Thermal and luminescent properties of 2 μm emission in thulium-sensitized holmium-doped silicate-germanate glass
In this paper, we present the luminescent properties of Tm3+∕Ho3+ co-doped new glass. A series of silicategermanate glass was prepared by the conventional melt-quenching method. In the Tm3+∕Ho3+ co-doped silicategermanate glass, a strong emission of 2 μm originating from the Ho3+:5I7 → 5I8 transition can be observed under conventional 808 nm pumping. The characteristic temperatures, structure, and absorption spectra have been measured. The radiative properties of Ho33+ in the prepared glass were calculated. The emission cross section of Ho33+ ions transition can reach 4.78 × 10?21 cm2 around 2 μm, and the FWHM is as high as 153 nm. The energy transfer efficiency between Ho3+ and Tm3+ has a large value (52%), which indicates the Tm3+∕Ho3+ co-doped silicategermanate glass is a suitable candidate for the 2 μm laser. Moreover, the energy transfer mechanism between Tm3+ and Ho3+ ions was investigated.(61370049, 61308090, 61405182, 51172252, 51372235, 51472225); International Science & Technology Cooperation Program of China (2013DFE63070); Public TechnicalInternational Cooperation Project of the Science Technology Department of Zhejiang Province (2015c340009).
基金项目：Natural Science Foundation of Zhejiang Province of China (LY15E020009, LY13F050003, LR14E020003); National Natural Science Foundation of China (NSFC)
Ying Tian：Institute of Optoelectronic Technology, China Jiliang University, Hangzhou 310018, China
Bingpeng Li：College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China
Xufeng Jing：Institute of Optoelectronic Technology, China Jiliang University, Hangzhou 310018, China
Junjie Zhang：College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China
Shiqing Xu：College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, Chinaemail:email@example.com
Hellmut Eckert：Institut für Physikalische Chemie, WWU Münster, Corrensstra?e 30, D 48149 Münster, Germany
Xianghua Zhang：Laboratory of Glasses and Ceramics, UMR 6226 CNRS-University of Rennes Cedex 135042, France
【1】B. Richards, A. Jha, Y. Tsang, and W. Sibbett, “Tellurite glass lasers operating close to 2 μm,” Laser Phys. Lett. 7, 177–193 (2010).
【2】G. J. Koch, M. Petros, J. Yu, and U. N. Singh, “Precise wavelength control of a single-frequency pulsed Ho:Tm:YLF laser,” Appl. Opt. 41, 1718–1721 (2002).
【3】K. Scholle, E. Heumann, and G. Huber, “Single mode tm and Tm, Ho: LuAG lasers for LIDAR applications,” Laser Phys. Lett. 1, 285–290 (2004).
【4】R. Cao, M. Peng, L. Wondraczek, and J. Qiu, “Superbroad nearto-mid-infrared luminescence from Bi5 3+ in Bi5(AlCl4)3,” Opt. Express 20, 2562–2571 (2012).
【5】S. Li, P. Wang, H. Xia, J. Peng, L. Tang, Y. Zhang, and H. Jiang, “Tm3+ and Nd3+ singly doped LiYF4 single crystals with 3–5 μm mid-infrared luminescence,” Chin. Opt. Lett. 12, 021601 (2014).
【6】A. Hemming, S. Bennetts, N. Simakov, A. Davidson, J. Haub, and A. Carter, “High power operation of cladding pumped holmiumdoped silica fiber lasers,” Opt. Express 21, 4560–4566 (2013).
【7】C. Liu, C. Ye, Z. Luo, H. Cheng, D. Wu, Y. Zheng, Z. Liu, and B. Qu, “High-energy passively Q-switched 2 μm Tm3+-doped double-clad fiber laser using graphene-oxide–deposited fiber taper,” Opt. Express 21, 204–209 (2013).
【8】L. Yi, M. Wang, S. Feng, Y. Chen, G. Wang, L. Hu, and J. Zhang, “Emission properties of Ho3+: 5I7 → 5I8 transition sensitized by Er3+ and Yb3+ in fluorophosphates glasses,” Opt. Mater. 31, 1586–1590 (2009).
