It is known that the spectroscopic properties of 3d impurities in crystals
are very sensitive to the environment of the ion and can be changed conside
rably by using different matrices. The crystal structure of KCaF3 has been
previously determined by the Rietveld profile method. At room temperature,
KCa1-xMnxF3 (x < 0.1) crystallizes in monoclinic C-2h (B2(1)/m) symmetry. T
he local geometries around Mn2+ in this crystals, in their ground and excit
ed states, are the primary properties that govern the spectroscopic behavio
r of these systems, which enjoy of fundamental and technological interest.
The present work reports the absorption and luminescence spectra of the Mn2
+-doped KCaF3 (fluoroperovskite). The luminescence spectra recorded over a
range of temperatures are dominated by wide bands, corresponding to the T-4
(1)(G) --> (6)A(1)(G), Mn2+ transition. The lifetime (tau = f(T)) of the fi
rst excited state T-4(1)(G) was measured as a function of temperature. The
lifetime of the Mn2+ emission, in this crystal have been found to be temper
ature independent (tau < 7 mu s). The absorption and emission spectra of Mn
2+ (3d(5)) in KCaF3 are analyzed using a C-4 crystal-field hamiltonian. The
calculated energy levels are in good agreement with those obtained experim
entally. The resulting crystal-field parameters B-nm are a good representat
ion of the crystal-field interactions of Mn2+ in KCaF3. (C) 1999 Elsevier S
cience B.V. All rights reserved.