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Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO2

D'acunto, Giulio LU ; Tsyshevsky, Roman ; Shayesteh, Payam LU ; Gallet, Jean Jacques ; Bournel, Fabrice ; Rochet, François ; Pinsard, Indiana ; Timm, Rainer LU orcid ; Head, Ashley R. LU and Kuklja, Maija , et al. (2023) In Chemistry of Materials 35(2). p.529-538
Abstract

The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and... (More)

The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO2 surface.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemistry of Materials
volume
35
issue
2
pages
529 - 538
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85146032849
  • pmid:36711051
ISSN
0897-4756
DOI
10.1021/acs.chemmater.2c02947
language
English
LU publication?
yes
id
36c5aad7-6c58-4631-beb7-e507d838471e
date added to LUP
2023-02-16 11:43:53
date last changed
2024-04-14 04:06:18
@article{36c5aad7-6c58-4631-beb7-e507d838471e,
  abstract     = {{<p>The surface chemistry of the initial growth during the first or first few precursor cycles in atomic layer deposition is decisive for how the growth proceeds later on and thus for the quality of the thin films grown. Yet, although general schemes of the surface chemistry of atomic layer deposition have been developed for many processes and precursors, in many cases, knowledge of this surface chemistry remains far from complete. For the particular case of HfO2 atomic layer deposition on a SiO2 surface from an alkylamido-hafnium precursor and water, we address this lack by carrying out an operando atomic layer deposition experiment during the first cycle of atomic layer deposition. Ambient-pressure X-ray photoelectron spectroscopy and density functional theory together show that the decomposition of the metal precursor on the stoichiometric SiO2 surface in the first half-cycle of atomic layer deposition proceeds via a bimolecular reaction mechanism. The reaction leads to the formation of Hf-bonded methyl methylene imine and free dimethylamine. In addition, ligand exchange takes place involving the surface hydroxyls adsorbed at defect sites of the SiO2 surface.</p>}},
  author       = {{D'acunto, Giulio and Tsyshevsky, Roman and Shayesteh, Payam and Gallet, Jean Jacques and Bournel, Fabrice and Rochet, François and Pinsard, Indiana and Timm, Rainer and Head, Ashley R. and Kuklja, Maija and Schnadt, Joachim}},
  issn         = {{0897-4756}},
  language     = {{eng}},
  number       = {{2}},
  pages        = {{529--538}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Chemistry of Materials}},
  title        = {{Bimolecular Reaction Mechanism in the Amido Complex-Based Atomic Layer Deposition of HfO<sub>2</sub>}},
  url          = {{http://dx.doi.org/10.1021/acs.chemmater.2c02947}},
  doi          = {{10.1021/acs.chemmater.2c02947}},
  volume       = {{35}},
  year         = {{2023}},
}