Direct formation of organic semiconducting single crystals by solvent vapor annealing on a polymer base film

We report single crystal formation of organic semiconducting small molecules via solvent vapor annealing (SVA) on a polymer base film (PBF). The soluble PBF strongly assists the self-assembly of small molecules to form single crystals; this sharply contrasts typical SVA where the inorganic base film such as SiO ₂ plays little or no role. We use a matrix of organic solvents and polymers to systematically investigate the re-crystallization of dioctylbenzothienobenzothiophene (C8-BTBT) by SVA on polymer surfaces. Crystallization by SVA clearly correlates with the miscibility of solvents and PBFs. The PBF dramatically increases the amount of condensed solvent on the surface. The additional solvent enhances the molecular mobility of small molecules to allow self-assembly in a distance over hundreds of microns, and stimulates crystal growth via Ostwald ripening. Based on this mechanism, the final crystal size of small molecules can be controlled to vary from tens of microns to millimetres simply by modifying the thickness of the base film. The approach was successfully applied to several semiconducting small molecules to form single crystals that exhibited field-effect response. Hence SVA on PBF is presented as a general and promising method for the direct fabrication of organic single crystals on polymer dielectrics.