Investigation and Control of Charge Transport Anisotropy in Highly Oriented Friction-Transferred Polythiophene Thin Films.

Highly oriented thin films of poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) were prepared by friction-transfer technique followed by their characterization using polarized absorption spectroscopy, angle-dependent polarized Raman spectroscopy, and X-ray diffraction (XRD) techniques. Orientation in high-molecular-weight () polymers is hampered by chain folding or entanglements, which limit their macromolecular orientation. Interestingly, utilizing high-molecular-weight PBTTT ( > 50 kDa) and friction-transfer technique, successful fabrication of highly oriented thin films with very high dichroic ratio (∼30) was demonstrated. The role of the substrate's surface energy and its impact on the field-effect mobility (μ) of the oriented thin films were comprehensively investigated. The influence of annealing the thin films as prepared on the bare and self-assembled monolayer (SAM)-treated SiO surfaces exhibiting differential trends of μ was systematically investigated. This was explained by partial and complete conformational transformation of macromolecules on bare and SAM-treated SiO surfaces, respectively, after annealing them beyond liquid crystalline phase transition temperature, as revealed by in-plane and out-of-plane XRD results. On bare SiO, optimum μ up to 0.03 cm V s along the backbone orientation was obtained for the thin films annealed to 120 °C; whereas, it reached up to 0.36 cm V s on SAM-treated SiO after annealing at 200 °C. Finally, a charge transport mechanism was proposed taking evidence from the anisotropic optical and electrical characteristics of the friction-transferred PBTTT films into consideration.