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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
Published on: May 23, 2018
Oxygen self-doping in hollandite-type vanadium oxyhydroxide nanorods
Igor Djerdj1, Denis Sheptyakov, Fabia Gozzo
1Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
Journal of the American Chemical Society
|August 2, 2008
Summary
Researchers synthesized novel semiconducting VO 1.52(OH) 0.77 nanorods using a nonaqueous liquid-phase route. These materials exhibit unique hollandite-type structures and self-doping behavior, offering insights into vanadium oxide chemistry.
Area of Science:
- Materials Science
- Solid-State Chemistry
- Nanotechnology
Background:
- Vanadium oxides are known for their diverse structural and electronic properties.
- Understanding the synthesis and properties of novel vanadium-based nanostructures is crucial for advanced applications.
- The formation of semiconducting nanorods with specific morphologies presents opportunities for tailored material design.
Purpose of the Study:
- To synthesize single-crystalline, semiconducting VO 1.52(OH) 0.77 nanorods via a nonaqueous liquid-phase route.
- To elucidate the crystal structure, composition, morphology, and electronic properties of the synthesized nanorods.
- To investigate the mechanism of semiconducting behavior and magnetic interactions within the material.
Main Methods:
- Nonaqueous liquid-phase synthesis using vanadium oxychloride and benzyl alcohol.
- Characterization by neutron and synchrotron powder X-ray diffraction.
- Morphological and compositional analysis using SEM, HRTEM, EDX, and SAED.
- Electrical conductivity measurements (DC) and magnetic susceptibility studies.
- Ab initio density-functional calculations (LSDA + U) for electronic structure analysis.
Main Results:
- Formation of single-crystalline VO 1.52(OH) 0.77 nanorods with ellipsoidal morphology (up to 500 nm length, 100 nm diameter).
- Identification of a hollandite-type structure with oxide ions and OH groups in the channels.
- Formal vanadium valence of +3.81 (V(4+)/V(3+) ratio ~4), indicating self-doping.
- Semiconducting behavior with a band gap of 0.64 eV, explained by small polaron hopping.
- Evidence of frustrated antiferromagnetic interactions below 25 K.
Conclusions:
- The nonaqueous synthesis route successfully produced novel semiconducting VO 1.52(OH) 0.77 nanorods with a unique hollandite-type structure.
- The electronic conductivity is attributed to electron hopping between V(3+) and V(4+) sites, facilitated by self-doping from oxide ions in the channels.
- The material exhibits complex magnetic behavior, suggesting charge ordering of V(3+) sites.
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