CVD of Pure Copper Films from Amidinate Precursor

Krisyuk, Vladislav V.; Aloui, Lyacine; Prud’homme, Natalie; Сысоев, С. В.; Senocq, François; Samélor, Diane; Vahlas, Constantin

doi:10.1149/1.3526142

Cited by 34 publications

(37 citation statements)

References 28 publications

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“…Soft wet‐chemical synthesis in organic solvents from metal–organic complexes is an important method to obtain metal or metal alloy nanoparticles . Metal amidinates are important precursors for metal nanoparticles for thin metal films from low‐pressure chemical vapor deposition (CVD) and atomic layer deposition (ALD) …”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4] Metal amidinates are important precursors for metal nanoparticles [5,6] for thin metal films from low-pressure chemical vapor deposition( CVD) and atomic layer deposition (ALD). [7,8] Herein, we report the use of metal amidinates [M{MeC-(NiPr) 2 } n ]o fm anganese,i ron, cobalt, nickel, and coppera sp recursors for the synthesis of nanomaterials in ionic liquids (ILs) or in propylene carbonate (PC) to yield selectively transitionmetal nanoparticles (M 0 -NPs) or metal fluoride nanoparticles (MF 2 -NPs) as stable colloids (Scheme1). Depending on the used IL (fluorous or non-fluorous) and the used metal amidinates,w eo btained phase-pure metal M 0 -orMF 2 -NPs.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

et al. 2016

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Decomposition of transition‐metal amidinates [M{MeC(NiPr)2}n] [M(AMD)n; M=MnII, FeII, CoII, NiII, n=2; CuI, n=1) induced by microwave heating in the ionic liquids (ILs) 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIm][PF6]), 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate (triflate) ([BMIm][TfO]), and 1‐butyl‐3‐methylimidazolium tosylate ([BMIm][Tos]) or in propylene carbonate (PC) gives transition‐metal nanoparticles (M‐NPs) in non‐fluorous media (e.g. [BMIm][Tos] and PC) or metal fluoride nanoparticles (MF2‐NPs) for M=Mn, Fe, and Co in [BMIm][BF4]. FeF2‐NPs can be prepared upon Fe(AMD)2 decomposition in [BMIm][BF4], [BMIm][PF6], and [BMIm][TfO]. The nanoparticles are stable in the absence of capping ligands (surfactants) for more than 6 weeks. The crystalline phases of the metal or metal fluoride synthesized in [BMIm][BF4] were identified by powder X‐ray diffraction (PXRD) to exclusively Ni‐ and Cu‐NPs or to solely MF2‐NPs for M=Mn, Fe, and Co. The size and size dispersion of the nanoparticles were determined by transmission electron microscopy (TEM) to an average diameter of 2(±2) to 14(±4) nm for the M‐NPs, except for the Cu‐NPs in PC, which were 51(±8) nm. The MF2‐NPs from [BMIm][BF4] were 15(±4) to 65(±18) nm. The average diameter from TEM is in fair agreement with the size evaluated from PXRD with the Scherrer equation. The characterization was complemented by energy‐dispersive X‐ray spectroscopy (EDX). Electrochemical investigations of the CoF2‐NPs as cathode materials for lithium‐ion batteries were simply evaluated by galvanostatic charge/discharge profiles, and the results indicated that the reversible capacity of the CoF2‐NPs was much lower than the theoretical value, which may have originated from the complex conversion reaction mechanism and residue on the surface of the nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

et al. 2016

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“…1 A process to deposit a uniform and continuous thin film ( < 2 nm) of copper in high aspect ratio structures is desirable in order to meet the demands of current trends in integrated circuit technology. Deposition techniques including physical vapour deposition (PVD), 2 electrodeposition, 3 chemical vapour deposition (CVD), 4 and atomic layer 1-17 | 1 deposition (ALD) 5 have been applied with the aim of obtaining such a thin film. However, it is extremely difficult to deposit thin films of Cu at this thickness and instead islands of Cu tend to be more favourable.…”

Section: Introductionmentioning

confidence: 99%

Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption

Maimaiti

Nolan

Elliott

2014

Phys. Chem. Chem. Phys.

