Haopeng
Wei‡
ab,
Yihao
Zheng‡
*ab,
Xingcai
Zhang
cd,
Ping
Liang
ab,
Xiaokai
Xu
ab,
Chaofan
Hu
ab,
Xuejie
Zhang
ab,
Bingfu
Lei
ab,
Yingliang
Liu
*ab and
Jianle
Zhuang
*ab
aKey Laboratory for Biobased Materials and Energy of Ministry of Education/Guangdong Provincial Engineering Technology Research Center for Optical Agriculture, College of Materials and Energy, South China Agricultural University, Guangzhou 510642, China. E-mail: chemzhengyh@163.com; tliuyl@scau.edu.cn; zhuangjl@scau.edu.cn
bGuangdong Laboratory for Lingnan Modern Agriculture, Guangzhou 510642, China
cSchool of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA
dSchool of Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
First published on 4th May 2022
A rapid construction strategy is for the first time developed to achieve the composite structure of NaYF4:Yb,Er and carbon dots (CDs) through electrostatic interactions in only half a minute. The resulting NaYF4:Yb,Er@CDs nanocomposites have superior dual-mode luminescence properties, showing promising application prospects in the field of advanced optical anti-counterfeiting.
To the best of our knowledge, the currently reported luminescent materials for optical anti-counterfeiting have some problems. For traditional semiconductor quantum dots, the prominent toxicity problem restricts their development in the application of anti-counterfeiting.10,11 Perovskite nanocrystals exhibit lots of limitations in the anti-counterfeiting field due to their poor environmental stability, harsh synthesis process, and high cost.12,13 There are also many unfavorable factors for the application of organic luminescent materials in anti-counterfeiting, such as complicated molecular design, poor air stability, and non-negligible toxicity.14,15 Recently, carbon dots (CDs) have attracted intense attention and interest in security applications such as anti-counterfeiting, information encryption, and fingerprint identification, because of their excellent optical properties, easy preparation and structural regulation, good photostability, environmental friendliness, and low toxicity and cost.16–20 Nevertheless, the single downconversion (DC) luminescence mode and the well-known aggregation-caused quenching (ACQ) effect still make it difficult for pure CDs to directly achieve more complex anti-counterfeiting.21–23 To this end, we conceive combining CDs with upconversion (UC) materials to achieve dual-mode optical anti-counterfeiting, which can improve the safety factor and increase the difficulty of being forged. It is well known that lanthanide-doped upconversion nanoparticles (UCNPs) have excellent upconversion luminescence (UCL) properties and easily modified surface structures.24–27 However, it is difficult to combine UCNPs and CDs by constructing a single core–shell structure because of their lattice mismatch. In order to overcome this problem, many research groups have tried other methods. Wu et al. and Song et al. incorporated as-prepared UCNPs into the reaction system of CDs, in which the CDs were synthesized in situ and attached to the surface of the UCNPs.28,29 Unfortunately, this kind of construction is unstable, and the CDs could fall off relatively easily. Our group and others have tried to embed the CDs into the silica shell on the surface of UCNPs to obtain stable dual-mode luminescent nanocomposites, but a complex sol–gel method was required in the preparation process.30,31 Xing et al. achieved the covalent coupling of carboxyl groups on the surface of CDs and amine groups on the surface of UCNPs through the amidation reaction.32 This method is limited due to its long reaction time, low efficiency, high technical requirements and poor reproducibility. More importantly, the surface functional groups involved in the reaction can change the surface state of CDs, which will affect or even quench the luminescence of CDs. Therefore, it is highly desirable to construct a stable dual-mode luminescent nanocomposite by a facile and efficient method that does not change the surface groups of CDs.
In this work, we propose a novel and rapid strategy to construct composite structures of NaYF4:Yb,Er UCNPs and CDs through electrostatic interactions. The surface potentials of the as-prepared carboxylate radical-functionalized CDs and branched PEI-modified UCNPs are opposite, which provides an electrostatic driving force for rapid adsorption. After the addition of NaYF4:Yb,Er UCNPs to the CD solution, the CDs immediately begin to be adsorbed by NaYF4:Yb,Er, and the entire adsorption process can be completed in only half a minute. The branched PEI ligand chains on the surface of NaYF4:Yb,Er not only strongly adsorb CDs to form a stable composite structure, but also act as a matrix to disperse CDs and inhibit their aggregation. The resulting NaYF4:Yb,Er@CDs nanocomposites show excellent dual-mode luminescence properties and great application potential in the field of anti-counterfeiting.
