The number of isolated Mn2+ ions and Mn2+ clusters in ZnS:Mn powder and thin films has been studied using Mn2+ spectra measured at room temperature with an X-band electron-paramagnetic-resonance spectrometer. While the concentration of the isolated Mn2+ ions decreases with increasing Mn concentration, the concentration of the clusters increases. At low Mn concentration, the Mn2+ ion substitutes for the Zn ion in ZnS:Mn in the cubic phase. At high Mn concentrations, where the ZnS powder has a dominant hexagonal phase, the Mn ion still prefers to substitute for Zn in ZnS:Mn at the cubic site rather than at the hexagonal site.

The fluorescence emission and excitation spectra of white-light emitting SrS: Pr, F thin film electroluminescent devices have been investigated. It was determined from the results obtained that the dominant electroluminescence mechanism was that the ionization of Pr3+ centers occurs first, then subsequently recombination with electrons occurs, and finally Pr3+ center transitions give rise to luminescence. The emission mechanism of SrS: Pr, F seems to be the same as that of a SrS: Pr, K electroluminescent device, except for the appearance of strong peaks around 610–670 nm. The impurity excitation peak in the lower excitation energy, longer-wavelength region in the FL spectrum may be an important factor for the selection of an effective white-light emitting EL material. The electron paramagnetic resonance experiment of SrS: Pr, F was performed on powder and thin film specimens. The hyperfine structure of an isolated Mn2+ ion was observed in this SrS: Pr, F thin film. This Mn center which was substituted for Sr, seems to contribute to the strong red emission in the white EL spectrum.

We observed a decrease of the number of effective emission centers Mn2+ in the aged ZnS:Mn electroluminescence (EL) devices compared to the fresh EL devices using the electron-paramagnetic-resonance technique. Such phenomena can take place during the operation of the EL device, since the isolated Mn can easily diffuse into another site and forming cluster. Another possible explanation is that Mn2+ changes into Mn1+ or Mn3+ by transferring the electronic charge of the isolated Mn2+ to the neighboring Mn ions via sulfur and/or sulfur vacancy. As a result, luminance is lowered due to the decrease in the number of efficient emission centers of isolated Mn2+.

We have investigated light-emission characteristics of a white-light-emitting electroluminescent device with a doubly doped ZnS:Pr,Ce,F phosphor layer. We found that optimum codoping of Ce enhances the emission characteristics compared to the electroluminescent device with a singly doped ZnS:Pr,F layer. We also found that introducing an additional thin-insulating SixNy interlayer between the lower insulating layer and the phosphor layer significantly stabilizes the aging characteristics and improves the luminous efficiency.