Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films
Abstract
The beginning steps of the thermal chemistry of Cu(I)-2-(tert-butylimino)-5,5-dimethyl-pyrrolidinate on metal surfaces were characterized using temperature-programmed desorption experiments and density functional theory (DFT). The relative stability of the initial dimer relative to its dissociation on metal surfaces was evaluated. Several molecular desorption temperatures were identified on Ni(110), but all correspond to dimers, either containing the initial Cu ions or after their removal; no monomer was ever detected. DFT calculations also indicated preferential bonding on Cu(110) as a dimer, albeit with a distorted configuration, via the Cu atoms and in registry with the lattice of the substrate. Furthermore, a potential dissociation pathway of the adsorbed dimer was identified involving the partial detachment of the ligands via the scission of one Cu–N bond at the time and migration to adjacent surface sites. This process is accompanied by the reduction of the Cu centers of the metal–organic complex, indicating that it may be the rate-limiting reaction that leads to further fragmentation of the ligands.
- Authors:
-
[2]
- Univ. Nacional Autonoma de Mexico (UNAM), Ensenada, BC (Mexico)
- Univ. of California, Riverside, CA (United States)
- Univ. Nacional Autonoma de Mexico (UNAM), Ensenada, BC (Mexico); Univ. of California, Riverside, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, Riverside, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1593410
- Grant/Contract Number:
- SC0001839
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Research
- Additional Journal Information:
- Journal Volume: 35; Journal Issue: 7; Journal ID: ISSN 0884-2914
- Publisher:
- Materials Research Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; surface chemistry; atomic layer deposition; adsorption
Citation Formats
Guerrero-Sánchez, Jonathan, Chen, Bo, Takeuchi, Noboru, and Zaera, Francisco. Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films. United States: N. p., 2019.
Web. doi:10.1557/jmr.2019.293.
Guerrero-Sánchez, Jonathan, Chen, Bo, Takeuchi, Noboru, & Zaera, Francisco. Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films. United States. https://doi.org/10.1557/jmr.2019.293
Guerrero-Sánchez, Jonathan, Chen, Bo, Takeuchi, Noboru, and Zaera, Francisco. Mon .
"Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films". United States. https://doi.org/10.1557/jmr.2019.293. https://www.osti.gov/servlets/purl/1593410.
@article{osti_1593410,
title = {Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films},
author = {Guerrero-Sánchez, Jonathan and Chen, Bo and Takeuchi, Noboru and Zaera, Francisco},
abstractNote = {The beginning steps of the thermal chemistry of Cu(I)-2-(tert-butylimino)-5,5-dimethyl-pyrrolidinate on metal surfaces were characterized using temperature-programmed desorption experiments and density functional theory (DFT). The relative stability of the initial dimer relative to its dissociation on metal surfaces was evaluated. Several molecular desorption temperatures were identified on Ni(110), but all correspond to dimers, either containing the initial Cu ions or after their removal; no monomer was ever detected. DFT calculations also indicated preferential bonding on Cu(110) as a dimer, albeit with a distorted configuration, via the Cu atoms and in registry with the lattice of the substrate. Furthermore, a potential dissociation pathway of the adsorbed dimer was identified involving the partial detachment of the ligands via the scission of one Cu–N bond at the time and migration to adjacent surface sites. This process is accompanied by the reduction of the Cu centers of the metal–organic complex, indicating that it may be the rate-limiting reaction that leads to further fragmentation of the ligands.},
doi = {10.1557/jmr.2019.293},
journal = {Journal of Materials Research},
number = 7,
volume = 35,
place = {United States},
year = {2019},
month = {10}
}
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