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At least 1,729 records · Page 96

Direct Evidence of Graphene-Induced Molecular Reorientation in Polymer Films

For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improvement of graphene field-effect transistors by hexamethyldisilazane surface treatment

We report the improvement of the electrical characteristics of graphene field-effect transistors (FETs) by hexamethyldisilazane (HMDS) treatment. Both electron and hole field-effect mobilities are increased by 1.5 × –2×, accompanied by effective residual carrier concentration reduction. Dirac point also moves closer to zero Volt. Time evolution of mobility data shows that mobility improvement saturates after a few hours of HMDS treatment. Temperature-dependent transport measurements show small mobility variation between 77 K and room temperature (295 K) before HMDS application. But mobility at 77 K is almost 2 times higher than mobility at 295 K after HMDS application, indicating reduced carrier scattering. Performance improvement is also observed for FETs made on hydrophobic substrate–an HMDS-graphene-HMDS sandwich structure. Raman spectroscopic analysis shows that G peak width is increased, G peak position is down shifted, and intensity ratio between 2D and G peaks is increased after HMDS application. We attribute the improvements in electronic transport mainly to enhanced screening and mitigation of adsorbed impurities from graphene surface upon HMDS treatment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced UV detection by non-polar epitaxial GaN films

Nonpolar a-GaN (11-20) epilayers were grown on r-plane (1-102) sapphire substrates using plasma assisted molecular beam epitaxy. High resolution x-ray diffractometer confirmed the orientation of the grown film. Effect of the Ga/N ratio on the morphology and strain of a-GaN epilayers was compared and the best condition was obtained for the nitrogen flow of 1 sccm. Atomic force microscopy was used to analyze the surface morphology while the strain in the film was quantitatively measured using Raman spectroscopy and qualitatively analyzed by reciprocal space mapping technique. UV photo response of a-GaN film was measured after fabricating a metal-semiconductor-metal structure over the film with gold metal. The external quantum efficiency of the photodetectors fabricated in the (0002) polar and (11-20) nonpolar growth directions were compared in terms of responsivity and nonpolar GaN showed the best sensitivity at the cost of comparatively slow response time.

36 MATERIALS SCIENCE↗

Ultrafast Raman thermometry in driven YBa 2 C u 3 O 6.48

Signatures of photoinduced superconductivity have been reported in cuprate materials subjected to a coherent phonon drive. A “cold” superfluid was extracted from the transient Terahertz conductivity and was seen to coexist with “hot” uncondensed quasiparticles, a hallmark of a driven-dissipative system of which the interplay between coherent and incoherent responses is not well understood. Here, time resolved spontaneous Raman scattering was used to probe the lattice temperature in the photoinduced superconducting state of YBa 2 ⁢C⁢u 3 ⁢O 6.48 . An increase in lattice temperature of up to 140 K was observed by measuring the time dependent Raman scattering intensity of an undriven “spectator” phonon mode. This value is consistent with the estimated increase in quasiparticle temperature measured under the same excitation conditions. These temperature changes provide quantitative information on the nature of the driven state and its decay, and may suggest a strategy to optimize this effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Enhanced thermal stability by introducing TiN diffusion barrier layer between W and SiC

The combination of W and SiC has many applications such as a hot cell of a thermionic energy converter, nuclear material, and high temperature microelectronics. In this study, a 2 µm thick TiN film is introduced as a diffusion barrier between SiC and W to avoid the inter-diffusion reaction at high temperature. Additionally, the effect of annealing temperature on the surface morphology and microstructure of the TiN film is studied to explore its high temperature stability. Then 500 nm W film is sputtered on the TiN film to characterize the inter-diffusion and stability of the W/TiN/SiC multilayer at 1100°C by XRD, Raman spectroscopy and cross-sectional EDS mapping techniques. The results indicate that the W/TiN/SiC multilayer is very stable even when heated at 1100°C for 25 hours.

