Primary ions from a gas-cluster ion beam (GCIB) are used to investigate metal and silicon surfaces by mass spectroscopy of the secondary ions, as well as to study the nature of cluster-ion interactions with surfaces. The GCIB consists of condensed nanodroplets of either argon, oxygen, or nitrogen gas from which the singly charged cluster ions are generated. The effects of beam acceleration (similar to10-25 kV) and flux (ion current density similar to50-500 nA/cm(2)) are reported. Secondary-ion analysis is done with a quadrupole mass spectrometer in an ultrahigh vacuum chamber. Argon GCIB incident upon metal surfaces of Al, Au, Cu, Ta, and NiFe all result in strong emission of small metal-cluster ions, metal-argon excimers and various other compound ions. Argon GCIB incident upon Al films and Si wafer surfaces generate strong fluxes of small cluster ions (i.e., Al-n(+) and Si-n(+) for n = 2-10) which decay in emission intensity (with increasing n) approximately by a power law with exponent similar to2.8 and similar to1.0, respectively. Oxygen GCIB upon Al and Si generate strong fluxes of AlnOm+ and SinOm+ compound ions, respectively, with n = 1-5 and m greater than or equal to n. Nitrogen GCIB upon Al and Si generate fluxes of nitride compounds. The beam conditions utilized are similar to those known to significantly reduce fine-scale surface roughness (i.e., ion smoothen) and concurrently etch at a rate of similar to1 nm/min. Native oxide films on Al, Cu, Ta, and NiFe metals are depth profiled under various GCIB conditions, thus characterizing mechanisms of cluster-ion interaction with metals. The native surface of a Ta film is investigated in some detail. The TaO+ and C+ ion emissions show a two-part decay and growth, respectively, with accumulating argon-GCIB fluence. These are well fit with exponential functions and the characteristic rates are found to depend linearly on GCIB flux and acceleration. The oxidized surfaces exhibit a minimum threshold in acceleration of similar to7 kV which corresponds to only similar to3 eV per incident argon atom. After the surface oxide is removed by the GCIB, no threshold is observed. The native oxides and Fe/Ni, ratio are depth profiled for a permalloy (NiFe) film showing resolution of the thin oxide layer differentiated from the somewhat thicker metal layer that is enriched with Fe. (C) 2003 American Vacuum Society.