Crystal field, phonon coupling and emission shift of Mn²⁺ in ZnS:Mn nanoparticles

The Mn²⁺ emission wavelengths are at 591, 588, 581 and 570 nm, respectively, for the ∼10, ∼4.5, ∼3.5 nm sized nanoparticles and the ZnS:Mn nanoparticles formed in an ultrastable zeolite-Y. To reveal the cause for the shift, the crystal field and phonon coupling were investigated. The results show that the predominant factor for the shift is the phonon coupling, whose strength is size dependent and is determined by both the size confinement and the surface modification of the nanoparticles. Although the crystal field strength decreases with the decreasing of the particle size, its change has little contribution to the emission shift of Mn²⁺ in ZnS:Mn nanoparticles.