Cracking study of pentakis(dimethylamino)tantalum vapors by Knudsen cell mass spectrometry

Organometallic molecules are commonly used as gaseous precursors in Atomic Layer Deposition/Chemical Vapor Deposition (ALD/CVD) processes. However, the use of these molecules, which are generally thermally unstable at temperatures close to the deposition temperature, requires an understanding of their gas-phase chemical behavior. The thermal cracking of the gaseous precursor, pentakis(dimethylamino) tantalum (PDMAT), generally adopted in the ALD/CVD TaN deposition processes, has been studied in the temperature range from 343 to 723K using a specific reactor coupled with a high-temperature mass spectrometer. This reactor - built as tandem Knudsen cells - consists of two superimposed cells. The first stage reactor - an evaporation cell - provides an input saturated vapor flow operating from room temperature to 333K. The second stage cell, named the cracking cell, operated from 333 to 723K in the present study. Experiments showed the appearance of many gaseous species when the cracking temperature increased and, in particular, dimethylamine, corresponding to the saturated organic branches of PDMAT. Decomposition products of the HNC(2)H(6) branch were observed at relatively high temperature, namely above 633K. This gas-phase study - as for the preceding saturated one - shows the presence of oxygen-containing molecules in PDMAT cracked vapor. Thus, it explains the systematic presence of oxygen contamination in the deposited TaN films observed in ALD/CVD industrial processes.