Extreme Orientational Uniformity in Large-Area Floating Films of Semiconducting Polymers for Their Application in...

Layer-by-layer fabrication of uniformly oriented thin films over large areas by cost-effective solution-based approaches can open new horizons for the realization of high-performance organic circuits in various applications. In this work, fabrication of a large-area ≈40 cm² film with uniform orientation is reported for poly(3,3‴-dialkylquaterthiophene) (PQT) using a unidirectional floating film transfer method (UFTM). Orientation characteristics and charge transport anisotropy were analyzed using polarized UV-vis spectral mapping and fabrication of bottom-gated organic field-effect transistors (OFETs) from different regions. Films were found to be highly oriented with an optical dichroic ratio of ca. 15. Orientation characteristics reveal that films were highly oriented along the width of the film, covering >70% of the area, and angle-dependent field-effect mobilities are in good agreement with the orientation of the polymer backbones. These highly oriented films resulted in charge transport anisotropy of 8.9. An array of bottom-gated OFETs fabricated along the length of single large-area (≈15 × 2.5 cm²) thin film demonstrated the average field-effect mobility of 0.0262 cm²/(V s) with a very narrow standard deviation of 12.6%. We also demonstrated that film thickness can be easily tuned from 5.6 to 45 nm by increasing the PQT concentration, and field-effect mobility is highly reproducible even when the film thickness is 10 nm. Microstructural characterization of the thus-prepared large-area thin films revealed the edge-on stacked polymer backbones and surface roughness of <1 nm as probed by grazing incidence X-ray diffraction and atomic force microscopy, respectively. Flexible OFETs with bottom-gate top-contact geometry were also fabricated, having average field-effect mobility of 0.0181 cm²/(V s). There was no considerable change in mobility after bending the flexible devices at different radii.