Synthesis and Optical Properties of Europium-Doped ZnS: Long-Lasting Phosphorescence from Aligned Nanowires


  • This work was financially supported by the China Postdoctoral Science Foundation (No. 2005037108), the Special Funds for Major State Basic Research Project of China (No. G2000068303), the National Natural Science Foundation of China (Nos. 60276014 and 60006001), and the National High Technology Research and Development Program of China (Nos. 2002AA311070, 2002AA311020, and 2002AA311170).


Quasi-aligned Eu2+-doped wurtzite ZnS nanowires on Au-coated Si wafers have been successfully synthesized by a vapor deposition method under a weakly reducing atmosphere. Compared with the undoped counterpart, incorporation of the dopant gives a modulated composition and crystal structure, which leads to a preferred growth of the nanowires along the [01equation image0] direction and a high density of defects in the nanowire hosts. The ion doping causes intense fluorescence and persistent phosphorescence in ZnS nanowires. The dopant Eu2+ ions form an isoelectronic acceptor level and yield a high density of bound excitons, which contribute to the appearance of the radiative recombination emission of the bound excitons and resonant Raman scattering at higher pumping intensity. Co-dopant Cl ions can serve not only as donors, producing a donor–acceptor pair transition with the Eu2+ acceptor level, but can also form trap levels together with other defects, capture the photoionization electrons of Eu2+, and yield long-lasting (about 4 min), green phosphorescence. With decreasing synthesis time, the existence of more surface states in the nanowires forms a higher density of trap centers and changes the crystal-field strength around Eu2+. As a result, not only have an enhanced Eu2+ 4f65d1–4f7 intra-ion transition and a prolonged afterglow time been more effectively observed (by decreasing the nanowires' diameters), but also the Eu2+ related emissions are shifted to shorter wavelengths.