Ca_3Y_2Si_3O_(12)∶Tm~(3+),Yb~(3+)上转换发光粉的制备与发光性能研究
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摘要
采用高温固相法成功制备了Ca_3Y_2Si_3O_(12)∶Tm~(3+),Yb~(3+)上转换蓝色发光材料。在980 nm红外激光器激发下,发光粉呈现强烈的蓝光(475 nm)和近红外光(810 nm)以及较弱的红光(650 nm)发射,分别归因于Tm~(3+)离子的~1G_4→~3H_6、~3H_4→~3H_6和~1G_4→~3F_4能级跃迁。随着Yb~(3+)离子浓度的增加,发光粉上转换发射强度和发光亮度均呈现先增强后减弱的变化趋势。在最佳掺杂浓度下(Yb~(3+)摩尔分数为15%),蓝、红光强度分支比为12∶1,色坐标为(0.129 2,0.152 3)。在3.9 W/cm~2激发功率密度下,发光亮度可达6.8 cd/m~2。上述结果证实,所制备发光粉呈现优异的蓝光上转换发射特性并具有潜在的应用价值。发光强度和激发光功率关系表明,所得上转换发射为三光子和双光子吸收过程。借助Tm-Yb体系能级结构详细讨论了上转换发射的跃迁机制。
Ca_3Y_2Si_3O_(12)∶Tm~(3+),Yb~(3+) up-conversion phosphors were synthesized by solid-state reaction method at 1 400 ℃,and the up-conversion luminescence( UCL) properties of the phosphor were studied under 980 nm excitation. The phosphor exhibits strong blue light( 475 nm) and near infrared light( 810 nm),as well as weak red( 650 nm) light,which correspond to ~1G_4→~3H_6,~3H_4→~3H_6 and ~1G_4→~3F_4 transitions of Tm~(3+) ion,respectively. The UCL intensity and brightness of the phosphor increased firstly and then decreased with the increasing Yb~(3+) concentration,and the optimum concentration is 15%. Under the best doping concentration(Yb~(3+) mole fraction of 15%),the intensity ratio of blue and red emissions is calculated to be 12∶1,and the chromaticity coordinate of the phosphor locates at the blue region( 0. 129 2,0. 152 3). Furthermore,the brightness of the phosphor can reach 6. 8 cd/m~2 as the exciting power density is increased to be 3. 9 W/cm~2. These measurement results indicate that the phosphor exhibits excellent blue UCL property and application potential. The dependence of the UCL intensity on excitation power proves that the observed emissionsare obtained via three and two absorption processes. The transition mechanism of the phosphor excited at 980 nm is discussed in detail.
Ca_3Y_2Si_3O_(12)∶Tm~(3+),Yb~(3+) up-conversion phosphors were synthesized by solid-state reaction method at 1 400 ℃,and the up-conversion luminescence( UCL) properties of the phosphor were studied under 980 nm excitation. The phosphor exhibits strong blue light( 475 nm) and near infrared light( 810 nm),as well as weak red( 650 nm) light,which correspond to ~1G_4→~3H_6,~3H_4→~3H_6 and ~1G_4→~3F_4 transitions of Tm~(3+) ion,respectively. The UCL intensity and brightness of the phosphor increased firstly and then decreased with the increasing Yb~(3+) concentration,and the optimum concentration is 15%. Under the best doping concentration(Yb~(3+) mole fraction of 15%),the intensity ratio of blue and red emissions is calculated to be 12∶1,and the chromaticity coordinate of the phosphor locates at the blue region( 0. 129 2,0. 152 3). Furthermore,the brightness of the phosphor can reach 6. 8 cd/m~2 as the exciting power density is increased to be 3. 9 W/cm~2. These measurement results indicate that the phosphor exhibits excellent blue UCL property and application potential. The dependence of the UCL intensity on excitation power proves that the observed emissionsare obtained via three and two absorption processes. The transition mechanism of the phosphor excited at 980 nm is discussed in detail.
引文
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[3]徐森元,郑标,林林,等.单个Ag@Si O2立方体对Na YF4∶Er3+,Yb3+纳米颗粒上转换发光等离子体增强[J].硅酸盐学报,2016,44(7):969-975.XU S Y,ZHENG B,LIN L,et al..Plasmon enhanced upconversion fluorescence of Na YF4∶Er3+,Yb3+nanoparticles with single Ag@Si O2nanocube[J].J.Chin.Ceram.Soc.,2016,44(7):969-975.(in Chinese)
[4]何光辉,毕雪晴,宋维业,等.Na YF4∶Yb3+,Tm3+/Cd Se纳米异质结构的近红外上转换发光性能[J].发光学报,2015,36(5):491-496.HE G H,BI X Q,SONG W Y,et al..NIR upconversion luminescence of Na YF4∶Yb3+,Tm3+/Cd Se nanoheterostructures[J].Chin.J.Lumin.,2015,36(5):491-496.(in Chinese)
[5]ZOU X L,IZUMITANI T.Fluorescence mechanisms and dynamics of Tm3+singly doped and Yb3+,Tm3+doubly doped glasses[J].J.Non-Cryst.Solids,1993,162(1-2):58-67.
