Journal of Vacuum Science & Technology A, Vol.19, No.6, 2751-2761, 2001
Spectroscopic study of plasma using zirconium tetra-tert-butoxide for the plasma enhanced chemical vapor deposition of zirconium oxide
Plasma enhanced chemical vapor deposition of zirconium oxide using zirconium tetra-tert-butoxide (ZTB) as a metalorganic precursor, Ar as a carrier of the ZTB vapor, and O-2 as an oxidant was investigated by using optical emission spectroscopy (OES), Langmuir probe, and x-ray photoelectron spectroscopy (XPS). The electron temperature (T-e) and the O-2 to Ar flow rate ratio (O-2/Ar) were found to dominate the plasma chemistry: the T-e determined the maximum Zr and Zr+ emission intensities at an intermediate pressure of 45 mTorr, the high C/C-2 emission intensity ratio in the oxygen-rich plasma, and the transition between the dissociation-dominated chemistry at low pressures and the recombination-dominated chemistry at high pressures. The O-2/Ar ratio changed the relative abundance of various atomic and diatomic species in the plasma: both ionic and atomic Zr species were depleted with the addition of O-2 and a significant amount of ZrO and CO was produced. The O-2/Ar ratio and T-e determined the concentration ratio of C/O and C-2/O in the plasma, the production and dissociation rates of diatomic molecules (C-2, CH, CO, and OH), and the degree of decomposition. From XPS, x-ray diffraction, and OES measurements, the deposited ZrO2 was found to be stoichiometric and amorphous at O-2/Ar ratios greater than or equal to0.2, and hydrocarbon molecules rather than atomic carbon were more responsible for the carbon incorporation into the film. The carbon content in the film could be controlled by monitoring and varying the OES intensity ratio of C-2 at 516.52 nm to O at 777.42 nm.