Highly enhanced nonlinear optical absorption with ultrafast charge transfer of reduced graphene oxide hybridized by an azobenzene derivative

Abstract

Graphene-based materials have been attracted many attentions due to their excellent properties and potential applications in many fields. Graphene also provides a flexible substrate to develop novel functional materials by hybridizing with other organic or inorganic components. Herein, we report the functionalization of reduced graphene oxide (RGO) with an azobenzene derivative (BNB-t8) containing the π-conjugated moiety and hydrogen bonding groups, to improve the optical and nonlinear optical properties of RGO. With the introducing of BNB-t8, a new absorption band is formed and dominates the absorption spectrum, clearly demonstrates that the BNB-t8 has been hybridized with RGO, by combining the analysis of Raman and XRD data. Femtosecond Z-scan results present a highly enhanced saturable optical absorption of BNB-t8/RGO hybrid compared with that of RGO. By optimizing the hybridization ratio of BNB-t8 to RGO, the saturable absorption coefficient of BNB-t8/RGO hybrid reaches to −237 m/W, 38 times larger than that of RGO (−6.2 m/W). In the meantime, the third-order susceptibility χ (3) of BNB-t8/RGO hybrid is aslo enhanced by 8 times to be 5.18×10 −13 esu. These enhancements of nonlinear optical properties of BNB-t8/RGO hybrid mainly arise from the charge transfer from RGO to BNB-t8. Femtosecond transient absorption measurements reveal that the charge separation takes place in 0.28 ps and the charge recombination in 2.0 ps, indicating a strong electron coupling and thus an enhanced electron delocalization in BNB-t8/RGO hybrid compared with those in RGO. We suggest that the noncovalent π-π interaction plays the dominant role for enhancing the electron delocalization of RGO after hybridizing with BNB-t8, while the hydrogen bonding interaction reinforce the coupling interaction between BNB-t8 and RGO moieties in the hybrid. The as-prepared BNB-t8/RGO hybrid with high saturable absorption coefficient with an ultrafast response presents a potential candidate as saturable absorber of mode-locked laser.