纳米金膜及金壳表面局域等离激元对上转换荧光波长的选择调控
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摘要
基于贵金属表面局域等离子体共振(LSPR)调控上转换荧光的研究绝大部分集中于纳米颗粒或纳米棒,即使同一复合结构对上转换荧光(UCL)也有或增强或猝灭的截然相反的报道,而对于进一步提高上转换荧光材料的效率和强度以满足更广泛的应用需求则越来越引起人们高度关注。本文通过构筑两种纳米金/上转换纳米晶复合结构,系统研究了各自的表面局域等离激元对上转换荧光的增强和猝灭效应,基于微结构表征及对稳态、瞬态荧光光谱的分析,阐述了波长依赖的上转换荧光增强和猝灭机理。结果显示超薄纳米金壳结构对Ho~(3+)、Fe~(3+)共掺杂纳米晶的绿光发射选择性地增强了25倍,源于激发光能量与LSPR能量匹配的激发增强机制,而在覆盖有超薄纳米金膜的上转换纳米晶复合结构中却观察到了金膜引起的Er上转换荧光猝灭,同时红绿比随金膜厚度增加而增大,来自于金膜对激发光的散射、金膜的LSPR吸收带与绿光发射能级耦合引起无辐射跃迁几率增加,绿光上转换荧光强度下降相对显著,UCL寿命变短。
Two types of plasmonic nanostructure i.e. the ultra-thin gold nanoshell and the sputtered gold nanofilm combined with upconverting nanocrystals are designed and fabricated. The enhancing effect of gold nanoshells on the upconversion luminescence(UCL) and the quenched UCL induced by the gold nanofilm are observed, respectively. The wavelength dependent enhancement and quenching mechanisms are elucidated on the basis of the microstructure characterizations, steady state and transient spectral analysis. Green emission of Ho ions has been selectively enhanced by the ultra-thin gold nanoshell outside of NaYF_4∶Yb, Ho,Fe nanocrystals, and the excitation enhancement mechanism is stemmed from the coupling of LSPR with NIR excitation energy. In contrast, sputtered gold film on the top of the NaYF_4∶Yb,Er@SiO_2 nanocrystal exhibits the quenching effect, likely originating from the scattering of the excitation light and the increase of nonradiative transition probability of the green emission state due to its coupling with LSPR absorption band, which is responsible for the decline of UCL intensity as well as the shortened green UCL lifetime.
Two types of plasmonic nanostructure i.e. the ultra-thin gold nanoshell and the sputtered gold nanofilm combined with upconverting nanocrystals are designed and fabricated. The enhancing effect of gold nanoshells on the upconversion luminescence(UCL) and the quenched UCL induced by the gold nanofilm are observed, respectively. The wavelength dependent enhancement and quenching mechanisms are elucidated on the basis of the microstructure characterizations, steady state and transient spectral analysis. Green emission of Ho ions has been selectively enhanced by the ultra-thin gold nanoshell outside of NaYF_4∶Yb, Ho,Fe nanocrystals, and the excitation enhancement mechanism is stemmed from the coupling of LSPR with NIR excitation energy. In contrast, sputtered gold film on the top of the NaYF_4∶Yb,Er@SiO_2 nanocrystal exhibits the quenching effect, likely originating from the scattering of the excitation light and the increase of nonradiative transition probability of the green emission state due to its coupling with LSPR absorption band, which is responsible for the decline of UCL intensity as well as the shortened green UCL lifetime.
引文
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[21] LENG J,TANG J,XIE W Y,et al..Impact of pH and urea content on size and luminescence of upconverting Y2O3∶Yb,Er nanophosphors [J].Mater.Res.Bull.,2018,100:171-177.
[22] XIANG G T,ZHANG J H,HAO Z D,et al..Solvothermal synthesis and upconversion properties of about 10 nm orthorhombic LuF3∶Yb3+,Er3+ rectangular nanocrystals [J].J.Colloid Interface Sci.,2015,459:224-229.
