Abstract:
CsCdBr3 has a quasi-linear crystal structure. It consists of covalently bound [CdBr]6 4- chains separated by chains of Cs+ ions. The trivalent rare-earth (RE) ions substitute for divalent Cd ions forming predominantly pair centers of the type RE3+-(Cd vacancy)-RE3+. A minority of RE ions forms "single-ion" centers with more distant charge compensation. The electronic structure around the band gap is determined by the [CdBr]6 4- octahedra. The lowest excitonic states of the lattice are charge-transfer states of these octahedra. At low temperatures they form self-trapped excitons which become mobile around 80 K. In addition we find defect-localized excitons at the RE pairs and single ions with slightly modified spectra. There is a strong energy transfer between the RE ions and the defect-localized excitons in both directions with transition times below 10-8s. For the cooperative fluorescence transition 1D2 × 1G 4 → 3H4 × 3H4 in Pr3+: CsCdBr3 a frequency-modulated vibronic sideband spectrum was found with up to four repetitions of the frequency of the localized optical phonon mode at the ion pair. © 2004 Elsevier B.V. All rights reserved.
