Dopant-enhanced ablation of nitrocellulose by a nitrogen laser

The photoetching behavior of pure nitrocellulose and of nitrocellulose dyed with stilbene-420, coumarin-120 and rhodamine 6G by 337 nm nitrogen laser pulses has been studied. Ablation with a low power nitrogen laser is hereby reported for the first time. A two step photochemical mechanism is proposed to account for the ablation of the pure material. With the addition of dyes strongly absorbing at 337 nm the photoetching rate of nitrocellulose can be increased significantly. This increase is proportional to the molar extinction coefficient of the dye at 337 nm and its concentration in the polymer. The photoetching mechanism and the energy transfer processes from the dye to the polymer are discussed in detail.     

Isotope effects in the interaction of hydrogen and deuterium with a rhodium (110) surface

The adsorption of H₂ and D₂ on a Rh (110) surface at 100 K leads to a sequence of ordered phases, among others 1×2 phases at _H =0.5 and at _H =1.5 which likely involve a partial surface reconstruction consisting of a small perpendicular displacement of Rh surface atoms. The structure of the adsorbate phases is strongly correlated with the binding energy of the adsorbed phases. Three H (D) binding states (₁,₂ and) are populated at saturation as determined by thermal desorption spectroscopy (TDS). Whereas the peak temperature of the state is invariant with the hydrogen isotope, the D ₁ state appears at a 8 Klower and theD ₂ state at a 5 Khigher temperature than the respective H states. Generally the D phases exhibit a better long-range order than the H phases. The rate of adsorption is identical for the first three adsorbed phases but D₂ adsorbs appreciably faster in the 1×2–3H and the final l×1–2H phases.Zero point energy effects as well as a H coverage dependent local interaction model could account for the observed effects.     

Photoredox laser chemistry of transition metal oxides

Received: 26 May 1997/Accepted: 17 July 1997     

Isotope effects in the kinetics of simultaneous H and D thermal desorption from Pd

The kinetics of simultaneous hydrogen and deuterium thermal desorption from PdH_xD_y has been investigated. A novel experimental approach for the study of the transition state (TS) characteristics of the surface recombination reaction is proposed based on the analysis of the H and D partitioning into H₂, HD and D₂ molecules. It has been found that the hydrogen molecular isotopes distribution is determined by the energy differences of the corresponding TS of the atom-atom recombination reactions. On the other hand, the mechanisms and activation energies of the desorption process have been obtained. At 420 K, the desorption reaction changes from a surface recombination limiting mechanism during desorption from β-PdH_xD_y to a reaction limited by the rate of β to α phase transformation during the two phase coexistence. Surface recombination reaction becomes again rate limiting above 480 K, due to a change in the catalytic properties of the Pd surface. TS energies obtained from the kinetic analysis of the thermal desorption spectra are in good accordance with those obtained from the analysis of the H₂, HD and D₂ distributions. Anomalous TS energies have been observed for the H-D recombination reaction, which may be related to the heteronuclear character of this molecule.     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.     

On the reaction kinetics in laser-induced photochemical gas-phase processing

Model calculations on laser-induced photolytic gas-phase processing have shown that the concentrations of photogenerated species and the reaction rates depend not only on the electronic properties of precursor molecules and on the wavelength and intensity of the laser excitation, but also on the size of the laser focus, the type of the substrate material and, significantly, on the material and geometry of the reaction chamber. In particular, it has been demonstrated that a dependence of the reaction rate,W, on the radius of the laser beam on the substrate surface,w _o, according toWw ₀ ^–n cannot be employed, in general, in a simple way to separate adsorbed-phase and gas-phase contributions to the reaction rate as claimed in previous investigations. Even in pure photolytic gas-phase processing, the exponentn can vary within the range 0<n<=2, depending on the various different parameters and material properties.     

Plasma and surface modeling of the deposition of hydrogenated carbon films from low-pressure methane plasmas

The elementary mechanisms are described which determine the plasma and surface processes during the plasma-enhanced chemical vapour deposition of hydrogenated carbon films from methane. Corresponding model calculations are reviewed and critically discussed in comparison to experimental results. A realistic modeling requires the simultaneous and self-consistent treatment of plasma and surface effects. Several experimental data sets on plasma parameters and the growth and the composition of the films have been reproduced successfully. However, a broader experimental data base is needed for more critical tests of the models. The reliability of the modeling, in particular of the surface effects, is still limited due to the poor availability of elementary data.     

