Classification and structure of silicon carbide phases

Molecular-mechanical and semiempirical quantum-mechanical methods have been applied to simulate and calculate a geometrically optimized structure of clusters of polymorphic types of silicon carbide, and their structural parameters and some properties (densities, sublimation energies) have been determined. A classification of silicon carbide phases has been proposed, which shows the possible existence of twenty one SiC phases whose atoms are at crystallographically equivalent sites. The structures of seventeen proposed silicon carbide phases have been described and studied for silicon carbide for the first time.     

连续碳纤维增强碳化硅的辐照效应

连续碳纤维增强碳化硅材料除了具有碳化硅材料固有的低中子活化性能,低衰变热性能和低氚渗透性能等优点以外,还具有密度低、线性膨胀系数小、高比强度、高比模量、耐高温、抗氧化、抗蠕变、抗热震、耐化学腐蚀、耐盐雾、优良的电磁波吸收特性等一系列优异性能,是各类核工程重要的潜在候选材料。在核聚变工程应用领域,连续碳纤维增强碳化硅材料作为第一壁材料不可避免地会受到各种辐射粒子的影响。研究清楚这些辐射粒子对它的辐照效应对其在核工程领域的安全使用至关重要。采用蒙特卡罗方法与分子动力学方法进行模拟计算,研究了氕、氘、氚和氦四种粒子对连续碳纤维增强碳化硅的辐照效应。SRIM和LAMMPS计算结果表明:当入射原子能量为100 eV,连续碳纤维增强碳化硅中碳的浓度在80%~85%时,氕、氘、氚和氦原子的溅射率存在最小值;入射粒子的种类对溅射率的影响显著,氦原子的溅射率大于氘原子和氚原子,而氘原子和氚原子的溅射率相差不大但均显著大于氕原子;溅射率随入射能量的增加先迅速增加后逐渐减小,氕、氘、氚和氦原子入射能量分别在200,400,600和800 eV时存在溅射率最大值;当氦原子入射能量为100 eV时,溅射率随入射角度的增加而逐渐减少。这些结果对连续碳纤维增强碳化硅材料在核工程上的应用具有一定的参考意义。Continuous carbon fiber reinforced silicon carbide material has the low neutron activation, low decay heat performance and tritium permeability, which are inherent performance of silicon carbide materials. It also has other advantages such as low density, small linear expansion coefficient, specific strength and specific modulus, high temperature resistance, oxidation resistance, creep resistance, thermal shock, resistance to chemical corrosion, salt fog resistance, excellent electromagnetic wave absorption properties, etc. It is an important potential candidate material in various field of nuclear engineering. In the field of nuclear fusion engineering applications, continuous carbon fiber reinforced silicon carbide as the first wall material will inevitably be bombarded by a variety of radiation particles. The radiation effect is critical to its safe use in nuclear engineering. The Monte Carlo method and the molecular dynamics method were used to study the radiation effect of protium, deuterium, tritium and helium on continuous carbon fiber reinforced silicon carbide. The SRIM and LAMMPS simulation results show that when the incident energy is 100 eV and the concentration of carbon in the continuous carbon fiber reinforced silicon carbide is about 80% ~ 85%, the sputtering yield of protium, deuterium, tritium and helium atoms have the minimum values. The kind of incident particle has a significant effect on the sputtering yield. The sputtering yield of helium atoms is larger than that of tritium atoms and deuterium atoms. There is not much difference between the sputtering yield of deuterium atoms and tritium atoms, and both the sputtering yield of deuterium atoms and tritium atoms are larger than that of protium atoms. The sputtering yield initially increases rapidly with the increase of the incident energy and then decreases gradually. The incident energy of the protium, deuterium, tritium and helium atoms has the maximum value of the sputtering yield at 200, 400, 600 and 800 eV, respectively. When the incident energy of helium atoms is 100 eV, the sputtering yield decreases while the increase of the incident angle. These results can provide a certain reference for the application of continuous carbon fiber reinforced silicon carbide materials in nuclear engineering.     

Synthesis of carbides in the arc plasma

A method of synthesis of iron, silicon, titanium, and tungsten carbides in an argon arc between graphite electrodes is developed. It is found that iron, silicon, and titanium atoms introduced into the interelectrode gap cause the voltage drop across the gap to decrease, whereas tungsten atoms increase this voltage. The X-ray diffraction analysis of synthesized powders reveals carbide and graphite crystallites. Their relative concentrations are estimated from the intensities of the respective reflection peaks. The morphological examination of the synthesized particles shows that titanium carbide particles are the largest and iron carbide ones are the finest. Raman spectra taken of the powders confirm the presence of graphite and carbide crystallites.     

