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Initial growth process of pentacene molecules on clean Si(001)-2 × 1 substrate was investigated by scanning tunneling microscopy. It is found that the wetting layer, which is not crystalline but disordered, forms before the growth of a first crystalline layer. The wetting layer consists of double layer of the flatly adsorbed pentacene molecules. The formation of the wetting double layer is discussed. The first crystalline layer that is grown on the disordered wetting layer with standing-up pentacene molecules consists of some domains that differ in their crystal structures. Among them, a new pentacene crystal structure is found that can form only on the first layer. In contrast, the second crystalline layer has only single domain. Moreover, we investigated the electronic properties of the pentacene layers by the current–voltage measurements. The pentacene layers are semiconducting with a band gap of about 4 eV.

Adsorption of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on the Ge(001) surface was studied using scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and the density-functional theory (DFT) calculations. Only single adsorption configuration of the PTCDA molecule was observed at low coverages on the Ge(001) at room temperature, unlike on the Si(001) where several adsorption configurations were reported. This indicates that the PTCDA molecules on the Ge(001) were more mobile than those on the Si(001). Atomic structure of the adsorption configuration on the Ge(001) was determined by comparison between the STM experiments and the DFT calculations. Bias-dependent STM images, STS, and calculated projected density of state curves show nontrivial hybridization of molecular orbitals with surface states of the Ge substrate. Interactions of the PTCDA molecule with the Ge and the Si surfaces were in detail analyzed by the DFT calculation, considering five main competing contributions to the adsorption energy: formation energy of polar covalent Ge–O (Si–O) bonds, energy of molecular deformation, interaction energy of Ge atoms with the perylene core of PTCDA, energy of dimer buckling deformation, and van der Waals interaction energy. The analysis explains different adsorption behaviors between the Ge and the Si substrates.

The epitaxial silicon oxynitride (SiON) layer grown on a 6H-SiC(0001) surface is studied with core level photoemission spectroscopy. Si 2p spectra show three spectral components other than the bulk one. Chemical shifts and emission angle dependence of these components are well explained within a framework of a determined structure model of the SiON layer.

Room temperature deposition of noble metals of Au, Ag and Cu on a clean Si(111)2×1 surface is studied through photoemission using synchrotron radiation in order to clarify the phenomenon of room temperature alloyed interface formation (RTAIF) at metal (M)-semiconductor(S) contacts. Ag atoms behave differently on a clean Si(111)2×1 surface from the point of view of the RTAIF, in spite of the fact that Ag belongs to the same group as Au and Cu in the periodic table. As for the phenomenon of the RTAIF, experimental results are examined in the light of the “chemical bonding model” proposed by some of the authors and others.