Plasma deposition of hydrogenated amorphous silicon: Studies of the growth surface

This review focusses on the plasma-surface interactions and surface processes involved in a-Si: H thin film growth. We restrict our discussion of growth fluxes to a summary, and do not address plasma kinetics. In recent years, powerful in situ experiments have been carried out on the growing film surface, which reveal the adsorption, penetration, reaction, and elimination of precursor species, as well as the atomic-scale morphology and composition of the growth zone. Good data sets are available both for PACVD and reactive magnetron sputter deposition. These form an interesting comparison, since the former process is dominated by the hydrogen-rich radical SiH₃ at low energy, and the latter by energetic atomic Si and H. We review the key experiments and conclusions, underlining those aspects which are well established and those which remain qualitative; and we discuss the transition from amorphous to fine-grained polycrystalline film growth at high hydrogen pressures in terms of the surface mechanisms. This field is now entering a scientific stage where a detailed theory of low-temperature, plasma-assisted growth can be developed.     

Formation of monoclinic zirconia at the anodic face of tetragonal zirconia polycrystalline solid electrolytes

The stability of yttria tetragonal zirconia polycrystalline (Y-TZP) materials with and without the addition of alumina has been investigated during charge flow in solid electrolyte cells. A considerable amount of monoclinic zirconia is formed (up to 50–60%) on the anodic side of the solid electrolyte discs during current flow. The thickness of the surface layer in which maximum transformation takes place was determined to be 3–4.5 m. On the cathodic side, the amount of monoclinic zirconia detected was relatively small (< 5%). The amount of monoclinic formed on the anodic side varied with the microstructure of the ceramic and was considerably less in materials free of pores and with uniform grain size distribution. Relaxation experiments indicate that the tetragonal to monoclinic zirconia phase transformation is related to the oxygen evolution reaction and is not due to oxygenion transport within the solid electrolyte. The observed behaviour has been explained in terms of the creation of space charge layers at the electrode/electrolyte interface leading to the saturation of vacancies by oxygen ions and instability of the tetragonal phase in the surface region on the anodic side of the solid electrolyte.     

Laser-photoetching characteristics of polymers with dopants

The photoetching behavior of poly(methylmethacrylate), poly(dimethylglutarimide) and chlorinated poly(methylstyrene) doped with pyrene and 4-aminobenzoylhydrazide excited by 308 nm excimer-laser pulses has been studied. Some common laser-etching characteristics including the reduction of the threshold fluence for ablation, the enhancement of etching efficiency and the existence of optimal conditions regarding the laser fluence and dopant concentration for generating clean and smooth etching patterns are identified. The photoetching mechanism and the potential application of the doping technique to material processing are discussed.     

On the adsorption and desorption of H2 at metal surfaces

Recent technological developments have made possible measurements of the distribution of internal levels of molecules desorbing from a hot surface. Such measurements provide new information concerning the desorption process and the potential energy surface (PES) that governs it. Associative, or re-combinative desorption is of particular interest because the distributions of internal levels reflect the manner in which the molecular bond is formed as the desorbing species leaves the surface. As the simplest associative desorption systems, H₂ and D₂ adsorbing on and desorbing from metal surfaces deserve special attention and serve as prototypes for systems with a more complex chemistry. In this note I review briefly from the theoretical point of view some features of the interaction of H₂ with metals and their relevance to associative adsorption and dissociative sticking.     

Chemical vapor deposition of diamond

In the recent decade a multitude of diamond thin film production methods has been developed, generally based on chemical vapor deposition processes from thermally or plasma activated gas phases. Diagnostic studies, growth experiments and numerical kinetic investigations have in recent years lead to an improved understanding of the prerequisites of continuous diamond growth and of the chemical processes involved. While the mechanism of carbon incorporation into the diamond surface is not yet known completely, the gas-phase species which are essential in a diamond-growth atmosphere can be narrowed to a small number, whose role in the gas-phase chemistry is quite well known.     

Suppression of silicon (001) surface reactivity using a valence-mending technique

It is experimentally shown that, by terminating dangling bonds on Si(001) with a monatomic layer of selenium, the chemical reactivity of the surface is suppressed. In the case of nickel silicidation, transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy reveal that Se passivation suppresses Ni silicidation by over 100 °C as compared to the bare Si(001) surface. The formation of Ni subsilicide (Ni₂Si) is not observed on Se-passivated Si(001). This interfacial silicidation appears to be linked with changes in electrical behavior of the interface between titanium and Se-passivated Si(001), which we reported previously.     

Enhancement of pulsed laser removal of metal oxides by electrochemical control

Pulsed laser irradiation of oxidized metallic surfaces in an electrolytic cell under proper voltage conditions is demonstrated to be a promising new approach for effective removal of oxide films. Systematic measurements on simulated corrosion-product films by optical reflectance profile and energy dispersive X-ray spectroscopy are used to study the physical mechanisms of this novel phenomenon, the physical conditions for its observation and its possible generality. It was observed that the utilization of a basic electrolyte solution and the imposition of a certain cathodic potential prior to laser irradiation is an essential requirement for a high removal efficiency. This new technique has potential applications in metallurgy, semiconductor fabrication technology and decontamination of nuclear power plans and is suitable for maskless patterning of oxidized surfaces.     

