Gaseous mixtures of germane or methylgermane with ammonia and methylgermane
with phosphine have been studied by ion trap mass spectrometry. Rate const
ants of reactions of the primary ions and of the most important secondary i
on species are reported, together with the calculated collisional rate cons
tants and efficiencies of reaction. The GeHn+ (n = 0-3) ions, formed by ele
ctron ionization of both GeH4 and CH3GeH3, react with ammonia yielding, amo
ng others, the GeHn+ (n = 2-4) ion family, which, in a successive and slow
reaction with NH3, only give the unreactive ammonium ion. Also, the CH3GeHn
+ (n = 1, 2) species do not form Ge-N bonds, whereas secondary ions of germ
ane, such as Ge2H2+, produce species containing germanium and nitrogen toge
ther. In the CH3GeH3/PH3 mixture a great number of ions are formed with rat
her high rate constants from primary ions of both reagent molecules and fro
m phosphorus containing secondary ions. GePHn+ (n = 2-4) ions further react
with methylgermane leading to cluster ions with increasing size such as Ge
2PHn+ and Ge2CPHn+. The experimental conditions favoring the chain propagat
ion of ions containing Ge and N, or Ge and P, with or without C, important
in the chemical vapor deposition of materials of interest in photovoltaic t
echnology, are discussed. (C) 1999 Elsevier Science B.V.