Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

Characterization of Cat-CVD grown Si–C and Si–C–O dielectric films for ULSI applications

Si–C films with the Si compositions ranging from 40 to 70% have been grown by Cat-CVD using dimethylsilane [DMSi, Si(CH₃)₂H₂] compounds. Tetraethoxysilane [TEOS, Si(OC₂H₅)₄] and dimethyldimethoxysilane [DMDMOS, Si(CH₃)₂(OCH₃)₂] gas source gave us Si–C–O (C-doped SiO_x) films with wide ternary alloy compositions. The dielectric constant of a Si–C film has been evaluated by C–V measurements (at 1 MHz) using Al/Si–C/n-Si(001)/Cu MIS structure. The relative dielectric constant value of a Si–C film was estimated to be 3.0. The resistivity of the Si–C layer with 1 mm diameter and 0.24 μm thickness was estimated to be more than 24.5 Gohm·cm. These results gave us promising characteristics of Si–C and Si–C–O films grown by alkylsilane- and alcoxysilane-based Cat-CVD.     

The process window for diamond deposition from the vapor phase with sulfur in the C–H–O feed gas mixtures

Theoretical predictions using a modified radical species ternary diagram for C–H–O system indicate that addition of sulfur expands the C–H–O gas phase compositional window for diamond deposition. Sulfur addition to no-growth domain increases the carbon super-saturation by binding the oxygen and the addition of sulfur to the non-diamond domain reduces the heavy carbon super-saturation by decreasing C_nH_m species concentration in the gas phase. The overall effect of sulfur addition to gas phase mixtures is characterized as that of oxygen addition to the C–H system, i.e. expansion of the compositional window over which diamond can be deposited from the gas phase. In addition, the increasing sulfur concentration to diamond domain feed gases beyond 2000 ppm did not affect the steady state gas phase composition but the quality of diamond was reduced.     

Effect of substrate temperature on the deposition of C–N films by pulsed high-temperature C–H–N Plasma CVD

Rather than using conventional low-temperature plasma, the pulsed high-temperature plasma was used to synthesize C–N films. CH₄+N₂ mixture was used as the gas source. The effect of substrate temperature on the deposition was studied. It was found that with the increase of substrate temperature, the deposition rate dropped drastically, the content of H in the films decreased and the hardness of the films was improved; The N/C ratio, however, changed only by a small degree, suggesting that the C and N has been well combined by using high-temperature plasma.     

The formation of a SiOx interfacial layer on low-k SiOCH materials fabricated in ULSI application

The characterizations of SiOCH films using oxygen plasma treatment depends linearly on the O₂/CO flow rate ratio. According to the results of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses, it was found that the carbon composition decreases with increasing O₂/CO flow rate ratio, because more carbon in the Si–O–C and Si–CH₃ bonds on the film surface would be converted by oxygen radicals. It was believed that the oxygen plasma could oxidize the SiOCH films and form a SiO_x interfacial capping layer without much porosity. Moreover, the result of FTIR analysis revealed that there was no water absorbed on the film. A SiO₂-like capping layer formed at the SiOCH film by the O₂/CO flow rate ratio of 0.75 had nearly the same dielectric properties from the result of capacitance–voltage (C–V) measurement in our research.     

Surface hardening of biomedical Ti–29Nb–13Ta–4.6Zr and Ti–6Al–4V ELI by gas nitriding

The microstructure and hardness near the surface of a biomedical titanium alloy, Ti–29Nb–13Ta–4.6Zr (TNTZ), subjected to gas nitriding at 1023–1223 K was investigated in comparison with the conventional biomedical Ti–6Al–4V ELI (Ti64). After gas nitriding, the microstructure near the specimen surface was observed by optical microscopy, X-ray diffraction (XRD), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). In both alloys, two types of titanium nitrides (TiN and Ti₂N) are formed and the phase is precipitated by gas nitriding. Furthermore, the oxygen impurity in the gas nitriding atmosphere reacts with the titanium nitrides; thus, TiO₂ is formed at the outermost titanium nitride layer. The surface hardening was also evaluated by Vickers hardness measurement. The Vickers hardness near the surface of TNTZ and Ti64 increases significantly by gas nitriding.     

