CVD synthesis and characterization of thin Mo2C crystals

In this study, we present an investigation on the growth of thin Mo₂C crystals via chemical vapor deposition using CH₄. Optical microscopy (OM), scanning electron microscopy (SEM), atomic force microscopy(AFM), and Raman spectroscopy studies show that the morphology and the thickness of Mo₂C crystals are strongly affected by the impurities in the system, the thickness of the copper substrate, and the graphene presence on Cu surface prior to Mo₂C formation. Our studies show that during the CVD process, orthorhombic Mo₂C crystals grow along the [100] direction on two different regions: directly on Cu surface or on graphene covered regions. Mo₂C crystals that form on graphene are found to be thinner and less defective compared to the ones formed on the Cu surface. This is attributed to graphene acting as an additional diffusion barrier for Mo atoms diffusing through the copper. In addition to the graphene beneath the Mo₂C crystal, Raman studies indicate that graphene may grow also on top of the Mo₂C crystal, forming a graphene/Mo₂C/graphene sandwich structure which may offer interesting properties for electronic applications.     

Growth kinetics of MWCNTs synthesized by a continuous-feed CVD method

Unlike two-step chemical vapor deposition (CVD) methods using pre-deposited catalyst particles, in a continuous-feed CVD process, the liquid feed (consisting of catalytic precursor and hydrocarbon source) is continuously supplied into the reactor causing catalyst particle formation, nucleation of carbon nanotubes (CNTs) and CNT growth to occur simultaneously throughout the reaction period. In order to observe these processes, CVD experiments were conducted for different durations (30 s to 3 h) and the product multiwalled carbon nanotubes (MWCNTs) were characterized using scanning electron microscopy. It was found that the nanotubes did not grow in the vapor phase and that substrates played an important role in the growth by providing a place for them to anchor before growth took place. Based on transmission electron microscopy images, it has been suggested that MWCNTs grew by root-growth mechanism from the catalyst particles that were deposited on the substrate during the early stages. At long process times, continuously supplied feed gas produced additional catalyst particles which were deposited mostly on the growing nanotube mat. Due to weak catalyst-mat interaction, the additional nanotubes grew by tip growth. A comprehensive MWCNT growth model has been presented for the continuous-feed CVD.     

Reactivity of perovskite-type precursor in MWCNTs synthesis

Ni catalysts were tested in the synthesis of multi-wall carbon nanotubes (MWCNTs) by catalytic decomposition of methane at low temperature. The selectivity of MWCNTs formation was determined using transmission electron microscopy (TEM). The catalytic performance of the supported-Ni catalysts obtained by perovskite reduction was discussed based on the X-ray diffraction (XRD), TEM and scanning electronic microscopy (SEM) results. The characteristics of the nanotubes obtained by decomposition of methane were mainly dependent on the homogeneity of nickel particles and less on the reaction conditions.     

The role of hydrogen in methanol synthesis over copper catalysts

The experimental observation that the activity of a series of zinc oxide supported copper catalysts is related to the surface area of the copper is examined in the light of recent evidence that hydrogen spillover from copper to zinc oxide is facile. A model is proposed which explains the effect of zinc oxide on copper in terms of a reversible transfer of hydrogen between copper and zinc oxide. It is suggested that therate determining step normally occurs on the surface of the copper but that therate of reaction can be dependent on the availability of spillover hydrogen from the zinc oxide.     

The distribution of hydrogen in polycrystalline CVD diamond

The location of the hydrogen prevalent in chemical vapor deposition (CVD) diamond has long been of much interest, not least because of the information it reveals about the H-driven growth mechanism. We have used micro-scanning elastic recoil detection analysis to map the hydrogen distribution in three dimensions in polycrystalline CVD diamond. The interface between two CVD layers, one grown with, and one grown without oxygen in the growth mixture has been studied for its hydrogen concentration. An upper limit on bulk hydrogen concentration has been determined. The possibility of hydrogen trapping in the bulk is also discussed.     

Catalyst deactivation in CVD synthesis of carbon nanotubes

A computational fluid dynamics (CFD) model with multistep chemical reactions was applied to predict the yield of multiwalled carbon nanotubes produced from our xylene-based chemical vapor deposition (CVD) reactor. Two-step xylene decomposition in the gas phase and catalytic decomposition of hydrocarbons to nanotubes on the growth surfaces were adopted based on exhaust-gas composition measurements. Using the experimentally obtained exhaust-gas concentrations, we conducted inverse calculations to determine apparent rate constants of the catalytic surface reactions. During the CVD process, catalyst deactivation was observed probably due to carbon formation on the catalyst surface. Its effect on the apparent rate constant was empirically correlated with a simple exponential equation. Applying the CFD model, we predicted the local yielding rate of nanotubes along the axis of the reactor. The total yield was then computed by integrating the local yielding rate over the growth surfaces and compared favorably (∼95%) with the experimental results. The proposed model is expected to help researchers optimize the process parameters to achieve the maximum nanotube yield.     

