Engineering the Self-Assembly Induced Emission of Cu Nanoclusters by Au(I) Doping.

Aggregation-induced emission (AIE) and self-assembly induced emission (SAIE) effects have been employed to tune the emission properties of metal nanoclusters (NCs). However, it is still not possible to further enhance the photoluminescence quantum yields (PLQYs) and control the emission colors of the NCs using AIE and SAIE. On the basis of our recent work studying the contribution of Cu(I) defects in the SAIE of Cu NCs, in this article, Au(I) was doped into Cu NC self-assembled nanosheets (NSASs) to construct a more stable Au(I)-centered state. As a result, the PLQYs, emission stability, and tunability of emission colors of the Cu NSASs were significantly improved. Detailed studies reveal that the doped Au(I) induces a Au(I)-Cu(I) metallophilic interaction, which leads to a ligand-to-Cu-Au charge transfer, which facilitates the relaxation of excited electrons via a radiative pathway, thereby enhancing the emission intensity. The charge transfer from Cu to Au lowers the energy, thus leading to the red-shift of PL emission. Au(I) is likely doped into the Cu NSASs rather than in individual NCs, because 0.3% Au doping is enough to alter the emission properties. By mixing Au(I)-doped Cu NSASs with different emission colors (due to different Au doping percentages) as color conversion materials on commercially available 365 nm GaN chips, a white light-emitting diode prototype is fabricated.