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At least 1,405 records · Page 78

Mechanically interlocked pyrene-based photocatalysts

Triplet excited-state organic chromophores present countless opportunities for applications in photocatalysis. Here we describe an approach to the engineering of the triplet excited states of aromatic chromophores, which involves incorporating pyrene into pyridinium-containing mechanically interlocked molecules (MIMs). The π-extended nature of the pyrenes enforces [π···π] stacking, affording an efficient synthesis of tetrachromophoric octacationic homo[2]catenanes. These MIMs generate triplet populations and efficient intersystem crossing on account of the formation of a mixed charge-transfer/exciplex electronic state and a nanoconfinement effect, which leads to a high level of protection of the triplet state and extends the triplet lifetimes and yields. These compounds display excellent catalytic activity in photo-oxidation, as demonstrated by the aerobic oxidation of a sulfur-mustard simulant. Furthermore this research highlights the benefits of using the mechanical bond to fine-tune the triplet photophysics of existing aromatic chromophores, providing an avenue for the development of unexplored MIM-based photosensitizers and photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resonant two-photon photoelectron imaging and adiabatic detachment processes from bound vibrational levels of dipole-bound states

Anions cannot have Rydberg states, but anions with polar neutral cores can support highly diffuse dipole-bound states (DBSs) as a class of interesting electronically excited states below the electron detachment threshold. The binding energies of DBSs are extremely small, ranging from a few to few hundred wavenumbers and generally cannot support bound vibrational levels below the detachment threshold. Thus, vibrational excitations in the DBS are usually above the electron detachment threshold and they have been used to conduct resonant photoelectron spectroscopy, which is dominated by state-specific autodetachment. Here we report an investigation of a cryogenically-cooled complex anion, the enantiopure (R)-(–)-1-(9-anthryl)-2,2,2-trifluoroethanolate (R-TFAE–). The neutral R-TFAE radical is relatively complex and highly polar with a non-planar structure (C 1 symmetry). Photodetachment spectroscopy reveals a DBS 209 cm–1 below the detachment threshold of R-TFAE– and seven bound and eight above-threshold vibrational levels of the DBS. Resonant two-photon detachment (R2PD) via the bound vibrational levels of the DBS exhibits strictly adiabatic photodetachment behaviors by the second photon, in which the vibrational energies in the DBS are carried to the neutral final states, because of the parallel potential energy surfaces of the DBS and the corresponding neutral ground electronic state. Relaxation processes from the bound DBS levels to the ground and low-lying electronically excited states of R-TFAE– are also observed in the R2PD photoelectron spectra. Finally, the combination of photodetachment and resonant photoelectron spectroscopy yields frequencies for eight vibrational modes of the R-TFAE radical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of pattern transfer process on roughness of block copolymer patterns from directed self-assembly

Block copolymer-directed self-assembly (DSA) remains promising for improving pattern quality and reducing the stochastic variations that challenge high numerical aperture extreme ultraviolet lithography. Equally critical is refining pattern transfer methods for accurately transferring the rectified DSA features to the underlying substrate. We compare two atomic layer deposition (ALD)-based techniques: sequential infiltration synthesis (SIS) and dry liftoff, applied to polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DSA patterns. Both methods utilize aluminum oxide hard masks, with one synthesized through infiltration into the PMMA domains and the other through conformal ALD coating. High-resolution scanning electron micrographs were analyzed to measure line edge, width, and placement roughness for both the line (PMMA) and space (PS) features. Although both methods yielded similar overall 3σ rms roughness, they differed significantly in the frequency-dependent power spectral density (PSD) profiles. SIS reduced line placement roughness at length scales associated with the polymer pitch, but increased space width roughness at low frequencies, whereas dry liftoff mimicked the frequency content of the original guiding pattern. This study underscores the importance of PSD evaluation in selecting optimal pattern transfer strategies for specific applications.

Block copolymers↗

The Synthesis of Manganese Hydroxide Nanowire Arrays for a High-Performance Zinc-Ion Battery

The morphology, microstructure as well as the orientation of cathodic materials are the key issues when preparing high-performance aqueous zinc-ion batteries (ZIBs). In this paper, binder-free electrode Mn(OH)2 nanowire arrays were facilely synthesized via electrodeposition. The nanowires were aligned vertically on a carbon cloth. The as-prepared Mn(OH)2 nanowire arrays were used as cathode to fabricate rechargeable ZIBs. The vertically aligned configuration is beneficial to electron transport and the free space between the nanowires can provide more ion-diffusion pathways. As a result, Mn(OH)2 nanowire arrays yield a high specific capacitance of 146.3 Ma h g−1 at a current density of 0.5 A g−1. They also demonstrates ultra-high diffusion coefficients of 4.5 × 10−8~1.0 × 10−9 cm2 s−1 during charging and 1.0 × 10−9~2.7 × 10−11 cm−2 s−1 during discharging processes, which are one or two orders of magnitude higher than what is reported in the studies. Furthermore, the rechargeable Zn//Mn(OH)2 battery presents a good capacity retention of 61.1% of the initial value after 400 cycles. This study opens a new avenue to boost the electrochemical kinetics for high-performance aqueous ZIBs.

