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At least 937 records · Page 52

In‐Operando Spatiotemporal Imaging of Coupled Film‐Substrate Elastodynamics During an Insulator‐to‐Metal Transition

Abstract The drive toward non‐von Neumann device architectures has led to an intense focus on insulator‐to‐metal (IMT) and the converse metal‐to‐insulator (MIT) transitions. Studies of electric field‐driven IMT in the prototypical VO 2 thin‐film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO 2 substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in‐operando spatiotemporal imaging of the coupled elastodynamics using X‐ray diffraction microscopy of a VO 2 film channel device on TiO 2 substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase‐field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical‐triggering of the IMT via ionizing defects and an active “IMT‐like” substrate layer are critical aspects to consider in device applications.

36 MATERIALS SCIENCE↗

Crystallographic registry in epitaxial V3O5 thin films

Crystallographic orientation plays a central role in determining transport properties in correlated oxides with low-hysteresis metal–insulator transitions. Here, V3O5 thin films were grown on Al2O3 (0001) and their crystallographic registry was evaluated using x-ray diffraction and cross-sectional transmission electron microscopy. θ–2θ measurements show a single out-of-plane orientation defined by the (202) reflection. Azimuthal φ-scans of the V3O5 (310) reflection exhibit twelve discrete maxima over 360°, indicating a finite set of in-plane orientations imposed by the substrate symmetry. High-resolution TEM and fast Fourier transform analysis confirm crystallographic coherence at the film–substrate interface. The electrical conductivity exhibits a metal–insulator transition at TMIT ≈ 423 K with no measurable thermal hysteresis and a total change of ~1.6 orders of magnitude between 300 and 480 K. These results establish crystallographic registry in epitaxial V3O5 thin films and provide a structurally well-defined system for future studies of orientation-dependent transport.\r\nT

36 MATERIALS SCIENCE↗

Luminescence and electrical properties of single ZnO/MgO core/shell nanowires

To neutralise the influence of the surface of ZnO nanowires for photonics and optoelectronic applications, we have covered them with insulating MgO film and individually contacted them for electrical characterisation. We show that such a metal-insulator-semiconductor-type nanodevice exhibits a high diode ideality factor of 3.4 below 1 V. MgO shell passivates ZnO surface states and provides confining barriers to electrons and holes within the ZnO core, favouring excitonic ultraviolet radiative recombination, while suppressing defect-related luminescence in the visible and improving electrical conductivity. The results indicate the potential use of ZnO/MgO nanowires as a convenient building block for nano-optoelectronic devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Modular anode assemblies and methods of using the same for electrochemical reduction

Modular anode assemblies are used in electrolytic oxide reduction systems for scalable reduced metal production via electrolysis. Assemblies include a channel frame connected to several anode rods extending into an electrolyte. An electrical system powers the rods while being insulated from the channel frame. A cooling system removes heat from anode rods and the electrical system. An anode guard attaches to the channel frame to prevent accidental electrocution or damage during handling or repositioning. Each anode rod may be divided into upper and lower sections to permit easy repair and swapping out of lower sections. The modular assemblies may have standardized components to permit placement at multiple points within a reducing system. Example methods may operate an electrolytic oxide reduction system by positioning the modular anode assemblies in the reduction system and applying electrical power to the plurality of anode assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New Techniques to Evaluate the Incendiary Behavior of Insulators

New techniques for evaluating the incendiary behavior of insulators is presented. The onset of incendive brush discharges in air is evaluated using standard spark probe techniques for the case simulating approaches of an electrically grounded sphere to a charged insulator in the presence of a flammable atmosphere. However, this standard technique is unsuitable for the case of brush discharges that may occur during the charging-separation process for two insulator materials. We present experimental techniques to evaluate this hazard in the presence of a flammable atmosphere which is ideally suited to measure the incendiary nature of micro-discharges upon separation, a measurement never before performed. Other measurement techniques unique to this study include; surface potential measurements of insulators before, during and after contact and separation, as well as methods to verify fieldmeter calibrations using a charge insulator surface opposed to standard high voltage plates. Key words: Kapton polyimide film, incendiary discharges, brush discharges, contact and frictional electrification, ignition hazards, insulators, contact angle, surface potential measurements.

Buhler, Charles↗

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells (Final Report)

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co2O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres.

