Multinuclear Copper(I) Guanidinate Complexes

Willcocks, Alexander M.; Robinson, Thomas; Roche, Christopher; Pugh, Thomas; Richards, Stephen P.; Kingsley, Andrew J.; Lowe, John P.; Johnson, Andrew L.

doi:10.1021/ic201602m

Cited by 37 publications

(27 citation statements)

References 65 publications

(47 reference statements)

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“…Moreover, a low-temperature process (ideally at r160 1C) is desirable for Cu ALD in order to avoid the agglomeration of Cu at elevated temperatures. 6 Recently, a number of Cu precursors have been tested for chemical vapor deposition and ALD applications, such as b-diketiminates, 7,8 b-diketonates, [9][10][11] amidinates, 12,13 aminoalkoxides, 14 guanidinate, 15,16 iminopyrrolidinate. 17,18 Among them, the Cu b-diketonate family is promising because of its high stability and relatively low vapor pressure.…”

Section: Introductionmentioning

confidence: 99%

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study

Schuster

Schulz

et al. 2015

Phys. Chem. Chem. Phys.

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Atomistic mechanisms for the atomic layer deposition using the Cu(acac)2 (acac = acetylacetonate) precursor are studied using first-principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)2 chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac-ligands. A sequential dissociation and reduction of the Cu precursor [Cu(acac)2 → Cu(acac) → Cu] are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)2 on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)2 on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by-products CO2 and H2O are observed during the reaction between Cu(acac)2 and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)2 follows the order H > O3 > H2O.

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Section: Introductionmentioning

confidence: 99%

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study

Schuster

Schulz

et al. 2015

Phys. Chem. Chem. Phys.

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“…Therefore, it is this attractive force that suppresses the Coulomb repulsion between two [PL-Cu] + , resulting in the formation of [PL-diCu-PL] 2+ . Notably, the 3d 10 -3d 10 attraction of the Cu + ions has already been reported and applied in inorganic materials (32)(33)(34).…”

Section: Cumentioning

confidence: 98%

Anomalous behavior of membrane fluidity caused by copper-copper bond coupled phospholipids

Jiang

Zhang

Zhou

et al. 2018

Sci Rep

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Membrane fluidity, essential for cell functions, is obviously affected by copper, but the molecular mechanism is poorly understood. Here, we unexpectedly observed that a decrease in phospholipid (PL) bilayer fluidity caused by Cu was more significant than those by Zn and Ca, while a comparable reduction occurred in the last two ions. This finding disagrees with the placement in the periodic table of Cu just next to Zn and far from Ca. The physical nature was revealed to be an anomalous attraction between Cu cations, as well as the induced motif of two phospholipids coupled by Cu-Cu bond (PL-diCu-PL). Namely, upon Cu ion binding to a negatively charged phosphate group of lipid, Cu was reduced to Cu. The attraction of the cations then caused one Cu ion simultaneously binding to two lipids and another Cu, resulting in the formation of PL-diCu-PL structure. In contrast, this attraction cannot occur in the cases of Zn and Ca ions. Remarkably, besides lipids, the phosphate group also widely exists in other biological molecules, including DNA, RNA, ADP and ATP. Our findings thus provide a new view for understanding the biological functions of copper and the mechanism underlying copper-related diseases, as well as lipid assembly.

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“…Similarly, a recent paper describes trimeric, heteroleptic copper(I) guanidinates isolated from the attempted synthesis of [Me2NC(N t Bu)2Cu]2. [121] We believe the ring of the iminopyrrolidinates reported herein was necessary to slightly reduce the steric bulk and permit the isolation of 2 as a dimeric species The 1 H NMR of 2 was simple, suggesting a symmetrical oligomeric solution structure, similar to known copper guanidinate dimers. [120] However, compound 1 showed a more complex 1 H NMR.…”

Section: Resultsmentioning

confidence: 76%

“…[Me2NC(N t Bu)2Cu]2. [121] Compared to this trimer, the ring of the iminopyrrolidinate reduced the steric bulk to permit the isolation of 1 as the more typical dimer, as seen by single crystal X-ray diffraction. The structure of 1 is consistent with previously known amidinate [119] and guanidinate [120] systems ( Figure 6.3.2, Table 6.3.1).…”

Section: Resultsmentioning

confidence: 99%

“…Although this suggested that the precursor chemisorbed "whole" at the surface, literature suggests that the alkyl group at the chelate position might be lost at high temperatures. [121] The line width of the solid-state NMR did not permit unambiguous identification of the tert-butyl moiety, so another experiment was needed. The silica with the deposited monolayer was rinsed with D2O to etch off the surface species, and a high resolution 1 H NMR was collected ( Figure 6 respectively.…”

Section: Resultsmentioning

confidence: 99%

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Development of Volatile Inorganic Compounds and Their Application for Chemical Vapour Deposition of Metal and Metal Oxide Thin Films

Kurek¹

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Chemical vapour deposition is a necessary and important technology for the manufacture of nano-thin metal films. The reactivity and thermal stability of the metal complexes used in this process are key to the deposition process.Through logical design, guanidinate ligands have evolved into iminopyrrolidinates to prevent decomposition pathways. These ligands were first tested on aluminum metal centres. Iminopyrrolidinates have been further stabilized with additional methyl moieties and have led to promising new copper precursors. Copper metal is desirable for interconnecting material in electronics due to its high conductivity.The reactivity of 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyl disilazide has been explored and yielded three new copper metal compounds.Sputtered thin films of gold have been used in metal assisted chemical etching to produce high aspect ratio structures on the surface of silicon substrates. PrefaceHere are the full bibliographical details for all reproduced publications included in this thesis. The supervisor, Seán T. Barry, and the student, Agnieszka Kurek, confirm that the student was fully involved in setting up and conducting the research, obtaining data and analyzing results, as well as preparing and writing the material presented in the co-authored articles integrated in this thesis. Additionally, the supervisor confirms the information provided by the student in this preface.To cite material from this thesis, please cite both this thesis and the relevant article from the chapter, if the chapter is based on a published work. Kurek, A.; Gordon, P.G.; Karle, S.; Devi, A.; Barry, S.T. Recent Advances Using Guanidinate Ligands for Chemical Vapour Deposition (CVD) and Atomic Layer Deposition (ALD) Applications, Aust. J. Chem. 2014, 67, 989-996. Wasslen, Y.A.; Kurek, A.; Johnson, P.A.; Pigeon, T.C.; Monillas, W.H.; Yap, G.P.A.; Barry, S.T. Coyle, J.P.; Pallister, P.J.; Kurek, A.; Sirianni, E.R.; Yap, G.P.A.; Barry, S.T. Copper Iminopyrrolidinates: A Study of Thermal and Surface Chemistry, Inorg. Chem. 2013, 52, 910.

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Multinuclear Copper(I) Guanidinate Complexes

Cited by 37 publications

References 65 publications

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study

Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study

Anomalous behavior of membrane fluidity caused by copper-copper bond coupled phospholipids

Development of Volatile Inorganic Compounds and Their Application for Chemical Vapour Deposition of Metal and Metal Oxide Thin Films

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