Electron Microscopy of Defects in Epitaxical β-SiC Thin Films Grown on Silicon and Carbon {0001} Faces of α-SiC Substrates

Defects present in β-SiC thin films epitaxically grown on hexagonal 6 H α-SiC substrates via chemical vapor deposition have been characterized by transmission electron microscopy. These defects are different from those previously observed in β-SiC films grown on (100) silicon, which were predominantly stacking faults and microtwins. The most common defects in the films grown on α-SiC were large domains rotated 60° with respect to each other and were identified as double positioning boundaries. These boundaries are a special type of incoherent twin boundary. Differences observed in films grown on either the silicon or carbon face of the {0001}α-SiC are characterized as a function of the mechanism of formation of the defects and type of substrate used for growth.     

Nonequiaxial Grain Growth and Polytype Transformation of Sintered α-Silicon Carbide and β-Silicon Carbide

α(6 H )- and β(3 C )-SiC powders were sintered with the addition of AlB₂ and carbon. α-SiC powder could be densified to ∼98% of the theoretical density over a wide range of temperatures from 1900° to 2150°C and with the additives of 0.67–2.7 mass% of AlB₂ and 2.0 mass% of carbon. Sintering of the β-SiC powder required a temperature of >2000°C for densification with these additives. Grains in the α-SiC specimens grew gradually from spherical-shaped to plate-shaped grains at 2000°C; the 6 H polytype transformed mainly to 4 H . On the other hand, grains in the β-SiC largely grew at >2000°C; the 3 C polytype transformed to 4 H , 6 H , and 15 R . The stacking faults introduced in grains were denser in β-SiC than in α-SiC. The rapid grain growth in the β-SiC specimen was attributed to polytype transformation from the unstable 3 C polytype at the sintering temperature.     

Scanning Tunneling Microscopy of Cubic Silicon Carbide Surfaces

Scanning tunneling microscopy is used to study β-SiC(001) surfaces. The β-SiC(001) single crystals were epitaxially grown by a two-steep chemical vapor deposition process on Si(001) wafer substrates. The overall surface topography of β-SiC is generally much rougher than that of Si wafers. Atomically resolved images corresponding to 3 × 2 and c (2 × 2) geometries of the β-SiC(001) surface are presented. Our results agree with models constructed from Si dimers for these structures. The larger-scale images show that the surface is under compressive stress and exhibits high density of defects, e.g., antiphase boundaries (APB's), in some areas. Images with unusual superstructures are also shown.     

Characterization of β-Silicon Carbide by Silicon-29 Solid-State NMR, Transmission Electron Microscopy, and Powder X-ray Diffraction

Increased interest in ceramic materials, particularly for high-temperature, high-stress applications, has created the need for rapid and reliable analytical techniques to monitor microcrystalline structure of commercial ceramic powders. A comparative evaluation of commercially available β-SiC powders is undertaken to analyze the potential of nuclear magnetic resonance (NMR) in the characterization of β-SiC powder. NMR provides an acceptable, rapid method for characterization of powders both during powder manufacturing as well as for powder analyses priror to sintering studies. The results of transmission electron microscopy and X-ray diffraction are correlated with the NMR spectra to explain some newly observed features in the NMR spectra of β-SiC powders and to illustrate the sensitivity of NMR to microcrystalline disorder.     

Stacking Faults in Chemically-Vapor-Deposited Beta Silicon Carbide

A high density of planar defects, often forming closed figures on {111} planes, was observed in chemically-vapor-deposited β-SiC. The defects were identified as extrinsic stacking faults by electron diffraction contrast analysis.     

Microstructural Development of Silicon Carbide Containing Large Seed Grains

Fine (}0.1μm) β-SiC powders, with 3.3 wt% large (}0.44μm) α-SiC or β-SiC particles (seeds) added, were hot-pressed at 1750°C and then annealed at 1850°C to enhance grain growth. Microstructural development during annealing was investigated using image analysis. The introduction of larger seeds into β-SiC accelerated the grain growth of elongated large grains during annealing, in which no appreciable β→α phase transformation occurred. The growth of matrix grains in materials with β-SiC seeds was slower than that in materials with α-SiC seeds. The material with β-SiC seeds, which was annealed at 1850°C for 4 h, had a bimodal microstructure of small matrix grains and large elongated grains. In contrast, the material with α-SiC seeds, also annealed at 1850°C for 4 h, had a uniform microstructure consisting of elongated grains. The fracture toughnesses of the annealed materials with α-SiC and β-SiC seeds were 5.5 and 5.4 MPa·^1/2, respectively. Such results suggested that further optimization of microstructure should be possible with β-SiC seeds, because of the remnant driving force for grain growth caused by the bimodal microstructure.     