Ion channeling studies of hydrogen in homoepitaxially grown CVD diamond

Using ion channeling measurements in conjunction with the resonant ¹H(¹⁵N,αγ)¹²C nuclear reaction or with proton Rutherford backscattering spectrometry we studied the incorporation of hydrogen from the plasma into homoepitaxial (100) and (111) CVD diamond films. The measured hydrogen concentration and the structural defect density of the diamond lattice derived from proton channeling yields were observed to be correlated. Hydrogen lattice location studies for different incident ion channeling directions showed no dominant fraction of H occupying either one of the two theoretically predicted sites. These results suggest that in CVD films with quite high dislocation densities and relative H concentrations above 10⁻³, hydrogen is predominantly incorporated at structural defect sites uncorrelated with the lattice symmetry.     

PAM-g-PVA/MWCNTs导电复合材料的制备及表征

以硝酸铈胺-PVA为氧化还原引发体系,制备了丙烯酰胺接枝聚乙烯醇（PAM-g-PVA）聚合物,采用共混法,在接枝聚合物中掺杂多壁碳纳米管制备了PAM-g-PVA/MWCNTs气敏传感导电薄膜材料,研究了在不同饱和蒸气中的气敏响应性。结果表明,导电薄膜在乙酸乙酯、正丙醇饱和有机溶剂蒸气中显示负蒸气系数效应（NVC）,在丙酮和盐酸饱和蒸气中为正气系数效应（PVC）,但随着电阻的增加,导电薄膜在盐酸饱和蒸气中呈现负蒸气系数效应。     

Effects of partial and total methane flows on the yield and structural characteristics of MWCNTs produced by CVD

Multi-walled carbon nanotubes (MWCNTs) were produced in a chemical vapor deposition (CVD) process employing methane and argon as hydrocarbon and carrier gas over supported sol-gel Co-Mo/MgO catalysts. A detailed study about the influence of the gas flow of both hydrocarbon and carrier gas on carbon yield, morphology, structure and graphitization degree is presented. Methane partial pressure, methane total flow rate, as well as the flow ratios of methane to argon and methane to hydrogen (reducing gas) were the parameters systematically varied. The results reveal that high MWCNT yields in the produced materials are strongly related to the methane partial pressure and the methane total flow, while a high degree of graphitization is more closely linked to the use of argon gas as inert atmosphere.     

Raman scattering characterization of CVD graphite films

Raman spectroscopic study has been performed for thin graphite films grown on nickel substrates by chemical vapor deposition from a mixture of hydrogen and methane activated by a direct current discharge. Depending on the growth conditions, the CVD films are composed of graphene layers parallel to the substrate surface or of plate-like crystallites with the predominant orientation of their graphene layers perpendicular to the substrate surface. A comparison of the Raman spectra for the CVD films and for the highly oriented pyrolytic graphite has been performed. The mechanisms governing the Raman scattering process in the films are discussed. An important role of a double resonance mechanism in the Raman spectra of these graphite-based materials has been revealed. The Raman band positions and intensities and their dependence on excitation wavelength confirm a high degree of the structural order in the CVD graphite films.     

Study the effect of O2 addition on hydrogen incorporation in CVD diamond

The effect of a small amount of O₂ addition on film quality and hydrogen incorporation in chemical vapour deposition (CVD) diamond films was investigated and the films were grown using a 5-kW microwave plasma CVD reactor. Film quality and bonded hydrogen were characterized using micro-Raman and Fourier transform infrared (FTIR) spectroscopy, respectively. It was found that in general for films grown using CH₄/H₂ plasma both without and with O₂ addition, the hydrogen incorporation increases with increasing substrate temperature, while a small amount of O₂ addition (O₂/CH₄=0.1) into CH₄/H₂ (4%) plasma strongly suppresses the incorporation of hydrogen into the film. Raman spectra show that the added oxygen improved film quality by etching and suppressing the amorphous carbon component formed in the film. The above effect of oxygen addition on hydrogen incorporation and film quality is discussed according to the growth mechanism of CVD diamond. The CVD diamond specific hydrogen related IR vibration at 2828 cm⁻¹ appears as a sharp and strong peak only in the FTIR spectra of poor quality films grown at high temperature both without and with O₂ addition, but it appears much stronger in the film grown without O₂ addition. This result experimentally excludes the assignment of the 2828 cm⁻¹ peak arises from hydrogen bonded to oxygen related defect in the literature.     

