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Composition-dependent charge transfer and phase separation in the V1-xRexO2 solid solution.

D Mikhailova1, N N Kuratieva2, Y Utsumi3

  • 1Karlsruhe Institute of Technology (KIT), Institute for Applied Materials (IAM), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany. daria.mikhailova@kit.edu and Institute for Complex Materials, IFW Dresden, Helmholtzstr. 20, D-01069 Dresden, Germany and Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden, Germany. yuki.utsumi@synchrotron-soleil.fr.

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|January 17, 2017
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Summary
This summary is machine-generated.

Rhenium doping in vanadium dioxide (VO2) causes phase separation and multiple transition temperatures due to varying rhenium valence states. Single-phase materials are achieved with pure Re6+ or Re4+ doping.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Condensed Matter Physics

Background:

  • Vanadium dioxide (VO2) exhibits a metal-to-insulator transition (MIT) sensitive to dopant valence.
  • Rhenium (Re) dopants in VO2 can adopt multiple valence states (+4 to +7), influencing its properties.

Purpose of the Study:

  • To investigate the structural and electronic properties of V1-xRexO2 solid solutions.
  • To understand the effect of rhenium valence states on the MIT and phase behavior of VO2.

Main Methods:

  • Synchrotron X-ray powder diffraction (SXRPD) for structural analysis (80–1200 K).
  • Magnetization and specific heat measurements to detect phase transitions.
  • X-ray photoelectron spectroscopy (XPS) to determine Re valence states.

Main Results:

  • V1-xRexO2 exhibits two polymorphs similar to VO2: monoclinic (P21/c) and tetragonal (P42/mnm).
  • Phase separation into two isostructural phases occurs for 0.03 < x ≤ 0.15 below 1000 K.
  • Two distinct MIT temperatures were observed for phase-separated compositions.
  • Re valence states range from Re6+ (low doping) to mixed Re4+/Re6+ and nearly pure Re4+ (high doping).

Conclusions:

  • Single-phase V1-xRexO2 materials are achievable with solely Re6+ or Re4+ doping.
  • Intermediate Re doping levels lead to phase separation due to coexisting Re valence states.
  • The observed phase separation and multiple MITs are directly linked to the mixed valence states of rhenium in VO2.