Abstract

Organic field effect transistors (OFETs) using crystalline organic semiconductors are of great interest because of their well-defined structural and electronic properties to study the intrinsic charge carrier transport mechanisms in π-conjugated molecular solids, as well as to unravel their potential to be applied as a novel type of electronic device. In the present study, the valence band structure of the channel region of an OFET is proposed based on photoemission results of a well-defined interface between a dielectric molecular monolayer and single crystals of 5,6,11,12-tetraphenyltetracene (rubrene) which is known to exhibit the highest field effect mobility of all organic semiconductors at room temperature. Commensurate growth of clusters of tetratetracontane (TTC; n-C44H90) on the rubrene single crystal surface and their morphological transformation into a uniform overlayer were observed by atomic force microscopy. Photoelectron spectroscopy measurements at various electron take-off angles were then conducted to derive the valance band width of the rubrene single crystal covered by the TTC overlayers. The valence band width at this hetero-interface was found to be equivalent to that of the pristine rubrene, which suggests an unchanged ‘band effective mass ħ2(d2E/dk||2)’ of accumulated holes even at the vicinity of hydrocarbon-based gate dielectrics.

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