Rate-determining process in chemical vapor deposition of SiC on off-axis -SiC

Homoepitaxial growth on off-axis α-SiC at reduced pressures in a horizontal cold-wall chemical vapor deposition (CVD) system operating at has been investigated. The growth rate was found inversely proportional to the square root of total pressure or the partial pressure of H₂, a carrier gas. A model to explain the experimental results is proposed, where the rate-determining process in CVD is competition between Si species and hydrogen atoms for C (carbon) dangling bonds at SiC step edges.     

Cracking assisted nucleation in chemical vapor deposition of silicon nanoparticles on silicon dioxide

Deposition of sub-monolayer silicon on SiO₂/Si(1 0 0) greatly facilitates nucleation in subsequent thermal chemical vapor deposition (CVD) of silicon nanoparticles. Sub-monolayer seeding is accomplished using silicon atoms generated via disilane decomposition over a hot tungsten filament. The hot-wire process is nonselective towards deposition on silicon and SiO₂, is insensitive to surface temperature below 825 K, and gives controlled coverages well below 1 ML. Thermal CVD of nanoparticles at 1×10⁻⁴ Torr disilane and temperatures ranging from 825 to 925 K was studied over SiO₂/Si(1 0 0) surfaces that had been subjected to predeposition of Si or were bare. Seeding of the SiO₂ surface with as little as 0.01 ML is shown to double the nanoparticle density at 825 K, and densities are increased twenty fold at 875 K after seeding the surface with 30% of a monolayer.     

Low-temperature Si epitaxy on large-grained polycrystalline seed layers by electron–cyclotron resonance chemical vapor deposition

The epitaxial thickening of polycrystalline Si films on glass substrates is of great interest for the realization of crystalline Si thin film solar cells and other large-area thin film devices. In this paper we report on the epitaxial growth of Si at temperatures below on polycrystalline seed layers using electron–cyclotron resonance chemical vapor deposition. The Si seed layers were prepared by aluminum-induced crystallization. The quality of the ECRCVD-grown films strongly depends on the orientation of the underlying seed layer grains. Due to a mainly favorable orientation of the seed layers more than 73% of the substrate area were epitaxially thickened. It turned out that a (1 0 0) preferential orientation is favorable for epitaxial thickening. This, however, is not the only requirement for successful low-temperature epitaxial growth of Si.     

Predicted nitrogen doping concentrations in silicon carbide epitaxial layers grown by hot-wall chemical vapor deposition

A simple quantitative model for the surface adsorption of nitrogen has been developed to simulate the doping incorporation in intentionally doped 4H–SiC samples during epitaxial growth. Different reaction schemes are necessary for the two faces of SiC. The differences are discussed, and implications to the necessary model adjustments are stressed. The simulations are validated by experimental values for a large number of different process parameters with good agreement.     

Fabrication of nano-crystalline silicon thin film at low temperature by using a neutral beam deposition method

Low temperature (<80 °C) neutral beam deposition (LTNBD) was investigated as a new approach to the fabrication and development of nano-crystalline silicon (nc-Si), which has better properties than that of amorphous silicon (α-Si). The difference between LTNBD and conventional PECVD is that the film formation energy of the nc-Si in LTNBD is supplied by controlled neutral beam energies at a low temperature rather than by heating. Especially, in this study, the characteristics of the nc-Si thin film were investigated by adding 10% of an inert gas such as Ne, Ar or Xe to SiH₄/H₂. Increasing the beam energy resulted in an increase in the deposition rate, but the crystallinity was decreased, due to the increased damage to the substrate. However, the addition of a higher mass inert gas to the gas mixture at a fixed beam energy resulted not only in a higher deposition rate but also in a higher crystallization volume fraction. The high resolution transmission electron microscopy image showed that the grown film is composed of about 10 nm-size grains.     

Electrical properties and deep levels spectra of bulk SiC crystals grown by hybrid physical–chemical vapor transport method

Concentrations of nitrogen shallow donors, boron shallow acceptors, charge carriers, and electron traps were measured as a function of position along the growth axis in a series of undoped 6H–SiC boules grown by sublimation method with and without addition of hydrogen to the growth atmosphere. Elemental analysis by secondary ion mass spectrometry and measurements of electrical properties indicate that the addition of hydrogen suppresses nitrogen incorporation and formation of all electron traps. Concentration of boron is not affected by hydrogen presence. The addition of hydrogen to the growth ambient improves the uniformity of nitrogen incorporation and deep trap distribution along the growth axis. The results are interpreted as due to increased carbon transport and corresponding shift of crystal stoichiometry toward carbon-rich side of the SiC existence range.     

