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Ho3+/Yb3+共掺杂50SiO2-50PbF2玻璃陶瓷的上转换和中红外荧光特性

[Upconversion and mid-infrared fluorescence properties of Ho3+/Yb3+ co-doped 50SiO2-50PbF2 glass ceramic].

作者信息

Zhang Xiao-guang, Ren Guo-zhong, Yang Huai

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2014 Aug;34(8):2060-4.

Abstract

In the present paper, the upconversion and mid-infrared fluorescence properties of Ho3+/Yb3+ co-doped 50SiO2- 50PbF2 glass ceramic (GC) were studied. The GC has the following composition (in mol%): 50SiO2-50PbF2-1YbF3-0. 5HoF3. The mixtures of about 10 g were placed in a corundum crucible and melted at 1000 degrees C for 15 min in a SiC electric furnace in air and then poured on a brass plate. The GCs were obtained just by heat treatment at 450 degrees C. The X-ray diffraction pattern of the GC indicates that very small size crystals were precipitated in the precursor glass by heat treatment. The GCs have as high transmittance as glasses. The GCs have higher absorption cross section and narrower absorption peaks compared to the corresponding glasses, indicating that fluoride is doped with Ho ions. The Judd-Ofelt intensity parameters were determined from the absorption spectrum and Judd-Ofelt theory. The omega2 value is 0.17 x 10(-20) cm2 lower than that of fluoride glass ZBLA (2.28 x 10(-20) cm2), because of Ho3+ doping in PbF2 microcrystal. The intense green upconversion light was observed in Ho3+/Yb3+ co-doped 50SiO2-50PbF2 GCs excited by 980 nm laser diode. A main emission band centered around 540 nm (green), and three week emission bands centered around 420 nm(violet), 480 nm (blue), and 650 nm (red) which correspond to the Ho3+ : ((5)F4-->(5)I8) ((5)G-->(5)I8), ((8)K3--(5)I8) and ((5)F5-->(5)I8) transitions, respectively, were simultaneously observed in GCs. Compared with the glass sample, GCs have significantly intension in the green and blue upconversion fluorescence, and not significant change in the red upconversion fluorescence. Those changes are because that Ho ion in GCs locates in lower phonon energy environment than in glasses. Lower phonon energy can make the nonradiative relaxation rate reduce, which improves the green light upconversion efficiency, at the same time reduces the population of the intermediate energy level ((5)I7) of the red light radiation. The 2.9 microm mid-infrared light was observed in GC sample, but not in glass precursor excited by 980 nm laser diode.

摘要

在本文中,研究了Ho3+/Yb3+共掺杂的50SiO2-50PbF2玻璃陶瓷(GC)的上转换和中红外荧光特性。该玻璃陶瓷具有以下组成(摩尔百分比):50SiO2-50PbF2-1YbF3-0.5HoF3。将约10g的混合物置于刚玉坩埚中,在空气中的碳化硅电炉中于1000℃熔化15分钟,然后浇铸在黄铜板上。通过在450℃进行热处理即可获得玻璃陶瓷。玻璃陶瓷的X射线衍射图谱表明,通过热处理在前体玻璃中析出了非常小尺寸的晶体。玻璃陶瓷具有与玻璃一样高的透过率。与相应的玻璃相比,玻璃陶瓷具有更高的吸收截面和更窄的吸收峰,这表明氟化物中掺杂了Ho离子。根据吸收光谱和贾德-奥费尔特理论确定了贾德-奥费尔特强度参数。由于Ho3+掺杂在PbF2微晶中,ω2值比氟化物玻璃ZBLA(2.28×10-20cm2)的低0.17×10-20cm2。在980nm激光二极管激发的Ho3+/Yb3+共掺杂的50SiO2-50PbF2玻璃陶瓷中观察到强烈的绿色上转换光。在玻璃陶瓷中同时观察到一个以540nm(绿色)为中心的主发射带,以及三个以420nm(紫色)、480nm(蓝色)和650nm(红色)为中心的较弱发射带,它们分别对应于Ho3+的((5)F4-->(5)I8)、((5)G-->(5)I8)、((8)K3--(5)I8)和((5)F5-->(5)I8)跃迁。与玻璃样品相比,玻璃陶瓷在绿色和蓝色上转换荧光方面有显著增强,而在红色上转换荧光方面变化不明显。这些变化是因为玻璃陶瓷中的Ho离子所处的声子能量环境比玻璃中的低。较低的声子能量可使非辐射弛豫速率降低,这提高了绿色光的上转换效率,同时减少了红色光辐射的中间能级((5)I7)的粒子数。在玻璃陶瓷样品中观察到了2.9μm的中红外光,但在980nm激光二极管激发的玻璃前驱体中未观察到。

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