The present work reviews laser-induced electronic processes of structural instability on
covalent semiconductor surfaces. In particular, we concentrate on the mechanism of the
instability that takes place at the intrinsic sites of reconstructed surface structures. In order
to elucidate the primary processes involved, we focus our attention on experimental results
obtained by scanning tunnelling spectroscopy studies, to reveal surface structural changes
at the atomic level, and by post-ionization spectroscopy studies, to probe desorption
processes with high sensitivity. First, the results obtained for reconstructed Si
surfaces and {110} surfaces of III–V compound semiconductors are systematically
surveyed. The instability is characterized by local bond rupture at intrinsic surface
sites that show important common features. Also, we find significantly different
aspects of the instability, which depend on the basic properties of surfaces. Based
on the characteristics revealed by the experimental results, we then propose a
mechanistic model based on the generalized two-hole localization mechanism, and
demonstrate, through the quantitative analysis of typical experimental results, that
the model describes all the important features quantitatively and consistently.