Laser-induced etching and deposition of W using a-SiO<Subscript>2</Subscript> microspheres

A regular lattice of a-SiO₂ microspheres on a quartz support is used as a microlens array for laser-induced surface patterning by etching and deposition of W in atmospheres of WF₆ and WF₆+H₂, respectively. Received: 22 July 2002 / Accepted: 30 July 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +43-732/2468-9242, Email: dieter.baeuerle@jku.at     

Strain-induced changes in electronic structures and work function for (0 0 1), (1 1 0) and (1 1 1) of AlCu3

Studies of strain-induced changes in surface properties of metal/alloy surface have long been concerned by lot of scientists. However, the strain effects on the work function (WF), and in particular, its physical mechanism have not been well understood. In this paper, we employed a first-principles method to study the effects of biaxial strain in WF on the (0 0 1), (1 1 0) and (1 1 1) surfaces of AlCu₃. The relationship among the WF change, atomic relaxation and charge transfer induced by strain was discussed. The calculated results showed that tensile strain decreased the WF, while the compressive strain increased the WF; a larger atomic relaxation often followed with a larger WF change. The sensitivity of the WF with respect to the strain was strongly dependent on the direction of the surface or the density of atom packed plane of the surface.     

Formation of combustible gases during interaction of tungsten and zirconium with supercritical fluid H2O/CO2

Oxidation of bulk samples of tungsten (923 K) and zirconium (773 and 873 K) by H₂O/CO₂ supercritical fluid (molar ratio [CO₂]/[H₂O] = 0.17–0.26) at a pressure of about 300 atm is investigated. Oxidation produces monoclinic WO₃, monoclinic W₁₉O₅₅, monoclinic ZrO₂, H₂, CO, CH₄, and carbon (on the surface of tungsten oxide). Differences in oxidation mechanisms for tungsten and zirconium are revealed. CO₂ molecules take part in the oxidation of tungsten only after oxide formation in reaction with H₂O. Zirconium is oxidized fully, and oxidation of tungsten terminates in the formation of the oxide layer at the metal surface.     

183Tungsten NMR studies

With a Fourier-transform spectrometer, especially developed for nuclei with weak NMR signals, the signal of¹⁸³W in a liquid diamagnetic sample was detected for the first time. The¹⁸³W Larmor frequencies and chemical shifts of WF₆, of [WO₄]^{– -} in aqueous solution, and of WCl₆ dissolved in CS₂ were determined with high accuracy. The¹⁸³W resonance is referred to that of the proton in H₂O and the magnetic moment of¹⁸³W in WF₆ isµ=0.116224 5 (7)µ _N. The scalar coupling constant in WF₆ was determined: |J(¹⁸³W–¹⁹F)|=(40.7±1.5) Hz; an upper limit for the coupling constant |J(¹⁸³W–¹⁷O)| in the [WO₄]^{– -} ion is given. The relaxation timesT ₁ andT ₂ of the¹⁸³W resonance in WF₆ were measured by steady state techniques.     

Kinetics of chemical vapor deposition of SiC from methyltrichlorosilane and hydrogen

In this study, the dependence of the deposition rate on processing parameters, such as temperature, and partial pressure is studied by chemical vapor deposition from mixture of methyltrichlorosilane (CH₃SiCl₃, MTS) and hydrogen. The kinetics investigation is carried out in a tubular, hot-wall reactor coupled to a sensitive magnetic suspension microbalance. The results show that the active energy limited by surface reactions is 188 kJ/mol. In the case, the deposition rate is linear to the partial pressure of MTS and the square of partial pressure of hydrogen. SiCl₂ and CH₃ are proposed as the effective precursor for SiC. A reaction model was proposed concluding gas phase reactions and surface reactions. The theoretical relation between deposition rate and partial pressures of MTS and H₂ was in a good accordance with experimental results.     