Structural characterization of CxByNz (x=0.1 to x=0.2) layers obtained by laser-driven synthesis

C_xB_yN_z layers have been prepared by laser-assisted chemical vapour deposition (CVD) in a gas atmosphere containing C₂H₄, B₂H₆ and NH₃ where the starting composition ratio could vary in a large range. The characterization of these C–B–N materials was made by XRD, EPMA, XPS, optical and scanning electron microscopy. The chemical composition of C–B–N layers tended to a composition C₁B₆N₃ on the line BN–‘B₃C’. The turbostratic structure of C–B–N layers could be influenced and modified as a function of composition. XPS investigations confirmed the single-phase nature and the existence of bonding between all the elements. Some planar structures, containing especially CB₂N groups, were suggested for the ‘unit cell’ of these C–B–N solid solutions, in agreement with EPMA and XPS analysis.     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.     

Structure, bonding state and in-vitro study of Ca–P–Ti film deposited on Ti6Al4V by RF magnetron sputtering

Experimental investigation of functionally graded calcium phosphate-based bio-active films on Ti–6Al–4V orthopaedic alloy prepared in an RF magnetron sputtering plasma reactor is reported. The technique involves concurrent sputtering of Hydroxyapatite (HA) and Ti targets, which results in remarkably enhanced adhesion of the film to the substrate and stability of the interface. The films have been characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The XPS data show that the films are composed of O, Ca, P and Ti, and reveal the formation of O=P groups and hybridization of O–Ca–P. The XRD pattern shows that the Ca–P thin films are of crystalline calcium oxide phosphate (4CaO·P₂O₅) with preferred orientation varying with processing parameters. High-resolution optical emission spectra show that the emission of CaO is dominant. The CaO, PO and CaPO species are strongly influenced by deposition conditions. The introduction of Ti element during deposition provides a stable interface between bio-inert substrates Ti–6Al–4V and bioactive HA coating. In-vitro cell culturing tests suggest excellent biocompatibility of the Ca–P–Ti films.     

Influence of milling time on the processing of Fe–TiCN composites

Fe–TiCN composites were prepared according to conventional powder metallurgical techniques. Composite powders of iron and titanium carbonitride have been prepared by a high-energy milling route. A proper characterisation of powders is necessary and it was carried out by different means: scanning electron microscopy (SEM) to study the particle morphology and microstructure; X-ray diffraction (XRD) to find possible transformations during the milling; chemical analyses to determine the percentage of oxygen, carbon and nitrogen; and particle size distribution. The sintering process was carried out at different temperatures under N₂–10H₂–0.1CH₄ atmosphere. The density, chemical composition and Vickers hardness (HV30) was measured, and their microstructures were observed by using scanning electron microscopy. As a result of the study it is clear that the higher the C/N ratio, higher hardness are related with the microstructure; an increase in the C/N ratio, the hard phase is finer and more disperse throughout the matrix.     

Laser boronising of Ti–6Al–4V as a result of laser alloying with pre-placed BN

This paper discusses the effect of CO₂ laser alloying of pre-placed BN coating with Ti–6Al–4V alloy. The formation of titanium boride and titanium nitride investigated using energy dispersive X-ray diffraction (EDXRD) result were related to the microhardness and microstructure. The nitrogen and boron diffusion during the laser boronising process identified using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectrometry (XPS) analysis was compared with the EDXRD results. The surface hardness HV1500–1700 observed at the boronised layer was five to six times higher than that of untreated Ti–6Al–4V alloy. This was compared with needle platelet and dendrite type microstructures. Theoretically estimated surface temperature values were used to interpret the compound formation in the laser alloyed layer.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

Thaumasite––direct, woodfordite and other possible formation routes

Two main formation routes for thaumasite exist below 15 °C. One is the direct route from C–S–H reacting with appropriate carbonate, sulfate, Ca²⁺ ions and excess water. The other route is the woodfordite route from ettringite reacting with C–S–H, carbonate, Ca²⁺ ions and excess water, in which thaumasite arises through the intermediate formation of the solid solution woodfordite. The woodfordite route for thaumasite formation appears to be relatively quicker (although still slow) than the direct route, presumably because with the former the ettringite already has the octahedral [M(OH)₆] units that can facilitate the critical change from [Al(OH)₆]³⁻ to [Si(OH)₆]²⁻ groupings. Both routes are mutually dependent on each other. The presence of magnesium salts can modify the path to thaumasite formation. High pressure might be able to stabilise [Si(OH)₆]²⁻ groupings and allow thaumasite to become formed above 15 °C. This possibility is discussed.     

