Origin of saturated green emission from europium in zinc thiogallate

Abstract

Europium doped zinc thiogallate, ZnGa2S4:Eu2+, has been reported as a saturated green emitting phosphor, suitable as conversion phosphor in white LEDs for lighting or displays. Up to now, no direct proof for the incorporation of Eu2+ in ZnGa2S4 has been given. We combined X-ray diffraction (XRD), cathodoluminescence in electron microscopy (SEM-CL) and X-ray absorption spectroscopy (XAS) to study the incorporation of the europium ions in the host material. The previously reported green luminescence was found to originate from small amounts of unintentionally formed EuGa2S4, and not from europium ions incorporated into ZnGa2S4. EuGa2S4 has a low quantum efficiency (< 20%) and shows strong thermal quenching, already below room temperature. The XAS data analysis suggests that a certain amount of europium might occupy octahedral voids inside the zinc thiogallate lattice in a divalent state. The zinc ion next to these interstitial dopants is then removed for charge compensation. Notwithstanding the possible, but limited, incorporation of Eu2+ in ZnGa2S4, these ions do not activate any luminescence as was shown with SEM-CL.