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At least 415 records · Page 23

Efficient Intermolecular Energy Exchange and Soft-ionization of Water at Nanoplatelet Interfaces

X-ray, energetic photon and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy transfer processes that ultimately determine the manifold of system responses to the deposited excess energy. In weakly bound gas- and solution-phase samples, intermolecular Coulomb decay (ICD) and electron-transfer mediated decay (ETMD) can occur with neighboring atoms or molecules leading to efficient transfer of the excess energy to the surroundings. In ionic solids such as metal-oxides, intra- and inter-atomic Auger decay produces localized final states that lead to lattice damage and typically removal of cations from the substrate. The relative importance of Auger stimulated damage (ASD) versus ICD and ETMD in micro-solvated nanoparticle interfaces is not known. Though ASD is generally expected, essentially no lattice damage and very efficient ICD and ETMD resulting from ionization and electronic excitation of micro-solvated boehmite (AlOOH) nanoplatelets has been observed. Efficient energy transfer and soft ionization of interfacial molecules is likely a general phenomenon at gas-oxyhydroxide nanoparticle interfaces where the density of states of the ionized chemisorbed species significantly overlap the core hole states of the solid.

Jones, Brant M.↗

Automated syringe sampler

A number of sampling services are disposed in a rack which slides into a housing. In response to a signal from an antenna, the circutry elements are activated which provide power individually, collectively, or selectively to a servomechanism thereby moving an actuator arm and the attached jawed bracket supporting an evaculated tube towards a stationary needle. One open end of the needle extends through the side wall of a conduit to the interior and the other open end is maintained within the protective sleeve, supported by a bifurcated bracket. A septum in punctured by the end of the needle within the sleeve and a sample of the fluid medium in the conduit flows through the needle and is transferred to a tube. The signal to the servo is then reversed and the actuator arm moves the tube back to its original position permitting the septum to expand and seal the hole made by the needle. The jawed bracket is attached by pivot to the actuator to facilitate tube replacement.

Purgold, G. C.↗

Modeling of Optoelectronic Devices

Ultrafast modulation of semiconductor quantum well (QW) laser is of technological importance for information technology. Improvement by order(s) of magnitude in data transfer rate is possible as terahertz (THz) radiation is available for heating the laser at picosecond time scale. Optical gain modulation in the QW is achieved via temperature modulation of electron-hole plasma (EHP). Applications include free-space THz communication, optical switching, and pulse generation. The EHP in the semiconductor QW is described with a two-band model. Semiconductor Bloch equations with many-body effects are used to derive a hydrodynamical model for the active QW region. Because of ultrafast carrier-carrier scatterings in the order of 50 fs, EHP follows quasiequilibrium Fermi-Dirac distributions and THz field interacts incoherently with it. Carrier-longitudinal optical (LO) phonon scatterings and coherent laser-EHP interaction are treated microscopically in our physical model. A set of hydrodynamical equations for plasma density, temperature, and laser envelop amplitude are derived and Runge-Kutta method is adopted for numerical simulation. A typical 8 nm GaAs/Al(0.3)Ga(0.7) As single QW at 300 K is used. Additional information is contained in the original extended abstract.

Li, Jian-Zhong↗

Ultrafast terahertz spectroscopy provides insight into charge transfer efficiency and dynamics in artificial photosynthesis

Terahertz (THz) spectroscopy provides a noncontact method to measure the ultrafast dynamics and photoconductivity of mobile carriers in semiconducting materials. This has proven useful in studying artificial photosynthesis devices which use semiconductor photoelectrodes. In this work, we present a brief introduction to optical-pump THz-probe (OPTP) spectroscopy, a technique that provides unique and useful insight into interfacial electron transfer (from the surface-attached dye to the conduction band of the semiconductor) in dye-sensitized photoelectrochemical cells. Compared with more familiar methods like visible transient absorption spectroscopy, OPTP spectroscopy stands out in offering both sub-picosecond time resolution as well as sensitivity to mobile carriers (electrons and holes) in the semiconductor portion of artificial photosynthesis devices. The mobile carriers are crucial to device performance as only they pass to the other half cell to complete the reaction. In order to highlight these advantages and illustrate the types of questions OPTP spectroscopy can address, we discuss three case studies. In the first, OPTP spectroscopy is used to measure the injection rates from a set of six different dyes, revealing the effect of the energetics and lifetimes of the dye excited states on interfacial electron transfer. The subsequent case studies investigate the influence of varying the moieties which bind to the surface (anchors), as well as the moieties that connect the chromophore with these anchors (linkers). OPTP spectroscopy was used to measure the interfacial electron transfer rate as these moieties were varied.

