Morphology Tailoring of ZnWO4 Crystallites/Architectures and Photoluminescence of the Doped RE3+ Ions (RE = Sm, Eu, Tb, and Dy).

Abstract

Tartrate (Tar2-) was originally employed in this work as a chelating/structure-directing agent for hydrothermal crystallization of ZnWO4, where the decisive roles of Tar2-/Zn2+/WO42- molar ratio, solution pH (7-10), and the use of ethylene glycol (EG) cosolvent in phase/morphology evolution were deciphered in detail. It was unambiguously manifested that Tar2- may remarkably retard the intrinsically preferred [001] growth of ZnWO4, transform 1D nanorods to 0D nanoparticles and then to 2D platelets, and meanwhile induce face-to-face alignment of the platelets to form spheroidal, ellipsoidal and snowflakelike 3D architectures, where the 2D crystallites were revealed to develop via oriented attachment (colattice) of non-(00l) facets. A lower solution pH and excessive WO42- were clearly shown to enhance and offset the effect of Tar2-, which led to ellipsoidal assemblies of substantially larger 2D crystallites and suppressed 2D growth/3D assembly of ZnWO4 crystallites, respectively. With the spheroidal architectures for example, doping ZnWO4 with RE3+ yielded (Zn0.98RE0.02)WO4 phosphors (RE = Sm, Eu, Tb, and Dy, respectively) that show luminescence overlapped from the typical linelike and broad-band (∼350-700 nm) emissions of RE3+ and WO6, respectively. The luminescence color of the sample was found to drift away from the blue corner of the CIE chromaticity diagram with RE3+ doping and to be dependent on the type of RE3+.