Metallic phase transition metal dichalcogenide quantum dots showing different optical charge excitation and decay pathways

The charge excitation and decay pathways of two-dimensional heteroatomic quantum dots (QDs) are affected by the quantum confinement effect, bandgap structure and strong exciton binding energy. Recently, semiconducting transition metal dichalcogenides (TMDs) have been intensively studied; however, the charge dynamics of metallic phase QDs ( m QDs) of TMDs remain relatively unknown. Herein, we investigate the photophysical properties of TMD- m QDs of two sizes, where the TMD- m QDs show different charge excitation and decay pathways that are mainly ascribed to the defect states and valence band splitting, resulting in a large Stokes shift and two excitation bands for maximum photoluminescence (PL). Interestingly, the dominant excitation band redshifts as the size increases, and the time-resolved PL peak redshifts at an excitation wavelength of 266 nm in the smaller QDs. Additionally, the lifetime is shortened in the larger QDs. From the structural and theoretical analysis, we discuss that the charge decay pathway in the smaller QDs is predominantly affected by edge oxidation, whereas the vacancies play an important role in the larger QDs. Metallic phase transition metal dichalcogenides quantum dots show different pathways of optical charge excitation and decay according to the size and sort of defects, resulting into the large Stoke shift, two bands for charge excitation, and TRPL peak shift. This result is mainly ascribed to the valance band splitting and the emerging defect states originated from atomic vacancy of basal plane and edge oxidation.