Tm，Ho：BaY_2F_8晶体生长及性能研究
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摘要
Tm,Ho:BaY2F8激光晶体是一种新型的近红外激光晶体材料,通过激发能够发射出2μmm的激光。2μm激光具有传输性能好,易被生物组织吸收,对人眼无害等优点,现在被广泛应用于军事,医疗,生物等各种领域。运用Tm,Ho:BaY2F8激光晶体的上转换特性,可以实现激光的上转换输出。
本文介绍了Tm,Ho:BaY2F8激光晶体从多晶料到晶体的合成及生长。利用XRD,TG-DSC,荧光光谱及扫描电子显微分析等手段研究了多晶料及晶体的结构和性能。
通过XRD分析得出,采用高温固相法在最佳温度960℃下合成的Tm,Ho:BaY2F8多晶料,晶粒尺寸范围为200—550nm,结晶度为76.88%；并发现运用双坩埚进行实验能够提高合成的多晶料的质量。
采用提拉法生长出来了5%Tm,0.5%Ho:BaY2F8晶体,并对晶体进行了XRD、吸收和激发光谱分析。光谱分析结果表明：Tm,Ho:BaY2F8晶体在700到850nm范围内的吸收峰对应Tm3+离子的3H6→3H4能级跃迁；晶体在1400nm到2100nm范围内的吸收峰对应Tm3+离子的3H6→3F4能级跃迁和Ho3+离子的5I8→5I7能级跃迁；运用780nm激光激发晶体能够得到波长为2.056μm的近红外激光。
运用水热法成功的生长出了Tm,Ho:BaY2F8纳米晶。通过XRD光谱分析得出了最佳的工艺参数；通过扫描电子显微分析对生长出的晶体进行了形貌结构分析；通过荧光光谱分析得出掺杂浓度为5%Tm3+和0.5%Ho3+的Tm,Ho:BaY2F8(？)内米晶的上转换效率最高。
Tm,Ho:BaY2Fg laser crystal is a new type of near-infrared laser crystal materials, which is excited to be obtained 2um laser.2μm laser have a lot of advantages, such as good transmission performance, easyly be absorbed by biological tissue, Human eye harmless and so on. Now it has been widely used in the military, medicine, biology etc. The upconversion performance of Tm,Ho;BaY2F8 laser crystal can realize laser upconversion output.
In the paper, it is introduced that the Tm,Ho:BaY2F8 polycrystalline material had be obtained and Tm,Ho:BaY2F8 laser crystal had be grown. XRD, TG-DSC, fluorescent spectroscopy and Field emission scanning electron microscopy have been used to study structure and spectral properties of polycrystalline material and crystal.
The XRD results showed that Tm,Ho:BaY2Fg polycrystalline material was obtained at 960℃by the High-temperature solid-phase method. Crystal particle size was about 200nm-550nm, and the degree of crystallinity was 76.88%. that double crucible is used in experiment can improve polycrystalline material quality.
5%Tm,0.5%Ho:BaY2F8 crystal is grown by Czochralski method, which is analysised by XRD, Absorption spectroscopy and Stimulate spectrum. The absorption bands between 700nm and 85Onm attributed to the Tm3+:3H6→3H4 level transition. The absorption bands between 1400nm and 2100nm attributed to the Tm3+:JH6→3F4 level transition and Ho3+:5I8→5I7 level transition.5%Tm，0.5%Ho:BaY2F8 crystal is stimulated by 780nm laser to get 2.056μm near infrared laser.
Tm,Ho:BaY2F8nanoscale crystals is successfully grown by hydrothermal method. We had got the best process parameters by XRD concluded. Crystal morphology was analysised by Field emission scanning electron microscopy. According to the fluorescence spectrum analysis, the results showed that when the doping concentration 5%Tm3+and 0.5%Ho3+of Tm,Ho:BaY2F8 nanoscale crystals, the Up-conversion efficiency is the highest.
