Electronic carbides

ForHj and HeH, the region between the nuclei on the z axis always gives a positive binding force. Find the smallest values of the atomic number Zx and the charge n for the one-electron carbide XC" such that there is an antibinding region on the z axis exactly halfway between the nuclei. 

Figure C2.17.6. Transmission electron micrograph and its Fourier transfonn for a TiC nanocrystal. High-resolution images of nanocrystals can be used to identify crystal stmctures. In tliis case, tire image of a nanocrystal of titanium carbide (right) was Fourier transfonned to produce tire pattern on tire left. From an analysis of tire spot geometry and spacing, one can detennine that tire nanocrystal is oriented witli its 11001 zone axis parallel to tire viewing direction [217].

Figure C2.17.7. Selected area electron diffraction pattern from TiC nanocrystals. Electron diffraction from fields of nanocrystals is used to detennine tire crystal stmcture of an ensemble of nanocrystals [119]. In tliis case, tliis infonnation was used to evaluate the phase of titanium carbide nanocrystals [217].

Only the carbon atom can gain four electrons this only happens when it is combined with extremely electropositive elements and this state may be regarded as exceptional. Bonding in carbides is almost invariably predominantly covalent. 

Drilhng. Glass is dtiUed with carbide or bonded-diamond dtiUs under a suitable coolant such as water or kerosene. Other drilling processes include a metal tube rotating about its axis (core drilling), an ultrasonic tool in combination with an abrasive slurry, or an electron beam. Tolerances less than 0.1 mm are readily obtained with diamond-core drilling and, if required, holes smaller than 25 )J.m-dia can be made with the electron-beam method. 

Research and development in the field ate stiU continuing at a fast pace, particularly in the area of absorption and emission characteristics of the polymers. Several reasons account for this interest. First, the intractable polydimethyl silane [30107-43-8] was found to be a precursor to the important ceramic, siUcon carbide (86—89). Secondly, a number of soluble polysdanes were prepared, which allowed these polymers to be studied in detail (90—93). As a result of studies with soluble polymers it became cleat that polysdanes are unusual in their backbone CJ-conjugation, which leads to some very interesting electronic properties. 

Fig. 13. Transmission electron micrograph (tern) showing dislocations in aluminum in the region near a siUcon carbide particle, SiC. ...

Fig. 17. Structuie of U-700 after piecipitation hardening temperature of 1168 C/4 h + 1079" C/4 h + 843 C/24 h + TGO C/IG h with air cooling from each temperature. A grain boundary with precipitated carbides is passing through the center of the electron micrograph. Matrix precipitates are y -Nij(TiAl).

By far the most common iadustrial refractories are those composed of single or mixed oxides of Al, Ca, Cr, Mg, Si, and Zr (see Tables 1, 4, and 6). These oxides exhibit relatively high degrees of stabiHty under both reduciag and oxidizing conditions. Carbon, graphite, and siHcon carbide have been used both alone and ia combination with the oxides. Refractories made from these materials are used ia toa-lot quantities, whereas siHcides are used ia relatively small quantities for specialty appHcation ia the auclear, electronic, and aerospace iadustries. 

Flaws in the anodic oxide film are usually the primary source of electronic conduction. These flaws are either stmctural or chemical in nature. The stmctural flaws include thermal crystalline oxide, nitrides, carbides, inclusion of foreign phases, and oxide recrystaUi2ed by an appHed electric field. The roughness of the tantalum surface affects the electronic conduction and should be classified as a stmctural flaw (58) the correlation between electronic conduction and roughness, however, was not observed (59). Chemical impurities arise from metals alloyed with the tantalum, inclusions in the oxide of material from the formation electrolyte, and impurities on the surface of the tantalum substrate that are incorporated in the oxide during formation. 

If pure, the carbides of Groups 1 and 2 are characterized by their transparency and lack of conductivity. The carbides of Group 3, ie. Sc, Y, the lanthanides, and the actinides, ate opaque. Some, depending on composition, show metallic luster and electroconductivity. The cation may exist in the MC2 phases of this group, and the remaining valence electron apparendy imparts pardy metaUic character to these compounds. 

