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At least 1,711 records · Page 95

Tuning Electronic Structure of Single Layer MoS 2 through Defect and Interface Engineering

Transition-metal dichalcogenides (TMDs) have emerged in recent years as a special group of two-dimensional materials and have attracted tremendous attention. Among these TMD materials, molybdenum disulfide (MoS 2 ) has shown promising applications in electronics, photonics, energy, and electrochemistry. In particular, the defects in MoS 2 play an essential role in altering the electronic, magnetic, optical, and catalytic properties of MoS 2 , presenting a useful way to engineer the performance of MoS 2 . The mechanisms by which lattice defects affect the MoS 2 properties are unsettled. In this work, we reveal systematically how lattice defects and substrate interface affect MoS 2 electronic structure. We fabricated single-layer MoS 2 by chemical vapor deposition and then transferred onto Au, single-layer graphene, hexagonal boron nitride, and CeO 2 as substrates and created defects in MoS 2 by ion irradiation. Here, we assessed how these defects and substrates affect the electronic structure of MoS 2 by performing X-ray photoelectron spectroscopy, Raman and photoluminescence spectroscopies, and scanning tunneling microscopy/spectroscopy measurements. Molecular dynamics and first-principles based simulations allowed us to conclude the predominant lattice defects upon ion irradiation and associate those with the experimentally obtained electronic structure. We found that the substrates can tune the electronic energy levels in MoS 2 due to charge transfer at the interface. Furthermore, the reduction state of CeO 2 as an oxide substrate affects the interface charge transfer with MoS 2 . The irradiated MoS 2 had a faster hydrogen evolution kinetics compared to the as-prepared MoS 2 , demonstrating the concept of defect controlled reactivity in this phase. Our findings provide effective probes for energy band and defects in MoS 2 and show the importance of defect engineering in tuning the functionalities of MoS 2 and other TMDs in electronics, optoelectronics, and electrochemistry.

42 ENGINEERING↗

Calorimetric measurements on Li{sub 4}C{sub 60} and Na{sub 4}C{sub 60}

We show specific heat data for Na{sub 4}C{sub 60} and Li{sub 4}C{sub 60} in the range 0.4-350 K for samples characterized by Raman spectroscopy and X-ray diffraction. At high temperatures, the two different polymer structures have very similar specific heats both in absolute values and in general trend. The specific heat data are compared with data for undoped polymeric and pristine C{sub 60}. At high temperatures, a difference in specific heat between the intercalated and undoped C{sub 60} polymers of 100 J K{sup −1} mol{sup −1} is observed, in agreement with the Dulong-Petit law. At low temperatures, the specific heat data for Li{sub 4}C{sub 60} and Na{sub 4}C{sub 60} are modified by the stiffening of vibrational and librational molecular motion induced by the polymer bonds. The covalent twin bonds in Li{sub 4}C{sub 60} affect these motions to a somewhat higher degree than the single intermolecular bonds in Na{sub 4}C{sub 60}. Below 1 K, the specific heats of both materials become linear in temperature, as expected from the effective dimensionality of the structure. The contribution to the total specific heat from the inserted metal ions can be well described by Einstein functions with T{sub E} = 386 K for Li{sub 4}C{sub 60} and T{sub E} = 120 K for Na{sub 4}C{sub 60}, but for both materials we also observe a Schottky-type contribution corresponding to a first approximation to a two-level system with ΔE = 9.3 meV for Li{sub 4}C{sub 60} and 3.1 meV for Na{sub 4}C{sub 60}, probably associated with jumps between closely spaced energy levels inside “octahedral-type” ionic sites. Static magnetic fields up to 9 T had very small effects on the specific heat below 10 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of phonon modes in gallium nitride nanowires deposited by thermal CVD

