Interaction between the silyl and silylen centres in the deposits prepared by pulsed laser ablation of silicon monoxide and ammonia, methylamine and dimethylamine

Abstract

Silicon suboxide films were prepared by TEA CO2 pulsed laser ablation (PLA) of the silicon monoxide target in the Kr atmosphere. The deposits were examined by means of Fourier transformed infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR) and X-ray photoelectron spectroscopy (XPS). The generated point defects in the films – mostly silyl ≡Si· (E’ center) and silylen =Si: – were allowed to react with the gaseous ammonia NH3, methylamine MeNH2 and dimethylamine Me2NH after the ablation. As a result, the functional groups ≡SiNHxMey (x+y=2) were formed. The reactivity of the deposits are due to silyl ≡Si· and silylen =Si: radicals as deduced by comparison of the initial concentration of the silyl radicals (5.3–9.8×1019 /g, EPR) – and the newly formed -(Si)NH bonds (3.6×1019 /g, FTIR). The observed absorption bands ν(SiH) at 2223, 2214 and 2220 cm-1 could be assigned to =(O2)Si(H)NH2, =(O2)Si(H)NHMe and =(O2)Si(H)NMe2 species. The singlet line in EPR spectrum of the native deposit before exposition is due to the silyl radical with free valence on the silicon backbonded via oxygen and another silicon atom. After exposition either to NH3 or MeNH2 the silyl concentration rapidly decreased to several % of its original value.