Process study of thermal plasma chemical vapor deposition of diamond,part II: Pressure dependence and effect of substrate pretreatment

The effect of pressure during thermal plasma chemical vapor deposition of diamond films has been investigated for a pressure range from 100 to 760 Torr. The maximum growth rate in our experiments occurs at 270 Torr for substrate temperatures around 1000°C. The existence of an optimum pressure for diamond deposition may he related to the balance between generation and recombination of atomic hydrogen and carbon-containing active species in front of the substrate. To estimate the concentrations of atomic hydrogen and methyl radicals under thermal plasma conditions, calculations based on thermodynamic equilibrium have been performed. This approximate evaluation provides useful guidelines because rapid diffusion results in a near frozen chemistry within the boundary layer. The effect of substrate pretreatment on diamond deposition depends on the type of substrate used. Two growth modes have been observed-layer growth and island growth of diamond crystals on various substrates. Screw dislocations have been observed in diamond deposition in thermal plasmas, and defects such as secondary nucleations are more concentrated along (III) directions than along (100) directions.     

Plasma chemical vapor deposition of TiN

Experiments indicate that the temperature in chemical vapor deposition (CVD) of TiN can be decreased from about 1000°C in conventional CVD to about 500°C by the application of a D.C. nonequilibrium plasma. The hardness of the TiN film is greater than 2000 kg/mm² (Vickers). The effect of pressure, ratio of gas mixture, and discharge parameters on the film deposition rate, its hardness, and microstructures has been studied.     

A general atmospheric pressure chemical vapor deposition synthesis and crystallographic study of transition-metal sulfide one-dimensional nanostructures

A series of transition-metal sulfide one-dimensional (1D) nanostructures have been synthesized by means of a general atmospheric pressure, chemical vapor deposition (APCVD) strategy. Vapour-liquid-solid (VLS) and vapour-solid (VS) mechanisms, along with the results of SEM and TEM observations, were used to explain the formation of these nanostructures. The regularity of the growth in the direction of the hexagonal nanowire is explored; we find that it prefers to grow along (1 0 0), (1 1 0), or (0 0 x) directions owing to particular crystal structures. The adopted synthetic route was expected to provide abundant useful 1D building blocks for the research of mesoscopic physics and fabrication of nanoscale devices.     

Carbon nanotubes for supercapacitors:Consideration of cost and chemical vapor deposition techniques

In this topic,we first discussed the requirement and performance of supercapacitors using carbon nanotubes(CNTs) as the electrode,including specific surface area,purity and cost.Then we reviewed the preparation technique of single walled CNTs(SWNTs) in relatively large scale by chemical vapor deposition method.Its catalysis on the decomposition of methane and other carbon source,the reactor type and the process control strategies were discussed.Special focus was concentrated on how to increase the yield,selectivity,and purity of SWNTs and how to inhibit the formation of impurities,including amorphous carbon,multiwalled CNTs and the carbon encapsulated metal particles,since these impurities seriously influenced the performance of SWNTs in supercapacitors.Wish it be helpful to further decrease its product cost and for the commercial use in supercapacitors.     

Effects of temperature on the properties of TiO2 photocatalysts prepared by the chemical vapor deposition (CVD) method

In this study, a TiO₂ film was prepared in an annular reactor by the chemical vapor deposition (CVD) method. Results indicated that anatase crystals were formed, except for at a deposition temperature of 200°C without calcination. At a calcination temperature of 850°C, anatase crystal was the major species formed with a small amount of rutile crystals. After conducting a photocatalytic reaction of toluene, the best activity was found with a preparation temperature of 350°C for the deposition, and 550°C for calcination.     

Chemical vapor deposition of metal borides: 6. The formation of neodymium boride thin film materials from polyhedral boron clusters and metal halides by chemical vapor deposition

The chemical vapor deposition (CVD) of crystalline thin films of neodymium hexaboride (NdB₆) was achieved using either nido ‐pentaborane(9) or nido ‐decaborane(14) with neodymium(III) chloride on different substrates. The highly crystalline NdB₆ films were formed at relatively moderate temperatures (835 °C, ca. 1 µm/h) and were characterized by scanning electron microscopy, X‐ray emission spectroscopy, X‐ray diffraction and glow discharge mass spectrometry. The NdB₆ polycrystalline films were found to be pure and uniform in composition in the bulk material. Depositions using CoCl₂, NdCl₃ and B₅H₉ as the CVD precursors resulted in the formation of a mixture of NdB₆ and CoB phases, rather than the ternary phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Parametric study of atmospheric-pressure diamond synthesis with an inductively coupled plasma torch