Ordered arrays of epitaxial silicon nanowires produced by nanosphere lithography and chemical vapor deposition

Gold dot arrays on (1 1 1) Si substrates obtained through nanosphere lithography (NSL) combined with sputtering and annealing in Ar at 1000 °C are used to catalyze vapor liquid solid (VLS) epitaxial growth of silicon nanowires (Si NWs) using chemical vapor deposition (CVD) with SiH₄ in Ar. The NWs grow primarily epitaxially on the underlying (1 1 1) Si wafer following the four independent 〈1 1 1〉 directions. The diameter distribution of the wires reflects the diameter distribution of the catalyst gold dot arrays and is therefore predictable. The wire length depends on the size of the gold catalyst for the same CVD parameters. The wire position is foreseeable within the limits of the pattern geometrical quality, but one-to-one growth of NWs to gold dots is not always observed, probably due to (very locally) the remaining presence of silicon oxide. Overall, this inexpensive patterning method for obtaining high-quality crystalline VLS Si NWs by CVD fulfills the requirements of many device applications, where patterning control, quality and reproducibility of the nanostructures are crucial.     

Epitaxial growth of graphitic carbon on C-face SiC and Sapphire by chemical vapor deposition (CVD)

Epitaxial, graphitic carbon thin films were directly grown on C-face/(0 0 0 1¯) SiC and (0 0 0 1) sapphire by chemical vapor deposition (CVD), using propane as a carbon source and without any catalytic metal on the substrate surface. Raman spectroscopy shows the signature of multilayer graphene/graphite growth on both the SiC and sapphire. Raman 2D-peaks have Lorentzian lineshapes with FWHM of ∼60 cm⁻¹ and the ratio of the D-peak to G-peak intensity (I_D/I_G) linearly decreases (down to 0.06) as growth temperature is increased. The epitaxial relationship between film and substrates were determined by X-ray diffraction. On both substrates, graphitic layers are oriented parallel to the substrate, but exhibit significant rotational disorder about the surface normal, and predominantly rhombohedral stacking. Film thicknesses were determined to be a function of growth time, growth temperature, and propane flow rate.     

Tip-growth mode and base-growth mode of Au-catalyzed zinc oxide nanowires using chemical vapor deposition technique

Tip-growth and base-growth modes of Au-catalyzed zinc oxide nanowires (ZnO NWs) were synthesized on Au-film pre-deposited silicon substrates using Chemical Vapor Deposition (CVD) technique. The diameter of tip-growth Au-catalyzed ZnO NWs was proportional to the Au film thickness, whereas the areal density of these NWs was inversely proportional to the Au film thickness. It would be more appropriate to explain the growth of Au-catalyzed ZnO NWs by a combination of Vapor–Liquid–Solid and Vapor–Solid (VLS–VS) mechanisms instead of the conventional VLS mechanism, regardless of tip-growth or base-growth mode of Au-catalyzed ZnO NWs. The competition between the VLS and VS mechanism in the effectiveness of capturing the adsorbed Zn and O atoms would determine the final morphology of ZnO NWs. In addition, Au catalyst promoted the growth rate of NWs as compared to the self-catalyzed ZnO NWs.     

Polar dependence of impurity incorporation and yellow luminescence in GaN films grown by metal-organic chemical vapor deposition

We have investigated the unintentional impurities, oxygen and carbon, in GaN films grown on c-plane, r-plane as well as m-plane sapphire by metal-organic chemical vapor deposition. The GaN layer was analyzed by secondary ion mass spectroscopy. The different trend of the incorporation of oxygen and carbon has been explained in the polar (0 0 0 1), nonpolar (1 1 2¯ 0) and semipolar (1 1 2¯ 2) GaN by a combination of the atom bonding structure and the origin direction of the impurities. Furthermore, it has been found that there is a stronger yellow luminescence (YL) in GaN with higher concentration of carbon, suggesting that C-involved defects are originally responsible for the YL.     