Preparation and Characterization of Aluminum-Doped Silicon Carbide by Combustion Synthesis

Al-doped β-SiC powders were synthesized via combustion reaction of the Si/C system in a 0.1 MPa nitrogen atmosphere, using polytetrafluoroethylene as the chemical activator and Al as the dopant. The β-SiC powders produced have fine spherical particles and narrow particle size distribution. The impurity phase of Al₂O₃ is generated and the doped β-SiC contains N component when Al content is up to 10%. The electric permittivities of β-SiC samples were determined in the frequency range of 8.2–12.4 GHz. Results show that the β-SiC doped with 10% Al has the highest real part ɛ' and imaginary part ɛ" of permittivity. The mechanism of dielectric loss by doping has been discussed.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part II, Effects of Planar Defects and Seeds in the Starting Powder

The effects of planar-defect density in a β-SiC starting powder and the addition of α-SiC seeds to that powder on microstructural evolution in liquid-phase-sintered (LPS) SiC have been studied separately. Planar-defect density is altered by appropriate heat treatment of an as-received β-SiC starting powder. It was found that a decrease in the planar-defect density in the powder retards the β→α phase transformation rate. It is proposed that, because nucleation of α-SiC occurs on the planar defects present in the β-SiC starting powders, the nucleation rate and the attendant rate of transformation decrease with a reduction in planar-defect density. Consequently, this reduces the frequency of formation of elongated β/α composite grains, resulting in lower average aspect ratios, as the initial untransformed β-SiC grains coarsen in an equiaxed manner. In contrast, addition of external α-SiC seeds has no effect on the β→α phase transformation rate, although a significant reduction in the average aspect ratio occurs. It is proposed that preferential equiaxed coarsening of the α-SiC seeds over elongated coarsening of β/α composite grains occurs, resulting in a reduction of overall coarsening anisotropy.     

Effects of Boron, Carbon, and Iron Content on the Stacking Fault Formation during Synthesis of β-SiC Particles in the System SiO2-C-H2

Through the systematic addition of B, C, and Fe, additive effects on the stacking fault formation and the morphology of the particles formed during reaction synthesis of β-SiC were investigated in the present study. The whisker content of the synthesized product and the formation mechanism of whiskers were closely related to the stacking fault density. The addition of B inhibited whisker formation probably because of isotropic imperfection and the suppression of surface diffusion. Increase in the reduction force by using an active carbon source and also adding excess carbon led to an increase in stacking fault density through enhanced whisker formation. In the presence of Fe, the synthesized β-SiC whiskers appeared to possess only a small amount of stacking faults. The growth mechanism was different with Fe; i.e., isotropic growth occurred via a dissolution-precipitation reaction through a liquid phase in the Fe-Si system.     

Comparison of Microwave Hybrid and Conventional Heating of Preceramic Polymers to Form Silicon Carbide and Silicon Oxycarbide Ceramics

Six different preceramic polymers were pyrolyzed via conventional and microwave hybrid heating; these polymers provide a range of carbon content and local atomic coordination. The products were compared with each other using X-ray diffractometry and transmission electron microscopy. Nanocrystalline β-SiC was the principal crystal phase detected, and the amount and size of the nanocrystals increased as the processing temperature increased. Differences were observed in the amount and size of the β-SiC nanocrystals and the graphitization of residual carbon between the microwave hybrid heating and the conventional oven heating of polycarbosilanes. Conventional heating of a high-carbon polysiloxane in an oven (in flowing argon) produced a greater amount of β-SiC from carbothermal reduction at high temperature. Microwave hybrid heating led to better β-SiC nanocrystal development for polyureasilazane.     

