Here we report a drastic enhancement of nonlinear absorption behaviour and exceptional optical limiting action of two core-shell systems (Au@graphite and Ag@graphite) prepared by adopting a fairly easy way in which we did not use any graphitic substrate. We carried out pulsed laser ablation of Au and Ag targets in toluene, monosubstituted benzene from which graphite layers of nanometer thickness has emerged as a result of photochemical reactions. The prepared samples were characterized and analyzed by UV/Vis spectroscopy, Raman spectroscopy, and TEM. Theoretical simulations of the core-shell nanostructures were done by the finite-difference time-domain method underlined the quenching of SPR in the case of both Au and Ag NPs by the graphitic layers evolved from toluene. Au and/or Ag@graphite core-shell structure exhibited a huge improvement in the nonlinear absorption behaviour and the optical limiting efficiency of these systems is found to be better than that of many benchmark optical limiters. The enhancement in nonlinear absorption property and the limiting actions of these systems were attributed to the enhanced excited-state absorption as well as free-carrier absorption arose as a result of the modification in the electronic structure of graphite on core-shell formation. Moreover, the metallic NPs also enhances nonlinear absorption through free-carrier absorption free-carrier absorption. So we believe these results are quite useful for guiding the characterization, monitoring the synthesis of similar nanostructures and for, the development of nanohybrids with desired properties for nonlinear optical, optoelectronic and photocatalytic applications.

Abstract. In this communication, we report synthesis and characterization of new D-A conjugated polymers (P1-P3) consisting of electron-donating (D) 3,4-didodecyloxythiophene, electron-accepting (A) 1,3,4-oxadiazole unit and non-conjugation linkers. The conjugated segment in P1-P3 contains only five aromatic rings resulting in short conjugation length, but has an alternate D-A arrangement which significantly enhances the intramolecular charge transfer (ICT) interaction within the segment. As a result, these polymers exhibited low optical band gap in the range 2.51-2.76 eV. Fluorescence emission studies revealed that the polymer thin films emit intense blue light with emission maxima in the wavelength rage 430-480 nm. All three polymers undergo both oxidation and reduction processes under electrochemical conditions. Further, these polymers (P1-P3) exhibit low-lying HOMO and LUMO levels as a result of D-A structure of the conjugated segment. Polymer light-emitting devices were fabricated using these polymers as emissive layer with a device configuration of ITO/MoO 3 /polymer/LiF/Al. The test device based on P2 emitted blue light with a low threshold voltage of 5 V. Z-scan studies reveal that the polymers exhibit a strong optical limiting behavior. The value of the nonlinear absorption coefficient (β) of polymers is of the order 10 −11 m/W which indicates that these materials may be accomplished for fabricating optical limiters.

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