Yb~（3+）/Er~（3+）/Tm~（3+）/Ho~（3+）共掺氟氧化物玻璃光谱特性研究
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摘要
随着人们对上转换发光研究的深入,近年来出现了一种稀土掺杂氟氧化物上转换发光玻璃,它具有氟化物玻璃低声子能量的光学特性又有氧化物玻璃的良好的物理化学稳定性和高的机械强度,并且可通过可控析晶析出氟化物晶相,氟化物晶相的声子能量很低,稀土离子富集在氟化物晶相中,从而可极大地提高稀土离子的上转换发光效率。因此,氟氧化物发光玻璃有望成为一种极具发展前景的稀土掺杂发光材料,在光通信、上转换激光、三维显示以及数据存储等领域得到广泛应用。
本文针对高效环保及低成本的要求,采用较廉价的碱土氟化物(BaF_2)和稀土氧化物(Yb_2O_3、Er_2O_3、Tm_2O_3、HO_2O_3)为原料,制备了一系列yb~(3+)、Er~(3+)、Tm~(3+)、Ho~(3+)稀土离子双掺、三掺和四掺的氟氧化物玻璃,研究这些稀土离子在玻璃基质中的发光性质。在980nm激光激发下,yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)共掺的氟氧化物玻璃可获得蓝色、绿色和红色上转换发光;随着Er~(3+)离子浓度的增加,红、绿、蓝三种上转换发光强度都降低;随着Ho~(3+)离子浓度的增加,蓝色上转换发光强度急剧降低,绿色上转换发光强度降低较缓慢,而红色上转换发光强度变化不大;随着Tm~(3+)离子浓度的增加,红色和绿色上转换发光强度降低,蓝色上转换发光强度则是先增加后降低,这主要是稀土离子间由于交叉弛豫和反向能量传递引起的。当Er~(3+)离子的掺杂量为0.5%、Ho~(3+)离子的掺杂量为0.3%、Tm~(3+)离子的掺杂量为0.1%时,Yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)共掺氟氧化物玻璃发出上转换白光。
With the in-depth study of upconversion luminescence,there has been a rare-earth ions doped oxyfluoride upconversion luminescence glass in recent years.It combines the low phonon energy of fluoride glass's optical properties with the good physical and chemical stability and high mechanical strength of oxide glass,and can be precipitated by controlled crystallization of fluoride crystal phase.Because of the low phonon energy of fluoride crystal phase,the rare-earth ions concentrate in the fluoride crystal phase,which can greatly enhance the upconversion luminescence of rare-earth ions efficiency.Therefore,the fluoride-oxide luminescent glasses are expected to become highly promising rare-earth doped luminescent materials,and were widely used in optical communication,up-conversion laser,three-dimensional display and data storage areas.
Concerning the requirements of effective environmental protection and low cost,a series of Yb~(3+),Er~(3+),Tm~(3+),Ho~(3+) ions double,triple and quadruple doped oxyfluoride glass were prepared by using the cheaper alkaline-earth fluoride(BaF_2) and rare earth oxides(Yb_2O_3, Er_2O_3,Tm_2O_3,Ho_2O_3) as raw materials.The luminescence properties of these rare-earth ions in the host glasses were studied.The blue,green and red upconversion luminescence were obtained in the Yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)co-doped oxyfluoride glass under the 980nm laser excitation.With the growth of the Er~(3+) ion concentration,the red,blue and green up-conversion luminescence intensity decrease.With the growth of the Ho~(3+) ion concentration,the blue up-conversion luminescence intensity decrease sharply,the green decrease slowly,while the red change little.With the growth of the Tm~(3+) ions concentration, the red and green up-conversion luminescence intensity decrease,while the blue up-conversion luminescence intensity increased firstly and then decreased,mainly due to cross-relaxation and reverse energy transfer of rare earth ions.When the Er~(3+) ion doped amount of 0.5%,Ho~(3+) ion doping amount of 0.3%,Tm~(3+) ion doping amount of 0.1%,the Yb~(3+)/Er~(3+)/Ho~(3+)/Tm~(3+)co-doped oxyfluoride glass can emit the white light.
