Ion-enhanced chemical etching of ZrO2 in a chlorine discharge

Chlorine plasma is found to chemically etch ZrO2 thin films in an electron cyclotron resonance reactor, and the etch rate scaled linearly with the square root of ion energy at high ion energies with a threshold energy between 12-20 eV. The etching rate decreased monotonically with increasing chamber pressures, which corresponds to reduced electron temperatures. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the reaction etching products. No Zr, 0, or ZrCl were detected as etching products, but highly chlorinated zirconium compounds (ZrCl2, ZrCl3, and ZrCl4) and ClO were found to be the dominant etching products. ZrCl3 was the dominant etching products at low ion energies, while ZrCl4 became dominant at higher ion energies. This is consistent with greater momentum transfer and enhanced surface chlorination, as determined by x-ray photoelectron spectroscopy, at increased ion energies. Several ion-enhanced chemical reactions are proposed to contribute to the ZrO2 etching. (C) 2002 American Vacuum Society.