Rare earth upconversion nanophosphors: synthesis, functionalization and application as biolabels and energy transfer donors

This review focused on rare earth upconversion nanophosphors (UCNPs), a particular class of emitters whose photoluminescence mechanism is of fundamental difference from that of conventional dyes and semiconductor quantum dots. We in the first section gave a brief summary on a variety of synthetic methodologies developed during the past decades. Instead of presenting an exhaustive reference list, we selected only a few representative examples, illustrating the merits and limits of each involved synthetic route. Then we surveyed the recent progress in the functionalization techniques for these nanomaterials, depicting the modification in microstructures and improvement in properties with respect to the parent nanoparticles. And finally, we emphasized their application in the research fields of biolabeling and energy transfer, narrating their superior performance benefiting from the unique excitation and emission properties.

Preparation and Characterization of Red Luminescent Ca_(0.8)Zn_(0.2)TiO_3∶ Pr^(3+), Na^+ Nanophosphor

Nanophosphor with the nominal composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ （CZTOPN） was synthesized at relatively low temperature by the sol-gel method. Metal ions were dispersed by citric acid in ethylene glycol solvent and then react with Ti（OC4H9）4 to form sol and gel. The decomposition process of the precursor, and crystallization and particle size of CZTOPN were examined by thermal analysis （TG-DSC）, powder X-ray diffraction （XRD）, and scan election microscopy （SEM）. Results of TG-DSC and XRD reveal that the composition of Ca0.8 Zn0.2 TiO3 ： Pr3 ＋ , Na^＋ changes with the sintering temperature. SEM data indicate that the diameter of particles is under 50 nm even if the sintering temperature increases to 1000 ℃. In contrast to a solid state reaction, the excitation spectra of samples synthesized by the sol-gel method shift blue about 10 nm and the emission intensity at 617 nm increases significantly.

Energy transfer in Tb^(3+),Yb^(3+) codoped Lu_2O_3 near-infrared downconversion nanophosphors

Tb3＋ and Yb3＋ codoped Lu2O3 nanophosphors were synthesized by the reverse-strike co-precipitation method. The obtained Lu2O3：Tb3＋,Yb3＋ nanophosphors were characterized by X-ray diffraction （XRD） and photoluminescence （PL） spectra. The XRD results showed that all the prepared nanophosphors could be readily indexed to pure cubic phase of Lu2O3 and indicated good crystallinity. The Tb3＋→Yb3＋ energy transfer mechanisms in the UV-blue region in Lu2O3 nanophosphors were investigated. The experimental results showed that the strong visible emission around 543 nm from Tb3＋ （5D4→7F5） and near-infrared （NIR） emission around 973 nm from Yb3＋ （2F5/2→2F7/2） of Lu2O3：Tb3＋,Yb3＋ nanophosphors were observed under ultraviolet light excitation, respectively. Tb3＋ could be effectively excited up to its 4f75d1 state and relaxed down to the 5D4 level, from which the energy was transferred cooperatively to two neighboring Yb3＋. The Yb3＋ concentration dependent luminescent properties and lifetimes of both the visible and NIR emissions were also studied. The lifetime of the visible emission decreased with the increase of Yb3＋ concentration, verifying the efficient energy transfer from the Tb3＋ to the Yb3＋. Cooperative energy transfer （CET） from Tb3＋ to Yb3＋ was discussed as a possible mechanism for the near-infrared emission. When doped concentrations were 1 mol.% Tb3＋ and 2 mol.% Yb3＋, the intensity of NIR emission was the strongest.

稀土上转换发光纳米材料的研究进展

综述了水热合成、三氟乙酸稀土盐热分解和液相共沉淀法制备疏水稀土上转换发光纳米材料(UCNPs)的最新进展;随后介绍了5种将疏水UCNPs转化成生物兼容的UCNPs的表面修饰方法;最后介绍了笔者课题组在UCNPs生物应用方面的研究进展,主要包括DNA纳米传感器、生物成像和生物系统发电。

纳米Ca_(0.8)Zn_(0.2)TiO_3∶Pr^(3+),Na^+荧光粉的合成和红色发光性质

采用溶胶-凝胶法在较低温度下合成了Ca0.8Zn0.2TiO3∶Pr3+,Na+纳米荧光粉。金属离子预先分散在溶有柠檬酸的乙二醇溶液中。通过TG-DSC,XRD和SEM对前驱物的分解、晶化和颗粒大小进行了研究。TG-DSC和XRD表明材料的组成随灼烧温度而变化;SEM表明1000℃合成材料的粒径在100nm以下。与高温固相法合成的材料相比,激发光谱主峰发生蓝移,红色发射峰617nm显著增强。

