Meeting the high demand for lanthanide-doped luminescent nanocrystals across a broad range of fields hinges upon the development of a robust synthetic protocol that provides rapid, just-in-time nanocrystal preparation. However, to date, almost all lanthanide-doped luminescent nanomaterials have relied on direct synthesis requiring stringent controls over crystal nucleation and growth at elevated temperatures. Here we demonstrate the use of a cation exchange strategy for expeditiously accessing large classes of such nanocrystals. By combining the process of cation exchange with energy migration, the luminescence properties of the nanocrystals can be easily tuned while preserving the size, morphology and crystal phase of the initial nanocrystal template. This post-synthesis strategy enables us to achieve upconversion luminescence in Ce3+ and Mn2+-activated hexagonal-phased nanocrystals, opening a gateway towards applications ranging from chemical sensing to anti-counterfeiting.
With the rapid development of nanoscience and nanotechnology, lanthanide-doped upconversion nanocrystals1,2,3,4,5 have recently emerged as an important class of luminescent materials, owing to their potential applications ranging from biological imaging6,7,8 and multiplexing sensing9,10,11 to security encoding12,13,14 and volumetric display15. Despite significant progress made, the vast majority of approaches for making upconversion nanocrystals have involved de novo synthetic techniques such as hydrothermal reaction16,17, co-precipitation18,19,20 and thermal decomposition21,22,23. To access different colour emissions24,25,26, one has to perform a new set of reactions and require stringent control over a variety of experimental conditions, including the amount of dopant precursors and surfactants, solvent type, reaction time and temperature. This practice is clearly time-consuming and resource-intensive, and often leads to variation in particle size, phase and morphology16,20.
Cation exchange reactions at the nanoscale have recently emerged as a powerful tool for controlling composition and phase in colloidal semiconductor nanocrystals27,28,29,30,31. These reactions present an alternative solution for modulating emission colours in upconversion nanocrystals. However, different from the band-gap luminescence nature of quantum dots32,33,34,35,36, the emission from the upconversion nanocrystals stems directly from the lanthanides infused in the host lattice37,38,39,40,41. It is important to note that realizing efficient upconversion luminescence typically requires the homogeneous placement of sensitizer and activator ions in rather close proximity, as is the case for NaYF4 nanoparticles co-doped with Yb3+ and Er3+ (ref. 4). Although a high doping concentration of Yb3+ theoretically favours luminescence enhancement42,43,44, upconversion nanocrystals with a large Yb3+ content (for example, NaYbF4) are highly sensitive to the concentration quenching effect that depletes excitation energy and thus suppresses luminescence. This dilemma makes the cation exchange strategy practically unsuitable for emission colour modulation using conventional host materials (for example, NaYF4, NaLuF4 and NaYbF4; refs 45, 46, 47, 48).
It has been well-established that Gd3+-based host materials could effectively bridge the gap of energy transfer from sensitizers to activators through long-range energy migration in the sub-lattice24,41. Because of its large energy gap (∼4.0 eV) between the ground state (8S7/2) and the lowest excited state (6P7/2), the Gd3+ ion also serves as an ideal energy reservoir to suppress the concentration quenching of sensitized luminescence in crystalline nanophosphors.
Here we reason that utilization of a Gd3+-based host lattice may leverage multicolour synthesis in upconversion nanocrystals through cation exchange under mild conditions. By making use of myriad energy transfer pathways between dopant ions, our approach proves useful for accessing a plethora of optical nanomaterials of uniform size, shape and phase (Fig. 1). In particular, we achieve upconversion emission from Ce3+ or Mn2+ doped in hexagonal-phased nanocrystals. This allows us to generate a record long-lived luminescence of ∼600 ms for Mn2+-activated nanocrystals.