Polycrystalline diamond coatings have been deposited run molybdenum and silicon substrates using an inductively coupled, atmospheric-pressure plasma torch. Growth rates are on the order of 10 hr. The inductively coupled plasma reactor is found to produce a uniform, well-characterized growth environment for experimental and computational .study of the atmospheric-pressure diamond growth regime. Growth morphology is found to be sensitive to reactor conditions such as substrate surface temperature and methane-to-hydrogen feed ratio. An experimental parametric study of these variables is performed and the resultant growth analyzed by scanning electron microscopy, Raman spectroscopy, and X-ray diffraction Spectroscopic analysis of the gas phase is also performed. Results indicate that the, substrate temperature range over which diamond growth occurs shifts toward higher temperatures as the methane-to-hydrogen feed ratio is increased. The growth rate is observed to reach a maximum with varying methane-to-hydrogen feed ratio at constant substrate temperature. Raman analysis of the deposits indicates that higher-quality diamond is achieved at the highest limits of substrate temperature for a given methane-to-hydrogen ratio. Higher-quality diamond is also observed to be, formed at lower methane-to-hydrogen feed ratios.     

Atmospheric pressure chemical vapor deposition: an alternative route to large-scale MoS2 and WS2 inorganic fullerene-like nanostructures and nanoflowers

Large-scale MoS2 and WS2 inorganic fullerene-like (IF) nanostructures (onionlike nanoparticles, nanotubes) and elegant three-dimensional nanoflowers (NF) have been selectively prepared through an atmospheric pressure chemical vapor deposition (APCVD) process with the reaction of chlorides and sulfur. The morphologies were controlled by adjusting the deposition position, the deposition temperature, and the flux of the carrier gas. All of the nanostructures have been characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). A reaction mechanism is proposed based on the experimental results. The surface area of MoS2 IF nanoparticles and the field-emission effect of as-prepared WS2 nanoflowers is reported.     

Magnetic property and structural study of nickel supported on reduced graphene oxide prepared by chemical vapor deposition

Nickel supported on reduced graphene oxide was synthesized by chemical vapor deposition technique. The crystal structure and magnetic properties of the prepared sample were studied by means of Raman spectrometry, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP-OES), and vibrating sample magnetometry (VSM). The result of Raman spectroscopy revealed the structure of few-layer graphene as the support for Ni nanoparticles. XP spectrum confirmed the presence of metallic Ni on the a few-layer graphene surface. TE micrograph showed that the nickel nanoparticles were sphere shaped and the mean particle size is about 20 nm deposited on the reduced graphene oxide. The magnetic study showed the ferromagnetic behavior of 3.2 wt% nickel over reduced graphene oxide at room temperature.     

Study on the anti‐reflection and structure evolution of hydrogenated amorphous carbon grown by plasma chemical vapor deposition

In this work, the interrelation between the anti‐reflective property and the component, especially the sp² content, was studied. The results showed that the refraction index n increased from 2.2 to 3.3 with the direct current negative bias increasing. The reflection result R successful fall by 11.9% because of the existence of hydrogenated amorphous carbon anti‐reflective coatings. Both the refraction index and reflectivity decreasing correspond to a more graphitic microstructure character. Moreover, the optical property evolution of the films was explained by the chemical vapor deposition mechanism based on the ion sub‐plantation model and two‐phase model. Copyright © 2014 John Wiley & Sons, Ltd.     

Substrate temperature effects on film chemistry in plasma deposition of organics. III. Analysis by static secondary ion mass spectrometry

Static secondary ion mass spectrometry (SIMS) was used to examine the effect of reducing the substrate temperature during the radio frequency plasma deposition of organic films. Studies of two polymerizable plasma precursors (2-hydroxyethyl methacrylate and acrylic acid) and one nonpolymerizable precursor (acetone) deposited without substrate cooling and with liquid nitrogen cooling are presented. Acetone deposited with methanol/dry ice cooling was also investigated. Spectra of polymerizable precursors were analyzed by comparison to spectra for the corresponding conventionally-polymerized polymer films [i.e., poly(hydroxyethyl methacrylate) and poly(acrylic acid)]. Acetone spectra were interpreted by reference to SIMS analysis of plasma-deposited films prepared from isotopically-labelled acetone and to reference homopolymers. Comparison of the SIMS spectra of films deposited at different substrate temperatures indicates that a reduction in substrate temperature generally results in higher intensity of peaks characteristic of oxygenated ion structures. SIMS also suggests that the reduction of substrate temperature results in less polymer unsaturation and fewer structures which form by hydrogen redistribution during the deposition process. These results support the hypothesis that deposition at low substrate temperatures leads to an increase in the proportion of precursor incorporated into the film without substantial fragmentation. Corroborative results from high resolution x-ray photoelectron spectroscopy (XPS) and assays for precursor functional groups by chemical derivatization reactions in conjunction with XPS are also presented. © 1992 John Wiley & Sons, Inc.     