本文介绍了Tm,Ho:BaY2F8激光晶体从多晶料到晶体的合成及生长。利用XRD,TG-DSC,荧光光谱及扫描电子显微分析等手段研究了多晶料及晶体的结构和性能。
通过XRD分析得出,采用高温固相法在最佳温度960℃下合成的Tm,Ho:BaY2F8多晶料,晶粒尺寸范围为200—550nm,结晶度为76.88%；并发现运用双坩埚进行实验能够提高合成的多晶料的质量。
采用提拉法生长出来了5%Tm,0.5%Ho:BaY2F8晶体,并对晶体进行了XRD、吸收和激发光谱分析。光谱分析结果表明：Tm,Ho:BaY2F8晶体在700到850nm范围内的吸收峰对应Tm3+离子的3H6→3H4能级跃迁；晶体在1400nm到2100nm范围内的吸收峰对应Tm3+离子的3H6→3F4能级跃迁和Ho3+离子的5I8→5I7能级跃迁；运用780nm激光激发晶体能够得到波长为2.056μm的近红外激光。
运用水热法成功的生长出了Tm,Ho:BaY2F8纳米晶。通过XRD光谱分析得出了最佳的工艺参数；通过扫描电子显微分析对生长出的晶体进行了形貌结构分析；通过荧光光谱分析得出掺杂浓度为5%Tm3+和0.5%Ho3+的Tm,Ho:BaY2F8(？)内米晶的上转换效率最高。
Tm,Ho:BaY2Fg laser crystal is a new type of near-infrared laser crystal materials, which is excited to be obtained 2um laser.2μm laser have a lot of advantages, such as good transmission performance, easyly be absorbed by biological tissue, Human eye harmless and so on. Now it has been widely used in the military, medicine, biology etc. The upconversion performance of Tm,Ho;BaY2F8 laser crystal can realize laser upconversion output.
In the paper, it is introduced that the Tm,Ho:BaY2F8 polycrystalline material had be obtained and Tm,Ho:BaY2F8 laser crystal had be grown. XRD, TG-DSC, fluorescent spectroscopy and Field emission scanning electron microscopy have been used to study structure and spectral properties of polycrystalline material and crystal.
The XRD results showed that Tm,Ho:BaY2Fg polycrystalline material was obtained at 960℃by the High-temperature solid-phase method. Crystal particle size was about 200nm-550nm, and the degree of crystallinity was 76.88%. that double crucible is used in experiment can improve polycrystalline material quality.
5%Tm,0.5%Ho:BaY2F8 crystal is grown by Czochralski method, which is analysised by XRD, Absorption spectroscopy and Stimulate spectrum. The absorption bands between 700nm and 85Onm attributed to the Tm3+:3H6→3H4 level transition. The absorption bands between 1400nm and 2100nm attributed to the Tm3+:JH6→3F4 level transition and Ho3+:5I8→5I7 level transition.5%Tm，0.5%Ho:BaY2F8 crystal is stimulated by 780nm laser to get 2.056μm near infrared laser.
Tm,Ho:BaY2F8nanoscale crystals is successfully grown by hydrothermal method. We had got the best process parameters by XRD concluded. Crystal morphology was analysised by Field emission scanning electron microscopy. According to the fluorescence spectrum analysis, the results showed that when the doping concentration 5%Tm3+and 0.5%Ho3+of Tm,Ho:BaY2F8 nanoscale crystals, the Up-conversion efficiency is the highest.
引文
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[3]A.L.Schawlow and C.H.Townes.Infrared and Optical Masers[J].Phys.Rev.1958.112,1940-1949.
[4]T.H.Maiman.Stimulated optical radiation in ruby [J].Nature.1960.187.493-494.
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[7]邵怀宗,张振亚,陈广民等Nd:YLF激光晶体生长研究[J].激光与红外,1994,6：38-41.
[8]徐军,苏良碧,徐晓东等.激光晶体的现状及发展趋势[J].无机材料学报.2006,21(5)：1025-1030.
[9]Yu Jirong et al. An all solid-state 2-μm laser system for space coherent wind Lidar[J]. IEEE.2000.0-7803-5846-5/00.
[10]Baronti B et al.. Room temperature 2μm Tm. Ho:YLF laser. Optics and Laser in Engineering,2003.39:277-282.
[11]肖思国,阳效良,刘政威.掺Ho3+氟化物材料上转换发光的实验研究[J].稀土,2001,22(5)：9-12.