Electronic Structure of Graphene on Silicon Carbide Intercalated with Silicon and Cobalt Atoms

Physics of the Solid State - The ab initio calculations have been performed for the spin-polarized band structure of graphene on silicon carbide intercalated with cobalt and silicon atoms. The...     

Magnetism of hydrogen-irradiated silicon carbide

Spin-polarized density functional theory is used to study two-hydrogen defect complexes in silicon carbide. We find that the magnetism depends on the distances of the two hydrogen atoms. Magnetism appears when the two hydrogen defects are distant from each other, and magnetism cancels out if they are close to each other. The critical distance between the two hydrogen defects is determined.     

Temperature-dependent interfacial stiffness of the disorder layer in a thin Cu3Au alloy film

Epitaxial silicon carbide thin films grown on a silicon substrate were examined by short wavelength ( 0.71 A from a molybdenum anode) x-ray diffraction to study their atomic distortion and internal layer roughness. Up to 5 order Bragg peaks along (100) were measured and crystallographic structure factors were obtained. Electron density distributions along the surface normal were reconstructed via Fourier transform. In comparing to the ideal situation, it was found that, due to the lattice mismatch, the silicon atoms are no longer fixed on the same atomic plane, thus the corresponding electron distribution maxima were broadened. Also, the maxima for carbon atoms are flattened, indicating the randomized locations.     

New method for growing silicon carbide on silicon by solid-phase epitaxy: Model and experiment

A new method of solid-state epitaxy of silicon carbide (SiC) on silicon (Si) is proposed theoretically and realized experimentally. Films of various polytypes of SiC on Si(111) grow through a chemical reaction (at T = 1100–1400°C) between single-crystal silicon and gaseous carbon oxide CO (at p = 10–300 Pa). Some silicon atoms transform into gaseous silicon oxide SiO and escape from the system, which brings about the formation of vacancies and pores in the silicon near the interface between the silicon and the silicon carbide. These pores provide significant relaxation of the elastic stresses caused by the lattice misfit between Si and SiC. X-ray diffraction, electron diffraction, and electron microscopy studies and luminescence analysis showed that the silicon carbide layers are epitaxial, homogeneous over the thickness, and can contain various polytypes and a mixture of them, depending on the growth conditions. The typical pore size is 1 to 5 μm at film thicknesses of ～20 to 100 nm. Thermodynamic nucleation theory is generalized to the case where a chemical reaction occurs. Kinetic and thermodynamic theories of this growth mechanism are constructed, and the time dependences of the number of new-phase nuclei, the concentrations of chemical components, and the film thickness are calculated. A model is proposed for relaxation of elastic stresses in a film favored by vacancies and pores in the substrate.     

Structural heteroepitaxy during topochemical transformation of silicon to silicon carbide

Silicon carbide samples synthesized from silicon by topochemical substitution of atoms are studied by the ion channeling method. The results of the analysis unambiguously demonstrate the occurrence of structural heteroepitaxy. The lattice of synthesized silicon carbide of hexagonal polytype 6H is epitaxially matched in the 〈0001〉 direction with the lattice grating grid array network of an initial substrate silicon in the 〈111〉 direction. The main features of structural self-coupling matching in this epitaxial heterocomposite are revealed. Despite the very large silicon carbide and silicon lattice parameter mismatch, the misfit dislocation density at the interface is low, which is a feature of the topochemical substitution method leading to comparable structures.     

Electron paramagnetic resonance in neutron-transmutation-doped semiconductors with a changed isotopic composition

Potential applications of electron paramagnetic resonance (EPR) for investigating and controlling the process of neutron transmutation doping (NTD) of semiconducting germanium, silicon, and silicon carbide are discussed. It is shown that EPR enables one to control the process of annealing of radiation-induced defects in semiconductors subject to neutron irradiation and to detect the shallow donors restored in the process of annealing of donor-compensating defects by observing EPR signals from these donors. EPR can be used to separately detect isolated donors and clusters of two, three, and more exchange-bound donor atoms and thereby determine the degree of nonuniformity of the impurity distribution over the crystal. Neutron transmutation doping is demonstrated to produce a fairly uniform arsenic-donor distribution in a germanium crystal. It is argued that semiconductors enriched in the selected isotopes should be used for NTD. The results of an investigation of phosphorus donors in silicon carbide are presented.     

