Resolution of an ancient surface science anomaly: Work function change induced by N adsorption on W{100}

For many decades it has been assumed that an adsorbate centered above a metal surface and with a net negative charge should increase the work function of the surface. However, despite their electronegativity, N adatoms on W{100} cause a significant work function decrease. Here we present a resolution of this anomaly. Using density functional theory, we demonstrate that while the N atom carries a negative charge, of overriding importance is a reduction in the surface overspill electron density into the vacuum, when that charge is engaged in bonding to the adatom. This novel interpretation is fundamentally important in the general understanding of work function changes induced by atomic adsorbates.

TIME-RESOLVED OPTICAL-EMISSION AND ELECTRON-ENERGY DISTRIBUTION FUNCTION MEASUREMENTS IN RF PLASMAS

Comparisons between experimentally measured time-dependent electron energy distribution functions and optical emission intensities are reported for low-frequency (100 and 400 kHz) radio-frequency driven discharges in argon. The electron energy distribution functions were measured with a time-resolved Langmuir probe system. Time-resolved optical emissions of argon resonance lines at 687.1 and 750.4 nm were determined by photon-counting methods. Known ground-state and metastable-state excitation cross sections were used along with the measured electron energy distribution functions to calculate the time dependence of the optical emission intensity. It was found that a calculation using only the ground-state cross sections gave the best agreement with the time dependence of the measured optical emission. Time-dependent electron density, electron temperature, and plasma potential measurements are also reported.

TIME-RESOLVED ELECTRON-ENERGY DISTRIBUTION FUNCTION MEASUREMENTS IN A PULSED MAGNETIC MULTIPOLE HYDROGEN DISCHARGE

The time evolution of measured plasma parameters, including the electron energy distribution function (EEDF), in the discharge and post-discharge regime of a pulsed hydrogen magnetic multipole plasma is presented. The time necessary for the plasma to reach equilibrium has been established as 160-mu-s. The present results clarify the mechanisms which initiate the discharge. The decay rates of the charged-particle density and energy in the post-discharge have been measured. These measurements indicate that particle transport to the wall is the dominant loss mechanism for both charged-particle density and energy. The time-resolved EEDF is found to be non-Maxwellian in the discharge and Maxwellian in the late post-discharge.

Negative ion enhancement in caesium-seeded hydrogen discharges - a volume or surface effect?

Measurements of plasma parameters, including H- ion densities, made in conjunction with wall temperature, visible and vacuum ultraviolet emission spectroscopy verify that there is little caesium in the plasma volume of the H- ion source. Surface work function measurements indicate that there is significant caesium coverage of the inner walls of the ion source. It is found that, as the work function of a test surface decreases due to caesium seeding, the H- ion fraction in the discharge volume increases. These observations combine to indicate that, in the present source, the H- ion enhancement mechanism is a surface dominated effect. (C) 1999 American Institute of Physics. [S0003- 6951(99)04744-0].

The role of Na surface species on oxygen charge transfer in the Pt/YSZ system

The role of sodium surface species in the modification of a platinum (Pt) catalyst film supported on 8 mol% yttria-stabilised-zirconia (YSZ) was investigated under a flow of 20 kPa oxygen at 400 °C. Cyclic and linear sweep voltammetry were used to investigate the kinetics of the oxygen charge transfer reaction. The Pt/YSZ systems of both ‘clean’ and variable-coverage sodium-modified catalyst surfaces were also characterised using SEM, XPS and work function measurements using the Kelvin probe technique.

Samples with sodium coverage from 0.5 to 100% were used. It was found that sodium addition modifies the binding energy of oxygen onto the catalyst surface. Cyclic voltammetry experiments showed that higher overpotentials were required for oxygen reduction with increasing sodium coverage. In addition, sodium was found to modify oxygen storage and/or adsorption and diffusion increasing current densities at higher cathodic overpotential. Ex situ XPS measurements showed the presence of sodium hydroxide, carbonate and/or oxide species on the catalyst surface, while the Kelvin probe technique showed a decrease of approximately 250 meV in the work function of samples with more than 50% sodium coverage (compared to a nominally ‘clean’ sample).

Chemisorption and reactivity of furan on Pd{111}

XPS, HREELS, ARUPS and Delta phi data show that furan chemisorbs non-dissociatively on Pd{111} at 175 K, the molecular plane being significantly tilted with respect to the surface normal. Bonding involves both the oxygen lone pair and significant a interaction with the substrate. The degree of decomposition that accompanies molecular desorption is a strong function of coverage: similar to 40% of the adsorbate desorbs molecularly from the saturated monolayer. Decomposition occurs via decarbonylation to yield COa and H-a followed by desorption rate limited loss of H-2 and CO. It seems probable that an adsorbed C3H3 species formed during this process undergoes subsequent stepwise dehydrogenation ultimately yielding H-2 and C-a.

Performance assessment of nanoscale double- and triple- gate FinFETs

This is the first paper to describe performance assessment of triple and double gate FinFETs for High Performance (HP), Low Operating Power (LOP) and Low Standby Power (LSTP) logic technologies is investigated. The impact of gate work-function, spacer width, lateral source/drain doping gradient, fin aspect ratio, fin thickness on device performance, has been analysed in detail and guidelines are presented to meet ITRS specification at 65 and 45 nm nodes. Optimal design of lateral source/drain doping profile can not only effectively control short channel effects, yielding low off-current, but also achieve low values of intrinsic gate delay.

