K离子掺杂增强NaErF_4体系上转换发光
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摘要
制备了一系列Na_(1-x)K_xErF_4@NaLuF_4的核壳纳米结构,核中K~+掺杂摩尔分数变化范围为0%~8%。XRD分析结果揭示这些具有不同K掺杂浓度的纳米粒子均为!-相纳米结构。研究结果表明:随着K~+浓度的增加,纳米结构中Er~(3+)~650 nm处的红带发光强度呈现先增强后减弱的规律,当K~+摩尔分数为4%时,Na_(0.96)K_(0.04)ErF_4@NaLuF_4纳米晶的发光强度达到最大,为未掺杂K~+的NaErF_4@NaLuF_4纳米晶发光强度的3.7倍。其发光增强的原因在于K~+的掺杂降低了Er~(3+)微环境晶场宇称对称性,提高了Er~(3+)离子~4F_(9/2)→~4I_(5/2)能级辐射跃迁几率,进而增强了Er~(3+)的650 nm红带的上转换发光强度。
The nanostructures composing of Na_(1-x)K_xErF_4@NaLuF_4 core@ shell were synthetized with0%-8% K~+ doping mole fraction in the cores. XRD results reveal that all of the nanoparticles are the hexagonal structure. The research results show that the intensity of UCL at ~ 650 nm increases at first and then decreases with K+concentration under 980 nm excitation. The intensity is enhanced 3. 7 times with 4% K~+ doping,compared with that of NaErF_4@NaLuF_4 core @ shell without K~+ doping. Furthermore,the slopes of relationship between UCL intensity and pumping power are from1.91 to 1.76,for the two nanostructures undoped and doped with 4% K~+,respectively. Our results suggest that the strategy of K~+ doping in NaErF_4@NaLuF_4 nanoparticles is an efficient solution to improve the luminescence efficiency of NaErF_4@NaLuF_4 nanosystem.
The nanostructures composing of Na_(1-x)K_xErF_4@NaLuF_4 core@ shell were synthetized with0%-8% K~+ doping mole fraction in the cores. XRD results reveal that all of the nanoparticles are the hexagonal structure. The research results show that the intensity of UCL at ~ 650 nm increases at first and then decreases with K+concentration under 980 nm excitation. The intensity is enhanced 3. 7 times with 4% K~+ doping,compared with that of NaErF_4@NaLuF_4 core @ shell without K~+ doping. Furthermore,the slopes of relationship between UCL intensity and pumping power are from1.91 to 1.76,for the two nanostructures undoped and doped with 4% K~+,respectively. Our results suggest that the strategy of K~+ doping in NaErF_4@NaLuF_4 nanoparticles is an efficient solution to improve the luminescence efficiency of NaErF_4@NaLuF_4 nanosystem.
引文
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[2]WANG F,BANERJEE D,LIU Y,et al..Upconversion nanoparticles in biological labeling,imaging,and therapy[J].Analyst,2010,135(8):1839-1854.
[3]HEER S,KMPE K,GDEL H U,et al..Highly efficient multicolour upconversion emission in transparent colloids of lanthanide-doped Na YF4nanocrystals[J].Adv.Mater.,2004,16(23-24):2102-2105.
[4]李慧,杨魁胜,祁宁,等.Yb3+/Er3+掺杂氟氧化物微晶玻璃的制备与发光性能[J].中国光学,2011,4(6):672-677.LI H,YANG K S,QI N,et al..Preparation and luminescence properties of Yb3+/Er3+-codoped oxyfluoride glass ceramics[J].Chin.Opt.,2011,4(6):672-677.(in Chinese)
[5]臧雪梅,田亚蒙,赵昕,等.钬镱掺杂波导适用型锗酸盐玻璃上转换荧光光子定量[J].光子学报,2016,45(9):916002.ZANG X M,TIAN Y M,ZHAO X,et al..Quantification of photon upconversion in holmium and ytterbium doped waveguide-typed germanate glasses[J].Acta Photon.Sinica,2016,45(9):916002.(in Chinese)
[6]BOYER J C,VAN VEGGEl F C J M.Absolute quantum yield measurements of colloidal Na YF4∶Er3+,Yb3+upconverting nanoparticles[J].Nanoscale,2010,2(8):1417-1419.
[7]吴中立,吴红梅,唐立丹,等.Tm3+/Yb3+共掺氟氧化物碲酸盐玻璃的上转换发光及光学温度传感[J].光子学报,2017,46(9):916003.WU Z L,WU H M,TANG L D,et al..Up-conversion light-emitting and optical temperature sensing for Tm3+/Yb3+codoped oxyfluoride tellurite glass[J].Acta Photon.Sinica,2017,46(9):916003.(in Chinese)
[8]VETRONE F,NACCACHE R,MAHALINGAM V,et al..The active-core/active-shell approach:a strategy to enhance the upconversion luminescence in lanthanide-doped nanoparticles[J].Adv.Funct.Mater.,2009,19(18):2924-2929.
[9]HAASE M,SCHAEFER H.Upconverting nanoparticles[J].Angew.Chem.Int.Ed.,2011,50(26):5808-5829.
[10]ZHONG Y,TIAN G,GU Z,et al..Elimination of photon quenching by a transition layer to fabricate a quenching-shield sandwich structure for 800 nm excited upconversion luminescence of Nd3+sensitized nanoparticles[J].Adv.Mater.,2014,26(18):2831-2837.
[11]JOHNSON N J J,HE S,DIAO S,et al..Direct evidence for coupled surface and concentration quenching dynamics in lanthanide-doped nanocrystals[J].J.Am.Chem.Soc.,2017,139(8):3275-3282.
[12]ZUO J,LI Q,XUE B,et al..Employing shell to eliminate concentration quenching in photonic upconversion nanostructure[J].Nanoscale,2017,9(23):7941-7946.
[13]JUDD B R.Optical absorption intensities of rare-earth ions[J].Phys.Rev.,1962,127(3):750-761.
[14]丁艳丽,张晓丹,梁雪娇,等.Na+掺杂对Li YF4∶Er3+/Yb3+上转换发光性能的影响[J].发光学报,2014,35(5):536-541.DING Y L,ZHANG X D,LIANG X J,et al..Influence of Na+doping on upconversion luminescence of Li YF4∶Er3+/Yb3+microcrystals[J].Chin.J.Lumin.,2014,35(5):536-541.(in Chinese)
[15]ZHAO C,KONG X,LIU X,et al..Li+ion doping:an approach for improving the crystallinity and upconversion emissions of Na YF4∶Yb3+,Tm3+nanoparticles[J].Nanoscale,2013,5(17):8084-8089.
[16]翟雪松,刘世虎,范柳燕,等.强上转换发光的Li Lu1-xYbxF4∶Tm@Li Gd F4核壳纳米晶的制备[J].发光学报,2017,38(9):1149-1154.ZHAI X S,LIU S H,FAN L Y,et al..Preparation of Li Lu1-xYbxF4∶Tm@Li Gd F4core-shell nanocrystals with enhanced upconversion luminescence[J].Chin.J.Lumin.,2017,38(9):1149-1154.(in Chinese)
[17]QIAN H S,ZHANG Y.Synthesis of hexagonal-phase core-shell Na YF4nanocrystals with tunable upconversion fluorescence[J].Langmuir,2008,24(21):12123-12125.
[18]POLLNAU M,GAMELIN D R,LTHI S R,et al..Power dependence of upconversion luminescence in lanthanide and transition-metal-ion systems[J].Phys.Rev.B,2000,61(5):3337.