Interplaybetween Long-Range Crystal Order and Short-RangeMolecular Interactions Tunes Carrier Mobility in Liquid Crystal Dyes

摘要

We investigated the influence of molecular packing on the optical and electrical properties of the liquid crystalline dye 4,7-bis[5-(2-fluoro-4-pentyl-phenyl)-2-thienyl]-2,1,3-benzothiadiazole (FPPTB). FPPTB is crystalline at room temperature, exhibits a nematic phase at temperatures above 149 °C and is in an isotropic melt at temperatures above 230 °C. Solution processed FPPTB films were subject to thermal annealing through these phase transition temperatures and characterized with X-ray diffraction and polarized optical microscopy. Cooling FPPTB films from the nematic and isotropic phases increased crystal domain size, but also induced local structural variations in the molecular packing of crystalline FPPTB. The decrease in long-range order was correlated with an increase in short-range π–π interactions, leading to changes in molecular aggregation which persisted even when the FPPTB films were cooled to room temperature. Annealing-induced changes in molecular aggregation were confirmed with optical spectroscopy. The carrier mobility in FPPTB films increased over 2 orders of magnitude from (2.2 ± 0.4) × 10^–5 cm² V^–1 s^–1 in as-spun films toμ = (5.0 ± 0.8) × 10^–3 cm² V^–1 s^–1 in films cooled fromthe isotropic melt. We discuss the relationship between thermal stabilityand high carrier mobility values in terms of the interplay betweenlong-range molecular order and increased π–π interactionsbetween molecular pairs in the FPPTB film.