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The sensitization with Yb3+ of other rare earth ions emission is intensively used in the last years for increasing excitation efficiency of infrared (diode laser) pumped solid state lasers. It proved as a good sensitizer for Pr3+ emission in various matrices. The spectral investigations for the elucidation of the nature of multisite structure of Pr3+ in YAG and of the Yb3+ co-doping on Pr3+:YAG are presented in this paper. In Pr3+:YAG two types of multisites have been observed: perturbed Pr3+ sites by nonstoichiometric defects and strongly coupled Pr3+ - Pr3+ near neighbor pairs. Pr3+ spectra in Yb3+, Pr3+:YAG show new lines assigned to near neighbor Pr3+ - Yb3+ pairs and Pr3+ - Yb3+ - Yb3+ triads.
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