Growth of Silicon Carbide Bulk Crystals by Physical Vapor Transport Method and Modeling Efforts in the Process Optimization

Silicon carbide bulk crystals were grown in an induction-heating furnace using the physical vapor transport method. Crystal growth modeling was performed to obtain the required inert gas pressure and temperatures for sufficiently large growth rates. The SiC crystals were expanded by designing a growth chamber having a positive temperature gradient along the growth interface. The obtained 6H-SiC crystals were cut into wafers and characterized by Raman scattering spectroscopy and X-ray diffraction, and the results showed that most parts of the crystals had good crystallographic structures.

Growth of Silicon Carbide Bulk Crystals by Physical Vapor Transport Method and Modeling Efforts in the Process Optimization

Silicon carbide bulk crystals were grown in an induction-heating furnace using the physical vapor transport method. Crystal growth modeling was performed to obtain the required inert gas pressure and temperatures for sufficiently large growth rates. The SiC crystals were expanded by designing a growth chamber having a positive temperature gradient along the growth interface. The obtained 6H-SiC crystals were cut into wafers and characterized by Raman scattering spectroscopy and X-ray diffraction, and the results showed that most parts of the crystals had good crystallographic structures.

I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.

Characterization of m-plane ZnO thin film on gamma-LiAlO2 (100) substrate by metal-organic chemical vapor deposition

Non-polar (1 (1) over bar 00)m-plane ZnO thin film has been prepared on gamma-LiAlO2 (100)substrate via the low pressure metal organic chemical vapor deposition. Obvious intensity variation of the E-2 mode in the polarized Raman spectra and the absorption edge shift in the polarized optical transmission spectra indicate that the m-plane film exhibits optical anisotropy, which have applications in certain optical devices, such as the UV modulator and polarization-dependent beam switch. From the atomic force microscopy images, highly-oriented uniform-sized grains of rectangular shape were observed. (c) 2008 Elsevier B.V. All rights reserved.

SiO2 coating of silver nanoparticles by photoinduced chemical vapor deposition.

Gas-phase silver nanoparticles were coated with silicon dioxide (SiO2) by photoinduced chemical vapor deposition (photo-CVD). Silver nanoparticles, produced by inert gas condensation, and a SiO2 precursor, tetraethylorthosilicate (TEOS), were exposed to vacuum ultraviolet (VUV) radiation at atmospheric pressure and varying temperatures. The VUV photons dissociate the TEOS precursor, initiating a chemical reaction that forms SiO2 coatings on the particle surfaces. Coating thicknesses were measured for a variety of operation parameters using tandem differential mobility analysis and transmission electron microscopy. The chemical composition of the particle coatings was analyzed using energy dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The highest purity films were produced at 300-400 degrees C with low flow rates of additional oxygen. The photo-CVD coating technique was shown to effectively coat nanoparticles and limit core particle agglomeration at concentrations up to 10(7) particles cm(-3).

The parameter space of graphene chemical vapor deposition on polycrystalline Cu

A systematic study of the parameter space of graphene chemical vapor deposition (CVD) on polycrystalline Cu foils is presented, aiming at a more fundamental process rationale in particular regarding the choice of carbon precursor and mitigation of Cu sublimation. CH 4 as precursor requires H 2 dilution and temperatures ≥1000 °C to keep the Cu surface reduced and yield a high-quality, complete monolayer graphene coverage. The H 2 atmosphere etches as-grown graphene; hence, maintaining a balanced CH 4/H 2 ratio is critical. Such balance is more easily achieved at low-pressure conditions, at which however Cu sublimation reaches deleterious levels. In contrast, C 6H 6 as precursor requires no reactive diluent and consistently gives similar graphene quality at 100-150 °C lower temperatures. The lower process temperature and more robust processing conditions allow the problem of Cu sublimation to be effectively addressed. Graphene formation is not inherently self-limited to a monolayer for any of the precursors. Rather, the higher the supplied carbon chemical potential, the higher the likelihood of film inhomogeneity and primary and secondary multilayer graphene nucleation. For the latter, domain boundaries of the inherently polycrystalline CVD graphene offer pathways for a continued carbon supply to the catalyst. Graphene formation is significantly affected by the Cu crystallography; i.e., the evolution of microstructure and texture of the catalyst template form an integral part of the CVD process. © 2012 American Chemical Society.

