The oxygenated phenomena of the undoped large-grain and small-grain polycrystalline diamond films

The polycrystalline diamond films in this research were deposited using a methane/hydrogen gas mixture in a microwave plasma assisted chemical vapor deposition system. Large-grain, several μm size crystallite, diamond films and small-grain, sub-micron size crystallite, diamond films were prepared by diamond paste and diamond powder nucleation method, respectively. It is found that there is no oxygen incorporated into the diamond films during the microwave plasma chemical vapor deposition process at the synthesis temperature between 900°C and 1000°C. However, the oxygenated phenomena did appear for both of the large-grain and the small-grain polycrystalline diamond films after the films were exposed to air for a period of time. It was shown that the large-grain diamond films are oxygenated more than the small-grain diamond films as the samples were exposed to air for a period of time and also after the chemical cleaning treatment. It is indicated that the oxygenated phenomena of the diamond films come from two contributors, the diamond crystallite surfaces and the diamond grain boundaries. The reaction between the diamond grain boundaries and the air is fast and the oxidized dangling bonds are hard to remove. However, the oxidized dangling bonds on the diamond crystallite surfaces are gradually formed and are easily etched away by the hydrogen plasma.     

Separation of germanium and silicon oxides by plasma-chemical deposition of germanosilicate glass in a moving plasma column

The optical transmission spectrum of germanosilicate glass deposited by surface plasma chemical vapor deposition on the inner surface of a quartz tube revealed interference resonances typical of multilayer dielectric coatings with alternating refractive indices. It is shown that this effect can be attributed to the longitudinal inhomogeneity of the plasma composition and specifically to an axial shift of the concentration maxima of germanium and silicon oxide. As a plasma having a nonuniform composition moves along the tube, a layer of glass is formed with a strong transverse germanium concentration gradient. It is established that in surface plasma chemical vapor deposition the axial separation of the regions of deposition of the silicon and germanium oxides increases if the glass is synthesized under conditions of oxygen deficiency. Pis’ma Zh. Tekh. Fiz. 25, 55–61 (July 12, 1999)     

Erratum: Separation of germanium and silicon oxides by plasma-chemical deposition of germanosilicate glass in a moving plasma column [Tech. phys. lett. 25, 530–532 (1999)]

The optical transmission spectrum of germanosilicate glass deposited by surface plasma chemical vapor deposition on the inner surface of a quartz tube revealed interference resonances typical of multilayer dielectric coationgs with alternating refractive indices. It is shown that this effect can be attributed to the longitudinal inhomogeneity of the plasma composition and specifically to an axial shift of the concentration maxima of germanium and silicon oxide. As a plasma having a nonuniform composition moves along the tube, a layer of glass is formed with a strong transverse germanium concentration gradient. It is established that in surface plasma chemical vapor deposition the axial separation of the regions of deposition of the silicon and germanium oxides increases if the glass synthesized under conditions of oxygen deficiency. Pis’ma Zh. Tekh. Fiz. 25, 55–61 (July 12, 1999) The online version of the original article can be found at     

Effects of high hydrogen dilution ratio on surface topography and mechanical properties of hydrogenated nanocrystalline silicon thin films

Hydrogenated nanocrystalline silicon thin films were deposited with high hydrogen dilution ratio by plasma enhanced chemical vapor deposition technique. The effects of high hydrogen dilution on the surface topography and mechanical properties of the films were studied with atomic force microscopy and TriboIndenter nano indenter. The results indicate that the average grain size in films deposited with high hydrogen dilution is about 3.18 ± 0.02 nm. The surface roughness and densification of the films decrease with the increase of hydrogen dilution ratio at certain range, resulting in the enhancement of the elastic modulus E and hardness H. Oppositely, the increase of hydrogen dilution can increase the surface roughness induced by the increase of the cavities on the film surfaces, and lead to the decrease of the elastic modulus and hardness correspondingly. In this paper, the detailed analysis and discussion were carried out to investigate the mechanism of the observed phenomena.     

Correlation between diamond grain size and hydrogen incorporation in nanocrystalline diamond thin films

Hydrogen-incorporated nanocrystalline diamond thin films have been deposited in microwave plasma enhanced chemical vapour deposition (CVD) system with various hydrogen concentrations in the Ar/CH₄ gas mixture. The bonding environment of carbon atoms was detected by Raman spectroscopy and the hydrogen concentration was determined by elastic recoil detection analysis. Incorporation of H₂ species into Ar-rich plasma was observed to markedly alter the microstructure of diamond films. Raman spectroscopy results showed that part of the hydrogen is bonded to carbon atoms. Raman spectra also indicated the increase of non-diamond phase with the decrease in crystallite size. The study addresses the effects of hydrogen trapping in the samples when hydrogen concentration in the plasma increased during diamond growth and its relation with defective grain boundary region.     