Optical emission spectroscopy study of positive direct current bias enhanced diamond nucleation

High nucleation density and crystalline diamond films were deposited on a mirror-polished Si(100) substrate by horizontal microwave plasma chemical vapor deposition using a two step process consisting of positive direct current (dc) bias enhanced nucleation and growth. Optical emission spectroscopy was employed to investigate in situ the plasma emission characterization during positive biasing process. Emission lines from the Balmer series of atomic hydrogen, molecular hydrogen, CH, C₂, and Ar were observed in the visible and ultraviolet ranges when CH₄, H₂, and Ar were used as the reactant gases. The dependence of plasma emission spectra on the deposition parameters, such as biasing voltage, methane concentration and working pressure was investigated. The relative concentrations of neutral atomic hydrogen were estimated by using the Ar emission at 750.4 nm as an actinometer. A significant variation in the emission intensity of the radicals was measured with a change in the biasing voltage. The correlation between the spectra of some species and the quality of diamond films was studied. The results show that CH and C₂ both were important precursor in the diamond deposition, while C₂ was associated with the presence of amorphous phase in the films during positive dc biasing process.     

加热和光照条件下Ru/TiO2催化二氧化碳甲烷化研究

本研究利用浸渍法制备了Ru/TiO₂催化剂, 并在光照和加热两种条件下考察了其催化二氧化碳与氢的反应, 发现催化剂在两种条件下均可引发显著的甲烷化反应(CO₂ + 4H₂ → CH₄ + 2H₂O)。结果显示, 在光照和加热(150~350℃)条件下, CH₄为唯一含C产物。而在更高温度的加热条件下(>400℃)除了生成CH₄外, 还产生少量CO副产物, 表明反应温度对产物选择性有显著影响。随着反应温度由150℃升高到550℃, 对于不同负载量的担载Ru催化剂, CO₂转化率均先增加后降低, 其中在Ru担载量为1.5wt%Ru/TiO₂催化剂上CO₂转化率在350℃时达到最高, 为77.58%。而在温度>400℃条件下, CO的选择性也随反应温度的升高而逐渐增加。综合反应结果和XRD、XPS和N₂吸附-脱附等表征结果, 发现二氧化碳与氢在光照和加热条件下(150~550℃)反应机制不同。在光照条件下, 光激发电子首先被金属Ru捕获, 进而将吸附在金属Ru上的二氧化碳还原, 活性物种经由RuC中间体形成CH₄。而加热条件下(150~550℃), H₂先被Ru活化成氢原子, 氢原子还原吸附在催化剂表面的CO₂形成RuC中间体, 最后RuC中间体进一步加氢生成CH₄。虽然在两种反应条件下经历相同的中间体, 但是中间体的形成路径不同, 即反应物CO₂被活化的方式不同, 因而产物选择性不同。     

Sensitivity enhancement for H2 gas detection using a SnO2–Ag2O–PdOx nanocrystalline system

Thick film H₂ sensors were fabricated using SnO₂ loaded with Ag₂O and PdO_x. The composition that gave highest sensitivity for H₂ was in the wt.% ratio of SnO₂:Ag₂O:PdO_x as 93:5:2. The nano-crystalline powders of SnO₂–Ag₂O–PdO_x composites synthesized by sol–gel method were screen printed on alumina substrates. Fabricated sensors were tested against gases like H₂, CH₄, C₃H₈, C₂H₅OH and SO₂. The composite material was found sensitive against H₂ at the working temperature 125 °C, with minor interference of other gases. H₂ gas as low as 100 ppm can be detected by the present fabricated sensors. It was found that the sensors based on SnO₂–Ag₂O–PdO_x nanocrystalline system exhibited high performance, high selectivity and very short response time to H₂ at ppm level. These characteristics make the sensor to be a promising candidate for detecting low concentrations of H₂.     

FTIR spectroscopy of hydrogen, carbon monoxide, and methane adsorbed and co-adsorbed on zinc oxide

Adsorption of dihydrogen, carbon monoxide and methane, and co-adsorption of H₂/CO, H₂/CH₄ and CO/CH₄ on zinc oxide was studied by means of Fourier transform infrared spectroscopy. Besides the already known dissociation of dihydrogen and molecular adsorption of CO, methane was found to be adsorbed molecularly on coordinatively unsaturated Zn²⁺ ions. Adsorption lowers the CH₄ symmetry from T_d to C_3v, which is reflected in activation of the v₁ (symmetric stretching) mode and discrete frequency shifts of the v₃ (antisymmetric stretching) and ν₄ (bending) modes. Co-adsorption of the above gases on ZnO having pre-adsorbed hydrogen results, in all cases, in a bathochromic shift of the v(Zn–H) band and a hypsochromic shift of the v(O–H) band, which originally appear at 1710 and 3492 cm⁻¹, respectively. The magnitude of these shifts depends upon the nature of the co-adsorbed gas.     