[12]张新陆,王月珠,李立等.端面抽运Tm, Ho:YLF激光器热转换系数及热透镜效应的研究[J].物理学报,2007,56(4)：2196-2201.
[13]张兴宝,王月珠,姚宝权等.双掺Tm, Ho氟化钇锂激光器的研究进展[J].激光与光电子学进展,2004,41(10)：29-33.
[14]Norman P.Barnes Keith E.Murray Mahendra GJani et al.Diode-pumped Ho,Tm:YLF laser pumping an AgGaSe2 parametric oscillator[J].J.Opt.Am.B.1994,12:2422-2426.
[15]D.GATTI.G.GALZERANO.A.TONCELLI et al.Actively mode-locked Tm-Ho:LiYF4 and Tm-Ho:BaY2F8 lasers [J]. Applied Physics B.2007.86:269-273.
[16]Kenneth M.Dinndorf.Harold Miller.Anna Tabirian.Two Micron Diode-Pumped Laser Operation of Tm.Ho: BaY2F8[J].OSA.1999.
[17]张守贵,阮永丰,李文润.新型激光基质晶体BaY2F8结晶习习性的探索[J].人工晶体学报,2003,32(6)：640-643.
[18]Johnson L F,Guggenheim HJ.New laser lines in the visible from Er3+Inos in BaY2F8[J].Appl.Phys.Lett.1972. 20(12):474.
[19]L.F.Johnson and J.J Guggenheim.Laser emission at 3.0μm from Dy:BaY2F8. Appl [J].Phys.Lett.vol2,pp 96-98,1973.
[20]A Tabirian. S.C.Buchter.H P.Jenssen.A Cassaho.and H J Hoffman et al.Efficient room temperature cascade laser action at 1.4 and 3.9μm in Ho:BYF[M].presented at CLEO Conf.Baltimore.MD.1999.
[21]李宝凌,阮永丰,王军等.掺铥(Tm3+)的BaY2F8粉体的制备及上转换发光[J].中国激光,2000,7(6)：551.
[22]张献明,苏海全,叶泽人等BaY2F8:Ce, Eu中Ce3-->Eu3+的能量传递和Ce3-->Eu3+的电子转移[J].高等学校化学学报,2001,3：358-361.
[23]M.Mazzera-A.Baraldi.M.Tonelli et al.Electron-phonon interaction in Tm3+.Ho3+.and Dy3+ doped BaY2F8 single crystals [J].Optical Materials.2008.
[24]张守超,阮永丰,李广慧等.BaY2F8晶体生长基元与结晶机理的探讨[J].人工晶体学报.2007.36(3)：485-489.
[25]Anna M.Tabirian.Hans P.Jenssen and Arlete Cassanho.Efficient.Room Temperature Mid-Infrared Laser at 3.9um in Ho:BaY2F8[J].OSA.2001.
[26]R.E.Peale.H.Weidner and P.L.Summers.Comparative Fourier Spectroscopy of Ho3+ and Yb3+in KYF4 BaY2F8 and YLiF4[J].OSA/ASSL.1993.
[27]W.M.Patterson.A.Mocofanescu.M.Shelk-Bahae ed al.Laser cooling in rare earth doped BaY2F8 crystals [J].OSA/FIO.2005.
[28]Nicola Coluccelli,Gianluca Galzerano.Paolo Laporta. Room-temperature Q-switched Tm:BaY2F8 laser pumped by CW diode laser[J].OSA.2006.2.
[29]Junichi Ohwaki. Yuhu Wang. Atsushi shibukawa. et al. Infrared-to-visible up-conversion material [J], US patent, No.5541012.1996.
[30]何捍卫.周科朝.熊翔等.红外-可见光的上转换材料研究进展[J].中国稀土学报.2003,21(2)：123-128.
[31]裴晓将,侯延冰.徐征.水热法合成稀土氟化物材料YLiF4:Er.Tm.Yb的上转换发光特性[J].光谱学与光谱分析,2005.25(6)：819-823.
[32]张希艳,卢利平，柏朝晖等.稀土发光材料[M].北京：国防工业出版社.2005.
[33]赵谡玲,侯延冰,董金凤.稀土离子上转换发光的研究[J].半导体光学,2000,21(4)：241-244.
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