Light emission from scanning tunnelling microscope on polycrystalline Au films - what is happening at the single-grain level?

When operated with a metallic tip and sample the scanning tunnelling microscope constitutes a nanoscale, plasmonic light source yielding broadband emission up to a photon energy determined by the applied bias. The emission is due to tunnelling electron excitation and subsequent radiative decay of localized plasmon modes, which can be on the lateral scale of a single metal grain (similar to 25 nm) or less. For a Au-tip/Au-polycrystalline sample under ambient conditions it is found that the intensity and spectral content of the emitted light are not dependent on the lateral grain dimension, but are predominantly determined by the tip geometry. However, the intensity increases strongly with increasing film thickness (grain depth) up to 20-25 nm or approximately the skin depth of the Au film. Photon maps can show less emissive grains and two classes of this occurrence are distinguished. The first is geometrical in origin - a double-tip structure in this case - while the second is due to a contamination-induced lowering of the local work function that causes the tunnel gap to increase. It is suggested that differences in work-function lowering between grains presenting different crystalline facets, combined with an exponential decay in emitted light intensity with tip - sample distance, leads to grain contrast. These results are relevant to tip-enhanced Raman scattering and the fabrication of micro/nano-scale planar, light-emitting tunnel devices.

The human micro-vascular enclothelial cells in vitro interaction with atomic-nitrogen-doped diamond-like carbon thin films

This paper reports the initial response of atomic nitrogen doped diamond like carbon (DLC) to endothelial cells in vitro. The introduction of nitrogen atoms/molecules to the diamond like carbon structures leads to an atomic structural change favorable to the attachment of human micro-vascular enclothelial cells. Whilst the semi-conductivity induced by nitrogen in DLC is thought to play a part, the increase in the inion-bonded N atoms and N-2 molecules in the atomic doped species (with the exclusion of the charged species) seems to contribute to the improved attachment of human microvascular endothelial cells. The increased endothelial attachment is associated with a lower work function and slightly higher water contact angle in the atomic doped films, where the heavy charged particles are excluded. The films used in the study were synthesized by the RF PECVD technique followed by post deposition doping with nitrogen, and afterwards the films were characterized by XPS, Raman spectroscopy, SIMS and Kelvin probe. The water contact angles were measured, and the counts of the adherent endothelial cells on the samples were carried out. This study is relevant and contributory to improving biocompatibility of surgical implants and prostheses.

Promotion of Ceria Catalysts by Precious Metals: Changes in Nature of the Interaction under Reducing and Oxidizing Conditions

By depositing ceria over supported precious metal (PM) catalysts and characterizing them with in situ diffuse reflectance UV (DR UV) and in situ Raman spectroscopy, we have been able to prove a direct correlation between a decrease in ceria band gap and the work function of the metal under reducing conditions. The PM ceria interaction results in changes on the ceria side of the metal ceria interface, such that the degree of oxygen vacancy formation on the ceria surface also correlates with the precious metal work function. Nevertheless, conclusive evidence for a purely electronic interaction could not be provided by X-ray photoelectron spectroscopy (XPS) analysis. On the contrary, the results highlight the complexity of the PM ceria interaction by supporting a spillover mechanism resulting from the electronic interaction under reducing conditions. Under oxidizing conditions, another effect has been observed; namely, a structural modification of ceria induced by the presence of PM cations. In particular, we have been able to demonstrate by in situ Raman spectroscopy that, depending on the PM ionic radius, it is possible to create PM ceria solid solutions. We observed that this structural modification prevails under an oxidizing atmosphere, whereas electronic and chemical interactions take place under reducing conditions.

Long-Range Lateral Dopant Diffusion in Tungsten Silicide Layers

Novel diode test structures have been manufactured to characterize long-range dopant diffusion in tungsten silicide layers. A tungsten silicide to p-type silicon contact has been characterized as a Schottky barrier rectifying contact with a silicide work function of 4.8 eV. Long-range diffusion of boron for an anneal at 900 °C for 30 min has been shown to alter this contact to become ohmic. Long-range diffusion of phosphorus with a similar anneal alters the contact to become a bipolar n-p diode. Bipolar diode action is demonstrated experimentally for anneal schedules of 30 min at 900 °C, indicating long-range diffusion of phosphorus (~38 µm), SIMS analysis shows dopant redistribution is adversely affected by segregation to the silicide/oxide interface. The concept of conduit diffusion has been demonstrated experimentally for application in advanced bipolar transistor technology. © 2009 IEEE.

Developments in performance-based testing of concrete

Implementation of both design for durability and performance-based standards and specifications are limited by the lack of rapid, simple, science-based test methods for characterizing the transport properties and deterioration resistance of concrete. To this end, this paper presents the background rationale and current developments in the application of electrical property measurements - conductivity in this instance - as a testing methodology to evaluate the relative performance of a range of concrete mixes. The technique can not only be used on standard specimens (e.g. cubes), but also lends itself to in-situ monitoring thereby allowing measurements to be obtained on the as-placed concrete. It is the latter which forms the focus of the current work. Conductivity measurements are presented for concretes with and without supplementary cementitious materials (SCM's) from demoulding up to 400-days. It is shown that electrical conductivity measurements display a continual decrease over the entire test period and attributed to the pore structure refinement due to hydration and pozzolanic reaction in those concretes containing blast furnace slag or fly ash. The term Formation Factor is introduced to rank concrete performance in terms of is resistance to chloride penetration.