Preparation and luminescence properties of cyanine dye-sensitized upconversion nanocomposites
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摘要: 利用有机染料敏化上转换纳米材料可以拓展近红外光吸收，然而染料在纳米粒子表面易于聚集限制了上转换发光的提高。本文以花菁IR820为原料，在强碱作用下合成了含有四苯乙烯基团的2-(4-(1, 2,2-三苯基乙烯基)苯氧基)环己烯-1-基)乙烯基)-3,3-二甲基-3H-苯并[f]吲哚-1-基)丁烷-1-磺酸盐(CyBTSO)；利用自组装方法制备了IR820、CyBTSO敏化的上转换纳米复合材料，并对它们的结构和形貌等进行了表征。测试了染料在溶液、聚集态的光物理性能及染料敏化复合材料的上转换发光，系统研究了染料分子结构与上转换发光性能之间的关系。结果表明：四苯乙烯基团的引入不仅有利于提高CyBTSO的荧光量子产率和寿命，还能增强其稳定性，并抑制其在纳米粒子表面的聚集。与IR820相比，CyBTSO在纳米粒子表面的稳定性提高了1.7倍，负载量提高了3倍。在808 nm激发下，CyBTSO敏化纳米粒子的上转换发光强度比β-NaYF4:Yb20%,Er2%(980 nm)提高了69倍。本文为设计高效、稳定的上转换材料提供了理论借鉴。Abstract: Organic dye-sensitized upconversion nanomaterials can expand the absorption of near-infrared light, but dye-aggregation on the surface of nanoparticles limits the improvement of upconversion luminescence. In this paper, sodium 4-(2-((E)-2-((E)-3-((E)-2-(3,3-dimethyl-1-(4-sulfonatobutyl)-1,3-dihydro-2H-benzo[f]indol-2-ylidene)ethylidene)-2-(4-(1,2,2-triphenylvinyl)phenoxy)cyclohex-1-en-1-yl)vinyl)-3,3-dimethyl-3H-benzo[f]indol-1-ium-1-yl)butane-1-sulfonate (CyBTSO) containing tetrastyrene group was synthesized from cyanine IR820 in the presence of strong alkali. IR820 and CyBTSO sensitized upconversion nanocomposites were prepared by a self-assembly method, and their structures and morphologies were characterized. The photophysical properties of dyes in solution and condensed state, as well as the upconversion luminescence of dye-sensitized nanocomposites were investigated. The relationship between molecular structure and upconversion luminescence was systematically studied. It is found that the introduction of tetrastyrene group is not only beneficial to improve the fluorescence quantum yield and lifetime of CyBTSO, but also to enhance its stability and inhibit its aggregation on the nanoparticle surface. Compared with IR820, the stability and the loading amount of CyBTSO on the nanoparticle surface are increased by 1.7 and 3 times, respectively. As a result, a 69-fold enhancement of upconversion luminescence in CyBTSO-sensitized nanocompo-sites excited at 808 nm is achieved compared to that in β-NaYF4:Yb20%, Er2% excited at 980 nm. This work provides a theoretical reference for the development of upconversion materials with high upconversion efficiency and stability.
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Key words:
- cyanine derivatives /
- nanocomposites /
- upconversion luminescence /
- dye aggregation /
- energy transfer
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图 2 β-NaYF4:Yb20%,Er2%的TEM图像 ((a), (b)) 和XRD图谱 (c)
Figure 2. TEM images ((a), (b)) and XRD pattern (c) of β-NaYF4:Yb20%,Er2%
图 3 β-NaYF4:Yb20%,Er2%表面配体为油酸、IR820和CyBTSO及无配体的FTIR图谱
Figure 3. FTIR spectra of oleic acid-capped β-NaYF4:Yb20%,Er2%, ligand free β-NaYF4:Yb20%,Er2% and IR820 and CyBTSO sensitized β-NaYF4:Yb20%,Er2%
UCNPs—β-NaYF4:Yb20%,Er2%; OA—Oleic acid
图 4 IR820和CyBTSO在乙醇溶液中的紫外-可见吸收 (a) 和荧光光谱 (b) (5×10-6 mol/L)
Figure 4. Absorption (a) and PL (b) spectra for IR820 and CyBTSO in ethanol (5×10-6 mol/L)
图 5 IR820 ((a), (c))、CyBTSO ((b), (d)) 与β-NaYF4:Yb20%,Er2%复合前后的荧光衰减曲线
Figure 5. Fluorescence decay curve of R820 ((a), (c)) and CyBTSO ((b), (d)) in the absence and presence of β-NaYF4:Yb20%,Er2%
τ—Fluorescence lifetime
图 6 乙醇中不同浓度的IR820 (a) 和CyBTSO (b) 敏化β-NaYF4:Yb20%,Er2%(1 mg/mL)上转换发射光谱；(c) 染料敏化上转换发光强度(540 nm)与染料浓度之间的关系；(d) 在808或980 nm(10 W·cm-2)激光泵浦下，β-NaYF4:Yb20%,Er2%(1 mg/mL)与有机染料复合前后的上转换光谱
Figure 6. Upconversion spectra of β-NaYF4:Yb20%,Er2% (1 mg/mL) with different concentrations of IR820 (a) and CyBTSO (b) for sensitization in ethanol; (c) Changes in the upconversion intensity (540 nm) with different concentrations of sensitizers; (d) Upconversion spectra of β-NaYF4:Yb20%,Er2% (1 mg/mL) in the presence and absence of sensitizer in ethanol under 820 or 980 nm excitation with a power density of 10 W·cm-2
图 7 染料敏化上转换纳米体系中IR820和CyBTSO归一化吸光度(最长吸收波长)随时间的变化趋势(乙醇)
Figure 7. Normalized absorbance values at the longest absorption band of IR820 and CyBTSO in the dye-sensitized nanocomposites as a function of time (in ethanol)
图 8 IR820 ((a), (b)) 和CyBTSO ((c), (d)) 在不同含量环己烷/丙酮溶液中紫外-可见吸收光谱(归一化)和荧光光谱(2×10−5 mol/L)
Figure 8. Absorption (normalized) and PL spectra of IR820 ((a), (b)) and CyBTSO ((c), (d)) in cyclohexane/acetone mixtures with different volume fractions of cyclohexane (2×10−5 mol/L)
图 9 IR820 (a) 和CyBTSO (b) 在β-NaYF4:Yb20%,Er2%(1 mg/mL)表面的归一化吸收光谱
Figure 9. Normalized absorption spectra of IR820 (a) and CyBTSO (b) attached on β-NaYF4:Yb20%,Er2% (1 mg/mL)
表 1 IR820和CyBTSO光物理性质
Table 1. Photophysical properties of IR820 and CyBTSO
Compound λabs/nm ε/(mol−1·L·cm−1) λem/nm Φ/% τ/ns IR820 754 825 9.4×104 849 2.1 0.65 CyBTSO 740 810 5.9×104 831 3.3 1.00 Notes: λabs—Absorption bands; ε—Molar absorption coefficient of the longest absorption band; λem—Peak position of PL; Φ—Quantum yields; τ—Fluorescence lifetime. 
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