The morphology and structure were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and energy dispersive spectroscopy (EDS) elemental mapping. As shown in Fig. 1a, the as-prepared CDs are uniform and monodisperse spherical particles with a diameter of about 2.1 nm (Fig. S2, ESI†). The HRTEM image of CDs in the inset of Fig. 1a exhibits clear lattice fringes with a 0.21 nm spacing, which is close to the (100) plane of graphite carbon.33–35 It can be observed from Fig. 1b that the as-prepared NaYF4:Yb,Er UCNPs show a typical sphere-like structure of about 50 nm size. The HRTEM images corresponding to the red squares in Fig. 1c demonstrate apparent lattice fringes with 0.31 nm and 0.25 nm spacing, which can be assigned to the (111) plane of cubic NaYF4 and the (020) plane of graphite carbon for the adsorbed CDs, respectively.33–35 The high-angle annular dark field (HAADF)-STEM image (Fig. 1d) and EDS elemental mapping (Fig. 1e–k) of NaYF4:Yb,Er@CDs composites further confirm the preferential distribution of the CDs containing oxygen and sulfur elements on the surface of NaYF4 particles and also prove the successful doping of Yb3+ and Er3+ ions.
The crystal phase and surface functional groups were investigated by X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. As shown in Fig. 2a, the diffraction peaks in the XRD pattern of NaYF4:Yb,Er are well matched with the cubic NaYF4 (JCPDS No. 77-2042). The weak and broad peak appearing in the XRD pattern of the NaYF4:Yb,Er@CDs nanocomposites can generally be attributed to the amorphous CDs.36,37 The surface functional groups of CDs, NaYF4:Yb,Er, and NaYF4:Yb,Er@CDs are shown in the FT-IR spectra of Fig. 2b. For the CDs, the broad absorption band at 3050–3600 cm−1 is assigned to the stretching vibrations of –OH/N–H. The characteristic peaks at 1640, 1580, and 1200 cm−1 indicate the presence of CO, CC, and CS, respectively. Importantly, the absorption peak at 1350 cm−1 is ascribed to the vibration of carboxylate radicals (COO) in carboxylate groups, which are negatively charged groups. For the NaYF4:Yb,Er UCNPs, the absorption band at 2750–3000 cm−1 and the absorption peak at 1450 cm−1 are attributed to the stretching and bending vibrations of CH2, respectively. The broad absorption band at 3150–3650 cm−1 and the absorption peak at 1630 cm−1 are assigned to the vibrations of amine groups including NH2 and NH in PEI ligands, which belong to positively charged groups. It can be seen that the absorption processes of related groups at 3150–3650 and 1630 cm−1 in the NaYF4:Yb,Er@CDs were significantly enhanced, suggesting the adsorption of CDs. Furthermore, the zeta potentials of NaYF4:Yb,Er and CDs were determined to be +40.3 mV and −42.9 mV (Table S1, ESI†), respectively, which directly indicated that CDs were adsorbed on the surface of NaYF4:Yb,Er particles. Because part of the charges were offset, the zeta potential of the NaYF4:Yb,Er@CDs composites was +10.8 mV, which further confirmed the successful combination of CDs and NaYF4:Yb,Er owing to strong electrostatic interactions.