[23] ZHANG F,WAN Y,YU T,et al..Uniform nanostructured arrays of sodium rare-earth fluorides for highly efficient multicolor upconversion luminescence [J].Angew.Chem.Int.Ed.,2007,46(42):7976-7979.
[24] 董浩,朱光平,代凯,等.Ho3+-Yb3+共掺杂La2O3上转换发光性质的研究 [J].江西师范大学学报(自然科学版),2018,42(5):459-463.DONG H,ZHU G P,DAI K,et al..The study on upconversion luminescence properties of Ho3+-Yb3+codoped La2O3 [J].J.Jiangxi Normal Univ.(Nat.Sci.),2018,42(5):459-463.(in Chinese)
[25] GEDDES C D,LAKOWICZ J R.Editorial:metal-enhanced fluorescence [J].J.Fluoresc.,2002,12(2):121-129.
[26] CAMPION A,GALLO A R,HARRIS C B,et al..Electronic energy transfer to metal surfaces:a test of classical image dipole theory at short distances [J].Chem.Phys.Lett.,1980,73(3):447-450.王月(1997-),女,吉林松原人,硕士研究生,2017年于吉林化工学院获得学士学位,主要从事纳米光子学材料及应用的研究。E-mail:215518030@qq.com陈力(1974-),男,黑龙江五常人,博士,教授,2007年于中国科学院长春光学精密机械与物理研究所获得博士学位,主要从事低维掺杂材料光物理及纳米光子学的研究。E-mail:chenli@ccut.edu.cn
[2] FENG W,SUN L D,YAN C H.Ag nanowires enhanced upconversion emission of NaYF4∶Yb,Er nanocrystals via a direct assembly method [J].Chem.Comm.,2009,(29):4393-4395.
[3] HAN S Y,SAMANTA A,XIE X J,et al..Gold and hairpin DNA functionalization of upconversion nanocrystals for imaging and in vivo drug delivery [J].Adv.Mater.,2017,29(18):1700244.
[4] LUTHER J M,JAIN P K,EWERS T,et al..Localized surface Plasmon resonances arising from free carriers in doped quantum dots [J].Nat.Mater.,2011,10(5):361-366.
[5] HE J J,ZHENG W,LIGMAJER F,et al..Plasmonic enhancement and polarization dependence of nonlinear upconversion emissions from single gold nanorod@SiO2@CaF2∶Yb3+,Er3+ hybrid core-shell-satellite nanostructures [J].Light Sci.Appl.,2017,6:e16217-1-11.
[6] PERASSI E M,CANALI L R,CORONADO E A.Enhancement and confinement analysis of the electromagnetic fields inside hot spots [J].J.Phys.Chem.C,2009,113(16):6315-6319.
[7] ITO Y,MATSUDA K,KANEMITSU Y.Mechanism of photoluminescence enhancement in single semiconductor nanocrystals on metal surfaces [J].Phys.Rev.B,2007,75(3):033309-1-4.
[8] ZHANG H,XU D,HUANG Y,et al..Highly spectral dependent enhancement of upconversion emission with sputtered gold island films [J].Chem.Commun.,2011,47(3):979-981.
[9] PRIYAM A,IDRIS N M,ZHANG Y.Gold nanoshell coated NaYF4 nanoparticles for simultaneously enhanced upconversion fluorescence and darkfield imaging [J].J.Mater.Chem.,2011,22(3):960-965.
[10] HAN S Y,DENG R,XIE X J,et al..Enhancing luminescence in lanthanide-doped upconversion nanoparticles [J].Angew.Chem.Int.Ed.,2014,53(44):117002-11715.
[11] LI L,GREEN K,HALLEN H,et al..Enhancement of single particle rare earth doped NaYF4∶Yb,Er emission with a gold shell [J].Nanotechnology,2015,26(2):025101-1-9.
[12] LIU Y M,XIA Y,JIANG Y,et al..Coupling effects of Au-decorated core-shell β-NaYF4∶Er/Yb@SiO2 microprisms in dye-sensitized solar cells:plasmon resonance versus upconversion [J].Electrochim.Acta,2015,180:394-400.
