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Bi-Arrhenius Diffusion and Surface Trapping of ^{8}Li^{+} in Rutile TiO_{2}.

A Chatzichristos1,2, R M L McFadden2,3, M H Dehn1,2

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Lithium-8 diffusion in rutile titanium dioxide shows surface trapping. The diffusion rate exhibits a bi-Arrhenius temperature dependence with distinct activation energies above and below 200 K.

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Area of Science:

  • Materials Science
  • Surface Science
  • Solid-State Physics

Background:

  • Understanding ion diffusion in metal oxides is crucial for applications like catalysis and electronics.
  • Rutile TiO2 is a widely studied material with significant technological relevance.
  • Surface interactions and diffusion pathways can differ substantially from bulk behavior.

Purpose of the Study:

  • To quantify the diffusion rate of lithium-8 (8Li+) near the surface of single-crystal rutile TiO2.
  • To investigate the temperature dependence of lithium diffusion and identify potential trapping mechanisms at the surface.
  • To elucidate the energy barriers governing lithium diffusion in the near-surface region.

Main Methods:

  • Utilized a radiotracer technique with ion-implanted 8Li+.
  • Employed alpha particle detection from 8Li decay to monitor depth profiles over time.
  • Performed measurements on oriented single-crystal rutile TiO2 surfaces.

Main Results:

  • Observed that implanted 8Li+ diffuses and becomes trapped at the (001) surface of TiO2.
  • Determined a bi-Arrhenius temperature dependence for 8Li+ diffusivity.
  • Identified two distinct activation energies: 0.3341(21) eV above 200 K and a significantly lower barrier of 0.0313(15) eV below 200 K.

Conclusions:

  • The (001) surface of rutile TiO2 acts as a trapping site for diffusing lithium.
  • The diffusion process is characterized by different energy barriers at low and high temperatures, suggesting distinct diffusion mechanisms or defect interactions.
  • Further investigation into the origins of surface trapping and the low-temperature barrier is warranted.