Asymmetry ratio as a parameter of Eu~(3+) local environment in phosphors
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摘要
Study of the local environment of certain ion is quite a complex problem. Due to the unique luminescent properties, Eu~(3+) ions can be used as a structural probe. In this paper, effect of doping concentration,excitation wavelength and excitation mechanism on asymmetry ratio was systematically studied using Y_3Al_5O_(12):Eu~(3+), YVO_4:Eu~(3+) and Y_2O_3:Eu~(3+)nanophosphors. The asymmetry ratio gives information about the local surrounding and environmental changes around the Eu~(3+) ions. Asymmetry ratios of YAG:Eu~(3+)and YVO_4:Eu~(3+) nanopowders were calculated using standard technique and the obtained average values were found to be 0.75 and 8.2, respectively. However, it is found that standard method of asymmetry ratio calculation is suitable only for samples where all Eu~(3+) ions occupy one site. The "multisite model" of asymmetry ratio calculation was developed and used for Y_2O_3:Eu~(3+) nanocrystalline powders. Average value of asymmetry ratio for Eu~(3+) ions occupied "normal" sites is 6.0 and for Eu~(3+) ions occupied "defect"sites is 2.3.
Study of the local environment of certain ion is quite a complex problem. Due to the unique luminescent properties, Eu~(3+) ions can be used as a structural probe. In this paper, effect of doping concentration,excitation wavelength and excitation mechanism on asymmetry ratio was systematically studied using Y_3Al_5O_(12):Eu~(3+), YVO_4:Eu~(3+) and Y_2O_3:Eu~(3+)nanophosphors. The asymmetry ratio gives information about the local surrounding and environmental changes around the Eu~(3+) ions. Asymmetry ratios of YAG:Eu~(3+)and YVO_4:Eu~(3+) nanopowders were calculated using standard technique and the obtained average values were found to be 0.75 and 8.2, respectively. However, it is found that standard method of asymmetry ratio calculation is suitable only for samples where all Eu~(3+) ions occupy one site. The "multisite model" of asymmetry ratio calculation was developed and used for Y_2O_3:Eu~(3+) nanocrystalline powders. Average value of asymmetry ratio for Eu~(3+) ions occupied "normal" sites is 6.0 and for Eu~(3+) ions occupied "defect"sites is 2.3.
Study of the local environment of certain ion is quite a complex problem. Due to the unique luminescent properties, Eu~(3+) ions can be used as a structural probe. In this paper, effect of doping concentration,excitation wavelength and excitation mechanism on asymmetry ratio was systematically studied using Y_3Al_5O_(12):Eu~(3+), YVO_4:Eu~(3+) and Y_2O_3:Eu~(3+)nanophosphors. The asymmetry ratio gives information about the local surrounding and environmental changes around the Eu~(3+) ions. Asymmetry ratios of YAG:Eu~(3+)and YVO_4:Eu~(3+) nanopowders were calculated using standard technique and the obtained average values were found to be 0.75 and 8.2, respectively. However, it is found that standard method of asymmetry ratio calculation is suitable only for samples where all Eu~(3+) ions occupy one site. The "multisite model" of asymmetry ratio calculation was developed and used for Y_2O_3:Eu~(3+) nanocrystalline powders. Average value of asymmetry ratio for Eu~(3+) ions occupied "normal" sites is 6.0 and for Eu~(3+) ions occupied "defect"sites is 2.3.
引文
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2.Faucher L,Guay Begin AA,Lagueux J,Cote MF,Petitclerc E,Fortin MA.Ultra small gadolinium oxide nanoparticles to image brain cancer cells in vivo with MRI.Contrast Media Mol Imag.2011;6:209.
3.Guo H,Zhang H,Wei RF,Zheng MD,Zhang LH.Preparation,structural and luminescent properties of Ba_2Gd_2Si_4O_(13):Eu~(3+)for white LEDs.Opt Express.2011;19:A201.