Effect of β-to-α Phase Transformation on the Microstructural Development and Mechanical Properties of Fine-Grained Silicon Carbide Ceramics

Ultrafine β-SiC powders mixed with 7 wt% Al₂O_3, 2 wt% Y₂O₃, and 1.785 wt% CaCO₃ were hot-pressed and subsequently annealed in either the absence or the presence of applied pressure. Because the β-SiC to α-SiC phase transformation is dependent on annealing conditions, the novel processing technique of annealing under pressure can control this phase transformation, and, hence, the microstructures and mechanical properties of fine-grained liquid-phase-sintered SiC ceramics. In comparison to annealing without pressure, the application of pressure during annealing greatly suppressed the phase transformation from β-SiC to α-SiC. Materials annealed with pressure exhibited a fine microstructure with equiaxed grains when the phase transformation from β-SiC to α-SiC was <30 vol%, whereas materials annealed without pressure developed microstructures with elongated grains when phase transformation was >30 vol%. These results suggested that the precise control of phase transformation in SiC ceramics and their mechanical properties could be achieved through annealing with or without pressure.     

Effect of Initial α-Phase Content on Microstructure and Mechanical Properties of Sintered Silicon Carbide

By using α- and β-SiC starting powders with similar particle sizes, the effects of initial α-phase content on the microstructure and the mechanical properties of the liquid-phase-sintered and subsequently annealed materials were investigated. The microstructures developed were analyzed by image analysis. When β-SiC powder was used, the grains became elongated. The average diameter decreased with increasing α-SiC content and the aspect ratio showed a maximum at 10%α-SiC and decreased with increasing α-SiC content in the starting powder. Such results suggest that microstructure can be controlled by changing α-phase content in starting powders. The strength increased with increasing α-SiC content in the starting powder while the fracture toughness decreased with increasing α-SiC content. There may be a trade-off in improving both the strength and toughness in SiC ceramics sintered with oxide additives.     

SiC Crystals Derived from β-SiC Powder Using a Conically Converging Shock-Wave Technique

α-SiC and β-SiC crystals are prepared from vapor by sublimation of β-SiC powder subjected to a conically converging shock-wave generated by detonating an explosive charge. α-SiC crystals are mainly 6H modifications and their features are plates, pyramids, needles, and filaments grown in the [0001] direction; 4H-SiC filaments are also obtained. α-SiC rods having a triangular cross section develop parallel to the [111] direction.     

Microstructure/Properties Relations of Advanced Materials Computer Simulations of Diffraction Effects due to Stacking Faults in -SiC: I, Simulation Results

X-ray diffraction (XRD) patterns from nominally β-SiC specimens often differ from those expected for the cubic crystal structure. These differences include the presence of additional peaks, enhanced background intensities, peak broadening, changes in relative peak heights, and shifts in peak positions. It has long been recognized that they are due to the presence of stacking faults, and models relating the experimental observations to stacking fault population have continued to evolve. The presence and relative magnitude of these features vary among different β-SiC specimens. In this work, computer simulations were used to show that the variations are closely related to differences in the type and spatial distribution of stacking faults in each specimen. In these simulations, stacking sequences were generated using a selectively activated 1-D Ising model with a Boltzmann-type probability function for specifying errors, which allows a wide variety of fault configurations to be generated. Direct correlations between different features in the XRD data to the underlying fault population are demonstrated, which are discussed in this paper. It is also shown that this computer model is general, in the sense that many of the models presented in prior work can be interpreted as limiting cases of it.     

Microstructural Evolution in Liquid-Phase-Sintered SiC: Part I, Effect of Starting Powder

The effect of starting SiC powder (β-SiC or α-SiC), with simultaneous additions of Al₂O₃ and Y₂O₃, on the microstructural evolution of liquid-phase-sintered (LPS) SiC has been studied. When using α-SiC starting powder, the resulting microstructures contain hexagonal platelike α-SiC grains with an average aspect ratio of 1.4. This anisotropic coarsening is consistent with interface energy anisotropy in α-SiC. When using β-SiC starting powder, the β→α phase transformation induces additional anisotropy in the coarsening of platelike SiC grains. A strong correlation between the extent of β→α phase transformation, as determined using quantitative XRD analysis, and the average grain aspect ratio is observed, with the maximum average aspect ratio reaching 3.8. Based on these observations and additional SEM and TEM characterizations of the microstructures, a model for the growth of these high-aspect-ratio SiC grains is proposed.     

