Zirconia films were deposited in vacuum from an electron-beam hearth with simultaneous ion bombardment from a Kaufman source. The effects of argon, oxygen and nitrogen ions were investigated, together with those of temperature and substrate type. For amorphous substrates, without ions, X-ray and electron diffraction showed that amorphous films were produced at room temperature. Deposition on to 300°C amorphous substrates produced the monoclinic form. Ion assistance converted the structure to cubic. It was found that deposition on to KCI (100) substrates also produced the cubic form at elevated temperatures, with or without ions. High-resolution microscopy showed that these films were crystallographically oriented with either or normal to the KCI substrate. The Raman spectra of films on fused silica substrates were correlated with the X-ray diffraction scans and the conditions under which the Raman spectrum could be used as a reliable indicator of microstructure were found.