Hydrothermal synthesis and luminescent properties of microtubes constructed by fluffy Zns:Mn2+ with nanostructures

Tubular micrometer-sized ZnS:Mn2+ constructed by fluffy nanostructures were fabricated in the mixed solutions of water and ethanol in a fixed volume ratio with the aid of ethylenediamine. In the X-ray diffraction pattern, the products obtained in the presence and absence of ethylenediamine show the wurtzite and sphalerite phases, respectively. Field-emission scanning electron microscopic images reveal the evolution process from nanowires to fluffy ZnS:Mn2+ to microtubes with the reaction times of 2, 4, and 8 hours at 100 degrees C, and the basal nanowires are below 10 nm in diameter. Photoluminescence and photoluminescence excitation spectra were investigated. The results suggest that the wurtzite phase, instead of the sphalerite phase ZnS:Mn2+ is luminescence-active for the 4T1 -6A1 transition of the Mn2+ in the ZnS host. The excitation spectra monitored at orange emission bands exhibit sharp peaks at 320, 326 and 327 nm with increasing reaction times of 2, 4, and 8 hours, respectively, indicating the energy transfer from ZnS host to Mn2+ ions, and the blue-shifts compared with the band gap absorption of the bulk counterpart (344 nm) are also observed due to the quantum confinement effects. The formation mechanism of the wurtzite one-dimensional nanostructures at such a low temperature is proposed based on a molecular template mechanism involving the bidentate coordinating ligand, ethylenediamine, and the possible formation mechanism of novel tubular structure are also discussed.