Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions
Abstract
We report that atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H2O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computational models based on crystalline Al2O3 substrates and closely aligned with the heat predicted by standard heats of formation. The pyroelectric thin-film calorimeter offers submilisecond temporal resolution that uniquely and clearly resolves precursor delivery and reaction kinetics. Both half-reactions are observed to exhibit multiple kinetic rates, with average TMA half-reaction rates at least 2 orders of magnitude faster than the H2O half-reaction kinetics. Comparing the experimental heat with published computational literature and additional first-principles modeling highlights the need to refine our models and mechanistic understanding of even the most ubiquitous ALD reactions.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1905993
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 33; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; atomic layer deposition; computational modeling; precursors; surface reactions; thermodynamic modeling
Citation Formats
Bielinski, Ashley R., Kamphaus, Ethan P., Cheng, Lei, and Martinson, Alex B.F. Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions. United States: N. p., 2022.
Web. doi:10.1021/jacs.2c05460.
Bielinski, Ashley R., Kamphaus, Ethan P., Cheng, Lei, & Martinson, Alex B.F. Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions. United States. https://doi.org/10.1021/jacs.2c05460
Bielinski, Ashley R., Kamphaus, Ethan P., Cheng, Lei, and Martinson, Alex B.F. Tue .
"Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions". United States. https://doi.org/10.1021/jacs.2c05460. https://www.osti.gov/servlets/purl/1905993.
@article{osti_1905993,
title = {Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions},
author = {Bielinski, Ashley R. and Kamphaus, Ethan P. and Cheng, Lei and Martinson, Alex B.F.},
abstractNote = {We report that atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H2O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computational models based on crystalline Al2O3 substrates and closely aligned with the heat predicted by standard heats of formation. The pyroelectric thin-film calorimeter offers submilisecond temporal resolution that uniquely and clearly resolves precursor delivery and reaction kinetics. Both half-reactions are observed to exhibit multiple kinetic rates, with average TMA half-reaction rates at least 2 orders of magnitude faster than the H2O half-reaction kinetics. Comparing the experimental heat with published computational literature and additional first-principles modeling highlights the need to refine our models and mechanistic understanding of even the most ubiquitous ALD reactions.},
doi = {10.1021/jacs.2c05460},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 144,
place = {United States},
year = {Tue Aug 09 00:00:00 EDT 2022},
month = {Tue Aug 09 00:00:00 EDT 2022}
}
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