Energy dispersive spectroscopy analysis of aluminium segregation in silicon carbide grain boundaries

The aluminium distribution in polycrystalline SiC hot‐pressed with aluminium, boron and carbon additives was studied using X‐ray energy‐dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The Al excess in homophase SiC grain boundary films was determined, taking into account dissolved Al in the SiC lattice. In the spot‐EDS analysis, an electron beam probe with a calibrated diameter was formed, and the total beam–specimen interaction volume was defined, taking the beam spreading through crystalline TEM foil into consideration. EDS spectra were collected from regions containing intergranular films and adjacent matrix grains, respectively. A theoretical treatment was presented and experimental errors were estimated, with a further discussion about the effects of foil thickness. Experimental examples are given, followed by statistical EDS analyses for grain boundary films in SiC samples hot‐pressed with increased amounts of Al additions. The results demonstrated a substantial Al segregation in the nanometer‐wide intergranular films in all samples. Al additions higher than 3 wt% saturated the Al concentrations in SiC grains and in grain boundary films. The effect of foil thickness, and the parameters for determining the optimum incident beam diameter in the EDS analysis are discussed.     

A comparison of the microstructure of silicon nitride-silicon carbide composites made with and without deoxidized starting material

Two different types of silicon carbide (SiC) matrix composites, with either 10 wt% or 20 wt% silicon nitride (Si₃N₄) reinforcement, were fabricated to investigate the effect of pretreatment on the resulting composite micro-structure. The first type of composite was prepared from as-received α-SiC and α-Si₃N₄ powders, while the second type was prepared from powder compacts that had been deoxidized to eliminate surface silica on the powder particles. The composites were hot isostatically pressed in tantalum cans at 2373 K for 1h under a pressure of 200 MPa. Density measurements showed that full theoretical density was achieved for the composites prepared from the as-received powders, while much lower densities were obtained for the composites prepared from the deoxidized green compacts. Almost all of the α-SiC transformed into β-SiC, and almost all the α-Si₃N₄ transformed into α-Si₃N₄ in the composites made from the as-received powders, while in the composites made from the deoxidized material the α-SiC remained untransformed and both α-Si₃N₄ and β-Si₃N₄ phases were present in significant quantities. High-resolution transmission electron microscopy and Fresnel fringe imaging were used to identify the grain boundary and interphase boundary structure. Most interfaces were found to be covered with ? 1 nm thick amorphous intergranular films in the composites prepared from as-received powders, whereas most interfaces were found to be free of such amorphous intergranular films in the composites prepared from the deoxidized material. Taken together, the presence of intergranular films at the interfaces and the results from density measurements are consistent with the densification and reverse α → β-SiC transformation taking place in the composites made from as-received powders by a liquid-phase sintering route. An incomplete liquid-phase sintering mechanism is also able to explain the microstructure observed in the composites made from the deoxidized material.     

Buried amorphous-layer impact on dislocation densities in silicon

The impact of amorphous layers on dislocation densities in silicon piezoresistors was investigated by means of transmission electron microscopy and chemical etching. Mechanical bevel polishing at a shallow angle and selective etching were applied to assess the dislocation depth distributions. It was found that, despite the presence of additional defects after recrystallization, the initial presence of a buried amorphous layer reduced, after annealing, the dislocation density in the depletion region of a p–n junction, compared with the case of a shallower, surface amorphous layer.     

The remote electron beam-induced current analysis of grain boundaries in semiconducting and semi-insulating materials

When no charge collecting p-n junction or Schottky barrier is present in the specimen, but two contacts are applied, conductive mode scanning electron microscope (SEM) observations known as remote electron beam-induced current (REBIC) can be made. It was described as "remote" EBIC because the contacts to the specimen can lie at macroscopic distances from the beam impact point. In recent years, REBIC has been found to be useful not only for studies of grain boundaries in semiconducting silicon and germanium, but also in semi-insulating materials such as the wider bandgap II-VI compounds and electroceramic materials like varistor ZnO and positive temperature coefficient resistor (PTCR) BaTiO3. The principles of this method are outlined. Accounts are given of the five forms of charge collection and resistive contrast that appear at grain boundaries (GBs) in REBIC micrographs. These are (1) terraced contrast due to high resistivity boundary layers, (2) peak and trough (PAT) contrast due to charge on the boundary, (3) reversible contrast seen only under external voltage bias due to the beta-conductive effect in a low conductivity boundary layer, (4) dark contrast due to enhanced recombination, and (5) bright contrast apparently due to reduced recombination. For comparison, the results of the extensive EBIC studies of GBs in Si and Ge are first outlined and then the results of recent REBIC grain boundary studies in both semiconducting and semi-insulating materials are reviewed.     

