Attenuated total reflectance spectroscopy of simultaneous processes: Corrosion inhibition of cuprous oxide by benzotriazole

Attenuated total reflectance (ATR) spectroscopy was used to perform in situ studies of the corrosion inhibition of cuprous oxide (Cu₂O) by benzotriazole (BTA) in aqueous solution at concentrations from 1 to 20 μM. Because two separate processes occur simultaneously, that of Cu₂O corrosion and corrosion inhibition by BTA adsorption, the spectral information was subjected to deconvolution by a conjugate gradient minimization algorithm. Under these conditions, a solution phase concentration of 7-10 μM BTA nearly completely inhibited the corrosion of Cu₂O in deionized water. Using a Langmuir adsorption model, this represented only 25% of the maximally covered surface area.     

H and P solid-state NMR of trimethylphosphine adsorbed on heteropolytungstate supported on silica

Trimethylphosphine (TMP) has been used as an NMR probe in order to determine the acidity of Keggin-type 12-tungstophosphoric heteropolyacid (HPW), pure and supported on silica, dehydrated at 473 K. Adsorption of TMP on pure dehydrated HPW leads to the formation of trimethylphosphonium ions (TMPH⁺) characteristic of the presence of strong Brönsted acid sites. TMP replaces the water molecules lost by dryness and allows the Keggin secondary structure to recover.Silica interacts with TMP by two kinds of acid sites: with weak acid support sites through the isolated silanol groups and with strong Brönsted acid, which lead to the formation of TMPH⁺, through the hydrogen-bonded silanol groups. Silica only interacts with HPW through its isolated silanol groups.     

Ammonia adsorption and decomposition on silica supported Rh nanoparticles observed by in situ attenuated total reflection infrared spectroscopy

Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is applied to study NH₃, adsorbed from the gas phase, and its decomposition products, i.e. NH_x species, on Rh nanoparticles, produced by spincoating from a RhCl₃ solution in water followed by reduction. A silicon ATR crystal with a hydroxilated SiO₂ layer acts as the support for the nanoparticles. Upon exposure to NH₃ in the vacuum chamber, NH₃ adsorbed to both silica and Rh is detected (sensitivity ∼5 × 10⁻⁵ absorbance units). Interaction of the NH₃ with the silica OH groups is observed around ∼2840 cm⁻¹ in combination with peaks showing the disappearance of unperturbed OH vibrations between 3500 and 3700 cm⁻¹. In addition, NH bend vibrations at 1634 cm⁻¹ and NH stretch vibrations at 3065 and 3197 cm⁻¹ are observed for substrate temperatures between 20 and 100 °C. The latter two correspond to NH on Rh, as verified with a sample without Rh, and probably correspond to undecomposed NH₃. Moreover, they remain after evacuation, suggesting strongly bound species. For a substrate temperature of 75 and 100 °C, additional NH stretch peaks at 3354 and 3283 cm⁻¹ are observed, possibly due to NH₂ intermediates, indicating NH₃ decomposition. It is shown that ATR-FTIR can contribute to the sensitive detection of adsorption and decomposition of gaseous species on realistic planar model catalysts.     

Optical extinction spectroscopy of single silver nanoparticles

The extinction spectrum of single silver nanoparticles with size ranging from 20 to 80 nm is investigated with the spatial modulation spectroscopy technique using either a tunable laser or a white lamp as the broadband source. Results are in good agreement with the prediction of the Mie theory, permitting to extract the nanoparticle size from the measured absolute value of the optical extinction cross-section. In contrast, the deduced refractive index of the nanoparticle environment and the reduction of the electron mean free path show a large dependence on the precise value of the bulk silver dielectric function.     