【9】B. S. Yong, H. T. Lim, Y. G. Choi, Y. S. Kim, and J. Heo, “2.0 μm emission properties and energy transfer between Ho3+ and Tm3+ in PbO-Bi2O3-Ga2O3 glasses,” J. Am. Ceram. Soc. 83, 787–791 (2000).
【10】Y. Ju, W. Liu, B. Yao, T. Dai, J. Wu, J. Yuan, J. Wang, X. Duan, and Y. Wang, “Diode-pumped tunable single-longitudinal-mode Tm, Ho:YAG twisted-mode laser,” Chin. Opt. Lett. 13, 111403 (2015).
【11】G. Gao, L. Hu, H. Fan, G. Wang, K. Li, S. Feng, S. Fan, H. Chen, J. Pan, and J. Zhang, “Investigation of 2.0 μm emission in Tm3+ and Ho3+ co-doped TeO2-ZnO-Bi2O3 glasses,” Opt. Mater. 32, 402–405 (2009).
【12】G. Gao, L. Hu, H. Fan, G. Wang, K. Li, S. Feng, S. Fan, H. Chen, J. Pan, and J. Zhang, “Investigation of 2.0 μm emission in Tm3+ and Ho3+ co-doped TeO2-ZnO-Bi2O3 glasses,” Opt. Mater. 32, 402–405 (2009).
【13】L. Kong, G. Xie, P. Yuan, L. Qian, S. Wang, H. Yu, and H. Zhang, “Passive Q-switching and Q-switched mode-locking operations of 2 μm Tm:CLNGG laser with MoS2 saturable absorber mirror,” Photo. Res. 3, A47–A50 (2015).
【14】W. Zhang, L. Rong, J. Ren, Y. Jia, and S. Qian, “Judd-Ofelt analysis and mid-infrared emission properties of Ho3+-Yb3+ co-doped tellurite oxy-halide glasses,” Proc. SPIE 8906, 89060 (2013).
【15】G. Chen, Q. Zhang, G. Yang, and Z. Jiang, “Mid-infrared emission characteristic and energy transfer of Ho3+-doped tellurite glass sensitized by Tm3+,” J. Fluoresc. 17, 301–307 (2007).
【16】S. D. Jackson, “The effects of energy transfer upconversion on the performance of Tm3+/Ho3+-doped silica fiber lasers,” IEEE Photon. Technol. Lett. 18, 1885–1887 (2006).
【17】Q. Zhang, J. Ding, Y. Shen, G. Zhang, G. Lin, J. Qiu, and D. Chen, “Infrared emission properties and energy transfer between Tm3+ and Ho3+ in lanthanum aluminum germanate glasses,” J. Opt. Soc. Am. B 27, 975–980 (2010).
【18】T. Wei, C. Tian, M. Z. Cai, Y. Tian, X. F. Jing, J. J. Zhang, and S. Q.Xu, “Broadband 2 μm fluorescence and energy transfer evaluation in Ho3+/Er3+ codoped germanosilicate glass,” J. Quant. Spectrosc. Radiat. Transfer 161, 95–104 (2015).
【19】W. Fan, L. Htein, B. H. Kim, P. R. Watekar, and W. T. Han, “Upconversion luminescence in bismuth-doped germanesilicate glass optical fiber,” Opt. Laser Technol. 54, 376–379 (2013).
【20】M. Li, G. Bai, Y. Guo, L. Hu, and J. Zhang, “Investigation on Tm3+-doped silicate glass for 1.8 μm emission,” J. Lumin. 132, 1830–1835 (2012).
【21】S. S. Bayya, G. D. Chin, J. S. Sanghera, and I. D. Aggarwal, “Germanate glass as a window for high energy laser systems,” Opt. Express 14, 11687–11693 (2006).
【22】Z. Yang, S. Xu, L. Hu, and Z. Jiang, “Thermal analysis and optical transition of Yb3+, Er3+ co-doped lead-germanium-tellurite glasses,” J. Mater. Res. 19, 1630–1637 (2004).