Electronic properties of a silicon carbide nanotube under uniaxial tensile strain: a density function theory study

The electronic properties of an armchair (4,4) single-walled silicon carbide nanotube (SWSiCNT) with the length and diameter of 22.4 and 6.93 Å, respectively under different tensile strains are investigated by density functional theory (DFT) calculation. The change of highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO) gap of the nanotube has been observed during the elongation process. Our results show that the gap will significantly decrease linearly with the increase of axial strain. Two different slopes are found before and after an 11% strain in the profiles of the HOMO–LUMO gap. The radial buckling has been performed to investigate the radial geometry of nanotube. The partial density of states (PDOS) of two neighboring Si and C atoms of the nanotube are further studied to demonstrate the strain effect on the electronic structure of SiC nanotube. The PDOS results exhibit that the occupied states of Si atom and the unoccupied states of C atom are red-shifted and blue-shifted under stretching, respectively. Mulliken charge analysis reveals that Si and C atoms will become less ionic under the larger strain. The electron differences of silicon carbide nanotube (SiCNT) on tensile loading are also studied.     

Epitaxial growth of cadmium sulfide films on silicon

A 300-nm-thick cadmium sulfide epitaxial layer on silicon was grown for the first time. The grown was performed by the method of evaporation and condensation in a quasi-closed volume at a substrate temperature of 650°C and a growth time of 4 s. In order to avoid a chemical reaction between silicon and cadmium sulfide (at this temperature, the rate constant of the reaction is ~10³) and to prevent etching of silicon by sulfur, a high-quality silicon carbide buffer layer ~100 nm thick was preliminarily synthesized by the substitution of atoms on the silicon surface. The ellipsometric, Raman, electron diffraction, and trace element analyses showed a high structural perfection of the CdS layer and the absence of a polycrystalline phase.     

Epitaxial growth of cadmium telluride films on silicon with a buffer silicon carbide layer

An epitaxial 1–3-μm-thick cadmium telluride film has been grown on silicon with a buffer silicon carbide layer using the method of open thermal evaporation and condensation in vacuum for the first time. The optimum substrate temperature was 500°C at an evaporator temperature of 580°C, and the growth time was 4 s. In order to provide more qualitative growth of cadmium telluride, a high-quality ~100-nm-thick buffer silicon carbide layer was previously synthesized on the silicon surface using the method of topochemical substitution of atoms. The ellipsometric, Raman, X-ray diffraction, and electron-diffraction analyses showed a high structural perfection of the CdTe layer in the absence of a polycrystalline phase.

     

Real time investigation of the growth of silicon carbide nanocrystals on Si(1 0 0) using synchrotron X-ray diffraction

The growth of silicon carbide nanocrystals on Si(1 0 0) is studied by synchrotron surface X-ray diffraction (SXRD) during annealing at high temperature. A chemisorbed methanol monolayer is used as carbon source, allowing to have a fixed amount of carbon atoms to feed the growth. At room temperature, minor changes in the 2 × 1 reconstruction of silicon are observed due to the formation of Si-O-CH₃ and Si-H bonds from methanol molecules. When annealed at 500 °C, carbon incorporation into the silicon leads only to local modifications of the surface structure. Above 600 °C, tri-dimensional silicon carbide nanocrystals growth takes place, together with surface roughening and sharp decrease of domain sizes of the 2 × 1 reconstruction. The different processes taking place at each temperature are clearly distinguished and identified during the real time SXRD measurements.     

Synthesis of epitaxial silicon carbide films through the substitution of atoms in the silicon crystal lattice: A review

