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A Study on the Defect Structure of $TiO_2$ (Rutile) by Electrical Conductivity Measurements

  • Son, Jae-Cheon;Yu, In-Kyu
    • The Korean Journal of Ceramics
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    • v.2 no.3
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    • pp.131-136
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    • 1996
  • The electrical conductivity of polycrystalline TiO2 samples was measured over the temperature range 1000°-1400℃ and from 0.21 to 10-16 atm of oxygen. Based on the excellent fit observed between the theoretically derived relatin σ3=(Aσ+B)Po2-1/2+D'σ2 and the experimental conductivity data, the nonstoichimetric defect structure of TiO2 was rationalized in terms of a defect model involving quasi-free electrons and both singly and doubly ionized oxygen vacancies. The standard enthalpy of formation for the following defect reactions in TiO2. (a) OO={{{{ { 1} over {2 } }}O2(g)+VO+e'; Δ{{{{ { H}`_{o } ^{a } }}=5.15(eV) (b) OO={{{{ { 1} over {2 } }}O2(g)+VO+2e'; Δ{{{{ { H}`_{0 } ^{ a} }}=6.30(eV) (c) VO=VO+e'; Δ{{{{ { H}`_{0 } ^{a } }}=1.15(eV) were determined from the temperature dependence of A and B obtained from the above relation and from the experimental expression between the electron mobility and temperature. The electrical conductivity of TiO2 in air below approximately 950℃ appears, on the basis of this investigation, to be impurity controlled due to the presence of aluminum rather than intrinsic conduction.

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