Metalorganic precursor decomposition and oxidation mechanisms in plasma-enhanced ZrO2 deposition

Abstract

We investigated the gas phase reaction mechanisms in the ZrO2-deposition plasma using zirconium tert-butoxide (ZTB) as a metalorganic precursor, Ar as a carrier of the ZTB vapor, and O2 as an oxidant using quadrupole mass spectrometry (QMS). Zirconium containing ions including Zr+, ZrO+, ZrO2H+, ZrO3H3+, and ZrO4H5+ were clearly observed in the plasma, and ions of higher zirconium oxidation states become progressively favored at higher O2-to-ZTB carrying Ar flow rate ratio (O2/Ar), increased chamber pressure, and decreased microwave power. The average oxidation state calculated from the partition of ZrOxHy+ varied from 0.5 to 2.1 in the process range covering O2/Ar of 0 to 4, pressure of 5 to 40 mTorr, and power of 150 to 700 W. Based on the QMS analyses, we proposed two main opposing reaction paths responsible for the complex gas phase reactions, i.e., serial dissociations and serial oxidations. The increase in the electron temperature and density resulted in the shift of ZrOxHy+ to lower oxidation states by enhancing the dissociation of Zr–O bond and by depleting oxygen through gas phase reactions. The repartitioning of the ZrOxHy+ species was also contributed by their different Zr–O dissociation energies. To ascertain the effect of various process variables, we monitored the time evolutions of O2+ and ZrOxHy+ intensities as we abruptly change a process variable: the chemical effect (O2/Ar) led to gradual changes in their intensities, whereas physical effects (pressure and power) caused an abrupt step change in accordance with an instant response of the plasma electrons.