Effect of the SiO2/Na2O ratios on the structure and crystallization properties of photo-thermo-refractive glass

Abstract

Photo-thermo-refractive (PTR) glass is a type of functional optical glass material with multi-component and multivalent particles, which is a substrate material for volume Bragg gratings (VBGs) and widely used in high power laser, holography and other applications. Recording VBGs in PTR glass involves photo-thermo-induced crystallization (UV exposure and subsequent heat treatment), while spontaneous crystallization in the unexposed area is one of the important reasons for the light scattering loss of PTR glass, which can also lead to a decrease in the refractive index modulation and absolute diffraction efficiency of the prepared VBGs. In order to optimize spontaneous crystallization of PTR glass, we analyzed the effects of variations in the SiO2/Na2O ratio on the structure and crystallization behaviors of SiO2–Na2O–Al2O3–ZnO–NaF PTR glass using Raman spectroscopy, FTIR spectroscopy, DSC, XRD, and SEM. As the molar ratio (Rm) of SiO2/Na2O increases from 3.37 to 5.38, the polymerization of the silica network structure is significantly enhanced, the crystallization activation energy of original PTR glass increases from 93.52 kJ/mol to 285.23 kJ/mol, and the crystal growth index decreases from 3.57 to 1.49. In the isothermal crystallization process, we observed that increasing the SiO2/Na2O ratio significantly decreases the grain density and homogenizes the grain distribution of sodium fluoride (NaF) crystals under long-time crystallization conditions, which contributes to maintaining the high transmittance of the crystallized PTR glass in both visible and near-infrared regions.