Mechanistic studies of copper thin-film growth from Cu[sup I] and Cu[sup II] [beta]-diketonates

Journal Article · Wed Feb 10 04:00:00 UTC 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00056a028· OSTI ID:5988628

Girolami, G S; Jeffries, P M ^[1]; Dubois, L H ^[2]

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1. Univ. of Illinois, Urbana (United States)
2. AT T Bell Lab., Murray Hill, NJ (United States)

The kinetics and mechanism of copper film growth from the reactions of bis(acetylacetonato)copper(II), bis(hexafluoroacetylacetonato)copper(II), and (vinyltrimethylsilane)(hexafluoroacetylacetonato)copper(I) (Cu(hfac)(vtms)) with copper single crystal surfaces were investigated. Experiments were performed using vibrational spectroscopy (reflection infrared and high-resolution electron energy loss spectroscopies) as well as mass spectrometry (temperature-programmed desorption and integrated desorption mass spectrometries). Both ligand desorption and dissociation were observed upon pyrolysis of these molecules under ultra-high-vacuum conditions. The authors demonstrate that adsorbed [beta]-diketonate ligands decompose in a stepwise fashion at temperatures above [approximately] 375 K to yield adsorbed CF[sub 3] and ketenylidene ([triple bond]C-C[triple bond]O) intermediates. These further decompose above [approximately] 500 K to leave surface carbon, a major contaminant in copper films grown from Cu[sup II] [beta]-diketonates. Clean films can be grown from the pyrolysis of Cu(hfac)(vtms) at pressures above 10[sup [minus]5] Torr, however. The implications of the results relative to the mechanism of copper film growth at elevated pressures are also discussed. 54 refs., 14 figs., 2 tabs.

• DOE Contract Number: FG02-91ER45439
• OSTI ID: 5988628
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:3; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201 -- Chemical & Physicochemical Properties
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
CHEMICAL REACTIONS
COPPER
COPPER COMPOUNDS
CRYSTAL GROWTH
DATA
DECOMPOSITION
DESORPTION
DISSOCIATION
ELECTRON SPECTROSCOPY
ELEMENTS
ENERGY-LOSS SPECTROSCOPY
EXPERIMENTAL DATA
FILMS
INFORMATION
LIGANDS
MASS SPECTROSCOPY
METALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYROLYSIS
SORPTION
SPECTROSCOPY
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
ULTRAHIGH VACUUM