4.Manigandan R,Giribabu K,Suresh R,Munusamy S,Muthamizh S,Dhanasekaran T,et al.Synthesis,growth and photo luminescence behaviour of Gd_2O_2SO_4:Eu~(3+)nanophosphors:the effect of temperature on the structural,morphological and optical properties.RSC Adv.2015;5:7515.
5.Xia ZG,Liang YJ,Yu DY,Zhang MF,Huang WZ,Tong MH,et al.Photoluminescence properties and energy transfer in color tunable BaY_2Si_3O_(10):Ce,Tb phosphors.Opt Laser Technol.2014;56:387.
6.Xia ZG,Liu RS.Tunable blue-green color emission and energy transfer of Ca_2Al_3O_6F:Ce~(3+),Tb~(3+)phosphors for near-UV white LEDs.J Phys Chem C.2012;116:15604.
7.Zhu C,Chaussedent S,Liu S,Zhang Y,Monteil A,Gaumer N,et al.Composition dependence of luminescence of Eu and Eu/Tb doped silicate glasses for LED applications.J Alloys Compd.2013;555:232.
8.Huignard A,Buissette V,Franville A-C,Gacoin T,Boilot J-P.Emission processes in YVO_4:Eu nanoparticles.J Phys Chem B.2003;107:6754.
9.Zhou YH,Lin J,Wang SB,Zhang HJ.Preparation of Y_3Al_5O_(12):Eu phosphors by citric-gel method and their luminescent properties.Opt Mater(Amst).2002;20:13.
10.Gupta BK,Haranath D,Saini S,Singh VN,Shanker V.Synthesis and characterization of ultra-fine Y_2O_3:Eu~(3+)nanophosphors for luminescent security ink applications.Nanotechnology.2010;21:55607.
11.Kano T,Shionoya S,Yen WM.Phosphor Handbook.Boca Raton:CRC;1999:177.
12.Oomen E,Van Dongen A-MA.Europium(Ⅲ)in oxide glasses:dependence of the emission spectrum upon glass composition.J Non Cryst Solids.1989;111:205.
13.Tanner PA.Some misconceptions concerning the electronic spectra of tripositive europium and cerium.Chem Soc Rev.2013;42:5090.
14.Hassairi MA,Hernandez AG,Kallel T,Dammak M,Zambon D,Chadeyron G,et al.Spectroscopic properties and Judd-Ofelt analysis of Eu~(3+)doped GdPO_4nanoparticles and nanowires.J Lumin.2016;170:200.
15.Zhang ZW,Wang LJ,Yang SS,Chen WG,Chu XJ.Synthesis and characterizations of novel Ba_2La_8(SiO_4)_6O_2:Eu~(3+)oxyapatite phosphors.Dye Pigment.2017;142:272.
16.Wang YQ,Tang JQ,Huang XY.Jiang L Luminescence properties of Eu~(3+):NaGd(WO_4)_2 nanoparticles and nanorods.J Rare Earths.2016;34:118.
17.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Manshina AA,Mikhailov MD.Eu3+concentration effect on luminescence properties of YAG:Eu~(3+)nanoparticles.Opt Mater(Amst).2014;37:306.
18.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Platonova NV,Pulkin SA,Manshina AA,et al.Concentration effect on structural and luminescent properties of YVO_4:Nd~(3+)nanophosphors.Mater Res Bull.2015;70:799.
19.Kolesnikov IE,Golyeva EV,Kurochkin AV,Mikhailov MD.Structural and luminescence properties of MgAl_2O_4:Eu~(3+)nanopowders.J Alloys Compd.2016;654:32.
20.Kolesnikov IE,Povolotskiy AV,V Tolstikova D,Manshina AA,Mikhailov MD.Luminescence of Y_3Al_5O_(12):Eu~(3+)nanophosphors in blood and organic media.J Phys D Appl Phys.2015;48:75401.