Photoreflectance investigation of hydrogenated (InGa)(AsN)/GaAs heterostructures

The optical response of as grown and hydrogenated In_0.32Ga_0.68As_1-yN_y/GaAs single quantum wells (y = 0, 0.027) has been investigated from T = 80 K to room temperature by photoreflectance. Three excitonic spectral features detected in the N free sample shift to lower energy in the N containing sample and back to higher energy upon H irradiation of the N containing sample. In the hydrogenated sample, a progressive change with increasing temperature of the nature of the lowest energy transition from an excitonic to a band-to-band character has been explained in terms of an increasing release of carriers from traps formed by H and N clusters. A reduction in the oscillator strength of the lowest energy transition and an increase in the binding energy of the heavy-hole exciton have been explained in terms of an increase in the electron effective mass upon N introduction into the In_xGa_1-xAs lattice. Received 23 June 2002 Published online 19 November 2002     

Optical properties of silver clusters formed by ion irradiation

Precipitation of silver clusters in silica is achieved by different methods: ion implantation, ion beam mixing of superimposed layers and ion irradiation of films deposited by means of co-sputtering or sol-gel technique. Main features of the nanoparticles depending on the preparation method are investigated by TEM. The optical extinction resonance of these clusters is analysed in terms of sizes and interaction between the clusters on the basis of calculations. We found that resonances in sputtered and gel films with low metal concentrations are well described by plasmon polaritons in isolated clusters and calculations based on Mie theory allow the study of their growth under irradiation. This theory is not appropriate to describe the optical response of silver clusters in silica implanted with Ag concentrations higher than 5 at.% or in ion beam mixed films, because of the interaction between clusters. Using an effective medium model, it is demonstrated that the random dispersion of clusters in implantation films causes fluctuations and, on average, an increase of the clusters polarization. On the contrary, the particular arrangement of the clusters with a bimodal size distribution in ion beam mixed films induces a screening effect between the clusters of largest size. Received 10 January 2002 / Received in final form 26 April 2002 Published online 19 July 2002     

Investigation of evolution hydrocarbon species on a Si surface during methane plasma with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry

We investigated evolution of hydrocarbon species on a Si surface during methane plasma both with and without substrate bias, using infrared spectroscopy in multiple internal reflection geometry (MIR-IRAS). We found that the relative density of the sp³-CH or sp³-CH₂ species to the sp³-CH₃ species was low in the low exposure regions, but that the relative density of the sp³-CH or sp³-CH₂ species increased as the exposure was higher. Substrate temperatures rose as the plasma exposure was higher. The changes of ratios would be ascribed to the substrate heating effect by plasma exposure, which would enhance the etching and/or hydrogen abstraction effects. We also found the change of CH_1-2/CH₃ ratios was enhanced when the high substrate bias was applied. The enhancement of the ratio was due to ion effects.     

Importance of lattice contraction in surface plasmon resonance shift for free and embedded silver particles

The size evolution of the surface plasmon resonance was investigated for free and embedded silver particles between about 2 to 10 nm in size. The crystal lattice of such particles as analyzed by high resolution electron microscopy show linear contraction with reciprocal particle size. Based on this, a model was presented by combining the lattice contraction of particles and the free path effect of electrons to predict the size evolution of the resonance. The results reveal a contribution of the lattice contraction to the resonance shift according to a roughly linear relation that changes slightly with particle radius (> 1.0 nm) and surrounding media. This surface plasmon resonance shift proceeds linearly with reciprocal size for Ag particles in vacuum and argon, but for Ag particles embedded in glass it appears to be independent of the radius down to nearly 1 nm. All predictions are quantitatively compared to previously reported experimental data and a good agreement is obtained. An unusual red-shift observed for Ag particles in glass may be attributed to a thermal expansion mismatch induced lattice dilatation. Received 26 July 2000 and Received in final form 14 September 2000     

A morphological study of vicinal surface growth based on a hybrid algorithm

A hybrid algorithm that combines a phase-field model and a lattice gas model evolving according to a kinetic Monte-Carlo (KMC) simulation scheme is used to investigate the dynamics of vicinal surface growth during vapor phase epitaxy. The algorithm is computationally far more efficient than pure KMC schemes, and this gain in efficiency does not correspond to a loss in information on the kinetics of individual atoms. We present numerical studies on the temperature dependence of macroscopic properties of the growing surface, evaluating the relevant stochastic processes (attachment, detachment, diffusion and island dynamics) as a function of their rates. We show that the temperature at which step flow is replaced by island nucleation depends on incoming flux, diffusion parameters and interstep distance. Moreover, we validate these finding by comparison to experiments and by analytical investigations.     

