Perceptible exciton-to-trion conversion and signature of defect mediated vibronic modes and spin relaxation in nanoscale WS2 exposed to γ-rays.

In this work, we report manifested optical, optoelectronic and spin-spin relaxation features of a few layered tungsten disulphide (WS2) nanosheets subjected to energetic γ-photons (∼1.3 MeV) emitted from a Co60 source. Upon intense irradiation (dose = 96 kGy), a slight departure from the pure hexagonal phase was realized with the introduction of the trigonal phase at large. Moreover, in the Raman spectra, as a consequence of the radiation-induced effect, an apparent improvement of the E-to-A mode intensity and a reduction in phonon lifetimes have been realized, with the latter being dependent on the linewidths. The emergence of the new peak (D) maxima observable at ∼406 cm-1 in the Raman spectra and ∼680 nm in the photoluminescence (PL) spectra can be attributed to the introduction of defect centres owing to realization of sulphur vacancies (V S) in the irradiated nanoscale WS2. Additionally, neutral exciton to charged exciton (trion) conversion is anticipated in the overall PL characteristics. The PL decay dynamics, while following bi-exponential trends, have revealed ample improvement in both the fast parameter (0.39 ± 0.01 ns to 1.88 ± 0.03 ns) and the slow parameter (2.36 ± 0.03 ns to 12.1 ± 0.4 ns) after γ-impact. We attribute this to the finite band gap expansion and the incorporation of new localized states within the gap, respectively. A declining exciton annihilation rate is also witnessed. The isotropic nature of the electron paramagnetic resonance spectra as a consequence of γ-exposure would essentially characterize a uniform distribution of the paramagnetic species in the system, while predicting a three-fold improvement of relative spin density at 96 kGy. Exploring defect dynamics and spin dynamics in 2D nanoscale systems does not only strengthen fundamental insight but can also offer ample scope for designing suitable components in the areas of miniaturized optoelectronic and spintronic devices.