36 MATERIALS SCIENCE↗

Testing and Characterization to Develop a Mechanistic Explanation for Unsaturated Drift of Fiber Optic Sensors during High-Dose Irradiation

The primary limitation for any optical fiber-based sensor for nuclear reactor applications is radiation-induced attenuation (RIA) of the transmitted and/or reflected signals. Based on several recent studies, RIA is tolerable for some fused silica optical fibers with the proper choice of sensing wavelength and fiber dopants. For extreme temperature applications (> 1000°C), sapphire optical fibers have been proposed; however, recent optical transmission measurements performed on bulk sapphire samples showed prohibitively large RIA. For some sensors, radiation-induced dimensional changes in the fiber materials can also cause significant drift. Moreover, the drift that was observed in numerous experiments performed in the High Flux Isotope Reactor (HFIR), the Advanced Test Reactor, the Massachusetts Institute of Technology Reactor, and other international facilities far exceeded what would be expected based on compaction of fused silica glass. Clearly, additional work is needed to better understand the origins of both RIA and radiation-induced drift in both silica and sapphire optical fiber-based sensors before these sensors can be reliably deployed for nuclear applications. This work evaluated the underlying mechanisms that may be responsible for RIA and drift in silica and sapphire materials. First, detailed characterization was performed on bulk fused silica glass samples that were previously irradiated to different neutron fluences at different temperatures to better understand the structural changes that drive radiation-induced drift in the absence of coating effects that are discussed later. Results show that the non-monotonic compaction that occurs with increasing neutron fluence continues up to fast neutron fluences approaching 10 22 n/cm 2 , which has important implications for physics-based models that may be used to compensate for the sensor drift. Initial Raman spectroscopy and synchrotron x-ray diffraction provide insights into the nature of the structural changes. Next, detailed characterizations were performed on silica fibers with various coatings that were subjected to several different thermal treatments. The hypothesis is that the coatings convert to carbon-rich materials that compact under irradiation, putting a large compressive strain on the fiber. Out-of-pile testing confirms that both polyimide and acrylate fiber coatings convert to glassy carbon (GC) materials when heated under inert conditions, and the degree of order (i.e., graphitization) increases with increasing temperature. The results provide increasingly strong evidence that the combination of polymeric coatings and inert (or vacuum) conditions render fiber optic sensors susceptible to significant radiation-induced drift that would not otherwise exist in uncoated fibers. Finally, transmission electron microscopy was performed on bulk sapphire samples that were irradiated to two neutron fluences at different temperatures to gain insights into the potential mechanisms driving the prohibitive RIA at higher neutron fluences and temperatures. Contrary to previous hypotheses, results show that scattering from radiation-induced voids cannot explain the observed RIA. Similarly, models for scattering losses from dislocation loops also do not agree with the experimental results. Instead, fitting to the experimental data shows that increased absorption from aluminum vacancy centers is the most likely explanation for the the prohibitively large RIA that was observed at high irradiation temperature and dose. In addition, the voids that formed in these single-crystal samples were found to align along the basal plane (a-axis) as opposed to that seen in previous observations of c-axis alignment in polycrystalline samples, which could have important implications for anisotropic swelling and other phenomena that could affect sensor performance at high neutron fluence.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Testing and Characterization to Develop a Mechanistic Explanation for Unsaturated Drift of Fiber Optic Sensors during High-Dose Irradiation

The primary limitation for any optical fiber-based sensor for nuclear reactor applications is radiation-induced attenuation (RIA) of the transmitted and/or reflected signals. Based on several recent studies, RIA is tolerable for some fused silica optical fibers with the proper choice of sensing wavelength and fiber dopants. For extreme temperature applications (> 1000°C), sapphire optical fibers have been proposed; however, recent optical transmission measurements performed on bulk sapphire samples showed prohibitively large RIA. For some sensors, radiation-induced dimensional changes in the fiber materials can also cause significant drift. Moreover, the drift that was observed in numerous experiments performed in the High Flux Isotope Reactor (HFIR), the Advanced Test Reactor, the Massachusetts Institute of Technology Reactor, and other international facilities far exceeded what would be expected based on compaction of fused silica glass. Clearly, additional work is needed to better understand the origins of both RIA and radiation-induced drift in both silica and sapphire optical fiber-based sensors before these sensors can be reliably deployed for nuclear applications. This work evaluated the underlying mechanisms that may be responsible for RIA and drift in silica and sapphire materials. First, detailed characterization was performed on bulk fused silica glass samples that were previously irradiated to different neutron fluences at different temperatures to better understand the structural changes that drive radiation-induced drift in the absence of coating effects that are discussed later. Results show that the non-monotonic compaction that occurs with increasing neutron fluence continues up to fast neutron fluences approaching 10 22 n/cm 2 , which has important implications for physics-based models that may be used to compensate for the sensor drift. Initial Raman spectroscopy and synchrotron x-ray diffraction provide insights into the nature of the structural changes. Next, detailed characterizations were performed on silica fibers with various coatings that were subjected to several different thermal treatments. The hypothesis is that the coatings convert to carbon-rich materials that compact under irradiation, putting a large compressive strain on the fiber. Out-of-pile testing confirms that both polyimide and acrylate fiber coatings convert to glassy carbon (GC) materials when heated under inert conditions, and the degree of order (i.e., graphitization) increases with increasing temperature. The results provide increasingly strong evidence that the combination of polymeric coatings and inert (or vacuum) conditions render fiber optic sensors susceptible to significant radiation-induced drift that would not otherwise exist in uncoated fibers. Finally, transmission electron microscopy was performed on bulk sapphire samples that were irradiated to two neutron fluences at different temperatures to gain insights into the potential mechanisms driving the prohibitive RIA at higher neutron fluences and temperatures. Contrary to previous hypotheses, results show that scattering from radiation-induced voids cannot explain the observed RIA. Similarly, models for scattering losses from dislocation loops also do not agree with the experimental results. Instead, fitting to the experimental data shows that increased absorption from aluminum vacancy centers is the most likely explanation for the the prohibitively large RIA that was observed at high irradiation temperature and dose. In addition, the voids that formed in these single-crystal samples were found to align along the basal plane (a-axis) as opposed to that seen in previous observations of c-axis alignment in polycrystalline samples, which could have important implications for anisotropic swelling and other phenomena that could affect sensor performance at high neutron fluence.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Chiral Recognition: A Spin-Driven Process in Chiral Oligothiophene. A Chiral-Induced Spin Selectivity (CISS) Effect Manifestation

