Observation of coupled plasmon-polariton modes of plasmon waveguides for electromagnetic energy transport below the diffraction limit

We investigate the possibility of using arrays of closely spaced metal nanoparticles as plasmon waveguides for electromagnetic energy below the diffraction limit of light. Far-field spectroscopy on arrays of closely spaced 50 nm Au particles fabricated using electron beam lithography reveals the presence of near-field optical particle interactions that lead to shifts in the plasmon resonance frequencies for longitudinal and transverse excitations. We link this observation to a point-dipole model for energy transfer in plasmon waveguides and give an estimate of the expected group velocities and energy decay lengths for the fabricated structures. A near-field optical excitation and detection scheme for energy transport is proposed and demonstrated. The fabricated structures show a high propagation loss of about 3 dB / 15 nm which renders a direct experimental observation of energy transfer impossible. The nature of the loss and ways to decrease it by an order of magnitude are discussed. We also present finite-difference time-domain simulations on the energy transfer properties of plasmon waveguides

Hydrogen-induced CO displacement from the Pt(111) surface: an isothermal kinetic study

Chemisorbed CO can be completely removed from the Pt(111) surface in the temperature range 318 to 348 K for hydrogen pressures above 2 x 10-2 Torr. Thermal desorption of CO in this temperature range in the absence of hydrogen removes only a fraction of the adsorbed CO. A series of in situ isothermal kinetic experiments are presented in this paper which show that CO displacement in the presence of 0.2 Torr of hydrogen is a first-order process in CO coverage with an activation energy of 10.9 kcal/mol. We propose that the origin of this effect is that repulsive intereactions between coadsorbed atomic hydrogen and carbon monoxide induce high desorption rates of CO characteristic of high CO coverages, presumably due to lower values of the desorption activation energy. The importance of these results is to show that high coverages of coadsorbed hydrogen resulting from substantial overpressures of H2 may substantially modify desorption activation energies, and thus the coverages and kinetic pathways available, even for strongly chemisorbed species. These phenomena may play an important role in surface reactions which occur at high pressure.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/29038/1/0000071.pd

Investigation of W-SiC compositionally graded films as a divertor material

W-SiC composite material is a promising plasma-facing material candidate alternative to pure W due to the low neutron activation, low impurity radiation, and low tritium diffusivity of SiC while leveraging the high erosion resistance of the W armor. Additionally, W and SiC have high thermomechanical compatibility given their similar thermal expansion rates. The present study addresses the synthesis and performance of compositionally graded W-SiC films fabricated by pulsed-DC magnetron sputtering. Compositional gradients were characterized using transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS), and crystallographic information was obtained using electron diffraction and X-ray diffraction (XRD). Samples were exposed to L-mode deuterium plasma discharges in the DIII-D tokamak using the Divertor Material Evaluation System (DiMES). Post-mortem characterizations were performed using scanning electron microscopy (SEM) and XRD. Electron diffraction and XRD showed that the compositionally graded W-SiC films were composed of polycrystalline W and amorphous SiC with amorphous W+SiC interlayers. No macroscopic delamination or microstructural changes were observed under mild exposure conditions. This study serves as a preliminary examination of W-SiC compositionally graded composites as a potential candidate divertor material in future tokamak devices.Comment: Published in Journal of Nuclear Material

Chemistry of bimetallic and alloys surfaces

We have continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strength, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. In the past 18 months, we have continued to study how alkali promoters strongly affect the reactions of hydrocarbons on Pt and Ni surfaces by altering the electronic structure and inducing significant site-blocking effects. We have shown that bismuth coadsorption provides benchmark data on ensemble sizes required for chemical reactions on Pt and Ni surfaces. Surface alloys of Sn/Pt are being used for detailed probing of ensemble sizes and also reactive site requirements. 22 refs

Chemistry of bimetallic and alloy surfaces

In the first funding period, we continued our work on elucidating the underlying principles that govern chemical reactions occurring on bimetallic and alloy surfaces. Our goal is to aid in the atomic level explanation of the reactivity and selectivity of alloy and bimetallic cluster catalysts and to provide a fundamental basis for the design of new catalysts with improved performance. Our approach is to use a battery of surface science methods to obtain fundamental data on the thermochemistry and kinetics of the adsorption and reaction of molecules on extensively characterized, single-crystal bimetallic surfaces. We measure changes in chemisorption bond strengths, adsorption site distributions, and hydrocarbon fragment stability and reactivity and correlate these results with the geometric and electronic structure of the metal atoms on the surface. Often, our aim is to carefully design experiments that isolate the several factors (e.g., ensemble and ligand effects) that control surface chemistry and catalysis on bimetallic and alloy surfaces in order to better understand the importance of each contribution. Some of the highlights and noteworthy accomplishments made during the first period of this grant are given

Chemical Modification of Surface Properties

Chemically tailoring materials to have new and unique surface properties has enormous potential in a wide variety of applications for interfacial phenomena in materials science and catalysis. Recent work from our laboratory on model systems designed to explain how changes in geometric and electronic structure of metal surfaces affect surface chemistry are discussed. Specifically, the influence of potassium and bismuth coadsorption with small molecules on a Pt(111) single crystal surface will be described. We will also discuss the chemical reactivity of palladium metal monolayers and thin films which have been recently reported to have dramatically altered geometric and electronic structure. 31 refs., 3 figs