30 DIRECT ENERGY CONVERSION↗

Highly-Active and Contaminant-Tolerant Cathodes for Durable Solid Oxide Fuel Cells

The objective of this project is to investigate the fundamental degradation methods occurring in solid oxide fuel cell (SOFC) cathodes when exposed to chromium and carbon dioxide contamination and to rationally design alkaline earth-based catalysts to increase stability and tolerance to contaminate poisoning. With a mechanistic and fundamental understanding of the degradation methods, advanced catalytic surface modifications can be applied to reduce degradation. The specific technical objectives are: (1) To identify/develop new catalysts (alkaline-earth based-) that are compatible chemically with the state-of-the-art cathode materials at high temperatures required for fabrication and with contaminates commonly encountered under operating conditions; (2) To improve the infiltration process for optimal control of the thickness, composition, and uniformity of the catalyst coatings; (3) To evaluate the electro-catalytic activity toward ORR of the chemically-stable materials when exposed to different types of contaminants using electrical conductivity relaxation measurements on bar samples and performance evaluation of catalyst-infiltrated cathodes; (4) To unravel the contamination-tolerant mechanisms of the new catalyst coatings under realistic environmental conditions (with different types of contaminants) using powerful in situ and in operando characterization techniques performed on model cells with thin-film/pattern electrodes, as guided by modeling and simulation; (5) To establish scientific basis for rational design of new catalysts of high tolerance to contaminants; (6) To validate the long term stability of modified LSCF cathodes in commercially available cells/stacks under ROC. Alkaline earth-based catalysts have been systematically explored and tested under various contamination conditions. BaCoO 3-δ (BCO) was shown to produce the best catalytic activity enhancement as well as stability in a variety of contaminating conditions, including CO 2 and chromium. The microstructural evolution was investigated with SEM, EDS, and Raman spectroscopy, showing the BCO catalyst prevents the formation of insulating SrCrO 4 by forming electrically conductive BaCrO 4 . Electrochemical relaxation measurements determined the BCO catalyst coatings increased the surface diffusion coefficient but did not significantly affect the diffusion coefficient and determined an optimum surface modification layer of 100 nm. A novel Ba 0.9 Co 0.7 Fe 0.2 Nb 0.1 O x (BCFN) catalyst was also shown to have excellent stability in chromium containing atmospheres. A novel surface sol-gel (SSG) surface modification, which offers superior thickness and compositional control, was applied to SOFCs to produce BaO catalyst coatings. SSG BaO coatings were shown to produce conformal coatings on the electrode surface, greatly 4 increasing stability in chromium containing atmospheres. An atomic level mechanistic approach was applied to investigate the stability of PrBa 0.8 Ca 0.2 Co 2 O 5+δ (PBCC) with respect to a variety of common contaminants, demonstrating thermodynamically its superior stability in CO 2 containing atmospheres. Finally, the best catalyst coatings demonstrated in this project, BCO and PBCC, were applied to full cells which demonstrated superior stability for over 300 hours in CO 2 and Cr atmospheres

01 COAL, LIGNITE, AND PEAT↗

Bi-directional tuning of thermal transport in SrCoO x with electrochemically induced phase transitions

Unlike the wide-ranging dynamic control of electrical conductivity, there does not exist an analogous ability to tune thermal conductivity by means of electric potential. The traditional picture assumes that atoms inserted into a material’s lattice act purely as a source of scattering for thermal carriers, which can only reduce thermal conductivity. In contrast, here we show that the electrochemical control of oxygen and proton concentration in an oxide provides a new ability to bi-directionally control thermal conductivity. On electrochemically oxygenating the brownmillerite SrCoO 2.5 to the perovskite SrCoO 3–δ , the thermal conductivity increases by a factor of 2.5, whereas protonating it to form hydrogenated SrCoO 2.5 effectively reduces the thermal conductivity by a factor of four. This bi-directional tuning of thermal conductivity across a nearly 10 ± 4-fold range at room temperature is achieved by using ionic liquid gating to trigger the ‘tri-state’ phase transitions in a single device. We elucidated the effects of these anionic and cationic species, and the resultant changes in lattice constants and lattice symmetry on thermal conductivity by combining chemical and structural information from X-ray absorption spectroscopy with thermoreflectance thermal conductivity measurements and ab initio calculations. This ability to control multiple ion types, multiple phase transitions and electronic conductivity that spans metallic through to insulating behaviour in oxides by electrical means provides a new framework for tuning thermal transport over a wide range.

36 MATERIALS SCIENCE↗

Experimental observation of Wannier levels in semi-insulating gallium arsenide.

Optical absorption in an electric field has been of increased interest in recent years since Callaway predicted that the Wannier levels may be observable in direct-transition semiconductors such as GaAs. In this work, such levels have been observed for the first time and found to be in substantial agreement with the Callaway theory.