High-rate deposition of nanostructured SiC films by thermal plasma PVD

With ultrafine SiC powder as starting material, thermal plasma physical vapor deposition has been applied successfully to the deposition of SiC films on Si substrates. The control of processing parameters such as substrate temperature, powder feeding rate and composition of plasma gases, permits the deposition of SiCfilms on a wide area of around 400 cm² with a variety of microstructures fromamorphous to nanostructured and with various morphologies from dense to columnar. For the nanostructured case, the crystallite size was between 3 and 15 nm and the maximum deposition rate calculated based on the actual deposition duty time reached 200 nm/s. The deposition mechanism is discussed briefly.     

氢流量对纳米SiC薄膜微结构和光学特性的影响

采用螺旋波等离子体增强化学气相沉积技术进行了氢化纳米晶态SiC薄膜的沉积,研究了氢流量对其微结构和光学特性的影响.结果显示,随着氢气流量的增大,薄膜的沉积速率先增大后减小,所生长薄膜晶化度显著提高.在较低氢流量条件下,薄膜光学带隙的大小由氢的刻蚀与悬键终止作用共同控制,并呈先减小后增大的趋势.在高氢流量条件下,强的氢刻蚀使薄膜具有较高的晶化度,虽然薄膜中整体氢含量有所下降,但存在于纳米碳化硅晶粒表面键合氢的相对密度持续增大,纳米碳化硅晶粒数量的增加和晶粒尺寸的减小所导致的量子限制效应使薄膜的光学带隙继续展宽.     

Effects of substrate size on properties of carbon coatings on glass cylinder substrates prepared by thermal chemical vapor deposition

The effect of the substrate size on the properties of carbon coatings that are deposited on the glass cylinder substrates by thermal chemical vapor deposition is investigated. Experimental results show that the deposition rate of carbon coatings decreases as the diameter of the glass cylinder increases, because the residence time of the precursor gas in the deposition zone decreases and the deposition area of the substrate increases. Experimental results also reveal that the surface roughness and electrical resistivity of carbon coatings decrease as the diameter of the glass cylinder increases, while the degree of ordering and crystallite size of the carbon coatings increase.     

Preparation of TiO2, Ag-doped TiO2 nanoparticle and TiO2–SBA-15 nanocomposites using simple aqueous solution-based chemical method and study of their photocatalytical activity

Nanocrystalline TiO₂, Ag-doped TiO₂ and TiO₂–SBA-15 nanocomposites have been synthesised using a simple aqueous solution-based chemical method. Nanocrystalline TiO₂ was synthesised by calcining the precursor prepared by using ethylenediamine tetraacetic acid and TiCl₃ in aqueous medium. Formation of crystalline phase (anatase, rutile or mixed phase) and crystallite size were found to be dependent on calcination temperature. To enhance the photocatalytic activity, Ag-doped TiO₂ was synthesised by doping of Ag during the synthesis step of TiO₂. TiO₂–SBA-15 nanocomposites were synthesised by impregnation method. Pure anatase TiO₂ nanoparticle was formed in the amorphous matrix of the silicate SBA-15, even though the loading of the TiO₂ in the silicate matrix was as low as 5?wt%. The synthesised materials were characterised using thermal analysis, powder X-ray diffraction method, surface area and porosimetry analysis, diffuse reflectance analysis and transmission electron microscopy. The photocatalytic property of the synthesised materials was investigated towards the degradation of methyl orange under sunlight exposure and monitored by UV–visible spectrophotometer. Ag-doped TiO₂ exhibited enhanced photocatalytic activity than undoped TiO₂. TiO₂–SBA-15 nanocomposites showed impressive photocatalytic activity even with 10?wt% TiO₂ loading.     

Growth of Polyglycidol in Porous TiO2 Nanoparticle Networks via Initiated Chemical Vapor Deposition: Probing Polymer Confinement Under High Nanoparticle Loading

Initiated chemical vapor deposition (iCVD) enables the uniform growth of polyglycidol (PGL) within mesoporous layers of TiO₂ nanoparticle networks. Through the cationic ring opening polymerization of glycidol, conformal deposition of PGL by iCVD results in up to 91% of the available pore space being filled. This yields polymer nanocomposites with high nanoparticle loading of 82 wt% and 54 vol%. The glass transition of the PGL nanocomposite is found to increase significantly by 50 °C–60 °C compared to the bulk PGL polymer. This marked temperature rise has been attributed to significant hydrogen bonding interaction of the oxygen and hydroxyl groups in the polymer with the hydroxyl groups on the surface of the TiO₂ nanoparticles. Such interactions under polymer confinement are only possible as a result of the tight integration of the polymer and inorganic materials afforded by the iCVD approach.     

Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying

Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900?°C was also activated in a carbon dioxide atmosphere at 900?°C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77?K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05?nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20?m(2)?g(-1) displayed a reasonably high hydrogen uptake at 77?K with a maximum hydrogen sorption of 3.6?wt% at 2.5?MPa. These results suggest that CA are promising candidate hydrogen storage materials.     

High-rate deposition of nanostructured SiC films by thermal plasma PVD

With ultrafine SiC powder as starting material, thermal plasma physical vapor deposition has been applied successfully to the deposition of SiC films on Si substrates. The control of processing parameters such as substrate temperature, powder feeding rate and composition of plasma gases, permits the deposition of SiC films on a wide area of around 400 cm² with a variety of microstructures from amorphous to nanostructured and with various morphologies from dense to columnar. For the nanostructured case, the crystallite size was between 3 and 15 nm and the maximum deposition rate calculated based on the actual deposition duty time reached 200 nm/s. The deposition mechanism is discussed briefly.     

Effect of Co-Mo catalyst preparation and CH4/H2 flow on carbon nanotube synthesis

Abstract

Supported Co-Mo catalysts with a given ratio of metals were prepared from polyoxomolybdate Mo₁₂O₂₈(μ₂-OH)₁₂{Со(H₂O)₃}₄ using impregnation and combustion methods. Effects of the type of catalyst and the ratio and flow of methane and hydrogen gases on the structure of carbon nanotubes (CNTs) synthesized by catalytic chemical vapor deposition (CCVD) method were studied using transmission electron microscopy and Raman spectroscopy. The catalyst prepared by combustion method yielded mainly individualized CNTs, while the CNTs were highly entangled or bundled when impregnation method was used. In both cases, addition of hydrogen to methane led to reduction of the CNT yield. The samples synthesized using two different catalysts and the same CH₄/H₂ ratio and flow of gases were tested in electrochemical capacitors. A higher specific surface area of the CNTs grown over impregnation-prepared catalyst caused a better performance at scan rates from 2 to 1000?mV/s.     

Exploiting the Kubas Interaction in the Design of Hydrogen Storage Materials

Hydrogen adsorption and storage using solid‐state materials is an area of much current research interest, and one of the major stumbling blocks in realizing the hydrogen economy. However, no material yet researched comes close to reaching the DOE 2015 targets of 9 wt% and 80 kg m^?3 at this time. To increase the physisorption capacities of these materials, the heats of adsorption must be increased to ～20 kJ mol^?1. This can be accomplished by optimizing the material structure, creating more active species on the surface, or improving the interaction of the surface with hydrogen. The main focus of this progress report are recent advances in physisorption materials exhibiting higher heats of adsorption and better hydrogen adsorption at room temperature based on exploiting the Kubas model for hydrogen binding: (η²‐H₂)–metal interaction. Both computational approaches and synthetic achievements will be discussed. Materials exploiting the Kubas interaction represent a median on the continuum between metal hydrides and physisorption materials, and are becoming increasingly important as researchers learn more about their applications to hydrogen storage problems.     

Raman studies of aluminum induced microcrystallization of n Si:H films produced by PECVD

We performed a Raman scattering study of aluminum induced microcrystallization of thin films of phosphorous-doped hydrogenated amorphous silicon (n⁺ a-Si:H). These thin films of heavily doped n⁺ a-Si:H were prepared by plasma enhanced chemical vapor deposition. Afterwards, aluminum was deposited and followed by an annealing process at 523 K in a nitrogen environment during several hours. Raman results reveal the formation of microcrystalline regions distributed in the amorphous matrix, induced by the film annealing in the presence of the aluminum. We have used the spatial correlation model to estimate from the Raman signal the microcrystallite size and its relation with the annealing time. The estimated crystallite size was found to be between 6.8 and 9.5 nm and the broadening and downshift of the signals are explained in terms of the crystallite size and lattice expansion effects due to the annealing process. Conductivity values of the samples as a function of the annealing time are explained in terms of the contributions from the amorphous and from the microcrystalline phases.     

Synthesis of carbon nanotube-TiO(2) nanotubular material for reversible hydrogen storage

A material consisting of multi-walled carbon nanotubes (MWCNTs) and larger titania (TiO(2)) nanotube arrays has been produced and found to be efficient for reversible hydrogen (H(2)) storage. The TiO(2) nanotube arrays (diameter ～60?nm and length ～2-3?μm) are grown on a Ti substrate, and?MWCNTs a few μm in length and ～30-60?nm in diameter are grown inside these TiO(2) nanotubes using chemical vapor deposition with cobalt as a catalyst. The resulting material has been used in H(2) storage experiments based on a volumetric method using the pressure, composition, and temperature relationship of the storage media. This material can store up to 2.5?wt% of H(2) at 77?K under 25?bar with more than 90% reversibility.     