59 BASIC BIOLOGICAL SCIENCES↗

The Growth of Central Black Hole and the Ionization Instability of Quasar Disk

A possible accretion model associated with the ionization instability of quasar disks is proposed to address the growth of the central black hole harbored in the host galaxy. The evolution of quasars in cosmic time is assumed to change from a highly active state to a quiescent state triggered by the S-shaped ionization instability of the quasar accretion disk. For a given external mass transfer rate supplied by the quasar host galaxy, ionization instability can modify accretion rate in the disk and separates the accretion flows of the disk into three different phases, like a S-shape. We suggest that the bright quasars observed today are those quasars with disks in the upper branch of S-shaped instability, and the faint or 'dormant' quasars are simply the system in the lower branch. The middle branch is the transition state which is unstable. We assume the quasar disk evolves according to the advection-dominated inflow-outflow solutions (ADIOS) configuration in the stable lower branch of S-shaped instability, and Eddington accretion rate is used to constrain the accretion rate in each phase. The mass ratio between black hole and its host galactic bulge is a nature consequence of ADIOS. Our model also demonstrates that a seed black hole (BH) similar to those found in spiral galaxies today is needed to produce a BH with a final mass 2 x 10(exp 8) solar mases.

Lu, Ye↗

SOHO Ultraviolet Coronagraph Spectrometer (UVCS) Mission Operations and Data Analysis

The scientific goal of UVCS is to obtain detailed empirical descriptions of the extended solar corona as it evolves from a period of minimum activity to maximum and to use these descriptions to identify and understand the physical processes responsible for coronal heating, solar wind acceleration, coronal mass ejections (CME's), and the phenomena that establish the plasma properties of the solar wind as measured by the CELIAS/SOHO experiment. We must observe a wide range of conditions (e.g., heating rate, impulsive mass ejections, magnetic field opening) in order to choose among competing theoretical explanations of the observed coronal structures and dynamics. During the first year of scientific observations (1 April 1996 through 31 March 1997), the LTVCS made the first extensive ultraviolet spectroscopic observations above the base of the solar corona. Those observations revealed extremely high most probable speeds along the line of sight for O(5+) in polar coronal holes above 2 solar radii from sun center and smaller such speeds for H(0) and protons. Doppler dimming and pumping diagnostics indicated that O(5+) and H(0) I reached supersonic outflow velocities within 2 solar radii. The observations appeared to be consistent with O95+) heating and direct momentum transfer by high frequency MHD waves through ion cyclotron resonance. Equatorial streamers were found to appear much different when observed in O VI, Fe XII and Mg X than when observed in H I Lyman-alpha or visible light. This led G. Noci to suggest that the elemental abundance of O, Fe, and Mg are lower in the dark center region of the O VI streamer image than it is in the brighter outer legs of the streamer. The O VI line ratio indicated a much smaller outflow speed in streamers than in the surrounding coronal holes. Spectroscopic observations of CME's in June and December 1996 showed large Doppler shifts indicating macroscopic flows of up to 200 km/s transverse to the apparent motion of the CME. The December event displayed factor of 500 intensity increases in H I Lyman lines and bright emissions in cool ion lines like C III 977 A indicating that the origin of some of the gas was a prominence. UVCS also observed two comets, several stars and interplanetary hydrogen. In the current reporting period, the initial results were published and detailed analyses including self consistent empirical models were developed. The research results were reported, published or submitted/accepted for publication. New observations were made to uncover additional information about the surprising results of the first year and other new observations revealed more surprises. A UVCS Tutorial was developed to familiarize potential users of UVCS data with the data products, analysis techniques and coronal models needed to analyze the data.

