Determination of the supramolecular arrangement of Dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene films fabricated by Physical Vapor Deposition and possible implications for electronic devices

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Organic thin films have been used as active layers and are an alternative to inorganic materials in order to improve the performance of electronic devices. Recently, Dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) became an important compound in organic electronics due to its optical and electrical properties, which are dependent on the supramolecular arrangement. Thus, in this work we determined the supramolecular arrangement of organic thin films of DNTT (DNTT PVD films) fabricated by Physical Vapor Deposition (PVD). Ultraviolet-visible absorption spectra showed the controlled growth of the films within the range from 17 to 120 nm and the formation of aggregates (J- and H-), as the H-aggregate was favored by the thickness. The emission spectra revealed that excimers are responsible for the emission in DNTT PVD films and the increase in solution concentration led to the formation of H-aggregates primarily. The molecular organization of the films, determined by selection rules of Fourier Transform Infrared absorption spectroscopy, suggested that the molecules had a preferential chain-on organization for 120 nm thickness film. Complementary, X-Ray Diffraction data showed that DNTT PVD film was practically monocrystalline with monoclinic cell unit, also determined for the 120 nm thickness film. Atomic Force Microscopy measurements revealed that DNTT film had a homogeneous surface (roughness around 6 nm for the film with 120 nm thickness) with grains of uniform size and geometry. Thus, based on the characteristics of the supramolecular arrangement (especially the molecular organization and increase of H-aggregates with the thickness of DNTT PVD film and the results found in the literature), it was possible to analyze probable implications of chain-on molecular organization and the increase of H-aggregates with the film thickness on the mobility of charge carriers of devices, such as diodes and transistors, in which they are applied.