Influence of hydrogen on the mechanical properties and microstructure of DLC films synthesized by r.f.-PECVD

This paper aims to investigate the influence of hydrogen on the variation of mechanical properties and microstructure of diamond-like carbon (DLC) films synthesized by radio frequency plasma chemical vapor deposition (r.f.-PECVD). The DLC films were deposited on a silicon substrate (p-type). The reactant gases employed in this paper are a mixture of acetylene and hydrogen. The ratio of hydrogen in the gas mixture was successively varied to clarify its influence on the roughness, thickness, microstructure, hardness, modulus, residual stress and wear depth for the DLC films. The results reveal that increasing the concentration of hydrogen decreases thickness and roughness. Meanwhile, increasing the hydrogen concentration causes the decrease of sp³ ratio, hardness as well as modulus. Finally, wear behavior is correlated to the surface morphology and hydrogen concentration for deposition with hydrogen-containing reactant gas.     

Field emission characteristics of chromium carbide capped carbon nanotips

In this study, field emission characteristics of two carbon based nanomaterials, carbon nanotips and chromium carbide capped carbon nanotips, were discussed. Both of these materials were synthesized by bias-assisted microwave plasma chemical vapor deposition with hydrogen and methane as reactants. Ultra-sharpness of the carbon nanotips and the composite structure of chromium carbide capped carbon nanotips have shown unique structural and electrical properties. I-V measurements were carried out to investigate the field emission characteristics. The chromium carbide capped carbon nanotips showed superior field emission stability compared to carbon nanotips under constant current emission.     

Deposition and characterization of smooth ultra-nanocrystalline diamond film in CH4/H2/Ar by microwave plasma chemical vapor deposition

The smooth ultra-nanocrystalline diamond (UNCD) films were prepared by microwave plasma chemical vapor deposition (MWCVD) using argon-rich CH₄/H₂/Ar plasmas with varying argon concentration from 96% to 98% and negative bias voltage from 0 to −150 V. The influences of argon concentration and negative bias voltage on the microstructure, morphology and phase composition of the deposited UNCD films are investigated by using scanning electron microscopy (SEM), X-ray diffraction (XRD), atom force microscopy (AFM), and visible and UV Raman spectroscopy. It was found that the introduction of argon in the plasma caused the grain size and surface roughness decrease. The RMS surface roughness of 9.6 nm (10 micron square area) and grain size of about 5.7 nm of smooth UNCD films were achieved on Si(100) substrate. Detailed experimental results and mechanisms for UNCD film deposition in argon-based plasma are discussed. The deposited highly smooth UNCD film is also expected to be applicable in medical implants, surface acoustic wave (SAW) devices and micro-electromechanical systems (MEMS).     

Biological evaluation of ultrananocrystalline and nanocrystalline diamond coatings

Nanostructured biomaterials have been investigated for achieving desirable tissue-material interactions in medical implants. Ultrananocrystalline diamond (UNCD) and nanocrystalline diamond (NCD) coatings are the two most studied classes of synthetic diamond coatings; these materials are grown using chemical vapor deposition and are classified based on their nanostructure, grain size, and sp³ content. UNCD and NCD are mechanically robust, chemically inert, biocompatible, and wear resistant, making them ideal implant coatings. UNCD and NCD have been recently investigated for ophthalmic, cardiovascular, dental, and orthopaedic device applications. The aim of this study was (a) to evaluate the in vitro biocompatibility of UNCD and NCD coatings and (b) to determine if variations in surface topography and sp³ content affect cellular response. Diamond coatings with various nanoscale topographies (grain sizes 5–400?nm) were deposited on silicon substrates using microwave plasma chemical vapor deposition. Scanning electron microscopy and atomic force microscopy revealed uniform coatings with different scales of surface topography; Raman spectroscopy confirmed the presence of carbon bonding typical of diamond coatings. Cell viability, proliferation, and morphology responses of human bone marrow-derived mesenchymal stem cells (hBMSCs) to UNCD and NCD surfaces were evaluated. The hBMSCs on UNCD and NCD coatings exhibited similar cell viability, proliferation, and morphology as those on the control material, tissue culture polystyrene. No significant differences in cellular response were observed on UNCD and NCD coatings with different nanoscale topographies. Our data shows that both UNCD and NCD coatings demonstrate in vitro biocompatibility irrespective of surface topography.