基于磁响应光子晶体与量子点的多重变色防伪研究

doi:10.6023/A22090399

摘要/Abstract

结合Fe₃O₄@SiO₂ (M)超顺磁胶体粒子动态连续的磁致变色和碲化镉量子点(CdTe QDs)瞬时发射的光致发光特性, 采用聚二甲基硅氧烷(PDMS)弹性体封装含有M胶体粒子和CdTe QDs的乙二醇(EG)微液滴, 制得了具有多重变色功能的M/QDs/EG/PDMS复合薄膜. 利用光学显微镜、光纤光谱仪、荧光光谱仪、数码相机、拉力试验机对复合薄膜的内部结构、光学性质及力学性能进行表征. 结果表明, 在外界磁场的诱导下, 复合薄膜瞬时呈现明亮的结构色, 且随着磁场强度的降低, 复合薄膜的衍射波长发生连续红移, 移动范围可达145 nm. 此外, 在紫外光的激发下, 复合薄膜可呈现特定波长的荧光发射, 具备良好的光致发光特性. 同时, 复合薄膜断裂伸长率可达132%, 表现出良好的弹性, 这为其附着在不同材料表面实现防伪应用提供了基础. 进一步地, 通过图案化设计, 可制得响应变色迅速、图案隐现可逆、颜色变化多样的防伪薄膜, 这有利于其在信息加密和高级别防伪领域中的应用.

关键词: 超顺磁胶体粒子, 量子点, 磁致变色, 光致发光, 防伪

Counterfeiting is a growing global problem, which could be effectively curbed by developing novel anti- counterfeiting materials. Responsive photonic crystals (RPCs) are one kind of promising materials for anti-counterfeiting because of their vivid rainbow effect and stimulus responsive discoloration performance. In addition to RPCs, photoluminescence materials with intrinsic emission color, can also be used for anti-counterfeiting. As one of the most common photoluminescence materials, quantum dots (QDs) exhibit narrow emission width, saturated color, and tunable emission due to the quantum confinement effect. Despite RPCs and QDs with tunable colors have shown great potential for anti-counterfeiting and information encryption, most of their color variations are actuated by a single mode, which hinders their advanced applications. In this paper, taking advantage of the dynamic continuous magnetochromic property of Fe₃O₄@SiO₂ (M) superparamagnetic colloids in organic solvents and the photoluminescence behavior of CdTe quantum dots (CdTe QDs) under the excitation of UV light, a M/QDs/EG/PDMS composite film with multimodal color-switching function for anti-counterfeiting was fabricated by encapsulating ethylene glycol (EG) droplets containing M colloids and CdTe QDs in elastomeric polydimethylsiloxane (PDMS). The internal structure, optical and mechanical properties were characterized by optical microscope, fiber optical spectrometer, fluorescence spectrometer, digital camera and tensile testing machine. The results showed that the composite film exhibited bright structural color instantaneously under application of a magnetic field. The diffraction wavelength of the composite film displayed a continuous red or blue shift with the decrease or increase of the magnetic field intensity, and the red or blue shifting range could reach 145 nm. Moreover, the composite film could emit bright fluorescence under the excitation of UV light and exhibited good photoluminescence function. In addition, the composite film showed good elasticity and the percentage of breaking elongation of the film could reach 132%, which provides a foundation for the application of anti-counterfeiting by attaching on the surface of different materials. Furthermore, through the patterned design, a patterned anti-counterfeiting film with rapid response to color change, reversible pattern hiding, and various color changes can be prepared, which is conducive to its application in the field of information encryption and advanced anti-counterfeiting.

Key words: superparamagnetic colloids, quantum dots, magnetochromic, photoluminescence, anti-counterfeiting

引用此文

王文涛, 赵高崇, 杨柳, 周意诚, 丁黎明. 基于磁响应光子晶体与量子点的多重变色防伪研究[J]. 化学学报, 2022, 80(12): 1576-1582.

