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 HfO 2 are accessible only at substantially elevated temperatures (1720 and 2600 °C, respectively). Here, we demonstrate that the core–shell arrangement of VO 2 and amorphous HfO 2 promotes outwards oxygen diffusion along an electropositivity gradient and yields an epitaxially matched V 2 O 3 /HfO 2 interface that allows for the unprecedented stabilization of the metastable cubic polymorph of HfO 2 under ambient conditions. Free-standing cubic HfO 2 , 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 HfV 2 O 7 . Variable temperature powder X-ray diffraction demonstrate that the prepared HfV 2 O 7 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.
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Free-standing bilayered vanadium oxide films synthesized by liquid exfoliation of chemically preintercalated δ-Li x V 2 O 5 · n H 2 O
A free-standing film composed of bilayered vanadium oxide nanoflakes is for the first time synthesized using a new low-energy process. The precursor powder, δ-Li x V 2 O 5 · n H 2 O, was prepared using a simple sol–gel based chemical preintercalation synthesis procedure. δ-Li x V 2 O 5 · n H 2 O was dispersed and probe sonicated in N -methyl pyrrolidone to exfoliate the bilayers followed by vacuum filtration resulting in the formation of a free-standing film with obsidian color. X-ray diffraction showed lamellar ordering of a single-phase material with a decreased interlayer distance compared to that of the precursor powder. Scanning electron microscopy images demonstrated stacking of the individual nanoflakes. This morphology was further confirmed with scanning transmission electron microscopy that showed highly malleable nanoflakes consisting of ∼10–100 vanadium oxide bilayers. One of the most important consequences of this morphological rearrangement is that the electronic conductivity of the free-standing film, measured by the four-probe method, increased by an order of magnitude compared to conductivity of the pressed pellet made of precursor powder. X-ray photoelectron spectroscopy measurements showed the coexistence of both V 5+ and V 4+ oxidation states in the exfoliated sample, possibly contributing to the change in electronic conductivity. The developed approach provides the ability to maintain the phase purity and crystallographic order during the exfoliation process, coupled with the formation of a free-standing film of enhanced conductivity. The produced bilayered vanadium oxide nanoflakes can be used as the building blocks for the synthesis of versatile two-dimensional heterostructures to create innovative electrodes for electrochemical energy storage applications.
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- Award ID(s):
- 1752623
- PAR ID:
- 10223692
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 2
- Issue:
- 8
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 2711 to 2718
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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