Complex chemistry DNS of n-heptane spray autoignition at high pressure and intermediate temperature conditions

Direct Numerical Simulations (DNS) of turbulent n-heptane sprays autoigniting at high pressure (P=24bar) and intermediate air temperature (Tair=1000K) have been performed to investigate the physical mechanisms present under conditions where low-temperature chemistry is expected to be important. The initial turbulence in the carrier gas, the global equivalence ratio in the spray region, and the initial droplet size distribution of the spray were varied. Results show that spray ignition exhibits a spotty nature, with several kernels developing independently in those regions where the mixture fraction is close to its most reactive value ξMR (as determined from homogeneous reactor calculations) and the scalar dissipation rate is low. Turbulence reduces the ignition delay time as it promotes mixing between air and the fuel vapor, eventually resulting in lower values of scalar dissipation. High values of the global equivalence ratio are responsible for a larger number of ignition kernels, due to the higher probability of finding regions where ξ=ξMR. Spray polydispersity results in the occurrence of ignition over a wider range of mixture fraction values. This is a consequence of the inhomogeneities in the mixing field that characterize these sprays, where poorly mixed rich spots are seen to alternate with leaner ones which are well-mixed. The DNS simulations presented in this work have also been used to assess the applicability of the Conditional Moment Closure (CMC) method to the simulation of spray combustion. CMC is found to be a valid method for capturing spray autoignition, although care should be taken in the modelling of the unclosed terms appearing in the CMC equations. © 2013 The Combustion Institute.

Photoluminescence properties of tensile-strained GaAsP/GaInP single quantum wells grown by metal organic chemical vapor deposition

Tensile-strained GaAsP/GaInP single quantum well (QW) laser diode (I-D) structures have been grown by low-pressure metal organic chemical vapor deposition (LP-MOCVD) and related photoluminescence (PL) properties have been investigated in detail. The samples have the same well thickness of 16 nm but different P compositions in a GaAsP QW. Two peaks in room temperature (RT) PL spectra are observed for samples with a composition larger than 0.10. Temperature and excitation-power-dependent PL spectra have been measured for a sample with it P composition of 0.15. It is found that the two peaks have a 35 meV energy separation independent of temperature and only the low-energy peak exists below 85 K. Additionally, both peak intensities exhibit a monotonous increase as excitation power increases. Analyses indicate that the two peaks arise from the intrinsic-exciton recombination mechanisms of electron-heavy hole (e-hh) and electron-light hole (e-hh). A theoretical calculation based oil model-solid theory, taking, into account the spin-orbit splitting energy, shows good agreement with our experimental results. The temperature dependence of PL intensity ratio is well explained using the spontaneous emission theory for e-hh and e-hh transitions. front which the ratio can be characterized mainly by the energy separation between the fill and Ill states.

Phase-separation suppression in GaN-rich side of GaNP alloys grown by metal-organic chemical vapor deposition

The GaN-rich side of GaNP ternary alloys has been successfully synthesized by light-radiation heating and low-pressure metal-organic chemical vapor deposition. X-ray diffraction (XRD) rocking curves show that the ( 0002) peak of GaNP shifts to a smaller angle with increasing P content. From the GaNP photoluminescence (PL) spectra, the red shifts from the band-edge emission of GaN are determined to be 73, 78 and 100 meV, respectively, in the GaNP alloys with the P contents of 1.5%, 5.5% and 7.5%. No PL peak or XRD peak related to GaP is observed, indicating that phase separation induced by the short-range distribution of GaP-rich regions in the GaNP layer has been effectively suppressed. The phase-separation suppression in the GaNP layer is associated with the high growth rate and the quick cooling rate under the given growth conditions, which can efficiently restrain the accumulation of P atoms in the GaNP layer.

Parameters determining crystallinity in beta-SiC thin films prepared by catalytic chemical vapor deposition

The effects of deposition gas pressure and H-2 dilution ratio (H-2/SiH4+CH4+H-2), generally considered two of dominant parameters determining crystallinity in beta-SiC thin films prepared by catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD method, on the films properties have been systematically studied. As deposition gas pressure increase from 40 to 1000 Pa, the crystallinity of the films is improved. From the study of H-2 dilution ratio, it is considered that H-2 plays a role as etching gas and modulating the phases in beta-SiC thin films. On the basis of the study on the parameters, nanocrystalline beta-SiC films were successfully synthesized on Si substrate at a low temperature of 300degreesC. The Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) spectra show formation of beta-SiC. Moreover, according to Sherrer equation, the average grain size of the films estimated is in nanometer-size. (C) 2003 Elsevier B.V. All rights reserved.