本文针对高效环保及低成本的要求,采用较廉价的碱土氟化物(BaF_2)和稀土氧化物(Yb_2O_3、Er_2O_3、Tm_2O_3、HO_2O_3)为原料,制备了一系列yb~(3+)、Er~(3+)、Tm~(3+)、Ho~(3+)稀土离子双掺、三掺和四掺的氟氧化物玻璃,研究这些稀土离子在玻璃基质中的发光性质。在980nm激光激发下,yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)共掺的氟氧化物玻璃可获得蓝色、绿色和红色上转换发光;随着Er~(3+)离子浓度的增加,红、绿、蓝三种上转换发光强度都降低;随着Ho~(3+)离子浓度的增加,蓝色上转换发光强度急剧降低,绿色上转换发光强度降低较缓慢,而红色上转换发光强度变化不大;随着Tm~(3+)离子浓度的增加,红色和绿色上转换发光强度降低,蓝色上转换发光强度则是先增加后降低,这主要是稀土离子间由于交叉弛豫和反向能量传递引起的。当Er~(3+)离子的掺杂量为0.5%、Ho~(3+)离子的掺杂量为0.3%、Tm~(3+)离子的掺杂量为0.1%时,Yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)共掺氟氧化物玻璃发出上转换白光。
With the in-depth study of upconversion luminescence,there has been a rare-earth ions doped oxyfluoride upconversion luminescence glass in recent years.It combines the low phonon energy of fluoride glass's optical properties with the good physical and chemical stability and high mechanical strength of oxide glass,and can be precipitated by controlled crystallization of fluoride crystal phase.Because of the low phonon energy of fluoride crystal phase,the rare-earth ions concentrate in the fluoride crystal phase,which can greatly enhance the upconversion luminescence of rare-earth ions efficiency.Therefore,the fluoride-oxide luminescent glasses are expected to become highly promising rare-earth doped luminescent materials,and were widely used in optical communication,up-conversion laser,three-dimensional display and data storage areas.
Concerning the requirements of effective environmental protection and low cost,a series of Yb~(3+),Er~(3+),Tm~(3+),Ho~(3+) ions double,triple and quadruple doped oxyfluoride glass were prepared by using the cheaper alkaline-earth fluoride(BaF_2) and rare earth oxides(Yb_2O_3, Er_2O_3,Tm_2O_3,Ho_2O_3) as raw materials.The luminescence properties of these rare-earth ions in the host glasses were studied.The blue,green and red upconversion luminescence were obtained in the Yb~(3+)/Er~(3+)/Tm~(3+)/Ho~(3+)co-doped oxyfluoride glass under the 980nm laser excitation.With the growth of the Er~(3+) ion concentration,the red,blue and green up-conversion luminescence intensity decrease.With the growth of the Ho~(3+) ion concentration,the blue up-conversion luminescence intensity decrease sharply,the green decrease slowly,while the red change little.With the growth of the Tm~(3+) ions concentration, the red and green up-conversion luminescence intensity decrease,while the blue up-conversion luminescence intensity increased firstly and then decreased,mainly due to cross-relaxation and reverse energy transfer of rare earth ions.When the Er~(3+) ion doped amount of 0.5%,Ho~(3+) ion doping amount of 0.3%,Tm~(3+) ion doping amount of 0.1%,the Yb~(3+)/Er~(3+)/Ho~(3+)/Tm~(3+)co-doped oxyfluoride glass can emit the white light.
引文
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[2]王大珩等.显示技术与产业-21世纪展望[J].1999显示技术与产业发展研讨会.北京,1999
[3]陈晓波,李美仙,闻鸥等.Er:ZBLAN玻璃的一光束上转换立体显示的初步研究[J].光谱学与光谱分析.2003,23(3):431-434
