Tetraethoxysilane (TEOS : SiO
4(C
2H
5)
4) is widely used to fabricate silicon-dioxide insulator thin films in LSI device technologies. We have already reported that TEOS is photo-dissociated to result in oxide layer deposition at room temperature by a vacuum ultraviolet excimer lamp (λ=172 nm). In this paper, we have observed the initial stages of oxide layer deposition on silicon clean surfaces with the scanning tunneling microscope (STM) and time-of-flight (TOF) mass spectrometer. An argon excimer lamp (λ=126 nm) is used for the photo-chemical vapor deposition (CVD). TEOS molecules have been dissociated to be SiO
4(C
2H
5)
n(n=1, 2, 3) groups on the clean surfaces. The 126 nm photons dissociate the molecules or radicals to Si-O
m(m=1, 3, 4) after 2 min. Finally, the Si-O
m adsorbed molecules and Si atoms in the substrate are re-arranged to be a disorder structure by the photons.
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