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Enhanced photoluminescence from mixed-valence Eu-doped nanocrystalline silicate glass ceramics

Guojun Gao, Ning Da, Sindy Reibstein, and Lothar Wondraczek

Open Access Open Access

Abstract

Intense photoluminescence was observed from mixed-valence Eu-doped nanocrystalline BaAl2Si2O8/LaBO3 glass ceramics. For preparation in air, the ratio between Eu3+ and Eu2+ luminescence depends on synthesis temperature. XRD, TEM and IR absorption spectra were employed to characterize the crystallization process and structural properties of the precursor glass and corresponding glass ceramics. When annealed at 950 °C, the material exhibited photoluminescence more than ten times stronger than was found in its glassy state. Spectroscopic data indicate that during such a heat treatment, even in air, a significant part of the Eu3+ ions is reduced to Eu2+. Lifetime of the 5D0 state of Eu3+ increases with increasing heat treatment temperature. Eu3+ species are largely incorporated on La3+ sites in LaBO3 crystallites whereas Eu2+ locates on Ba2+ sites in the hexacelsian phase. A mechanism for the internal reduction of Eu3+ to Eu2+ is proposed. Spectroscopic properties of the material suggest application in additive luminescent light generation.

©2010 Optical Society of America

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Figures (7)
Fig. 1
Fig. 1 XRD pattern of as-made Eu-doped SABBL and corresponding samples after annealing at various temperatures (left). Right: Bright field image showing diffraction contrast of needle-shaped hexacelsian and globular LaBO3 crystallites. Inset: Corresponding diffraction pattern, resulting from contributions of several crystals with different orientation.

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Fig. 2
Fig. 2 FTIR absorption spectra of SABBL samples. In (A) the deconvolution of the spectrum of the as-made glass is shown. (B) shows spectra of samples after annealing at different temperatures.

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Fig. 3
Fig. 3 Eu3+-excitation (A) and emission (B) spectra of as-melted glass and SABBL samples after annealing at various temperatures. Inset of (B): Zoom at the spectral region of 500-570 nm.

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Fig. 4
Fig. 4 Asymmetry ratio of the emission intensities of Eu3+ transitions of 5D0→7F2 and 5D0→7F1 for as-melted as well as annealed (2h) SABBL samples for different annealing temperatures.

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Fig. 5
Fig. 5 Luminescence decay curve of Eu3+ emission resulting from 5D0→7F2 (A) and 5D0→7F1 (B) in as-melted Eu-doped SABBL and after annealing at various temperatures. Inset: Exponential plot of the same data, shown for clarity.

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Fig. 6
Fig. 6 Eu2+-excitation (A) and emission (B) spectra of as-melted glass and SABBL samples after annealing at various temperatures. Inset of (B): Zoom at the spectral region of 375-675 nm.

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Fig. 7
Fig. 7 Luminescence decay curve of Eu2+ emission from SABBL after annealing for 2 h at 950 °C. Inset: Exponential plot of the same data, shown for clarity.

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Equations (3)

Equations on this page are rendered with MathJax. Learn more.

3Ba 2 + + 2Eu 3 + → V ″ Ba + 2 [ Eu 3 + ] B a •
V ″ Ba → V × Ba + 2e
2 [ Eu 3 + ] B a • + 2e → 2 [ Eu 2 + ] B a •
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