球形BaZnF_4∶Yb,Er纳米颗粒的热分解法合成及其上转换发光性质
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摘要
采用热分解法制备了Ba Zn F4∶Yb,Er纳米颗粒。通过荧光分光光度计、X射线粉末衍射仪(XRD)和透射电子显微镜(TEM)对样品进行了表征。合成样品的形貌为球形,晶相为四方相,平均粒径为8 nm。当敏化剂Yb3+和激活剂Er3+的掺杂摩尔分数分别为20%和4%时,样品的发光性能较好。绿光和红光发射对应的辐射跃迁分别为Er3+离子的2H11/2→4I15/2(绿光)和4S3/2→4I15/2(绿光),以及Er3+离子的4F9/2→4I15/2(红光)。
A series of BaZn F4∶ Er3 +,Yb3 +upconversion luminescence nanoparticles with various doping concentrations were synthesized via thermal decomposition method. X-ray diffraction( XRD),transmission electron microscope( TEM) and fluorescence spectrophotometer were used to investigate the morphology,crystal structure and upconversion properties of the samples. The morphology of the sample is ball shape with an average size about 8 nm. 4% Er3+and 20% Yb3+are the best doping mole fraction. Red and green emissions were observed for the synthesized samples under 980 nm excitation. The red and green emissions are corresponding to the transitions2H11 /2→4I15 /2( Green),4S3 /2→4I15 /2( Green) of Er3 +,4F9 /2→4I15 /2( Red) of Er3+ions,respectively.
A series of BaZn F4∶ Er3 +,Yb3 +upconversion luminescence nanoparticles with various doping concentrations were synthesized via thermal decomposition method. X-ray diffraction( XRD),transmission electron microscope( TEM) and fluorescence spectrophotometer were used to investigate the morphology,crystal structure and upconversion properties of the samples. The morphology of the sample is ball shape with an average size about 8 nm. 4% Er3+and 20% Yb3+are the best doping mole fraction. Red and green emissions were observed for the synthesized samples under 980 nm excitation. The red and green emissions are corresponding to the transitions2H11 /2→4I15 /2( Green),4S3 /2→4I15 /2( Green) of Er3 +,4F9 /2→4I15 /2( Red) of Er3+ions,respectively.
引文
[1]Naccache R,Speghini A,Capobianco J,et al.Colloidal Tm3+/Yb3+-doped Li YF4nanocrystals:Multiple luminescence spanning the UV to NIR regions via low-energy excitation[J].Adv.Mater,2009,21(40):4025-4028.
[2]De G J H,Si Q,Meng G L B Q.Solvothermal synthesis and white upconversion luminescence properties of La0.789Yb0.20-Ho0.001Tm0.01F3nanocubes[J].Chem.J.Chin.Univ.(高等学校化学学报),2011,8(8):1692-1696(in English).
[3]Wu Q L,Pei J F,De G J H.One-pot synthesis of hollow structured upconversion luminescentβ-Na YF4∶Yb0.2Er0.02nanoparticles[J].J.Lumin.,2014,152:192-194.
[4]Shang S J,Yuan X M,Wang Y Q,et al.Application of ultrasonic dispersion in preparation of small particles(Y,Gd)-BO3∶Eu3+powder[J].Chin.J.Liq.Cryst.Disp.(液晶与显示),2010,25(2):186-191(in Chinese).
[5]Huang M W,Meng F I,Yuan X H,et al.Research on upconversion spectra of Na Y1-x-yF4∶Yb3+y/Tm3+xnanoparticles[J].Chin.J.Lumin.(发光学报),2008,29(1):192-194(in Chinese).
[6]Zhang J H,Lv W,Hao Z D,et al.Color-tunable white-light emitting Ba Mg2Al6Si9O30∶Eu2+,Tb3+,Mn2+phosphors via energy transfer[J].Chin.Opt.(中国光学),2012,5(3):203-208(in Chinese)
[7]De G J H,Meng G L B Q,Si Q.Bright white light through up-conversion of single NIR source fromβ-Na Gd0.794Yb0.200-Ho0.001Tm0.005F4nanoparticles[J].Chin.J.Lumin.(发光学报),2010,31(5):737-742(in Chinese).
[8]Yi G S,Chow G M.Water-soluble Na YF4∶Yb,Er(Tm)/Na YF4/polymer core/shell/shell nanoparticles with significant enhancement of upconversion fluorescence[J].Chem.Mater.,2007,19(3):341-343.
[9]Naccache R,Vetrone F,Mahalingam V,et al.Controlled synthesis and water dispersibility of hexagonal phase Na Gd F4∶Ho3+/Yb3+nanoparticles[J].Chem.Mater.,2009,21(4):717-723.
[10]Chen D,Huang P,Yu Y,et al.Dopant-induced phase transition:A new strategy of synthesizing hexagonal upconversion Na YF4at low temperature[J].Chem.Comm.,2011,47(20):5801-5803.
[11]Auzel F.Upconversion and anti-Stokes processes with f and d ions in solids[J].Chem.Rev.,2004,104(1):139-174.