Gallium nitride nanowires (GaN-NWs) of diameters ranging from 20 to 80 nm were grown on the p-type Si substrate by Thermal Chemical Vapor Deposition (TCVD) using Iron (Fe) catalyst via VLS mechanism. Raman and FTIR spectra reveal the presence of broad transverse optic (TO) and longitudinal optic (LO) phonon peak spreads over 500-600 cm{sup −1} and 720 cm{sup −1} respectively. The detail deconvolution of integrated transverse and longitudinal phonon analysis reveals phonon confinement brought out by incorporation of hydrogen atom. The red shifts of TO and LO phonon peak position indicates nanosized effect. I{sub A1(LO)}/I{sub A1(TO)} increases from 0.073 to 1.0 and their respective fwhm{sub A1(LO)}/fwhm{sub A1(TO)} also increases from 0.71 to 1.31 with increasing H{sub 2} flow rate. E{sub 1}(LO) - E{sub 1}(TO) and A{sub 1}(LO) - A{sub 1}(TO) increases from 173.83 to 190.73 and 184.89 to 193.22 respectively. Apart from this usual TO and LO phonon, we have found Surface Optic (SO) phonon at 671 cm{sup −1} in FTIR spectra. The intensity of PL peak increases with increasing H{sub 2} dilution reveals efficient passivation of defect centre at surface of GaN-NWs.

36 MATERIALS SCIENCE↗

Automated retrieval of cloud and aerosol properties from the ARM Raman lidar, part 1: feature detection

A Feature detection and EXtinction retrieval (FEX) algorithm for the Atmospheric Radiation Measurement (ARM) program’s Raman lidar (RL) has been developed. Presented here is part 1 of the FEX algorithm: the detection of features including both clouds and aerosols. The approach of FEX is to use multiple quantities— scattering ratios derived using elastic and nitro-gen channel signals from two fields of view, the scattering ratio derived using only the elastic channel, and the total volume depolarization ratio— to identify features using range-dependent detection thresholds. FEX is designed to be context-sensitive with thresholds determined for each profile by calculating the expected clear-sky signal and noise. The use of multiple quantities pro-vides complementary depictions of cloud and aerosol locations and allows for consistency checks to improve the accuracy of the feature mask. The depolarization ratio is shown to be particularly effective at detecting optically-thin features containing non-spherical particles such as cirrus clouds. Improve-ments over the existing ARM RL cloud mask are shown. The performance of FEX is validated against a collocated micropulse lidar and observations from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) satellite over the ARM Darwin, Australia site. While we focus on a specific lidar system, the FEX framework presented here is suitable for other Raman or high spectral resolution lidars.

Thorsen, Tyler J.↗

In Situ Synthesis of 3D Interconnected Graphene-Reinforced Copper Composites

Graphene shows great potential in composite applications, but the performance of traditional graphene-metal composites is poorer than desired due to the uneven dispersion of graphene in the matrix. This study provides an effective method to grow high-quality graphene on the surface of 3D porous copper using a combination of chemical vapor deposition and spark plasma sintering to obtain a dense 3D-interconnected graphene/Cu composite. Transmission electron microscopy and scanning electron microscopy showed that graphene-coated copper and Raman analysis showed high-quality graphene. The tensile strength of the 3D graphene/Cu composite was 425 MPa, which is ~ 25% higher than that of pure Cu, and the coefficient of friction (0.33) is about 45% lower than that of pure Cu (0.58). The formation of high-quality 3D graphene interconnects in the Cu matrix results in a higher mechanical strength, better friction properties and superior electrical and thermal conductivity of the composite compared to those of pure Cu.

