Superior structural and electronic properties for amorphous silicon–germanium alloys deposited by a low temperature hot wire chemical vapor deposition process

Very good electronic properties of hot-wire CVD a-Si,Ge:H alloys have been established by junction capacitance methods. The samples were deposited using a tantalum filament maintained at about 1800 °C instead of the usual 2000 °C tungsten filament process. Urbach energies below 45 meV were found, as well as annealed defect densities below 10¹⁶ cm⁻³, for Ge fractions up to 30 at.%. However, samples with 10¹⁹ cm⁻³ levels of oxygen exhibited much broader Urbach energies and higher defect densities. Light induced degradation was examined in detail for one a-Si,Ge:H alloy sample and compared to the behavior of PECVD grown a-Si:H alloys of similar optical gap.     

Advances in hot wire chemical vapor deposition technology for the synthesis of novel silicon thin films materials

We report in this paper on fabrication of an advanced hot wire chemical vapor deposition technique. We introduced for the first time ‘box-type’ ceramics filament holder in hot-wire CVD technology. The surface topography and atomic-scale structure of the films synthesized by the new ceramics hot-wire CVD technique have been compared with that of films prepared with that of standard hot-wire CVD.     

Synthesis of polycrystalline silicon thin films with ‘icosahedral’ symmetry by ceramics hot wire chemical vapor deposition

We report on synthesis and materials physics of polycrystalline silicon thin films deposited on glass with rarely observed ‘five-fold’ symmetry or ‘icosahedral’ symmetry. We invented these ‘novel form’ of polycrystalline silicon thin films by ceramics hot wire chemical vapor deposition (hot-wire CVD). A new physical effect in hot-wire CVD technology has been proposed that controls the nucleation and growth of silicon thin films on glass substrate.     

Catalyzed chemical vapor deposition of one-dimensional nanostructures and their applications

This article reviews progress in the growth of one-dimensional nanomaterials such as carbon nanotubes and inorganic nanowires. Catalyzed chemical vapor deposition has been the preferred method to grow these materials for various applications requiring controlled growth on patterned and unpatterned substrates. Both thermal and plasma chemical vapor deposition techniques have been widely used in the case of carbon nanotubes. In addition to the discussion on growth, a review of applications for one-dimensional nanostructures and future directions is provided.     

Thermodynamic analysis of gas phase chemistry in hot wire chemical vapor deposition of a-Si:H and μc-Si:H

Gas phase reactions amongst filament-generated radicals play a crucial role in growth and properties of films deposited by hot wire chemical vapor deposition (HWCVD) technology. Gas phase species of interest are SiH₄, H₂, Si, H, SiH₃, SiH₂ and SiH. Partial pressures of these species for different sets of deposition conditions have been determined from the standard Gibbs free energy data. Equilibrium concentrations of the film forming precursors have been determined. The effect of the various process parameters on the equilibrium concentration of the precursors has been studied. H, Si and SiH are found to be the dominant species in gas phase above a filament temperature of 2300 K. However SiH₃ and SiH₂ concentration peaks are between 1900 and 2300 K, of the filament temperature.     

Smooth diamond films grown by hot filament chemical vapor deposition on positively biased silicon substrates

Smooth diamond films have been grown by hot filament chemical vapor deposition under DC bias on mirror-polished Si(100) substrates. Films of a few micrometers thickness were obtained in 30 min. The films were found to have d-spacing at 2.06 and 2.11 Å by X-ray diffraction. Raman spectra showed very broad peaks at 1329 (1336) and 1591 cm^-1. The films have a high density of planar defects and large internal stresses.     

Noncatalytic synthesis of carbon nanotubes by chemical vapor deposition

A new method is proposed to obtain uniform arrays of multiwall carbon nanotubes without catalysts. Nanotubes have been formed by carbon condensation from a hydrogen-methane gas mixture activated by a dc discharge. Structural and morphological investigations of the obtained material were performed by Raman spectroscopy, scanning and transmission electron microscopy, energy-dispersive X-ray analysis, and electron energy loss spectroscopy. It is shown that the obtained nanotubes contain no impurities that could act as catalysts. Based on these experimental data, it is concluded that the nanotube synthesis under study is noncatalytic. Possible mechanisms of this synthesis are considered.     

