Quantitative analysis of the surface quenching effect of lanthanide-doped upconversion nanoparticles in solvents
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摘要: 激光诱导的稀土纳米粒子的上转换发光由于具有独特的光学效应，多年来一直受到人们的广泛研究。其中，溶剂对纳米粒子表面效应的影响是该类材料在实际应用中面临的一个普遍问题，传统的分析方法对溶剂的作用难以给出定量化的分析结果。针对这一困难，本文利用Monte Carlo计算模拟方法，从离子-离子相互作用的微观层面上重构出宏观的上转换发光现象，进而分别给出了纳米粒子表面效应在4种不同的水相溶剂：水、甲醇、乙醇和N，N-二甲基甲酰胺（DMF）中的定量化分析结果。稳态和动力学光谱测试结果均表明，溶剂水中的上转换纳米粒子表面猝灭速率最高，甲醇和乙醇中次之，DMF中最低，这可归因于溶剂中羟基基团及其活性对于上转换纳米粒子表面猝灭效应的影响。进一步，通过计算模拟获得了NaYF4：20% Yb，2% Er上转换纳米粒子中，Yb3+激发态（2F5/2）表面猝灭速率的定量化数值，分别为：2.5×104 s-1（DMF）、1×105 s-1（甲醇和乙醇）、5×105 s-1（水）。Abstract: Laser-induced upconversion luminescence of lanthanide-doped nanoparticles has attracted great interest from researchers for many years due to its unique optical properties. The influence of solvents on the surfaces of these nanoparticles is a common problem in practical applications of these materials. However, traditional analysis methods are incapable of quantifying the influences of solvents. In response to this difficulty, we used a Monte Carlo simulation to reconstruct macroscopic upconversion luminescence at the microscopic level of ion-ion interaction. Then, we succeeded in obtaining quantified analysis results of the surface effects from four different aqueous solvents, which were water, methanol, ethanol and N, N-dimethylformamide(DMF). Both steady-state and dynamic spectra results show that the surface quenching rate of the upconversion nanoparticles in the highest to the lowest order of the four solvents are water, methanol, ethanol and DMF, which is attributed to the hydroxyl group and its activity. The computational simulation results show that the surface quenching rates of the Yb3+ excited state(2F5/2) in NaYF4:20%Yb, 2%Er upconversion nanoparticles in the four solvents are 2.5×104 s-1(DMF), 1×105 s-1(methanol and ethanol) and 5×105 s-1(water), which confirms our hypothesis.
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图 1 (a) NaYF4:20%Yb, 2%Er上转换纳米粒子的SEM图片(图中标尺为100 nm)及其(b)XRD图谱(与NaYF4六角相标准图谱进行对比，编号：16-0334)
Figure 1. (a)SEM image of NaYF4:20%Yb, 2%Er upconversion nanoparticles(scale bar is 100 nm) and its X-ray powder diffraction spectra(b)(compared with the Joint Committee on Powder Diffraction Standards, file number 16-0334)
图 2 (a) 上转换纳米粒子在4种不同溶剂中的上转换发光光谱图(Ex:980 nm, 激发光功率密度为100 W/cm2，纳米粒子浓度均为50 mg/mL)。(b)4种溶剂中的纳米粒子上转换发光强度对比结果(以DMF溶剂中的发光强度归一化，光谱积分区域：500~700 nm)
Figure 2. (a)The emission spectra of upconversion nanoparticles in four different solvents(Ex:980 nm, power density is 100 W/cm2, the concentration of nanoparticles is 50 mg/mL). (b)Comparison of upconversion luminescence intensities(spectra integration region:500~700 nm) in four different solvents (normalized by the luminescence intensity of nanoparticles in DMF solvent)
图 3 980 nm的纳秒脉冲光激发下，纳米粒子在不同溶剂中的发光离子Er3+的上转换发光(540 nm)(a)以及敏化离子Yb3+的斯托克斯发光(1 040 nm)(b)的荧光衰减曲线
Figure 3. Under the excitation of 980 nm nanosecond pulsed light, the lifetime curves of (a)upconversion luminescence(540 nm) of activator Er3+ and (b)Stokes luminescence (1 040 nm) of sensitizer Yb3+ of the nanoparticles in different solvents
图 4 (a) 基于Monte Carlo计算模拟的上转换发光微观物理图像。(b)NaYF4:20%Yb, 2%Er上转换纳米粒子中离子间相互作用的计算模拟参数
Figure 4. (a)Upconversion luminescence microphysical image based on Monte Carlo computational simulation. (b)Computational simulation parameters of the interaction between ions in NaYF4:20%Yb, 2%Er upconversion nanoparticles
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