36 MATERIALS SCIENCE↗

Structure of a stratified CH 4 flame with H 2 addition

To explore the effect of H 2 addition (20 percent by volume) on stratified-premixed methane combustion in a turbulent flow, an experimental investigation on a new flame configuration of the Darmstadt stratified burner is conducted here. Major species concentrations and temperature are measured with high spatial resolution by 1D Raman-Rayleigh scattering. A conditioning on local equivalence ratio (range from φ = 0.45 to φ = 1.25) and local stratification is applied to the large dataset and allows to analyze the impact of H 2 addition on the flame structure. The local stratification level is determined as Δφ/ΔT at the location of maximum CO mass fraction for each instantaneous flame realization. Due to the H 2 addition, preferential diffusion of H 2 is different than in pure methane flames. In addition to diffusing out of the reaction zone where it is formed, particularly in rich conditions, H 2 also diffuses from the cold reactant mixture into the flame front. For rich conditions (φ = 1.05 to φ = 1.15) H 2 mass fractions are significantly elevated within the intermediate temperature range compared to fully-premixed laminar flame simulations. This elevation is attributed to preferential transport of H 2 into the rich flame front from adjacent even richer regions of the flow. Additionally, when the local stratification across the flame front is taken into account, it is revealed that the state-space relation of H 2 is not only a function of the local stoichiometry but also the local stratification level. In these flames H 2 is the only major species showing sensitivity of the state-space relation to an equivalence ratio gradient across the flame front.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Clean Graphene Electrodes on Organic Thin-Film Devices via Orthogonal Fluorinated Chemistry

Graphene is a promising flexible, highly transparent, and elementally abundant electrode for organic electronics. Typical methods utilized to transfer large-area films of graphene synthesized by chemical vapor deposition on metal catalysts are not compatible with organic thin-films, limiting the integration of graphene into organic optoelectronic devices. This article describes a graphene transfer process onto chemically sensitive organic semiconductor thin-films. The process incorporates an elastomeric stamp with a fluorinated polymer release layer that can be removed, post-transfer, via a fluorinated solvent; neither fluorinated material adversely affects the organic semiconductor materials. We used Raman spectroscopy, atomic force microscopy, and scanning electron microscopy to show that chemical vapor deposition graphene can be successfully transferred without inducing defects in the graphene film. To demonstrate our transfer method’s compatibility with organic semiconductors, we fabricate three classes of organic thin-film devices: graphene field effect transistors without additional cleaning processes, transparent organic light-emitting diodes, and transparent small-molecule organic photovoltaic devices. Furthermore, these experiments demonstrate the potential of hybrid graphene/organic devices in which graphene is deposited directly onto underlying organic thin-film structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. Here, this study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.e., nickel hydroxide (Ni(OH) 2 ), nickel oxyhydroxide (NiOOH), and nickel dioxide (NiO 2 ), were constructed using density functional theory-based simulations. Various experimental methods, including cyclic voltammetry, in situ Raman spectroscopy, and electrochemical titration, were employed to probe the surface redox processes of nickel oxide thin films. Our findings indicate that the ABAB stacking sequence of Ni(OH) 2 lacks stability under oxidizing conditions to host the surface oxidation (deprotonation) events, while the AABBCC stacking sequence of NiOOH is energetically favorable due to the presence of interlayer hydrogen bonding. Rapid charge transfer facilitated by interlayer hydrogen bonding accounts for the higher reactivity of partially oxidized/reduced NiOOH (001) surfaces compared to Ni(OH) 2 (001) and NiO 2 (001) surfaces with the same stoichiometry, where interlayer hydrogen bonding is absent. Insights presented in this work can offer guidelines for optimizing operational conditions and tailoring the surface structures and oxidation states of nickel oxides to enhance performance in applications such as electrocatalysis and supercapacitors.

36 MATERIALS SCIENCE↗

Structural phase transition and erasable optically memorized effect in layered γ-In{sub 2}Se{sub 3} crystals

