In-situ crystallization of CoCr2O4 in tellurite glass with enhanced optical nonlinear limiting, photoluminescence, and magnetic properties: Influence of Co content

Abstract

This article reports the in-situ growth of spinel CoCr2O4 nanocrystals (NC) in tellurite glass through tailoring the Co content by melt-quenching method. The microstructure, optical, and magnetic properties of NC/ glass systems were systematically studied using various techniques. Well-defined 30 nm crystallization of CoCr2O4 (space group of Fd3m) homogeneously distributed in the glassy matrix and the concurrent formation of cubic BiCoO3 (space group of P4mm) when the Co content exceeds 3%. The coexistence of multivalence and coordination states of Co and Cr significantly modified the glass structure with conversion of TeO4→TeO3, BO4→BO3, and CoO4→CoO6 units. Exceptional performance of the glass containing 5% Co-tuned CoCr2O4 was obtained, showcasing the decrease of Eg (2.09 eV), strong ferro-magnetization of 7.04 emu/g, large α3 (4.88×10−10 m/W) and good optical limiting property (threshhold of 1.31×1012 W/m2). Furthermore, the same glass showed excellent red emission between 650 and 800 nm under the excitation of 460 nm, with an increased lifetime (2.648 ms) and good stability of 90.7% within 25–300 °C. The emission mechanism was discussed. EPR analysis confirmed the active role and spin-states of magnetic Cr and Co ions, contributing synergistically to the improved optical and magnetic properties of the glasses.