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The mechanisms of formation of induced intrinsic and impurity radiative states, which consist of intrinsic and impurity electron–hole-trapping center states in irradiated Ca2P2O7−Mn and Ca2P2O7 phosphates, were investigated using thermoactivation and vacuum-ultraviolet spectroscopy methods. These centers are excited at photon energies of 4.0 eV and 4.5 eV, which are within the matrix’s transparency region. New radiative-induced states at 3.06 eV and 2.92 eV are demonstrated to be generated upon the excitation of anions by photons with energies of 5.0 and 5.64 eV. This process is due to charge transfer from the ion to the impurities, specifically Mn2+(O2−−Mn2+) and the neighboring ion O 2−−(P2O7)4−. Furthermore, upon the excitation of matrix anions with photon energies exceeding the band gap (8.0–8.25 eV), electron-trapping by impurities such as Mn2+ and (P2O7)4− ions results.

The creation of a combined radiative state at 2.95–3.1 eV in the phosphor CaSO4−Dy 3+ has been investigated using vacuum ultraviolet and thermoactivation spectroscopy methods. It is shown that the combined radiative electronic state is formed from the radiative electronic states of the impurity electronic trapping centers Dy 2+− SO4− and the intrinsic electronic radiative states SO43−−SO4− during the excitation of the anion complex SO42−, as a result of charge transfer from the excited anion complex O 2−−Dy 3+ to the impurities and the neighboring anion complex O2−− SO42−. In the CaSO4−Dy phosphor, the combined radiative electronic state and impurity emission of Dy 3+, 2.16 eV and 2.56 eV are excited by photons with energies of 3.95–4.0 eV and 4.5–4.6 eV. Energy transfer from the matrix to the Dy 3+ impurities is revealed upon thermal exposure as a result of the ionization of the electronic capture centers of Dy2+ and SO43−.