We have grown In{sub 2}Se{sub 3} layered-type crystals using chemical vapor transport method with ICl{sub 3} as the transport agent. The as-grown crystals show two different color groups of black shiny for α-phase In{sub 2}Se{sub 3} and red to yellow for γ-phase In{sub 2}Se{sub 3}. High-resolution transmission electron micro scopy verifies crystalline state and structural polytype of the as-grown In{sub 2}Se{sub 3}. The results indicate that the α-In{sub 2}Se{sub 3} crystals present more crystalline states than those of the other amorphous γ-In{sub 2}Se{sub 3}. The amorphous effect on the advancing of optoelectronic property of γ-In{sub 2}Se{sub 3} shows erasable optical-memorized effect in the disordered and polycrystalline γ-In{sub 2}Se{sub 3} layers. Laser-induced photodarkening and annealed-recovery test verified that a reversible structural-phase transition of γ↔α can occur inside the γ-In{sub 2}Se{sub 3}. Thermoreflectance and Raman scattering measurements are carried out to identify the inter-phase transformation of the γ-In{sub 2}Se{sub 3} polycrystals using different heat treatments. Direct band gaps and Raman vibration modes for the γ- and α-In{sub 2}Se{sub 3} crystalline phases are, respectively, characterized and identified. The character of γ↔α inter-phase transition promotes feasible optical and optoelectronic applications of the γ-In{sub 2}Se{sub 3} material in optical memory, optics, and solar-energy devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Parametric instability of a relativistically strong electromagnetic wave.

The stability of a circularly polarized electromagnetic wave that is strong enough to make plasma electrons, but not ions, relativistic is studied. Small perturbations are considered which propagate parallel to the large-amplitude driver. A relativistically strong wave can be unstable on time scales as short as twice its own oscillation period, and decays into a forward-going plasma oscillation and either one or two electromagnetic waves. Ion motion introduces an additional instability which can be important at short perturbation wavelengths, where the driver would otherwise be stable. The unstable ion and electron modes both have potential for producing anomalously large acceleration of relativistic particles, as well as significant amounts of backscattered light. These effects may be important in two applications: (1) the use of intense lasers to heat or compress plasma, and (2) the plasma surrounding a pulsar, if the pulsar is losing energy by radiation of electromagnetic waves at its rotation frequency. Instability persists in the nonrelativistic regime, reducing to stimulated Raman scattering as a special case.

Max, C. E.↗

Nanowire Electron Scattering Spectroscopy

Nanowire electron scattering spectroscopy (NESS) has been proposed as the basis of a class of ultra-small, ultralow-power sensors that could be used to detect and identify chemical compounds present in extremely small quantities. State-of-the-art nanowire chemical sensors have already been demonstrated to be capable of detecting a variety of compounds in femtomolar quantities. However, to date, chemically specific sensing of molecules using these sensors has required the use of chemically functionalized nanowires with receptors tailored to individual molecules of interest. While potentially effective, this functionalization requires labor-intensive treatment of many nanowires to sense a broad spectrum of molecules. In contrast, NESS would eliminate the need for chemical functionalization of nanowires and would enable the use of the same sensor to detect and identify multiple compounds. NESS is analogous to Raman spectroscopy, the main difference being that in NESS, one would utilize inelastic scattering of electrons instead of photons to determine molecular vibrational energy levels. More specifically, in NESS, one would exploit inelastic scattering of electrons by low-lying vibrational quantum states of molecules attached to a nanowire or nanotube.

Hunt, Brian↗

Efficient control of ultrafast optical nonlinearity of reduced graphene oxide by infrared reduction

Simultaneous occurrence of saturable absorption nonlinearity and two-photon absorption nonlinearity in the same medium is well sought for the devices like optical limiter and laser mode-locker. Pristine graphene sheet consisting entirely of sp{sup 2}-hybridized carbon atoms has already been identified having large optical nonlinearity. However, graphene oxide (GO), a precursor of graphene having both sp{sup 2} and sp{sup 3}-hybridized carbon atom, is increasingly attracting cross-discipline researchers for its controllable properties by reduction of oxygen containing groups. In this work, GO has been prepared by modified Hummers method, and it has been further reduced by infrared (IR) radiation. Characterization of reduced graphene oxide (RGO) by means of Raman spectroscopy, X-ray photoelectron spectroscopy, and UV-Visible absorption measurements confirms an efficient reduction with infrared radiation. Here, we report precise control of non-linear optical properties of RGO in femtosecond regime with increased degrees of IR reduction measured by open aperture z-scan technique. Depending on the intensity, both saturable absorption and two-photon absorption effects are found to contribute to the non-linearity of all the samples. Saturation dominates at low intensity (∼127 GW/cm{sup 2}) while two-photon absorption becomes prominent at higher intensities (from 217 GW/cm{sup 2} to 302 GW/cm{sup 2}). The values of two-photon absorption co-efficient (∼0.0022–0.0037 cm/GW for GO, and ∼0.0128–0.0143 cm/GW for RGO) and the saturation intensity (∼57 GW/cm{sup 2} for GO, and ∼194 GW/cm{sup 2} for RGO) increase with increasing reduction, indicating GO and RGO as novel tunable photonic devices. We have also explained the reason of tunable nonlinear optical properties by using amorphous carbon model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Broadband nonreciprocal thermal emissivity and absorptivity