21.Mamonova DV,Kolesnikov IE,Golyeva EV,Mikhailov MD,Pulkin SA,Smirnov VM.Synthesis and study of Y_2O_3:Eu~(3+)nanoparticles.Nanotechnol Russ.2015;10:701.
22.Kolesnikov 1,Povolotskiy A,Mamonova D,Lahderanta E,Manshina A,Mikhailov M.Photoluminescence properties of Eu~(3+)ions in yttrium oxide nanoparticles:defect vs normal sites.RSC Adv.2016;6:76533.
23.Kolesnikov IE,Mamonova DV,Lahderanta E,Kurochkin AV,Mikhailov MD.The impact of doping concentration on structure and photoluminescence of Lu_2O_3:Eu~(3+)nanocrystals,J Lumin.2017;187:26.
24.Pcchini MPPMP.Method of Preparing Lead And Alkaline Earth Titanates and Niobates and coating Method Using the Same to Form a Capacitor.U.S.Patent,3,330,697.1967-07-11.
25.Zhang ZJ,Shi J,Wang XY,Liu SD,Wang X.Vibrational and luminescent properties of LaPO_4:Eu~(3+)with different preparation conditions.J Rare Earths.2016;34:1103.
26.Li SC,Yu LX,Sun JJ,Man XQ.Synthesis and photoluminescent characteristics of Eu~(3+)-doped MMoO_4(M=Sr,Ba)nanophosphors by a hydrothermal method.J Rare Earths.2017;35:347.
27.Ravichandran D,Roy R,Chakhovskoi AG,Hunt CE,White WB,Erdei S.Fabrication of Y_3Al_5O_(12):Eu thin films and powders for field emission display applications.J Lumin.1997;71:291.
28.Hreniak D,H(o|¨)ls(a|¨)J,Lastusaari M,Strek W.Effect of grain size and concentration of active ions on structural and optical behavior of Eu~(3+)-dopcd Y_3Al_5O_(12)nanocrystallites.J Lumin.2007;122-123:91.
29.Muresan LE,Popovici EJ,Perhaita 1,Indrea E,Silipas TD.Effect of the europium doping on the structural and luminescent properties of yttrium aluminum garnet.Mater Sci Eng B.2013;178:248.
30.Xia GD,Zhou SM,Zhang JJ,Wang SM,Liu YM,Xu J.Sol-gel combustion synthesis and luminescent properties of nanocrystalline YAG:Eu~(3+)phosphors.J Cryst Growth.2005;283:257.
31.Lu CH,Hsu WT.Hsu CH.Lu HC,Cheng BM.Structural analysis and vacuum ultraviolet excited luminescence properties of sol-gel derived Y_3Al_5O_(12):Eu~(3+)phosphors.J Alloys Compd.2008;456:57.
32.Jung YR,Yang HK,Moon BK,Choi BC,Jeong JH,Kim JH,et al.Sol-gel combustion synthesis and photoluminescent properties of YAG:Eu phosphors.Surf Rev Lett.2010:17:73.
33.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Pulkin SA,Manshina AA,Mikhailov MD.Concentration effect on photoluminescence of Eu3+-doped nanocrystalline YVO4.J Lumin.2015;158:469.
34.Zhou YH,Lin J.Morphology control and luminescence properties of YVO_4:Eu phosphors prepared by spray pyrolysis.Opt Mater(Amst).2005;27:1426.
35.Devaraju MK,Yin S,Sato T.Solvothermal synthesis,controlled morphology and optical properties of Y_2O_3:Eu~(3+)nanocrystals.J Cryst Growth.2009;311:580.
36.Hreniak D.Doskocz J,Guchowski P,Lisiecki R,Strek W,Vu N,et al.Enhancement of luminescence properties of Eu~(3+):YVO_4 in polymeric nanocomposites upon UV excitation,J Lumin.2011;131:473.
