Development of Formulations for a-SiC and Manganese CMP and Post-CMP Cleaning of Cobalt.

摘要

We have investigated the chemical mechanical polishing (CMP) of amorphous SiC (a-SiC) and Mn and Post CMP cleaning of cobalt for various device applications. During the manufacture of copper interconnects using the damascene process the polishing of copper is followed by the polishing of the barrier material (Co, Mn, Ru and their alloys) and its post CMP cleaning. This is followed by the a-SiC hard mask CMP. Silicon carbide thin films, though of widespread use in microelectronic engineering, are difficult to process by CMP because of their hardness and chemical inertness. The earlier part of the SiC work discusses the development of slurries based on silica abrasives that resulted in high a-SiC removal rates (RRs). The ionic strength of the silica dispersion was found to play a significant role in enhancing material removal rate, while also providing very good post-polish surface-smoothness. For example, the addition of 50 mM potassium nitrate to a pH 8 aqueous slurry consisting of 10 wt % of silica abrasives and 1.47 M hydrogen peroxide increased the RR from about 150 nm/h to about 2100 nm/h. The role of ionic strength in obtaining such high RRs was investigated using surface zeta-potentials measurements and X-ray photoelectron spectroscopy (XPS). Evidently, hydrogen peroxide promoted the oxidation of Si and C to form weakly adhered species that were subsequently removed by the abrasive action of the silica particles. The effect of potassium nitrate in increasing material removal is attributed to the reduction in the electrostatic repulsion between the abrasive particles and the SiC surface because of screening of surface charges by the added electrolyte.;We also show that transition metal compounds when used as additives to silica dispersions enhance a-SiC removal rates (RRs). Silica slurries containing potassium permanganate gave RRs as high as 2000 nm/h at pH 4. Addition of copper sulfate to this slurry further enhanced the RRs to ∼3500 nm/h at pH 6. Furthermore, addition of a low concentration of 250 ppm Brij-35 to this slurry suppressed the RRs of silicon dioxide to zero, while retaining the RRs of a-SiC at ∼2700 nm/h , a combination of RRs that is appropriate for hard mask polishing.;The second part of this thesis focuses on the polishing of manganese which was proposed as a "self-forming" barrier material to prevent copper diffusion in advanced generation (22 nm and smaller) Si devices. A major challenge associated with such a self-forming Mn barrier for Cu interconnects in sub-22nm devices is galvanic corrosion that can occur at the Cu-Mn interface during chemical mechanical planarization. In the present work, it was shown that an aqueous solution of sucrose, BTA and potassium periodate reduces the corrosion potential gap between Cu and Mn to ∼ 0.01 V at pH 10 while also lowering the galvanic currents significantly and hence can be an excellent candidate for a polishing slurry. We discuss the role of these reagents and the inhibiting film that can be formed at the interface of the bimetallic system in this solution. Preliminary polishing results for Cu and Mn using a silica-based slurry formulated with this solution are also presented.;The third part involves the development of compositions for Post CMP cleaning of cobalt barriers in advanced generation (22 nm and smaller). The thickness of the cobalt films was found to impact the corrosion behavior of the films. Thinner films of cobalt were found be more prone to galvanic corrosion in the presence of copper. The corrosion currents were low for both Cu and Co in all the solutions tested but the galvanic currents varied significantly. It was found that while BTA was not able to suppress the galvanic corrosion between Cu and Co (2000 A) at pH 8, either 60 mM of 3 Amino 1,2,4 triazole or 30 mM of 3 Amino 5 methyl thio 1,2,4 triazole were able to suppress the galvanic corrosion between Cu and Co (2000 A) to < 0.3 micro amperes per square cm at pH 8. These compositions however were not able to suppress the galvanic corrosion of Co (20 A) films. Changing the pH to 10 did not improve the results. Furthermore, addition of several complexing agents and other corrosion inhibitors also did not lower the Ecorr of Co (20 A) and Cu. Further experiments are being conducted to identify compositions to protect Co and Cu from corrosion. (Abstract shortened by UMI.).