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The electrodeposition of copper from supercritical CO2/acetonitrile mixtures and from supercritical trifluoromethane

The electrodeposition of copper from supercritical CO2/acetonitrile mixtures and from supercritical trifluoromethane
The electrodeposition of copper from supercritical CO2/acetonitrile mixtures and from supercritical trifluoromethane
The electrochemistry of [Cu(hfac)2], where hfac is hexafluoroacetylacetonate, and [Cu(MeCN)4]+ were investigated in liquid acetonitrile (MeCN), supercritical CO2/MeCN and supercritical trifluoromethane (CHF3) at 310–311 K and 17–20 MPa using either [NBun4][BF4] or [NBun4][B{3,5-(CF3)2C6H3}4] as the supporting electrolyte. In liquid acetonitrile it is possible to deposit metallic Cu from both ([Cu(MeCN)4][BF4]) and [Cu(hfac)2] but voltammetry for the [Cu(hfac)2] system is more complex and there is evidence of stripping of the Cu by reaction with Cu(II). Voltammetry of the two copper complexes in scCO2/MeCN showed typical plating and stripping features but with slightly increased diffusion limited currents for copper reduction due to the decreased viscosity of the supercritical solvent. In scCO2/MeCN the Cu(I) complex, tetrakis(acetonitrile)copper(I) tetrafluoroborate ([Cu(MeCN)4][BF4]), was found to produce better quality copper deposits than the Cu(II) complex ([Cu(hfac)2]). The Cu(I) complex has the advantages that it is stable and does not undergo comproportionation with copper(0) and that its ligands are totally compatible with the scCO2/MeCN solvent system. The solubility of ([Cu(MeCN)4][BF4]) is limited in scCO2/MeCN but can be significantly improved by changing the anion for tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([B{3,5-(CF3)2C6H3}4]-). It was possible to deposit smooth copper films of high purity and low resistivity (down to 4.0 × 10-6 Ohm.cm) from the Cu(I) complex. Copper was also deposited from supercritical CHF3 using [Cu(hfac)2] as a precursor. Although the plating and stripping features in the voltammetry are complicated by the lack of cosolvent and electroreduction of the solvent or free ligands, it was possible to produce copper films with resistivities as low as 5.8 × 10-6 Ohm.cm.
1463-9076
11744-11752
Cook, David
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Bartlett, Philip N.
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Zhang, Wenjian
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Levason, William
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Reid, Gillian
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Ke, Jie
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Su, Wenta
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George, Michael W.
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Wilson, James
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Smith, David
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Mallik, Kanad
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Barrett, Edward
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Sazio, Pier
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Cook, David
0fca0ffb-eef4-422f-b513-ce9a1f7de7cc
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Zhang, Wenjian
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Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Ke, Jie
e4b531d4-7642-4367-9a4e-d06f126c2599
Su, Wenta
78e12e98-09de-461d-8af3-91e5b0e018b7
George, Michael W.
09040935-b1da-4a63-ad2e-5ba29e39f80a
Wilson, James
aec7fd40-41c6-4f44-a1b0-ff60f03676b5
Smith, David
d9b2c02d-b7ea-498b-9ea1-208a1681536f
Mallik, Kanad
013bdafd-6ae0-463e-89a4-6ef1301c5c2f
Barrett, Edward
21ede4b9-38bb-448e-a0ef-dc99e1610ef0
Sazio, Pier
0d6200b5-9947-469a-8e97-9147da8a7158

Cook, David, Bartlett, Philip N., Zhang, Wenjian, Levason, William, Reid, Gillian, Ke, Jie, Su, Wenta, George, Michael W., Wilson, James, Smith, David, Mallik, Kanad, Barrett, Edward and Sazio, Pier (2010) The electrodeposition of copper from supercritical CO2/acetonitrile mixtures and from supercritical trifluoromethane Physical Chemistry Chemical Physics, 12, (37), pp. 11744-11752.

Record type: Article

Abstract

The electrochemistry of [Cu(hfac)2], where hfac is hexafluoroacetylacetonate, and [Cu(MeCN)4]+ were investigated in liquid acetonitrile (MeCN), supercritical CO2/MeCN and supercritical trifluoromethane (CHF3) at 310–311 K and 17–20 MPa using either [NBun4][BF4] or [NBun4][B{3,5-(CF3)2C6H3}4] as the supporting electrolyte. In liquid acetonitrile it is possible to deposit metallic Cu from both ([Cu(MeCN)4][BF4]) and [Cu(hfac)2] but voltammetry for the [Cu(hfac)2] system is more complex and there is evidence of stripping of the Cu by reaction with Cu(II). Voltammetry of the two copper complexes in scCO2/MeCN showed typical plating and stripping features but with slightly increased diffusion limited currents for copper reduction due to the decreased viscosity of the supercritical solvent. In scCO2/MeCN the Cu(I) complex, tetrakis(acetonitrile)copper(I) tetrafluoroborate ([Cu(MeCN)4][BF4]), was found to produce better quality copper deposits than the Cu(II) complex ([Cu(hfac)2]). The Cu(I) complex has the advantages that it is stable and does not undergo comproportionation with copper(0) and that its ligands are totally compatible with the scCO2/MeCN solvent system. The solubility of ([Cu(MeCN)4][BF4]) is limited in scCO2/MeCN but can be significantly improved by changing the anion for tetrakis[3,5-bis(trifluoromethyl)phenyl]borate ([B{3,5-(CF3)2C6H3}4]-). It was possible to deposit smooth copper films of high purity and low resistivity (down to 4.0 × 10-6 Ohm.cm) from the Cu(I) complex. Copper was also deposited from supercritical CHF3 using [Cu(hfac)2] as a precursor. Although the plating and stripping features in the voltammetry are complicated by the lack of cosolvent and electroreduction of the solvent or free ligands, it was possible to produce copper films with resistivities as low as 5.8 × 10-6 Ohm.cm.

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e-pub ahead of print date: 19 August 2010
Published date: 7 October 2010

Identifiers

Local EPrints ID: 177665
URI: http://eprints.soton.ac.uk/id/eprint/177665
ISSN: 1463-9076
PURE UUID: 63b80497-1b62-4113-88ee-b57b37012481
ORCID for Philip N. Bartlett: ORCID iD orcid.org/0000-0002-7300-6900
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Pier Sazio: ORCID iD orcid.org/0000-0002-6506-9266

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Date deposited: 18 Mar 2011 11:33
Last modified: 07 Nov 2017 14:06

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Contributors

Author: David Cook
Author: Wenjian Zhang
Author: William Levason ORCID iD
Author: Gillian Reid
Author: Jie Ke
Author: Wenta Su
Author: Michael W. George
Author: James Wilson
Author: David Smith
Author: Kanad Mallik
Author: Edward Barrett
Author: Pier Sazio ORCID iD

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