The oxidation of hydrogen-terminated porous silicon surfaces produced
by electrochemical etching has been studied using transmission FTIR sp
ectroscopy. The surface is passivated to oxidation by surface hydrogen
below about 523 K. Above this temperature as hydrogen depletion occur
s by H-2 evolution, Si surface dangling bond sites, capable of O-2 dis
sociation, are involved in initiating the first stage of oxidation. Tw
o reactions are observed. The first, O insertion into Si-Si back-bonds
, leads to -OySiHx surface species which exhibit frequency shifts to t
he blue compared to parent SiHx stretching modes. In addition, Si-O-Si
modes are also observed to form. The second reaction involves oxygen
atom insertion into Si-H bonds to produce isolated Si-OH surface speci
es.