37.Choi S,Moon YM,Jung HK.Luminescent properties of PEG-added nanocrystalline YVO_4:Eu~(3+)phosphor prepared by a hydrothermal method.J Lumin.2010;130:549.
38.Buijs M,Meyerink a,Blasse G.Energy transfer between Eu~(3+)ions in a lattice with two different crystallographic sites:Y_2O_3:Eu~(3+),Gd_2O_3:Eu~(3+)and Eu_2O_3.J Lumin.1987;37:9.
39.Cui H,Zhu PF,Zhu HX,Li HD,Cui QL Photoluminescence properties and energy transfer in Y_2O_3:Eu~(3+)nanophosphors.Chinese Phys.B.2014;23:57801.
40.Golyeva EV,Tolstikova DV,Kolesnikov IE,Mikhailov MD.Effect of synthesis conditions and surrounding medium on luminescence properties of YVO_4:Eu~(3+)nanopowders.J Rare Earths.2015:33:129.
41.Liu BJ,Gu M,Liu XL,Ni C,Wang D,Xiao LH,et al.Effect of Zn~(2+)and Li~+codoping ions on nanosized Gd_2O_3:Eu~(3+)phosphor.J Alloys Compd.2007;440:341.
42.Krishna RH,Nagabhushana BM,Nagabhushana H,Murthy NS,Sharma SC,Shivakumara C,et al.Effect of calcination temperature on structural,photoluminescence,and thermoluminescence properties of Y_2O_3:Eu~(3+)nanophosphor.J Phys Chem C.2013;117:1915.
43.Ganjkhanlou Y,Kazemzad M,Hessari FA.Chromaticity dependence on Eu concentration in Y_2O_3:Eu nanopowders.Nanobr Reports Rev.2010;5:111.
2.Faucher L,Guay Begin AA,Lagueux J,Cote MF,Petitclerc E,Fortin MA.Ultra small gadolinium oxide nanoparticles to image brain cancer cells in vivo with MRI.Contrast Media Mol Imag.2011;6:209.
3.Guo H,Zhang H,Wei RF,Zheng MD,Zhang LH.Preparation,structural and luminescent properties of Ba_2Gd_2Si_4O_(13):Eu~(3+)for white LEDs.Opt Express.2011;19:A201.
4.Manigandan R,Giribabu K,Suresh R,Munusamy S,Muthamizh S,Dhanasekaran T,et al.Synthesis,growth and photo luminescence behaviour of Gd_2O_2SO_4:Eu~(3+)nanophosphors:the effect of temperature on the structural,morphological and optical properties.RSC Adv.2015;5:7515.
5.Xia ZG,Liang YJ,Yu DY,Zhang MF,Huang WZ,Tong MH,et al.Photoluminescence properties and energy transfer in color tunable BaY_2Si_3O_(10):Ce,Tb phosphors.Opt Laser Technol.2014;56:387.
6.Xia ZG,Liu RS.Tunable blue-green color emission and energy transfer of Ca_2Al_3O_6F:Ce~(3+),Tb~(3+)phosphors for near-UV white LEDs.J Phys Chem C.2012;116:15604.
7.Zhu C,Chaussedent S,Liu S,Zhang Y,Monteil A,Gaumer N,et al.Composition dependence of luminescence of Eu and Eu/Tb doped silicate glasses for LED applications.J Alloys Compd.2013;555:232.
8.Huignard A,Buissette V,Franville A-C,Gacoin T,Boilot J-P.Emission processes in YVO_4:Eu nanoparticles.J Phys Chem B.2003;107:6754.
9.Zhou YH,Lin J,Wang SB,Zhang HJ.Preparation of Y_3Al_5O_(12):Eu phosphors by citric-gel method and their luminescent properties.Opt Mater(Amst).2002;20:13.
10.Gupta BK,Haranath D,Saini S,Singh VN,Shanker V.Synthesis and characterization of ultra-fine Y_2O_3:Eu~(3+)nanophosphors for luminescent security ink applications.Nanotechnology.2010;21:55607.