纳米稀土磷酸盐红色荧光粉的合成及性能

以Gd,Y和Eu的硝酸盐与(NH4)2HPO4为原料,采用室温固相反应合成出前驱体,再经过900℃煅烧2h得到(Gd,Y,Eu)PO4纳米荧光粉,运用TG-DTA、XRD、TEM、固体荧光等技术,研究了荧光粉的形成过程、晶体尺寸、形貌及发光性能.结果表明:荧光粉属于单斜晶系,独居石结构的正磷酸盐,空间群为P21/n,平均粒径为60 nm,分散性好,有较高的热稳定性.在396 nm紫外光激发下,纳米荧光粉发出Eu3+的特征红色荧光,发射主峰在613nm,归属于Eu3+离子的5D0→7F2跃迁,该纳米粉体是一种性能优良的荧光材料.

纳米稀土磷酸盐(Gd，Y)PO4：Tb的室温固相合成及发光性能

Green nanophosphors(Gd,Y)PO4:Tb were prepared by solid state chemical reaction of precursors at room temperature.The formation process,particle-size,shape and fluorescence properties of the phosphor were characterized by means of XRD,TEM and solid fluorescence techniques.The results indicate the nanophosphor of(Gd,Y)PO4:Tb belong to the monoclinic system,its space group is P21/ n,its average particle size is 35nm,has better particle dispersion.The phosphor exhibits green fluorescence when excited by ultraviolet radiation of 380nm wavelength.The strongest peak is at 545nm,which assigned to 5D4→7F5 transition of Tb3+ ion.The phosphor is a kind of efficient green-emitting luminescence material.

稀土上转换纳米发光材料研究进展

上转换纳米发光材料（UCNPs）是一种能在长波长光激发下发出短波长光的发光材料。在较多的研究中UCNPs在980nm红外光激发下,能发出不同颜色的可见光,可以显著提高信噪比,所以UCNPs在三维立体显示、上转换激光器、红外探测、防伪识别、生物检测等诸多领域都具有广阔的应用前景。从稀土上转换纳米发光材料的基质和稀土离子及其光学性能方面概述了近几年稀土上转换纳米发光材料的研究进展。

具有协同表面配体的水溶性稀土上转换发光纳米材料用于活体淋巴结显像

通过水热法,以油酸和两亲性聚乙烯吡咯烷酮(PVP)为协同表面配体,一步水热合成水溶性稀土上转换发光纳米材料(NaYF4:20%Yb 1%Tm)。稀土纳米粒径尺寸平均为16 nm,在水溶液中稳定单分散,具有较强上转换发光。具有较低的细胞毒性,可用于上转换发光细胞成像。并进一步用于活体淋巴结显像,表现出高的信噪比。

纳米LaPO_4∶Eu^(3+)的制备及其光学性质研究

利用溶剂热法,在190℃保温12h的条件下制备纳米La0.995Eu0.005PO4晶体。对所制备的样品进行了XRD、TEM和荧光光谱测试,分析了由于PO43-浓度不同而引起的样品形貌及光学性质的变化。利用J-O理论由发射光谱计算了La0.995Eu0.005PO4的光学跃迁强度参数Ω2和Ω4,根据XRD分析、TEM及光学跃迁强度参数,发现PO43-浓度会对La0.995Eu0.005PO4的光学性质造成影响。

溶剂热法一步合成纳米Gd_2O_2S∶Eu^(3+)发光粉

以六水硝酸钆、六水硝酸铕、无水乙醇、乙二胺、硫代甘油、硫脲和升华硫为主要实验原料,通过溶剂热法一步合成纳米Gd_2O_2S∶Eu^(3+)发光粉。采用X射线衍射(XRD),场发射扫描电镜(FE-SEM)和光致发光光谱(PL)等手段对合成产物进行表征。在本研究中,不同硫源影响合成产物的组成和结晶性。合适的硫源为升华硫,其较优的摩尔比为5。此工艺条件下合成的Gd_2O_2S为近球形,团聚较明显,颗粒大小约为30~50 nm。在260 nm的紫外光激发下,Gd_2O_2S∶Eu^(3+)发光粉的主发射峰位于628 nm,归属于Eu^(3+)离子的~5D_0-~7F_2跃迁。Gd_2O_2S∶Eu^(3+)的发光强度受Eu^(3+)离子掺杂浓度影响很大,Eu^(3+)离子的猝灭浓度为4%,其相应的余辉衰减时间为0.5216μs,色坐标为(0.5976,0.3153),属于红光区。

