Surface-selective deposition of palladium and silver films from metal-organic precursors. A novel metal-organic chemical vapor deposition redox transmetalation process

Journal Article · Wed Dec 01 04:00:00 EST 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00077a092· OSTI ID:5161632

Lin, W; Warren, T H; Nuzzo, R G; Girolami, G S ^[1]

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1. Univ. of Illinois, Urbana-Champaign, IL (United States)

We report the first surface-selective depositions of Pd and Ag films from metal-organic precursors. We also describe mechanistic studies of this process by in situ kinetic and spectroscopic studies conducted in ultrahigh vacuum. We have studied three precursors containing the hexafluoroacetylacetonato (hfac) ligand: Pd(hfac)[sub 2] (1), Ag(hfac)(PMe[sub 3]) (2), and AF(hfac)(PMe[sub 3])[sub 2] (3). These compounds (especially 1) are reasonably volatile and sublime readily in vacuo at temperatures of 20-50[degree]C. Chemical vapor depositions from these precursors have been conducted at 200-245[degree]C both under vacuum (10[sup [minus]4] Torr) and in the presence of H[sub 2]. In the presence of H[sub 2], Pd(hfac)[sub 2] readily gives micron-thick films of pure palladium metal on glass, silicon, copper, tungsten, aluminum, and nickel at temperatures as low as 200[degrees]C. Mass spectrometic analysis of the byproducts suggests that deposition of Pd involves the reaction of Pd(hfac)[sub 2] with H[sub 2] to form hexafluoroacetylacetone (hfacH). Similar surface-independent depositions of Ag films are observed for the silver precursors under an H[sub 2] atmosphere. This redox transmetalation route may be generally applicable provided that the redox potentials are favorable and that the surface atoms can be carried away as a volatile hfac complex. 33 refs., 1 fig.

• DOE Contract Number: FG02-91ER45439
• OSTI ID: 5161632
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:24; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360101* -- Metals & Alloys-- Preparation & Fabrication
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201 -- Chemical & Physicochemical Properties
CHEMICAL COATING
CHEMICAL VAPOR DEPOSITION
DEPOSITION
ELEMENTS
FILMS
HYDROGEN
LIGANDS
MASS SPECTROSCOPY
METALS
NONMETALS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PALLADIUM
PLATINUM METALS
REDOX PROCESS
REPROCESSING
SEPARATION PROCESSES
SILVER
SPECTROSCOPY
SURFACE COATING
THIN FILMS
TRANSITION ELEMENTS
ULTRAHIGH VACUUM
X-RAY SPECTROSCOPY