25 ENERGY STORAGE↗

Vibrational energy exchange in CO-CO collisions at low temperature

The V-V exchange rates for CO in the ground electronic state have been measured at a temperature of 75 K. The rates determined were for the processes CO(nu = n) + CO(nu = 0) yields CO(nu = n - 1) + CO(nu = 1) - increment E, with n lying in the closed interval from 2 to 8. The values obtained are close to published 100 K data, thus indicating an insensitivity to temperature. It appears that multirotational quantum jumps may be important in explaining the measured rates.

Gower, M. C.↗

Plasma diffusion into the wake of Venus

A model of the diffusion of ionosheath plasma into the wake region of Venus is presented. It is shown that particle diffusion, which is assumed to be a consequence of the fluctuating magnetic field observed in the wake of Venus by Pioneer Venus and Veneras 9 and 10, can explain the plasma observations made in the wake by Veneras 9 and 10. The pressure due to these diffusing particles when balanced against the ionospheric pressure yield ionopause heights less than 1000 km for zenith angles less than about 135 deg. The model also predicts significant fluxes of low energy electrons and ions for zenith angles less than 135 deg, which are capable of producing the observed nightside ionosphere.

Gombosi, T.↗

Measurement of electrical parameters and current components in the bulk of silicon solar cells

A review and illustration of electrical measurements for determination of the bulk parameters in silicon solar cells is given. The presentation concentrates on transient and small signal admittance measurements. These measurements yield accurate and reliable values of the base lifetime and the surface recombination velocity at the back contract without inaccuracies that normally results from electrons and holes in the p/n junction space charge region. This then allows the determination of the recombination current in each region of the cell. As an example, current components in the emitter, low doped base, high doped base and junction space charge region of the back surface field cell are obtained. Such analysis is essential in determining the relative importance of the base and the emitter and, thus, the region that limits the cell efficiency.

Neugroschel, A.↗

Electrostatic shocks as nonlinear ion acoustic waves

A cold fluid approach is presented which yields exact double-layer solutions that can be used to model electrostatic S-type shocks. Solutions derived from the two-temperature electron model are presented in order to show the range of amplitudes and scale lengths possible for this plasma model and to examine how shock properties depend on orientation of the shock. The dependence of various double-layer quantities on plasma composition is then considered for the cold electron beam model. Double-layer solutions pertinent to describing electrostatic shocks are pointed out.

Witt, E.↗

Transition region, corona, and solar wind in coronal holes - Some two-fluid models

A model is presented which treats the heating of the corona and the heating and acceleration of the solar wind as a single process, namely, the turbulent dissipation of solar-generated Alfven waves at the Kolmogorov rate. This model is similar to that described by Hollweg (1986), except that the electron temperature and the proton temperature are allowed to have different values. It is found that, similar to the findings of Hollweg, solutions which yield base pressures in the observed range lead to solar wind flows which are much too slow at 1 AU; a new feature is the appearance of proton temperature peak near 3-4 solar radii. Thus, this model seems to be also unsatisfactory. Several possible resolutions are discussed.

Hollweg, Joseph V.↗

Deposition Of Pinhole-Free CoSi2 Film

New fabrication method produces pinhole-free film of cobalt silicide on silicon substrate. In new method, cobalt and silicon evaporated from electron-beam sources onto substrate of silicon having <111> crystal orientation. Materials deposited in stoichiometric ratio of two silicon atoms to one of cobalt, yielding single-crystal CoSi2 film 5 to 10 nm thick. Layer of amorphous silicon 1 to 2 nm thick deposited on CoSi2. Specimen then annealed at 550 degree C for 10 min. Absence of pinholes critical to operation of multilayer devices employing CoSi2 layers, such as metal base transistor.

Lin, True-Lon↗

Planning time-optimal robotic manipulator motions and work places for point-to-point tasks

A method is presented which combines simple time-optimal motions in an optimal manner to yield the minimum-time motions for an important class of complex manipulator tasks composed of point-to-point moves such as assembly, electronic component insertion, and spot welding. This method can also be used to design manipulator actions and work places so that tasks can be completed in minimum time. The method has been implemented in a computer-aided design software system. Several examples are presented. Experimental results show the method's validity and utility.

Dubowsky, S.↗

Growth of improved quality 3C-SiC films on 6H-SiC substrates

Previously reported chemical vapor deposition of 3C-SiC on 6H-SiC has resulted in films with a high density of double positioning boundaries (DPBs). It is found that growth on as-grow faces of 6H-SiC crystals can yield films that are largely free of DPBs. The (111) 3C-SiC films, up to 12 microns thick, were evaluated by optical and electron microscopy and low-temperature photoluminescence (LTPL). The LTPL spectra of the films were similar to those of high quality Lely-grown 3C-SiC.