Kohl, John L.↗

Thermal-structural mission analyses of air-cooled gas turbine blades

Cyclic temperature and stress-strain states in cooled turbine blades were calculated for a simulated mission of an advanced technology aircraft engine. TACT1 (three dimensional heat transfer) and MARC (nonlinear structural analysis) computer programs were used to analyze impingement cooled airfoils, with and without leading-edge film cooling. Creep was the predominant damage mode, particularly around film cooling holes. Radially angled holes exhibited less creep than holes normal to surface. Beam-type analyses of all-impingement cooled airfoils gave fair agreement with MARC results for initial creep.

Kaufman, A.↗

Thermal-structural mission analyses of air-cooled gas turbine blades

Cyclic temperature and stress-strain states in cooled turbine blades were calculated for a simulated mission of an advanced technology aircraft engine. TACTl (three dimensional heat transfer) and MARC (nonlinear structural analysis) computer programs were used to analyze impingement cooled airfoils, with and without leading-edge film cooling. Creep was the predominant damage mode, particularly around film cooling holes. Radially angled holes exhibited less creep than holes normal to surface. Beam-type analyses of all-impingement cooled airfoils gave fair agreement with MARC results for initial creep.

Kaufman, A.↗

Spatially Enhanced Electrostatic Doping in Graphene Realized via Heterointerfacial Precipitated Metals

Forming heavily-doped regions in 2D materials, like graphene, is a steppingstone to the design of emergent devices and heterostructures. Here, a selective-area approach is presented to tune the work-function and carrier density in monolayer graphene by spatially synthesizing sub-monolayer gallium beneath the 2D-solid. The localized metallic gallium is formed via precipitation from an underlying diamond-like carbon (DLC) film that is spatially implanted with gallium-ions. By controlling the interfacial precipitation process with annealing temperature, spatially precise ambipolar tuning of the graphene work-function is achieved, and the tunning effect preserved upon cooling to ambient conditions. Consequently, charge carrier densities from ≈1.8 × 10 10 cm -2 (hole-doped) to ≈7 × 10 13 cm -2 (electron-doped) are realized, confirmed by in situ and ex situ measurements. The theoretical studies corroborated the role of gallium at the heterointerface on charge transfer and electrostatic doping of the graphene overlayer. Specifically, sub-monolayer gallium facilitates heavy n-doping in graphene. Extending this doping strategy to other implantable elements in DLC provides a new means of exploring the physics and chemistry of highly-doped 2D materials.

36 MATERIALS SCIENCE↗

Hot carrier extraction from 2D semiconductor photoelectrodes

Hot carrier-based energy conversion systems could double the efficiency of conventional solar energy technology or drive photochemical reactions that would not be possible using fully thermalized, “cool” carriers, but current strategies require expensive multijunction architectures. Using an unprecedented combination of photoelectrochemical and in situ transient absorption spectroscopy measurements, we demonstrate ultrafast (<50 fs) hot exciton and free carrier extraction under applied bias in a proof-of-concept photoelectrochemical solar cell made from earth-abundant and potentially inexpensive monolayer (ML) MoS 2 . Our approach facilitates ultrathin 7 Å charge transport distances over 1 cm 2 areas by intimately coupling ML-MoS 2 to an electron-selective solid contact and a hole-selective electrolyte contact. Our theoretical investigations of the spatial distribution of exciton states suggest greater electronic coupling between hot exciton states located on peripheral S atoms and neighboring contacts likely facilitates ultrafast charge transfer. Our work delineates future two-dimensional (2D) semiconductor design strategies for practical implementation in ultrathin photovoltaic and solar fuel applications.

