Atomic excitation phenomena in sputtering have been studied with the following combinations of projectile and target. (i) Be, B, Mg, Al, and Si bombarded with 80 keV Ar+ at UHV as well as with the target chamber backfilled with oxygen. (ii) Mg bombarded with 80 keV O+, F+, Ne+, Na+ Cl+, and Ar+. (iii) MgO, MgF2, MgCl2, MgSO4, and several alkali halides bombarded with 80 keV Ar+ at UHV. Results are discussed. It is concluded that the excited-state formation takes place as electron tunneling at a fairly large separation between the target surface and the particle being sputtered. It is suggested with composite targets containing a metal element that excitation takes place predominantly at locations of the target surface where the work function is low, due to a thin, metallic surface layer, and that production of ground-state, positive secondary ions mainly takes place at target surface regions with high work function. For semiconductors, the changes caused by presence of oxygen are related to the change of the bonds in the solid from being of covalent nature to being fractionally ionic.