Atomic layer deposition (ALD) has become the method of choice for many applications requiring the controlled growth of thin films on solid surfaces. However, the use of metalorganic precursors typical in these depositions adds significant complexity to the chemistry involved. Unfortunately, it is difficult to obtain direct information about the surface species that participate in the reaction mechanisms of ALD. Here we illustrate the value of using time-of-flight secondary ion mass spectrometry (ToF-SIMS) for this purpose. A particular example is provided, a study of the first cycle of deposition of platinum using trimethyl(methylcyclopentadienyl) platinum (IV), or MeCpPt(CH3)(3), on silicon oxide surfaces. In previous investigations of this process, we have determined that the low reactivity of the MeCpPt(CH3)(3) precursor, which hinders fast deposition, can be partially overcome by gas-phase electron-impact activation. What has not been clear is what chemical species form on the solid surface as a result of such activation. Here we show that the MeCp ligand is quite stable and that it remains intact and coordinated to the Pt atoms upon adsorption on the surface. It was also established that some of the methyl groups may remain bound to the Pt center: the main species detected on the silicon oxide surfaces were MeCpPt and MeCpPt(CH3). On the other hand, it appears that no Pt intermediates without MeCp ligands are formed during this initial adsorption. Finally, O-2 treatment of these surfaces at elevated temperature to complete the first ALD cycle leads to the complete removal of all the organic ligands: no evidence for MeCp or methyl groups is seen in the ToF-SIMS traces from the final samples.