Metal organic chemical vapor deposition of ZnO from β‐ketoiminates

ZnO is a high‐mobility electron conductor being considered for high‐throughput electronics in flexible and transparent formats. We demonstrated the Zn β‐ketoiminate system, based on acetylacetimine with N‐propyl, isopropyl, and butyl groups, as a vehicle for preparing ZnO thin films for electronic applications. Surface carbon was a primary impurity, and the precursors studied afforded films with the lowest surface carbon contamination at deposition temperatures near 400°C. Thermal annealing of the films reduced the surface carbon content and afforded semiconducting materials. Annealing also gave larger‐grained, better connected films. Thinner films were associated with semiconducting as opposed to ohmic behavior; such films will be adaptable for transparent logic circuits. Copyright © 2012 John Wiley & Sons, Ltd.     

Ab initio study of aluminum chemical vapor deposition from dimethylaluminum hydride: a gas phase reaction mechanism

The effect of preheating of dimethylaluminum hydride (DMAH) as a gas on the epitaxial growth in aluminum chemical vapor deposition (Al-CVD) is studied theoretically. The chemical changes of DMAH in the gas phase such as unimolecular decomposition reactions, bimolecular reactions and polymerizations are treated using ab initio molecular orbital method (MP2/6-31G**) and density functional theory (B3P86/LanL2DZ). The gas phase equilibrium composed of the previous reaction products under the usual experimental conditions for Al-CVD is also investigated in detail as the initial stage of the CVD process. From the energetics point of view, unimolecular decomposition reactions and bimolecular reactions hardly occur, however, polymerizations of DMAH take place readily at the low temperatures found in Al-CVD. A large amount of DMAH-dimer and a small amount of DMAH-monomer and trimer coexist in the equilibrium state.     

Substrate temperature effects on film chemistry in plasma depositions of organics. II. Polymerizable precursors

The influence of substrate temperature during plasma deposition on the chemistry of the organic films formed was examined. Plasma ionization of precursor gases that are polymerizable by conventional mechanisms was studied. Film chemistry was analyzed by x-ray photoelectron spectroscopy (XPS). Monomers that polymerize by a free radical mechanism [2-hydroxyethyl methacrylate (HEMA) and hexafluorobutadiene (HFB)] form more regular polymers (i.e. with less molecular rearrangement) by plasma deposition at low substrate temperatures than monomers that polymerize by ionic mechanisms [ethylene oxide (EO) and tetrahydrofuran (THF)]. In all cases, lowering the substrate temperature during deposition produces films with elemental composition virtually identical to that of the precursor gas. Comparison of high-resolution XPS spectra of the deposited films with those for model polymers suggests that functional groups in the monomers used to generate the plasma are incorporated to a greater extent at low substrate temperatures. The effect of plasma power on the degree of precursor structure retention obtained when reduced substrate temperatures are employed was also examined. Plasma deposition of HEMA at low substrate temperatures and low plasma power produces thin films which are, by core level XPS, indistinguishable from HEMA polymerized by conventional methods. EO and THF films coated at low substrate temperatures on glass, polyethylene, or polytetrafluoroethylene varied widely in surface chemistry due to differences in film uniformity. Film quality (uniformity) is enhanced for these low reactivity precursors by pretreating substrates with an argon plasma. © 1992 John Wiley & Sons, Inc.     

Luminescence properties of Cu‐ion‐implanted and annealed ZnO thin films deposited by chemical vapor deposition and pulsed laser deposition

Ion implantation techniques were used to study the effect of an MgO additive on the luminescence properties induced by Cu in ZnO thin films. Cu ions (accelerating voltage of 75 keV, dose of 4.5 × 10¹⁴ ions/cm²) were implanted at room temperature in nondoped and Mg‐doped ZnO thin films. After annealing, emissions in the visible region originating from Cu phosphor were observed at 510 nm in CVD‐ZnO and at 450 nm in Mg‐doped ZnO (MZO) thin films. The Cu depth profile shows distortion in the low‐concentration region of CVD‐ZnO. After the annealing, the Cu implant was homogenized in thin films, and then the Cu concentration was determined to be 1.5 × 10¹⁹ ions/cm³ in CVD‐ZnO and 5.6 × 10¹⁸ ions/cm³ in MZO thin films. Copyright © 2005 John Wiley & Sons, Ltd.     

Plasma deposition of silicon nitride-like thin films from organosilicon precursors

Plasmas containing hexamethyldisilazane or hexamethylcyclotrisilazane and nitrogen or ammonia were used to deposit silicon nitride-like films at low substrate temperature (T<60°C). Optical properties (refractive index and absorption coefficient), chemical composition of the deposit and film growth rate were examined with respect to the deposition parameters (rf power, pressure and feed composition). As deposited films from ammonia containing mixtures were silicon nitride-like, contained carbon, and were nearly oxygen free. Furthermore, only Si−N, Si−H, and N−H bonds were identified in as-deposited films. The reactive Si−H bonds progressively transformed into Si−O bonds as the films were exposed to air. Films deposited from highly ammonia-diluted mixtures, high RF power and low pressure showed the highest stability with refractive indices as high as 1.8.