We have applied a variety of analytical tools to educe the composition and morphology of thin films of hafnium dioxide deposited under a variety of conditions. Surface analytical techniques include scanning electron microscopy, transmission electron microscopy, electron diffraction, Rutherford backscattering spectrometry, and X-ray photoelectron spectroscopy. The results from these measurements are correlated with the observed optical properties. Electron diffraction reveals that films deposited below 300-degrees-C are amorphous and spectrophotometry uncovers a small optical inhomogeneity. The refractive index and inhomogeneity are strongly influenced by the oxygen backfill present during film condensation. Ion-assisted deposition (IAD) removes the optical inhomogeneity, increases the refractive index, and eliminates the air-to-vacuum spectral shift observed in films deposited without IAD. In addition, low energy IAD is found to increase the refractive indices of the films without affecting the optical inhomogeneity. This is explained by the preferential sputtering of hydroxide from the growing film surface by the low energy ions.