Preparation and characterization of copper(I) amides

Tsuda, Tetsuo; Watanabe, Katsuhiko; Miyata, Kazuyuki; YAMAMOTO, H.; Saegusa, Takeo

doi:10.1021/ic50222a071

Cited by 71 publications

(45 citation statements)

References 3 publications

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“…(8) Mesitylcopper (I), (Strem Chemicals), CuMes, was purified twice by recrystallization in toluene. (9) Each precursor was dissolved in C 1 C 4 ImNTf 2 , under inert conditions at 5x10 -2 M. The obtained solution was decomposed under 0.9 MPa of H 2 at 100 °C for 4 hours to form metallic nanoparticles (NPs). (5) These NPs were observed by Transmission Electron Microscopy (TEM) using a Philips CM120 120 kV and by High Resolution Transmission Electron Microscopy (HRTEM) using a Jeol JEM 2010FEF (field effect gun energy filtering) 200 kV.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Arquillière¹,

Santini²,

Haumesser³

et al. 2011

ECS Trans.

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Bimetallic nanoparticles can be used in a variety of applications such as catalysis, in advanced magnetic or optical devices or as starting materials to form continuous metallic layers. In this study, we report the synthesis of bimetallic ruthenium-copper (Ru-Cu) nanoparticles in ionic liquids. For this purpose, solutions of ionic liquids containing a mixture of precursors of Ru and Cu were decomposed under dihydrogen. Small, crystalline and well dispersed Ru-CuNPs (2.5 ± 0.6 nm) were obtained, which are significantly smaller than the pure Ru or pure CuNPs formed under the same conditions. Our analyses suggest that these NPs have a Ru core -Cu shell structure. This structure is expected from thermodynamical and kinetics data. Moreover, this could explain the dramatic size reduction observed when mixing the two metals.

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Section: Methodsmentioning

confidence: 99%

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Arquillière¹,

Santini²,

Haumesser³

et al. 2011

ECS Trans.

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“…[18] Suitable and easily accessible Cu + salts of WCAs are unknown and the best available Cu I starting materials prior to…”

Section: H T U N G T R E N N U N G (Ch 3 )A C H T U N G T R E N N U Nmentioning

confidence: 99%

Cu[Al(OR^F)₄] Starting Materials and their Application in the Preparation of [Cu(S_n)]⁺(n=12, 8) Complexes

Santiso‐Quiñones

Higelin

Schaefer

et al. 2009

Chemistry A European J

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An effective route to stable, almost-"naked" Cu(I) salts of weakly coordinating anions (WCAs) of the type [Al(OR(F))4]- has been developed. Born-Fajans-Haber cycles and theoretical calculations suggest that this methodology is useful for the generation of Cu(I) salts regardless of the larger WCA used. The first homoleptic Cu(I)-arene complex [Cu(1,2-F2C6H4)2](+)[Al{OC(CF3)3}4]- (1), the first Cu(I)-methylenechloride complex [Cu(CH2Cl2)Al{OC(CH3)(CF3)2}4] (2), and the donor-free dimer [CuAl{OCH(CF3)2}4]2 (3) were synthesized in quantitative yields by sonicating Li[Al(OR(F))4] (R(F)=C(CF3)3, C(CH3)(CF3)2, or CH(CF3)2), AgF, and a three-fold excess of CuI in 1,2-F2C6H4 (1) or CH2Cl2 (2, 3). Substances 1-3 are good starting materials for further Cu(I) chemistry, and the reaction of 1-3 with the weak Lewis base cyclooctasulfur gave the first Cu(I)-sulfur complexes of type [Cu(S12)(S8)](+)[Al{OC(CF3)3}4]- (4), [Cu(CH2Cl2)(S12)](+)[Al{OC(CF3)3}4]- (5), [A1Cu(1,5-eta1,eta1-S8)CuA1] (6; A1=[Al{OC(CH3)(CF3)2}4]-), and a Cu(I)-S8 1D coordination polymer with [Cu2(S8)2A(2)(2)] (7; A2=[Al{OCH(CF3)2}4]-), as a monomeric repeat unit. Complexes 4 and 5 are the first example of any metal coordinated to cyclo-S12 and 4 is the first example of a complex having an element in two allotropic modifications as a ligand.

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“…It is known that copper(I) amides typically produce a tetrameric structure, 9 and copper(I) amides are more thermally stabile than alkyl or alkoxo species. 10 Thus, it has been difficult to isolate a thermally stable copper amide precursor that exhibits sufficient volatility to be considered for CVD or ALD. However, monomeric copper(I) species are well-studied in catalysis.…”

Section: Introductionmentioning

confidence: 99%

Deposition of Copper by Plasma-Enhanced Atomic Layer Deposition Using a Novel N-Heterocyclic Carbene Precursor

et al. 2013

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Access to the full text of the published version may require a subscription. Rights AbstractTwo novel N-heterocyclic carbene (NHC)-containing copper(I) amides are reported as atomic layer deposition (ALD) precursors. 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyldisilazide (1) and 4,5-dimethyl-1,3-diisopropyl-imidazol-2-ylidene copper hexamethyldisilazide (2) were synthesized and structurally characterized. The thermal behaviour of both compounds was studied by thermogravimetric analysis (TGA), and they were both found to be reasonably volatile compounds. Compound 1 had no residual mass in the TGA and showed long-term stability at temperatures as high as 130 °C, while 2 had a residual mass of 7.4 %. Copper metal with good resistivity was deposited using 1 by plasma-enhanced atomic layer deposition. The precursor demonstrated self-limiting behaviour indicative of ALD, and gave a growth rate of 0.2 Å/cycle. Compound 2 was unsuccessful as an ALD precursor under similar conditions. Density functional theory calculations showed that both compounds adsorb dissociatively onto a growing copper film as long as there is some atomic roughness, via cleavage of the Cu-carbene bond.

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Preparation and characterization of copper(I) amides

Cited by 71 publications

References 3 publications

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Cu[Al(OR^F)₄] Starting Materials and their Application in the Preparation of [Cu(S_n)]⁺(n=12, 8) Complexes

Deposition of Copper by Plasma-Enhanced Atomic Layer Deposition Using a Novel N-Heterocyclic Carbene Precursor

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Preparation and characterization of copper(I) amides

Cited by 71 publications

References 3 publications

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Synthesis of Copper and Copper-Ruthenium Nanoparticles in Ionic Liquids for the Metallization of Advanced Interconnect Structures

Cu[Al(ORF)4] Starting Materials and their Application in the Preparation of [Cu(Sn)]+(n=12, 8) Complexes

Deposition of Copper by Plasma-Enhanced Atomic Layer Deposition Using a Novel N-Heterocyclic Carbene Precursor

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Cu[Al(OR^F)₄] Starting Materials and their Application in the Preparation of [Cu(S_n)]⁺(n=12, 8) Complexes