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Ab initio investigation of surface chemistry of alumina ALD on hydroxylated γ-alumina surface

(2015) JOURNAL OF PHYSICAL CHEMISTRY C. 119(23). p.13050-13061
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Abstract
Atomic layer deposition (ALD) of alumina using trimethyl aluminum (TMA) and water on amorphous alumina is analyzed using periodic-dispersion corrected DFT calculations. The energetics of the investigated reactions suggest that monomethyl aluminum (MMA) is the most abundant reaction intermediate at ALD operating conditions. The dominant reaction path toward the methylation of the surface is found to be adsorption of TMA on bridge oxygen via Lewis acid-base complex formation followed by ligand exchange reactions (LERs) with hydroxyls and surface water in its vicinity. Further adsorption and LERs of TMA leads to a saturated methylated surface (similar to 6.4 CH3 nm(-2)) which is in agreement with experimental observations and infrared spectra. The surface restructuring that is observed in almost all the reactions investigated seems to play an important role in the formation of conformal alumina films.
Keywords
BINARY REACTION SEQUENCE, ATOMIC LAYER DEPOSITION, OXIDE THIN-FILMS, DENSITY-FUNCTIONAL THEORY, FINDING SADDLE-POINTS, AUGMENTED-WAVE METHOD, MINIMUM ENERGY PATHS, ELASTIC BAND METHOD, 1ST PRINCIPLES, AL2O3 FILMS

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Citation

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MLA
Sandupatla, Aditya Shankar, et al. “Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface.” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 119, no. 23, 2015, pp. 13050–61, doi:10.1021/acs.jpcc.5b02382.
APA
Sandupatla, A. S., Alexopoulos, K., Reyniers, M.-F., & Marin, G. (2015). Ab initio investigation of surface chemistry of alumina ALD on hydroxylated γ-alumina surface. JOURNAL OF PHYSICAL CHEMISTRY C, 119(23), 13050–13061. https://doi.org/10.1021/acs.jpcc.5b02382
Chicago author-date
Sandupatla, Aditya Shankar, Konstantinos Alexopoulos, Marie-Françoise Reyniers, and Guy Marin. 2015. “Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface.” JOURNAL OF PHYSICAL CHEMISTRY C 119 (23): 13050–61. https://doi.org/10.1021/acs.jpcc.5b02382.
Chicago author-date (all authors)
Sandupatla, Aditya Shankar, Konstantinos Alexopoulos, Marie-Françoise Reyniers, and Guy Marin. 2015. “Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface.” JOURNAL OF PHYSICAL CHEMISTRY C 119 (23): 13050–13061. doi:10.1021/acs.jpcc.5b02382.
Vancouver
1.
Sandupatla AS, Alexopoulos K, Reyniers M-F, Marin G. Ab initio investigation of surface chemistry of alumina ALD on hydroxylated γ-alumina surface. JOURNAL OF PHYSICAL CHEMISTRY C. 2015;119(23):13050–61.
IEEE
[1]
A. S. Sandupatla, K. Alexopoulos, M.-F. Reyniers, and G. Marin, “Ab initio investigation of surface chemistry of alumina ALD on hydroxylated γ-alumina surface,” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 119, no. 23, pp. 13050–13061, 2015.
@article{6879552,
  abstract     = {{Atomic layer deposition (ALD) of alumina using trimethyl aluminum (TMA) and water on amorphous alumina is analyzed using periodic-dispersion corrected DFT calculations. The energetics of the investigated reactions suggest that monomethyl aluminum (MMA) is the most abundant reaction intermediate at ALD operating conditions. The dominant reaction path toward the methylation of the surface is found to be adsorption of TMA on bridge oxygen via Lewis acid-base complex formation followed by ligand exchange reactions (LERs) with hydroxyls and surface water in its vicinity. Further adsorption and LERs of TMA leads to a saturated methylated surface (similar to 6.4 CH3 nm(-2)) which is in agreement with experimental observations and infrared spectra. The surface restructuring that is observed in almost all the reactions investigated seems to play an important role in the formation of conformal alumina films.}},
  author       = {{Sandupatla, Aditya Shankar and Alexopoulos, Konstantinos and Reyniers, Marie-Françoise and Marin, Guy}},
  issn         = {{1932-7447}},
  journal      = {{JOURNAL OF PHYSICAL CHEMISTRY C}},
  keywords     = {{BINARY REACTION SEQUENCE,ATOMIC LAYER DEPOSITION,OXIDE THIN-FILMS,DENSITY-FUNCTIONAL THEORY,FINDING SADDLE-POINTS,AUGMENTED-WAVE METHOD,MINIMUM ENERGY PATHS,ELASTIC BAND METHOD,1ST PRINCIPLES,AL2O3 FILMS}},
  language     = {{eng}},
  number       = {{23}},
  pages        = {{13050--13061}},
  title        = {{Ab initio investigation of surface chemistry of alumina ALD on hydroxylated γ-alumina surface}},
  url          = {{http://doi.org/10.1021/acs.jpcc.5b02382}},
  volume       = {{119}},
  year         = {{2015}},
}

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