Copper metalorganic chemical vapor deposition reactions of hexafluoroacetylacetonate Cu(I) vinyltrimethylsilane and bis (hexafluoroacetylacetonate) Cu(II) adsorbed on titanium nitride

Cu is receiving increasing attention as a replacement for Al in future Si ultra‐large‐scale integrated circuits due to its lower resistivity and potentially better reliability in terms of electromigration resistance and stress‐induced voiding. Metalorganic chemical vapor deposition (MOCVD) of Cu offers the advantages of conformal coverage and selective growth. Whatever the means of deposition, a diffusion barrier and adhesion layer such as TiN is required. To understand the nucleation mechanisms of Cu film growth on TiN during MOCVD, we have studied the thermal decomposition of two metalorganic precursors, hexafluoroacetylacetonate Cu(I) vinyltrimethylsilane [CuI(hfac)(vtms)], and bis (hexafluoroacetylacetonate) Cu(II) [CuII(hfac)2] by x‐ray photoelectron spectroscopy and temperature programmed desorption mass spectrometry in an ultrahigh vacuum (UHV) system.Experiments were carried out on polycrystalline air‐exposed (i.e., oxidized) TiN and N2 ion beam sputter‐cleaned TiN. These surfaces are representati...