Low-temperature deposition of crystalline silicon nitride nanoparticles by hot-wire chemical vapor deposition

The nanocrystalline alpha silicon nitride (α-Si₃N₄) was deposited on a silicon substrate by hot-wire chemical vapor deposition at the substrate temperature of 700 °C under 4 and 40 Torr at the wire temperatures of 1430 and 1730 °C, with a gas mixture of SiH₄ and NH₃. The size and density of crystalline nanoparticles on the substrate increased with increasing wire temperature. With increasing reactor pressure, the crystallinity of α-Si₃N₄ nanoparticles increased, but the deposition rate decreased.     

Tetragonal tungsten oxide nanobelts synthesized by chemical vapor deposition

Tungsten trioxide (WO₃) nanobelts in tetragonal structure were grown on Si substrates by a hot-wall chemical vapor deposition (CVD) method without using catalysts. The products were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and photoluminescence (PL) spectrum. The width of the nanobelts is in the range of 50–100 nm with width-to-thickness ratios of 5–10 and lengths of up to tens of micrometers. These nanobelts grew along the [0 0 1] direction and can be identified as the tetragonal WO₃ structures. Raman and PL measurements indicate the high quality of the nanobelts. The vapor–solid growth mechanism could be applicable in our experiment.     

Growth of high quality ZnSe on closely lattice-matched InGaAs substrates by metal organic chemical vapor deposition

Epitaxial ZnSe layers have been grown by metal organic chemical vapor deposition (MOCVD) on GaAs and InGaAs substrates over the temperature range 400–500°C, using either diisopropyl selenide or diethyl selenide with diethyl zinc. The latter combination leads to improved optical and crystal quality at a growth temperature of 500°C. The narrowest double crystal rocking curve width is 100 arcsec in the lattice-matched case with a 3.5% InAs content in the InGaAs substrate, comparable to films grown by molecular beam epitaxy (MBE). Both n- and p-type dopants have been incorporated to fabricate p/n homojunction structures.     

Growth behavior of CuPc films by physical vapor deposition

Various Cu‐phthalocyanine (CuPc) films were grown from physical vapor deposition on top of indium‐tin‐oxide glass substrates by controlling substrate temperature (T_sub), source temperature (T_sou), and growth time. From side‐view SEM pictures, the growth rates for these CuPc films are estimated and can be categorized into three regions. From the Arrhenius plot of growth rate versus 1/T_sub, the activation energy E_A can be obtained. As T_sou = 390 °C, for region (A) with T_sub < 140 °C, the growth of CuPc films is dominated by the adhesion process with E_A = 810 meV. For region (B) with 140 °C < T_sub < 320 °C, the growth is then limited by the steric character associated with the organic molecular solids with E_A = 740 meV. For region (C) with T_sub > 320 °C, the re‐evaporation of the CuPc adhered molecules from the interface becomes dominant. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Impact of chlorine dissociation for modified chemical vapor deposition

Modified chemical vapor deposition (MCVD) is the platform technology used to create a wide range of silica-based optical fibers. This paper reports on the extension of the reaction scheme embedded within a computational fluid dynamics model of the MCVD process to include chlorine dissociation and recombination. Simulations employing this modified kinetic scheme indicate that chlorine dissociation acts primarily as a ‘heat sink’ in cases where the operating conditions promote a high peak temperature in the narrow reaction zone where most of the SiCl₄ oxidation occurs. The extended model allows a wider range of operating parameters to be examined in terms of the deposition profile of silica ‘soot’ particles on the substrate tube wall.     

Synthesis of nonstoichiometric zirconium carbide whiskers by chemical vapor deposition

Nonstoichiometric zirconium carbide crystals with various compositions were prepared by chemical vapor deposition. Two gaseous mixtures, zirconium tetrachloride and argon, toluene and hydrogen, were introduced to the reaction zone where a graphite substrate was heated between 1200 and 1400°C. The deposition rate was proportional to the partial pressure of toluene. The compositional ratio of n_C/n_Zr in the gaseous mixture from 2.0 to 6.0 was found to be optimum for producing needle-like crystals. Needle-like crystal with smaller size were formed when the ratio of n_C/n_Zr was smaller than 2.0, and less needle-like crystals accompanied with more carbon were also produced when the ratio of n_C/n_Zr was larger than 6.0. The temperature of the substrate suitable for the growth of needle crystals was in the range from 1250 to 1300°C. The lattice constants of the products varied as a function of the ratio of n_C/n_Zr in the gaseous mixtures.     

