Towards Efficient White‐light Emission in Sulfur Dots through Surface Charge Engineering

Abstract Sulfur dots (SDs) have emerged as promising photoluminescence (PL) materials owing to their intrinsic merits such as abundant electronic effects, outstanding biocompatibility and available photocatalytic activity. Typically based on quantum confinement effects, SDs are reported usually confined emission in blue‐to‐green region. However, it is challenging to achieve their broad emission tunability in the visible region, restricted by inherent band gap of bulk sulfur (ca. 2.79 eV). Herein, we present white‐light‐emitting SDs achieved by surface charge engineering that hybridizes the surface of SDs with oleylamine. The resulting SDs exhibit broadband emissions (full width at half maximum of 187 nm) with PL quantum yields of up to 12.1 % and Commission International de I'Eclairage color coordinates of (0.27, 0.32). Detailed experimental and theoretical analysis reveal that the strong orbital coupling between oleylamine and sulfur on the hybrid surfaces of the SDs causes electron delocalization, leading to the generation of low‐energy charge transfer (CT) states. These CT states are highly sensitive to sulfur‐oleylamine hybrid structures, which complicate the transition dynamics and promote multi‐energy emissions, accounting for efficient white‐light emission. The demonstration of white‐light SDs based on surface charge engineering is an important step towards the development of sulfur‐based PL materials.