CMP compositions containing a soluble peroxometalate complex and methods of use thereof
View Patent ↗The present invention provides a chemical-mechanical polishing (CMP) composition for polishing a ruthenium-containing substrate in the presence of hydrogen peroxide without forming a toxic level of ruthenium tetroxide during the polishing process. The composition comprises (a) a catalytic oxidant comprising a water-soluble peroxometalate complex, an oxidizable precursor of a peroxometalate complex, or a combination thereof, (b) a particulate abrasive; and (c) an aqueous carrier. The peroxometalate complex and the precursor thereof each have a reduced form that is oxidizable by hydrogen peroxide to regenerate the peroxometalate complex during chemical-mechanical polishing. CMP methods for polishing ruthenium-containing surfaces with the CMP composition are also provided.
1. A chemical-mechanical polishing (CMP) method for polishing a ruthenium-containing substrate in the presence of hydrogen peroxide without forming a toxic level of ruthenium tetroxide, comprising the steps of:
(a) contacting a surface of the ruthenium-containing substrate with a polishing pad and an aqueous CMP composition in the presence of hydrogen peroxide; and
(b) causing relative motion between the polishing pad and the substrate while maintaining a portion of the CMP composition and hydrogen peroxide in contact with the surface between the pad and the substrate for a time period sufficient to abrade at least a portion of the ruthenium present in the substrate from the surface;
wherein the CMP composition comprises (i) a catalytic oxidant comprising a water-soluble peroxometalate complex and an oxidizable precursor of a peroxometalate complex, the peroxometalate complex and the precursor thereof each having a reduced form that is oxidizable by hydrogen peroxide to generate the peroxometalate complex during chemical-mechanical polishing, wherein the water soluble peroxometalate complex is selected from the group consisting of an isoperoxotungstate compound, a peroxotitanate compound and a titanium hydroperoxosilicate compound, and wherein the oxidizable precursor of the peroxometalate complex is selected from the group consisting of an acidic tungsten-containing compound and a titanate compound; (ii) a particulate abrasive; and (iii) an aqueous carrier.
2. The method of claim 1 wherein the particulate abrasive is present in the composition in an amount in the range of about 0.5 to about 10 percent by weight.
3. The method of claim 1 wherein the particulate abrasive has a mean particle size in the range of about 5 to about 50 nm.
4. The method of claim 1 wherein the catalytic oxidant is present in the composition in an amount in the range of about 0.05 to about 1 percent by weight.
5. The method of claim 1 wherein the peroxometalate complex comprises an isoperoxotungstate compound.
6. The method of claim 1 wherein the peroxometalate complex comprises a peroxotitanate compound.
7. The method of claim 1 wherein peroxometalate complex comprises a titanium hydroperoxosilicate compound.
8. The method of claim 1 wherein the oxidizable precursor of the peroxometalate complex comprises an acidic tungsten-containing compound.
9. The method of claim 8 wherein the acidic tungsten-containing compound is selected from the group consisting of tungstic acid, polytungstic acid, phosphotungstic acid, and a combination of two or more of the foregoing.
10. The method of claim 1 wherein the oxidizable precursor of the peroxometalate complex comprises a titanate compound.
11. The method of claim 10 wherein the titanate compound is selected from the group consisting of a titanium(IV) citrate complex, a titanium(IV) lactate complex, and a combination thereof.