Ferroelectric Organic Semiconductor: [1]Benzothieno[3,2-b][1]benzothiophene-Bearing Hydrogen-Bonding -CONHC14H29 Chain.

An alkylamide-substituted [1]benzothieno[3,2-b][1]benzothiophene (BTBT) derivative of BTBT-CONHC14H29 (1) and C8H17-BTBT-CONHC14H29 (2) were prepared to design the multifunctional organic materials, which can show both ferroelectric and semiconducting properties. Single-crystal X-ray structural analyses of short-chain (-CONHC3H7) derivatives revealed the coexistence of two-dimensional (2D) electronic band structures brought from a herringbone arrangement of the BTBT π core and the one-dimensional (1D) hydrogen-bonding chains of -CONHC3H7 chains. The thin films of 1 and 2 fabricated on the Si/SiO2 substrate surface have monolayer and bilayer structures, respectively, resulting in conducting layers parallel to the substrate surface, which is suitable for a channel layer of organic field-effect transistors (OFETs). The thin film of 1 indicated a hole mobility µFET = 2.4 × 10-5 cm2 V-1 s-1 and threshold voltage VTh = - 29 V, whereas that of 2 showed a µFET = 2.1 × 10-2 cm2 V-1 s-1 and threshold voltage VTh = -9.7 V. Both 1 and 2 formed the smectic E (SmE) phase above 410 and 369 K, respectively, where the existence of a hole transport pathway was confirmed in the SmE phase. The ferroelectric hysteresis behavior was observed in bulk 1 and 2 in the polarization-electric field (P-E) curves at the SmE phase. 1 showed the remanent polarization Pr = 2.3 µC cm-2 and coercive electric field Ec = 5.2 V µm-1, whereas the Pr and Ec of 2 were 3.4 µC cm-2 and 7.0 V µm-1 at the conditions of 453 K and 1 Hz. Introduction of alkylamide units into the BTBT π core has the potential to develop the external stimulus-responsive organic semiconductors brought from both ferroelectricity and semiconducting properties.

Conformational Change of Alkyl Chains at Phase Transitions in Thin Films of an Asymmetric Benzothienothiophene Derivative.

Among many promising organic semiconducting materials, 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10) shows outstanding device performances for organic field-effect transistors. This compound has a highly ordered liquid crystalline state, i.e., the smectic E (SmE) phase. Although the transition from the crystalline state to the SmE phase is believed to accompany melting of the alkyl chains, no spectroscopic evidence has been found so far. In this study, the conformational change of the decyl chains in Ph-BTBT-C10 films across the phase transition is analyzed by temperature-dependent measurements in situ using infrared spectroscopy. The spectral analysis reveals that the polycrystalline film has latent conformational disorder (the gauche conformer), the rate of which becomes more pronounced with the heat treatment. As expected, melting of the decyl chains is observed above the transition temperature to the SmE phase. This study also highlights the discovery of some key bands sensitive to the phase transitions in liquid crystalline organic semiconductors.