[6]HUANG B,ZHOU Y X,CHENG P,et al..The 1.85μm spectroscopic properties of Er3+/Tm3+co-doped tellurite glasses containing silver nanoparticles[J].J.Alloys Compd.,2016,686:785-792.
[7]CHEN G H,YAO L Q,ZHONG H J,et al..Luminescent properties and energy transfer behavior between Tm3+and Dy3+ions in co-doped phosphate glasses for white LEDs[J].J.Lumin.,2016,178:6-12.
[8]MISIAK M,STREK W,ARABASZ S,et al..The effect of intentional potassium co-doping on the luminescent properties of Yb3+and Tm3+dopedα-Na YF4core and core-shell nanoparticles[J].J.Lumin.,2016,178:34-42.
[9]FENG Z G,XIA H P,WANG C,et al..1.8μm luminescent properties and energy transfer of Yb3+/Tm3+co-dopedα-Na YF4single crystals[J].J.Alloys Compd.,2016,680:26-30.
[10]GAO D L,TIAN D P,CHONG B,et al..Spectral tuning via multi-phonon-assisted Stokes and anti-Stokes excitations in La F3∶Tm3+nanoparticles[J].J.Alloys Compd.,2016,678:212-218.
[11]HUANG X Y.Enhancement of near-infrared to near-infrared upconversion luminescence in sub-10-nm ultra-small La F3∶Yb3+/Tm3+nanoparticles through lanthanide doping[J].Opt.Lett.,2015,40(22):5231-5234.
[12]WANG S Q,QIU J B,WANG Q,et al..Energy transfer and visible-infrared quantum cutting photoluminescence modification in Tm-Yb codoped YPO4inverse opal photonic crystals[J].Appl.Opt.,2015,54(22):6827-6831.
[13]KUMARI A,SONI A K,DEY R,et al..White light emission and optical heating in Er3+-Tm3+-Yb3+codoped La2O3phosphor[J].J.Display Technol.,2016,12(1):99-105.
[14]付作岭,董晓睿,盛天琦,等.纳米晶体中稀土离子的发光性质及其变化机理研究[J].中国光学,2015,8(1):139-144.FU Z L,DONG X R,SHENG T Q,et al..Luminescene properties and various mechanisms of rare earth ions in the nano-crystals[J].Chin.Opt.,2015,8(1):139-144.(in Chinese)
[15]KLASENS H A,HOEKSTRA A H,COX A P M.Ultraviolet fluorescence of some ternary silicates activated with lead[J].J.Electrochem.Soc.,1957,104(2):93-100.
[16]MOORE P B,ARAKI T.Atomic arrangement of merwinite,Ca3Mg[Si O4]2,an unusual dense-packed structure of geophysical interest[J].Am.Mineral.,1972,57:1355-1374.
[17]WU J,ZHANG P,JIANG C D,et al..Preparation and luminescence properties of green phosphors Ca3Y2Si3O12∶Tb3+,Ce3+[J].Chin.J.Inorg.Chem.,2015,31(6):1201-1206.
[18]KADUKAR M R,YAWALKAR P W,CHOITHRANI R,et al..Mechanoluminescence,thermoluminescence,photoluminescence studies on Ca3Y2Si3O12∶RE3+(RE3+=Dy3+and Eu3+)phosphors[J].Luminescence,2015,30(8):1219-1225.
[19]ZHAOG G L,KOZUKA H,LIN H,et al..Sol-gel preparation of Ti1-xVxO2solid solution film electrodes with conspicuous photoresponse in the visible region[J].Thin Solid Films,1999,339(1-2):123-128.
[20]CHUNG J H,RYU J H,LEE S Y,et al..Effect of Yb3+and Tm3+concentrations on blue and NIR upconversion luminescence in Yb3+,Tm3+co-doped Ca Mo O4[J].Ceram.Int.,2013,39(2):1951-1956.
[21]LI L,CAO X Q,ZHANG Y,et al..Synthesis and upconversion luminescence of Lu2O3∶Yb3+,Tm3+nanocrystals[J].Trans.Nonferr.Met.Soc.China,2012,22(2):373-379.