Vinyltrimethylsilane (VTMS) as a probe of chemical reactivity of a TiCN diffusion barrier-covered silicon surface.
This paper presents the first molecular level investigation of chemical reactivity of a surface of an amorphous diffusion barrier film deposited on a Si(100)-2 x 1 single crystal. Vinyltrimethylsilane (VTMS) is chosen as a probe molecule because of its chemical properties and because of its role as a ligand in a common copper deposition precursor, hexafluoroacetylacetonato-copper-vinyltrimethylsilane, (hfac)Cu(VTMS). The surface chemistry of vinyltrimethylsilane on titanium carbonitride-covered Si(100)-2 x 1 has been investigated using multiple internal reflection Fourier transform infrared spectroscopy (MIR-FTIR), Auger electron spectroscopy (AES), thermal desorption mass spectrometry, and computational analysis. On a film with nominal surface stoichiometry TiC(x)N(y) (x approximately y approximately 1) preannealed to 800 K, VTMS adsorbs molecularly at cryogenic temperatures even at submonolayer coverages; the major pathway for its temperature-programmed evolution is desorption. Adsorption at room temperature leads to chemisorption via a double-bond attachment. A set of computational models was designed to investigate the possible adsorption sites for a VTMS molecule on a TiCN-covered Si(100)-2 x 1 surface. A comparison of the computational predictions for a variety of possible adsorption sites with the results of thermal desorption and infrared measurements suggests that approximately 90% of the adsorbed VTMS is chemisorbed along the Ti-C bond while approximately 10% is chemisorbed on a Ti corner atom, the minority site of the surface. The Ti-N bond is not participating in the chemisorption process.
Pirolli
Laurent
L
Department of Chemistry and Biochemistry, University of Delaware, Newark Delaware 19716, USA.
Teplyakov
Andrew V
AV