylene (TV) unit to afford copolymers P1–P4. The thermal, optical, and electrochemical properties and crystallinity of the copolymers were thoroughly investigated. Extensive OFET device optimization using different solvents and annealing temperatures resulted in the best charge mobility of 0.09 cm2 V –1 s –1 for the electron-deficient bithiazole BTzS copolymer P1 and 0.36 cm2 V –1 s –1 for the DTS copolymer P3.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small-Angle X-Ray Scattering

The fundamental understanding of nanostructures of liquid electrolytes is expected to enable transformative gains in electrochemical energy storage capacities. However, the solvation structures and molecular dynamics in electrolytes are hard to probe, which limits further performance improvements in macroscopic properties such as ionic conductivity, viscosity, and stability. Small-angle X-ray scattering (SAXS), a non-destructive method for nanostructures characterization in liquids, offers a unique perspective on molecular clusters, anion-cation pairs, solvation sheath, percolating network, aggregates, and domain sizes of electrolytes. Notably, the SAXS method has excellent time-resolution, enabling the study of molecular dynamics by operando characterization. This review focuses on the microscopic understanding of liquid electrolytes by SAXS and operando SAXS. The unique capabilities of X-ray scattering for intra- and inter-molecular relationship and nanostructure characterization of electrolytes are highlighted.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Water content of carbon dioxide at hydrate forming conditions

There is an interest to ensure sub-saturated water content in lines containing carbon dioxide in applications such as enhanced oil recovery and carbon sequestration, to reduce risks of hydrate blockage and corrosion. The water content of carbon dioxide at various temperatures and pressures has been measured in the past, but there is no consistent set of measurements that could be used for carbon dioxide storage and transportation design work. The solubility of water in a carbon dioxide rich gas phase at hydrate forming conditions was measured in this work. Pressures ranged from 12.06 to 29.30 bar along two isotherms, 1 °C and -7 °C, all within the gaseous carbon dioxide and hydrate stability zone. For the first time in these types of measurements, the solid phase was also characterized and confirmed to be carbon dioxide hydrate via X-ray computed tomography, simultaneous with water content measurements of the gas phase. Once carbon dioxide hydrate conversion had reached a maximum value (65% estimated by X-ray computed tomography), the equilibrium water content was measured. Prior to reaching this maximum carbon dioxide hydrate conversion, the water content in carbon dioxide was observed to decrease as liquid water converted to carbon dioxide hydrate. Furthermore, this slow conversion to hydrate, metastability of the hydrate phase, or unexpected phases may be responsible for the large discrepancy between prior data sets for similar carbon dioxide water content measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the Rheo-electric Performance of Aqueous Suspensions of Oxidized Carbon Black

Here, the macroscopic properties of carbon black suspensions are primarily determined by the agglomerate microstructure built of primary aggregates. Conferring colloidal stability in aqueous carbon black suspensions should thus have a drastic impact on their viscosity and conductivity. Carbon black was treated with strong acids following a wet oxidation procedure. An analysis of the resulting particle surface chemistry and electrophoretic mobility was performed in evaluating colloidal stability. Changes in suspension microstructure due to oxidation were observed using small-angle X-ray scattering. Utilizing rheo-electric measurements, the evolution of the viscosity and conductivity of the carbon black suspensions as a function of shear rate and carbon content was thoroughly studied. The carboxyl groups installed on the carbon black surface through oxidation increased the surface charge density and enhanced repulsive interactions. Electrostatic stability inhibited the formation of the large-scale agglomerates in favor of the stable primary aggregates in suspension. While shear thinning, suspension conductivities were found to be weakly dependent on the shear intensity regardless of the carbon content. Most importantly, aqueous carbon black suspensions formulated from electrostatically repulsive primary aggregates displayed a smaller rise in conductivity with carbon content compared to those formulated from attractive agglomerates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An automated system to define the optimal operating settings of cryogenic calorimeters

Cryogenic macro-calorimeters instrumented with NTD thermistors have been developed for several decades. The choice of the optimal bias current is crucial for a proper operation of these detectors, both in terms of energy resolution and stability. In this paper we present a set of automatic measurements and analysis procedures for the characterization and optimization of the working configuration of the NTD thermistors. The presented procedures were developed for CUORE, an array of 988 cryogenic macro-calorimeters instrumented with NTD thermistors that has been taking data since 2017. These procedures made it possible to characterize a large number of detectors in a reliable way. They are suitable enough to be used also in other large arrays of cryogenic detectors, such as CUPID.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Subnanometer Thick Native sp 2 Carbon on Oxidized Diamond Surfaces

