A thin-amorphous MnOx layer using self-forming barrier process with a Cu-Mn alloy shows good adhesion and diffusion barrier properties between copper and dielectric layer, resulting in excellent reliability for stress and electromigration. Meanwhile, chemical vapor deposition (CVD) can be employed for conformal deposition of the barrier layer in narrow trenches and vias for future technology node. In our previous research, a thin and uniform amorphous MnOx layer could be formed on TEOS-oxide by thermal metal-organic CVD (MOCVD), showing a good diffusion barrier property. In addition, a good adhesion strength is necessary between a Cu line and a dielectric layer not only to ensure good SM and EM resistance but also to prevent film delamination under mechanical or thermal stress conditions during fabrication process such as chemical mechanical polishing or high temperature annealing. To date, no information is available with regard to the adhesion property of CVD-MnOx. In this work, we report diffusion barrier property in further detail and adhesion property in PVD-Cu/CVD-MnOx/SiO2/Si. The temperature dependence of the adhesion property is correlated with the chemical composition and valence state of Mn investigated with SIMS and Raman spectroscopy.

Substrates were p-type Si wafers having a plasma-TEOS oxide of 100nm in thickness. CVD was carried out in a deposition chamber. A manganese precursor was vaporized and introduced into the deposition chamber with H2 carrier gas. After the CVD, a Cu overlayer was deposited on some samples using a sputtering system in load lock chamber of the CVD machine. The diffusion barrier property of the MnOx film was investigated in annealed samples at 400 oC for 100 hours in a vacuum of better than 1.0×10-5 Pa. The Adhesion property of Mn oxide was investigated by Scotch tape test in the as-deposited and in the annealed Cu/CVD-MnOx/TEOS samples. The obtained samples were analyzed for thickness and microstructure with TEM, chemical bonding states of the MnOx layer with XPS, and composition of each layer with SIMS.

In the CVD deposition below 300 °C, no Cu delamination was observed both in the as-deposited and in the annealed Cu/CVD-MnOx/SiO2 samples. On the other hand, in the CVD deposition at 400 °C, the Cu films were delaminated from the CVD-MnOx/TEOS substrates. The XPS peak position of Mn 2p and Mn 3s spectra indicated that the valence state of Mn in the as-deposited barrier layer below 400 °C was 2+. Composition analysis with SIMS as well as Raman also indicated the presence of a larger amount of carbon at 400 °C than at less than 300 °C. The good adhesion between Cu and MnO could be attributed to an amount of carbon inclusion in the CVD barrier layer.