Effect of Substrate Orientation on Interfacial and Bulk Character of Chemically Vapor Deposited Monocrystalline Silicon Carbide Thin Films

The high breakdown electric field, saturated electron drift velocity, and melting (decomposition) point of SiC have given continual impetus to research concerned with the development of thin films having minimum concentrations of line and planar defects and electronic devices for severe environments. To this end, epitaxial growth via chemical vapor deposition of monocrystalline films of β-SiC on Si (100) and 6 H -SiC {0001} substrates and 6 H -SiC on vicinal 6 H -SiC {0001} substrates have been conducted. High concentrations of stacking faults, microtwins, and inversion domain boundaries were produced in films grown directly on Si (100) as a result of a lattice parameter difference of ∼ 20% and the presence of single (or odd number) atomic steps on the substrate surface. Growth on Si (100) oriented 3° to 4° toward [011] completely eliminated the IDBs (but not the other defects) due to the preferential formation of double steps with dimerization axes on the upper terraces parallel to the step edges. Growth of β-SiC films on 6 H {0001} lowered the density of all defects but resulted in the formation of a new defect, namely, double positioning boundaries. The latter were eliminated by using 6 H {0001} oriented 3° toward [1120]. The defect density in these last films, relative to those grown on on-axis Si (100), was reduced substantially (to ∼10⁵ cm/cm³). However, the resulting film was 6 H -SiC. Significant improvements in electrical properties of simple devices were obtained as the defect density was progressively decreased.     

Fabrication and Mechanical Properties of Silicon Carbide-Silicon Nitride Composites with Oxynitride Glass

A microstructure that consisted of uniformly distributed, elongated β-Si₃N₄ grains, equiaxed β-SiC grains, and an amorphous grain-boundary phase was developed by using β-SiC and alpha-Si₃N₄ powders. By hot pressing, elongated β-Si₃N₄ grains were grown via alpha right arrow β phase transformation and equiaxed β-SiC grains were formed because of inhibited grain growth. The strength and fracture toughness of SiC have been improved by adding Si₃N₄ particles, because of the reduced defect size and the enhanced bridging and crack deflection by the elongated β-Si₃N₄ grains. Typical flexural-strength and fracture-toughness values of SiC-35-wt%-Si₃N₄ composites were 1020 MPa and 5.1 MPam^1/2, respectively.     

In Situ Growth of β-SiC Nanowires in Porous SiC Ceramics

Polycarbosilane (PCS) was used as a precursor to prepare porous silicon carbide (SiC) ceramics with in situ growth of β-SiC nanowires. The pore size of the as-prepared porous ceramics was 1.37 μm in average, and had a narrow distribution. The nanowires with diameters ranging from ∼10 to 50 nm existed in the channels of the porous body. Their morphology, microstructure, and composition were characterized by field emission scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy, which confirmed that the nanowires had a single-crystal β-SiC structure with the 〈111〉 growth direction. A vapor–liquid–solid process was discussed as a possible growth mechanism of the β-SiC nanowires.     

Formation of Silica-Coated Carbon Powder and Conversion to Spherical β-Silicon Carbide by Carbothermal Reduction

Spherical β-SiC powders that are a few micrometers in size have been prepared by heating a mixture of phenolic resin powder and fine-grained fumed silica at 1600°C in argon. The overall process is composed of two consecutive steps: (i) the formation of silica-coated spherical carbon powder and (ii) carbothermal reduction. The irregularly shaped resin powder transforms to a spherical-shaped morphology in the first step, and the resulting silica-coated spherical carbon powder is converted to β-SiC in the second step. The key factor in the first step is the utilization of fumed silica that has hydrophobic surface functional groups. Hydrophobic interactions at the point of intimate contact between the resin powder and the silica likely reduce the surface energy of the resin powder, thereby discouraging interparticle coalescence. The resulting β-SiC powder exhibits a radially developed columnar microstructure. Hollow β-SiC spheres also can be prepared by controlling the reaction conditions in the carbothermal reduction step.