11.Kano T,Shionoya S,Yen WM.Phosphor Handbook.Boca Raton:CRC;1999:177.
12.Oomen E,Van Dongen A-MA.Europium(Ⅲ)in oxide glasses:dependence of the emission spectrum upon glass composition.J Non Cryst Solids.1989;111:205.
13.Tanner PA.Some misconceptions concerning the electronic spectra of tripositive europium and cerium.Chem Soc Rev.2013;42:5090.
14.Hassairi MA,Hernandez AG,Kallel T,Dammak M,Zambon D,Chadeyron G,et al.Spectroscopic properties and Judd-Ofelt analysis of Eu~(3+)doped GdPO_4nanoparticles and nanowires.J Lumin.2016;170:200.
15.Zhang ZW,Wang LJ,Yang SS,Chen WG,Chu XJ.Synthesis and characterizations of novel Ba_2La_8(SiO_4)_6O_2:Eu~(3+)oxyapatite phosphors.Dye Pigment.2017;142:272.
16.Wang YQ,Tang JQ,Huang XY.Jiang L Luminescence properties of Eu~(3+):NaGd(WO_4)_2 nanoparticles and nanorods.J Rare Earths.2016;34:118.
17.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Manshina AA,Mikhailov MD.Eu3+concentration effect on luminescence properties of YAG:Eu~(3+)nanoparticles.Opt Mater(Amst).2014;37:306.
18.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Platonova NV,Pulkin SA,Manshina AA,et al.Concentration effect on structural and luminescent properties of YVO_4:Nd~(3+)nanophosphors.Mater Res Bull.2015;70:799.
19.Kolesnikov IE,Golyeva EV,Kurochkin AV,Mikhailov MD.Structural and luminescence properties of MgAl_2O_4:Eu~(3+)nanopowders.J Alloys Compd.2016;654:32.
20.Kolesnikov IE,Povolotskiy AV,V Tolstikova D,Manshina AA,Mikhailov MD.Luminescence of Y_3Al_5O_(12):Eu~(3+)nanophosphors in blood and organic media.J Phys D Appl Phys.2015;48:75401.
21.Mamonova DV,Kolesnikov IE,Golyeva EV,Mikhailov MD,Pulkin SA,Smirnov VM.Synthesis and study of Y_2O_3:Eu~(3+)nanoparticles.Nanotechnol Russ.2015;10:701.
22.Kolesnikov 1,Povolotskiy A,Mamonova D,Lahderanta E,Manshina A,Mikhailov M.Photoluminescence properties of Eu~(3+)ions in yttrium oxide nanoparticles:defect vs normal sites.RSC Adv.2016;6:76533.
23.Kolesnikov IE,Mamonova DV,Lahderanta E,Kurochkin AV,Mikhailov MD.The impact of doping concentration on structure and photoluminescence of Lu_2O_3:Eu~(3+)nanocrystals,J Lumin.2017;187:26.
24.Pcchini MPPMP.Method of Preparing Lead And Alkaline Earth Titanates and Niobates and coating Method Using the Same to Form a Capacitor.U.S.Patent,3,330,697.1967-07-11.
25.Zhang ZJ,Shi J,Wang XY,Liu SD,Wang X.Vibrational and luminescent properties of LaPO_4:Eu~(3+)with different preparation conditions.J Rare Earths.2016;34:1103.
26.Li SC,Yu LX,Sun JJ,Man XQ.Synthesis and photoluminescent characteristics of Eu~(3+)-doped MMoO_4(M=Sr,Ba)nanophosphors by a hydrothermal method.J Rare Earths.2017;35:347.
27.Ravichandran D,Roy R,Chakhovskoi AG,Hunt CE,White WB,Erdei S.Fabrication of Y_3Al_5O_(12):Eu thin films and powders for field emission display applications.J Lumin.1997;71:291.
