Anti-Site Defects-Assisted Enhancement of Electrogenerated Chemiluminescence from in Situ Mn²⁺-Doped Supertetrahedral Chalcogenide Nanoclusters

Understanding and revealing the connection between defects and dopant for improving electrogenerated chemiluminescence (ECL) efficiency remain a constant challenge. In this work, the in situ Mn2+-doped Mn1.36Zn5.64In28S56 supertetrahedral chalcogenide semiconductor nanoclusters (NCs) with an ECL efficiency as high as 27.1% was obtained, the corresponding ECL behaviors were investigated, and the vital role of more anti-site defects (ADs) introduced in situ on the ECL emission was elucidated. The ADs can not only give rise to the ECL emission peak at 494 nm but also assist transfer of electrons to induce and enhance the ECL emission at 627 nm from doped Mn2+ in the NCs. Furthermore, based on the fact that dissolved oxygen can enhance the ECL intensity, a highly sensitive ECL sensor for the determination of dissolved oxygen was developed. This insight into the fundamental interactions between Mn2+ dopants and defects in NC host may open new opportunities for the design of novel ECL materials to promote their application potential in electrochemical analysis and imaging.