168

163

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We studied the reduction of CuO(111) surface using density functional theory (DFT) with the generalized gradient approximation corrected for on-site Coulomb interactions (GGA + U) and screened hybrid DFT (HSE06 functional). The surface reduction process by oxygen vacancy formation and H2 adsorption on the CuO(111) surface is investigated as two different reduction mechanisms. It is found that both GGA + U and HSE06 predict the same trend in the relative stability of oxygen vacancies. We found that loss of the subsurface oxygen is initially thermodynamically favourable. As the oxygen vacancy concentration increases, mixture of subsurface and surface vacancies is energetically preferred over full reduction of the surface or subsurface monolayer. The reduction of Cu2+ to Cu+ is found to be more favourable than that of Cu+ to Cu0 in the most stable vacancy structures at all concentrations. Consistent with the oxygen vacancy calculations, H2 adsorption occurs initially on under-coordinated surface oxygen. Water molecules are formed upon the adsorption of H2 and this gives a mechanism for H2 reduction of CuO to Cu. Ab initio atomistic thermodynamics shows that reducing CuO to metallic Cu at the surface is more energetically difficult than in the bulk so that the surface oxide protects the bulk from reduction. Using H2 as the reducing agent, it is found that the CuO surface is reduced to Cu2O at approximately 360 K and that complete reduction from Cu2O to metallic Cu occurs at 780 K

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“…Soft, wet‐chemical synthesis in organic solvents from metal–organic complexes is an important route to nanometals and allows the preparation of metals and alloys in the nanometer scale regime . Metal amidinates (Scheme ) have been investigated and widely used as precursors for metal nanoparticles and thin metal films in low‐pressure chemical vapor deposition (CVD) or atomic layer deposition (ALD) …”

Section: Introductionmentioning

confidence: 99%

Soft, Wet‐Chemical Synthesis of Metastable Superparamagnetic Hexagonal Close‐Packed Nickel Nanoparticles in Different Ionic Liquids

Wegner

Rutz

Schütte

et al. 2017

Chemistry A European J

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The microwave-induced decomposition of bis{N,N'-diisopropylacetamidinate}nickel(II) [Ni{MeC(NiPr) } ] or bis(1,5-cyclooctadiene)nickel(0) [Ni(COD) ] in imidazolium-, pyridinium-, or thiophenium-based ionic liquids (ILs) with different anions (tetrafluoroborate, [BF ] , hexafluorophosphate, [PF ] , and bis(trifluoromethylsulfonyl)imide, [NTf ] ) yields small, uniform nickel nanoparticles (Ni NPs), which are stable in the absence of capping ligands (surfactants) for more than eight weeks. The soft, wet-chemical synthesis yields the metastable Ni hexagonal close-packed (hcp) and not the stable Ni face-centered cubic (fcc) phase. The size of the nickel nanoparticles increases with the molecular volume of the used anions from about 5 nm for [BF ] to ≈10 nm for [NTf ] (with 1-alkyl-3-methyl-imidazolium cations). The n-butyl-pyridinium, [BPy] , cation ILs reproducibly yield very small nickel nanoparticles of 2(±1) nm average diameter. The Ni NPs were characterized by high-resolution transmission electron microscopy (HR-TEM) and powder X-ray diffraction. An X-ray photoelectron spectroscopic (XPS) analysis shows an increase of the binding energy (E ) of the electron from the Ni 2p orbital of the very small 2(±1) nm diameter Ni particles by about 0.3 eV to E =853.2 eV compared with bulk Ni , which is traced to the small cluster size. The Ni nanoparticles show superparamagnetic behavior from 150 K up to room temperature. The saturation magnetization of a Ni (2±1 nm) sample from [BPy][NTf ] is 2.08 A m kg and of a Ni (10±4 nm) sample from [LMIm][NTf ] it is 0.99 A m kg , ([LMIm]=1-lauryl-3-methyl- imidazolium). The Ni NPs were active catalysts in IL dispersions for 1-hexene or benzene hydrogenation. Over 90 % conversion was reached under 5 bar H in 1 h at 100 °C for 1-hexene and a turnover frequency (TOF) up to 1330 mol (mol ) h or in 60 h at 100 °C for benzene hydrogenation and TOF=23 mol (mol ) h .

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CVD of Pure Copper Films from Amidinate Precursor

Cited by 34 publications

References 28 publications

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

Synthesis of Metal Nanoparticles and Metal Fluoride Nanoparticles from Metal Amidinate Precursors in 1-Butyl-3-Methylimidazolium Ionic Liquids and Propylene Carbonate

Reduction mechanisms of the CuO(111) surface through surface oxygen vacancy formation and hydrogen adsorption

Soft, Wet‐Chemical Synthesis of Metastable Superparamagnetic Hexagonal Close‐Packed Nickel Nanoparticles in Different Ionic Liquids

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