Evaluation of Phosphite and Phosphane Stabilized Copper(I) Trifluoroacetates as Precursors for the Metal-Organic Chemical Vapor Deposition of Copper

Copper has become the material of choice for metallization of high-performance ultra-large scale integrated circuits. As the feature size is continuously decreasing, metal-organic chemical vapor deposition (MOCVD) appears promising for depositing the Cu seed layer required for electroplating, as well as for filling entire interconnect structures. In this work, four novel organophosphane and organophosphite Cu(I) trifluoroacetates were studied as precursors for Cu MOCVD. Details are reported on CVD results obtained with Tris(tri-n-butylphosphane)copper(I)trifluoroacetate, (ⁿBu₃P)₃CuO₂CCF₃. Solutions of this precursor with acetonitrile and isopropanol were used for deposition experiments on 100 mm Si wafers sputter-coated with Cu, Cu/TiN, and Al(2 % Si)/W. Experiments were carried out in a cold-wall reactor at a pressure of 0.7 mbar, using a liquid delivery approach for precursor dosage. On Cu seed layers, continuous films were obtained at low deposition rates (0.5 to 1 nm/min). At temperatures above 320°C, hole formation in the Cu films was observed. Deposition on TiN led to the formation of single copper particles and etching of the TiN, whereas isolating aluminum oxyfluoride was formed after deposition on Al(Si)/W. It is concluded that the formation of CF₃ radicals during decarboxylation has a negative effect on the deposition results. Furthermore, the precursor chemistry needs to be improved for a higher volatility of the complex