Qin Guan-shi, Qin Wei-ping, Chen Bao-jiu, E Shu-lin, Ge Zhong-jiu, Ren Xin-guang, Huang Shi-hua
Changchun Institute of Optics, Fine Mechanics and Physics, Laboratory of Excited States Processes, Chinese Academy of Sciences, Changchun 130021, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2002 Oct;22(5):705-8.
In this paper, high efficiency and low threshold upconversion from IR to red is reported, for Er3+ and Tm3+ co-doped fluoride-oxide glass-ceramic under 978 nm LD excitation. The component of sample in experiment is 65GeO2-25NaF-8.5BaF2-1Er2O3-0.5 Tm2O3, and the prepared method is obtained. The upconversion emission spectra under 978 nm LD excitation is measured at room temperature. Analyzing it, we find that introduction of Tm3+ into Er3+ doped system preferentially quenches the green upconversion fluorescence from 4S3/2 level of Er3+ duo to the efficient cross-relaxation of 4I13/2-->4I15/2 (Er): 3H6-->3H4 (Tm) which can significantly reduce the upconversion efficiency from 4I13/2 level to the emitting 4S3/2 level, and the Tm3+ behaves as a good sensitizer of the red upconversion from the 4F9/2 level of Er3+ which is mainly populated by the cross-relaxation of 3H4-->3H6 (Tm): 4I11/2-->4F9/2 (Er). However, at low Er3+ concentration (2 mol%), it is impossible for strong red upconversion. X-ray analysis is done, there are lots of nanocrystallites in MFG glass-ceramic. So we think, this red upconversion is attributed to Er3+ enriched fluoride microcrystallites, which makes the cross-relaxation of 3H4-->3H6 (Tm): 4I11/2-->4F9/2 (Er) more effective, therefore their active optical properties may be optimised. In the end, the relationship between LD working current and intensity of upconversion luminescence is discussed, the results confirm that both red and green upconversion processes are consisted by two photons.
本文报道了在978 nm激光二极管激发下,铒离子(Er3+)和铥离子(Tm3+)共掺杂氟氧化物微晶玻璃实现了从红外到红光的高效低阈值上转换。实验中样品的成分为65GeO2 - 25NaF - 8.5BaF2 - 1Er2O3 - 0.5Tm2O3,并给出了制备方法。在室温下测量了978 nm激光二极管激发下的上转换发射光谱。通过分析发现,将Tm3+引入Er3+掺杂体系中,由于4I13/2→4I15/2(Er):3H6→3H4(Tm)的有效交叉弛豫,优先猝灭了Er3+的4S3/2能级发出的绿色上转换荧光,这会显著降低从4I13/2能级到发射4S3/2能级的上转换效率,并且Tm3+是Er3+从4F9/2能级进行红色上转换的良好敏化剂,该能级主要通过3H4→3H6(Tm):4I11/2→4F9/2(Er)的交叉弛豫进行填充。然而,在低Er3+浓度(2 mol%)下,无法实现强烈的红色上转换。进行了X射线分析,发现在微晶玻璃(MFG)中有大量纳米微晶。因此我们认为,这种红色上转换归因于富含Er3+的氟微晶,这使得3H4→3H6(Tm):4I11/2→4F9/2(Er)的交叉弛豫更有效,从而可以优化它们的有源光学性质。最后,讨论了激光二极管工作电流与上转换发光强度之间的关系,结果证实红色和绿色上转换过程均由双光子组成。