100 °C-Langmuir–Blodgett Method for Fabricating Highly Oriented, Ultrathin Films of Polymeric Semiconductors

The Langmuir–Blodgett (LB) and Langmuir–Schaefer techniques facilitate thermodynamic favorability at an air–water interface, at which nanoscale molecular aggregations can be manipulated by micrometer- or millimeter-scale mechanics. The customary use of an aqueous subphase has limitations in the available temperature and spread materials. We present a general strategy to replace the aqueous subphase with an inert, low-vapor-pressure liquid, ethylene glycol. As a representative spread material that requires high-temperature processes, a semicrystalline polymeric semiconductor was investigated. We successfully demonstrated that the polymeric semiconductor spreads homogeneously across the entire surface of ethylene glycol heated to 100 °C using an LB trough, and spontaneously forms multilayers. Comprehensive studies such as X-ray diffraction, optical spectroscopy, and charge transport measurements revealed that barrier compression of solid-state polymer thin films during a high-temperature LB process produced uniaxial alignment of the polymer main chain with an averaged dichroic ratio of about 8, by which the electron transport concomitantly became highly anisotropic. The LB method presented in this work could be used to deposit thin films under ultimate environments, e.g., below 0 °C or above 100 °C, minimizing the effects of the vapor pressure of the subphase.