Chemical vapor deposition of copper, copper(I) oxide, and silver from metal-organic precursors
Jeffries, Patrick Michael
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https://hdl.handle.net/2142/22496
Description
Title
Chemical vapor deposition of copper, copper(I) oxide, and silver from metal-organic precursors
Author(s)
Jeffries, Patrick Michael
Issue Date
1992
Doctoral Committee Chair(s)
Girolami, Gregory S.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Engineering, Materials Science
Language
eng
Abstract
Metal-organic chemical vapor deposition (MOCVD) from the tetrameric precursor copper(I) tert-butoxide, (Cu(O-t-Bu)) $\sb4$, results in the deposition of pure copper(I) oxide whiskers at 510 K and of copper metal with $\sim$2% oxygen contamination at 670 K. Quantitative analyses of the gaseous byproducts generated during the deposition, electron energy loss spectroscopy, and temperature programmed desorption experiments indicate that copper(I) oxide is formed by an elimination mechanism and copper metal is formed by deoxygenation of an initially deposited copper(I) oxide phase.
New volatile monomeric Cu$\sp{\rm II}$ alkoxides have been synthesized with the general formula Cu(OR)$\sb2$L, where OR is OCH(CF$\sb3)\sb2$ or OC(CH$\sb3$)(CF$\sb3)\sb2$ and L is a bidentate amine. These compounds were prepared by the reaction of Cu(OMe)$\sb2$ with HOR and the amine in diethyl ether. The degree of distortion from square planar geometry for these compounds was measured by EPR spectroscopy, UV-vis spectroscopy, and X-ray crystallography. At 570 K, these compounds are MOCVD precursors for the deposition of pure copper metal.
The surface chemistry of copper(I) and copper(II) $\beta$-diketonate complexes has been examined under ultrahigh vacuum conditions on copper single crystals by temperature programmed desorption studies, electron energy loss spectroscopy, infrared spectroscopy, and Auger spectroscopy. Above 200 K, the $\beta$-diketonate ligands migrate from the adsorbed copper compound to the copper surface. At $\sim$375 K, the ligands begin to fragment to give trifluoromethyl and ketenylidene surface species. Decarbonylation of the ketenylidene groups at $\sim$525 K leads to a carbon overlayer.
Silver films have been prepared by MOCVD from (CF$\sb3$CF = C(CF$\sb3$)Ag) $\sb4$ at 550 K. Studies of the deposition mechanism reveal that (CF$\sb3$CF = C(CF$\sb3$)Ag) $\sb4$ initially deposits AgF by an elimination reaction and AgF then loses fluorine to produce silver metal. The crystal structure of (CF$\sb3$CF = C(CF$\sb3$)Ag) $\sb4$ was determined and shows that the compound is a tetramer that consists of a square plane of silver atoms in which each edge is bridged by a perfluorobutenyl ligand.
The ruthenium alkyl complexes (Li(tmed)) $\sb2$(($\eta\sp4$-C$\sb 7$H$\sb8$)RuMe$\sb4$) and (Li(tmed)) $\sb2(\eta\sp5$-C$\sb8$H$\sb{11}$)RuMe$\sb4$) have also been prepared and characterized.
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