Koss, R. W.↗

Sequential versus Simultaneous Aging of EPDM Nuclear Cable Insulation Subjected to Elevated Temperature and Gamma Radiation

Electrical cables are integral to power, control, and instrumentation systems within nuclear power plants (NPPs). Exposure of cable systems within nuclear containment to elevated temperatures and gamma radiation during decades-long operation of NPPs can lead to degradation of cable polymeric insulation. Prediction of nuclear cable insulation degradation is complicated as thermal and radiation stress are not additive. In this work, we explore the relative effects of simultaneous and sequential thermal and gamma irradiation on the aging of ethylene-propylene-diene (EPDM) elastomer insulation to better understand realistic scenarios of cable insulation degradation. Cable insulation samples of EPDM were subjected to up to 320 kGy of gamma radiation at a dose rate of 300 Gy/hr in two heating scenarios: (1) simultaneously aged samples were heated at 150°C during irradiation and (2) sequentially aged samples were heated at 150°C for designated durations followed by corresponding periods of irradiation at ambient temperature. The mass, tensile elongation at break, and carbonyl index were assessed to quantify aging of the polymers. The simultaneous aging scenario was found to the more severe of the two for EPDM insulation degradation.

ethylene-propylene-diene elastomer, EPDM, nuclear ↗

Interfacial Rashba-Effect-Induced Anisotropy in Nonmagnetic-Material–Ferrimagnetic-Insulator Bilayers

Interfacial magnetic anisotropy in magnetic insulators has been largely unexplored. Recently, interface-induced skyrmions and electrical control of magnetization have been discovered in insulator-based heterostructures, which demand a thorough understanding of interfacial interactions in these materials. We observe a substantial, tunable interfacial magnetic anisotropy between Tm 3 Fe 5 O 12 epitaxial thin films and fifteen nonmagnetic materials spanning a significant portion of the periodic table, which we attribute to Rashba spin-orbit coupling. Our results show a clear distinction between nonmagnetic capping layers from the d-block and the p-block. Finally, this work offers a new path for controlling magnetic phases in magnetic insulators for low-loss spintronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Marking Electrical Wiring With Condition Indicators

A method is provided for marking electrical Wiring with condition indicators. One or more markers are added to one or both of the insulative material and a surface of an electrical conductor such that it bonds thereto. Each marker is capable of emanating into a surrounding atmospheric environment as a gaseous effluent in response to a specific condition experienced by the electrical conductor.

Yost, William T.↗

Aligned van der Waals Coupled Growth of Carbon Nanotubes to Hexagonal Boron Nitride

Abstract 1D carbon nanotubes (CNTs) are grown on hexagonal boron nitride (hBN) surfaces. The nanotubes show clear preference to align to specific crystal directions of the hBN substrate. Raman spectra confirm that the nanotubes consist of sp 2 carbon, while nanomanipulation shows that they are van der Waals coupled to the underlying hBN substrate. Scanning conductance and electric force microscopy show that the CNTs have significantly greater electrical conductance compared to the hBN. This integrated aligned growth of materials with similar lattices, yet having dissimilar dimensionality and electrical conducting properties, provides a promising route to achieving intricate nanoscale electrical circuits on high‐quality insulating substrates.

Nasseri, Mohsen↗

Surface Dynamics of Charge Transport in LaAlO 3 /SrTiO 3 with Time-Resolved Kelvin Probe Force Microscopy

Time-resolved Kelvin probe force microscopy (tr-KPFM) was used to map surface potential dynamics in LAO/STO under its critical thickness, where it acts as an insulator, as polarizing and depolarizing electric fields were applied to planar electrodes in ambient conditions. Two time constants, for polarization and relaxation (i.e., depolarization) each, were derived and were shown to be independent of the direction of electrical field, revealing the reproducibility and recovery of the surfaces. Ambient aging or recent electrical history did not change the surface kinetics as determined by tr-KPFM. During polarization, the faster time constant (~3–6 s) is likely associated with the transport of H+ ions through the full length of the channel. The slower time constant (~40–50 s), on the other hand, is observed across only half the channel width near the higher-potential–more positive–electrode, which is likely associated with an electrochemical reaction such as the dissociation of water. This slower time constant drops to ~10–20 s toward the middle of the channel which could represent the transport of OH– ions. Furthermore, during relaxation, the fast time constant is consistent with polarization and is correlated to the same mechanism while the slower time constant is higher than it was during polarization and may represent the reabsorption of moisture from the atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ferroelectricity in undoped hafnium oxide

We report the observation of ferroelectric characteristics in undoped hafnium oxide thin films in a thickness range of 4–20 nm. The undoped films were fabricated using atomic layer deposition (ALD) and embedded into titanium nitride based metal-insulator-metal (MIM) capacitors for electrical evaluation. Structural as well as electrical evidence for the appearance of a ferroelectric phase in pure hafnium oxide was collected with respect to film thickness and thermal budget applied during titanium nitride electrode formation. Using grazing incidence X-Ray diffraction (GIXRD) analysis, we observed an enhanced suppression of the monoclinic phase fraction in favor of an orthorhombic, potentially, ferroelectric phase with decreasing thickness/grain size and for a titanium nitride electrode formation below crystallization temperature. The electrical presence of ferroelectricity was confirmed using polarization measurements. A remanent polarization P{sub r} of up to 10 μC cm{sup −2} as well as a read/write endurance of 1.6 × 10{sup 5} cycles was measured for the pure oxide. The experimental results reported here strongly support the intrinsic nature of the ferroelectric phase in hafnium oxide and expand its applicability beyond the doped systems.

36 MATERIALS SCIENCE↗