【23】D. Dorosz, “Rare earth ions doped aluminosilicate and phosphate double clad optical fibres,” Bull. Polish Acad. Sci. 56, 103–111 (2008).
【24】G. Bai, L. Tao, K. Li, L. Hu, and Y. H. Tsang, “Enhanced light emission near 2.7 μm from Er-Nd co-doped germanate glass,” Opt. Mater. 35, 1247–1250 (2013).
【25】T. Xue, L. Zhang, L. Wen, M. Liao, and L. Hu, “Er3+ doped fluorogallate glass for mid-infrared applications,” Chin. Opt. Lett. 13, 081602 (2015).
【26】R. Xu, Y. Tian, L. Hu, and J. Zhang, “Broadband 2 μm emission and energy-transfer properties of thulium-doped oxyfluoride germanate glass fiber,” Appl. Phys. B 104, 839–844 (2011).
【27】A. Hruby, “Evaluation of glass-forming tendency by means of DTA,” J. Phys. B 22, 1187–1193 (1972).
【28】M. G. Drexhage, O. H. EI Bayoumi, and C. T. Moyniyan, “Preparation and properties of heavy-metal fluoride glasses containing ytterbium or lutetium,” J. Am. Ceram. Soc. 65, c168–c171 (1982).
【29】Y. Messaddeq and M. Poulain, “Stabilizing effect of aluminium, yttrium and zirconium in divalent fluoride glasses,” J. Non-Cryst. Solids 140, 41–46 (1992).
【30】F. Huang, X. Liu, W. Li, L. Hu, and D. Chen, “Energy transfer mechanism in Er3+ doped fluoride glass sensitized by Tm3+ or Ho3+ for 2.7 μm emission,” Chin. Opt. Lett. 12, 051601 (2014).
【31】K. Fukumi and S. Sakka, “Coordination state of Nb5+ ions in silicate and gallate glasses as studied by Raman spectroscopy,” J. Mater. Sci. 23, 2819–2823 (1988).
【32】A. Aronne, V. N. Sigaev, B. Champagnon, E. Fanelli, V. Califano, L. Z. Usmanova, and P. Pernice, “The origin of nanostructuring in potassium niobiosilicate glasses by Raman and FTIR spectroscopy,” J. Non-Cryst. Solids 351, 3610–3618 (2005).
【33】H. Verweij, “Raman study of the structure of alkali germanosilicate glasses, Lithium, sodium and potassium digermanosilicate glasses,” J. Non-Cryst. Solids 33, 55–69 (1979).
【34】Z. Yang, S. Xu, L. Hu, and Z. Jiang, “Density of Na2O-(3-x)SiO2-xGeO2 glasses related to structure,” Mater. Res. Bull. 39, 217–222 (2004).
【35】R. Xu, Y. Tian, L. Hu, and J. Zhang, “Structural origin and energy transfer processes of 1.8 μm emission in Tm3+ doped germanate glasses,” J. Phys. Chem. A. 115, 6488–6492 (2011).
【36】G. S. Henderson, D. R. Neuville, B. Cochain, and L. Cormier, “The structure of GeO2-SiO2 glasses and melts: A Raman spectroscopy study,” J. Non-Cryst. Solids 355, 468–474 (2009).
【37】E. V. Kolobkova, “Raman-spectroscopy study of the structure of niobium germanate glasses,” Soviet J. Glass Phys. Chem. 13, 176–181 (1988).
【38】K. Awazu and H. Kawazoe, “Strained Si-O–Si bonds in amorphous SiO2 materials: A family member of active centers in radio, photo, and chemical responses,” J. Appl. Phys. 94, 6243–6262 (2003).
【39】B. Judd, “Optical absorption intensities of rare-earth ions,” Phys. Rev. 127, 750–761 (1962).
【40】G. Ofelt, “Intensities of crystal spectra of rare-earth ions,” J. Chem. Phys. 37, 511–520 (1962).
【41】E. Rukmini and C. K. Jayasankar, “Spectroscopic properties of Ho3+ ion in zinc borosulphate glasses and comparative energy level analyses of Ho3+ ion in various glasses,” Opt. Mater. 4, 529–546 (1995).