Low temperature deposition of zinc oxide nanoparticles via zinc-rich vapor phase transport and condensation

ZnO nanoparticles as small as 80 nm were successfully synthesized using a modified vapor phase transport (VPT) process at substrate temperatures as low as 222 °C. Particle size distribution and morphology were characterized by scanning electron microscopy and atomic force microscopy. Energy dispersive X-ray spectroscopy and X-ray diffraction indicate the synthesis of high quality crystalline ZnO structures. Low temperature (4.2 K) photoluminescence (PL) spectroscopy was used to characterize the optical quality of the nanoparticles. Ultraviolet emission and a nanostructure specific feature at 3.366 eV are strong in the PL spectra. The 3.366 eV feature is observed to predominate the spectrum with decrease in particle size. This size effect corroborates the luminescence as a nanostructure-specific surface related exciton feature as previously speculated in the literature. In addition, self-assembled ZnO mesoparticles (>100 nm) were realized by increasing the growth time. Low growth temperatures of the particles allow for their potential utilization in flexible organic hybrid optoelectronics. However, this work focuses mainly on the modified synthesis and optical characterization of nanoparticles.     

Growth of SiC nanowires within stacked SiC fiber fabrics by a noncatalytic chemical vapor infiltration technique

An atmospheric pressure chemical vapor infiltration (CVI) process without metallic catalysts was applied for the growth of SiC nanowires within stacked SiC fiber fabrics. We investigated the effect of the concentration of a reactant gas (CH₃SiCl₃, MTS) on the growth behavior and microstructure of the SiC nanowires. At high concentration of MTS in a H₂+MTS mixture gas, one-dimensional (1D) SiC deposits with diameters of several hundreds of nanometers were formed. Microstructures of the 1D SiC deposits exhibited a strong positional dependency throughout the thickness direction of the stacked fabric due to a depletion of the MTS gas. On the other hand, single-crystalline SiC nanowires with average diameters of 50–60 nm could be obtained at a low concentration of MTS. The SiC nanowires also exhibited a homogeneous growth both in the plane of each fabric layer and throughout the thickness of the sample.     

Effects of growth temperature on the properties of ZnO/GaAs prepared by metalorganic chemical vapor deposition

A series of ZnO films were grown on GaAs(0 0 1) substrates at different growth temperatures in the range 250–720°C by metalorganic chemical vapor depostion. Field emission scanning electron microscopy was utilized to investigate the surface morphology of ZnO films. The crystallinity of ZnO films was investigated by the double-crystal X-ray diffractometry. The optical and electrical properties of ZnO films were also investigated using room-temperature photoluminescence and Hall measurements. Arrhenius plots of the growth rate versus reciprocal temperature revealed the kinetically limited growth behavior depending on the growth temperature. It was found that the surface morphology, structural, optical and electrical properties of the films were improved with increasing growth temperature to 650°C. All the properties of the film grown at 720°C were degraded due to the decomposition of ZnO film.     

Optimisation of low-temperature silicon epitaxy on seeded glass substrates by ion-assisted deposition

Using single crystalline Si wafer substrates, ion-assisted deposition (IAD) has recently been shown [J. Crystal Growth 268 (2004) 41] to be capable of high-quality high-rate epitaxial Si growth in a non-ultra-high vacuum (non-UHV) environment at low temperatures of about 600 °C. In the present work the non-UHV IAD method is applied to planar borosilicate glass substrates featuring a polycrystalline silicon seed layer and carefully optimised. Using thin-film solar cells as test vehicle, the best trade-off between various contamination-related processes (seed layer surface as well as bulk contamination) is determined. In the optimised IAD process, the temperature of the glass substrate remains below 600 °C. The as-grown Si material is found to respond well to post-growth treatments (rapid thermal annealing, hydrogenation), enabling respectable open-circuit voltages of up to 420 mV under 1-Sun illumination. This proves that the non-UHV IAD method is capable of achieving device-grade polycrystalline silicon material on seeded borosilicate glass substrates.     

Study of Ge epitaxial growth on Si substrates by cluster beam deposition

Ge epitaxial layers with reasonable quality were grown on Si (1 1 1) substrates by cluster beam deposition (CBD) process. Molecular dynamics study of the low energy Ge clusters deposition process utilizing the Stillinger–Weber two- and three-body interaction potentials was carried out to compare the experimental results. Both experimental and simulation results prove that the substrate temperature plays a dominant role in the epitaxial growth of Ge films in CBD process. The influence mechanisms of temperature are discussed.     

