Valence band structure of rubrene single crystals in contact with an organic gate dielectric

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 -C 44 H 90 ) 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 ħ 2 (d 2 E /d k || 2 )’ of accumulated holes even at the vicinity of hydrocarbon-based gate dielectrics.