Selective low-temperature chemical vapor deposition of copper from new copper(I) compounds

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Abstract
Chemical vapor deposition of copper, in hot- and warm-wall reactors from a variety of copper(I)compounds of general formula XCuLn where X = (3-diketonate and 13-ketoiminate and L = phosphine, olefin and alkyne, has been investigated. All compounds deposit high-purity copper, as determined by Auger electron spectroscopy, over the temperature range 100-400°C and pressure range 10 - 150mtorr, with resistivities in the range 1.8 - 5.1 µohmcm. Selective deposition has been studied as a function of theneutral Lewis base ligand, L. The (R-diketonate)Cu(phosphine) compounds have been show to deposit copper selectively onto Pt, W and Cu in the presence of Si02. The temperature range over which selectivity was observed was a function of the substituents on the 13-diketonate ligand. The ([3- diketonate)Cu(1,5-cyclooctadiene) and ([3-diketonate)Cu(alkyne) compounds studied to date did notexhibit selectivity for the above metal substrates over Si02. Deposition rates of up to 9,000Å/min at 200°C have been obtained in a cold-wall CVD reactor under surface reaction limited conditions. Activation energy parameters were measured from the temperature variation of the deposition rate were in the range 21 - 26kcal/mol for (hfac)Cu(PMe3), (hfac)Cu(1,5-cyclooctadiene) and (hfac)Cu(2-butyne). All three classes of compounds undergo a thermally induced disproportionation according to the general reaction shown below.

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