Luminescent properties of Eu^(3+) doped Gd_2WO_6 and Gd_2(WO_4)_3 nanophosphors prepared via co-precipitation method

Eu3＋ doped Gd2WO6 and Gd2（WO4）3 nanophosphors with different concentrations were prepared via a co-precipitation method. The structure and morphology of the nanocrystal samples were characterized by using X-ray diffraction （XRD） and field emission scanning electron microscopy （FE-SEM）, respectively. The emission spectra and excitation spectra of samples were measured. J-O parameters and quantum efficiencies of Eu3＋ 5D0 energy level were calculated, and the concentration quenching of Eu3＋ luminescence in different matrixes were studied. The results indicated that effective Eu3＋：5D0-7F2 red luminescence could be achieved while excited by 395 nm near-UV light and 465 nm blue light in Gd2WO6 host, which was similar to the familiar Gd2（WO4）3：Eu. Therefore, the Gd2WO6：Eu red phosphors might have a potential application for white LED.

Upconversion luminescence of Gd2O3:Er3+and Gd2O3:Er3+/silica nanophosphors fabricated by EDTA combustion method

Gd2O3:Er^3+nanophosphors were fabricated by the combustion method in presence of Na2 ethylene diamine tetra acetic acid(EDTA-Na2)as fuel at not high temperature(≤350℃)within a very short time of 5 min.The added concentration of Er^3+ions in Gd2O3 matrix was changed from 0.5 mol%to 5.0 mol%.The X-ray diffraction pattern of samples indicates the monoclinic structure of Gd2O3:Er^3+.The morphology and chemical composition analysis of the Gd2O3:Er^3+samples are characterized by a field emission scanning electron microscope(FESEM)and a Fourier-transform infrared spectrometer(FTIR).The photoluminescence(PL),photo luminescence excitation(PLE)and upconversion(UC)at room temperature of the prepared materials with different concentrations of Er^3+were investigated.The PL of Gd2O3:Er^3+nanomaterials are shown in visible at 545,594,623,648,688 nm under excitation at 275 nm.The emission bands from transitions of Er^3+from 2P3/2 to 4F9/2 are observed,UC luminescent spectra of the Gd2O3:Er^3+/silica nanocomposites under 976 nm excitation show the bands at 548 and 670 nm.The influence of excitation power at 980 nm for transitions were measured and calculated.The results indicate that the upconversion process of Gd2O3:Er^3+/silica is two photons absorption mechanism.The low temperature dependence of UC luminescent intensities of the main bands of Gd2O3:Er^3+was investigated towards development of a nanotemperature sensor in the range of 10-300 K.

Spectroscopic properties of Eu^(3+) doped YBO_3 nanophosphors synthesized by modified co-precipitation method

Y1-xEuxBO3 nanophosphors were synthesized by a modified co-precipitation method. The structure of the obtained nanocrystals was determined by X-ray diffraction （XRD） and transmission electron microscopy （TEM）. The average crystallite size was calculated from the full-width at half-maximum （FWHM） of the diffraction peaks by the Scherrer equation. The average particles size was 25±10 nm. The spectroscopic properties of the Y1-xEuxBO3 nanoborates were characterized by excitation and emission spectra under UV and VUV excitation. In order to improve colour purity, the chromaticity coordinates were also calculated.

