Cover Picture: Nucleation-Governed Reversible Self-Assembly of an Organic Semiconductor at Surfaces: Long-Range Mass Transport Forming Giant Functional Fibers (Adv. Funct. Mater. 18/2007)



The cover shows a fluorescence microscopy image of solvent-vapor annealed (SVA) films of an alkylated perylene-bis(dicarboximide), reported by Vincenzo Palermo, Klaus Müllen, Paolo Samorì, and co-workers on p. 3791. Upon exposure to tetrahydrofuran vapors, ultrathin films exhibiting needle-like structures rearrange into millimeter-long fibers, which have a sub-micrometer cross section. The SVA growth was found to be a nucleation-governed process leading to the formation of birefringent fibers on various substrates. (The result was obtained in the framework of the ESF-EUROCORES-SONS2-SUPRAMATES project.)

The use of solvent-vapor annealing (SVA) to form millimeter-long crystalline fibers, having a sub-micrometer cross section, on various solid substrates is described. Thin films of a perylene-bis(dicarboximide) (PDI) derivative, with branched alkyl chains, prepared from solution exhibit hundreds of nanometer-sized PDI needles. Upon exposure to the vapors of a chosen solvent, tetrahydrofuran (THF), the needles re-organize into long fibers that have a remarkably high aspect ratio, exceeding 103. Time- and space-resolved mapping with optical microscopy allows the self-assembly mechanism to be unravelled; the mechanism is found to be a nucleation-governed growth, which complies with an Avrami-type of mechanism. SVA is found to lead to self-assembly featuring i) long-range order (up to the millimeter scale), ii) reversible characteristics, as demonstrated through a series of assembly and disassembly steps, obtained by cycling between THF and CHCl3 as solvents, iii) remarkably high mass transport because the PDI molecular motion is found to occur at least over hundreds of micrometers. Such a detailed understanding of the growth process is fundamental to control the formation of self-assembled architectures with pre-programmed structures and physical properties. The versatility of the SVA approach is proved by its successful application using different substrates and solvents. Kelvin probe force microscopy reveals that the highly regular and thermodynamically stable fibers of PDI obtained by SVA exhibit a greater electron-accepting character than the smaller needles of the drop-cast films. The giant fibers can be grown in situ in the gap between microscopic electrodes supported on SiOx, paving the way towards the application of SVA in micro- and nanoelectronics.