Ukrainian Journal of Physical Optics

Spectroscopy of Mn-Doped Glasses Of CaO-Ga₂O₃-GeO₂ System
^1,2Padlyak B., ¹Vlokh O., ³Kuklinski B., ⁴Sagoo K.

¹Institute of Physical Optics, 23 Dragomanov St., 79005 Lviv, Ukraine
²Department of Physics, Kazimierz Wielki University of Bydgoszcz, 11 Weyssenhoff Sq., 85072 Bydgoszcz, Poland
³Institute of Experimental Physics, University of Gda?sk, 57 Wita Stwosza St., 80952 Gdansk, Poland
⁴Jobin Yvon IBH Ltd., 45 Finnieston St., G3 8JU Glasgow, UK

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The EPR, UV and visible optical spectra of absorption, luminescence excitation and emission, as well as the luminescence kinetics of impurity Mn²⁺ centres in Mn-doped glasses of CaO-Ga₂O₃-GeO₂ system have been measured and analysed. The EPR spectra of as-synthesised Mn-doped glasses consist of three broad bands with the effective g-factors g_eff ~ 4.3, 3.0 and 2.0. The observed spectra have been attributed to both the isolated Mn²⁺ (3d⁵, ⁶S_5/2) ions occupying octahedral sites and revealing a broad distribution of crystal field parameters, as well as small clusters of Mn²⁺ ions. The optical spectroscopy has shown that the manganese impurity is incorporated into octahedral sites of CaO-Ga2O3-GeO2 glass network as both Mn²⁺ and Mn³⁺ ions. The intense broad absorption band with the maximum near 460 nm is related to the spin-allowed ⁵E_g --> ⁵T_2g transition of Mn³⁺ ions in trigonally distorted octahedral sites of CaO-Ga₂O₃-GeO₂ glass network. The weak spin-forbidden absorption lines of Mn²⁺ ions have not been observed against the background of a strong absorption band of Mn³⁺. The observed luminescence band with the maximum in the vicinity of 650 nm is explained by T_1g --> ⁶A_1g transition of Mn²⁺ ions occurring in trigonally distorted octahedral sites. The luminescence decay curve of Mn²⁺ could be satisfactorily described within two-exponent approximation. The two different lifetimes (t₁ = 12.4 ms and t₂ = 3.98 ms at l_exc = 300 nm) correspond to the two types of Mn²⁺ centres with different local environments. A possible local structure of different Mn²⁺ centres in CaO-Ga₂O₃-GeO₂ glass network is discussed.

Keywords: germanate glasses; manganese ions; electron paramagnetic resonance; optical absorption; photoluminescence; luminescence decay

PACS: 42.70.Ce, 71.55.Jv, 76.30.Fc, 78.40.Pg, 78.55.Hx
Ukr. J. Phys. Opt. 7 1-10 doi: 10.3116/16091833/7/1/1/2006
Received: 04.11.2005

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