28.Hreniak D,H(o|¨)ls(a|¨)J,Lastusaari M,Strek W.Effect of grain size and concentration of active ions on structural and optical behavior of Eu~(3+)-dopcd Y_3Al_5O_(12)nanocrystallites.J Lumin.2007;122-123:91.
29.Muresan LE,Popovici EJ,Perhaita 1,Indrea E,Silipas TD.Effect of the europium doping on the structural and luminescent properties of yttrium aluminum garnet.Mater Sci Eng B.2013;178:248.
30.Xia GD,Zhou SM,Zhang JJ,Wang SM,Liu YM,Xu J.Sol-gel combustion synthesis and luminescent properties of nanocrystalline YAG:Eu~(3+)phosphors.J Cryst Growth.2005;283:257.
31.Lu CH,Hsu WT.Hsu CH.Lu HC,Cheng BM.Structural analysis and vacuum ultraviolet excited luminescence properties of sol-gel derived Y_3Al_5O_(12):Eu~(3+)phosphors.J Alloys Compd.2008;456:57.
32.Jung YR,Yang HK,Moon BK,Choi BC,Jeong JH,Kim JH,et al.Sol-gel combustion synthesis and photoluminescent properties of YAG:Eu phosphors.Surf Rev Lett.2010:17:73.
33.Kolesnikov IE,Tolstikova DV,Kurochkin AV,Pulkin SA,Manshina AA,Mikhailov MD.Concentration effect on photoluminescence of Eu3+-doped nanocrystalline YVO4.J Lumin.2015;158:469.
34.Zhou YH,Lin J.Morphology control and luminescence properties of YVO_4:Eu phosphors prepared by spray pyrolysis.Opt Mater(Amst).2005;27:1426.
35.Devaraju MK,Yin S,Sato T.Solvothermal synthesis,controlled morphology and optical properties of Y_2O_3:Eu~(3+)nanocrystals.J Cryst Growth.2009;311:580.
36.Hreniak D.Doskocz J,Guchowski P,Lisiecki R,Strek W,Vu N,et al.Enhancement of luminescence properties of Eu~(3+):YVO_4 in polymeric nanocomposites upon UV excitation,J Lumin.2011;131:473.
37.Choi S,Moon YM,Jung HK.Luminescent properties of PEG-added nanocrystalline YVO_4:Eu~(3+)phosphor prepared by a hydrothermal method.J Lumin.2010;130:549.
38.Buijs M,Meyerink a,Blasse G.Energy transfer between Eu~(3+)ions in a lattice with two different crystallographic sites:Y_2O_3:Eu~(3+),Gd_2O_3:Eu~(3+)and Eu_2O_3.J Lumin.1987;37:9.
39.Cui H,Zhu PF,Zhu HX,Li HD,Cui QL Photoluminescence properties and energy transfer in Y_2O_3:Eu~(3+)nanophosphors.Chinese Phys.B.2014;23:57801.
40.Golyeva EV,Tolstikova DV,Kolesnikov IE,Mikhailov MD.Effect of synthesis conditions and surrounding medium on luminescence properties of YVO_4:Eu~(3+)nanopowders.J Rare Earths.2015:33:129.
41.Liu BJ,Gu M,Liu XL,Ni C,Wang D,Xiao LH,et al.Effect of Zn~(2+)and Li~+codoping ions on nanosized Gd_2O_3:Eu~(3+)phosphor.J Alloys Compd.2007;440:341.
42.Krishna RH,Nagabhushana BM,Nagabhushana H,Murthy NS,Sharma SC,Shivakumara C,et al.Effect of calcination temperature on structural,photoluminescence,and thermoluminescence properties of Y_2O_3:Eu~(3+)nanophosphor.J Phys Chem C.2013;117:1915.
43.Ganjkhanlou Y,Kazemzad M,Hessari FA.Chromaticity dependence on Eu concentration in Y_2O_3:Eu nanopowders.Nanobr Reports Rev.2010;5:111.