A review of recent advances in the field of epitaxial growth of SiC films on Si by means of a new method of epitaxial substitution of film atoms for substrate atoms has been presented. The basic statements of the theory of the new method used for synthesizing SiC on Si have been considered and extensive experimental data have been reported. The elastic energy relaxation mechanism implemented during the growth of epitaxial SiC films on Si by means of the new method of substitution of atoms has been described. This method consists in substituting a part of carbon atoms for silicon matrix atoms with the formation of silicon carbide molecules. It has been found experimentally that the substitution for matrix atoms occurs gradually without destroying the crystalline structure of the matrix. The orientation of the film is determined by the “old” crystalline structure of the initial silicon matrix rather than by the silicon substrate surface only, as is the case where conventional methods are used for growing the films. The new growth method has been compared with the classical mechanisms of thin film growth. The structure and composition of the grown SiC layers have been described in detail. A new mechanism of first-order phase transformations in solids with a chemical reaction through an intermediate state promoting the formation of a new-phase nuclei has been discussed. The mechanism providing the occurrence of a wide class of heterogeneous chemical reactions between the gas phase and a solid has been elucidated using the example of the chemical interaction of the CO gas with the single-crystal Si matrix. It has been shown that this mechanism makes it possible to grow a new type of templates, i.e., substrates with buffer transition layers for growing wide-band-gap semiconductor films on silicon. A number of heteroepitaxial films of wide-band-gap semiconductors, such as SiC, AlN, GaN, and AlGaN on silicon, whose quality is sufficient for the fabrication of a wide class of micro- and optoelectronic devices, have been grown on the SiC/Si substrate grown by solid-phase epitaxy.     

Impurity Effects on Nucleation and Growth of SiC Clusters and Layers on Si(100) and Si(111)

Physics of the Solid State - A kinetic Monte Carlo model of silicon carbide growth on silicon surface is proposed. Based on this model, the growth of silicon carbide clusters on silicon in the...     

On the determination of the electronic component of the free energy of silicon carbide cluster in gas phase

A method for calculating the electronic component of the internal free energy of a silicon carbide cluster in the gas phase based on quantum-mechanical concepts is suggested. Under the given method, the basic irregular analogy between the crystal and the cluster, i.e. allowing for constancy of the energy of the bond among atoms independent of their number within the cluster, is avoided. The dependence of the energy of the electrons on temperature is considered on the basis of a Fermi distribution.     

On the chemical erosion of a carbon first wall proposed for Tokamak devices for controlled nuclear fusion

Preliminary results on the chemical attack of several carbon materials by hydrogen plasma are presented and compared with the literature data on the reaction of hydrogen atoms with carbon in an afterglow. The chemical erosion of silicon carbide and of pyrolytical graphite should not be dangerous for the ignition of fusion assuming that the reaction probability of hydrogen atoms with the particular material would not be increased due to radiation damage of the surface.     

Influence of the Plasma Kinetics on the Si/C Ratio of a-SixC1-x: H Thin Films Deposited by Reactive Magnetron Sputtering of a Si Target in Ar + CH4 Gas Mixtures

Possible sources of silicon and carbon atoms built-in amorphous hydrogenated silicon carbide thin films grown by reactive magnetron sputtering (RMS) in argon/methane gas mixtures are evaluated. It is found out that the plasma decomposition of methane molecules plays an essential role in providing of growing film surface by active hydrocarbon fragments, thus influencing significantly the film stoichiometry even though the methane partial pressure in the sputtering gas mixture is only 1.5–4.7%.     

Structural feature and electronic property of an (8, 0) carbon--silicon carbide nanotube heterojunction

A supercell of a nanotube heterojunction formed by an (8, 0) carbon nanotube (CNT) and an (8, 0) silicon carbide nanotube (SiCNT) is established, in which 96 C atoms and 32 Si atoms are included. The geometry optimization and the electronic property of the heterojunction are implemented through the first-principles calculation based on the density functional theory (DFT). The results indicate that the structural rearrangement takes place mainly on the interface and the energy gap of the heterojunction is 0.31eV, which is narrower than those of the isolated CNT and the isolated SiCNT. By using the average bond energy method, the valence band offset and the conduction band offset are obtained as 0.71 and --0.03eV, respectively.     

Silicon carbide nanocones: Computational analysis of chemical shieldings for pristine and boron/nitrogen decorated models

Density functional theory (DFT) calculations were performed to investigate the electronic and structural properties of pristine and boron/nitrogen (B/N) decorated models of a representative silicon carbide nanocone (SiCNC). The atoms of apexes and tips were differently decorated by B/N atoms to make all possible decorations of the investigated SiCNC. The evaluated parameters by the optimization processes and nuclear magnetic resonance (NMR) calculations indicated that the overall and atomic scale properties of the investigated SiCNCs are significantly dependent on the ways of decorations of Si/C atoms by B/N atoms. The Si/C atoms close to the decorated regions also exhibited notable changes in comparison to the pristine model.