Cavity ring-down spectroscopy of CH and CD radicals in a diamond thin film chemical vapor deposition reactor

A mixture of H₂ and CH₄ is passed over a hot-wire tungsten filament in a diamond thin film chemical vapor deposition reactor. The resulting CH radicals are measured in absorption using cavity ring-down spectroscopy (CRDS). The concentration of the CH radicals increases as the filament is approached. The rotational temperature measurements indicate a large temperature discontinuity between the filament and the CH in the gas phase. The pathways for CH production were investigated by replacing H₂ by D₂ in the feed gas mixture, which resulted in the exclusive production of CD. From this observation it is concluded that rapid H/D isotope exchange dominates in the gas phase. Nonperiodic temporal oscillations in the CH concentration are observed when a rhenium filament is used in place of a tungsten filament. The oscillations are attributed to the nonperiodic changes in the amount of carbon at the filament surface. Received: 21 August 2000 / Accepted: 23 August 2000 / Published online: 23 May 2001     

Adsorption-desorption studies using ESD of CCl2F2, C2H2F2 and C2F6 on tungsten

The behavior of the desorbing F⁺ ion current from electron bombarded CCl₂F₂, C₂H₂F₂ and C₂F₆ adsorbed on tungsten has been used to investigate the processes of adsorption and desorption of these gases. For tungsten near room temperature, measurements of the F⁺ ion current as a function of electron bombardment time indicated very similar or even identical F⁺-yielding adsorbed species resulting from adsorption of either CCl₂F₂ or C₂H₂F₂ and widely different species from C₂F₆. Cl⁺ ions were also observed to desorb from CCl₂F₂ ad-layers. The behavior of the Cl⁺ ion current with time during electron bombardment indicated electronic conversion between adsorbed binding modes. Complementary investigations on the interaction of CCl₂F₂, C₂H₂F₂ and C₂F₆ with tungsten were carried out by thermal desorption experiments in which the F⁺ ion signal was used to observe the coverage decrease of the F⁺-yielding species. The experiments were performed at tungsten temperatures in the 1200–1600 K range. It was concluded that the F⁺-yielding adsorbed species from CCl₂F₂ and C₂H₂F₂ were strongly bound to the tungsten surface. The F⁺-yielding species from C₂F₆ were found to be weakly bound. From a comparison of the ESD and thermal desorption results, the possibility of dissociative adsorption as well as the nature of the adsorbed species is discussed.     

Structure,the lattice dynamic,and the dielectric characteristics of Sr<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> films

Solid solution Sr_0.5Ba_0.5Nb₂O₆ films have been synthesized on a (111)Pt/(001)Si substrate by rf deposition in an oxygen atmosphere. The depolarized Raman spectra, the structure, and the dielectric characteristics of the films have been studied over a wide temperature range. It is found that the films were singlephase, had the tetragonal tungsten bronze structure, and had a pronounced axial texture with axis 001 directed perpendicular to the substrate surface. It is shown that the film material undergoes a diffuse phase transition to the state of a relaxor ferroelectric in the temperature range 300–425 K. Possible reasons of the regularities observed are discussed.     

Surface science studies of selective catalytic reduction of NO: Progress in the last ten years

Selective catalytic reduction (SCR) of NO_x is one of the important strategies in regulating NO_x emissions. In the past several decades, the reactions of NO_x (mainly NO) with H₂, CO, NH₃ and hydrocarbons have been extensively investigated under ambient conditions and have been summarized in numerous reviews. Nonetheless, many questions appear to be difficult to answer under ambient conditions, e.g., the pathways through which the reactions proceed. The introduction and development of modern surface science technology has played an indispensable role and is widely employed in the studies of the SCR of NO_x, greatly helping to elucidate the mechanisms of the reactions with CO, H₂, and NH₃. However, so far, there are few review papers systematically summarizing the progress of such studies.Recently, systematic surface science studies have been conducted on the mechanisms of SCR of NO with organic molecules including ethylene, benzene, and ethanol, which are much more complicated than those with H₂, CO and NH₃ and have drawn much less attention before. It is confirmed that these reactions can be reliably and most importantly, reproducibly probed by surface science technology, but a great deal of work remains to be done.Since Delmon et al. have provided a very thorough review of the researches on catalytic removal of NO (reactions with H₂, CO and NH₃) up to 1998, in which the reactions conducted both under ambient and UHV conditions were included, this review mainly concentrates on the progress made since 1998.     

