Positive ion chemistry of SiH4/NF3 gaseous mixtures studied by ion trap mass spectrometry.

The positive ion chemistry occurring in silane/nitrogen trifluoride gaseous mixtures has been investigated by ion trap mass spectrometry. Reaction sequences and rate constants have been determined for the processes involving the primary ions SiH(n)(+) (n = 0-3) and NF(x)(+) (x = 1-3) and the secondary ions obtained from their reactions with SiH(4) and NF(3). The SiH(n)(+) efficiently react with NF(3) and undergo cascades of abstraction and scrambling reactions which form the fluorinated and perfluorinated cations SiHF(m)(+) (m = 1, 2), SiH(2)F(+) and SiF(x)(+) (x = 0-3). Fluorinated Si(2)- clusters such as Si(2)H(2)F(+), Si(2)H(3)F(+) and Si(2)H(5)F(+) were also observed. The reaction of both SiH(3)(+) and SiH(2)F(+) with NF(3) produces the elusive fluoronitrenium ion NHF(+). Any NF(x)(+) reacts with SiH(4) mainly by charge transfer. Additional ionic products are, however, observed which suggest intimate reaction complexes. Worth mentioning is the formation of SiNH(2)(+) from the reaction of both NF(+) and NHF(+) with SiH(4). The primary ions NF(2)(+) and SiH(2)(+) are also "sink" species in our observed chemistry.