2D materials↗

Photo-Induced Charge Transfer of Fullerene and Non-Fullerene Conjugated Polymer Blends via Ab Initio Excited-State Dynamics

Organic conjugated polymers (CPs) are promising candidates for organic photovoltaic (OPV) devices due to their unique tunable mechanical and optoelectronic performance. Over the last decade, optoelectronic properties of narrow band gap CPs as a blend with acceptor units are largely optimized, which leads to noticeable progress in OPV technology. However, their power conversion efficiency is still lower than their organic counterparts (i.e., silicon), limiting their practical usage. In this study, we employ ab initio molecular dynamics to explore photo-induced charge transfer (CT) of the diketopyrrolopyrrole-based polymer as a blend with non-fullerene (i.e., ITIC) and fullerene (i.e., PCBM) acceptor units. The results of charge carrier dynamics induced by selected photoexcitation show that hole density redistribution in space is much faster than electron relaxation. We track the relaxation rates of charge carriers over time, where the derivative of the difference between the rate of electron and hole implies the current density at zero voltage. Furthermore, this can be utilized to characterize the CT performance of CPs blended with different acceptor units. Relaxation rate results indicate that CP blend with ITIC promises a better PV performance, illustrating that the current computational approach opens the door to determine bulk heterojunctions’ electronic performance for OPV devices and narrowing down the list of potential donor–acceptor candidates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

On the Effect of Beating during Nonlinear Frequency Chirping

Spectroscopic analyses of energetic particle (EP) driven bursts of MHD fluctuations in magnetically confined plasmas often exhibit chirps that occur simultaneously in groups of two or more. While the superposition of oscillations at multiple frequencies necessarily causes beating in the signal acquired by a localized external probe, self-consistent hybrid simulations of chirping EP modes in a JT-60U tokamak plasma have demonstrated the possibility of global beating, where the mode's electromagnetic field vanishes globally between beats and reappears with opposite phase [Bierwage et al., Nucl. Fusion 57, 016036 (2017)]. This implies that there can be a single coherent field mode that oscillates at multiple frequencies simultaneously when it is resonantly driven by multiple density waves in EP phase space. Conversely, this means that the EP density waves are mutually coupled and interfere with each other via the jointly driven field, a mechanism ignored in some theories of chirping. In this thesis-style treatise, we study the role of field pulsations in general and beating in particular using the Hamiltonian guiding center orbit-following code ORBIT with a reduced wave-particle interaction model in realistic geometry. Beating is found to drive the evolution of EP phase space structures. Additionally, a key mechanism is the pulsation of effective phase space islands combined with the alternation of their effective O- and X-points due to phase jumps between each beat. Observations: (1) Beating causes density wave fronts to advance radially in a pulsed manner and the resulting chirps become staircase-like. (2) The pulsations facilitate convective transfer of material between neighboring layers of phase space density waves. On the one hand, this may inhibit the early detachment of solitary phase space vortices. On the other hand, it facilitates the accumulation of hole and clump fragments into larger structures. (3) Long-range chirping is observed when massive holes or clumps detach and drift away from the turbulent belt around the seed resonance. It is remarkable that the detached vortices remain robust and,on average, maintain their concentric nested layers while being visibly perturbed by the field's continued beating.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effects of film injection angle on turbine vane cooling

Film ejection from discrete holes in the suction surface of a turbine vane was studied for hole axes (1) slanted 30 deg to the surface in the streamwise direction and (2) slanted 30 deg to the surface and 45 deg from the streamwise direction toward the hub. The holes were near the throat area in a five-row staggered array with 8-diameter spacing. Mass flux ratios were as high as 1.2. The data were obtained in an annular sector cascade at conditions where both the ratio of the boundary layer momentum thickness-to-hole diameter and the momentum thickness Reynolds number were typical of an advanced turbofan engine at both takeoff and cruise. Wall temperatures were measured downstream of each of the rows of holes. Results of this study are expressed as a comparison of cooling effectiveness between the in-line angle injection and the compound-angle injection as a function of mass flux ratio. These heat transfer results are also compared with the results of a referenced flow visualization study. Also included is a closed-form analytical solution for temperature within the film cooled wall.

