The versatile study of graphene derivatives has resurgence of interest on understanding its nonlinear optical response at different nanoscales. Nanostructured manganese dioxide: reduced graphene oxide (MnO2: rGO) hybrids were synthesized by reduction method by varying the content of rGO (5, 10, 15 & 20 wt%). X-ray Photoelectron Spectroscopy studies confirmed the surface functionalization of MnO2 on rGO. Field Emission Scanning Electron Microscopy (FESEM) and High-Resolution Tunnelling Electron Microscopy (HRTEM) witness that with respect to the content of rGO, the morphology of MnO2 varies radically from clusters to nanorods to nanowires over the surface of rGO sheets. Ground state absorption spectra of the hybrids have absorption edge at 268 nm corresponding to combined metal oxide charge transfer between rGO (π-π* transition of CC and n-π transition of C-O bonds) and MnO2 (d-d transition). Moreover, hierarchical MnO2 nanowire network resided on 2D rGO sheets involves broad absorption at the visible spectral domain due to polaron transition as well the localization of π- π* transited electrons that facilitates the probability of occurrence of excited state absorption. Intensity dependent open aperture Z-scan technique of the prepared hybrids using Q-switched Nd: YAG 532 nm nanopulsed laser reveals unusual transitions and enhanced nonlinear absorption. MnO2:(5 wt%) rGO shows saturable absorption (SA) at low intensity and changeover dynamically to reverse saturable absorption (RSA) at higher intensity. MnO2:(10 & 15 wt%) rGO exposes coupled nonlinear absorption (SA + RSA) owing to the combined effect of graphene (π-states) and MnO2 (σ-states). MnO2:(20 wt%) rGO exhibits a stronger RSA ascribed to sequential two photon absorption. The third-order nonlinear absorption coefficient and limiting threshold of MnO2: rGO (20 wt%) are 4.04 ×10-10 m/W and 0.84 ×1012 W/m2, which shows five-fold increase compared to bare rGO and MnO2. The obtained results propose that the optical nonlinearity of MnO2 nanowires surface functionalized rGO sheets can significantly be tuned to meet the requirements for fabricating laser safety devices.
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