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Title: 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:
 [1];  [2];  [3]; ORCiD logo [2]
  1. Univ. Nacional Autonoma de Mexico (UNAM), Ensenada, BC (Mexico)
  2. Univ. of California, Riverside, CA (United States)
  3. 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 Name: Journal of Materials Research; Journal ID: ISSN 0884-2914
Publisher:
Materials Research Society
Country of Publication:
United States
Language:
English
Subject:
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. doi: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. doi:10.1557/jmr.2019.293.
@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 = ,
volume = ,
place = {United States},
year = {2019},
month = {10}
}

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