Abstract
The EPR and luminescence spectra of fluorozirconate and fluorochlorozirconate glasses doped with various manganese compounds were studied to determine the oxidation state of manganese ions and the structure of their distribution. The luminescence spectra of both the fluorozirconate and the fluorochlorozirconate glasses showed the presence of only Mn2+ ions due to the 4T1(G) → 6A1 transition, regardless of the oxidation state of the manganese ions in the initial dopant compound. In the fluorozirconate glasses, Mn2+ ions have a green emission band at 550 nm, which is shifted to the red region to 615 nm after the substitution of chlorine for a part of the fluorine in the glass. The ratio of the content of free manganese ions to the content of ions in clusters in the synthesized glasses was investigated. It was determined that manganese ions in the glasses are mainly aggregated to form clusters, and an increase in the activator concentration leads to a decrease of the fraction of free ions. The differences in luminescence and EPR spectra between the fluorozirconate and fluorochlorozirconate glasses are explained by a change in the structure of the local environment of the manganese ions.
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REFERENCES
M. A. Noginov and G. D. Loutts, J. Opt. Soc. Am. B: Opt. Phys. 16, 3 (1999). https://doi.org/10.1364/JOSAB.16.000003
G. B. Loutts, M. Warren, L. Taylor, et al., Phys. Rev. B: Condens. Matter. 57, 3706 (1998). https://doi.org/10.1103/PhysRevB.57.3706
Z. Zhou, N. Zhou, M. Xia, et al., J. Mater. Chem. C 4, 9143 (2016). https://doi.org/10.1039/C6TC02496C
Y.-C. Lin, M. Karlsson, and M. Bettinelli, Top. Curr. Chem. 374, 21 (2016). https://doi.org/10.1007/s41061-016-0023-5
S. Adachi, J. Lumin. 197, 119 (2018). https://doi.org/10.1016/j.jlumin.2018.01.016
R. Hoshino, T. Nakamura, and S. Adachi, J. Solid State Sci. Technol. 5, R37 (2016). https://doi.org/10.1149/2.0151603jss
D. Chen, Y. Zhou, and J. Zhong, RSC Adv. 6, 86285 (2016). https://doi.org/10.1039/C6RA19584A
A. G. Paulusz, J. Electrochem. Soc. 120, 942 (1973). https://doi.org/10.1149/1.2403605
Y. K. Xu and S. Adachi, J. Appl. Phys. 105, 013525 (2009). https://doi.org/10.1063/1.3056375
D. T. Sviridov, R. K. Sviridova, and Yu. F. Smirnov, Optical Spectra of Transition Metal Ions in Crystals (Nauka, Moscow, 1976) [in Russian].
A. E. Nosenko, R. Leshchuk, and B. V. Padlyak, Radiat. Eff. Defects Solids 135, 55 (1995). https://doi.org/10.1080/10420159508229805
Q. Zhou, L. Dolgov, A. M. Srivastava, et al., J. Mater. Chem. C 6, 2652 (2018). https://doi.org/10.1039/C8TC00251G
R. R. Rakhimov, A. L. Wilkerson, G. B. Loutts, et al., Solid State Commun. 108, 549 (1998). https://doi.org/10.1016/S0038-1098(98)00403-7
H. Ohno, Phys. B (Amsterdam, Neth.) 376–377, 19 (2006). https://doi.org/10.1016/j.physb.2005.12.007
A. H. Macdonald, P. Schiffer, and N. Samarth, Nat. Mater. 4, 195 (2005). https://doi.org/10.1038/nmat1325
M. A. Zykin, T. G. Aminov, V. V. Minin, and N. N. Efimov, Russ. J. Inorg. Chem. 66, 113 (2021). https://doi.org/10.1134/S0036023621010137
R. Verstraete, H. F. Sijbom, K. Korthout, et al., J. Mater. Chem. C 5, 10761 (2017). https://doi.org/10.1039/C7TC02992F
Y. Tanabe and S. J. Sugano, Phys. Soc. Jpn. 9, 776 (1954). https://doi.org/10.1143/JPSJ.9.766
M. A. Buñuel, R. Alcalá, and R. Cases, J. Phys.: Condens. Matter 10, 9343 (1998). https://doi.org/10.1088/0953-8984/10/41/016
S. Kh. Batygov, M. N. Brekhovskikh, L. V. Moiseeva, et al., Inorg. Mater. 55, 1185 (2019). https://doi.org/10.1134/S0020168519110025
S. Adachi, ECS J. Solid State Sci. Technol. 9, 016001 (2020). https://doi.org/10.1149/2.0022001JSS
J. Li, J. Yan, D. Wen, et al., J. Mater. Chem. C 4, 8611 (2016). https://doi.org/10.1039/C6TC02695H
M. N. Brekhovskikh, S. Kh. Batygov, V. N. Makhov, et al., Phys. Status Solidi B 257, 1900457 (2020). https://doi.org/10.1002/pssb.201900457
Kerrington A. and E. McLachlan, Introduction to Magnetic Resonance with Applications to Chemistry and Chemical Physics (Harper and Row, New York, 1967).
E. I. Abdrashitova and G. T. Petrovskii, Dokl. AN SSSR 180, 166 (1968).
ACKNOWLEDGMENTS
The studies in this work were made using the equipment of the Center for Shared Use of Physical Investigation Methods, Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia; Prokhorov General Physics Institute, Russian Academy of Sciences, Moscow, Russia; Lebedev Physical Institute, Russian Academy of Sciences, Moscow, Russia; and Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia.
Funding
This work was supported by the Russian Science Foundation (project no. 18-13-00407).
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Batygov, S.K., Brekhovskikh, M.N., Moiseeva, L.V. et al. Optical and EPR Spectroscopy of Manganese Ions in Fluorozirconate Glasses. Russ. J. Inorg. Chem. 66, 1577–1582 (2021). https://doi.org/10.1134/S0036023621100028
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DOI: https://doi.org/10.1134/S0036023621100028