Synthesis and luminescent properties of Eu^(3+)doped Y_2WO_6 nanophosphors

Novel nanosized Y2WO6：Eu3＋ phosphors were synthesized via a co-precipitation reaction. The crystal structure of Y2WO6：Eu3＋sample was monoclinic phase characterized by using X-ray diffraction （XRD）. The particle size was about 80 nm ob-served by field emission scanning electron microscopy （FE-SEM）. The photoluminescence properties of Y2WO6：Eu3＋nanophos-phors were studied. The results indicated that Eu3＋ 5D0→7F2 red luminescence at 611 nm could be effectively excited by 394 nm near-UV light and 465 nm blue light in Y2WO6 host. The luminescence intensity was the strongest while the Eu3＋doping concentra-tion was 20%. And the chromaticity coordinates of this concentration is （0.651, 0.348）. The energy transfer type between the Eu3＋was determined to be the exchange interaction and the critical energy transfer distance （Dc） was calculated to be about 0.81 ang-strom. The J-O parameters, quantum efficiencies of Eu3＋ 5D0 energy level and Huang-Rhys factor of Y2WO6：Eu3＋nanophosphors were calculated. The calculated values indicated that Y2WO6：Eu3＋had a high capacity for activators and the electron-phonon cou-pling was weak. Therefore, the Y2WO6：Eu3＋nanophosphor is a nice red luminescent material and it may have a potential applica-tion in white LED.

Sol-gel synthesis and photoluminescence characterization of La_2Ti_2O_7:Eu^(3+) nanocrystals

Eu3＋ doped La2Ti2O7 nanocrystals with pure monoclinic phase and size of about 100 nm were prepared by a citric acid （CA） assisted sol-gel method. Techniques of thermo-gravimetric （TG） and differential scanning calorimetry （DSC）, X-ray diffraction （XRD）, as well as transmission electron microscopy （TEM） were employed to characterize the as-synthesized nanoparticles. Furthermore, photoluminescence （PL） performances of the Eu3＋ doped La2Ti2O7 nanocrystals were evaluated with focus on the effects of calcination temperature and Eu3＋ doping concentration on the photoluminescence properties.

Solvent induced shape change in CePO_4:Dy^(3+) nanophosphors and effect of metal ions: A photoluminescence study

The influence of different solvents and metal ions （Li^＋, Ba^2＋, Bi^3＋） on the crystallization behaviour, morphology and enhancement in photoluminescence intensity of Dy^3＋ doped CePO4 were investigated. Highly crystalline luminescent nanophosphors of CePO4：DY^3＋ re-dispersible in polar solvents were successfully prepared via a simple polyol route at 140 ℃. As-prepared Dy^3＋ doped CePO4 nanophosphors prepared in EG and DMF appeared to have crystalline monoclinic phase but exhibited hexagonal phase when prepared in water and water mixed solvents, The hexagonal phase transformed to monoclinic phase after heating at 900 ℃. TEM study revealed different shapes of the synthesized nanophosphors with change of solvents. The luminescence intensity of 4F9/2→6H15/2 at 478 nm （blue） was found to be more prominent than 4F9/2→6H13/2 at 572 nm （yellow）. The introduction of metal ions （Li＋, Ba2＋ and Bi3＋） in CePO4：Dy3＋ led to considerable luminescent enhancement. The nanophosphors were subsequently incorporated in polymer films of PVA which showed the characteristic emissions of Dy3＋. It also served as an effective method to improve the performance of polymer materials and brought about novel properties in them.

Synthesis and enhanced photoluminescence properties of red emitting divalent ion(Ca^(2+))doped Eu:Y_(2)O_(3)nanophosphors for optoelectronic applications

This work presents the synthesis of Y_(2)O_(3):Eu^(3+),χCa^(2+)(χ=0 mol%,1 mol%,3 mol%,5 mol%,7 mol%,9 mol%,11 mol%)nanophosphors with enhanced photoluminescence properties through a facile solution combustion method for optoelectronic,display,and lighting applications.The X-ray diffraction(XRD)patterns of the proposed nanophosphor reveal its structural properties and crystalline nature.The transmission electron microscope(TEM)results confirm the change in the shape of the particle and aggregation of particles after co-doping with Ca^(2+).Fourier transform infrared spectroscopy(FTIR)and Raman vibrations also confirm the presence of Y-O vibration and subsequently explain the crystalline nature,structural properties,and purity of the samples.All the synthesized nanophosphors samples emit intense red emission at 613 nm(~5D_(0)→~7 F_(2))under excitation with 235,394 and 466 nm wavelengths of Eu^(3+)ions.The photoluminescence(PL)emission spectra excited with 235 nm illustrate the highest emission peak with two other emission peaks excited with 466 and 394 nm that is 1.4 times higher than 466 nm and 1.9 times enhanced by 394 nm wavelength,respectively.The emission intensity of Y_(2)O_(3):Eu^(3+),χCa^(2+)(5 mol%)is increased 8-fold as compared to Eu:Y_(2)O_(3).Doping with Ca^(2+)ions enhances the emission intensity of Eu:Y_(2)O_(3)nanopho sphors due to an increase in energy transfer in Ca^(2+)→Eu^(3+)through asymmetry in the crystal field and by introduction of radiative defect centers through oxygen vacancies in the yttria matrix.It is also observed that the optical band gap and the lifetime of the~5D_(0)level of Eu^(3+)ions in Y_(2)O_(3):Eu^(3+),xCa^(2+)nanophosphor sample gets changed with a doping conce ntration of Ca^(2+)ions.Nanophosphor also reveals high thermal stability and quantum yield as estimating activation energy of 0.25 eV and 81%,respectively.CIE,CCT,and color purity values(>98%)show an improved red-emitting nanophosphor in the warm region of light,which makes this mate rial superior with a specific potential application for UV-based white LEDs with security ink,display devices,and various other optoelectronics devices.

