The Crystallization Effect on the Optical Properties of Oxyfluoride Glass-Ceramics Containing CaF2 Nanocrystals Doped with Y3+ Ions

Document Type : Original Research Article


Department of Materials Science and Engineering, University of Tabriz, Tabriz, Iran


In the present study, the oxyfluoride glasses of SiO2-Al2O3-CaF2 system containing different amounts of Y3+ ions were prepared through the convenient melting method. The crystallization temperatures and size of the CaF2 nanocrystals were obtained from DTA curves and XRD patterns, respectively. As a consequence, the optimum amount of Y2O3 dopant (0.5wt%) and the suitable composition for basic glass were determined from the viewpoints of better crystallization behavior and higher transparency. The FTIR spectra approved the presence of oxyfluoride glass-ceramic structure in samples. The optical parameters (Fermi energy level, Urbach energy, direct and indirect band gaps) were calculated using UV-Vis spectra. The decreasing trend of Fermi energy level for glass-ceramic samples crystallized at higher temperatures is related to better semiconducting behavior. Urbach energy and optical band gap of the glass-ceramic samples were reduced due to the increment of the structural order and the emergence of dangling bonds, respectively.


Main Subjects

Fedorov, P.P., Luginina, A. A., Popov, A. I., “Transparent oxyfluoride glass ceramics”, Journal of Fluorine Chemistry, Vol. 172, (2015), 22-50.
Polosan, S., Secu, C. E., “Optical properties of CaF2:Eu3+ nanocrystals embedded in transparent oxyfluoride glass ceramic”, Journal of Optoelectronics and Advanced Materials, Vol. 10, No. 8, (2008), 2134-2137.
Beall, G. H., Duke, D. A., “Transparent glass-ceramics”, Journal of Materials Science, Vol. 4, (1969), 340-352.
Shinozaki, K., Honma, T., Oh-ishi, K., Komatsu, T., “Fluorine deficient layer at the surface of transparent glass-ceramics with CaF2 nanocrystals”, Journal of Physics and Chemistry of Solids, Vol. 73, (2012), 683-687.
Babu, P., Jang, K. H., Rao, C.S., Shi, L., Jayasankar, C.K., Lavín, V., Seo, H.J., “White light generation in Dy3+-doped oxyfluoride glass and transparent glass-ceramics containing CaF2 nanocrystals”, Optics express, Vol. 19, (2011), 1836-1841.
Qiao, X., Fan, X., Wang, J., Wang, M., “Luminescence behavior of Er3+ ions in glass–ceramics containing CaF2 nanocrystals”, Journal of Non-Crystalline Solids, Vol. 351, (2005), 357-363.
Kishi, Y., Tanabe, S., “Infrared-to-visible upconversion of rare-earth doped glass ceramics containing CaF2 crystals”, Journal of alloys and compounds, Vol. 408, (2006), 842-844.
Wang, Y., Ohwaki, J., “New transparent vitroceramics codoped with Er3+ and Yb3+ for efficient frequency upconversion”, Applied Physics Letters, Vol. 63, No. 24, (1993), 3268-3270.
Fedotovs, A., Antuzevics, A., Rogulis, U., Kemere, M., Ignatans, R., “Electron paramagnetic resonance and magnetic circular dichroism of Gd3 + ions in oxyfluoride glass-ceramics containing CaF2 nanocrystals”, Journal of Non-Crystalline Solids, Vol. 429, (2015), 118-121.
Liu, M., Zhao, L., Liu, Y., Lan, Z., Chang, L., Li, Y., Yu, H., “Role of heavy metal ions in the formation of oxyfluoride glasses and glass ceramics”, Journal of Materials Science & Technology, Vol. 30, No. 12, (2014), 1213-1216.
Imanieh, M. H., Eftekhari Yekta, B., Marghussian, V., Shakhesi, S., Martin, I. R., “Crystallization of nano calcium fluoride in CaF2-Al2O3-SiO2 system”, Solid State Sciences, Vol. 17, (2013), 76-82.
Dejneka, M. J., “The luminescence and structure of novel transparent oxyfluoride glass-ceramics”, Journal of Non-Crystalline Solids, Vol. 239, (1998), 149-155.
Fu, J., Parker, J. M., Flower, P. S., Brown, R. M., “Eu3+ ions and CaF2-containing transparent glass-ceramics”, Materials Research Bulletin, Vol. 37, (2002), 1843-1849.
Chen, D., Wang, Y., Ma, E., Yu, Y., Liu, F., “Partition, luminescence and energy transfer of Er3+/Yb3+ ions in oxyfluoride glass ceramic containing CaF2 nano-crystals”, Optical Materials, Vol. 29, (2007), 1693-1699.
Hu, Z., Wang, Y., Ma, E., Chen, D., Bao, F., “Microstructures and upconversion luminescence of Er3+ doped and Er3+/Yb3+ co-doped oxyfluoride glass ceramics”, Materials chemistry and physics, Vol. 101, (2007), 234-237.