Monolithic integration of an InGaAsP-InP strained DFB laser and an electroabsorption modulator by ultra-low-pressure selective-area-growth MOCVD

The design and basic characteristics of a strained InGaAsP-InP multiple-quantum-well (MQW) DFB laser monolithically integrated with an electroabsorption modulator (EAM) by ultra-low-pressure (22 mbar) selective-area-growth (SAG) MOCVD are presented. A fundamental study of the controllability and the applicability of band-gap energy by using the SAG, method is performed. A large band-gap photoluminescence wavelength shift of 88 mn. was obtained with a small mask width variation (0-30 mu m). The technique is then applied to fabricate a high performance strained MQW EAM integrated with a DFB laser. The threshold current of 26 mA at CW operation of the device with DFB laser length of 300 mu m and EAM length of 150 mu m has been realized at a modulator bias of 0 V. The devices also exhibit 15 dB on/off ratio at an applied bias voltage of 5 V.

Crack-free InAlGaN quaternary alloy films grown on Si(111) substrate by metalorganic chemical vapor deposition

Crack-free In0.08Al0.25Ga0.67N quaternary films, with and without thick (> 1.5 mum) high-temperature-GaN (HTGaN) interlayer, have been grown on Si(1 1 1) substrates by a low-pressure metalorganic chemical vapor deposition (MOCVD) system. Mole fractions of In and Al in quaternary alloy layers are determined by Energy dispersive spectroscopy (EDS) and Rutherford backscattering spectrometry (RBS), which are recorded as similar to8% and similar to25-27%, respectively. High-resolution X-ray diffraction (HRXRD) and room temperature photoluminescence (RT-PL) results evidence the film's single crystal structure and the existence of local In- and/or Al-rich regions. Compared with GaN film grwon on Si(1 1 1) substrate, no crack is observed in the quaternary ones. Two explanations are proposed. First, mismatch-induced strain is relaxed significantly due to gradual changes of In concentration. Second, the weak In-N bond is likely to break when the sample is cooled down to the room temperature, which is expected to favor the releasing of thermal stress. (C) 2004 Elsevier B.V. All rights reserved.

Narrow stripe selective growth of oxide-free InGaAlAs/InGaAlAs MQWs by ultra-low pressure MOVPE

Narrow stripe selective growth of oxide-free InGaAlAs/InGaAlAs multiple quantum wells (MQWs) has been successfully performed on patterned InP substrates by ultra-low pressure MOVPE. Flat and clear interfaces were obtained for the narrow stripe selectively grown MQWs under optimized growth conditions. These selectively grown MQWs were covered by specific InP layers, which can keep the MQWs from being oxidized during the fabrication of the devices. The characteristics of selectively grown MQWs were strongly dependent on the mask stripe width. In particular, a PL peak wavelength shift of 73 nm, a PL intensity of more than 57% and a PL FWHM of less than 102 meV were observed simultaneously with a small mask stripe width varying from 0 to 40 mu m. The results were explained by considering the migration effect from the masked region (MMR) and the lateral vapour diffusion effect (LVD).

High-quality multiple quantum wells selectively grown on taper-patterned substrates by ultra-low-pressure MOCVD

High quality InGaAsP/InGaAsP multiple quantum wells ( MQWs) have been selectively grown by ultra-low-pressure (22 mbar) metal-organic chemical vapor deposition. A large bandgap energy shift of 46 nm and photoluminescence with FWHM less than 30 meV were obtained with a rather small mask width variation (15-30 mu m). In order to study the uniformity of the MQWs grown in the selective area, novel tapered masks were employed, and the transition effect W the tapered region was also studied. The energy detuning of the tapered region was observed to be saturated at larger ratios of the mask width to the tapered region length.

High-quality multiple quantum wells selectively grown with tapered masks by ultra-low-pressure MOCVD

An InGaAsP/InGaAsP multiple quantum wells (MQWs) selectively grown by ultra-low-pressure (22 mbar) metal-organic chemical vapor deposition was investigated in this article. A 46 nm photoluminescence peak wavelength shift was obtained with a small mask width variation (15-30 mu m). High-quality crystal layers with a photoluminescence (PL) ftill-width-at-half-maximum (FWHM) of less than 30 meV were achieved. Using novel tapered masks, the transition-effect of the tapered region was also studied. The energy detuning of the tapered region was observed to be saturated with the larger ratio of the mask width divided to the tapered region length. (C) 2005 Elsevier B.V. All rights reserved.