Surface modification, martensitic transformation, and optical properties of hydrogenated ZrO2 nanocondensates via pulsed laser ablation in water

Abstract

Pulsed laser ablation on Zr plate in water under Q-switch mode and a fluence of 700 and 800 mJ/pulse for a rather high power density of 1.5 and 1.7 × 1011 W/cm2, respectively, was employed to fabricate hydrogenated ZrO2 nanocondensates. X-ray diffraction and transmission electron microscopic observations indicated such nanocondensates are full of {111} and {100} facets and predominantly in monoclinic (m-) rather than cubic- and/or tetragonal (t-) crystal symmetry in particular when fabricated at 700 mJ/pulse. The hydrogenated ZrO2 nanocondensates underwent martensitic t → m transformation at a rather small critical size (ca. 20 nm) due to H+ signature and hence oxygen vacancy deficiency in the lattice. The resultant m-phase was free of twin and fault due to site saturation and rather limited growth of the nanosized particles. Spectroscopic characterizations indicated that the nanocondensates have a significant internal compressive stress, (H+, Zr2+, Zr3+) co-signature and hence a smaller band gap of 5.2–5.3 eV for potential applications in UV region.