Shakeri, M. S., Rezvani, M., “Optical band gap and spectroscopic study of lithium alumino silicate glass containing Y3+ ions”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 79, (2011), 1920-1925.
Singh, S., Kalia, G., Singh, K., “Effect of intermediate oxide (Y2O3) on thermal, structural and optical properties of lithium borosilicate glasses”, Journal of Molecular Structure, Vol. 1086, (2015), 239-245.
Kaur, G., Kumar, M., Arora, A., Pandey, O. P., Singh, K., “Influence of Y2O3 on structural and optical properties of SiO2-BaO-ZnO-xB2O3-(10-x) Y2O3 glasses and glass ceramics”, Journal of Non-Crystalline Solids, Vol. 357, (2011), 858-863.
Farahinia, L., Rezvani, M., “Optical property evaluation of oxyfluoride glasses doped with different amounts of Y3 + ions”, Journal of Non-Crystalline Solids, Vol. 425, (2015), 158-162.
Russel, C., “Nanocrystallization of CaF2 from Na2O/K2O/CaO/CaF2/Al2O3/SiO2 glasses”, Chem. Mater., Vol. 17, (2005), 5843-5847.
Mukherjee, D. P., Kumar Das, S., “Effects of nano silica on synthesis and properties of glass ceramics in SiO2-Al2O3-CaO-CaF2 glass system: A comparison,”, Journal of Non-Crystalline Solids, Vol. 368, (2013), 98-104.
Atalay, S., Adiguzel, H. I., Atalay, F., “Infrared absorption study of Fe2O3–CaO–SiO2 glass ceramics”, Materials Science and Engineering: A, Vol. 304, (2001), 796-799.
Groß, U., Rüdiger, S., Kemnitz, E., “Alkaline earth fluorides and their complexes: A sol-gel fluorination study”, Solid State Sciences, Vol. 9, (2007), 838-842.
Tahvildari, K., Ghammamy, Sh., Nabipour, H., “CaF2 nanoparticles: Synthesis and characterization”, International Journal of Nano Dimension, Vol. 2, (2012), 269-273
Hill, R., Wood, D. , Thomas, M., “Trimethylsilylation analysis of the silicate structure of fluoro-aluminosilicate glasses and the structural role of fluorine”, Journal of materials science, Vol. 34, (1999), 1767-1774.
Zhang, Y., Chen, D., “Multilayer integrated film bulk acoustic resonators”, Springer, Shanghai, (2013).
Faeghi Nia, A., “UV-Vis Absorption and Luminescence Spectrum of LAS: Tb3+/Gd3+ as a Laser Material”, International Journal of Engineering, Vol. 4, (2014), 609-614.
Sun, X., Gu, M., Huang, Sh., Jin, X., Liu, X., Liu, B., Ni, Ch., “Luminescence behavior of Tb3+ ions in transparent glass and glass- ceramics containing CaF2 nanocrystals”, Journal of Luminescence, Vol. 129, (2009), 773-777.
El-Diasty, F., Abdel Wahab, F. A., Abdel- Baki, M., “Optical band gap studies on lithium aluminum silicate glasses doped with Cr3+ ions”, Journal of applied physics, Vol. 100, (2006), 093511.
Khashan, M. A., El-Naggar, A. M., “A new method of finding the optical constants of a solid from the reflectance and transmittance spectrograms of its slab”, Optics Communications, Vol. 174, (2000), 445–453.
El-Kameesy, S. U., Eissa, H. M., Eman, S. A., El-Gamma, Y. A., “Fast Neutron Irradiation Effect on Some Optical Properties of Lead Borate Glass Doped with Samarium Oxide”, Egyptian Journal of Basic and Applied Sciences, Vol. 49, (2011), 67-70.
Mott, N. F., Davis, E. A., “Electronic processes in nanocrystalline materials”, Oxford university press, (2012).
Dwivedi, D. K., Pathak, H. P., Shukla, N., Kumar, A., “Effect of thermal annealing on structure and the optical band gap of amorphous Se 75-x Te 25 Sb x thin films by vacuum evaporation technique.”, Journal of Ovonic Research, Vol. 10, (2014), 15-22.
Hasegawa, S., Kitagawa, M., “Effects of annealing on localized states in amorphous Ge films”, Solid State Communications, Vol. 27, (1978), 855-858.
Rani, S., Sanghi, S., Agarwal, A., Seth, V. P., “Study of optical band gap and FTIR spectroscopy of Li2O.Bi2O3.P2O5 glasses”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 74, (2009), 673-677.
Babanejad, S. A., Ashrafi, F., Salarzadeh, N., Ashrafi, E., “Study the Optical properties of Amorphous Structure (Glassy) of B2O3-CdO Binary System”, Advances in Applied Science Research, Vol. 3, (2012), 743-748.
Al-Ghamdi,A. A., Khan, Sh. A., “Laser-induced changes on optical band gap of amorphous and crystallized thin films of Se75S25-xAGx”, Physica B: Condensed Matter, Vol. 404, (2009), 4262-4266.
Subrahmanyam, K., Salagram, M., “Optical band gap studies on (55-x)Na2O-xPbO-45P2O5 (SLP) glass system”, Optical Materials, Vol. 15, (2000), 181-186.