Synthesis and characterization
In a typical procedure, hexagonal phase NaGdF4:Yb/Tm@NaGdF4 core-shell nanocrystals were firstly synthesized as a model system by a co-precipitation procedure (Supplementary Fig. 1; ref. 24). Subsequently, surface-bound oleic acid molecules were removed by the treatment of HCl to generate ligand-free nanocrystals (Supplementary Figs 2 and 3). Cation exchange was then induced by mixing an aqueous solution containing a TbCl3 precursor with the as-prepared colloidal sample under ambient conditions for 1 h. High-resolution transmission electron microscopic (TEM) imaging reveals the single-crystalline hexagonal structure of the resulting nanocrystals after cation exchange (Fig. 2a and Supplementary Fig. 4). Low-resolution TEM imaging and the size distribution analysis of the nanocrystals before and after cation exchange show no obvious changes in the particle size and morphology (Fig. 2b and Supplementary Figs 5–7). In addition, X-ray diffraction of the samples confirms that the hexagonal phase is completely preserved after the post-synthetic treatment (Fig. 2c, Supplementary Figs 8 and 9 and Supplementary Note 1).
Electron energy loss spectroscopy analysis on a single nanoparticle reveals that the Tb3+ ions are mainly located within the outmost layers of the core-shell nanocrystals (Fig. 2d–f and Supplementary Fig. 10). To further substantiate the occurrence of cation exchange, we carried out inductively coupled plasma mass spectroscopy analysis of the colloidal sample after cation exchange. For a series of experiments, we found that the amount of Gd3+ ions discharged from the core-shell nanocrystals increases with increasing Tb3+ concentration (Supplementary Figs 11–14 and Supplementary Note 2).
Spectroscopic study of cation-exchanged nanocrystals
Through Gd3+-mediated energy migration in the core-shell structure, the excitation energy could be efficiently transferred from the Yb/Tm pair in the core layer to the activator ions in the shell layers upon cation exchange (Fig. 3a and Supplementary Figs 15 and 16). The cation exchange process can be visualized by monitoring the emission colour change of the colloidal samples before and after addition of the Tb3+ or Eu3+ precursor (Fig. 3b and Supplementary Movies 1 and 2). The luminescence spectra of the samples measured at room temperature show an increase in Tb3+ or Eu3+ emission intensity but a decrease in Gd3+ intensity with increasing concentrations of the exchange ions (Supplementary Figs 17 and 18).
The cation exchange process is generally controlled by three parameters: reaction time, temperature, and the ion concentration used for exchange in the solution (Supplementary Note 3). In our study, Tb3+-exchanged nanocrystals were taken as an example to study the influence of these three parameters on optical properties. We first investigated the time-dependent cation exchange at ambient conditions by monitoring the emission of a colloidal sample (NaGdF4:Yb/Tm@NaGdF4; 26.2 mg) after addition of TbCl3 (20 μmol). As shown in Fig. 3c, the intensity of Tb3+ emission gradually increased over time and reached a plateau after 8 min, at which time the cation exchange reached a dynamic equilibrium (Supplementary Fig. 19). We further performed the controls at different temperatures, and found that the emission can be greatly enhanced by increasing reaction temperature (Fig. 3d and Supplementary Fig. 20), indicating that high temperatures favour the cation exchange process. The emission intensity can also be boosted by slightly enriching the concentration of the exchange ions (Fig. 3e). The optimal concentration of Tb3+ for maximum particle emission was estimated to 5 mM (Supplementary Fig. 21).
Based on the above-mentioned optimization of reaction conditions, we successfully prepared Gd3+-based upconversion nanocrystals containing various types of activators (Eu3+, Dy3+, Ce3+, Mn2+) by the cation exchange approach (Fig. 3f, Supplementary Fig. 22, Supplementary Table 1 and Supplementary Note 4). It is worth noting that the upconversion emission of Ce3+ and Mn2+ is observed for the first time in hexagonal-phased NaGdF4 host materials (Supplementary Figs 23–27). Significantly, we obtained a record long-lived Mn2+ luminescence of ∼600 ms (lifetime: ∼56.7 ms) (Fig. 3g). The long decay time of Mn2+ emission can be used to resolve the spectral overlapping issue between Mn2+ and Tm3+ emissions by the time-gated spectroscopy (Fig. 3h). Interestingly, an emission colour change from cyan to green could be discerned by the naked eye on switching off of the 980-nm excitation source (Supplementary Movie 3).