In this paper it is experimentally demonstrated that the electron-spin/molecular-handedness interaction plays a fundamental role in the chiral recognition process. This conclusion is inferred comparing current versus potential (I-V) curves recorded using chiral electrode surfaces, which are obtained via chemisorption of an enantiopure thiophene derivative: 3,3'-bibenzothiophene core functionalized with 2,2'-bithiophene wings (BT 2 T 4 ). The chiral recognition capability of these chiral-electrodes is probed via cyclic voltammetry measurements, where, Ag nanoparticles (AgNPs) capped with enantiopure (BT 2 T 4 ) (BT 2 T 4 )@AgNP) are used as the chiral redox probe. Then, the interface handedness is explored by recording spin-polarized (I-V) curves in spin-dependent electrochemistry (SDE) and magnetic-conductive atomic force microscopy (mc-AFM) experiments. The quality of the interfaces is thoroughly cross-checked using X-ray photoemission spectroscopy, Raman, electrodesorption measurements, which further substantiate the metal(electrode)-sulfur(thiophene) central role in the chemisorption process. Spin-polarization values of about 15% and 30% are obtained in the case of SDE and mc-AFM experiments, respectively.

36 MATERIALS SCIENCE↗

Anomalous Surface Doping Effect in Semiconductor Nanowires

Surface doping is being used as an effective approach to improve the mechanical, optical, electronic, and magnetic properties of various materials. For example, experimental studies have proven that rare-earth element doping can enhance the optical properties of silicon nanostructures. However, the majority of previous investigations focused on either bulk materials or nanosized spherical crystals. Here we present a comparative study on semiconducting germanium (Ge) nanowires with and without surface doping by using multiple integrated characterization probes, including high resolution scanning/transmission electron microscopy (SEM/TEM), in situ high pressure synchrotron X-ray diffraction (XRD), and Raman spectroscopy. Our results reveal that under pressure the stability of the Ge-I phase (diamond structure) in erbium (Er)-doped Ge nanowires is enhanced compared to undoped Ge nanowires. We also found an increased stability of the Ge-II phase (body centered tetragonal structure) in Er-doped Ge nanowires during decompression. Furthermore, the presence of Er doping elevates the transition kinetics by showing a smaller pressure span needed for a complete Ge-I to Ge-II phase transformation. In contrast, Er doping has a negligible impact on the mechanical properties of Ge nanowires under high pressure, exhibiting a very different mechanical behavior from other foreign element-doped nanostructures. This anomalous doping effect was explained based on surface modification and decoration. Furthermore, these findings are of both fundamental and applied significance, because they not only provide a thorough understanding of the distinct role of surface doping in nanoscale materials, but also yield insight with regard to a given material’s design for favorable properties in semiconductor nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of proton irradiation on anatase TiO 2 nanotube anodes for lithium-ion batteries