Mechanisms of chemical vapor deposition of silicon

The distribution in the silicon epitaxial growth from SiCl₄ and hydrogen are observed in situ by IR absorption spectroscopy. Two methods are used complementarily, one is IR spectroscopy of reactants extracted from the reactor by a fine quartz tube which is not disturbing the reactions, and gives knowledge about the local distribution, the other is direct IR spectroscopy of hot reactants in the reactor which is useful to ascertain the results at the real high temperature situation. The intermediate species are SiHCl₃, SiH₂Cl₂ which is estimated from the induced emission bands at 500 and 570 cm^-1. HCl is a dominant waste product and contributes to reverse reactions. To investigate the reaction, HCl is intentionally injected into the reacting gas. This kind of injection method may also be very effective to analyze the reactions using other reactants such as SiCl₄, SiHCl₃ and SiH₂Cl₂.     

Properties of hydrogenated amorphous silicon prepared by chemical vapor deposition

Properties of hydrogenated amorphous silicon (a-Si:H) prepared by chemical vapor deposition (CVD) are reported and compared to corresponding properties of glow discharge a-Si:H. The CVD material was produced from mixtures of silane, disilane, trisilane and higher polysilanes in hydrogen carrier gas at one atmosphere total pressure, at substrate temperatures from 420 to 530 °C. The photovoltaic properties of our present CVD a-Si:H are somewhat inferior to those of the best glow discharge a-Si:H. However, as discussed below, there are some indications that higher quality CVD a-Si:H may be possible.     

Radical-assisted metalorganic chemical vapor deposition of ZnSe

Radical-assisted metalorganic chemical vapor deposition (MOCVD) of ZnSe has been performed by using diethylzinc (DEZn) and diethylselenide (DESe) as a source and azo-t-butane ((t-C₄H₉)₂N₂)and nitrogen trifluoride (NF₃) as co-reactants. The growth rate was significantly increased in the measured temperature range of 623 to 723 K.     

Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800–900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium–ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.     

Si/SiGe growth by low-energy plasma-enhanced chemical vapor deposition

Nowadays, microelectronic industry targets (in term of down-scaling and throughput) require some severe reduction of the SiGe epitaxial growth temperature or/and increase of the growth rate. A possible alternative to meet these requirements is low-energy plasma-enhanced chemical vapor deposition (LEPECVD). We have studied the deposition kinetics of silicon, silicon–germanium and germanium using LEPECVD. This new deposition technique offers promising advantages compared to thermally activated CVD such as low deposition temperature and high growth rate. Different regimes are observed depending on the growth temperature. High temperatures can be associated to a mix between thermally and plasma-activated deposition, whereas only plasma-assisted deposition occurs at low temperatures. Crystalline quality of the layers was checked through the mean of photoluminescence, which revealed no defects. A high growth rate (100 nm min⁻¹) that can be achieved very easily with LEPECVD allows to grow quickly very thick layers. We have used this technique to grow step-graded thick SiGe layers which are almost fully relaxed. Those virtual substrates exhibited the well-known cross-hatch pattern, with RMS roughness from 2 to 10 nm for pure Ge layers.     

Growth of amorphous SiO2 nano-wires on pre-oxidized silicon substrate via chemical vapor deposition

Without an additional silicon source, amorphous SiO₂ nano-wires were grown on the pre-oxidized silicon substrate with the assistance of Ni-based catalyst under ambient pressure. The as-grown amorphous SiO₂ nano-wires were characterized by X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy (HRTEM) and selected area diffraction. The micro-region chemical composition investigation on the as-grown amorphous SiO₂ nano-wires was carried out using X-ray energy dispersion spectroscopy (EDS) on the HRTEM. The present work focuses on the formation of atomic H on the surface of pure zinc powder by introducing moisture (N₂ + H₂O) into the furnace at high temperature. The growth mechanism has been discussed and attributed to the vapor–liquid–solid (VLS) mechanism instead of the adopted solid–liquid–solid (SLS) mechanism owing to the observed evidence of an etching reaction of atomic H at the SiO₂ buffer layer and/or that of H at the Si substrate to form a gaseous hydro-silicon radical (SiH_x) that is then transported to the growth sites. The intrinsic luminescent behavior of the amorphous SiO₂ nano-wires in the range of 350–430 nm was also reported and discussed. These results provide an alternative and simple procedure for nanostructures growth, which will be helpful to understand the growth mechanism of one dimensional SiO₂ nanostructures.