A body that violates Kirchhoff’s law of thermal radiation exhibits an inequality in its spectral directional absorptivity and emissivity. Achieving such an inequality is of fundamental interest as well as a prerequisite for achieving thermodynamic limits in photonic energy conversion and radiative cooling. Thus far, inequalities in the spectral directional emissivity and absorptivity have been limited to narrow spectral resonances, or wavelengths well beyond the infrared regime4. Bridging the gap from basic demonstrations to practical applications requires control over a broad spectral range of the unequal spectral directional absorptivity and emissivity. In this work, we demonstrate broadband nonreciprocal thermal emissivity and absorptivity by measuring the thermal emissivity and absorptivity of gradient epsilon-near-zero InAs layers of subwavelength thicknesses (50 nm and 150 nm) with an external magnetic field. The effect occurs in a spectral range (12.5–16 μm) that overlaps with the infrared transparency window and is observed at moderate (1 T) magnetic fields.

42 ENGINEERING↗

Many electron correlations in stage-1 graphene intercalation compounds

Many electron correlations in stage-1 graphene intercalation compounds (GICs) are studied in generalized-random-phase-approximation. With this approximation, we are able to study short range exchange and correlation effects in GICs. These exchange correlations leads to BCS superconducting states in which one electron correlates with another via its correlation hole to form a stable pair of electrons known as Cooper pair. Cooper pair energies are calculated as the excitations in S(q,ω) following a method similar to exciton energy calculations. Short range effects governing local field correction G(q,ω) are studied for all wave vectors and frequencies. We have found a reasonable agreement between our results and the earlier theoretical results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Direct Utilization of Coal Syngas in High Temperature Fuel Cells

This EPSCoR project had two primary goals: (i) to build infrastructure and work force at WVU to support long-term research in the area of fuel cells and related sciences; (ii) study effects of various impurities found in coal-syngas on performance of Solid Oxide Fuel Cells (SOFC). As detailed in this report the WVU research team has made significant accomplishments in both of these areas. What follows is a brief summary of these accomplishments: State-of-the-art test facilities and diagnostic tools have been built and put into use. These include cell manufacturing, half-cell and full-cell test benches, XPS, XRD, TEM, Raman, EDAX, SEM, EIS, and ESEM equipment, unique in-situ measurement techniques and test benches (Environmental EM, Transient Mass-Spectrometer-MS, and IR Optical Temperature measurements). In addition, computational capabilities have been developed culminating in a multi-scale multi-physics fuel cell simulation code, DREAM-SOFC, as well as a Beowulf cluster with 64 CPU units. We have trained 16 graduate students, 10 postdoctoral fellows, and recruited 4 new young faculty members who have actively participated in the EPSCoR project. All four of these faculty members have already been promoted to the tenured associate professor level. With the help of these faculty and students, we were able to secure 14 research awards/contracts amounting to a total of circa $5.0 Million external funding in closely related areas of research. Using the facilities mentioned above, the effects of PH3, HCl, Cl2, and H2S on cell performance have been studied in detail, mechanisms have been identified, and also remedies have been proposed and demonstrated in the laboratory. For example, it has been determined that PH3 reacts rapidly with Ni to from secondary compounds which may become softer or even melt at high temperature and then induce Ni migration to the surface of the cell changing the material and micro-structural properties of the cell drastically. It is found that the extent of steam and current load accelerate the degradation caused by PH3. A unique filtering technique has been proposed to reduce the effect of PH3. In addition, various cell materials have been proposed to reduce the rate of degradation caused by H2S. Furthermore, a three-dimensional, transient multi-physics model has been formulated to describe primary transport processes and electro-chemical reactions occurring within the cell. This model has been validated using data gathered from accelerated tests. The validated model then has been used to study the degradation rates under a range of operating conditions and impurity levels. This has resulted in a procedure that uses both experiments and simulations to predict the life-time of a cell operating with syngas with known concentration of trace impurities. Finally all the experience and knowledge gained has been disseminated via 39 journal papers and 43 presentations/posters/conference papers.

