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EPR Spectroscopy of Vacancies in KF: Mn2

Volume 20, Number 2 (April 1966) Page 113-114

Veigele, William J.


When nonstoichiometric impurities enter a crystal lattice substitutionally, they are charge compensated by defects such as vacancies or interstitials which associate with the impurity at nearby sites or are unassociated at distant sites. These impurity-defect complexes have characteristic parameters such as diffusion coefficients and binding energies which may be studied with electron paramagnetic resonance (EPR) spectroscopy. If c is the ion fraction impurity concentration for a particular defect, p the degree of association, cp the fraction of associated, and c (1-p) the fraction of unassociated impurity-defect complexes, application of the mass action law gives cp/[c (1-p)]2=K(T), where K(T) may be expressed such that

p/(1-p)2=zceE/kT, (1)

where z=6 is the number of distinct orientations of the complex and E is the Gibbs free energy of binding. A semilog plot against 1/kT of Eq. 1 would give E and c from the slope and intercept, respectively, of the resulting straight line.