Photogeneration of charge carrier correlated with amplified spontaneous emission in single crystals of a thiophene/phenylene co-oligomer

Abstract

Thiophene/phenylene co-oligomers have substantial promise for the use of not only organic electronics but also organic optical devices. However, considerably less is known about the correlation between their optical and optoelectronic properties. We have investigated the charge carrier generation in 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5) single crystals by flash-photolysis time-resolved microwave conductivity (TRMC) and transient absorption spectroscopy (TAS). It was found that the dependence of photocarrier generation efficiency on excitation photon density differed from that of emission efficiency once amplified spontaneous emission (ASE) and resultant spectrally narrowed emission occur upon exposure to 355 nm. In contrast, the dependences of emission and photocarrier generation efficiencies were identical when ASE was not involved at a different excitation wavelength (193 nm). An approximated analytical solution of rate equation considering ASE or singlet-singlet annihilation was applied to the experiments, exhibiting good agreement. On the basis of TRMC, TAS, and extinction coefficient of radical cation assessed by pulse radiolysis, the minimum charge carrier mobility was estimated, without electrodes, to be 0.12 cm(2) V(-1) s(-1). The dynamics of charge carrier and triplet excited state is discussed, accompanying with examination by time-dependent density functional theory. The present work would open the way to a deeper understanding of the fate of excited state in optically robust organic semiconducting crystals.