High resolution XPS characterization of chemical functionalised MWCNTs and SWCNTs

High resolution XPS analysis of chemical functionalised multi-wall carbon nanotubes (MWCNTs) and single wall carbon nanotubes (SWCNT) was done with ESCA300 (overall instrument resolution of 0.35 eV). Information to the degree of functionalisation was ascertained by argon ion bombardment of the samples followed by XPS analysis to detect the functional groups, the percentage atomic concentration of various elements present and whether or not the detected functional groups imposed a chemical shift on the CNT atoms. The results show that true chemical functionalisation was achieved and by argon ion bombardment these functional groups can be altered relative to the C 1s carbon atoms of the CNT. The choice of chemicals used for functionalisation, the techniques employed and the types of nanotubes treated are important factors in chemical characterisation. The carbon atom on the nanotube ring to which the functional group (atom) is bonded, the chirality of the CNT, the electronegativity of the functional group, the bond type and whether the CNT is single-wall or multi-wall, or cut (short) could play a role in determining the chemical shift on the CNTs atoms. These investigations are relevant to chemical functionalisation of carbon nanotubes for various applications for example DNA sensors and other biomedical sensors.     

A review of diamond synthesis by CVD processes

Diamond has some of the most extreme mechanical, physical and chemical properties of all materials. Within the last 50 years, a wide variety of manufacturing methods have been developed to deposit diamond layers under various conditions. The most common process for diamond growth is the chemical vapor deposition (CVD). Starting from the first publications until the latest results today, a range of different developments can be seen. Comparing the basic conditions and the process parameters of the CVD techniques, the technical limitations are shown. Processes with increased pressure, flow rate and applied power are the general tendency.     

Dimensional control of multi-walled carbon nanotubes in floating-catalyst CVD synthesis

Dimensional control in CVD synthesis of MWNT’s is significant and critical to a number of different applications. This study examines the dimensional effect of a number of synthesis variables on the products of floating-catalyst CVD, including catalyst concentration in the feedstock, nanotube growth time, and deposition substrate selection. Extensive diameter surveys are performed by TEM and compared with results from thermo-gravimetric analyses to Raman spectroscopy, offering a novel dimensional analysis of nanotubes grown by FC-CVD methods. CNT diameters are inversely proportional to the catalyst concentration with weak correlation over the range examined and are directly proportional to growth time. Results are combined with prior art to develop a new theory regarding catalyst particle formation over a range of catalyst concentrations. Carbon deposition occurs in two stages, the first characterized by accelerating deposition and increases in CNT diameter and length, the second by etching of the array and carbon deposition at a constant rate. Deposition substrates interact directly with the catalysts to strongly influence the resulting nanotube diameters, based upon the mobility of the catalysts on the substrate surface.     

Homogenizing role of hydrogen in the synthesis of multicomponent Carbohydrides and Nitridohydrides of transition metals in the combustion mode

This work presents the results of study of combustion with carbon of transition metals of IV, V and VI groups of the periodic system in atmospheres of argon, hydrogen, nitrogen and nitrogen-hydrogen mixture. The significance of hydrogen in the formation of single-phase products in the self-propagating high-temperature synthesis (SHS) mode was underlined. The combustion of carbon containing systems in argon resulted in the synthesis of two-phase carbides with FCC lattice. In contrary, the combustion of the same systems in hydrogen atmosphere leaded to the synthesis of single-phase carbo-hydrides. The products of combustion of transition metals in nitrogen atmosphere were the multiphase nitrogen-containing compounds. Their following re-ignition in hydrogen leaded to the synthesis of single-phase nitrido-hydrides. It was demonstrated that in all the studied systems, the combustion in hydrogen atmosphere leaded to the homogenized final synthesis products. The results of these processes were the formation of single-phase carbo- and nitrido-hydrides based on the metals of IV, V and VI groups. The presence of hydrogen in the crystal lattice of synthesized refractory carbides and nitrides facilitated easy dispersion of the compound to submicron sizes. After removal of hydrogen, the single phase structure was not violated. The described results may be of commercial value in the industry of refractory materials.     