多晶硅薄膜低温生长中的表面反应控制

报道用SiF₄和H₂的间接微波等离子体化学气相沉积方法低温生长多晶硅(poly-Si)薄膜.实验发现,等离子体中的离子、荷电集团对薄膜生长表面的轰击是影响薄膜结晶质量的重要因素之一.通过外加偏压抑制这些荷电粒子的动能是控制表面生长反应、制备高质量ploy-Si薄膜的有效方法.在合适的外加偏压下制备的poly-Si薄膜,氢含量仅约为0.9at%,中心位于520cm^-1的Raman特征峰半高宽约为4.4cm^-1. 关键词： 多晶硅薄膜 低温生长 表面生长反应 外加偏压     

等离子体增强化学气相沉积法制备立方氮化硼薄膜过程中的表面生长机理

利用感应耦合等离子体增强化学气相沉积法以Ar，He，N₂和B₂H₆为反应气体制备了高纯立方氮化硼薄膜.用四极质谱仪对等离子体状况进行了系统的分析，发现B₂H₆完全被电离而N₂只是部分被电离.H₂和过量的N₂在等离子体中生成大量中性的H原子和活化的N^*₂，它们与表面的相互作用严重地阻碍了立方 关键词： 立方氮化硼薄膜 等离子体 质谱     

Electrochromic colour centres in amorphous tungsten trioxide thin films

Amorphous tungsten trioxide films, investigated by the Raman scattering method, are shown to be composed of a spatial network of tightly bound (WO₆)_n·mH₂O clusters with a large number of terminal oxygen W=O and W-O-W bonds between clusters. The injected electrons in an amorphous tungsten trioxide film are localized in the tungsten 5d orbitals in an axially distorted octahedron, as is shown by ESR analysis. The optical absorption of a coloured amorphous tungsten trioxide film, as has previously been proposed, can be satisfactorily described by an intervalence charge-transfer transition between localized W⁵⁺ and W⁶⁺ states.     

Die Feldemission des wolframs nach der adsorption von Kohlenwasserstoffen

Field emission currents of electrons were measured for different planes of tungsten after the interaction of CH₄, C₂H₆, C₃H₈, and C₂H₄ at 78°K and 298°K and used to obtain work function and pre-exponential values from Fowler-Nordheim plots. A critical analysis of these data yields a conclusive result on surface potentials only if emitting areas and pre-exponentials are comparable.     

CO-H2-O2 reaction on a catalytic surface: A computer simulation study

The oxidation of carbon monoxide to form carbon dioxide and the oxidation of hydrogen to form water are the reactions of environmental and industrial importance. These two reactions have been studied independently by Monte Carlo computer simulation using Langmuir-Hinshelwood mechanism but no effort has been made to study the combined CO-H₂-O₂ reaction on these lines. Keeping in view the importance of this 3-component system, the surface coverages and production rates are studied as a function of CO partial pressure for different ratios of H₂ and O₂. The diffusion of reacting species on the surface as well as their desorption from the surface is also introduced to include temperature effects. The phase diagrams of the system are drawn to observe the behavior of these atoms/molecules on the surface and the production of CO₂ and H₂O are determined at different concentrations of H₂. The results are compared with 2-component systems.     

Surface science investigations of atomic layer deposition half-reactions using TaF5 and Si2H6

Fundamental adsorption and surface chemistry studies of TaF₅ and Si₂H₆ on a polycrystalline Ta surface were performed in ultra-high vacuum (UHV) in the range 303-523 K to understand if these precursors may be used in applications to grow Ta-based films by atomic layer deposition. TaF₅ uptake saturated in UHV conditions for less than 100 L exposure for adsorption on both clean Ta and on 144 L Si₂H₆-treated Ta. TaF₅ dissociatively adsorbed on clean Ta, and F ligands were determined to govern the self-limiting adsorption behavior. The extent of each “half-reaction”, the reaction of TaF₅ with a Si₂H₆-treated surface and the reaction of Si₂H₆ with a TaF₅-treated surface, increased with surface temperature and was dependent on SiH_xF_y byproduct desorption. Neither Si₂H₆ adsorption nor Si₂H₆ half-reaction reached saturation in UHV conditions, as measured by the surface Si concentration. F ligands were removed during the Si₂H₆ half-reaction, and residual F asymtotically approached a constant value.     

