Various amorphous semiconductor thin-film structures were investigated by electron-gas sputtered neutral mass spectrometry (SNMS) and secondary ion mass spectrometry (SIMS). For the latter technique, cesium bombardment in conjunction with the detection of positive MCs+ secondary ions (M stands for the element of interest) were employed. Using this detection scheme, quantification is demonstrated for a series of a-SixGe1-x:H samples. Data obtained on more complex pin-multilayers indicate generally a good agreement between SNMS and SIMS; while MCs+ SIMS is more sensitive for many elements, mass interferences can limit the analytical applicability of MCs+ molecular secondary ions.