Nanocrystallisation in oxyfluoride systems: mechanisms of crystallisation and photonic properties

Abstract

Rare earth (RE) doped oxyfluoride glass ceramics possess interesting optical properties with applications in telecommunications and optoelectronics, such as solid state lasers, optical amplifiers, etc. These materials combine the transparency and mechanical and chemical resistance of aluminosilicate glasses with the low phonon energy and facile incorporation of RE ions in the fluoride crystals. The incorporation of RE ions in the crystalline phases enhances the laser emission intensity, a major property of these materials. Transparency is achieved when crystal size is in the nanometric scale, usually below 40 nm, which avoids light scattering. A strict control of the nucleation and crystal growth processes is therefore necessary which requires a deep knowledge of the crystallisation mechanisms. The great activity and publications in this field in the last decades merit a review providing a comparative study of the different nanoglass ceramic systems, their structural and optical characterisation and their main properties and applications. This is the objective of this review paper which includes 227 references. A general discussion on glass nucleation and crystallisation theories and more relevant crystallisation parameters and characterisation techniques are put forward in the first section of the review, focused on nanocrystallisation processes in oxyfluoride systems. In the second section, the principal RE doped glass ceramics are presented. After a general introduction about the luminescence processes, including up- and down-conversion, the behaviour of RE elements in glasses and crystals are discussed. Glass ceramic compositions have been divided as follows: glass ceramics with a glass composition following Wang and Ohwaki’s oxyfluoride glass ceramic, and glass ceramics with different matrix compositions, arranged by crystalline phases. Relevant properties, mainly optical and laser, are described in each system along with the most relevant applications of these materials.

Keywords:

• Nanocrystallisation
• Glass ceramics
• Rare earth ions
• Luminescence
• Up-conversion
• Down-conversion

The authors acknowledge the financial support of Project INTERCONY, contract no. NMP4-CT-2006-033200 from the Sixth Framework of the European Union, as well as all members of the project for helpful discussions, the CSIC Incorporation Intramural Project 2007 60I002, and the project MAT 2010-20459. A. de Pablos-Martín is grateful to CSIC for a JAE contract.