Fig. 2 (a) XRD patterns of NaYF4:Yb,Er and NaYF4:Yb,Er@CDs, and the standard diffraction data of cubic NaYF4 (JCPDS No. 77-2042). (b) FT-IR spectra of CDs, NaYF4:Yb,Er, and NaYF4:Yb,Er@CDs. |
The optical properties of CDs, NaYF4:Yb,Er, and NaYF4:Yb,Er@CDs were investigated by fluorescence spectroscopy and absorption spectroscopy. As shown in Fig. 3a, the as-prepared CDs in DMSO solution have dual-emission peaks, including blue and red peaks. Under low-wavelength UV excitation, the CDs mainly emit blue light. As the excitation wavelength increases, the red emission gradually dominates over the PL spectra. In particular, the CDs exhibit pure red emission at about 640 nm under the excitation of green light. Such CDs with polychromatic optical properties at different excitation wavelengths are favorable for application in luminescence anti-counterfeiting. The inset in Fig. 3a shows the fluorescence image of the CD solution under UV lamp irradiation. In the NaYF4:Yb,Er@CDs nanocomposite powder, the CDs are uniformly adsorbed on the surface polymer ligand chains of NaYF4:Yb,Er particles, which can overcome the aggregation-caused quenching effect of solid CDs and consequently maintain the same fluorescence emission as in the solution. Therefore, we can observe the emission of CDs from the PL spectra of the NaYF4:Yb,Er@CDs nanocomposites in Fig. 3b. The inset shows the fluorescence image of the NaYF4:Yb,Er@CDs nanocomposites under UV light irradiation, which is similar to that of the CD solution in the inset of Fig. 3a. As shown in Fig. 3c, the normalized UCL spectra of NaYF4:Yb,Er and NaYF4:Yb,Er@CDs nanocomposites have the same emission peaks at 522 nm, 541 nm, and 654 nm. The images of NaYF4:Yb,Er and NaYF4:Yb,Er@CDs nanocomposites under 980 nm laser irradiation are shown in the insets of Fig. 3c. A notable phenomenon is that the red emission of NaYF4:Yb,Er@CDs nanocomposites is more stronger than that of pure NaYF4:Yb,Er (Fig. 3c and Fig. S3, ESI†), implying the existence of energy transfer between NaYF4:Yb,Er and CDs. Furthermore, there are spectral overlaps between the absorption spectrum of CDs and the UCL spectrum of NaYF4:Yb,Er (Fig. 3d), which provides a possibility for energy transfer from the green emission of Er3+ ions to CDs. In addition, the red emission wavelengths of CDs and NaYF4:Yb,Er are very close, which is beneficial for the red emission of CDs to be transmitted back to the red emissive energy level of Er3+, thus enhancing the red emission of NaYF4:Yb,Er. The luminescence decay curves and lifetime data are shown in Fig. S4 and Table S2 (ESI†). The almost unaltered UC green luminescence lifetimes (Fig. S4a, ESI†) of NaYF4:Yb,Er and NaYF4:Yb,Er@CDs suggest the radiation reabsorption of the green emission of Er3+ ions by CDs. The reduced red luminescence lifetime (Fig. S4b, ESI†) of NaYF4:Yb,Er@CDs compared to the pure CDs under 541 nm excitation as well as the enhanced UC red emission (Fig. 3c) of NaYF4:Yb,Er@CDs indicates the energy transfer from the excited state of CDs to the red emissive energy level of Er3+ ions through the resonance energy transfer process. Therefore, the energy transfer mechanism here is similar but not identical to our previous work.38 In addition, when such composites with internal energy transfer features are applied for anti-counterfeiting, it is difficult to imitate by using certain substitutes or simply mixing different luminescent materials. Taken together, the above results demonstrate that the NaYF4:Yb,Er@CDs nanocomposites possess dual-mode luminescence properties, which also further proves the successful combination of NaYF4:Yb,Er and CDs through electrostatic interactions. The structural stability of the NaYF4:Yb,Er@CDs nanocomposites was also investigated. On the one hand, stable composite structures were obtained when the CDs were adsorbed on the surface of NaYF4:Yb,Er. After 42 hours, the CDs were still not detached from the NaYF4:Yb,Er surface (Fig. S5a, ESI†). On the other hand, even if the as-prepared NaYF4:Yb,Er@CDs composites were immersed in common organic solvents and water with shaking, the CDs were still not separated from the composites (Fig. S5b, ESI†). Thus, these results proved the good stability of the NaYF4:Yb,Er@CDs composites.
Given the excellent dual-mode luminescence properties of NaYF4:Yb,Er@CDs nanocomposites, they were used for dual-mode anti-counterfeiting applications. As shown in Fig. 4a, “SC” and “AU” patterns were made with NaYF4:Yb,Er@CDs and NaYF4:Yb,Er, respectively. These letter patterns display specific and multicolor images under the irradiation of 365 nm UV light, a 980 nm laser, and 365 nm UV light & a 980 nm laser, respectively, which reflects the multi-mode excitation characteristics. After using a 550 nm cut-off filter, the images with other colors can be read, which further improves the anti-counterfeiting level. In addition, some logos for graphic security made with NaYF4:Yb,Er@CDs and NaYF4:Yb,Er also show the role of dual-mode anti-counterfeiting in Fig. 4b. In short, it is meaningful for advanced anti-counterfeiting to gain particular information with different color characteristics by dual-mode excitation.
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2ma00418f |
‡ These authors contributed equally to this work. |
This journal is © The Royal Society of Chemistry 2022 |