Structural analysis and luminescent study of thin film zinc germanate doped with manganese

Thin films of zinc germanate doped with manganese (Zn₂GeO₄:Mn) were fabricated by radio frequency magnetron sputtering, and their structural characteristics and luminescent properties were studied. The Zn₂GeO₄:Mn films exhibited a pronounced absorption edge at around 271 nm and a high optical transparency in the visible wavelength region with a peak transmittance of 0.927 at 691 nm. While the as-deposited Zn₂GeO₄:Mn films had an amorphous structure, the annealed films possessed a rhombohedral polycrystalline structure with a random crystallographic orientation of grains. The broad-band photoluminescence (PL) emission was observed from the annealed Zn₂GeO₄:Mn films. The PL emission spectrum showed a peak maximum at around 537 nm in the green range, which was accounted for by the intrashell transition of 3d⁵ orbital electrons from the ⁴T₁ lowest excitation state to the ⁶A₁ ground state in the divalent manganese ions. Two discrete peaks were observed in the PL excitation spectrum at 256 and 296 nm, which are considered to be associated with the band-to-band absorption of the host and the sub-band absorption from defect states, respectively. The green cathodoluminescence (CL) emission was obtained from the annealed Zn₂GeO₄:Mn films with a peak centered at around 534 nm, analogous to the PL emission spectrum.