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.

Economic boom and social mobility:The Irish experience

In this paper we examine the consequences for social mobility of the recent unprecedented period of economic growth experienced in Ireland and the implications of such developments for current theories of social fluidity. Contrary to suggestions that the "Celtic Tiger" experience has been associated with deepening problem marginalization, we found evidence for a substantial upgrading of the class structure, increased levels of social mobility and increased social fluidity in relation to long-range hierarchical mobility. Such increased openness could not be explained by changes in the mediating role of education. The pattern of change suggests that both the upgrading of the class structure and the recent unprecedented tightness of the labour market have led employers to increasingly apply criteria other than education in a manner that has facilitated increased social fluidity. The Irish case provides further support for the argument for reconsidering the balance that mobility research has struck between social fluidity and absolute mobility and encouraging increased attention to the evolution of firms and jobs. It also suggests that, in circumstances where policies in advanced industrial societies have shown an increasing tendency to diverge, increased social fluidity may come about as a consequence of very different economic and social policies. © 2006 Elsevier Ltd. All rights reserved.

Optimisation and scaling of interfacial GeO2 layers for high-k gate stacks on germanium and extraction of dielectric constant of GeO2

Germanium is an attractive channel material for MOSFETs because of its higher mobility than silicon. In this paper, GeO2 has been investigated as an interfacial layer for high-kappa gate stacks on germanium. Thermally grown GeO2 layers have been prepared at 550 degrees C to minimise GeO volatilisation. GeO2 growth has been performed in both pure O-2 ambient and O-2 diluted with N-2. GeO2 thickness has been scaled down to approximately 3 nm. MOS capacitors have been fabricated using different GeO2 thicknesses with a standard high-kappa dielectric on top. Electrical properties and thermal stability have been tested up to at least 350 degrees C. The K value of GeO2 was experimentally determined to be 4.5. Interface state densities (D-it) of less than 10(12) CM-2 eV(-1) have been extracted for all devices using the conductance method.

The Industrial Context of Occupational Mobility: Change in Structure

The neglect of a consideration of history has been a feature of mobility research. ‘History’ affects the results of analyses of social mobility by altering the occupational/industrial structure and by encouraging exchange mobility. Changes in industrial structure are rooted more directly in historical causes and can be seen as more fundamental than changes in occupational structure. Following a substantial review of the secondary literature on changes in industrial and occupational structure in Northern Ireland, loglinear analyses of intra- and intergenerational mobility tables for sociologically-derived cohort generations that incorporate occupational and industrial categories are presented. Structural and inheritance effects for industry are as significant as those for occupation. Given the well-established finding of ‘constant social fludity’ in mobility tables once structural effects are controlled, the inclusion of categorization by industry is necessary in order to reach an accurate understanding of occupational mobility and the role of historical change in mobility.

Tungsten Silicide Contacts to Polycrystalline Silicon and Silicon-Germanium Alloys

Novel CVD WSi2 technology with low series and contact resistance in SiGe HBTs was achieved. Specific contact resistance to Si1-xGex with 0

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.

The near-edge structure in energy-loss spectroscopy: many-electron and magnetic effects in transition metal nitrides and carbides

We investigate the ability of the local density approximation (LDA) in density functional theory to predict the near-edge structure in electron energy-loss spectroscopy in the dipole approximation. We include screening of the core hole within the LDA using Slater's transition state theory. We find that anion K-edge threshold energies are systematically overestimated by 4.22 +/- 0.44 eV in twelve transition metal carbides and nitrides in the rock-salt (B1) structure. When we apply this 'universal' many-electron correction to energy-loss spectra calculated within the transition state approximation to LDA, we find quantitative agreement with experiment to within one or two eV for TiC, TiN and VN. We compare our calculations to a simpler approach using a projected Mulliken density which honours the dipole selection rule, in place of the dipole matrix element itself. We find remarkably close agreement between these two approaches. Finally, we show an anomaly in the near-edge structure in CrN to be due to magnetic structure. In particular, we find that the N K edge in fact probes the magnetic moments and alignments of ther sublattice.

