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Molecular orientations for thin films of one-dimensional silicon polymers grown by vacuum evaporation have been assigned by near-edge X-ray absorption fine structure (NEXAFS) using linearly polarized synchrotron radiation. The polymer investigated was polydimethylsilane (PDMS) which is the simplest stable silicon polymer, and one of the candidate materials for one-dimensional molecular wire. For PDMS films deposited on highly oriented pyrolytic graphite (HOPG), four resonance peaks have been identified in the Si K-edge NEXAFS spectra. Among these peaks, the intensities of the two peaks lower-energy at 1842.0 eV and 1843.2 eV were found to be strongly polarization dependent. The peaks are assigned to the resonance excitations from the Si 1s to σ∗ pyz and σ∗ px orbitals localized at the Si–C and Si–Si bonds, respectively. Quantitative evaluation of the polarization dependence of the NEXAFS spectra revealed that the molecules are self-assembled on HOPG surface, and the backbones of the PDMS are oriented nearly parallel to the surface. The observed orientation is opposite to the previously observed results for PDMS on the other surfaces such as oxide (indium tin oxide) and metal (polycrystalline copper). The flat-lying feature of PDMS observed only on HOPG surface is attributed to the interaction between CH bonds in PDMS and π orbitals in HOPG surface.

Orientation of One-Dimensional Silicon Polymer Films Studied by X-Ray Absorption Spectroscopy