Oxygen-terminated diamond has a wide breadth of applications, which include stabilizing near-surface color centers, semiconductor devices, and biological sensors. Despite the vast literature on characterizing functionalization groups on diamond, the chemical composition of the shallowest portion of the surface (<1 nm) is challenging to probe with conventional techniques like XPS and FTIR. In this work, we demonstrate the use of angleresolved XPS to probe the first ten nanometers of both oxygen and hydrogen terminated (100) single-crystalline diamond grown via chemical vapor deposition (CVD). With the use of consistent peakfitting methods, the peak identities and relative peak binding energies were identified for sp 2 carbon, ether, hydroxyl, carbonyl, and C−H groups for both of these diamond surface terminations. For the oxygen-terminated sample, we also quantified the thickness of the sp 2 carbon layer situated on top of the bulk sp 3 diamond bonded carbon to be 0.3 ± 0.1 nm, based on the analysis of the Auger electron spectra and D-parameter calculations. These results indicate that the majority of the oxygen is bonded to the sp 2 carbon layer on the diamond, and not directly to the sp 3 diamond bonded carbon.

Carbon↗

Magneto-optical study of Nb thin films for superconducting qubits

Abstract Among the recognized sources of decoherence in superconducting qubits, the spatial inhomogeneity of the superconducting state and the possible presence of magnetic-flux vortices remain comparatively underexplored. Niobium is commonly used as a structural material in transmon qubits that host Josephson junctions, and excess dissipation anywhere in the transmon can become a bottleneck that limits overall quantum performance. The metal/substrate interfacial layer may simultaneously host pair-breaking loss channels (e.g. two-level systems) and control thermal transport, thereby affecting dissipation and temperature stability. Here, we use quantitative magneto-optical imaging of the magnetic-flux distribution to characterize the homogeneity of the superconducting state and the critical current density, j c , in niobium films fabricated under different sputtering conditions. The imaging reveals distinct flux-penetration regimes, ranging from a nearly ideal Bean critical state to strongly nonuniform thermo-magnetic dendritic avalanches. By fitting the measured magnetic-induction profiles, we extract j c and try to correlate it with film physical properties and with measured qubit internal quality factors. Our results indicate that the Nb/Si interlayer can be a significant contributor to decoherence and should be considered an important factor that must be optimized.

Datta, Amlan [Ames National Laboratory; Iowa State↗

2022 roadmap on low temperature electrochemical CO 2 reduction

Abstract Electrochemical CO 2 reduction (CO 2 R) is an attractive option for storing renewable electricity and for the sustainable production of valuable chemicals and fuels. In this roadmap, we review recent progress in fundamental understanding, catalyst development, and in engineering and scale-up. We discuss the outstanding challenges towards commercialization of electrochemical CO 2 R technology: energy efficiencies, selectivities, low current densities, and stability. We highlight the opportunities in establishing rigorous standards for benchmarking performance, advances in in operando characterization, the discovery of new materials towards high value products, the investigation of phenomena across multiple-length scales and the application of data science towards doing so. We hope that this collective perspective sparks new research activities that ultimately bring us a step closer towards establishing a low- or zero-emission carbon cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonstoichiometric Salt Intercalation as a Means to Stabilize Alkali Doping of 2D Materials

Although doping with alkali atoms is a powerful technique for introducing charge carriers into physical systems, the resulting charge-transfer systems are generally not air stable. Here, in this paper, we describe computationally a strategy towards increasing the stability of alkali-doped materials that employs stoichiometrically unbalanced salt crystals with excess cations (which could be deposited during, e.g., in situ gating) to achieve doping levels similar to those attained by pure alkali metal doping. The crystalline interior of the salt crystal acts as a template to stabilize the excess dopant atoms against oxidation and deintercalation, which otherwise would be highly favorable. We characterize this doping method for graphene, NbSe 2 , and Bi 2 Se 3 and its effect on direct-to-indirect band gap transitions, 2D superconductivity, and thermoelectric performance. Salt intercalation should be generally applicable to systems which can accommodate this “ionic crystal” doping (and particularly favorable when geometrical packing constraints favor nonstoichiometry).

