Ceramics impurities

Sihcon nitride occurs in two forms, a-Si N and P-Si N. Pure Si N is white, but the colors of commercial materials may be tan, gray, or black because of residual siUcon or impurities. Si N may be prepared by nitriding siUcon powder at 1200—1400°C or, for extremely fine-grained Si N, by the reaction of SiCl or SiH and N2 or NH (see also Advanced ceramics). 

Both anatase and mtile are broad band gap semiconductors iu which a fiUed valence band, derived from the O 2p orbitals, is separated from an empty conduction band, derived from the Ti >d orbitals, by a band gap of ca 3 eV. Consequendy the electrical conductivity depends critically on the presence of impurities and defects such as oxygen vacancies (7). For very pure thin films, prepared by vacuum evaporation of titanium metal and then oxidation, conductivities of 10 S/cm have been reported. For both siugle-crystal and ceramic samples, the electrical conductivity depends on both the state of reduction of the and on dopant levels. At 300 K, a maximum conductivity of 1 S/cm has been reported at an oxygen deficiency of... 

Haidness decreases with increasing porosity and increased grain size. SoHd solution impurities influence hardness, but it is often hard to separate the effect of the impurity on the hardness, from the effect of the impurity on other microstmctural effects that influence hardness such as grain size. Further information on hardness of ceramics is available (45). 

Semiconducting Ceramics. Most oxide semiconductors are either doped to create extrinsic defects or annealed under conditions in which they become non stoichiometric. Although the resulting defects have been carefully studied in many oxides, the precise nature of the conduction is not well understood. Mobihty values associated with the various charge transport mechanisms are often low and difficult to measure. In consequence, reported conductivities are often at variance because the effects of variable impurities and past thermal history may overwhelm the dopant effects. 

If an impurity (copper, say) is dissolved in a metal or ceramic (aluminium, for instance) at a high temperature, and the alloy is cooled to room temperature, the impurity may precipitate as small particles, much as sugar will crystallise from a saturated solution when it is cooled. An alloy of A1 containing 4% Cu ( Duralumin ), treated in this way, gives very small, closely spaced precipitates of the hard compound CUAI2. Most steels are strengthened by precipitates of carbides, obtained in this way. ... 

Fig. 4.4. Stages in zone refining o bar of impure silicon (a) We start with a bar that has a uniform concentration of impurity, Q. (b) The left-hand end of the bar is melted by o small electric tube furnace, making a liquid zone. The bar is encapsulated in a ceramic tube to stop the liquid running away. ( ) The furnace is moved off to the right, pulling the zone with it. (d) As the zone moves, it takes in more impurity from the melted solid on the right than it leaves behind in the freshly frozen solid on the left. The surplus pushes up the concentration of impurity in the zone, which in turn pushes up the concentration of impurity in the next layer of solid frozen from it. (e) Eventually we reach steady state, (f) When the zone gets to the end of the bar the concentrations in both solid and liquid increase rapidly, (g) How we set up eqn. (4.1).

Many inorganic solids lend themselves to study by PL, to probe their intrinsic properties and to look at impurities and defects. Such materials include alkali-halides, semiconductors, crystalline ceramics, and glasses. In opaque materials PL is particularly surface sensitive, being restricted by the optical penetration depth and carrier diffusion length to a region of 0.05 to several pm beneath the surface. 

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