Wentao Wang, Gaochong Zhao, Liu Yang, Yicheng Zhou, Liming Ding. Study on Multimodal Color-switching Anti-counterfeiting Based on Magnetically Responsive Photonic Crystals and Quantum Dots[J]. Acta Chimica Sinica, 2022, 80(12): 1576-1582.

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图/表 6

图1. (a) Fe3O4纳米团簇和(b) M胶体粒子的TEM图; 经过不同水热时间合成的CdTe QDs的TEM图: (c) 55 min, (d) 70 min, (e) 85 min

Figure 1. The TEM images of Fe3O4 clusters (a) and M colloids (b); the TEM images of CdTe QDs synthesized with different hydrothermal time: (c) 55 min; (d) 70 min; (e) 85 min

图2. (a) M/QDs/EG混合溶液(M胶体粒子浓度约10 mg/mL, CdTe量子点浓度约2 mg/mL)在撤销磁场和施加磁场条件下的溶液数码照片; (b) M/QDs/EG混合溶液在不同磁场强度下的反射光谱; (c, d) 含有不同粒径的CdTe QDs的M/QDs/EG混合溶液在UV下的照片及荧光光谱图: 绿色荧光(平均粒径2.05 nm); 橙色荧光(平均粒径2.70 nm); 红色荧光(平均粒径4.05 nm)

Figure 2. (a) Series digital photos of the mixed solution of M/QDs/EG (M ca. 10 mg/mL, CdTe QDs ca. 2 mg/mL) under the condition that the magnetic field is removed and applied; (b) reflectance spectra of the mixed solution of M/QDs/EG at various magnetic field strengths; (c, d) corresponding photographs and fluorescence spectra of the M/QDs/EG solution containing CdTe QDs with different average particle sizes under UV light: green-emission fluorescence (2.05 nm); orange-emission fluorescence (2.70 nm); red-emission fluorescence (4.05 nm)

图3. (a) M/QDs/EG/PDMS复合薄膜在撤销磁场和施加磁场条件下的数码照片; (b) M/QDs/EG/PDMS复合薄膜在不同磁场强度下的反射光谱和(c) CIE色度图; (d) M/QDs/EG/PDMS复合薄膜在不同磁场条件下的光学显微照片: (i) 未施加磁场; (ii) 施加磁场

Figure 3. (a) Series digital photographs of the M/QDs/EG/PDMS composite film under the condition that the magnetic field is removed and applied; (b) reflectance spectra and (c) CIE chromaticity plot of the composite film at various magnetic field strengths; (d) optical microscopy images of the M/QDs/EG/PDMS composite film under different magnetic field conditions: (i) no magnetic field applied; (ii) magnetic field applied

图4. UV光下含有不同粒径的CdTe QDs的M/QDs/EG/PDMS复合薄膜的数码照片(a), 荧光光谱图(b)和CIE色度图(c): (i) 2.05 nm, (ii) 2.70 nm, (iii) 4.05 nm

Figure 4. (a) Corresponding digital photographs, (b) fluorescence spectra and (c) CIE chromaticity plot of the M/QDs/EG/PDMS composite film containing CdTe QDs with different average particle sizes under UV light: (i) 2.05 nm, (ii) 2.70 nm, (iii) 4.05 nm

图5. PDMS薄膜和M/QDs/EG/PDMS复合薄膜的拉伸应力-应变曲线

Figure 5. Stress-strain curves of pure PDMS and the M/QDs/EG/PDMS composite film

图6. (a) 图案化复合薄膜的制备流程示意图; (b) 具有三叶草图案的复合薄膜UV光响应(Mode 1)及磁响应(Mode 2)变色数码照片

Figure 6. (a) Schematic illustration of patterned composite film preparation process; (b) color-switching digital photographs of UV light response (Mode 1) and magnetic response (Mode 2) of the composite film with clover pattern

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