The electronic structures and morphology of dinaphthothienothiophene (DNTT) thin films on highly oriented pyrolytic graphite (HOPG) and polycrystalline Au (pc-Au) substrates have been investigated using photoelectron spectroscopy and atomic force microscopy techniques to better correlate the charge-injection barrier with the interfacial structure. DNTT molecules follow Stranski–Krastanov-type growth mode, i.e., highly-dewetted islands/fibers above a relatively-wetted interfacial layer, on both the substrates, but distinctively different electronic structures. On the HOPG surface, the as-grown and thermal-annealed films show a broad and a sharp highest occupied molecular orbital (HOMO) bands, respectively. On the pc-Au surface, a significantly split HOMO band and a reduced hole-injection barrier are observed in a monolayer thick film, for the first time, which are absent in other thick films. Such splitting indicates a presence of a strong intermolecular interaction in the interfacial layer, presumably due to the frontier π-orbital overlapping arising from partially-covered densely-packed herringbone-like arranged molecules. The dewetted-fibers seem to form with up-right oriented molecules having negligible interaction, which desorb easily by thermal annealing to retain the highly-stable interfacial layer. The reduction of the hole-injection barrier at the DNTT/pc-Au interface, due to the formation of such interfacial layer having strong intermolecular interaction, has an immense importance in increasing the charge-injection efficiency from a practical electrode.
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