The role of defects in the charge transfer and transport properties of electrode materials for lithium-ion batteries has recently garnered increased interest. It is widely known that ion irradiation promotes the formation of defects within a crystalline solid. Within all ion species used for irradiation, protons are expected to create primarily simple Frenkel pair point defects without significantly changing the stoichiometry of the damaged region of the target material. This work investigates the effect of proton irradiation at varying temperatures on the electrochemical properties of anatase TiO 2 nanotube (TiO2-NT) electrode for lithium-ion battery applications. Anatase TiO 2 -NTs are irradiated at both room temperature (25 °C) and 250 °C and compared with non-irradiated control specimens. Characterization by Raman spectroscopy and XRD suggests that the irradiation at both temperatures does not alter the long-range order of the nanotubes. Yet, high-resolution TEM reveals that defect clusters are formed upon irradiation and increase in size with increasing temperature. Both irradiated samples exhibit increased capacity and enhanced rate capability compared with the non-irradiated control, which can be explained by increased storage sites as well as improved Li + diffusivity due to the presence of irradiation-induced defects. This study presents a unique perspective on pathways to engineer functional nanostructured electrode materials by tailoring irradiation conditions.

25 ENERGY STORAGE↗

A critical review of existing and emerging technologies and systems to optimize solid waste management for feedstocks and energy conversion

Solid waste generation and its accumulation is increasing at an alarming pace due to population growth and urbanization posing severe risks to health, safety, and natural ecosystems. Herein this review strategically addresses the challenges and solutions to increasing the sustainability footprint of solid waste management (SWM) systems by revealing multipronged approaches that reduce solid waste and handling costs while generating revenue and reducing greenhouse gas and related emissions. For example, the United States sends ~150 million tons of waste to landfills, which is composed of over 75% organic and recyclable materials having a potential to be diverted to alternative scenarios. The emergence of an automated upstream and downstream sorting process for solid waste to increase material diversion from landfills is a promising approach for creating sustainable SWM. The utilization of artificial-intelligence-enabled smart and automated systems at the home and industrial scales, comprehensive public re-education including awareness of the adverse effects of landfilled waste on the ecosystem, and more eco-friendly product development are required to significantly reduce landfills and their negative footprint.

09 BIOMASS FUELS↗

Engineering of a Coupled Nanocomposite as a High-Performance Protonic Ceramic Fuel Cell Cathode

The lack of high-performance cathode catalysts is a salient issue that bedeviled the commercialization of protonic ceramic fuel cells (PCFCs). Here, in this work, we report a remarkable electrocatalytic activity and stability enhancement of cathode electrodes by engineering a coupled nanocomposite. The as-prepared Pr 0.3 (Ba 0.5 Sr 0.5 ) 0.7 Co 0.8 Fe 0.2 O 3−δ nanocomposite possesses a bulk cubic phase on which homogeneous and intimate orthorhombic PrCo 0.5 Fe 0.5 O 3−δ nanoparticles are uniformly decorated. X-ray diffraction and Raman spectroscopy reveal the excellent thermal stability of the nanocomposite. It achieves a high peak power density of 1.02 W cm –2 based on protonic electrolytes at 600 °C. No noticeable structural degradation is observed over ∼210 h at 550 °C according to scanning electron microscopy analysis. This work demonstrates an effective strategy to boost the performance of perovskite oxides for PCFCs via nanocomposite engineering. It may apply to other catalyst designs and discoveries, such as for batteries, electrolyzers, and membrane reactors.

08 - HYDROGEN↗

Visualizing Surface Plasmons with Photons, Photoelectrons, and Electrons

Both photons and electrons may be used to excite surface plasmon polaritons, the collective charge density fluctuations at the surface of metal nanostructures. By virtue of their nanoscopic and dissipative nature, a detailed characterization of surface plasmon (SP) eigenmodes in real space-time ultimately requires joint sub-nanometer spatial and sub-femtosecond temporal resolution. The latter realization has driven significant developments in the past few years, aimed at interrogating both localized and propagating SP modes over the relevant length and time scales. In this mini-review, we briefly highlight different techniques we employ to visualize the enhanced electric fields associated with SPs. Specifically, we discuss recent hyperspectral optical microscopy, tip-enhanced Raman nano-spectroscopy, nonlinear photoemission electron microscopy, as well as correlated scanning transmission electron microscopy-electron energy loss spectroscopy measurements targeting prototypical plasmonic nanostructures and constructs. Through selected practical examples, we examine the information content in multidimensional images recorded by taking advantage of each of the aforementioned techniques. In effect, we illustrate how SPs can be visualized at the ultimate limits of space and time.

