Copper(I) carbene hydride complexes acting both as reducing agent and precursor for Cu ALD: a study through density functional theory

Dey, Gangotri; Elliott, Simon D.

doi:10.1007/s00214-013-1416-y

Cited by 14 publications

(24 citation statements)

References 40 publications

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“…[ 83 ] A copper(I) carbene hydride complex acting both as reducing agent and precursor for Cu ALD is proposed based on DFT calculations. [ 84 ] Like hydride, formate can be a source of electrons in metal ALD, as revealed in our calculations on the three-step ALD process published by Knisley et al involving the reaction of Cu(dmap) 2 , HCOOH and N 2 H 4 . [ 85 ] We fi nd that when a proton is abstracted by hydrazine from surface-bound formate (HCOO − ), the latter spontaneously decomposes into volatile CO 2 and donates two electrons to the surface.…”

Section: Progress Reportmentioning

confidence: 94%

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

et al. 2015

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Recent progress in the simulation of the chemistry of atomic layer deposition (ALD) is presented for technologically important materials such as alumina, silica, and copper metal. Self-limiting chemisorption of precursors onto substrates is studied using density functional theory so as to determine reaction pathways and aid process development. The main challenges for the future of ALD modeling are outlined.

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Section: Progress Reportmentioning

confidence: 94%

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

et al. 2015

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“…We therefore used DFT calculations to propose copper carbene hydride as a precursor for Cu ALD along with any other Cu precursor such as Cu(dmap) 2 . 43 The advantage of using two Cu precursors is that co-deposition of a second metal cannot occur.…”

Section: A Ligand-ligand Coupling To Reduce Metalmentioning

confidence: 99%

Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Elliott

Dey

Maimaiti

2017

The Journal of Chemical Physics

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Original citationElliott Reaction cycles for the atomic layer deposition (ALD) of metals are presented, based on the incomplete data that exist about their chemical mechanisms, particularly from density functional theory (DFT) calculations. ALD requires self-limiting adsorption of each precursor, which results from exhaustion of adsorbates from previous ALD pulses and possibly from inactivation of the substrate through adsorption itself. Where the latter reaction does not take place, an "abbreviated cycle" still gives self-limiting ALD, but at a much reduced rate of deposition. Here, for example, ALD growth rates are estimated for abbreviated cycles in H 2 -based ALD of metals. A wide variety of other processes for the ALD of metals are also outlined and then classified according to which a reagent supplies electrons for reduction of the metal. Detailed results on computing the mechanism of copper ALD by transmetallation are summarized and shown to be consistent with experimental growth rates. Potential routes to the ALD of other transition metals by using complexes of non-innocent diazadienyl ligands as metal sources are also evaluated using DFT. Published by AIP Publishing.

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“…This is the same model as used by Larsson et al 37 and in our previous studies 36,38 . There are few studies done previously of organic and organometallic adsorption onto a copper surface by Crispin et al 39 .…”

mentioning

confidence: 94%

“…A valence double zeta with polarization basis set denoted by def-SV(P) 33a was used for all electrons. We used the larger triple zeta basis set TZVPP 34 and dispersion functional D3 35 to check the accuracy of the level of calculation in a previous study 36 . It was seen that energy difference changed by 4-8%, especially when using the dispersion functional D3.…”

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Quantum Chemical Study of the Effect of Precursor Stereochemistry on Dissociative Chemisorption and Surface Redox Reactions During the Atomic Layer Deposition of the Transition Metal Copper

Dey¹,

Elliott²

2015

J. Phys. Chem. C

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Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu (II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu (II) /Cu (I) / Cu (0) intermediate complexes from the respective Cu (II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu 55 cluster. Cu (I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu 2 Et 2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu (I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

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Copper(I) carbene hydride complexes acting both as reducing agent and precursor for Cu ALD: a study through density functional theory

Cited by 14 publications

References 40 publications

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Modeling Mechanism and Growth Reactions for New Nanofabrication Processes by Atomic Layer Deposition

Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Quantum Chemical Study of the Effect of Precursor Stereochemistry on Dissociative Chemisorption and Surface Redox Reactions During the Atomic Layer Deposition of the Transition Metal Copper

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