Sequential addition of cations increases photoluminescence quantum yield of metal nanoclusters near unity.

Photoluminescence is one of the most intriguing properties of metal nanoclusters derived from their molecular-like electronic structure, however, achieving high photoluminescence quantum yield (PLQY) of metal core-dictated fluorescence remains a formidable challenge. Here, we report efficient suppression of the total structural vibrations and rotations, and management of the pathways and rates of the electron transfer dynamics to boost a near-unity absolute PLQY, by decorating progressive addition of cations. Specifically, with the sequential addition of Zn, Ag, and Tb into the 3-mercaptopropionic acids capped Au nanoclusters (NCs), the low-frequency vibration of the metal core progressively decreases from 144.0, 55.2 to 40.0 cm, and the coupling strength of electrons-high-frequency vibration related to surface motifs gradually diminishes from 40.2, 30.5 to 14.4 meV. Moreover, introducing cation additives significantly reduces electron transfer time from 40, 27 to 12 ps in the pathway from staple motifs to the metal core. This benefits from the shrinkage of the total structure that speeds up the shell-core electron transition, and in particular, the Tb provides a hopping platform for the excited electrons as their intrinsic ladder-like energy level structure. As a result, it allows a remarkable enhancement in PLQY, from 51.2%, 83.4%, up to 99.5%.