Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2的制备及上转换发光性质
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摘要
利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。
Er~(3 +) doped and Er~(3+)-Yb~(3+) co-doped Ca_(12)Al_(14)O_(32)F_2 were synthesized by solid-state reaction method at 1 250 ~oC and the upconversion luminescence(UCL) properties of the phosphor were studied under 980 nm excitation. The phosphor exhibits green(549 nm) and red(655 nm) emission, which corresponding to ~4S_(3/2), ~2H_(11/2)→~4I_(15/2) and ~4F_(9/2)→~4I_(15/2) transitions of Er~(3+) respectively. The UCL intensity of the single doped sample increased firstly and then decreased with the increasing Er~(3+ )concentration and the optimum concentration is 0.8%. The UCL intensity of Ca_(12)Al_(14)O_(32)F_2∶Er~(3+),Yb~(3+) prepared in reducing atmosphere is enhanced by 2 times, which might be due to the encaged ions. The dependence of the UCL intensity on excitation powder proves that the observed emissions are obtained via two absorption processes. The transition mechanism of phosphor excitation under 980 nm is discussed in detail.
Er~(3 +) doped and Er~(3+)-Yb~(3+) co-doped Ca_(12)Al_(14)O_(32)F_2 were synthesized by solid-state reaction method at 1 250 ~oC and the upconversion luminescence(UCL) properties of the phosphor were studied under 980 nm excitation. The phosphor exhibits green(549 nm) and red(655 nm) emission, which corresponding to ~4S_(3/2), ~2H_(11/2)→~4I_(15/2) and ~4F_(9/2)→~4I_(15/2) transitions of Er~(3+) respectively. The UCL intensity of the single doped sample increased firstly and then decreased with the increasing Er~(3+ )concentration and the optimum concentration is 0.8%. The UCL intensity of Ca_(12)Al_(14)O_(32)F_2∶Er~(3+),Yb~(3+) prepared in reducing atmosphere is enhanced by 2 times, which might be due to the encaged ions. The dependence of the UCL intensity on excitation powder proves that the observed emissions are obtained via two absorption processes. The transition mechanism of phosphor excitation under 980 nm is discussed in detail.
引文
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[3] WANG J,WEI T,LI X Y,et al..Near-infrared-light-mediated imaging of latent fingerprints based on molecular recognition [J].Angew.Chem.Int.Ed.Engl.,2014,53(6):1616-1620.
[4] DENG R R,XIE X J,VENDRELL M,et al..Intracellular glutathione detection using MnO2-nanosheet-modified upconversion nanoparticles [J].J.Am.Chem.Soc.,2011,133(50):20168-20171.
[5] LIU K,LIU X M,ZENG Q H,et al..Covalently assembled NIR nanoplatform for simultaneous fluorescence imaging and photodynamic therapy of cancer cells [J].ACS Nano,2012,6(5):4054-4062.
[6] CHEN Q S,XIE X J,HUANG B L,et al..Confining excitation energy in Er3+-sensitized upconversion nanocrystals through Tm3+-mediated transient energy trapping [J].Angew.Chem.Int.Ed.Engl.,2017,56(26):7605-7609.
[7] JIERATUM V.Iron and Copper Chalcogenides:Photovoltaic Absorber Candidates and YZrF7:A New Upconversion Host [D].Forbes:Oregon State University,2013.
[8] WANG Y B,WEI T,CHENG X W,et al..Insights into Li+-induced morphology evolution and upconversion luminescence enhancement of KSc2F7∶Yb/Er nanocrystals [J].J.Mater.Chem.C,2017,5(14):3503-3508.
[9] IKEDA T.First principles centroid molecular dynamics simulation of hydride innanoporous C12A7∶H- [J].J.Chem.Phys.,2017,146(20):204503.
[10] GAO A M,ZHU X F,WANG H J,et al..Reduction features of NO over a potassium-doped C12A7-O- catalyst [J].J.Phys.Chem.B,2006,110(24):11854-11862.
[11] SONG C F,SUN J Q,QIU S B,et al..Atomic fluorine anion storage emission material C12A7-F- and etching of Si and SiO2 by atomic fluorine anions [J].Chem.Mater.,2008,20(10):3473-3479.
[12] LI J,HUANG F,WANG L,et al..High density hydroxyl anions in a microporous crystal:[Ca24Al28O64] 4+·4(OH-) [J].Chem.Mater.,2005,17(10):2771-2774.
[13] COSTA U,BALLIRANO P.Improved powder X-ray data for the cement phase Ca12Al14O32F2(C11A7f) [J].Powder Diff.,2000,15(1):56-61.
[14] CHEN W P,ZHANG X Z,WANG L P.Synthesis and luminescence properties of blue-emitting phosphor Ca12Al14O32F2∶Eu2+ for white light-emitting diode [J].Luminescence,2017,32(6):952-956.
[15] LING H Y,HUANG J P,HOU B H,et al..Structure and photoluminescence of a blue-green-emitting phosphor for near-UV white LEDs [J].J.Am.Ceram.Soc.,2014,97(7):2116-2123.
[16] YANG X X,FU Z L,YANG Y M,et al..Optical temperature sensing behavior of high-efficiency upconversion:Er3+-Yb3+ co-doped NaY(MoO4)2 phosphor [J].J.Am.Ceram.Soc.,2015,98(8):2595-2600.
[17] DUBEY A,SONI A K,KUMARI A,et al..Enhanced green upconversion emission in NaYF4∶Er3+/Yb3+/Li+ phosphors for optical thermometry [J].J.Alloys Compd.,2017,693:194-200.
[18] LIU X L,LIU Y X,YAN D T,et al..Encaged-anion tunable luminescence of Ce3+-activated single host Ca12Al14O32Cl2 phosphor for UV pumped multi-color LEDs [J].Mater.Des.,2016,107:139-143.
[19] FAN Q,CUI X X,XU Y T,et al..Effect of the thermal treatment on the luminescence properties and dispersibility of LaF3∶Nd nanoparticles in solvents [J].Colloids Surf.A Physicochem.Eng.Asp.,2018,538:423-428.
[20] WANG C,CHENG X.Hydrothermal synthesis andupconversion properties of α-NaYF4∶Yb3+,Er3+ nanocrystals using citric acid as chelating ligand and NaNO3 as mineralizer [J].J.Nanosci.Nanotechnol.,2015,15(12):9656-9664.
[21] LIN H,MEREDITH G,JIANG S B,et al..Optical transitions and visible upconversion in Er3+ doped niobic tellurite glass [J].J.Appl.Phys.,2003,93(1):186-191.