Simultaneous oxidation of Mn2+ to Mn4+ by devitrification of transparent glassy Na2Ge4O9: Mn

Abstract

To generate red emissions, manganese (IV) ions have recently gained recognition as potent non-rare-earth activators. However, the oxide and fluoride hosts that offer suitable environments for Mn4+ require careful preparation, involving precise control of reaction parameters like redox equilibrium and temperature. In the current work, we show simultaneous oxidation of Mn2+ to Mn4+ by devitrification of glassy Na2Ge4O9: Mn under moderate atmospheric conditions and under the argon atmosphere. The G-sample was devitrified via thermal treatment after the parent glass, which shares the same chemical formula as dilithium tetragermanate (Na2Ge4O9), was created through the use of traditional melt-quenching (MQ). Optical spectroscopy and electron paramagnetic resonance (EPR) spectroscopic are utilized to confirm the Mn2+ oxidation to Mn4+ from glass stat to glass ceramic after thermal treatment. Due to the transition from Mn2+ to Mn4+, a sharp 668 nm emission peak is recorded whereas the red emission peaking at 611 nm monitored in glass is steadily reduced. The temperature-dependent PL spectra of the Na2Ge4O9:0.1Mn+4, red-emitting GC in the temperature range ∼295–490 K were recorded. The PL emission intensity decreases gradually with increasing the temperature. The technique showcased for producing Na2Ge4O9:Mn4+ phosphors could be expanded to synthesize other phosphors incorporating activators possessing a high oxidation state.