Blue emission in photoluminescence spectra of the red phosphor CaAlSiN3:Eu2+ at low Eu2+ concentration

Abstract

In red phosphor CaAlSiN3:Eu2+, unintentional blue emission occurs with increasing intensity at low Eu2+ concentrations and also at low measurement temperatures. Time-resolved photoluminescence measurements were used to confirm the decrease in red emission and increase in blue emission with the decreasing Eu2+ concentration. The peak timing of blue emission occurred faster than that of red emission, and long lasting luminescence of red emission was observed as well as that of blue emission. The Eu2+ concentration dependences of the red and blue emissions were similar to those of the g values 4.75 (Eu2+) and 2.0025 (nitrogen vacancies), respectively, which were observed from electron spin resonance (ESR) measurements. The origin of the blue emission is proposed to be nitrogen vacancy defects, which had about the same ESR signal intensity as that of Eu2+ ions in CaAlSiN3:Eu2+ containing 0.01 at. % Eu2+. The possibility of red emission also arising from excited electron tunneling or thermal pathways via nitrogen vacancies is discussed. Long lasting red emission was observed, which is proposed to involve trapped electrons remaining at nitrogen vacancies, yielding blue emission and inducing red emission from Eu2+ ions.