Prominent exciton emission dynamics and charged exciton (trion)-phonon coupling aspects in γ- irradiated WSe2 nanosheets

We report on the nature of charge-neutral exciton emission decay, exciton-trion conversion as well as their phonon coupling in exfoliated WSe2 nanosheets subjected to ~ 1.3 MeV energetic γ-photons. Steady-state photoluminescence (PL) spectra, upon deconvolution, showed prominent emission peaks at ~ 680 nm, ~ 712 nm, and ~ 730 nm and ascribed to 2s, and 1s excitons and trions respectively, while the chalcogen vacancy (VSe) mediated defect emission peak found at ~ 790 nm. From the X-ray photoelectron spectroscopy (XPS) analysis, we noticed a clear shifting of the fundamental peaks due to W and Se toward higher binding energy values and were attributed to the radiation-induced alteration in the oxidation states locally, taking advantage of the manifestation of point defects/vacancies. Moreover, the time-resolved PL spectra signify an anomalous variation in the fast parameter (0.4–0.86 ns), and with slow parameter (2.46–3.82 ns) getting slower with increasing γ-dose. A slight variation in the exciton-phonon coupling factor is noted with Se-ph < 1 indicating a weaker interaction and featuring maximal envelope over all the phonon replica near the zero-phonon line. In contrast, trion-phonon coupling factor, St-ph > 1, or < 1 depending on its spin degeneracy (ζ = 2 s + 1; with 2, for s = 1/2 and 4 for s = 3/2). The highest St-ph value determined was ~ 1.82 ± 0.2 which declines monotonically with increasing dose but remained greater than unity up to a γ-dose as high as 96 kGy. The implication of trion-phonon coupling has immense scope in nano-photovoltaics, and nano-electronics as well as heat sinks in nanogenerators. Graphical Abstract