EPR of Mn2+ and Eu2+ ions in the bulk and on the surface of AIBVII type single- and microcrystals

A new dimensional effect is investigated. It consists in a change of the microstructure of bulk impurity defects after a decrease in the crystal size. The results of studying the changes in the defect structure in (NaCl, KCl, LiF):Mn2+ and (NaCl, KCl, KBr):Eu2+ by electronic paramagnetic resonance (EPR) are presented. Samples of different sizes and nature are investigated: bulk-doped single crystals of large sizes; bulk-doped crystals of small sizes; powder samples of various degree of dispersity, which are obtained by crushing the samples of large sizes; and samples with direct doping of the surface. The spectra of three types are measured: the spectra of single crystals; the spectra of the powders with the sizes of the particlesd ≥ 1 mm; the spectra of the powders withd ≤ 3 μn (analogous spectra have the surface-doped samples). Considerable change in the EPR spectra as the samples are continuously crushed is due to the change of the paramagnetic center (PC) structure. In the case of bulk-doped single crystals the paramagnetic ion compensator is in the nearest cation coordination sphere. When the deformation caused by the surface region becomes large enough in the vicinity of PC, detachment and removal of the compensator from the impurity ion take place. As a result, the local symmetry of the PC is changed and is revealed in the EPR spectra.