01 COAL, LIGNITE, AND PEAT↗

Effects of microstructure on the oxidation behavior of A3 matrix‐grade graphite

Abstract The oxidation behavior of matrix‐grade graphite in air‐ or steam‐ingress accident scenarios is of great interest for high‐temperature gas reactors (HTGRs). In this study, the microstructures of two variants of matrix‐grade graphite based on the German A3‐3 and A3‐27 formulations were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy, and correlated to oxidation behavior observed through thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Through TEM imaging and selected area electron diffraction (SAED), a higher volume fraction of partially graphitized carbon was identified in the A3‐3 type graphite than in the A3‐27 type. This structure is believed to have contributed to the accelerated oxidation exhibited by A3‐3 in the chemical reaction‐controlled oxidation regime.

Bratten, Adam↗

Growth process of microcrystalline silicon studied by combined photoluminescence and Raman investigations

Plasma enhanced chemical vapor deposition of silicon on glass substrates leads to formation of silicon amorphous films with partial crystallization of nano-grains in the amorphous matrix. We studied the transition of amorphous to microcrystalline silicon during such deposition. Formation of silicon nano-grains was detected by means of photoluminescence and Raman spectroscopy. The crystalline fraction and the mean size of the nano-grains were estimated by the position and the intensity of the peaks in the Raman spectrum. We showed that the fraction of crystalline silicon in the layers and the size of the nano-grains are strongly dependent on the growth conditions. The photoluminescence spectra exhibit distinct features related to recombination in the amorphous and in the crystalline phases. A significant narrowing of the photoluminescence peak related to the amorphous phase with increasing crystalline fraction indicates a structural modification in the amorphous silicon. It suggests an ordering process occurring before the start of the actual crystallization. A peak at about 1.4 eV was associated with isolated nano-crystalline grains within the amorphous matrix. A correlation between the peak energy and grain size was found, indicating effects of carrier quantum confinement. The experimental results confirm the established theoretical models for growth of microcrystalline silicon films.

36 MATERIALS SCIENCE↗

Strong and Tough Cellulose Nanofibrils Composite Films: Mechanism of Synergetic Effect of Hydrogen Bonds and Ionic Interactions

Cellulose nanofibrils (CNFs) have been exploited for different applications, such as nanocomposites, gas separation, flexible electronics, and fuel cells, due to their unique properties. To fulfill different demands regarding the utilization of CNFs, one critical step is to develop strong and tough CNF composites. In this study, facile synthesis of strong and tough nanocellulose films was demonstrated using a strategy that employs the synergetic effect of hydrogen bonds and ionic interactions in the films. With the addition of chitosan (CS) and copper ion (Cu 2+ ), the tensile strength and Young’s modulus of the newly developed film (CNF-CS-Cu) increased by 104% and 75%, respectively; more impressively, the toughness of CNF-CS-Cu improved by 560% compared to pure CNF. The hydrogen bonds and ionic interactions in the films were verified by attenuated total reflectance infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Results confirmed that the combination of hydrogen bonds and ionic interactions could yield much better performance in nanocellulose films. The development of facile, low-cost, scalable, and ecofriendly processing methods and formulations for the fabrication of strong nanocellulose-based films are essential and would significantly impact widespread utilization of such materials for a variety of applications requiring high performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