Theoretical Chemistry Accounts

, 133:1433 | Cite as

A theoretical study of possible point defects incorporated into α-alumina deposited by chemical vapor deposition

  • C. ÅrhammarEmail author
  • F. Silvearv
  • A. Bergman
  • S. Norgren
  • H. Pedersen
  • R. Ahuja
Regular Article
Part of the following topical collections:
  1. Modeling Chemical Vapor Deposition and Atomic Layer Deposition


The energetics and electronic structure of carbon, chlorine, hydrogen, and sulfur in α-Al2O3 was investigated by first principles and thermodynamical calculations. These species are present in the gas phase during the synthesis of α-Al2O3 by chemical vapor deposition (CVD) but little is known of their solubility in this compound. The heat of formation from standard reference states of the elements varying the chemical potential of each element was calculated. An attempt to model the actual conditions in the CVD process was made, using the species and solid compounds present in a common CVD process as reference states. Our calculations suggest that sulfur from the catalyzing agent H2S will not solve in α-Al2O3 during deposition by CVD. It is found that the neutral chlorine and hydrogen interstitial defects display the lowest heat of formation, 281 and 280 kJ/mol, respectively, at the modeled CVD conditions. This energy is too high in order for neutral defects to form during CVD of α-Al2O3 at any significant amounts. The charged defects and their compensation were studied. Carbon substituting oxygen is found to be energetically favored under the modeled CVD conditions, considering carbon dioxide as competing species to solid solubility in α-Al2O3 at an energy of −128 kJ/mol. However, care needs to be taken when choosing the possible competing carbon-containing phases. Compensation of carbon substituting for oxygen by oxygen vacancies takes place at 110 kJ/mol from standard reference states, graphite, fcc-Al and O2. The carbon solubility in Al2O3 is difficult to measure with standard analysis techniques such as X-ray diffraction and energy dispersive X-ray spectroscopy, but several stable compounds in the Al–C–O are available in the literature.


Alumina CVD Carbon Chlorine Hydrogen Sulfur Ab initio 



We would like to acknowledge the Swedish Research Council (VR) for financial supports. Resources of the Swedish National Infrastructure for Computing (SNIC), National Supercomputer Center (NSC), and the Uppsala Multidisciplinary Center for Advanced Computational Science (UPPMAX) are also gratefully acknowledged.


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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • C. Århammar
    • 1
    Email author
  • F. Silvearv
    • 2
  • A. Bergman
    • 3
  • S. Norgren
    • 1
    • 4
  • H. Pedersen
    • 5
  • R. Ahuja
    • 3
  1. 1.Sandvik CoromantStockholmSweden
  2. 2.Applied Physics, Division of Material Science, Department of Engineering Sciences and MathematicsLuleå University of TechnologyLuleåSweden
  3. 3.Division of Materials Theory, Department of Physics and AstronomyUppsala UniversityUppsalaSweden
  4. 4.Ångström Laboratory, Department of Engineering Sciences, Applied Materials Science, Tribology GroupUppsala UniversityUppsalaSweden
  5. 5.Department of Physics, Chemistry and BiologyLinköping UniversityLinköpingSweden

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