Mechanism of associative oxygen desorption from Pt(111) surface

Mechanism of the associative desorption of oxygen from the Pt(111) surface has been studied on atomic level by means of DFT/GGA calculations and kinetic Monte Carlo simulations. It has been found that two oxygen adatoms can occur, with sufficient probability, in neighboring on-top sites, which is essential for formation and subsequent evaporation of the oxygen molecule. Monte Carlo simulations have demonstrated effectiveness of this channel for O₂ formation on Pt(111) and strongly support the suggested model of associative desorption from transition metal surfaces.     

Electronic structure of F,-center in MgO

The embedded-cluster numerical variational method has been developed to calculate the electronic structure of perfect MgO, F and F⁺-centers in MgO. The energy band, bulk density of states has been calculated by cluster Mg₁₄O₁₃, Mg₁₄O₁₂F⁺ and Mg₁₄O₁₂F. The calculated absorption energy for F⁺ and F centers is in good agreement with experimental data. In our calculated defect energy levels, that the first excited state of F⁺-center is at CB-3.46 eV, indicates the necessity of a large photoelectron yielding energy. We also calculate the radius of color center electron, and plot the map of charge-density distribution of valence electrons in which the structure of the color center is shown directly. Received 22 May 1998     

Micro-Raman spectroscopy of disordered and ordered sulfur phases on a passivated GaAs surface

The depletion layer width and band bending of passivated n-type Sn doped GaAs(1 0 0) between subsequent steps of chemical treatment as well as after a single run treatment were investigated by micro-Raman light scattering by longitudinal optical phonons and coupled phonon-plasmon modes. Experiments were carried out ex situ at room temperature. We conclude that all observed lineshape changes are due to band bending and to an amorphous surface phase represented by a broad spectral component. We applied two passivation methods. One was based on (NH₄)₂S_x solution and lasted 30 min. The second was based on the S₂Cl₂ solution and lasted 10 s. These enabled identification of surface regions of different amorphousness and for faster passivation places of enlarged and completely reduced band bending.     

Complexation and distribution of counterions in a grafted polyelectrolyte layer

The complexation and the distribution of various cations, bound to a poly(styrene sulfonate) brush, have been investigated using infra-red spectroscopy and neutron reflectivity. Small counterions (like tetremethylammonium) are distributed throughout the brush in such a way that a local electroneutrality is ensured. They also exchange readily with other bulk small cations. On the other hand, model polycations are irreversibly trapped to the brush despite a relative small number of ionic bonds involved in the complexation. These complexed polycations are localized at the outer border of the brush, forming a macromolecular barrier. However, this spatial segregation does not allow the buildup of polyelectrolyte multilayers. Cationic surfactants are associated stoichiometrically with the brush sulfonates but unlike small counterions, this complexation is “irreversible” and induces a restructuring of the polymer interface. Received 22 August 2000     

Behavior of adsorbed hydrogen on Ni(1 1 1) surface with reemitted slow-positron spectroscopy

We have measured reemitted slow-positrons from hydrogen-adsorbed Ni(1 1 1) surface on different adsorbing conditions. It is seem that the reemitted slow-positron yield is maximum in the (2 × 2)-2H superstructure on Ni(1 1 1) surface. The origin of the change in reemitted slow-positron due to different adsorbing conditions will be discussed.     

