Upconversion and Mid-Infrared Fluorescence Properties of Ho3+/Yb3+ Co-Doped 50SiO2-50PbF2 Glass Ceramic
ZHANG Xiao-guang1，2, REN Guo-zhong2，3, YANG Huai4
1. Department of Materials Physics and Chemistry, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China 2. Science and Technology on Electro-Optical Information Securiety Control Laboratory, Sanhe 065201, China 3. Key Laboratory of Low Dimensional Materials & Application Technology, Xiangtan University, Xiangtan 411105, China 4. Department of Advanced Materials and Nanotechnology, College of Engieering of Peking University, Beijing 100871, China
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 1 000 ℃ 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 ℃. 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 Ω2 value is 0.17×10-20 cm2 lower than that of fluoride glass ZBLA (2.28×10-20 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+: (5F4→5I8), (5G6→5I8), (8K3→5I8) and (5F5→5I8) 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 (5I7) of the red light radiation. The 2.9 μm mid-infrared light was observed in GC sample, but not in glass precursor excited by 980 nm laser diode.
[1] Wang Yuhu，Junichi Ohwaki. Appl. Phys. Lett., 1993, 63(24), 3268. [2] Qiao X S, Fan X P, Xue Z, et al. J. Alloys Compounds, 2011, 509(14)： 4714. [3] Georgescu S, Voiculescu A M, Matei C, et al. J. Luminescence, 2013, 143： 150. [4] Sontakke A D，Annapurna K. J. Appl. Phys., 2012, 112(1): 013510. [5] Driesen K, Tikhomirov V K, G?rller-Walrand C, et al. Appl. Phys. Lett.，2006, 88(7)： 073111. [6] Lahoz F, Martin I R, Briones A. J. Appl. Phys., 2004, 95(6)： 2957. [7] Judd B R. Phys. Rev., 1962, 127(3): 750. [8] Ofelt G S. J. Chem. Phys., 1962, 37(3): 511. [9] Carnall W T, Fields P R, Rajnak K. J. Chem. Phys., 1968, 49(10)： 4424. [10] Tanimura K, Shinn M D, Sibley W A, et al. Phys. Rev. B, 1984, 30(5): 2429.
