Epitaxial stabilization versus interdiffusion: synthetic routes to metastable cubic HfO 2 and HfV 2 O 7 from the core–shell arrangement of precursors Academic Article uri icon


  • Metastable materials that represent excursions from thermodynamic minima are characterized by distinctive structural motifs and electronic structure, which frequently underpins new function. The binary oxides of hafnium present a rich diversity of crystal structures and are of considerable technological importance given their high dielectric constants, refractory characteristics, radiation hardness, and anion conductivity; however, high-symmetry tetragonal and cubic polymorphs of HfO2 are accessible only at substantially elevated temperatures (1720 and 2600 °C, respectively). Here, we demonstrate that the core-shell arrangement of VO2 and amorphous HfO2 promotes outwards oxygen diffusion along an electropositivity gradient and yields an epitaxially matched V2O3/HfO2 interface that allows for the unprecedented stabilization of the metastable cubic polymorph of HfO2 under ambient conditions. Free-standing cubic HfO2, otherwise accessible only above 2600 °C, is stabilized by acid etching of the vanadium oxide core. In contrast, interdiffusion under oxidative conditions yields the negative thermal expansion material HfV2O7. Variable temperature powder X-ray diffraction demonstrate that the prepared HfV2O7 exhibits pronounced negative thermal expansion in the temperature range between 150 and 700 °C. The results demonstrate the potential of using epitaxial crystallographic relationships to facilitate preferential nucleation of otherwise inaccessible metastable compounds.

altmetric score

  • 5.7

author list (cited authors)

  • Fleer, N. A., Thomas, M. P., Andrews, J. L., Waetzig, G. R., Gonzalez, O., Liu, G., Guiton, B. S., & Banerjee, S.

citation count

  • 2

publication date

  • November 2019