Supramolecular Engineering of Oligothiophene Nanorods without Insulators: Hierarchical Association of Rosettes and Photovoltaic Properties

Supramolecular rosettes of oligothiophenes that do not bear long aliphatic tails have been designed as semiconducting nanomaterials for solution‐processable bulk heterojunction solar cells. The rosettes consist of six barbiturated thienyl[oligo(hexylthiophene)] units (Bar‐T‐hT_n; n=3,4,5) aggregated by multiple hydrogen bonds, which have been directly visualized by scanning tunneling microscopy (STM) at a solid–liquid interface. ¹H NMR spectroscopy in [D₈]toluene showed that Bar‐T‐hT_n exists as a mixture of monomers and small hydrogen‐bonded aggregates. Hierarchical organization of the hydrogen‐bonded aggregates took place through π–π stacking interactions upon casting their toluene solutions, resulting in the growth of highly ordered nanorods whose widths are consistent with the diameters of the rosettes. The nanorods could be generated in the presence of soluble fullerene derivatives via solution casting or the annealing of the resulting thin films. The solar cells fabricated based on these bulk heterojunction films showed power conversion efficiencies of 1–3 %, which are far higher than those of the non‐hydrogen‐bonded reference oligothiophene and the derivative that possesses long aliphatic tails.     

Second Harmonic Generation Measurements for Biomacromolecules: Celluloses

The molecular chain orientation of mercerized cellulose II was examined by optical second harmonic generation (SHG) measurements. The SHG intensities of several kinds of mercerized cellulose II were found to be much larger than those expected for a structural model with an antiparallel molecular chain orientation as proposed by X-ray studies. This result suggests that the orientation of mercerized cellulose II is parallel as suggested by molecular dynamics simulation. © 2004 The Optical Society of Japan     

Electric-field-induced polar biaxial order in a nontilted smectic phase of an asymmetric bent-core liquid crystal

A polarization reorientation process has been studied by means of optical second-harmonic generation in an optically uniaxial smectic phase of an asymmetric bent-core liquid crystal. A nontilted polar smectic order with a biaxial order is induced by applying an electric field to the uniaxial nonpolar smectic phase. This phenomenon was well simulated by the two-dimensional Langevin process, i.e., electric-field-induced continuous molecular reorientation against thermal agitation. The simulation suggests that about 200s of molecules form a polar domain and cooperatively respond to the applied field. The existence of the polar domains and their reorientation are consistent to the dielectric measurement; a high dielectric constant of about 60 at the kHz range is markedly suppressed by applying a bias field.     

Terabit all-optical logic based on ultrafast two-dimensional transmission gating

Terabit all-optical complementary logic is proposed using two successive time slots to represent a unique logical status. An organic molecular thin film is used as an array of optically controlled optical switches. By utilizing the planar structure of the film and its ultrafast optical response, proof-of-principle fully optical NOT and AND logic operations were demonstrated with 400-fs interval pulses.