Exploring one material for dual applications:A red-emitting Mg_(2)GeO_(4):Eu^(3+)nanophosphor for future generation energy efficient WLEDs and dosimetric applications

The envisaged design and developme nt of individual mate rials to excavate a broader spectrum of desired properties and offer multiple applications are highly necessitating.Keeping this in mind,a series of forsterite-structured Mg_(2)GeO_(4):Eu^(3+)(1 mol%-9 mol%)nanophosphors was synthesized via a solution combustion method using oxalyl dihydrazide as a fuel.The X-ray diffraction patterns confirm the orthorhombic crystal system with a Puma space group.Morphological results clearly show irregularly shaped cluster-like structures with aggregation of the particles.Employing diffuse reflectance spectra,the optical energy band gap of the Mg_(2)GeO_(4):Eu^(3+)(1 mol%-9 mol%)nanophosphors was estimated and obtained to be~4.12-4.32 eV.The photoluminescence emission spectra exhibit intense peaks at^(5)79,589,610,661,and 707 nm,which are due to characteristic^(5)D_(0)→^(7)F_(0),^(5)D_(0)→^(7)F_(1),^(5)Do→^(7)F_(2),^(5)D_(0)→^(7)F_(3)and^(5)D_(0)→^(7)F_(4)transitions of Eu^(3+)ions,respectively.The Commission International de L'Eclairage color coordinates are gradually tuned from pale red(0.5980,0.4012)to a pure red(0.6385,0.3611)region.Thermoluminescence glow peaks showcase excellent super-linear response at low doses ofγ-irradiations,indicating that the prepared phosphor can be used in thermoluminescent personal dosimetry which is a biological tissue equivalent.The aforementioned results demonstrate that the prepared Mg_(2)GeO_(4):Eu^(3+)(1 mol%-9 mol%)nanophosphors are considered an excellent candidate for dual applications,i.e.,red component in future generation white-light-emitting diodes(WLEDs)and personal dosimetric applications.

Synthesis and characterization of NaYF4:Yb3+,Er3+@silica-N=folic acid nanocomplex for bioimaginable detecting MCF-7 breast cancer cells

Upconversion nanophosphors are new promising nanomaterials to be used as biolabels for detection and imaging of cancer cells.These nanophosphors absorb long-wavelength excitation radiation in the infrared or near infrared region and emit shorter wavelength,higher energy radiation from ultraviolet to infrared.In this paper,we studied the hydrothermal method and optical properties of the functionalized NaYF4:Yb^3+,Er^3+for biomedical application.After synthesis,these NaYF4:Yb^3+,Er^3+nanophosphors were functionalized with aminosilanes and folic acid.Folic acid binds to the folate receptor on the surface of MCF-7 breast cancer cells and this binding promotes internalization of the nanophosphors via endocytosis.The sizes of the functionalized NaYF4:Yb^3+,Er^3+@silica-N=FA(folic acid)nanophosphors can be controlled with length of the rod about 300-800 nm and diameter of the rod about 100-200 nm.Phase structure of NaYF4:Yb^3+,Er^3+is in hexagonal crystal system.The photo luminescence(PL)spectra of the functionalized NaYF4:Yb^3+,Er^3+@silica-N=FA nanophosphors were measured.These nanophosphors emit in red color with the strongest band at 650 nm under 980 nm excitation.This result can provide NaYF4:Er^3+,Yb^3+@silica-N=FA complex for developing fluorescence label and image tool in cancer biology and medicine.