The observation of optical emissions in cation-exchanged nanocrystals and inductively coupled plasma mass spectroscopy analysis reveal that the cation exchange process is dependent critically upon the nature of the exchanged ion; for example, ionic radius and valence charge (Supplementary Fig. 28). To facilitate the exchange of the Gd3+ host lattice with Mn2+, an elevated temperature of 90 °C is needed to overcome the charge imbalance and lattice strain due to the size mismatch. To understand the cation exchange process, we carried out first-principles calculations by estimating the formation energies of hexagonal-phased NaGdF4 nanocrystals doped with various ions (Supplementary Fig. 29 and Supplementary Table 2;refs 49,50). Our calculations indicate that lanthanides can readily replace Gd atoms at ambient conditions. By comparison, doping of Mn atoms into the NaGdF4 lattice at room temperature requires a large excess of energies (∼1.82 eV). We further investigated the charge transfer within the doped nanocrystals by employing charge distribution analysis. It was found that the amount of charge transfer from the doped lanthanides (Eu, Dy, Ce, Tb) to the surrounding F atoms is comparable to that between Gd and F atoms. However, the calculated amount of charge transfer from Mn to F decreased by about 0.5448e relative to that between Gd and F, giving rise to reduced dipole polarizability and increased formation energy in Mn-doped nanocrystals. In addition, the significant difference in ionic size between Mn2+ and Gd3+ (∼13.8 pm) is another major factor that hinders the cation-exchange process.
Apart from the enhancement of cation exchange at the particle surface, the thermal fluctuation at a high temperature is likely to accelerate the diffusion of the exchanged ions from a particle’s surface to its inner region, so that an improved luminescence from the exchanged ions can be observed51,52. To confirm our hypothesis, we first mixed aqueous solutions of TbCl3 and NaGdF4:Yb/Tm@NaGdF4 at room temperature and then isolated the Tb3+-modified nanocrystals. Subsequently, we heated the nanocrystals at 90 °C for 1 h. As anticipated, we observed an increase in Tb3+ emission after heat treatment (Supplementary Fig. 30). Our calculations also suggest that the diffusion of doped ions (Tb3+, Eu3+, Dy3+, Ce3+ and Mn2+) in the NaGdF4 lattice can occur with ease (Supplementary Fig. 31). Taken together, these data indicate that the cation exchange and diffusion at elevated temperatures synergistically contribute to the increased emission of the exchanged cations (Supplementary Fig. 32 and Supplementary Note 5).
We next explored the applicability of this cation exchange approach to colour-tuning in other upconversion and downconversion systems. For instance, we observed an emission colour change for NaYbF4:Tb@NaTbF4 upconversion nanocrystals from green to yellow upon cation exchange of Tb3+ with Eu3+ at the particle’s surface (Fig. 4a, Supplementary Figs 33–35 and Supplementary Note 6). In the cases where a downconversion process was demonstrated, the substitution of Gd3+ in NaGdF4:Ce@NaGdF4 nanocrystals by a series of activators (Tb3+, Eu3+, Dy3+, Mn2+) resulted in Ce3+-sensitized multicolour emissions (Fig. 4b, Supplementary Fig. 36 and Supplementary Note 7). Importantly, the capability of our approach to modulating emission colours in lanthanide-doped nanocrystals allowed rapid access to a myriad of different colour spaces with minimum sample processing time (Fig. 4c,d).
The combination of cation exchange and energy migration in lanthanide-doped nanocrystals enables us to precisely tailor the luminescence to the colours of interest, providing the possibility to achieve long-lived luminescence in unexplored regimes of lifetime and without concerning variation in particle size, phase and morphology. As with any methodology, there are seemingly obvious drawbacks. For example, it requires a subset of lanthanide ions capable of participating in the energy migration. However, our data suggest that the advantages of the presented approach far outweigh its limitations. In particular, our approach allows the development of a general, green protocol for preparing multicolour nanoprobes, combining efficient and rapid sample synthesis with significantly reduced solvent and reagent consumption. As such it is anticipated that this technique will greatly expand the repertoire of possible upconversion nanomaterials, with relevant applications for fields as diverse as chemical sensing, biological imaging, photodynamic therapy and anti-counterfeiting.
Cation-exchanged nanocrystals were prepared by incubating aqueous solution containing ligand-free template nanocrystals and activator ions at ambient conditions for 1 h. Additional experimental details are provided in the Supplementary Methods.
