Li+ ion attachment mass spectrometry was used to detect Cu(1,1,1,5,5,5-hexafluoroacetylacetonate)(vinyltrimethylsilane) [Cu(h-fac)(tmvs)], a thermally labile precursor used in copper chemical vapor deposition (Cu-CVD), with the intent of developing improved methods for mass-spectrometric analysis of the CVD process. A uniquely designed quadrupole mass spectrometry (QMS) system coupled with a Li+ ion emitter and a laboratory-built direct introduction system of the sample provided the molecular ion of Cu(hfac)(tmvs) as the Li+ ion adduct for the first time. The use of this system demonstrates the feasibility of generating Li+ ion adduct for real-time monitoring of products encountered in Cu-CVD process facilities. (c) 2006 Elsevier B.V. All rights reserved.