Photoreflectance characterization of InAs/GaAs self-assembled quantum dots grown by ALMBE

We report on a photoreflectance investigation in the 0.8-1.5 eV photon energy range and at temperatures from 80 to 300 K on stacked layers of InAs/GaAs self-assembled quantum dots (QDs) grown by Atomic-Layer Molecular Beam Epitaxy. We observed clear and well-resolved structures, which we attribute to the optical response of different QD families. The dependence of the ground state transition energy on the number of stacked QD layers is investigated and discussed considering vertical coupling between dots of the same column. It is shown that Coulomb interaction can account for the observed optical response of QD families with different morphology coexisting in the same sample. Received 17 November 1999     

Spatial-dispersion and relativistic effects in the optical sum rules

We describe a procedure to take into account the spatial dispersion of the optical excitations in the susceptibility sum rules. We show that this implies that relativistic corrections of the same order must be considered. The final result is a decrease of the total oscillator strength equal to the ratio of the average electron kinetic energy with mc². We propose experiments with synchrotron radiation sources on crystals of heavy elements to observe the described effect. Received 5 June 2001     

Photophysics of C<Subscript>60</Subscript> and C<Subscript><Emphasis Type="Bold">60</Emphasis></Subscript><Superscript><Emphasis Type="Bold">-</Emphasis></Superscript> in faujasite zeolites

While the intercalation of C₆₀ and the formation of C ₆₀ ^- in the supercages of NaX and NaY are confirmed by using ¹²⁹Xe NMR and ESR, the photophysical properties of C₆₀ and C ₆₀ ^- are characterized by monitoring transient reflectance spectra and kinetics, fluorescence kinetics, and diffuse reflectance spectra. C ₆₀ ^- is considerably more abundant in NaY than in NaX. This difference is explained in terms of polarity difference between two zeolites. Both C₆₀ and C ₆₀ ^- have remarkably elongated excited-state lifetimes due to their collision-free environment in zeolitic nanocavities although C ₆₀ ^- has much shorter lifetimes than C₆₀. C ₆₀ ^- , in particular, shows intense absorption and emission due to its reduced symmetry in zeolites. Received 13 July 2001 and Received in final form 8 October 2001     

Molecular dynamics study of the equilibrium flux of gas molecules to a fractal/rough surface: Effects of gas atom diameter

The frequency of collisions of ideal gas molecules (argon) with a rough surface has been studied. The rough/fractal surface was created using the random deposition technique. By applying various depositions the surface roughness was controlled and, as a measure of irregularity, the fractal dimensions of the surfaces were determined. The surfaces were next immersed in ideal gas and the numbers of collisions with these surfaces were counted. The calculations were carried out using the simplified molecular dynamics simulation technique (only hard core repulsions were assumed). The calculations were performed for various ratios of gas phase atoms diameter to the surface substrate atoms diameter. The results obtained showed that the size of a gas phase atom has crucial influence on the relation between the frequency of collision and the surface fractal dimension     

Simulation study of random sequential adsorption of mixtures on a triangular lattice

Random sequential adsorption of binary mixtures of extended objects on a two-dimensional triangular lattice is studied numerically by means of Monte Carlo simulations. The depositing objects are formed by self-avoiding random walks on the lattice. We concentrate here on the influence of the symmetry properties of the shapes on the kinetics of the deposition processes in two-component mixtures. Approach to the jamming limit in the case of mixtures is found to be exponential, of the form: θ(t) ∼ θ_jam - Δθ exp(- t/σ), and the values of the parameter σ are determined by the order of symmetry of the less symmetric object in the mixture. Depending on the local geometry of the objects making the mixture, jamming coverage of a mixture can be either greater than both single-component jamming coverages or it can be in between these values. Results of the simulations for various fractional concentrations of the objects in the mixture are also presented.     

Ultraviolet photoelectron spectroscopy of Si 4 - to Si 1000 -

Using a new experimental setup we have measured UV (h ν = 6.4 eV) photoelectron spectra of cold silicon cluster anions Si _n ^- in a very broad size range. For sizes up to n = 46 the spectra exhibit rich structures. For larger sizes only smooth spectra have been obtained. No trace of a bandgap has been found even for clusters with more than 1000 atoms. Received 30 November 2000