Defects in Solids (Special Topics in Inorganic Chemistry) by Richard J. D. Tilley

By Richard J. D. Tilley

Presents a radical realizing of the chemistry and physics of defects, permitting the reader to govern them within the engineering of materials.Reinforces theoretical ideas by means of putting emphasis on genuine global procedures and applications.Includes forms of end-of-chapter difficulties: a number of selection (to try out wisdom of phrases and rules) and extra vast workouts and calculations (to construct talents and understanding).Supplementary fabric on crystallography and band constitution are integrated in separate appendices.

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The relationship between the energy gained or lost, DEn, and the frequency, n, or the wavelength, l, of the light absorbed or emitted, is En À E0 ¼ DEn ¼ hnn ¼ hc ln where En is the energy of the higher energy level (n ¼ 1, 2, 3, . ), h is Planck’s constant, and c is the speed of light. The first experiments that connected color with defects were carried out in the 1920s and 1930s by Pohl, who studied synthetic alkali halide crystals. A number of ways were discovered by which the colorless starting materials could be made to display intense colors.

Similarly, for ionic (Zr O2 ) a neutral oxygen atom at an occupied oxygen site acquires an effective charge of 2†, and is hence written O2† O . The same is true of the oxygen vacancy. Compared to a site occupied by an O22 ion, the site has an effective positive charge of 2†, so the vacancy is 2† . Formally, one can therefore write written VO 40 þ VO2† þ O2† CaO(ZrO2 ) À! CaZr O (1:8) The host crystal, ZrO2, is written in parentheses (ZrO2). 2. Now CaO is normally regarded as an ionic compound, as implied by the foregoing allocation of charges, so that ions should occupy the sites, not neutral atoms.

The formation energy of Schottky defects is described further in Chapter 2. 2 Frenkel Defects As already illustrated, it is also possible to imagine a defect related to ions in interstices, that is, interstitials. Such defects were first suggested as being of importance by Frenkel and are known as Frenkel defects. In this case, an atom or ion from one sublattice moves to a normally empty site (an interstitial site) in the crystal, leaving a vacancy behind (Fig. 15b). A Frenkel defect may involve either the 28 POINT DEFECTS cation or the anion sublattice.

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