Chemical vapor deposition of copper from Cu+1 precursors in the presence of water vapor

Abstract

Copper films have been deposited by low pressure chemical vapor deposition from mixtures of the Cu+1 precursor copper hexafluoroacetylacetonate vinyltrimethylsilane and water vapor. The addition of water vapor at the optimum concentration more than doubles the deposition rate and substantially reduces the nucleation time without adversely affecting the copper film resistivity, but excess amounts of water vapor significantly increase the copper resistivity. Auger electron spectroscopy analysis detects no impurities in copper films deposited under optimum water conditions, but detects oxygen in films deposited under excess water conditions, suggesting copper oxide formation.

Growth of Copper(I) Nitride by ALD Using Copper(II) Hexafluoroacetylacetonate, Water, and Ammonia as Precursors

“…In some previous studies of copper growth by CVD/ALD, water was used to enhance film nucleation and growth rate. [20][21][22][23] The addition of water was also found to have a large effect on copper film growth on the same substrate types as used in this study. 24 In this work, two different ALD sequences are applied, one including water ͓pulse sequence: Cu͑hfac͒ 2 /H 2 O/NH 3 ͔ and one without water ͓pulse sequence: Cu͑hfac͒ 2 /NH 3 ͔.…”

Nucleation and film growth during copper chemical vapor deposition using the precursor Cu(TMVS)(hfac)

“…Kim et al 17 also reported that shorter incubation times and enhanced growth rates could be achieved using water vapor. 7,17, 18 Mermet et al 7 reported that deposited film resistivity decreased upon annealing at 723 K for 30 min. Deposition for 30 min with water vapor flowing for the initial 30 s at 6.5 sccm resulted in pure copper films.…”

NUCLEATION REACTIONS AND FILM GROWTH OF COPPER ON TiN USING HEXAFLUOROACETYLACETONATE COPPER(I) TRIMETHYLVINYLSILANE

“…After copper nucleation by (2) or (3) in the case of Scheme 1, grain growth of copper will be continued on the nucleated copper as islands through the reaction (4) to (7). Therefore, the loss of selectivity reported in the literature(6) during copper CVD using Cu(H FA)(TMVS) may be closely related with the initial reaction of copper nucleation, i.e., the rate of disproportionation on the substrate and the rate of decomposition of Cu(HFA)(TMVS).…”