Environmental Molecular Sciences Laboratory↗

Plasmonic modification of electron-longitudinal-optical phonon coupling in Ag-nanoparticle embedded InGaN/GaN quantum wells

Surface plasmon enhanced GaN and InGaN quantum wells (QWs) show promise for use as room-temperature light emitters. The effectiveness of the plasmon enhancement, however, is limited by the strong electron/hole and longitudinal optical phonon coupling found in the III-V nitrides. The electron-phonon coupling within semiconductor QWs has been modified using silver nanoparticles embedded within the QWs. Direct evidence is provided for this change via confocal Raman spectroscopy of the samples. This evidence is augmented by Angle-dependent photoluminescence experiments which show the alteration of the electron-phonon coupling strength through measurement of the emitted phonon replicas. Together these demonstrate a direct modification of carrier-phonon interactions within the system, opening up the possibility of controlling the coupling strength to produce high-efficiency room-temperature light emitters.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Hole burning and higher-order photon effects in attosecond light-atom interaction

We have performed calculations of attosecond laser-atom interactions for laser intensities where interesting two- and three-photon effects become relevant. In particular, we examine the case of “hole burning” in the initial orbital. Hole burning is present when the laser-pulse duration is shorter than the classical radial period because the electron preferentially absorbs the photon near the nucleus. We also examine how the three-photon Raman process can lead to a time delay in the outgoing electron for the energy near one-photon absorption. For excitation out of the hydrogen 2s state, an intensity of 2.2 × 10 16 W/cm 2 leads to a 6-as delay of the outgoing electron. Here, we argue that this delay is due to the hole burning in the initial state.

74 ATOMIC AND MOLECULAR PHYSICS↗

Electronic topological transitions in cadmium under pressure studied via theoretical and experimental x-ray absorption spectroscopy

Here, an electronic topological transition (ETT) in cadmium below 1 GPa is investigated in situ with experimental x-ray absorption spectroscopy and projecting calculated core-valence excitons onto the band structure. These projections are a useful application of the Bethe-Salpeter equation approach that considers many-body effects. The method described herein can be used for systems that are otherwise difficult to probe in situ; therefore, it provides a generalizable approach to identifying and understanding ETTs under high pressure. Although pressure-induced ETTs are often probed using indirect structural responses, our own x-ray diffraction and Raman studies suggest a second-order structural transition around 3 GPa but are largely insensitive to or inconclusive for the previously studied ETT in this region.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Polaron-induced phonon localization and stiffening in rutile $\mathrm{TiO_2}$

Small polaron formation in transition metal oxides, like the prototypical material rutile $\mathrm{TiO_2}$, remains a puzzle and a challenge to simple theoretical treatment. In our combined experimental and theoretical study, we examine this problem using Raman spectroscopy of photoexcited samples and real-time time-dependent density functional theory (RT-TDDFT), which employs Ehrenfest dynamics to couple the electronic and ionic subsystems. We observe experimentally the unexpected stiffening of the $A_{1g}$ phonon mode under UV illumination and provide a theoretical explanation for this effect. Our analysis also reveals a possible reason for the observed anomalous temperature dependence of the Hall mobility. Finally, small polaron formation in rutile $\mathrm{TiO_2}$ is a strongly nonadiabatic process and is adequately described by Ehrenfest dynamics at time scales of polaron formation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Methylated Poly(ethylene)imine Modified Capacitive Micromachined Ultrasonic Transducer for Measurements of CO2 and SO2 in Their Mixtures

A gravimetric gas detection device based on surface functionalized Capacitive Micromachined Ultrasound Transducers (CMUTs) was designed, fabricated and tested for detection of carbon dioxide (CO2) and sulfur dioxide (SO2) mixtures in nitrogen. The created measurement setup of continuous data collection, integrated with an in-situ Fourier Transform Infrared (FT-IR) spectroscopy, allows for better understanding of the mechanisms and molecular interactions with the sensing layer (methylated poly(ethylene)imine) and its need of surface functionalization for multiple gas detection. During experimentation with CO2 gases, weak molecular interactions were observed in spectroscopy data. Linear sensor response to frequency shift was observed with CO2 concentrations ranging from 0.16 vol % to 1 vol %. Moreover, the Raman and FT-IR spectroscopy data showed much stronger SO2 and the polymer interactions, molecules were bound by stronger forces and irreversibly changed the polymer film properties. However, the sensor change in resonance frequency in the tested region of 1 vol % to 5 vol % SO2 showed a linear response. This effect changed not only the device resonance frequency but also affected the magnitude of electroacoustic impedance which was used for differentiating the gas mixture of CO2, SO2, in dry N2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