'Five-parameter' analysis of grain boundary networks by electron backscatter diffraction

This paper describes state‐of‐the‐art analysis of grain boundary populations by EBSD, with particular emphasis on advanced, nonstandard analysis. Data processing based both on misorientation alone and customised additions which include the boundary planes are reviewed. Although commercial EBSD packages offer comprehensive data processing options for interfaces, it is clear that there is a wealth of more in‐depth data that can be gleaned from further analysis. In particular, determination of all five degrees of freedom of the boundary population provides an exciting opportunity to study grain boundaries by EBSD in a depth that was hitherto impossible. In this presentation we show ‘five‐parameter’ data from 50 000 boundary segments in grain boundary engineered brass. This is the first time that the distribution of boundary planes has been revealed in a grain boundary engineered material.     

Facility for rapid preparation of silicon and silicide TEM specimens

A simple chemical jet polishing arrangement, for the thinning of semiconductors or metals for transmission electron microscopy (TEM), is described for the specific case of silicon and silicides. The effect of variation in three mechanical parameters on the profile and quality of the specimen is described, and the optimum conditions are determined. A proposed polishing solution is one part 48% HF mixed with one part fuming HNO₃. Reproducibility is only achieved in the presence of a relatively large concentration of nitrous acid in the polishing solution. The solution must also be relatively concentrated, as the reaction rate falls off rapidly with decreasing concentration.     

Segregation-induced hole drilling at grain boundaries

Grain boundaries in metals provide preferential sites for impurity atoms to segregate, forming an area of the metal with different chemical and physical properties compared to the bulk. This also means that the electron beam damage characteristics of the grain boundary might be different from that of the bulk. Segregation can be expected to make grain boundaries particularly vulnerable to electron-beaminduced hole drilling and beam damage, if the segregation produces a near two-dimensional compound with increased ionicity. Here we report preferential hole drilling at grain boundaries in an Fe-0–4 wt%P alloy. Such a phenomenon confirms evidence from energy-loss spectroscopy that charge transfer occurs between P and Fe at the grain boundary. It also explains why it is easier to detect phosphorus using EDX compared to PEELS, and suggests that the electron beam damage may be a major limiting factor in grain-boundary studies.     

High angle [001] twist boundaries in platelet colonies of BiSrCaCuO (2223) superconductor

The microstructure of BiPbSrCaCuO (2223) ceramic was studied by polarised light microscopy and the etch-pits technique. The high-angle twist grain boundaries in the platelet colonies were confirmed to be [001] coincidence type twisted boundaries or rotation twin boundaries with the (001) twinning plane.     

Reconstruction of 3D grain boundaries from rock thin sections,using an advanced polarised‐light microscopy method

Grain boundaries play a significant role in materials by initiating reactions and collecting impurities. Here we present FAGO (Fabric Analyser Grain boundary recOnstruction), a first step towards the automatic determination of three‐dimensional (3D) grain boundary geometry using polarised light. The trace of the grain boundaries from 2D rock thin sections are determined primarily from data acquired using an automatic fabric analyser microscope and the FAME software (fabric analyser‐based microstructure evaluation; Peternell and colleagues and Hammes and Peternell). Based on the Fabric Analyser G50's unique arrangement of nine differently oriented light sources the retardation can be determined independently for each light direction and at each pixel in the field of view. FAGO combines these retardation datasets for each individual pixel together with retardation profiles across grain boundaries, to determine the orientations of the boundaries. The grain boundary traces are then broken up into segments of equal orientation, using the profile‐obtained orientation data. Finally, a 3D grain boundary model is reconstructed. The data processing is almost fully automatic using the MATLAB® environment. Only minor manual inputs are required.     

磷在2.25CrlMo钢中的非平衡晶界偏聚动力学实验

采用2.25Cr1Mo工业用钢,通过俄歇电子能谱分析方法(AES),对磷在1050℃固溶处理、540℃恒温保持过程中的非平衡晶界偏聚浓度进行了测试,获得了磷在钢中的非平衡晶界偏聚动力学曲线,该曲线直接验证了非平衡晶界偏聚动力学理论中的Xu-Song模型。     