【42】B. Peng and T. Lzumitani, “Optical properties, fluorescence mechanisms and energy transfer in Tm3+, Ho3+ and Tm3+-Ho3+ doped near-infrared laser glasses, sensitized by Yb3+,” Opt. Mater. 4, 797–810 (1995).
【43】K. Binnemans, R. Deun, C. Walrand, and J. Adam, “Spectroscopic properties of trivalent lanthanide ions in fluorophosphates glasses,” J. Non-Cryst. Solids 238, 11–29 (1998).
【44】X. Li, X. Liu, L. Zhang, L. Hu, and J. Zhang, “Emission enhancement in Er3+/Pr3+-codoped germanate glasses and their use as a 2.7 μm laser material,” Chin. Opt. Lett. 11, 121601 (2013).
【45】M. Li, X. Liu, Y. Guo, L. Hu, and J. Zhang, “Energy transfer characteristics of silicate glass doped with Er3+, Tm3+, and Ho3+ for 2 μm emission,” J. Appl. Phys. 114, 243501 (2013).
【46】M. Wang, L. Yi, G. Wang, L. Hu, and J. Zhang, “Emission performance in Ho3+ doped fluorophosphates glasses sensitized with Er3+ and Tm3+ under 800 nm excitation,” Solid State Commun. 149, 1216–1220 (2009).
【47】D. E. McCumber, “Einstein relations connecting broadband emission and absorption spectra,” Phys. Rev. 136, A954–A957 (1964).
【48】X. Zou and H. Toratani, “Spectroscopic properties and energy transfer in Tm3+ singly-and Tm3+/Ho3+ doubly-doped glasses,” J. Non-Cryst. Solids 195, 113–124 (1996).
【49】R. Xu, M. Wang, Y. Tian, L. Hu, and J. Zhang, “2.05 μm emission properties and energy transfer mechanism of germanate glass doped with Ho3+, Tm3+, and Er3+,” J. Appl. Phys. 109, 053503 (2011).
【50】J. Ding, G. Zhao, Y. Tian, W. Chen, and L. Hu, “Bismuth silicate glass: a new choice for 2 μm fiber lasers,” Opt. Mater. 35, 85–88 (2012).
【51】Z. Yang, S. Xu, L. Hu, and Z. Jiang, “Thermal analysis and optical properties of Yb3+/Er3+codoped oxyfluoride germanate glasses,” J. Opt. Soc. Am. B 21, 951–957 (2004).
【52】D. Shi, Q. Zhang, G. Yang, and Z. Jiang, “Spectroscopic properties and energy transfer in Ga2O3-Bi2O3-PbO-GeO2 glasses codoped with Tm3+ and Ho3+,” J. Non-Cryst. Solids 353, 1508–1514 (2007).
【53】K. Li, Q. Zhang, S. Fan, L. Zhang, J. Zhang, and L. Hu, “Midinfrared luminescence and energy transfer characteristics of Ho3+/Yb3+codoped lanthanum-tungsten-tellurite glasses,” Opt. Mater. 33, 31–35 (2010).
【54】A. Braud, S. Girard, J. L. Doualan, M. Thuau, and R. Moncorgé, “Energy-transfer processes in Yb:Tm-doped KY3F10, LiYF4, and BaY2F8 single crystals for laser operation at 1.5 and 2.3 μm,” Phys. Rev. B. 61, 5280–5292 (2000).
【55】L. M. Fortes, L. F. Santos, M. C. Goncalves, R. M. Almeida, M. Mattarelli, M. Montagna, A. Chiasera, M. Ferrari, A. Monteil, S. Chaussedent, and G. C. Righini, “Er3+ ion dispersion in tellurite oxychloride glasses,” Opt. Mater. 29, 503–509 (2007).
Rong Chen, Ying Tian, Bingpeng Li, Xufeng Jing, Junjie Zhang, Shiqing Xu, Hellmut Eckert, and Xianghua Zhang, "Thermal and luminescent properties of 2 μm emission in thulium-sensitized holmium-doped silicate-germanate glass," Photonics Research 4(6), 214-221 (2016)