[13] TANG J,CHEN L,LI J,et al..Selectively enhanced red upconversion luminescence and phase/size manipulation via Fe3+ doping in NaYF4∶Yb,Er nanocrystals [J].Nanoscale,2015,7(35):14752-14759.
[14] 杨奉真,衣光舜,陈德朴,等.纳米NaYF4∶Yb,Ho上转换荧光粉的合成及其性质研究 [J].高等学校化学学报,2004,25(9):1589-1592.YANG F Z,YI G S,CHEN D P,et al..Synthesis and up-conversion luminescence properties of nanocrystal Yb,Ho Co-doped sodium yttrium fluoride [J].Chem.J.Chin.Univ.,2004,25(9):1589-1592.(in Chinese)
[15] MANURUNG R V,WU C T,CHATTOPADHYAY S.Tuning sputtered gold thickness to enhance absorption and emission in core-shell type erbium doped upconversion nanoparticles [J].J.Phys.Conf.Ser.,2018,985:012003.
[16] WANG F,LIU X G.Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals [J].Chem.Soc.Rev.,2009,38(4):976-989.
[17] WEN S H,ZHOU J J,ZHENG K Z,et al..Advances in highly doped upconversion nanoparticles [J].Nat.Commun.,2018,9(1):2415.
[18] XIE W Y,AN X T,CHEN L,et al..Tunable phase and upconverting luminescence of Gd3+ co-doped NaErF4∶Yb3+ nanostructures [J].Mater.Res.Bull.,2017,95:509-514.
[19] LI T,GUO C F,SUO H,et al..Dual-mode modulation of luminescence chromaticity in AgLa(MoO4)2∶Yb3+,Ho3+ up-conversion phosphors [J].J.Mater.Chem.C,2016,4(10):1964-1971.
[20] ZHANG J H,HAO Z D,LI J,et al..Observation of efficient population of the red-emitting state from the green state by non-multiphonon relaxation in the Er3+-Yb3+ system [J].Light Sci.Appl.,2015,4:e239-1-6.
[21] LENG J,TANG J,XIE W Y,et al..Impact of pH and urea content on size and luminescence of upconverting Y2O3∶Yb,Er nanophosphors [J].Mater.Res.Bull.,2018,100:171-177.
[22] XIANG G T,ZHANG J H,HAO Z D,et al..Solvothermal synthesis and upconversion properties of about 10 nm orthorhombic LuF3∶Yb3+,Er3+ rectangular nanocrystals [J].J.Colloid Interface Sci.,2015,459:224-229.
[23] ZHANG F,WAN Y,YU T,et al..Uniform nanostructured arrays of sodium rare-earth fluorides for highly efficient multicolor upconversion luminescence [J].Angew.Chem.Int.Ed.,2007,46(42):7976-7979.
[24] 董浩,朱光平,代凯,等.Ho3+-Yb3+共掺杂La2O3上转换发光性质的研究 [J].江西师范大学学报(自然科学版),2018,42(5):459-463.DONG H,ZHU G P,DAI K,et al..The study on upconversion luminescence properties of Ho3+-Yb3+codoped La2O3 [J].J.Jiangxi Normal Univ.(Nat.Sci.),2018,42(5):459-463.(in Chinese)
[25] GEDDES C D,LAKOWICZ J R.Editorial:metal-enhanced fluorescence [J].J.Fluoresc.,2002,12(2):121-129.
[26] CAMPION A,GALLO A R,HARRIS C B,et al..Electronic energy transfer to metal surfaces:a test of classical image dipole theory at short distances [J].Chem.Phys.Lett.,1980,73(3):447-450.王月(1997-),女,吉林松原人,硕士研究生,2017年于吉林化工学院获得学士学位,主要从事纳米光子学材料及应用的研究。E-mail:215518030@qq.com陈力(1974-),男,黑龙江五常人,博士,教授,2007年于中国科学院长春光学精密机械与物理研究所获得博士学位,主要从事低维掺杂材料光物理及纳米光子学的研究。E-mail:chenli@ccut.edu.cn
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