Femtosecond excited-state dynamics and ultrafast nonlinear optical investigations of ethynylthiophene functionalized porphyrin

Abstract

Ethynylthiophene functionalized D-π-A porphyrin (LG5) belongs to a class of porphyrin molecules with proven application in organic solar cell devices. In this report, we present a comprehensive optical and non-linear optical characterization of ethynylthiophene functionalized porphyrin molecule, denoted as LG5. Femtosecond transient absorption (TA) spectroscopy was used to study the ultrafast excited-state properties with 400 nm, 70 fs photoexcitation. Global and target fitting analysis of the obtained TA spectra established a reliable photophysical model of excited state population relaxation and extracted the various rate constants. Considering the good performance of LG5 as a photosensitizer in dye-sensitized solar cells (DSSCs), electron injection studies on LG5 sensitized mesoporous TiO2 were also performed. Both integrated and transient photoluminescence (PL) data for LG5 sensitized TiO2 samples confirms efficient electron injection. The target analysis on TA data of LG5–TiO2 films revealed a multi-step electron injection from different excited energy levels with both ultrafast (≈370 fs) and slow injections times. Additionally, the non-linear optical (NLO) properties of LG5 are studied using the single-beam Z-scan technique upon photoexcitation of 800 nm, 70 fs laser pulses. The open aperture data demonstrated two-photon absorption (2PA), and closed aperture data indicated the presence of positive nonlinear refraction. The calculated values of 2PA cross-section and 3rd order NLO susceptibility were 1723 GM and 1.89 × 10−13 esu (2.64×10−21m2V−2), respectively.