Heteroepitaxial growth of Cu2O thin film on ZnO by metal organic chemical vapor deposition

Cuprous oxide (Cu₂O) thin films were grown epitaxially on c-axis-oriented polycrystalline zinc oxide (ZnO) thin films by low-pressure metal organic chemical vapor deposition (MOCVD) from Copper(II) hexafluoroacetylacetonate [Cu(C₅HF₆O₂)₂] at various substrate temperatures, between 250 and 400 °C, and pressures, between 0.6 and 2.1 Torr. Polycrystalline thin films of Cu₂O grow as single phase with [1 1 0] axis aligned perpendicular to the ZnO surface and with in-plane rotational alignment due to (2 2 0)_Cu2O(0 0 0 2)_ZnO; [0 0 1]_Cu2O[1 2¯ 1 0]_ZnO epitaxy. The resulting interface is rectifying and may be suitable for oxide-based p–n junction solar cells or diodes.     

Correlations between photoluminescence and Hall mobility in GaN/sapphire grown by metalorganic chemical vapor deposition

We have investigated photoluminescence (PL) and electron Hall mobility for unintentionally doped GaN epitaxial layers grown by low-pressure metalorganic chemical vapor deposition on c-plane Al₂O₃ substrates. Four GaN films having identical dislocation density but remarkably different electron Hall mobility were exploited. At low temperature (12 K), a PL line associated with a bound exciton was observed and strong correlations were found between the Hall mobility and the PL intensity of the exciton transition. That is, relative PL intensity of the bound exciton to a donor-bound exciton monotonously increased with decreasing the electron mobility of the GaN films. This correlation was interpreted in terms of electrical compensation. Efforts to find the chemical origin of the PL line led to the conclusion that the BE line originated neither from threading dislocations nor from extrinsic point defects. Intrinsic acceptors such as Ga vacancy and GaN anti-site were suspected as plausible origin.     

Low-temperature growth of epitaxial (1 0 0) silicon based on silane and disilane in a 300 mm UHV/CVD cold-wall reactor

Epitaxial (1 0 0) silicon layers were grown at temperatures ranging from 500 to 800 °C in a commercial cold-wall type UHV/CVD reactor at pressures less than 7×10⁻⁵ Torr. The substrates were 300 mm SIMOX SOI wafers and spectroscopic ellipsometry was used to assess growth rates and deposition uniformities. High-resolution atomic force microscopy (AFM) was employed to verify the atomic terrace configuration that resulted from epitaxial step-flow growth. Deposition from disilane exhibited a nearly perfect reaction limit for low temperatures and high precursor flow rates (partial pressures) with measured activation energies of ≈2.0 eV, while a linear dependence of growth rate on precursor gas flow was found for the massflow-controlled regime. A similar behavior was observed in the case of silane with substantially reduced deposition rates in the massflow-limited regime and nearly a factor of 2 reduced growth rates deep in the reaction limited regime. High growth rates of up to 50 μm/h and non-uniformities as low as 1σ=1.45% were obtained in the massflow-limited deposition regime. Silicon layers as thin as 0.6 nm (4.5 atomic layers ) were deposited continuously as determined using a unique wet chemical etching technique as well as cross-sectional high-resolution transmission electron microscopy (HRTEM). In contrast, epitaxial silicon deposited in RPCVD at 10 Torr using disilane within the same temperature range showed imperfect reaction limitation. While activation energies similar to that of UHV/CVD were found, no partial pressure limitation could be observed. Furthermore, layers deposited using disilane in RPCVD exhibited a large number of defects that appeared to form randomly during growth. We attribute this effect to gas phase reactions that create precursor fragments and radicals—an effect that is negligible in UHV/CVD.     

Mixed-phase solidification of thin Si films on SiO2

Mixed-phase solidification (MPS) is a new beam-induced solidification method that can produce large-grained and highly (1 0 0)-surface textured polycrystalline Si films on SiO₂. The grains resulting from this mixed-phase solidification (MPS) method, which was conceived based on a well-known phenomenon of coexisting solid–liquid regions in radiatively melted Si films, are found to be essentially devoid of various intragrain defects that always plague, and subsequently degrade the utility of large-grained Si films previously obtained using other crystallization techniques. It is experimentally shown that multiple exposures are required in order to generate such a polycrystalline microstructure from an initial amorphous precursor. The observed trends are conceptually explained in terms of the melt being initiated primarily at grain boundaries in polycrystalline films, and melting and solidification subsequently proceeding laterally at interface-location specific rates as determined by the local thermodynamic factors, which include the anisotropic surface and interfacial energies of the grains, and the unusual local thermal profile—all transpiring within a near-equilibrium but nonisothermal and dynamic environment that needs to address the thermal and stability requirements associated with the coexisting solid–liquid regions.