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Mechanistic studies of palladium thin film growth from palladium(II) {beta}-diketonates. 1. Spectroscopic studies of the reactions of bis(hexafluoroacetylacetonato)palladium(II) on copper surfaces

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja944130h· OSTI ID:283000
; ; ;  [1]
  1. Univ. of Illinois, Urbana, IL (United States)

The reactions of bis(hexafluroacetylacetonato)palladium(II), Pd(hfac){sub 2}, on copper have been studied. Whereas multilayers of Pd(hfac){sub 2} desorb molecularly from copper surfaces between 200 and 270 K, submonolayer coverages of Pd(hfac){sub 2} react in a multistep sequence. At temperatures below 120 K, Pd(hfac){sub 2} transfers its hfac ligands to the copper surface and the metal center is reduced to Pd{sup 0}. The hfac groups adopt a variety of molecular orientations on the surface at 120 K but undergo an apparent ordering transition near 300 K that re-orients the hfac groups to an upright geometry (perpendicular to the surface plane). At low coverages on clean surfaces, further annealing results in the decomposition of the surface-bound hfac ligands to give adsorbed Pd atoms and COCF{sub 3}, CF{sub 3}, and fluoride species. These intermediates ultimately yield a partial monolayer of Pd atoms, a carbon(possibly graphitic) deposit, and a variety of organic products that desorb between 500 and 650 K; the desorbing flux after ionization consists of CF{sub 3}COF, COCF{sub 3},CF{sub 3} and Co fragments. The activation parameters for the decomposition of hfac groups on copper foils have been determined to be A = 1.3 x 10{sup 13} s{sup -1} and E{sub a} = 36.8 kcal mol{sup -1}. 54 refs., 13 figs., 2 tabs.

DOE Contract Number:
FG02-91ER45439
OSTI ID:
283000
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 25 Vol. 118; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English