Abstract
Optically pumped light amplification properties are investigated for low-dimensional organic crystals of thiophene/phenylene co-oligomer (TPCO) derivatives substituted with methoxy and cyano groups. Two-dimensional platelet single crystals of those TPCO derivatives are grown from solution and/or vapor phases. Their crystal structures are dependent on the molecular symmetry and substituent groups. The unsubstituted TPCOs belong to monoclinic crystals, while the methoxy-substituted ones crystallize in orthorhombic forms. The cyano-substituted TPCOs form triclinic or monoclinic structure which gives rise to coexistence of one-dimensional rodlike crystals along with platelet crystals in the vapor-phase growth. One-dimensional TPCO crystals are also prepared by hot-wall epitaxy on potassium chloride (KCl) surface. The unsubstituted TPCO molecules epitaxially orient along the <110> direction of KCl and crystallize in an orthogonally aligned needlelike morphology. Under optical pumping, their fluorescence is amplified by light confinement and self-waveguiding effects in the TPCO crystal cavities. Above a certain threshold of excitation fluence, amplified spontaneous emission (ASE) with spectrally narrowed bands appears. When a pair of parallel facets of the platelet crystal acts as a Fabry–Pérot (F-P) resonator, multimode laser oscillation is observed in the ASE bands. Similar F-P lasing is also obtained from one-dimensional rodlike and needlelike crystals. Moreover, time-resolved spectroscopy reveals unique pulse-shaped emission with time delay up to 300 ps for the two-dimensional platelet crystals at prethreshold excitation fluence. The origin of this time-delayed emission is discussed in terms of exited state coherence among uniaxially oriented TPCO molecules in the crystals.
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Yanagi, H., Mizuno, H., Sasaki, F., Hotta, S. (2015). Light Amplification in Low-Dimensional Crystals of Thiophene/Phenylene Co-oligomer Derivatives. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_38
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DOI: https://doi.org/10.1007/978-4-431-55357-1_38
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