[4]Downing E,Hesselink L,Ralston J,et al.A Three-color,Solid-Stade,Three-Dimensional Display[J].Science,1996,273:1185-1189
[5]陈晓波,侯延冰,宋峰等.ZBLAN:Pr,Yb上转换发光及在三维立体显示的应用[J].第七届全国基础光学、光物理学术报告会论文摘要专集.1996.5:408-409
[6]徐时清,马红萍,张在宣等.三维立体显示用稀土掺杂氟卤碲酸盐玻璃[J].稀有金属材料与工程.2005,34(7):1173-1176
[7]彭宝剑,王琼华.显示器用上转换红色发光材料的特性研究[J].激光杂志,2007,28(4):30-31
[8]R.Francini,F.Giovenale,U.M.Grassano,P.Laporta,S.Taccheo.Spectroscopy of Er and Er-Yb-doped phosphate glasses[J].Opt.Mat.2000,13,417-425
[9]H.T.Amorim,M.T.de Araujo,E.A.Gouveia,A.S.Gouveia-Neto,J.A.Medeiros-Neto,A.S.B.Sombra.Infrared to visible up-conversion fluorescence spectroscopy in Er-doped chalcogenide glass[J].J.Lumin.1988,78,271-277
[10]S.Q.Gu,S.Ramachandran,E.E.Reuter,D.A.Turnbull,J.T.Verdeyen,S.G.Bishop.Novel broad-ban excitation of Er luminescence in chalcogenide glasses[J].Appl.Phys.Lett.,1995,66(6):670-672
[11]P.V.dosSantos,M.T.de Araujo,A.S.Gouveia-Neto,J.A.Medeiros-Neto,A.S.B.Sombra.Optical thermometry through infrared excited upconversion fluorescence emission in Er~(3+)-and Er~(3+)-Yb~(3+)-doped chalcogenide glassed[J].IEEE J.Quant.Electron.,1999,35(2):395-399
[12]M.J.V.Bell,D.F.de Sousa,L.A.O.Nunes.Looping mechanism in Er-doped fluoroindogallate glass[J].Appl.Phys.,2000,87(12):8264-8267
[13]Stephens,R.R,McFarlane,R.A,Opt.Lett.,1993,18(1):3436
[14]Heine.F,Heumann.E,Danger.T,et al,Appl.Phys.Lett.1994,65(4):383-384
[15]Y.Wang,J.Ohwaki.New transparent vitro ceramics codeped with Er~(3+) and Yb~(3+) for efficient frequency upconversion[J].Appl.Phys.lett.,1993,63(24):3268-3270
[16]J.Mendez-Ramos,V.Lavin,I.R.Martin,U.R.Rodriguez-Mendoza,V.D.Rodrigueza,A.D.Lozano-Gorrin and P.Nunez.Role of the Eu~(3+) ions in the fomation of transparent oxyfluoride glass ceramics[J].Appl.Phys.,2001,89:5307-5310
[17]J.Mendez-Ramos,V.Lavin,I.R.Martin,U.R.Rodriguez-Mendoza,V.D.Rodrigueza,A.D.Lozano-Gorrin and P.Nunez.Site selective study of Eu~(3+)-doped transparent oxyfluride glass ceramics[J].Appl.Phys.,2003,94(4):2295-2301
[18]J.Qiu,R.Kanno,Y.Kawamoto,Y.Bando and K.Kurashima.Microstructure of transparent SiO_2-PbF_2-ErF_3glass ceramics with highly efficient Er~(3+) upconversion luminescence[J].Mater.Sci.Lett.,1998,17:653-655
[19]陈晓波,宋增福.Ho(0.5)Yb(5)氟氧化物玻璃的直接上转换增敏发光[J].光谱学与光谱分析.2003,23(3):426-430
[20]徐时清,杨中民,汪国年等.Er~(3+)/Yb~(3+)共掺杂氧氟硅酸盐玻璃的上转换发光[J].光学学报.2004,24(8):1103-1106.
[21]高钦翔,田强.声子之间的相互作用与品格热平衡[J].重庆大学学报(自然科学版),2002,25(1):106-108
[22]苏方宁,邓再德.声子态密度对掺稀土玻璃材料上转换发光强度的影响[J].玻璃与搪瓷,2007,35(2):1-5
[23]徐时清,黄俊,张丽艳等.Yb~(3+)敏化Tm~(3+)掺杂卤碲酸盐玻璃的上转换发光研究[J].光学学报.2006,55(8): 4304-4309
[24]孙坚,刘粤惠,杨中民等.Er~(3+)离子掺杂氧氟碲酸盐玻璃的上转换发光[J].稀有金属材料与工程.2008,37(1):76-79
[25]于晓波,赵听,李长敏等.光学玻璃最大声子能量的红外光谱估算[J].大连工业大学学报.2008,27(2):155-157
[26]宋峰.Er~(3+)/Yb~(3+)共掺磷酸盐玻璃的发光与1.54μm激光性能[J].名家讲坛.2007,144(4):15-25
[27]陆龙君,聂秋华,徐铁峰.Er~(3+)/Yb~(3+)共掺Bi_2O_3-GeO_2-Na_2O玻璃的上转换发光[J].中国激光.2006,33(8):66-70
[28]徐时清,杨中民,汪国年等.Er~(3+)/Yb~(3+)共掺氧氟硅酸盐玻璃的上转换发光[J].光学学报.2004,24(8):1103-1106
[29]张天杰,丁菲,毛艳丽.Er~(3+)离子掺杂的碲酸盐玻璃光谱性质分析[J].河南大学学报.2006,36(4):15-18
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