Tailoring precursors for deposition

synthesis structure and thermal studies of cyclopentadienyl copper(I) isocyanide complexes

Alex Willcocks, Thomas Pugh, J. Hamilton, S. D. Cosham, S. L. Sung, T. Heil, P. R. Chalker, P. A. Williams, G. Kociok-Kohn, A. L. Johnson

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Abstract

We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structure of the several complexes cyclopentadienyl-copper(I) isocyanide complexes have been unambiguously determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η5-C5H5)Cu(CNiPr)] (2a) and the tert-butyl isocyanide complex [(η5-C5H5)Cu(CNtBu)] (2b) as possible copper metal CVD precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et and iPr) have allowed the affect these changes would have on features such as stability, volatility and decomposition to be investigated. As part of this study the vapor pressures of the complexes [(η5-C5H5)Cu(CNtBu)] (2b), [(η5-MeC5H4)Cu(CNtBu)] (3b), [(η5-EtC5H4)Cu(CNtBu)] (4b) and [(η5-iPrC5H4)Cu(CNtBu)] (5b) over a 40-65 ºC temperature range have been determined. Low pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b, to synthesize thin films of metallic copper on silicon, gold and platinum substrates, under an atmosphere of hydrogen (H2). Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 °C and 300 oC, by SEM and AFM reveal temperature dependent growth features: Films grown at 300 oC are continuous and pin hole free, whereas those films grown at 180 oC consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 oC show a high degree of surface coverage with the formation of high density, continuous pin hole free thin films. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic copper.
Original languageEnglish
Pages (from-to)4869-4881
JournalInorganic Chemistry
Volume54
Issue number10
DOIs
Publication statusPublished - 18 May 2015

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Cyanides
Copper
copper
synthesis
Silicon
Substrates
Platinum
Gold
Thin films
platinum
thin films
Metals
vapor deposition
gold
Ligands
Low pressure chemical vapor deposition
ligands
x rays
volatility
silicon

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Tailoring precursors for deposition : synthesis structure and thermal studies of cyclopentadienyl copper(I) isocyanide complexes. / Willcocks, Alex; Pugh, Thomas; Hamilton, J.; Cosham, S. D.; Sung, S. L.; Heil, T.; Chalker, P. R.; Williams, P. A.; Kociok-Kohn, G.; Johnson, A. L.

In: Inorganic Chemistry, Vol. 54, No. 10, 18.05.2015, p. 4869-4881.

Research output: Contribution to journalArticle

Willcocks, Alex ; Pugh, Thomas ; Hamilton, J. ; Cosham, S. D. ; Sung, S. L. ; Heil, T. ; Chalker, P. R. ; Williams, P. A. ; Kociok-Kohn, G. ; Johnson, A. L. / Tailoring precursors for deposition : synthesis structure and thermal studies of cyclopentadienyl copper(I) isocyanide complexes. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 10. pp. 4869-4881.
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abstract = "We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structure of the several complexes cyclopentadienyl-copper(I) isocyanide complexes have been unambiguously determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η5-C5H5)Cu(CNiPr)] (2a) and the tert-butyl isocyanide complex [(η5-C5H5)Cu(CNtBu)] (2b) as possible copper metal CVD precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et and iPr) have allowed the affect these changes would have on features such as stability, volatility and decomposition to be investigated. As part of this study the vapor pressures of the complexes [(η5-C5H5)Cu(CNtBu)] (2b), [(η5-MeC5H4)Cu(CNtBu)] (3b), [(η5-EtC5H4)Cu(CNtBu)] (4b) and [(η5-iPrC5H4)Cu(CNtBu)] (5b) over a 40-65 ºC temperature range have been determined. Low pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b, to synthesize thin films of metallic copper on silicon, gold and platinum substrates, under an atmosphere of hydrogen (H2). Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 °C and 300 oC, by SEM and AFM reveal temperature dependent growth features: Films grown at 300 oC are continuous and pin hole free, whereas those films grown at 180 oC consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 oC show a high degree of surface coverage with the formation of high density, continuous pin hole free thin films. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic copper.",
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T1 - Tailoring precursors for deposition

T2 - synthesis structure and thermal studies of cyclopentadienyl copper(I) isocyanide complexes

AU - Willcocks, Alex

AU - Pugh, Thomas

AU - Hamilton, J.

AU - Cosham, S. D.

AU - Sung, S. L.

AU - Heil, T.

AU - Chalker, P. R.

AU - Williams, P. A.

AU - Kociok-Kohn, G.

AU - Johnson, A. L.

PY - 2015/5/18

Y1 - 2015/5/18

N2 - We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structure of the several complexes cyclopentadienyl-copper(I) isocyanide complexes have been unambiguously determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η5-C5H5)Cu(CNiPr)] (2a) and the tert-butyl isocyanide complex [(η5-C5H5)Cu(CNtBu)] (2b) as possible copper metal CVD precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et and iPr) have allowed the affect these changes would have on features such as stability, volatility and decomposition to be investigated. As part of this study the vapor pressures of the complexes [(η5-C5H5)Cu(CNtBu)] (2b), [(η5-MeC5H4)Cu(CNtBu)] (3b), [(η5-EtC5H4)Cu(CNtBu)] (4b) and [(η5-iPrC5H4)Cu(CNtBu)] (5b) over a 40-65 ºC temperature range have been determined. Low pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b, to synthesize thin films of metallic copper on silicon, gold and platinum substrates, under an atmosphere of hydrogen (H2). Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 °C and 300 oC, by SEM and AFM reveal temperature dependent growth features: Films grown at 300 oC are continuous and pin hole free, whereas those films grown at 180 oC consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 oC show a high degree of surface coverage with the formation of high density, continuous pin hole free thin films. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic copper.

AB - We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structure of the several complexes cyclopentadienyl-copper(I) isocyanide complexes have been unambiguously determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η5-C5H5)Cu(CNiPr)] (2a) and the tert-butyl isocyanide complex [(η5-C5H5)Cu(CNtBu)] (2b) as possible copper metal CVD precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et and iPr) have allowed the affect these changes would have on features such as stability, volatility and decomposition to be investigated. As part of this study the vapor pressures of the complexes [(η5-C5H5)Cu(CNtBu)] (2b), [(η5-MeC5H4)Cu(CNtBu)] (3b), [(η5-EtC5H4)Cu(CNtBu)] (4b) and [(η5-iPrC5H4)Cu(CNtBu)] (5b) over a 40-65 ºC temperature range have been determined. Low pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b, to synthesize thin films of metallic copper on silicon, gold and platinum substrates, under an atmosphere of hydrogen (H2). Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 °C and 300 oC, by SEM and AFM reveal temperature dependent growth features: Films grown at 300 oC are continuous and pin hole free, whereas those films grown at 180 oC consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 oC show a high degree of surface coverage with the formation of high density, continuous pin hole free thin films. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic copper.

UR - http://dx.doi.org/10.1021/acs.inorgchem.5b00448

U2 - 10.1021/acs.inorgchem.5b00448

DO - 10.1021/acs.inorgchem.5b00448

M3 - Article

VL - 54

SP - 4869

EP - 4881

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 10

ER -