Femtosecond photodissociation dynamics of HNO3 after exitation of the S3-state at 200 nm

The photodissociation dynamics of HNO₃ in the electronic S₃ (2 ¹ A ^′ ) state leading to the fragments OH and NO₂ was investigated in real time. HNO₃ was prepared either in a fluorescence cell at room temperature (LIF probing of OH) or rotationally cold in a molecular beam (probing of NO₂ by three-photon ionization). A 2 ¹ A ^′ lifetime of 60–80 fs could be obtained from the experimental results, indicating essentially barrierless dissociation. In addition, secondary dissociation of internally excited nascent fragments NO₂ ^* leading to products NO(X ² Π) and O(³ P) with a characteristic dissociation time of 2.3 ps was observed. This time is surprisingly long when compared with dissociation lifetimes of NO₂ from the literature, obtained after direct photoexcitation. The discrepancy is explained by differences in the preparation conditions of the dissociative state of NO₂. Received: 12 November 1999 / Published online: 13 July 2000     

Large area excimer laser induced deposition of titanium from titanium tetrachloride

Large area excimer laser induced deposition of titanium on fused silica from TiCl₄ is studied with an emphasis on process modeling. We show that several TiCl₄ monolayers can be adsorbed if the surface is adequately prepared and that the Ti thin film growth occurs through the photodecomposition of this adsorbed TiCl₄ layer. We propose two growth regimes. During an initiation phase, up to 3 nm in thickness, the adsorbed layer is photochemically decomposed giving a growth rate of 0.015 nm/pulse. In a second phase, the deposition rate increases to between 2 and 7 nm/pulse due to the laser heating of the preceding photochemically deposited titanium film. Between consecutive pulses, TiCl₄ molecules primarily from the adsorbed layer diffuse to the reaction zone leading to a new adsorbed layer ready to be transformed to solid titanium.     

Self-assembled monolayer of propylbenzoat on the bimetallic surface of Rb/Cr

Received: 17 November 1997/Accepted: 18 November 1997     

The influence of surface reconstruction on the kinetics of adsorption-desorption processes: A Monte Carlo study of a simple model

The influence of surface reconstruction on the kinetics of adsorption-desorption processes is studied through a simple two-position model by means of Monte Carlo simulation. Effects due to constraints on the translational motion of activated complexes and to heterogeneity are particularly investigated. Heterogeneity emerges as the most important factor to explain the huge variation of the preexponential Arrhenius parameter with coverage observed in the H/W(001) system. In the present model it is conjectured that heterogeneity originates from additional interactions of H with surface or sub-surface W atoms when hydrogen is adsorbed on sites where surface W atoms are farther apart due to reconstruction.     

Monolayers of diblock copolymer at the air-water interface: the attractive monomer-surface case

We have studied both experimentally and theoretically the surface pressure isotherms of copolymers of polystyrene-polyethyleneoxide (PS-PEO) at the air-water interface. The SCMF (single chain mean-field) theory provides a very good agreement with the experiments for the entire range of surface densities and is consistent with the experiments if an adsorption energy per PEO monomer at the air-water interface of about one k_{B T} is taken. In addition, the chain density profile has been calculated for a variety of surface densities, from the dilute to the very dense ones. The SCMF approach has been complemented by a mean-field approach in the low density regime, where the PEO chains act as a two-dimensional layer. Both theoretical calculations agree with the experiments in this region. Received: 19 June 1997 / Revised: 2 February 1998 / Accepted: 11 February 1998     

The angular behaviour of electrons inelastically scattered from the shape resonance for CO chemisorbed on Ni(110)

Recent vibrational high resolution electron energy loss experiments (HREELS) have shown evidence for molecular shape resonances in the inelastic scattering of electrons from chemisorbed molecules. Such resonances arise from the capture of the incident electron in a quasibound state of the molecule, leading to the formation of a temporary negative ion. They are manifest as an enhancement in the intensity of a specific vibrational mode at a characteristic incident electron energy. In contrast to gaseous species, the alignment which the surface provides for the chemisorbed species, can be exploited to determine the angular characteristics of the resonant state. In this work, we show evidence for a shape resonance, centred at an incident energy of 18 eV, for CO/Ni(110). The angular dependence of the scattered electron intensity has been measured for the CO stretching vibration. The results are discussed in terms of the spherical harmonic components of the resonant state, modified by vibrational broadening caused by low frequency bending modes associated with the bonding of the CO molecule to the surface.