[en] Optical doping is an attractive method to tailor photonic properties of semiconductor matrices for development of solid-state electroluminescent structures. For practical applications, thermal stability of emission obtained from these materials is required. Thermal processes can be conveniently investigated by two-color spectroscopy in the visible and the mid-infrared. Free-electron laser is a versatile high-brilliance source of radiation in the latter spectral range. In this contribution, we briefly review some of the results obtained recently by the two-color spectroscopy with a free-electron laser in different semiconductors optically doped with rare earth and transition metal ions. Effects leading to both enhancement and quenching of emission from optical dopants will be presented. For InP:Yb, Si:Er, and Si:Cu activation of particular optically induced non-radiative recombination paths will be shown. For Si:Er and Si:Ag, observation of a low temperature optical memory effect will be reported