Special features of the tungsten wire heat transfer and the WO3 nanoparticle synthesis in supercritical water

Special features of the tungsten wire (TW) heat transfer in supercritical water at P = 25 MPa and T ≤ 923 K are investigated, including the conditions of (WO₃) _n nanoparticle formation on the tungsten wire surface with the reaction kn〈W〉 + 3knH₂O = k(WO₃) _n + 3knH₂. Values of the heat transfer coefficient as a function of oxidation time and temperature were determined using the method of electric current flash heating of the tungsten wire. It has been found that due to WO₃ dissolution in supercritical water, there occurs oxide recondensation from the tungsten wire surface onto other design elements of the setup, which is accompanied by formation of monoclinic and rhombic WO₃, and also monoclinic FeWO₄.     

Chemical effects in the N7 VV Auger spectra from W(100) and W(110) surfaces

Fine structure in the N₇ VV Auger spectra from clean W(100) and W(110) surfaces has been interpreted by Lander's band model for the doubly ionized final state. It is shown that the energies of the prominent emissions in the spectra are similar for the two surfaces and furthermore are consistent with the self convolution of a bulk density of states for tungsten. An additional feature in the spectrum from the W(100) surface has been attributed to emission from an intrinsic surface state at ?0.4 eV. The localization of this state at the surface was confirmed by its sensitivity to adsorbates (H₂, CO, O₂ and I₂). During the interaction of these gases with the surface the Auger spectra always retained the features attributed to the bulk density of states which were modified only by a shift in the background intensity profile. New emission features in this part of the spectra were not seen except for the example of hydrogen adsorption when a single new emission could be seen on each of the two tungsten surfaces. However, each adsorbate produce either one (H₂) or two (CO, O₂ and I₂) new emissions at lower energies which were attributed to emissions from new adsorbate derived levels which reside at energies below the prominent features of the tungsten valence band. The location of these new adsorbate levels is compared and contrasted with the equivalent ultraviolet photoelectron spectroscopic determinations.     

WO3 oxide film formation on tungsten in O2/H2 discharges

The features of tungsten oxidation in a flowing O₂ or O₂/H₂ mixture glow discharge with a hollow cathode are investigated in the cathode, plasma, and afterglow regions at T = 300–350 K. The structure and composition of the samples are analyzed via reflection high-energy electron diffraction, reflection X-ray diffraction, electron probe microanalysis, and X-ray photoelectron spectroscopy. The results of analysis show that the metal surface is covered by a thin film (5–10 nm thick) of amorphous porous hydrated tungsten oxide (WO₃) after its exposure to the discharge and storage in air. The study of the film composition using a time-of-flight mass spectrometer indicates that the WO₃ film contains (WO₃) _n (n = 1–6) clusters and water molecules adsorbed in the pores. After exposure of the polycrystals to the O₂/H₂ discharge, the selective intense oxidation of individual grains is detected in the cathode region; the surrounding areas are subjected to weaker oxidation. The thicknesses of the WO₃ films on neighbouring grains differ by more than tenfold. Such grains can be the source of tungsten dust in plasma installations.     

Continuous-wave CO2 laser spectroscopy of SF6, WF6, and UF6

The linear absorption of CO₂ laser radiation in SF₆, WF₆, and UF₆ has been measured by using optoacoustic detection techniques. Absolute absorption coefficients per Torr as low as 1 × 10^?7 cm^?1 Torr^?1 in a 2-cm active path length could be measured by taking advantage of calibration measurements performed with SF₆.