Luminescence Characteristics of Green Grossular Garnets

Abstract

Some light green grossular garnets exhibit orange-red luminescence under long-wave and short-wave ultraviolet light. To characterize their luminescence behavior, we studied seven grossular garnets with typical colors ranging from light yellowish-green to intense green by using photoluminescence (PL), ultraviolet–visible (UV–Vis) spectroscopy, electron paramagnetic resonance (EPR), Electron Probe Microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In the PL spectra of these grossular garnets samples, a broad band exists at about 589 nm and three sharp peaks appear at 697, 702 and 716 nm. The three-dimensional fluorescence spectra reveal two luminescence emissions. They are (1) a broad band near 600 nm; and (2) a series of sharp peaks centered at 697, 702 and 716 nm. In the UV–Vis spectra, two prominent asymmetrical absorption bands near 430 and 605 nm are related to Cr3+ or Cr3+/V3+, and minor absorption peaks at 408 and 419/420 nm are related to Mn2+. EMPA and LA-ICP-MS analysis confirmed the existence of trace elements Ti, V, Cr and Mn. Furthermore, the EPR spectrum excluded the existence of V2+ and V4+ and confirmed the existence of Mn2+, Cr3+ and Fe3+. Regarding V, an interesting phenomenon was reported in which the intensity of luminescence could be suppressed in grossular garnets with higher concentrations of V. These results imply that chromium and manganese are the luminescence activators in grossular garnets, and vanadium is a powerful quencher.