Direct synthesis and characterization of optically transparent conformal zinc oxide nanocrystalline thin films by rapid thermal plasma CVD

We report a rapid, self-catalyzed, solid precursor-based thermal plasma chemical vapor deposition process for depositing a conformal, nonporous, and optically transparent nanocrystalline ZnO thin film at 130 Torr (0.17 atm). Pure solid zinc is inductively heated and melted, followed by ionization by thermal induction argon/oxygen plasma to produce conformal, nonporous nanocrystalline ZnO films at a growth rate of up to 50 nm/min on amorphous and crystalline substrates including Si (100), fused quartz, glass, muscovite, c- and a-plane sapphire (Al2O3), gold, titanium, and polyimide. X-ray diffraction indicates the grains of as-deposited ZnO to be highly textured, with the fastest growth occurring along the c-axis. The individual grains are observed to be faceted by (103) planes which are the slowest growth planes. ZnO nanocrystalline films of nominal thicknesses of 200 nm are deposited at substrate temperatures of 330°C and 160°C on metal/ceramic substrates and polymer substrates, respectively. In addition, 20-nm- and 200-nm-thick films are also deposited on quartz substrates for optical characterization. At optical spectra above 375 nm, the measured optical transmittance of a 200-nm-thick ZnO film is greater than 80%, while that of a 20-nm-thick film is close to 100%. For a 200-nm-thick ZnO film with an average grain size of 100 nm, a four-point probe measurement shows electrical conductivity of up to 910 S/m. Annealing of 200-nm-thick ZnO films in 300 sccm pure argon at temperatures ranging from 750°C to 950°C (at homologous temperatures between 0.46 and 0.54) alters the textures and morphologies of the thin film. Based on scanning electron microscope images, higher annealing temperatures appear to restructure the ZnO nanocrystalline films to form nanorods of ZnO due to a combination of grain boundary diffusion and bulk diffusion.PACS: films and coatings, 81.15.-z; nanocrystalline materials, 81.07.Bc; II-VI semiconductors, 81.05.Dz.     

Modified microwave method for the synthesis of visible light-responsive TiO2/MWCNTs nanocatalysts

Recently, TiO₂/multi-walled carbon nanotube (MWCNT) hybrid nanocatalysts have been a subject of high interest due to their excellent structures, large surface areas and peculiar optical properties, which enhance their photocatalytic performance. In this work, a modified microwave technique was used to rapidly synthesise a TiO₂/MWCNT nanocatalyst with a large surface area. X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller measurements were used to characterise the structure, morphology and the surface area of the sample. The photocatalytic activity of the hybrid nanocatalysts was evaluated through a comparison of the degradation of methylene blue dye under irradiation with ultraviolet and visible light. The results showed that the TiO₂/MWCNT hybrid nanocatalysts degraded 34.9% of the methylene blue (MB) under irradiation with ultraviolet light, whereas 96.3% of the MB was degraded under irradiation with visible light.     

Hydrothermal synthesis of size-dependent Pt in Pt/MWCNTs nanocomposites for methanol electro-oxidation

A hydrothermal method has been developed to prepare size-controlled Pt nanoparticles dispersed highly on multiwalled carbon nanotubes (Pt/MWCNTs). It was found that the size of Pt nanoparticles was strongly dependent on the solution pH in synthesis. The Pt nanoparticles with mean size of 3.0, 4.2 and 9.1 nm were obtained at pHs 13, 12 and 10 separately. After Pt/MWCNTs composites were fabricated, the different properties of cyclic voltammetry and chronoamperometry in electro-oxidation of methanol were found. The results showed that the smaller diameter Pt deposited Pt/MWCNTs nanocomposites exhibited higher electrocatalytic activity for methanol oxidation. By characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), size-dependent activities were identified.     

氯化氢合成生产中氯氢配比的控制

介绍氯化氢合成工艺流程,讨论生产过程中氢气过量或氯气过量的危害,分析氯氢配比异常的原因,提出了保证氯氢配比符合工艺条件的控制措施。     

CVD elaboration and in situ characterization of barium silicate thin films

This study is concerned with the elaboration of barium silicate thin films by metal organic chemical vapor deposition (MOCVD) and in situ characterization by X-ray photoemission spectroscopy (XPS) with an apparatus connected to the deposition reactor. The difficulty to find an efficient metal organic precursor for barium is described. After characterizations of the selected reactant, Ba(TMHD)₂tetraglyme, the development of an original specific vapor delivering source which allows reactant sublimation in the CVD reactor was performed. In the most optimized cases, including use of oxygen introduction during the deposition, barium silicate films were obtained. Moreover, non-negligible amounts of carbon and presence of barium oxide on the top of the layers were observed.