Prof. ZHOU Meng’s research team from the University of Science and Technology of China (USTC) of the Chinese Academy of Sciences (CAS), collaborating with Prof. WANG Quanming’s team from Tsinghua University (THU) achieved near-unity room-temperature photoluminescence quantum yield (PLQY) (>99%) in the near-infrared (NIR) emission of metal nanoclusters in solution. Their work was published in Science .
Gold nanoclusters (Au NCs) as NIR-emissive materials hold potential in biomedical applications. However, the PLQY of Au NCs in NIR region is typically low, often less than 10%. To address this problem, synthesized Au 22 ( t BuPhC≡C) 18 (Au 22 ) and its copper-doped counterpart, Au 16 Cu 6 ( t BuPhC≡C) 18 (Au 16 Cu 6 ) and study their photophysical properties. Single-crystal x-ray diffraction analysis revealed that Au 22 and Au 16 Cu 6 share similar structures. Au 22 showed an emission peak at 690 nm and Au 16 Cu 6 at 720 nm. The absolute PLQY of Au 22 and Au 16 Cu 6 in air were 9% and 95%, respectively. In deaerated solution, the PLQY of Au 16 Cu 6 reached 100% measured by both absolute and relative methods. Time-correlated single-photon counting measured the photoluminescence lifetimes of Au 22 and Au 16 Cu 6 to be 485 ns and 1.64 μs, respectively.
Further investigation of NCs’ excited-state dynamics through transient-absorption spectroscopy revealed that both NCs' luminescent states originated from the triplet state (T 1 ), with distinct dynamic processes observed in femtosecond transient-absorption spectroscopy. Under 380 nm excitation, Au 22 showed a slow rise of 148 ps, while Au 16 Cu 6 showed a rapid relaxation of 0.5 ps. Triplet sensitization experiments confirmed that these processes are attributed to ultrafast intersystem crossing (ISC) from singlet state (S 1 ) to T 1 . Due to copper doping, Au 16 Cu 6 has smaller ∆E st , significantly accelerating its ISC rate. As a result, Au 16 Cu 6 ultimately showcases PLQY close to 100%.
The approach to achieve near-unity PLQY could enable the development of highly emissive metal cluster materials. Specifically, this work demonstrates that near-unity PLQY can be attained with an alloy of gold-copper nanoclusters even in solution at room temperature, which will enable applications ranging from biological imaging to luminescent devices.
Science
Near-unity NIR phosphorescent quantum yield from a room-temperature solvated metal nanocluster
19-Jan-2024