Powell, J. A.↗

Protein crystal growth in microgravity

A series of protein-crystal growth experiments were performed on Space Shuttle flight STS-26 in September 1988 and STS-29 in March 1989. These proteins had been studied extensively in crystal-growth experiments on earth prior to the microgravity experiments. For those proteins which produced crystals of adequate size, 3D intensity data sets with electronic area detector systems were collected. Comparisons show that the microgravity-grown crystals of these proteins are larger, display more uniform morphologies, and yield diffraction data to significantly higher resolutions. Analyses of the 3D data sets indicate that the space-grown crystals are more highly ordered at the molecular level than their earth-grown counterparts.

Snyder, Robert↗

X-rays and gamma-rays from accretion flows onto black holes in Seyferts and X-ray binaries

Observations and theoretical models of X-ray/gamma ray spectra of radio quiet Seyfert galaxies and Galactic black hole candidates are reviewed. The spectra from these objects share the following characteristics: an underlying power law with a high energy cutoff above 200 keV; a Compton reflection component with a Fe K alpha line, and a low energy absorption by intervening cold matter. The X-ray energy spectral index, alpha, is typically in the range between 0.8 and 1 in Seyfert spectra, and that of the hard state spectra of the black hole candidates Cygnus X-1 and GX 339-4 is typically between 0.6 and 0.8. The Compton reflection component corresponds with cold matter covering a solid angle of between 0.8pi and 2pi as seen from the X-ray source. The broadband spectra of both classes of sources are well fitted by Compton upscattering of soft photons in thermal plasma. The fits yield a thermal plasma temperature of 100 keV and the Thomson optical depth of 1. All the spectra presented are cut off before the electron rest energy 511 keV, indicating that electron/positron pair production is an important process.

Zdziarski, Andrzej A.↗

The Zero-Point Field and the NASA Challenge to Create the Space Drive

This NASA Breakthrough Propulsion Physics Workshop seeks to explore concepts that could someday enable interstellar travel. The effective superluminal motion proposed by Alcubierre (1994) to be a possibility owing to theoretically allowed space-time metric distortions within general relativity has since been shown by Pfenning and Ford (1997) to be physically unattainable. A number of other hypothetical possibilities have been summarized by Millis (1997). We present herein an overview of a concept that has implications for radically new propulsion possibilities and has a basis in theoretical physics: the hypothesis that the inertia and gravitation of matter originate in electromagnetic interactions between the zero-point field (ZPF) and the quarks and electrons constituting atoms. A new derivation of the connection between the ZPF and inertia has been carried through that is properly co-variant, yielding the relativistic equation of motion from Maxwell's equations. This opens new possibilities, but also rules out the basis of one hypothetical propulsion mechanism: Bondi's "negative inertial mass," appears to be an impossibility.

Haisch, Bernhard↗

Characterization of Magnetospheric Spacecraft Charging Environments Using the LANL Magnetospheric Plasma Analyzer Data Set

An improved specification of the plasma environment has been developed for use in modeling spacecraft charging. It was developed by statistically analyzing a large part of the LANL Magnetospheric Plasma Analyzer (MPA) data set for ion and electron spectral signature correlation with spacecraft charging, including anisotropies. The objective is to identify a relatively simple characterization of the full particle distributions that yield an accurate predication of the observed charging under a wide variety of conditions.

Hardage, Donna↗

T-Shaped Emitter Metal Structures for HBTs

Metal emitter structures in a class of developmental InP-based high-speed heterojunction bipolar transistors (HBTs) have been redesigned to have T-shaped cross sections. T-cross-section metal features have been widely used in Schottky diodes and high-electron-mobility transistors, but not in HBTs. As explained, the purpose served by the present T cross-sectional shapes is to increase fabrication yields beyond those achievable with the prior cross-sectional shapes.

Fung, King Man↗

Molecular compositions, materials, and methods for efficient multiple exciton generation

Embodiments of the present invention provides compounds, compositions, and methods for their preparation that provide efficient intramolecular fission, such that local order and strong nearest neighbor coupling is no longer a design constraint. Inventive materials include organic oligomers and polymers designed to exhibit strong intrachain donor-acceptor interactions and provide intramolecular singlet fission, whereby triplet populations can be generated in very high yields of, e.g., 170% or more. The inventive disclosure is directed to polymers of the general formula: [SA-SD]n with a strong electron acceptor (SA), a strong electron donor (SD), and n a positive integer equal to or greater than two; methods for their preparation and monomers used therein, blends, mixtures and formulations containing them; the use of the polymers, blends, mixtures and formulations as semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these polymers, blends, mixtures or formulations.

36 MATERIALS SCIENCE↗