Photonic properties of novel Yb³⁺ doped germanium-lead oxyfluoride glass-ceramics for laser cooling applications

Abstract

In recent years, our research group has developed and studied new rare-earth doped materials for the promising technology of solid-state laser cooling, which is based on anti-stokes fluorescence. To the best of our knowledge, our group is the only one in Canada leading the research into the properties of nanoparticles, glasses and glass-ceramics for optical refrigeration applications. In the present work, optical properties of 50GeO₂-30PbF₂-18PbO-2YbF₃ glass-ceramics for laser cooling are presented and discussed as a function of crystallization temperature. Spectroscopic results show that samples have near infrared photoluminescence emission due to the ²F_5/2 – ²F_7/2 Yb³⁺ transition, centered at ~1016 nm with an excitation wavelength of 920 nm or 1011 nm, and the highest photoluminescence emission efficiency occurs for heat-treatment for 5 h at 350°C. The internal photoluminescence quantum yield varies between 99% and 80%, depending on the temperature of heat-treatment, being the most efficient under 1011 nm excitation. The ²F_5/2 lifetime increases from 1.472 to 1.970 ms for heat treatments at 330°C to 350°C, respectively, due to energy trapping and the low phonon energy of the nanocrystals. The sample temperature dependence was measured with a fiber Bragg grating sensor, as a function of input pump laser wavelength and processing temperature. These measurements show that the heating process approaches near zero for an excitation wavelength between 1020 and 1030 nm, which is an indication that phonons are removed effectivelly from the glass-ceramic materials, and they can be used for optical laser cooling applications. On the other hand, the temperature increase as a function of input laser power into samples remains constant between 920 and 980 nm wavelength excitation, a temperature variation of 36 K/W (temperature of 58°C/W) was attained under excitation at 950 nm, showing a possible use for biomedical applications to be explored.

Keywords

optical refrigeration / oxyfluoride glass-ceramics / Yb³⁺ doping / quantum yield / infrared emission / lifetime

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Acknowledgements

The authors acknowledge the Natural Sciences and Engineering and Research Council (NSERC) of Canada’s Strategic grants program, NSERC’s Discovery Grants program, the Canadian Excellence Research Chair (CERC) in Photonic Innovations and the Government of Canada’s Canada Research Chairs program for the financial support. The authors are also grateful to the Fonds Québecois de la Recherche sur la Nature et les Technologies (FQRNT) for the financial support and the Canada Foundation for Innovation (CFI) for infrastructure support. Also, this research project is supported by Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Brazilian agency, providing to Lauro J. Q. Maia a scholarship (Bolsa de estudos) from Estágio Sênior Program, Process nº 88881.121134/2016-01.

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