Elsevier

Materials Research Bulletin

Volume 73, January 2016, Pages 357-361
Materials Research Bulletin

Effect of Mn2+ ions on the enhancement red upconversion emission and energy transfer of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics

https://doi.org/10.1016/j.materresbull.2015.09.019Get rights and content

Highlights

  • Enhanced red UC emission of Mn–Tm–Yb co-doped glass-ceramics were prepared by Mn2+.

  • Ratio I698/I478 increases about ten-fold with increase of Mn2+ up to 4.0 mol.%.

  • Energy transfer between the Tm3+ ions and the Mn2+–Yb3+ dimer have been discussed.

  • Constitution of the ET Bridge between the Tm3+ and the Mn2+–Yb3+ dimer was proposed.

Abstract

The effects of Mn2+ ions on the enhancement red upconversion emission intensity of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics were investigated. The ratio I698nm/I478nm significantly increases about ten-fold with the increase of Mn2+ concentrations up to 4.0 mol.%. The red upconversion emission of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics is greatly enhanced, due to constitution of the energy transfer bridge. The upconversion mechanism, the energy transfer and back energy transfer processes between the (1G4  3H6), (3F2  3H6) transitions of Tm3+ ions and the ∣2F7/2, 4T1  2F7/2, 6A1〉 transitions of Mn2+–Yb3+ dimer were discussed.

Introduction

In the recent decades, the demand for development of novel rare-earth (RE) doped materials based on the infrared to visible frequency upconversion (UC) has been increased considerably, because of their potential applications such as multicolor display, energy solar cells, optoelectronic devices, etc. [1], [2], [3], [4], [5], [6], [7]. Among the RE ions, the Tm3+ ions is great interest because it exhibits strong fluorescence in the ultra-visible color regions [8], [9]. Furthermore, the efficiency UC of Tm3+ ions could be substantially improved, if appropriate sensitizer and energy transfer (ET) between the RE ions are implemented [10]. There has been a significant interest in the research due to the attractive emissions of Tm3+ ions in the visible and infrared regions [11], [12]. Recently, the ET processes between the Tm3+ ions and the RE ions have been also investigated, such as the ET processes between the Tm3+ ions with Ho3+, Er3+, Tb3+ and Yb3+ ions [13], [14], [15], [16]. And the effects of the metals transition on the enhancement UC emission intensity of Tm3+ ions have been studied [17], [18], [19]. However, the effect of Mn2+ ions on the enhancement red UC emission and the ET process between the Tm3+ ions and Mn2+–Yb3+ dimer in the glass-ceramics has not been reported up to now. On the other hand, the emission bands of Tm3+ ions are located in the range about 450–850 nm, corresponding to 1G4  3H6, 1G4  3F4, 3F2  3H6 and 3H4  3H6 transitions. While the bands of Mn2+ emission ions are located in the range about 460–700 nm [20]. Therefore, the possibility of the ET between the Tm3+ and Mn2+ ions is expected.

Based on the above considerations, in the present work, we mainly investigated the effect of Mn2+ ions on the enhancement red UC emission of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics. At the same time, the ET Bridge, UC mechanism and ET between the Mn2+–Yb3+ dimer and the Tm3+ ions were proposed.

Section snippets

Experimental

The glasses were prepared according to a conventional melt-quenching method. High purity SiO2, AlF3, TiO2, BaF2, LaF3, TmF3, MnCO3 and YbF3 were used as the starting materials. Compositions chosen in present study are presented in Table 1. The mixtures (about 10 g), which compacted into a platinum crucible, were set in an electric furnace. After holding at 1450 °C for 45 min under air atmosphere in an electric furnace, the melts were quenched by putting it onto a polished plate of stainless steel.

Results and discussion

The XRD patterns of STM-1 glass and glass-ceramics samples are shown in Fig. 1(a). From this figure, the prominent diffraction peak of Mn2+ is not observed in all four patterns. Moreover, the increase of XRD peaks is very small. These results may indicate that the Mn2+ ions are dispersed in to the glass matrix. The average of Ba2LaF7 crystallite size of the sample were about 15 nm, by using Scherrer’s formula [21]. At the same time, the X-ray photoelectron spectroscopy indicated the existence of

Conclusions

In this article, the effects of Mn2+ ions on the enhancement red UC emission of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics were successfully investigated. Compare with the precursor glass, the UC emission intensity of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics has significantly enhanced. The red UC emission intensity of Mn2+/Tm3+/Yb3+ tri-doped transparent glass-ceramics increases about thirteen-fold with the increase of the Mn2+ concentrations up to 4.0 mol.%. At the same

Acknowledgments

This work was supported by a grant from the National Natural Science Foundation of China (Nos. 51272097, 61265004, 61307111), the Nature and Science Fund from Yunnan Province Ministry of Education (No. 2011C13211708), Natural Science Foundation of Yunnan Province (2010ZC038), Postdoctoral Science Foundation of China (20110491759), Education Department Foundation of Yunnan Province (2011Y348) and Foundation of Yunnan province (2012FD009).

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