Properties and Mature of Bonding. The metaUic carbides are interesting materials that combine the physical properties of ceramics (qv) with the electronic nature of metals. Thus they are hard and strong, but at the same time good conductors of heat and electricity. 

The crystal stmeture and stoichiometry of these materials is determined from two contributions, geometric and electronic. The geometric factor is an empirical one (8) simple interstitial carbides, nitrides, borides, and hydrides are formed for small ratios of nonmetal to metal radii, eg, < 0.59. 

The properties and performance of cemented carbide tools depend not only on the type and amount of carbide but also on carbide grain size and the amount of biader metal. Information on porosity, grain size and distribution of WC, soHd solution cubic carbides, and the metallic biader phase is obtained from metaHographicaHy poHshed samples. Optical microscopy and scanning and transmission electron microscopy are employed for microstmctural evaluation. Typical microstmctures of cemented carbides are shown ia Figure 3. 

A progressive etching technique (39,40), combined with x-ray diffraction analysis, revealed the presence of a number of a polytypes within a single crystal of sihcon carbide. Work using lattice imaging techniques via transmission electron microscopy has shown that a-siUcon carbide formed by transformation from the P-phase (cubic) can consist of a number of the a polytypes in a syntactic array (41). 

Semiconducting Properties. Sihcon carbide is a semiconductor it has a conductivity between that of metals and insulators or dielectrics (4,13,46,47). Because of the thermal stabiUty of its electronic stmcture, sihcon carbide has been studied for uses at high (>500° C) temperature. The Hall mobihty in sihcon carbide is a function of polytype (48,49), temperature (41,42,45—50), impurity, and concentration (49). In n-ty e crystals, activation energy for ioniza tion of nitrogen impurity varies with polytype (50,51). 

Optical absorption measurements give band-gap data for cubic sihcon carbide as 2.2 eV and for the a-form as 2.86 eV at 300 K (55). In the region of low absorption coefficients, optical transitions are indirect whereas direct transitions predominate for quantum energies above 6 eV. The electron affinity is about 4 eV. The electronic bonding in sihcon carbide is considered to be predominantiy covalent in nature, but with some ionic character (55). In a Raman scattering study of vahey-orbit transitions in 6H-sihcon carbide, three electron transitions were observed, one for each of the inequivalent nitrogen donor sites in the sihcon carbide lattice (56). The donor ionization energy for the three sites had values of 0.105, 0.140, and 0.143 eV (57). 

The analysis of siUcon carbide involves identification, chemical analysis, and physical testing. For identification, x-ray diffraction, optical microscopy, and electron microscopy are used (136). Refinement of x-ray data by Rietveld analysis allows more precise deterrnination of polytype levels (137). 

Syntheses, crystallization, structural identification, and chemical characterization of high nuclearity clusters can be exceedingly difficult. Usually, several different clusters are formed in any given synthetic procedure, and each compound must be extracted and identified. The problem may be compounded by the instabiUty of a particular molecule. In 1962 the stmcture of the first high nuclearity carbide complex formulated as Fe (CO) C [11087-47-1] was characterized (40,41) see stmcture (12). This complex was originally prepared in an extremely low yield of 0.5%. This molecule was the first carbide complex isolated and became the foremnner of a whole family of carbide complexes of square pyramidal stmcture and a total of 74-valence electrons (see also Carbides, survey). 

Diamond and Refractory Ceramic Semiconductors. Ceramic thin films of diamond, sihcon carbide, and other refractory semiconductors (qv), eg, cubic BN and BP and GaN and GaAlN, are of interest because of the special combination of thermal, mechanical, and electronic properties (see Refractories). The majority of the research effort has focused on SiC and diamond, because these materials have much greater figures of merit for transistor power and frequency performance than Si, GaAs, and InP (13). Compared to typical semiconductors such as Si and GaAs, these materials also offer the possibiUty of device operation at considerably higher temperatures. For example, operation of a siUcon carbide MOSFET at temperatures above 900 K has been demonstrated. These devices have not yet been commercialized, however. 

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