Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Show simple item record Maimaiti, Yasheng Elliott, Simon D. 2016-11-03T10:23:56Z 2016-11-03T10:23:56Z 2016-08-11
dc.identifier.citation Maimaiti, Yasheng; Elliott, Simon D. (2016) 'Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc'. Chemistry Materials, 28 (17) :6282-6295. doi: 10.1021/acs.chemmater.6b02522 en
dc.identifier.volume 28 en
dc.identifier.issued 17 en
dc.identifier.startpage 6282 en
dc.identifier.endpage 6295 en
dc.identifier.issn 0897-4756
dc.identifier.doi 10.1021/acs.chemmater.6b02522
dc.description.abstract Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals. en
dc.description.sponsorship Science Foundation Ireland (ALDesign Project 09.IN1.I2628, Irish Centre for High Performance Computing (ICHEC)); Higher Education Authority (Irish Centre for High Performance Computing (ICHEC)) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Chemical Society en
dc.rights This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see en
dc.subject Density-functional theory en
dc.subject Minimum energy paths en
dc.subject Elastic band method en
dc.subject Amidinate precursor en
dc.subject Molecular-dynamics en
dc.subject Surface-chemistry en
dc.subject Hydrogen plasma en
dc.subject Reducing agent en
dc.subject 1st principles en
dc.subject Saddle-points en
dc.title Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Simon Elliott, Tyndall Theory Modelling & Design Centre, University College Cork, Cork, Ireland. +353-21-490-3000 Email: en
dc.internal.availability Full text available en Access to this article is restricted until 12 months after publication by the request of the publisher. en 2017-08-11 2016-11-03T10:13:48Z
dc.description.version Accepted Version en
dc.internal.rssid 370432001
dc.internal.wokid WOS:000383318500033
dc.contributor.funder Science Foundation Ireland en
dc.contributor.funder Higher Education Authority en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Chemistry Materials en
dc.internal.copyrightchecked No en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress en

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