Transparent Glass-Ceramics Produced by Sol-Gel: A Suitable Alternative for Photonic Materials

TLDR

Transparent glass‑ceramics, especially oxyfluoride compositions, exhibit attractive optical properties, and while melt‑quenching dominates production, sol‑gel synthesis has emerged as a viable alternative. This review surveys sol‑gel‑derived transparent glass‑ceramics, focusing on oxyfluoride systems, and outlines recent advances in synthesis and processing achieved by the authors. The authors examine sol‑gel fabrication of oxyfluoride glass‑ceramics, introduce a new SiO₂ precursor that lowers processing temperatures and removes hydroxyl groups, and detail methodological improvements over the past five years. Recent work has doubled the fluoride crystal fraction, produced the first NaGdF₄ glass‑ceramics, and demonstrated dopant‑induced crystal‑like spectra with higher efficiencies, confirming these materials as viable photonic alternatives.

Abstract

Transparent glass-ceramics have shown interesting optical properties for several photonic applications. In particular, compositions based on oxide glass matrices with fluoride crystals embedded inside, known as oxyfluoride glass-ceramics, have gained increasing interest in the last few decades. Melt-quenching is still the most used method to prepare these materials but sol-gel has been indicated as a suitable alternative. Many papers have been published since the end of the 1990s, when these materials were prepared by sol-gel for the first time, thus a review of the achievements obtained so far is necessary. In the first part of this paper, a review of transparent sol-gel glass-ceramics is made focusing mainly on oxyfluoride compositions. Many interesting optical results have been obtained but very little innovation of synthesis and processing is found with respect to pioneering papers published 20 years ago. In the second part we describe the improvements in synthesis and processing obtained by the authors during the last five years. The main achievements are the preparation of oxyfluoride glass-ceramics with a much higher fluoride crystal fraction, at least double that reported up to now, and the first synthesis of NaGdF4 glass-ceramics. Moreover, a new SiO2 precursor was introduced in the synthesis, allowing for a reduction in the treatment temperature and favoring hydroxyl group removal. Interesting optical properties demonstrated the incorporation of dopant ions in the fluoride crystals, thus obtaining crystal-like spectra along with higher efficiencies with respect to xerogels, and hence demonstrating that these materials are a suitable alternative for photonic applications.