Ruthenium CMP compositions and methods
View Patent ↗The present invention provides a chemical-mechanical polishing (CMP) composition for polishing a ruthenium-containing substrate in the presence of an oxidizing agent such as hydrogen peroxide without forming a toxic level of ruthenium tetroxide during the polishing process. The composition comprises a particulate abrasive (e.g., silica, alumina, and/or titania) suspended in an aqueous carrier containing a ruthenium-coordinating oxidized nitrogen ligand (N—O ligand), such as a nitroxide (e.g., 4-hydroxy-TEMPO). In the presence of the oxidizing agent, the N—O ligand prevents the deposition of ruthenium species having an oxidation state of IV or higher on the surface of the substrate, and concomitantly forms a soluble Ru(II) N—O coordination complex with oxidized ruthenium formed during CMP of the substrate. CMP methods for polishing ruthenium-containing surfaces with the CMP composition are also provided.
1. A method for polishing a substrate comprising ruthenium and silicon dioxide, the method comprising abrading a surface of the substrate comprising ruthenium and silicon dioxide with a CMP composition comprising about 1 to about 10 percent by weight of a particulate abrasive selected from the group consisting of alumina, titania, and a combination thereof, suspended in an aqueous carrier containing about 0.01 to about 0.5 percent by weight of a nitroxide compound; wherein, in the presence of hydrogen peroxide, the nitroxide compound is capable of preventing the deposition of ruthenium species having an oxidation state of IV or higher on the surface of the substrate, and concomitantly forming a soluble Ru(II) nitroxide coordination complex with oxidized ruthenium formed during CMP of the substrate.
2. A method for polishing a substrate comprising ruthenium and silicon dioxide, the method comprising abrading a surface of the substrate comprising ruthenium and silicon dioxide with a CMP composition comprising a particulate abrasive selected from the group consisting of (a) colloidal silica or (b) a combination of colloidal silica and titania, suspended in an aqueous carrier containing a nitroxide compound wherein, in the presence of an oxidizing agent, the nitroxide compound is capable of preventing the deposition of ruthenium species having an oxidation state of IV or higher on the surface of the substrate, and concomitantly, forming a soluble Ru(II) N—O coordination complex with oxidized ruthenium formed during CMP of the substrate.
3. A chemical-mechanical polishing (CMP) method for selectively removing ruthenium from the surface of a substrate in preference to silicon dioxide, the method comprising the steps of
(a) contacting a surface of a substrate comprising ruthenium and silicon dioxide with a polishing pad and an aqueous CMP composition in the presence of an oxidizing agent; and
(b) causing relative motion between the substrate and the polishing pad while maintaining a portion of the CMP composition and oxidizing agent in contact with the surface between the pad and the substrate for a period of time sufficient to abrade at least a portion of the ruthenium present in the substrate from the surface;
wherein the CMP composition contains a particulate abrasive selected from the group consisting of alumina, titania, and a combination thereof; the particulate abrasive being suspended in an aqueous carrier containing a ruthenium-coordinating oxidized nitrogen ligand (N—O ligand), the N—O ligand comprising a nitroxide compound; wherein, in the presence of the oxidizing agent, the N—O ligand is capable of preventing the deposition of ruthenium species having an oxidation state of IV or higher on the surface of the substrate, and concomitantly is capable of forming a soluble Ru(II) N—O coordination complex with oxidized ruthenium formed during CMP of the substrate.
4. The method of claim 3 wherein the particulate abrasive is present in the composition at a concentration in the range of about 1 to about 10 percent by weight.
5. The method of claim 3 wherein the N—O ligand is present in the composition at a concentration in the range of about 0.01 to about 0.5 percent by weight.
6. The method of claim 3 wherein the particulate abrasive is alpha-alumina.
7. The method of claim 3 wherein the N—O ligand comprises a nitroxide compound selected from the group consisting of 2,2,6,6-tetramethylpiperidinel-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, an imino nitroxide, a nitronyl nitroxide, and a combination thereof.
8. The method of claim 3 wherein the composition further comprises ascorbic acid.
9. The method of claim 8 wherein the ascorbic acid is present in the composition in an amount that is about equimolar to the amount of N—O ligand in the composition.
10. The method of claim 3 wherein the oxidizing agent comprises hydrogen peroxide.
11. The method of claim 10 wherein the hydrogen peroxide is present at a concentration in the range of about 1 to about 5 percent by weight, based on the combined weight of the composition and hydrogen peroxide.
12. A chemical-mechanical polishing (CMP) method for selectively removing dioxide from the surface of a substrate in preference to ruthenium, the method comprising the steps of:
(a) contacting a surface of a substrate comprising ruthenium and silicon dioxide with a polishing pad and an aqueous CMP composition in the presence of an oxidizing agent; and
(b) causing relative motion between the substrate and the polishing pad while maintaining a portion of the CMP composition and the oxidizing agent in contact with the surface between the pad and the substrate for a period of time sufficient to abrade at least a portion of the ruthenium present in the substrate from the surface;
wherein the CMP composition contains a particulate abrasive comprising colloidal silica suspended in an aqueous carrier containing a ruthenium-coordinating oxidized nitrogen ligand (N—O ligand), the N—O ligand comprising a nitroxide compound; and, in the presence of the oxidizing agent, the N—O ligand is capable of preventing the deposition of ruthenium species having an oxidation state of IV or higher on the surface of the substrate, and concomitantly is capable of forthing a soluble Ru(II) N—O coordination complex with oxidized ruthenium formed during CMP of the substrate.
13. The method of claim 12 wherein the particulate abrasive further comprises titania.
14. The method of claim 12 wherein the particulate abrasive is present in the composition at a concentration in the range of about 1 to about 10 percent by weight.
15. The method of claim 12 wherein the N—O ligand is present in the composition at a concentration in the range of about 0.01 to about 0.5 percent by weight.
16. The method of claim 12 wherein the N—O ligand comprises a nitroxide compound selected from the group consisting of 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, an imino nitroxide, a nitronyl nitroxide, and a combination thereof.
17. The method of claim 12 wherein the composition further comprises ascorbic acid.
18. The method of claim 17 wherein the ascorbic acid is present in the composition in an amount that is about equimolar to the amount of N—O ligand in the composition.
19. The method of claim 12 wherein the oxidizing agent comprises hydrogen peroxide.
20. The method of claim 19 wherein the hydrogen peroxide is present at a concentration in the range of about 1 to about 5 percent by weight, based on the combined weight of the composition and the hydrogen peroxide.