Study on surface and mechanical fiber characteristics and their effect on the adhesion properties to a polycarbonate matrix tuned by anodic carbon fiber oxidation

Polyacrylonitrile (PAN) based high strength carbon fibers were anodically oxidized using the galvanostatic mode in alkaline electrolyte solutions to influence the chemical surface composition. The change of chemical and physical properties was investigated using scanning electron microscopy (SEM), photoelectron spectroscopy (XPS), energy dispersive X-ray analysis (EDX) and contact angle as well as zeta (ζ)-potential measurements.

An initially improved wettability for polar liquids, particularly water, was observed for oxidized carbon fibers. This result was confirmed by ζ-potential measurements. The chemical state of the oxygen containing surface groups changes during anodic oxidation in K₂CO₃/KOH due to further oxidation of C–OH and C=O groups to COOH groups. Therefore the surface acidity increases, which leads to a shift of the isoelectric point to lower pH values and increases the negative ζ_plateau value. The ζ–pH as well as the ζ–concentration dependence show the same tendency. During anodic oxidation of carbon fibers in KNO₃/KOH electrolyte solution beside ‘normal’ (like C–OH, C=O and COOH) surface oxides also carboxylate groups (COO⁻K⁺) were formed at the fiber surface in contrast to an oxidation in K₂CO₃/KOH which introduces ‘normal' surface oxides. No influence could be observed of such an anodic oxidation on the single fiber tensile strength. Contact angle measurements of polycarbonate melt droplets onto single carbon fibers show no dependence of the surface composition. The interfacial shear strength, measured using the microdroplet pull-off test were compared with the thermodynamic work of adhesion. The calculated as well as the measured adhesion show the same absence of any influence of fiber treatment.     

Study on mechanism of C–H radicals’ recombination into acetylene in the process of coal pyrolysis in hydrogen plasma

According to computation results of C–H equilibrium systems, C₂H₂ and C₂H are the main hydrocarbon in the C–H equilibrium system at the temperature of approximately 3500 K. Because hydrogen plasma has the advantage of high temperature (over 3500 K), acetylene can be directly produced by coal pyrolysis in hydrogen plasma. In order to obtain high yields of acetylene, a quenching process is needed to fix the acetylene produced at high temperature. It is proved that an adequate quenching rate (0.775.8×10⁸ K/s) can avoid the decomposition of acetylene, but will not prevent C₂H radicals recombining into acetylene [Chem. Eng. Sci. 54 (1999) 957]. A dynamic chemical method is employed in this paper to study the mechanism of C₂H radicals’ recombination into acetylene in the quenching process. Primary experiments have also been carried out to study the process of coal pyrolysis in hydrogen plasma. It is shown by the calculation results that: (1) the reaction that really has an effect on acetylene yield in the quenching process is the recombination of C₂H and H₂, and not that of C₂H and H in traditional opinions; (2) if the recombination of C₂H and H₂ is taken into account, the total mass content of acetylene in the quenched gas may increase from 58% to 78% at the quenching rate which can prevent acetylene from decomposing. The experimental results prove that C₂H radicals really recombine into acetylene in the quenching process.     

Characterization and microstructural evolution of SiC(OAl) fibers to SiC(Al) fibers derived from aluminum-containing polycarbosilane

The SiC(OAl) fibers and the SiC(Al) fibers were fabricated by the use of aluminum-containing polycarbosilane (Al–PCS) precursor. The two types of fibers have been characterized. Chemical element analysis, AES, SEM, XRD, RMS and NMR have been employed. The chemical formula of SiC(OAl) fibers is SiC_1.31O_0.25Al_0.018 with C and O rich on the surface. The microstructure of SiC(OAl) fibers is a mixture of β-SiC nanocrystals, free carbon, and an amorphous silicon oxycarbide (Si–C–O phase), which have been confirmed by an amount of SiC₂O₂, SiCO₃, SiO₄ and SiC₃O units in the ²⁹Si MAS NMR spectrum. A small quantity of aluminum is embedded uniformly in the Si–C–O amorphous continuous phase. For SiC(Al) fibers, nearly stoichiometric composition was confirmed as chemical composition of SiC_1.03O_0.013Al_0.024. The fiber is composed of a large number of β-SiC crystallites, a small amount of -SiC crystalline and SiC amorphous phase. The aluminum in the SiC(Al) fibers mainly exists in two manners: Al–C bonds connected with the surfaces of the β-SiC grains and Al–O bonds, or Al₂O₃, to the amorphous phase.