Ultraviolet–visible spectra were measured on a SHIMADZU ultraviolet-3600 spectrophotometer. Fourier transform infrared spectroscopy spectra were recorded on a Varian 3100 fourier transform infrared spectrometer. Low-resolution TEM images were taken on a JEOL-1400 transmission electron microscope operating at an acceleration voltage of 100 kV. Scanning electron microscopy was carried out on a FEI NOVA NanoSEM 230 scanning electron microscope operated at 5 kV. Powder X-ray diffraction data was obtained on a Siemens D5005 X-ray diffractometer with Cu Kα radiation (λ=1.5406 Å). The upconversion luminescence spectra were recorded in an Edinburgh FSP920 equipped with a photomultiplier, in conjunction with 980 nm diode laser and a xenon arc lamp (Xe900). The measurement of luminescence lifetime was conducted using a lifetime spectrometer (FSP920, Edinburgh) equipped with a microsecond flash lamp as the excitation source. Upconversion luminescence microscopic images were obtained on an Olympus BX51 microscope with a Nikon DS-Ri1 imaging system adapted to a 980 nm diode laser. Digital photographs were taken with a Nikon D700 camera.
The authors declare that the data that support the findings of this study are available within the article and its Supplementary Information files. All other relevant data are available from the corresponding author upon request.
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This work is supported by the Singapore Ministry of Education (Grant R143000627112, R143000642112), Agency for Science, Technology and Research (A*STAR) under the contracts of 122-PSE-0014 and 1231AFG028 (Singapore), National Research Foundation, Prime Minister’s Office, Singapore under its Competitive Research Program (CRP Award No. NRF-CRP15-2015-03), National Basic Research Program of China (973 Program, Grant 2015CB932200), National Natural Science Foundation of China (61136003), and the CAS/SAFEA International Partnership Program for Creative Research Teams. Y.H. is grateful to KAUST Global Collaborative Research for the Academic Excellence Alliance (AEA) fund. We thank B. Zhou, Q. Sun, R. Deng, X. Xie, H. Xu and Q. Su for technical assistance and helpful discussion.
The authors declare no competing financial interests.
Supplementary Figures 1-36, Supplementary Tables 1-2, Supplementary Notes 1-7, Supplementary Methods and Supplementary References. (PDF 8207 kb)
(Cation exchange with Tb3+). To visualize the cation exchange reaction under ambient conditions, we mixed ligand-free NaGdF4:Yb/Tm@NaGdF4 nanocrystals (2.5 mL; ~50 mg) with Tb3+ precursors (100 μL; 0.2 M). Upon addition of TbCl3 solution, we observed a gradual change in particle emission from blue to cyan, indicating the occurrence of cation exchange between the nanocrystals and Tb3+ ions. In addition, the green emission appeared brighter over time. After several minutes, the emission color remained intact, suggesting the establishment of an equilibrium in cation exchange process. The origin of green emission from Tb3+ was confirmed by covering a long-pass 500 nm filter on the front of the camera. (MOV 3232 kb)
(Cation exchange with Eu3+). In a parallel experiment, we demonstrated the cation exchange between Eu3+ and Gd3+-based nanocrystals under ambient conditions. We added a 100- μL solution of EuCl3 (0.2 M) to a 2.5-mL water solution containing ligand-free NaGdF4:Yb/Tm@NaGdF4 nanocrystals (~50 mg). During the reaction, we observed a color change in particle emission from blue to red. The color change lasted for several minutes. (MOV 3138 kb)
(Cation exchange with Mn2+). For illustration of long luminescence lifetime of Mn2+, we irradiated the Mn2+-exchanged NaGdF4:Yb/Tm@NaGdF4 nanocrystals dispersed in a cuvette with a 980 nm laser. The colloidal solution emitted a cyan color. After switching off of the 980 nm laser, we visualized a color change from white to green. This color change is due to the diminished Tm3+ emission and Mn2+ afterglow luminescence. Note that we repeated this process three times and the phenomenon was reproducible. (MOV 351 kb)
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Han, S., Qin, X., An, Z. et al. Multicolour synthesis in lanthanide-doped nanocrystals through cation exchange in water. Nat Commun 7, 13059 (2016). https://doi.org/10.1038/ncomms13059
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