Polyfluorinated Naphthalene-bis-hydrazimide for Solution-Grown n-Type Semiconducting Films

[Image: see text] Naphthalene tetracarboxylic diimides (NDIs), possessing low-lying and tunable LUMO levels, are of wide interest for their aptitude to provide cost-effective, flexible, and environmentally stable n-type organic semiconductors through simple solution processing. NDI-based aromatic hydrazidimides are herein studied in relation to their chemical and environmental stability and as spin-coated stable thin films. In the case of the pentafluorinated residue, these were found to be crystalline, highly oriented, and molecularly flat (roughness = 0.3 nm), based on optical and atomic force microscopy, X-ray diffraction in specular and grazing incidence geometry, and X-ray reflectivity measurements. A new polymorph, previously undetected during the isolation of bulk powders or in their controlled thermal treatments, is found in the thin film and was metrically and structurally characterized from 2D GIWAXS patterns (monoclinic, P2/c, a = 17.50; b = 4.56; c = 14.24 Å; β = 84.8°). This new thin-film phase, TF-F5, is formed no matter whether silicon, glass, or polymethylmethacrylate substrates are used, thus opening the way to the preparation of solution-grown flexible semiconducting films. The TF-F5 films exhibit a systematic and rigorous molecular alignment with both orientation and packing favorable to electron mobility (μ = 0.02 cm(2) V(–1) s(–1)). Structural and morphological differences are deemed responsible for the absence of measurable conductivity in thin films of polyfluorinated analogues bearing −CF(3) residues on the hydrazidimide aromatic rings.