[12]Zhou J,Liu Z,Li F Y.Upconversion nanophosphors for small-animal imaging[J].Chem.Soc.Rev.,2012,41(3):1323-1349.
[13]Yao L M,Feng W,Li F Y,et al.A cyanine-modified nanosystem for in vivo upconversion luminescence bioimaging of methylmercury[J].J.Am.Chem.Soc.,2013,135:9869-9876.
[14]Heer S,Kmpe K,Güdel 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.
[15]Zeng J H,Su J,Li Z H,et al.Synthesis and upconversion luminescence of hexagonal-phase Na YF4∶Yb,Er3+phosphors of controlled size and morphology[J].Adv.Mater.,2005,17(17):2119-2123.
[16]Xiong L,Yang T,Yang Y,et al.Long-term in vivo biodistribution imaging and toxicity of polyacrylic acid-coated upconversion nanophosphors[J].Biomater.,2010,31(27):7078-7085.
[17]Mao Y,Huang J Y,Ostroumov R,et al.Synthesis and luminescence properties of erbium-doped Y2O3nanotubes[J].J.Phys.Chem.,2008,112(7):2278-2285.
[18]De G J H,Meng G L B Q,Si Q.Bright white upconvertion luminescence inβ-Na Gd0.794Yb0.20Ho0.005F4nanoparticles[J].Chem.Lett.,2010,39(11):1158-1159.
[19]Mai H X,Zhang Y W,Si R,et al.High-quality sodium rare-earth fluoride nanocrystals:Controlled synthesis and optical properties[J].J.Am.Chem.Soc.,2006,128(19):6426-6436.
[20]Boyer J C,Vetrone F,Cuccia L A,et al.Synthesis of colloidal upconverting Na YF4nanocrystals doped with Er3+,Yb3+and Tm3+,Yb3+via thermal decomposition of lanthanide trifluoroacetate precursors[J].J.Am.Chem.Soc.,2006,128(23):7444-7445.
[21]Chen G,Ohulchanskyy T Y,Kumar R,et al.Ultrasmall monodisperse Na YF4∶Yb3+/Tm3+nanocrystals with enhanced near-infrared to near-infrared upconversion photoluminescence[J].ACS Nano,2010,4(6):3163-3168.
[22]Bogdan N,Vetrone F,Ozin G A,et al.Synthesis of ligand-free colloidally stable water dispersible brightly luminescent lanthanide-doped upconverting nanoparticles[J].Nano Lett.,2011,11(2):835-840.
[23]Mai H X,Zhang Y W,Sun L D,et al.Size-and phase-controlled synthesis of monodisperse Na YF4∶Yb,Er nanocrystals from a unique delayed nucleation pathway monitored with upconversion spectroscopy[J].J.Phys.Chem.C,2007,111(37):13730-13739.
[24]Kim S W,Chang H Y,Halasyamani P S.Selective pure-phase synthesis of the multiferroic Ba MF4(M=Mg,Mn,Co,Ni,and Zn)family[J].J.Am.Chem.Soc.,2010,132(50):17684-17685.
[25]Liu N,Qin W,Qin G,et al.Highly plasmon-enhanced upconversion emissions from Au@β-Na YF4∶Yb,Tm hybrid nanostructures[J].Chem.Comm.,2011,47(27):7671-7673.
[26]Wang L,Yan R,Huo Z,et al.Fluorescence resonant energy transfer biosensor based on upconversion-luminescent nanoparticles[J].Angew.Chem.Int.Ed.,2005,44(37):6054-6057.
[27]Wang L,Li Y.Green upconversion nanocrystals for DNA detection[J].Chem.Comm.,2006(24):2557-2559.
[28]Lim S F,Riehn R,Ryu W S,et al.In vivo and scanning electron microscopy imaging of upconverting nanophosphors in caenorhabditis elegans[J].Nano Lett.,2006,6(2):169-174.
[2]De G J H,Si Q,Meng G L B Q.Solvothermal synthesis and white upconversion luminescence properties of La0.789Yb0.20-Ho0.001Tm0.01F3nanocubes[J].Chem.J.Chin.Univ.(高等学校化学学报),2011,8(8):1692-1696(in English).
[3]Wu Q L,Pei J F,De G J H.One-pot synthesis of hollow structured upconversion luminescentβ-Na YF4∶Yb0.2Er0.02nanoparticles[J].J.Lumin.,2014,152:192-194.
[4]Shang S J,Yuan X M,Wang Y Q,et al.Application of ultrasonic dispersion in preparation of small particles(Y,Gd)-BO3∶Eu3+powder[J].Chin.J.Liq.Cryst.Disp.(液晶与显示),2010,25(2):186-191(in Chinese).
[5]Huang M W,Meng F I,Yuan X H,et al.Research on upconversion spectra of Na Y1-x-yF4∶Yb3+y/Tm3+xnanoparticles[J].Chin.J.Lumin.(发光学报),2008,29(1):192-194(in Chinese).
