B-SiO2 films formed by chemical vapor deposition on silicon substrates were analyzed by time-of-flight secondary ion mass spectrometry using slow Xe44+ and Th70+ as primary ions. Boron concentrations of 2 X 10(21) Cm-3 determined directly from positive secondary ion spectra agree with results from elastic recoil detection measurements, indicating strong decoupling of positive secondary ion production probabilities from elemental ionization potentials in the intense electronic sputtering induced by highly charged ions. Results demonstrate advantages of highly charged ions for quantitative analysis of surface near layers of materials.