Composition-dependent structure and bandgaps in HfxZr1−xO2 thin films

ZrO2 as a wide-bandgap semiconductor with high dielectric constant and ferroelectric properties has been extensively studied. To explore the impact of chemical doping on the structure and optical performance of ZrO2, HfxZr1−xO2 (x = 0, 0.25, 0.5, 0.75, 1) thin films were prepared through pulsed laser deposition. X-ray diffraction reveals that the orthorhombic phase (o) (111) gradually transforms into the monoclinic phase (m) (−111) with the increase in Hf content from 0 to 1. Furthermore, optical property analysis demonstrates an increase in the optical bandgap from 5.17 to 5.68 eV with the increase in Hf doping content. Density functional theory calculations and x-ray photoelectron spectroscopy suggest that the widening of the bandgap in HZO films is associated with the hybridization of Zr 4d and Hf 5d orbitals.