In situ quadrupole mass spectrometry (QMS) has been integrated to an atomic layer deposition (ALD) reactor to achieve real-time chemical diagnostic and wafer-state metrology. The process investigated was tungsten ALD using WF6 and SiH4. The UHV-based substrate-heated ALD reactor incorporated a minireactor chamber to simulate the small reaction volume anticipated for manufacturing tools in order to achieve adequate throughput. Mass spectrometry revealed essential surface reaction dynamics through real-time signals associated with by-product generation as well as reactant introduction and depletion for each ALD half-cycle. The by-product QMS signal was then integrated in real time over each exposure and plotted against process cycle number to directly observe ALD film growth, leading to two valuable metrologies. First, the integrated by-product QMS value changes with cycle number, directly reflecting the nucleation kinetics. Specifically, QMS values increase with cycle number during the nucleation phase and then saturates as the film growth enters its steady-state growth phase. Second, summing the integrated by-product QMS signals over an entire deposition run provides an immediate measure of film thickness. The growth kinetics as measured by QMS is consistent with ex situ film characterization and is strongly dependent on process conditions and reactor chamber status. In the latter case, a clear first wafer effect was apparent when the system was left idle for a few hours, resulting in an apparent QMS signal difference during nucleation phase between the first wafer and nonfirst wafer cases. The dependence of QMS signals on chamber status is attributed to parallel reactions on the chamber wall, where different gas exposure history is encountered. The first wafer effect can be explained in a quantitative manner by considering the chamber wall as an additional wafer inside the ALD reactor. The first wafer effects can be reduced by proper preprocess treatment, and the linear correlation between QMS measurement and film thickness suggests a promising start for QMS-based ALD film thickness metrology. (c) 2007 American Vacuum Society.