Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface

Aditya Shankar Sandupatla; Konstantinos Alexopoulos; Marie Françoise Reyniers; Guy B. Marin

doi:10.1021/acs.jpcc.5b02382

Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface

Aditya Shankar Sandupatla
, Konstantinos Alexopoulos
, Marie Françoise Reyniers
, Guy B. Marin

Chemical Engineering

Research output: Contribution to journal › Article › peer-review

21 Scopus citations

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 (∼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.

Original language	English (US)
Pages (from-to)	13050-13061
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	119
Issue number	23
DOIs	https://doi.org/10.1021/acs.jpcc.5b02382
State	Published - Jun 11 2015

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/acs.jpcc.5b02382

Cite this

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title = "Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface",

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 (∼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 Konstantinos Alexopoulos and Reyniers, \{Marie Fran{\c c}oise\} and Marin, \{Guy B.\}",

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doi = "10.1021/acs.jpcc.5b02382",

language = "English (US)",

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T1 - Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface

AU - Sandupatla, Aditya Shankar

AU - Alexopoulos, Konstantinos

AU - Reyniers, Marie Françoise

AU - Marin, Guy B.

PY - 2015/6/11

Y1 - 2015/6/11

N2 - 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 (∼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.

AB - 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 (∼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.

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DO - 10.1021/acs.jpcc.5b02382

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SP - 13050

EP - 13061

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 23

ER -

Ab Initio Investigation of Surface Chemistry of Alumina ALD on Hydroxylated γ-Alumina Surface

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