2-dimensional systems↗

TTDAQ: A Continuous Flow, Timing and Trigger DAQ System

Final Scientific/Technical Report for DOE Award DE-SC0019581, “TTDAQ: A Continuous Flow, Timing and Trigger DAQ System.” The report summarizes Telluric Labs’ Phase II STTR work developing silicon-photonic building blocks for a software-defined, continuous-flow, trigger-less data acquisition system for next-generation high-energy and nuclear-physics detectors. The project focused on radiation-hard photonic integrated circuits, remote optical illumination, dense wavelength-division multiplexing, and a differential microring-resonator transceiver architecture designed to improve high-speed optical link stability and bandwidth. The report describes project objectives, technical accomplishments, AIM Photonics tape-outs, bench characterization, radiation-hardness testing, deferred integration work, and potential applications beyond physics readout.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Investigating the physical mechanisms that modify wind plant blockage in stable boundary layers

Abstract. Wind plants slow down the approaching wind, a phenomenon known as blockage. Wind plant blockage undermines turbine performance for front-row turbines and potentially for turbines deeper into the array. We use large-eddy simulations to characterize blockage upstream of a finite-size wind plant in flat terrain for different atmospheric stability conditions and investigate the physical mechanisms modifying the flow upstream of the turbines. To examine the influence of atmospheric stability, we compare simulations of two stably stratified boundary layers using the Weather Research and Forecasting model in large-eddy simulation mode, representing wind turbines using the generalized actuator disk approach. For a wind plant, a faster cooling rate at the surface, which produces stronger stably stratified flow in the boundary layer, amplifies blockage. As a novelty, we investigate the physical mechanisms amplifying blockage by evaluating the different terms in the momentum conservation equation within the turbine rotor layer. The velocity deceleration upstream of a wind plant is caused by an adverse pressure gradient and momentum advection out of the turbine rotor layer. The cumulative deceleration of the flow upstream of the front-row turbines instigates vertical motions. The horizontal flow is diverted vertically, reducing momentum availability in the turbine rotor layer. Although the adverse pressure gradient upstream of the wind plant remains unchanged with atmospheric stability, vertical advection of horizontal momentum is amplified in the more strongly stable boundary layer, mainly by larger shear of the horizontal velocity, thus increasing the blockage effect.

17 WIND ENERGY↗

Magneto-optical study of Nb thin films for superconducting qubits

Among the recognized sources of decoherence in superconducting qubits, the spatial inhomogeneity of the superconducting state and the possible presence of magnetic-flux vortices remain comparatively underexplored. Niobium is commonly used as a structural material in transmon qubits that host Josephson junctions, and excess dissipation anywhere in the transmon can become a bottleneck that limits overall quantum performance. The metal/substrate interfacial layer may simultaneously host pair-breaking loss channels (e.g., two-level systems, TLS) and control thermal transport, thereby affecting dissipation and temperature stability. Here, we use quantitative magneto-optical imaging of the magnetic-flux distribution to characterize the homogeneity of the superconducting state and the critical current density, $j_{c}$, in niobium films fabricated under different sputtering conditions. The imaging reveals distinct flux-penetration regimes, ranging from a nearly ideal Bean critical state to strongly nonuniform thermo-magnetic dendritic avalanches. By fitting the measured magnetic-induction profiles, we extract $j_{c}$ and correlate it with film physical properties and with measured qubit internal quality factors. Our results indicate that the Nb/Si interlayer can be a significant contributor to decoherence and should be considered an important factor that must be optimized.