Gauntner, J. W.↗

Bubble Generation in a Flowing Liquid Medium and Resulting Two-Phase Flow in Microgravity

An experimental and theoretical research program is described herein to study bubble generation in a liquid flow in a pipe under reduced gravity conditions. The objective of the work is to study the bubble size and frequency of the generation and the resulting two-phase flow but it also concerns the fluid mechanical aspects of boiling in forced flow in microgravity. By injecting a gas into a liquid flow in a pipe through a small hole in the pipe wall we will investigate how the bubble expands and detaches from the wall, without involving the complexities of boiling. The experiments will be conducted both under isothermal conditions and with heat transfer from the wall. In the experiments with heat transfer the effect of thermocapillarity on the bubble formation and detachment will be the main subject.

Kamotani, Yasuhiro↗

Ligand-Dependent Tuning of Interband and Intersubband Transitions of Colloidal CdSe Nanoplatelets

Although surface ligands of colloidal nanocrystals are known to adjust the absolute energy levels of valence and conduction bands of semiconductor nanocrystals, they typically have only minor influence on the band gap or effective masses. This changes in nanoplatelets. Ligand exchange of CdSe colloidal nanoplatelets induces large (up to 300 meV) bathochromic shifts of both interband and intersubband transitions. Here, three families of ligands-halides, thiolates, and phosphonates-are used to tune interband transitions, reflecting electron and hole confinement, across visible wavelengths and intersubband transitions, reflecting electron confinement, across the near-infrared spectral window. Furthermore, careful examination shows that delocalization from expansion of the nanoplatelet short axis, which was reported previously, cannot alone explain observed red shifts. Instead, comparison of intersubband, interband, and hole energy levels shows that ligand head group chemistry confers specific, idiosyncratic adjustments of the contribution of conduction and valence bands to the observed bathochromic shifts. Phosphonate ligands show the largest band gap reductions but the smallest red shift of intersubband transition energies; halide-exchanged samples displayed smaller reductions in band gap but large red shifts of intersubband transitions; thiolates fall in between. A related specificity is observed in hole states, which implicates ligand-responsive valence band curvature as an additional contribution driving optical changes. For nanoplatelets, surface ligand chemistry offers not only a tool to adjust the absolute energy level of conduction and valence bands but also an alternative route to preferential electron or hole band engineering that is normally achieved with inorganic shells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alignment-enhancing feed-through conductors for stackable silicon-on-sapphire wafers

Alignment-enhancing electrically conductive feed-through paths are provided for the high-speed low-loss transfer of electrical signals between integrated circuits of a plurality of silicon-on-sapphire bodies arrayed in a stack. The alignment-enhancing feed-throughs are made by a process involving the drilling of holes through the body, double-sided sputtering, electroplating, and the filling of the holes with solder by capillary action. The alignment-enhancing feed-throughs are activated by forming a stack of wafers and remelting the solder whereupon the wafers, and the feed-through paths, are pulled into alignment by surface tension forces.

Anthony, Thomas R.↗

Development of the Glenn Heat-Transfer (Glenn-HT) Computer Code to Enable Time-Filtered Navier-Stokes (TFNS) Simulations and Application to Film Cooling on a Flat Plate Through Long Cooling Tubes

Computational fluid dynamics (CFD) analysis using Reynolds-averaged Navier-Stokes (RANS) formulation for turbomachinery-related flows has enabled improved engine component designs. RANS methodology has limitations that are related to its inability to accurately describe the spectrum of flow phenomena encountered in engines. Examples of flows that are difficult to compute accurately with RANS include phenomena such as laminar/turbulent transition, turbulent mixing due to mixing of streams, and separated flows. Large eddy simulation (LES) can improve accuracy but at a considerably higher cost. In recent years, hybrid schemes that take advantage of both unsteady RANS and LES have been proposed. This study investigated an alternative scheme, the time-filtered Navier-Stokes (TFNS) method applied to compressible flows. The method developed by Shih and Liu was implemented in the Glenn-Heat-Transfer (Glenn-HT) code and applied to film-cooling flows. In this report the method and its implementation is briefly described. The film effectiveness results obtained for film cooling from a row of 30deg holes with a pitch of 3.0 diameters emitting air at a nominal density ratio of unity and two blowing ratios of 0.5 and 1.0 are shown. Flow features under those conditions are also described.

Ameri, Ali↗