Growth, Structures, and Properties of Li2Zn2(MoO4)3 and Co-doped Li2Zn2(MoO4)3

Abstract

On the basis of our previous work on the investigation of the subsolidus phase relation of the system ZnO- Li2O-MoO3, we for the first time successfully prepared single crystals of Li2Zn2(MoO4)3 (I) with dimensions up to 10 × 4 × 3 mm3 and Co-doped Li2Zn2(MoO4)3 (II) with a size of 15 × 10 × 3 mm3 by using the top-seeded solution growth method. The X-ray diffraction analysis shows that the Li+ cation and transition metal ion fill in the octahedral and trigonal prism interstice composed of surrounding MoO4 tetrahedrons. The UV−vis spectra show that by doping with Co2+, there is an obvious red shift of the absorption band at 276 nm with the steep absorption edge changing from 370 nm (I) to 430 nm (II). The band gaps of I and II calculated with CASTEP are ≪ 2.4 eV and ≪ 1.9 eV, respectively, indicating that Co2+ play roles in the change of the band gap of the host crystal. The X-ray powder analysis of the system Li2−2xZn2+x(MoO4)3 suggests the framework is stable over a range of composition for −0.1 ≤ x ≤ 0....