Nano laminate films with a nominal 5 nm HfO2-4 nm TiO2 bilayer architecture are sputter deposited on unheated fused silica and Au-coated glass substrates. Films on fused silica are postdeposition annealed from 573 to 1273 K and characterized by x-ray diffraction, scanning electron microscopy, Raman microscopy, and UV-visible-near IR spectrophotometry. The films show weak but progressive crystallization into orthorhombic (o) HfTiO4 when annealed up to 973 K. o-HfTiO4 is expected to form under bulk thermodynamic equilibrium conditions in the case of complete mixing of the bilayer components. Annealing above 973 K produces a crystallization sequence that is not predicted by bulk thermodynamics, ultimately involving o-HfTiO4 demixing to form monoclinic HfO2 doped with Ti and rutile TiO2 doped with Hf. These phases have a higher atomic density than o-HfTiO4 and segregate into discrete mesoscopic features. The authors propose that o-HfTiO4 demixing into higher density phases is a mechanism for thermal stress relief at high temperature. Demixing results in a major loss of optical transparency in the visible and ultraviolet spectral regions. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3474973]