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X-ray Crystallography02:18

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The size of the unit cell and the arrangement of atoms in a crystal may be determined from measurements of the diffraction of X-rays by the crystal, termed X-ray crystallography.
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Non-stoichiometric defects refer to a type of defect in the crystal structure of a compound where the ratio of its constituent elements deviates from the ideal stoichiometric ratio. There are two main types of non-stoichiometric defects: metal excess defects and metal deficiency defects.Metal excess defects occur when there is a slight surplus of metal ions than what is required by the stoichiometric ratio of the compound. For example, heating a sodium chloride crystal in sodium vapor results...
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Schottky defects arise when some lattice points in a crystal, such as those in NaCl, remain unoccupied, creating lattice vacancies without disturbing the overall electrical neutrality of the crystal. This defect is common in ionic crystals where the positive and negative ions are similar in size, as seen in sodium chloride and cesium chloride. The presence of Schottky defects enables the crystal to conduct electricity to a small extent through an ionic mechanism. Electric fields cause nearby...
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Related Experiment Video

Updated: Apr 14, 2026

Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain
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Oxygen diffusion in single crystal barium titanate.

Markus Kessel1, Roger A De Souza, Manfred Martin

  • 1Institut für Physikalische Chemie, RWTH Aachen University, Landoltweg 2, 52056 Aachen, Germany. desouza@pc.rwth-aachen.de.

Physical Chemistry Chemical Physics : PCCP
|April 23, 2015
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Summary

Oxygen diffusion in barium titanate (BaTiO3) single crystals was investigated using isotope exchange and ToF-SIMS. The study reveals distinct diffusion behaviors in the bulk and surface space-charge layer, providing insights into defect chemistry.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Defect Physics

Background:

  • Barium titanate (BaTiO3) is a crucial perovskite material with applications in electronics.
  • Understanding oxygen diffusion is vital for controlling BaTiO3 properties and performance.
  • Defect chemistry, particularly oxygen vacancies, significantly influences BaTiO3's electrical and ionic conductivity.

Purpose of the Study:

  • To investigate oxygen diffusion mechanisms in nominally undoped, (100) oriented BaTiO3 single crystals.
  • To differentiate diffusion behavior in the bulk and surface space-charge zones.
  • To establish a comprehensive understanding of the defect chemistry governing oxygen transport in BaTiO3.

Main Methods:

  • Isotope exchange experiments using (18)O2/(16)O2.
  • Depth profiling of isotope concentrations via time-of-flight secondary ion mass spectrometry (ToF-SIMS).
  • Diffusion modeling using a single solution to the diffusion equation with fitting parameters for surface exchange, space-charge potential, and bulk diffusion.

Main Results:

  • Oxygen diffusion profiles exhibit a two-part characteristic: slow diffusion in the oxygen vacancy-depleted surface layer and faster diffusion in the bulk.
  • The diffusion process was successfully modeled using surface exchange coefficient (ks*), space-charge potential (Φ0), and bulk diffusion coefficient (D*(∞)).
  • Analysis of temperature and oxygen activity dependencies provided insights into bulk and interfacial defect chemistry, yielding an oxygen vacancy diffusion coefficient (DV) and a global expression for vacancy diffusivity.

Conclusions:

  • The study provides a consistent model for oxygen diffusion in BaTiO3, accounting for both bulk and surface effects.
  • The determined activation enthalpy for vacancy migration (ΔHmig,V) is (0.70 ± 0.04) eV.
  • This research contributes to a deeper understanding of defect mechanisms in BaTiO3, crucial for material optimization.