Surface plasmon polariton propagation length: A direct comparison using photon scanning tunneling microscopy and attenuated total reflection

The propagation of surface plasmon polaritons (SPP's) is studied using a photon scanning tunneling microscope (PSTM) and conventional attenuated total reflection (ATR). The PSTM experiment uses localized (focused beam) launching or SPP's at a wavelength of 632.8 nm. Propagation of the SPP is observed as an exponentially decaying tail beyond the launch site acid the 1/e propagation length is measured directly for a series of Ag films of different thicknesses. The ATR measurements are used to characterize the thin film optical and thickness parameters, revealing, notably, the presence of a contaminating adlayer of Ag2S of typical dielectric function, 8.7 + i2.7, and thickness 1-2 nm. Values of the SPP propagation length, based on the ATR- derived film parameters used in the four-media implicit SPP dispersion relation, show very good agreement with those based on the PSTM images for the case of undercoupled or optimally coupled SPP modes. The observed propagation lengths are quantitatively analyzed taking explicit account of additional intrinsic damping due to the growth of the Ag2S layer and of reradiation of the SPP back into the prism outside the launch site. Finally, the PSTM images show excellent SPP beam confinement in the original propagation direction.

Nonlinear transport and localization in single-walled carbon nanotubes

We have measured the electrical transport properties of mats of single-walled carbon nanotubes (SWNT) as a function of applied electric and magnetic fields. We find that at low temperatures the resistance as a function of temperature R(T) follows the Mott variable range hopping (VRH) formula for hopping in three dimensions. Measurement of the electric field dependence of the resistance R(E) allows for the determination of the Bohr radius of a localized state a = 700nm. The magnetoresistance (MR) of SWNT mat samples is large and negative at all temperatures and fields studied. The low field negative MR is proportional to H2, in agreement with variable range hopping in two or three dimensions. 3D VRH indicates good intertube contacts, implying that the localization is due to the disorder experienced by the individual tubes. The 3D localization radius gives a measure of the ID localization length on the individual tubes, which we estimate to be >700 nm. Implications for the electron-phonon mean free path are discussed.

Power dissipation in nanoscale conductors: classical, semi-classical and quantum dynamics

Modelling Joule heating is a difficult problem because of the need to introduce correct correlations between the motions of the ions and the electrons. In this paper we analyse three different models of current induced heating (a purely classical model, a fully quantum model and a hybrid model in which the electrons are treated quantum mechanically and the atoms are treated classically). We find that all three models allow for both heating and cooling processes in the presence of a current, and furthermore the purely classical and purely quantum models show remarkable agreement in the limit of high biases. However, the hybrid model in the Ehrenfest approximation tends to suppress heating. Analysis of the equations of motion reveals that this is a consequence of two things: the electrons are being treated as a continuous fluid and the atoms cannot undergo quantum fluctuations. A means for correcting this is suggested.

Germanium MOS Capacitors with Hafnium Dioxide and Silicon Dioxide Dielectrics

Germanium (Ge) does not grow a suitable oxide for MOS devices. The Ge/dielectric interface is of prime importance to the operation of photo-detectors and scaled MOSTs. Therefore there is a requirement for deposited or bonded dielectric materials. MOS capacitors have been formed on germanium substrates with three different dielectric materials. Firstly, a thermally grown and bonded silicon dioxide (SiO2) layer, secondly, SiO2 deposited by atmospheric pressure CVD ‘silox’, and thirdly a hafnium oxide (HfO2) high-k dielectric deposited by atomic layer deposition (ALD). Ge wafers used were p-type 1 0 0 2 O cm. C–V measurements have been made on all three types of capacitors to assess the interface quality. ALD HfO2 and silox both display acceptable C–V characteristics. Threshold voltage and maximum and minimum capacitance values closely match expected values found through calculation. However, the bonded SiO2 has non-ideal C–V characteristics, revealing the presence of a high density of interface states. A H2/N2 post metal anneal has a detrimental effect on C–V characteristics of HfO2 and silox dielectrics, causing a shift in the threshold voltage and rise in the minimum capacitance value. In the case of hafnium dioxide, capacitor properties can be improved by performing a plasma nitridation of the Ge surface prior to dielectric deposition.

Understanding the dehydrogenation mechanism of tetrahydrocarbazole over palladium using a combined experimental and density functional theory approach

The mechanism of the dehydrogenation of tetrahydrocarbazole to carbazole over palladium has been examined for the first time. By use of a combination of deuterium exchange experiments and density functional theory calculations, a detailed reaction profile for the aromatization of tetrahydrocarbazole has been identified and validated by experiment. As with many dehydrogenation reactions, the initial hydrogen abstraction is found to have the highest reaction barrier. Tetrahydrocarbazole has four hydrogens which can, in principle, be cleaved initially; however, the theory and experiment show that the reaction is dominated by the cleavage of the carbon hydrogens at the carbon atoms in positions 1 and 4. The two pathways originating from these two C-H bond cleavage processes are found to have similar reaction energy profiles and both contribute to the overall reaction.