Abstract
In ionic crystals, there is an opportunity to create a rather unique type of defect complex by the introduction of aliovalent impurities, i.e., impurity ions which differ in charge from the corresponding solvent ion. When such impurities are introduced, additional defects (either vacancies or interstitial ions) must accompany the aliovalent ions in order to achieve charge compensation, the defect possessing an effective charge equal and opposite to that of the impurity ion. Accordingly, the two entities will experience a Coulomb attraction tending to produce, if the temperature is not too high, a dipole or defect complex which possesses a relatively strong binding energy. The existence of such complexes profoundly affects many of the properties of ionic crystals, including mechanical as well as electrical properties. This chapter is concerned mainly with information about ionic motions which can be obtained by studying such doped crystals. On the one hand, diffusion of the aliovalent ion may be very different from self-diffusion, due to the presence of the compensating defect. On the other hand, the methods of dielectric and anelastic relaxation may be used to observe the reorientation of the complex in an appropriate externally applied field (electric or stress field, respectively). These measurements, therefore, give direct information on the kinetics of the rate-controlling steps in the re-orientation process. Combining this information with corresponding information on kinetics of migration (from diffusion measurements or the study of the dipole aggregation), can give a rather complete picture of the various ionic motions which take place in the presence of aliovalent impurity ions.
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Nowick, A.S. (1972). Defect Mobilities in Ionic Crystals Containing Aliovalent Ions. In: Crawford, J.H., Slifkin, L.M. (eds) Point Defects in Solids. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-2970-1_3
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