Controlled plasmon-induced nonlinear absorption and optical limiting in Al/PVP composite nanofibers.

The effect of aluminum (Al) concentration on the surface plasmon resonance (SPR) band position of aluminum/polyvinylpyrrolidone (Al/PVP) composite nanofibers was investigated to strengthen nonlinear absorption (NLA) and widen its spectral range. With increasing Al content in PVP nanofibers, the SPR band was shifted towards excitation wavelength and an improved NLA response was achieved. The NLA response was examined both experimentally, by conducting Z-scan experiments, and theoretically, using two models. In the first model, the contributions of one-photon absorption (OPA), two-photon absorption (TPA), excited state absorption (ESA) and saturated absorption (SA) are considered. The second model, on the other hand, is a model that is widely used in the literature, and while taking into account the contributions of OPA and TPA, it neglects the ESA. The first model provides more accurate results due to the high concentration of free carriers in the samples examined. In order to reveal the contribution of Al to the nonlinear absorption, a laser excitation wavelength of 532 nm was chosen to minimize both the defect-assisted sequential and genuine two-photon absorption contributions of PVP. While the nonlinear absorption of pure PVP is quite weak, the NLA performance of Al/PVP nanofibers significantly improved as the Al content increased. As the amount of Al increased, the aggregation effect increased and a broadening and red shift in the SPR band were observed in the plasmonic behavior. This indicates a decreasing interparticle distance in Al particles. The sample with the highest amount of Al is anticipated as a potential candidate for optical limiting (OL) applications due to its superior NLA performance and SPR band furthest towards the near infrared (NIR) region, allowing a wider range of wavelength set to be used in OL applications.

Two-Photon Absorption Response of Functionalized BODIPY Dyes in Near-IR Region by Tuning Conjugation Length and Meso-Substituents.

BODIPY dyes substituted by phenol or -COOMe units at the meso-position (C8) with and without a distyryl group including a methoxy moiety at the -C3 and -C5 positions of the BODIPY have been synthesized to analyze the photophysical properties. To clarify the ground-state interaction, absorption and emission features were investigated in the THF environment. Extending the π-conjugation with the methoxy moiety at -C3 and -C5 positions of BODIPY leads to a spectral shifting of the absorption maxima toward red by 120 nm. In addition, attaching the -COOMe unit at the meso-position of the BODIPY structure increases nonradiative molecular relaxation as compared to compounds possessing phenol substituents at the same position. We have investigated the effect of phenol and a -COOMe group and π-extended conjugation length with a methoxy moiety on the properties of two-photon absorption (TPA) and electron transfer dynamics by performing open-aperture (OA) Z-scan and femtosecond transient absorption spectroscopy measurements, respectively. The synthesized BODIPY compounds with the distyryl group including the methoxy unit show TPA character due to the longer conjugation length and therefore intramolecular charge transfer ability. Based on the OA Z-scan experiments upon photoexcitation with 800 nm pulsed laser light, TPA cross-section values were obtained as 74 and 81 GM for the compounds possessing phenol and -COOMe units at the meso-position of BODIPY treated by distyryl group with methoxy moieties, respectively. Additionally, optical and electronic properties were calculated theoretically by using the DFT method.