Surface-induced aromatic stabilization (SIAS), a recently proposed mechanism leading to a formation of charge-transfer (CT) states at organic/metal (O/M) interfaces [G. Heimel, et al., Nat. Chem.5, 187 (2013)], was investigated for an aromatic hydrocarbon, diindenoperylene (DIP), by means of synchrotron radiation-based ultraviolet photoelectron spectroscopy (UPS). By employing DIP and noble metal substrates (Ag and Cu), we confirmed the formation of CT states, indicating that an inclusion of a specific functional group with a hetero-atom within adsorbate molecules as suggested before is not necessarily required for the formation of CT states mediated by the SIAS. With a comparison of the mother and analogue molecules, perylene and PTCDA, we discuss the structural requirement for the realization of the SIAS.

Structure-related ionization energy (IE) of vacuum-deposited titanyl-phthalocyanine (OTiPc) thin films was investigated by using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray diffractometry. Distinct molecular orientations (i.e. lying-flat and standing-up orientation) in different polymorphous (i.e. monoclinic β-phase and triclinic α-phase) were observed on a surface of polycrystalline (poly-) Au and octadecyltrichlorosilane-self assembled monolayer (OTS-SAM). For the two structures IE of the highest occupied molecular orbital (HOMO) of OTiPc thin films altered significantly by 0.55 eV. The different IE was attributed to surface dipole potential and strong intermolecular interaction.

A new class of high-vacuum organic deposition chamber was developed to study the structure and growth of organic semiconductor thin films. Using the chamber in situ real-time 2-dimensional grazing incidence x-ray diffraction (2D-GIXD) was measured during thin film growth of distyryl-oligothiophenes derivatives (DS2T) on SiO2 surface. An evolution of 2D-GIXD pattern was clearly observed during the growth due to the crystallization of the molecular domains consisting of standing-up orientation. A theoretical simulation on the experimental 2D-GIXD map provided a potential use of this system to determine the unit cell parameters in thin films. Thickness dependence and influence of air exposure on the film structure were also studied.

The surface electronic structures of conjugated regio regular and regio random poly (3- hexylthiophene) (rr-P3HT and rra-P3HT) thin films were studied by near edge X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy and Penning ionization electron spectroscopy (PIES). The distribution of the surface electronic states was controlled on rr-P3HT and rra-P3HT thin films with different molecular ordering by varying the coating process and PIES was adopted to observe the electronic states existing outside the surface.