Using scanning electron microscopy guidance, atomically resolved scanning tunneling microscopy investigations inside openings formed during the decomposition of a thick SiO2 film on a Si(111) surface have been performed. We report, for the first time, the presence of Ni atoms inside self-formed openings. The SiO2 decomposition as a function of annealing temperature and time was studied. By comparing self-formed and lithographically designed openings in the SiO2 layer we have shown that Ni contamination of the SiO2/Si(111) has a profound effect on the formation of self-induced lateral oxide openings.