Solvent-regulated Synthesis of Copper Nanocluster Assemblies and Its Application in Light-emitting Diodes

doi:10.6023/A24110348

Abstract

Photoluminescent copper nanoclusters have broad application prospects in lighting and display. However, the difficulty of photoluminescence wavelength regulation greatly limits its practical application. Now, more and more studies show that the photoluminescence of metal nanoclusters cannot be simply attributed to the quantum confinement effect of the metal core, metal-metal, metal-ligand and ligand-ligand interactions play a pivotal role in the emission process. Achieving the effective regulation of these weak interactions in metal nanoclusters is the current research focus in this field. Self-assembly is an effective strategy to regulate these weak interactions in metal nanoclusters. The variation of the spatial assembly structure of metal nanoclusters will affect the charge and energy transfer process, and then affect the photoelectric properties of metal nanoclusters. Although many strategies have been proposed to regulate the assembly structure of metal nanoclusters, most of the proposed strategies need to be carried out under heating conditions, which is not conducive to the large-scale production of metal nanocluster assemblies and limits its practical application. In this paper, copper nanocluster assemblies with yellow and blue emission have been successfully synthesized by a solvent-regulated strategy at room temperature. Different solvent environments lead to different assembly modes of copper nanoclusters, and finally two typical assembly structures of nanosheet and nanorod are formed. In a high boiling solvent, such as dibenzyl ether, the solubility and fluidity of copper clusters are poor, which is conducive to the formation of loose nanosheet assembly structure. In contrast, in a low boiling solvent, such as n-hexane, the solubility and fluidity of copper clusters are better and the clusters tend to form a dense nanorod assembly structure. The spacing of clusters in the assembly plays a pivotal role in its photoluminescence performance. Compared with the single-layer nanosheet structure, the nanorod structure adds the additional interlayer interaction. This results in additional Cu(I)…Cu(I) interaction and the increasing of spacing between adjacent sulfhydryl ligands on the cluster surface. Finally, the emission wavelength of copper nanoclusters blue shifted from ca. 550 nm to ca. 490 nm. This solvent-regulated synthesis strategy is simple, easy to operate and short in time consuming, which is conducive to the large-scale synthesis of copper nanoclusters. In addition, light-emitting diodes (LEDs) with different emission colors based on the synthesized metal nanocluster assemblies were successfully prepared.

Key words: copper nanoclusters, self-assembly, photoluminescence, light-emitting diodes

Cite this article

Taiqun Yang, Cheng Ye, Shen Zhou, Siqi Ding, Penghe Mi, Tianhui Wang, Lei Li, Guoqing Chen. Solvent-regulated Synthesis of Copper Nanocluster Assemblies and Its Application in Light-emitting Diodes[J]. Acta Chimica Sinica, 2025, 83(2): 87-92.

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Fig. & Tab. 5

Figure 1. Excitation and emission spectra of Cu NCs self-assembly synthesized in dibenzyl ether (a) and n-hexane (b); TEM images of as-synthesized Cu NCs self-assembly in dibenzyl ether (c) and n-hexane (d)

Figure 2. Emission spectra of Cu NCs self-assembly synthesized in 1,4-dioxane (black), ether (red) and ethyl acetate (blue), respectively (the emission was excited at 350 nm)

Figure 3. (a) XRD patterns of Cu NCs self-assembly nanosheets and nanorods, and (b) corresponding time-resolved luminescence decay profiles of nanosheets and nanorods (note: according to literature reports, the diffraction peak at ca. 7.7° is the third-order diffraction peak[14])

Figure 4. (a) Excitation (dashed line) and emission spectra (solid line) of synthesized gold nanocluster assemblies (inset: corresponding photographs of gold nanocluster assemblies under visible and UV light); (b) Corresponding time-resolved luminescence decay profiles; (c, d) SEM images of synthesized gold nanocluster assemblies

Figure 5. Photoluminescence spectra of as-fabricated LEDs based on different metal nanocluster assemblies with blue (a), yellow (b), red (c), and white (d) emission; (e) the CIE chromaticity coordinates of the as-fabricated WLED on the CIE 1931 color space (inset: corresponding photographs of these as-fabricated LEDs)

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