Sunday, September 4, 2022

Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions

Here is a new way that I have not seen before how to monitor the half-reactions in ALD by using The pyroelectric thin-film calorimeter. It offers submillisecond temporal resolution and resolves precursor delivery and reaction kinetics. Thank you, Riikka, for sharing on Twitter.
 
Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions
Ashley R. Bielinski, Ethan P. Kamphaus, Lei Cheng, and Alex B.F. Martinson*
J. Am. Chem. Soc. 2022, 144, 33, 15203–15210
Publication Date:August 9, 2022
https://doi.org/10.1021/jacs.2c05460

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 submillisecond 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.



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