The adsorption of nitro compounds
on the germanium surface serves
as a model system for understanding the formation of interfacial germanium
oxynitride. We have studied the adsorption and thermal reactions of
nitrobenzene on the Ge(100)-2 × 1 surface under ultrahigh vacuum
conditions. A combination of infrared spectroscopy, X-ray photoelectron
spectroscopy, and temperature-programmed desorption experiments together
with density functional theory calculations was used to elucidate
possible product structures and their associated reaction mechanisms.
Our study suggests that nitrobenzene initially forms a 1,3-dipolar
cycloaddition product with a Ge(100) surface dimer as the major species.
Minor side products are also formed at 300 K. Upon heating, some of
the adsorbates molecularly desorb, while a fraction of the adsorbates
undergo oxygen atom insertion into the surface, transforming them
into triplet nitrene products. The energetics and pathways of nitrobenzene
on the Ge surface are discussed in comparison with those seen on the
closely related Si(100)-2 × 1 surface, with some differences
arising from the smaller adsorption energy of organic adsorbates on
Ge.