Datta, Amlan [Ames Lab; Iowa State U.]↗

Linking thermoset ink rheology to the stability of 3D-printed structures

Thermoset polymer composites show promise for additive manufacturing (AM) applications to address some of the limitations of the more widely used thermoplastic feedstock materials. Thermosets offer attractive mechanical properties while providing excellent interlayer bonding, high thermal and chemical stability, and reduced energy consumption as a result of deposition at room temperature. However, since thermoset resins rely on a crosslinking reaction to solidify, rather than quickly cooling like thermoplastics, viscoelastic properties must be relied upon to maintain deposited shape after deposition until crosslinking can occur. This fact has not impeded development and characterization of new thermoset feedstocks on the small scale, but recent efforts to increase scale of thermoset printing have highlighted issues with structural stability under self-weight. This study addresses issues of self-weight by investigating the mechanisms that cause collapse of tall, thin printed walls. Using nanoclay- and fumed silica-filled epoxy feedstocks, this work compares the collapse height for printed walls to stability models based on yielding and buckling mechanics. Inputs for these models – shear yield stress and storage modulus – were taken directly from parallel plate rheometry measurements. Model predictions were found to be in good agreement with experimental results, where both yielding and buckling behavior were observed, provided the rheological properties after a shear excursion were used as inputs. This work establishes a direct link between basic rheological properties of the feedstock, geometry of the printed object, and achievable height. Overall, the results presented highlight the importance of understanding recovery behavior in thermoset feedstocks and provide valuable guidance on the development of more effective direct-ink writing feedstock materials.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of Polymeric Pore Former Microspheres using Modified Polymer Resin

Porosity in polymer parts is often desired to improve mechanical properties. Individual pores must be small enough that bulk mechanical properties are retained but significant enough to reduce the density of the material. Filler materials can be incorporated into polymer matrices and subsequently removed to create voids. The materials used to create the voids are known as pore-formers. The present research aims to create spherical pores in a silicone matrix by inserting and removing core materials or fillers post-cure. A method was developed to incorporate pore formers into an uncured polymer resin and remove the materials from the matrix. Polyethylene Glycol (PEG) and Polylactic Acid (PLA) microspheres are created and incorporated into silicone matrices as pore formers. Microspheres with controllable size distributions are formed via ultrasonic spray pyrolysis and emulsion formation. Microspheres are removed from the matrix by solvent extraction and calcination. PLA microspheres were modified by hydroxyl addition to the surface to study their solubility in water. PEG-PLA block copolymers are also synthesized and investigated, comparing their physical and chemical properties to the monomers to identify whether the block copolymer microspheres will be more easily removable than their monomeric microspheres. Moreover, other properties including thermal stability, rheology, and mechanical response are studied. The present dissertation provides a comprehensive understanding of the synthesis and characterization of PEG and PLA-based pore formers, toward the future development of feedstock for additive manufacturing porous structures.

Damptey, Ransford↗

Tuning Thermal Stability through Dopant Size in Chemically Doped DPP–Thiophene Polymers

Molecular doping of conjugated polymers (CPs) is a key strategy for improving the performance of organic electronics devices, particularly thermoelectrics. Doped donor–acceptor (D–A) conjugated polymers, characterized by a tunable energy gap between the Fermi level and the transport band, show great promise in achieving high electrical conductivity (σ) while preserving a favorable Seebeck coefficient (S). Despite the promising performance enhancement of chemically doped D–A polymers, their thermal stability remains largely underexplored, a crucial consideration for the long-term operation of organic thermoelectric devices. In this study, we investigated the dopant size-dependent thermal stability of a diketopyrrolopyrrole-thiophene (DPP-T) D–A copolymer, utilizing two p-dopants: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) and Mo(tfd-CO 2 Me) 3 . Temperature-dependent UV–vis–NIR spectroscopy revealed that DPP-T/F 4 TCNQ is more prone to dedoping under a high temperature thermal stress than DPP-T/Mo(tfd-CO 2 Me) 3 . Although the F 4 TCNQ doped polymer shows higher initial in-plane conductivity than its Mo(tfd-CO 2 Me) 3 counterpart, it undergoes a conductivity loss of more than an order of magnitude after annealing at 120 °C for 30 min. In contrast, the in-plane conductivity of DPP-T/Mo(tfd-CO 2 Me) 3 remains stable under the same thermal conditions. Thermogravimetric analysis ruled out dopant sublimation as a primary contributor to dedoping, leading us to attribute the conductivity loss in F 4 TCNQ-doped DPP-T to dopant phase separation and migration. This observation was further confirmed by X-ray scattering studies and nanoscale infrared microscopy and spectroscopy studies. This work could provide further insights into the thermal stability of doped conjugated polymers and suggests that incorporating bulkier dopants is an effective strategy to enhance the thermal robustness of doped DPP-type systems.

Conjugated polymers↗