Precursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correction

dc.check.infoAccess to this article is restricted until 12 months after publication by the request of the publisher.en
dc.contributor.authorMaimaiti, Yasheng
dc.contributor.authorElliott, Simon D.
dc.contributor.funderEnterprise Irelanden
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderScience Foundation Irelanden
dc.description.abstractCopper dimethylamino-2-propoxide [Cu(dmap)2] is used as a precursor for low-temperature atomic layer deposition (ALD) of copper thin films. Chemisorption of the precursor is the necessary first step of ALD, but it is not known in this case whether there is selectivity for adsorption sites, defects, or islands on the substrate. Therefore, we study the adsorption of the Cu(dmap)2 molecule on the different sites on flat and rough Cu surfaces using PBE, PBE-D3, optB88-vdW, and vdW-DF2 methods. We found the relative order of adsorption energies for Cu(dmap)2 on Cu surfaces is Eads (PBE-D3) > Eads (optB88-vdW) > Eads (vdW-DF2) > Eads (PBE). The PBE and vdW-DF2 methods predict one chemisorption structure, while optB88-vdW predicts three chemisorption structures for Cu(dmap)2 adsorption among four possible adsorption configurations, whereas PBE-D3 predicts a chemisorbed structure for all the adsorption sites on Cu(111). All the methods with and without van der Waals corrections yield a chemisorbed molecule on the Cu(332) step and Cu(643) kink because of less steric hindrance on the vicinal surfaces. Strong distortion of the molecule and significant elongation of Cu–N bonds are predicted in the chemisorbed structures, indicating that the ligand–Cu bonds break during the ALD of Cu from Cu(dmap)2. The molecule loses its initial square-planar structure and gains linear O–Cu–O bonding as these atoms attach to the surface. As a result, the ligands become unstable and the precursor becomes more reactive to the coreagent. Charge redistribution mainly occurs between the adsorbate O–Cu–O bond and the surface. Bader charge analysis shows that electrons are donated from the surface to the molecule in the chemisorbed structures, so that the Cu center in the molecule is partially reduced.en
dc.description.sponsorshipEnterprise Ireland (Collaborative Centre for Applied Nanotechnology (CCAN) ALD300 project, Irish Centre for High Performance Computing (ICHEC), SFI funded computational resources at the Tyndall National Institute); Science Foundation Ireland (ALDesign” Project, Grant 09.IN1.I2628); Higher Education Authority (Irish Centre for High Performance Computing (ICHEC))en
dc.description.statusPeer revieweden
dc.description.versionSubmitted Versionen
dc.identifier.citationY. Maimaiti and S. D. Elliott (2015) 'Precursor Adsorption on Copper Surfaces as the First Step During the Deposition of Copper: A Density Functional Study with van der Waals Correction'. Journal of Physical Chemistry C, DOI:
dc.identifier.journaltitleJournal of Physical Chemistry Cen
dc.publisherAmerican Chemical Societyen
dc.rightsThis document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry C, copyright © American Chemical Society after peer review. . To access the final edited and published work see DOI:
dc.subjectAtomic layer deposition (ALD)en
dc.titlePrecursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correctionen
dc.typeArticle (peer-reviewed)en
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