[6]Zhang J H,Lv W,Hao Z D,et al.Color-tunable white-light emitting Ba Mg2Al6Si9O30∶Eu2+,Tb3+,Mn2+phosphors via energy transfer[J].Chin.Opt.(中国光学),2012,5(3):203-208(in Chinese)
[7]De G J H,Meng G L B Q,Si Q.Bright white light through up-conversion of single NIR source fromβ-Na Gd0.794Yb0.200-Ho0.001Tm0.005F4nanoparticles[J].Chin.J.Lumin.(发光学报),2010,31(5):737-742(in Chinese).
[8]Yi G S,Chow G M.Water-soluble Na YF4∶Yb,Er(Tm)/Na YF4/polymer core/shell/shell nanoparticles with significant enhancement of upconversion fluorescence[J].Chem.Mater.,2007,19(3):341-343.
[9]Naccache R,Vetrone F,Mahalingam V,et al.Controlled synthesis and water dispersibility of hexagonal phase Na Gd F4∶Ho3+/Yb3+nanoparticles[J].Chem.Mater.,2009,21(4):717-723.
[10]Chen D,Huang P,Yu Y,et al.Dopant-induced phase transition:A new strategy of synthesizing hexagonal upconversion Na YF4at low temperature[J].Chem.Comm.,2011,47(20):5801-5803.
[11]Auzel F.Upconversion and anti-Stokes processes with f and d ions in solids[J].Chem.Rev.,2004,104(1):139-174.
[12]Zhou J,Liu Z,Li F Y.Upconversion nanophosphors for small-animal imaging[J].Chem.Soc.Rev.,2012,41(3):1323-1349.
[13]Yao L M,Feng W,Li F Y,et al.A cyanine-modified nanosystem for in vivo upconversion luminescence bioimaging of methylmercury[J].J.Am.Chem.Soc.,2013,135:9869-9876.
[14]Heer S,Kmpe K,Güdel 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.
[15]Zeng J H,Su J,Li Z H,et al.Synthesis and upconversion luminescence of hexagonal-phase Na YF4∶Yb,Er3+phosphors of controlled size and morphology[J].Adv.Mater.,2005,17(17):2119-2123.
[16]Xiong L,Yang T,Yang Y,et al.Long-term in vivo biodistribution imaging and toxicity of polyacrylic acid-coated upconversion nanophosphors[J].Biomater.,2010,31(27):7078-7085.
[17]Mao Y,Huang J Y,Ostroumov R,et al.Synthesis and luminescence properties of erbium-doped Y2O3nanotubes[J].J.Phys.Chem.,2008,112(7):2278-2285.
[18]De G J H,Meng G L B Q,Si Q.Bright white upconvertion luminescence inβ-Na Gd0.794Yb0.20Ho0.005F4nanoparticles[J].Chem.Lett.,2010,39(11):1158-1159.
[19]Mai H X,Zhang Y W,Si R,et al.High-quality sodium rare-earth fluoride nanocrystals:Controlled synthesis and optical properties[J].J.Am.Chem.Soc.,2006,128(19):6426-6436.
[20]Boyer J C,Vetrone F,Cuccia L A,et al.Synthesis of colloidal upconverting Na YF4nanocrystals doped with Er3+,Yb3+and Tm3+,Yb3+via thermal decomposition of lanthanide trifluoroacetate precursors[J].J.Am.Chem.Soc.,2006,128(23):7444-7445.
[21]Chen G,Ohulchanskyy T Y,Kumar R,et al.Ultrasmall monodisperse Na YF4∶Yb3+/Tm3+nanocrystals with enhanced near-infrared to near-infrared upconversion photoluminescence[J].ACS Nano,2010,4(6):3163-3168.
[22]Bogdan N,Vetrone F,Ozin G A,et al.Synthesis of ligand-free colloidally stable water dispersible brightly luminescent lanthanide-doped upconverting nanoparticles[J].Nano Lett.,2011,11(2):835-840.
[23]Mai H X,Zhang Y W,Sun L D,et al.Size-and phase-controlled synthesis of monodisperse Na YF4∶Yb,Er nanocrystals from a unique delayed nucleation pathway monitored with upconversion spectroscopy[J].J.Phys.Chem.C,2007,111(37):13730-13739.
[24]Kim S W,Chang H Y,Halasyamani P S.Selective pure-phase synthesis of the multiferroic Ba MF4(M=Mg,Mn,Co,Ni,and Zn)family[J].J.Am.Chem.Soc.,2010,132(50):17684-17685.
[25]Liu N,Qin W,Qin G,et al.Highly plasmon-enhanced upconversion emissions from Au@β-Na YF4∶Yb,Tm hybrid nanostructures[J].Chem.Comm.,2011,47(27):7671-7673.
[26]Wang L,Yan R,Huo Z,et al.Fluorescence resonant energy transfer biosensor based on upconversion-luminescent nanoparticles[J].Angew.Chem.Int.Ed.,2005,44(37):6054-6057.
[27]Wang L,Li Y.Green upconversion nanocrystals for DNA detection[J].Chem.Comm.,2006(24):2557-2559.
[28]Lim S F,Riehn R,Ryu W S,et al.In vivo and scanning electron microscopy imaging of upconverting nanophosphors in caenorhabditis elegans[J].Nano Lett.,2006,6(2):169-174.