Understanding enormous redshifts in highly concentrated Mn2+ phosphors

Abstract

Broad band near infrared (NIR) emission has recently been reported for a wide variety of concentrated Mn²⁺ phosphors. Typically, Mn²⁺ emits in the green to red spectral region, depending on local coordination. The enormous redshift to the NIR was explained by exchange coupling between Mn²⁺ neighbours at high Mn²⁺ dopant concentrations. However, the reported redshifts are an order of magnitude larger than expected for exchange coupling and also the absence of a shift in excitation spectra suggests that exchange coupling cannot explain the observations. Here, extensive concentration, temperature and time dependent luminescence studies are reported for Mg_1−xMn_xAl₂O₄ (x = 0.01–0.5). The results show that the broad band NIR emission originates from NIR emitting trap centers, possibly Mn³⁺. High Mn²⁺ dopant concentrations enable efficient energy migration over the Mn²⁺ sublattice to these traps, consistent with the same excitation spectra for the green Mn²⁺ and NIR trap emission. Upon cooling to cryogenic temperatures energy migration is hampered and the green Mn²⁺ emission increases, especially in the most concentrated systems. Finally, the relative intensity of the NIR emission was varied by changing synthesis conditions providing further support that the NIR emission in concentrated Mn²⁺ phosphors originates from NIR emitting centers and not exchange coupled Mn²⁺ pairs.