NaYF_4:Yb,Er上转换荧光纳米颗粒的共沉淀法合成及表征

摘要

以二乙二胺五乙酸(DTPA)为络合剂,采用共沉淀法合成了单分散的NaYF_4:Yb,Er上转换荧光纳米颗粒.通过X射线衍射(XRD)、透射电子显微镜(TEM)、荧光(FL)光谱、热重-差示扫描量热分析(TG-DSC)对合成的样品进行了表征.所合成纳米颗粒的粒径均一,通过改变络合剂DTPA的用最可使颗粒的平均粒径在20～120 nm范围内可调.纳米颗粒经煅烧后发生了由立方品型向六方晶型的转变,并伴随着荧光强度的大幅提升.还探讨了络合剂DTPA的用量、煅烧温度对纳米颗粒粒径、晶型及荧光性能的影响.研究结果表明:络合剂DTPA的加入虽然在一定程度上阻碍纳米颗粒由立方晶型向六方晶型的转变,但可获得单分散的小粒径纳米颗粒,其荧光强度仍能满足生物标记的要求.%Monodisperse NaYF_4 : Yb, Er upconversion fluorescent nanoparticles were firstly synthesized via a co-precipitation method in the presence of diethylenetriamine pentoacetic acid (DTPA). The nanoparticles were characterized by using of X-ray diffraction (XRD), transmission electron microscope (TEM), fluorescence (FL) spectrum, and thermogravimetry-differential scanning calorimetry (TG-DSC) analysis. The as-prepared nanoparticles were uniform, and their size could be controlled in a range of 20 to 120 nm by varying the amount of DTPA. During the precipitation reaction, DTPA molecules could form a complex with the rare earth ions, and then the rare earth ions were released slowly to react with F- ions, which slowed down the speed of the reaction. In addition, DTPA molecules could also be capped on surface of the growing nanoparticles, which prevented the nanoparticles from aggregation. After annealing, the nanoparticles were transformed from cubic phase to hexagonal phase, and their upconversion fluorescence intensity was enhanced remarkably. The synthesis conditions including the amount of chelating a-gents and temperature for annealing, which showed great influence on the size, phase and upconversion fluorescence intensity of the nanoparticles, were also discussed. It was confirmed by XRD and TG-DSC analysis that the presence of DTPA suppressed the cubic-to-hexagonal phase transition of the nanoparticles. However, while the small nanoparticles were obtained with well control, the annealed crystals synthesized by adding DTPA could still emit strong fluorescence under a low exciting power, which could well fulfill the demand for bio-labeling. These nanoparticles are envisioned to find potential applications in biological detections.