The effects of washing a collagen sample prior to TEM examination

Transmission electron microscopy (TEM) is an important analysis technique to visualize (bio)macromolecules and their assemblies, including collagen fibers. Many protocols for TEM sample preparation of collagen involve one or more washing steps to remove excess salts from the dispersion that could hamper analysis when dried on a TEM grid. Such protocols are not standardized and washing times as well as washing solvents vary from procedure to procedure, with each research group typically having their own protocol. Here, we investigate the influence of washing with water, ethanol, but also methanol and 2-propanol, for both mineralized and unmineralized collagen samples via a protocol based on centrifugation. Washing with water maintains the hydrated collagen structure and the characteristic banding pattern can be clearly observed. Conversely, washing with ethanol results in dehydration of the fibrils, often leading to aggregation of the fibers and a less obvious banding pattern, already within 1 min of ethanol exposure. As we show, this process is fully reversible. Similar observations were made for methanol and propanol. Based on these results, a standardized washing protocol for collagenous samples is proposed.     

TEM study of chirality in MoS2 nanotubes

The dark-field diffraction contrast of helical nanotubes (NTs) is shown to be asymmetric when an NT is tilted at appropriate angle with respect to the incident electron beam. This phenomenon was used for the chirality determination of multi-shell NTs observed in MoS₂ layered compound. Both kinds of NT — helical and non-helical — were found. In the case of helical NTs only right-hand chirality was observed.     

High resolution electron microscopy of interfaces in chlorinated phthalocyanine molecular crystals

Molecular images of chlorinated copper phthalocyanine have shown the arrangement of molecules at the interface between two crystals. Mismatch does not cause distortion or recrystallization for low index junctions but for more irregular interfaces strain causes alteration of the molecular tilt angle and accommodation of the mismatch by the formation of edge dislocations whose Burger's vectors are parallel to the interface.     

New developments in the characterization of dislocation loops from LACBED patterns

The characterization of the Burgers vector of dislocations from large‐angle convergent‐beam electron diffraction (LACBED) patterns is now a well‐established method. The method has already been applied to relatively large and isolated dislocation loops in semiconductors. Nevertheless, some severe experimental difficulties are encountered with small dislocation loops. By using a 2 µm selected‐area aperture and a carbon contamination point to mark the loop of interest, we were able to characterize both the plane and the Burgers vector of dislocation loops of a few tens of nanometres in size present in Al‐Cu‐Mg alloys.     

Microstructural analysis of silicon carbide monofilaments

In the development of monofilaments, a good understanding of the process/property relationships is essential. Transmission electron microscopy (TEM) is a powerful tool but too slow and expensive to be used routinely. Alternative, cheaper techniques have therefore been investigated. The microstructures of three SiC monofilaments (DERA Sigma SM1140+, Textron SCS-6 and Ultra-SCS) and some experimental samples were studied using a combination of TEM, electron microprobe analysis, Raman microprobe analysis, thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). It was found that the Raman technique was complementary to TEM and easily identified the presence of amorphous C and Si. These could not be seen by electron or X-ray diffraction techniques. DSC indicated the presence of free Si in the DERA Sigma SM1140+ monofilament by a distinctive peak at ∼1400 °C. TGA showed the reaction of monofilament components with gaseous species. The Textron SCS-6 and Ultra species lost weight as C was oxidized to gaseous CO. By contrast, the Sigma monofilament gained weight from formation of SiO₂ from the free Si. The separations of the transverse optical phonon peaks in the Raman spectra were correlated with the density of stacking faults in the SiC crystallites. This was similar in all monofilaments. Analysis of the polarization of the Raman scattering gave information on the orientation of crystallites. The crystallites in SM1140+ and SCS-6 were orientated predominantly with the <111> parallel to the radius. Preliminary interpretation of the polarized Raman scattering from Ultra-SCS indicated more than one orientation of crystallite. One possibility was a mixture of <111> and <110> directions parallel to the radius.     

On the accuracy of lattice-distortion analysis directly from high-resolution transmission electron micrographs

Lattice‐distortion analysis from high‐resolution transmission electron micrographs offers a convenient and fast tool for direct measurement of strains in materials over a large area. In the present work, we have evaluated the accuracy of the strain measurement when the effects of the realistic experimental variables are explicitly taken into account by the use of image simulation techniques. These variables are focal setting and variation, local thickness and orientation of the sample, as well as misalignments of the sample and the incident beam. The evaluation reveals that consistency of image features and contrast within the micrographs is desired for the analysis to eliminate effects of the variations of local focus value and specimen thickness. After proper orientation of a crystalline specimen, the misorientation of the object will not notably influence the strain measurement even though a local bending may exist within the sample. However, the incident beam of the microscope needs to be aligned carefully as the beam misalignment may introduce a notable artefact around the interface region.