# US 10,373,842 B2 · Composition and method used for chemical mechanical planarization of metals > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,373,842 B2 - Document ID: US10373842B2 - Status: Granted - Kind: B2 - Application number: 14/947,711 - Filed: 2015-11-20 - Published: 2016-03-17 - Granted: 2019-08-06 - Earliest claimed: 2003-01-03 - Assignees: Versum Materials US, LLC - Applicants: Versum Materials US, LLC - Inventors: Song Y. Chang; Mark Evans; Dnyanesh Chandrakant Tamboli; Stephen W. Hymes - Web page: https://patentgrep.com/patent/US10373842B2 ## CPC - H10P 52/403: {of conductive or resistive materials} - B24B 37/044: {characterised by the composition of the lapping agent} - C09G 1/02: containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)} - C09K 3/1463: {Aqueous liquid suspensions} - H10W 20/062: {by smoothing of conductive parts, e.g. by planarisation} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - B24B: MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING (grinding of gear teeth B23F, of screw-threads B23G1/36; by electro-erosion B23H; abrasive or related blasting B24C; tools for grinding, buffing or sharpening B24D; polishing compositions C09G1/00; abrasives C09K3/14; electrolytic etching or polishing C25F3/00; grinding arrangements for use on assembled railway tracks E01B31/17); DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS - C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10 ## Abstract Compositions for use in CMP processing and methods of CMP processing. The composition utilizes low levels of particulate material, in combination with at least one amino acid, at least one oxidizer, and water to remove a metal layer such as one containing copper to a stop layer with high selectivity. ## Claims ### Claim 1 A composition for use in removing copper from a surface of a wafer containing the copper laying above a stop layer consisting essentially of: 1) an oxidizing agent; 2) about 0.05% to about 5% by weight an amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof; 3) about 5 ppm to less than 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof; 4) at least one corrosion inhibitor; and 5) water; wherein the particulate material has a particle size in the range of about 4 nm to about 10,000 nm; and the composition facilitates removal of copper from the wafer surface while maintaining a rate of removal of copper to stop layer of at least 50:1. ### Claim 2 (depends on 1) The composition of claim 1 wherein the oxidizing agent is hydrogen peroxide and the amino acid is aminoacetic acid. ### Claim 3 (depends on 1) The composition of claim 1 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof. ### Claim 4 (depends on 1) The composition of claim 1 having a pH in a range between about 3.5 and about 9. ### Claim 5 (depends on 1) The composition of claim 1 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm. ### Claim 6 (depends on 1) The composition of claim 1, wherein the corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; I-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof. ### Claim 7 (depends on 6) The composition of claim 6 wherein the oxidizing agent is hydrogen peroxide; the amino acid is aminoacetic acid; and the corrosion inhibitor is 1,2,4-triazole. ### Claim 8 A composition for use in removing copper from a surface of a wafer containing the copper laying above a stop layer consisting of: hydrogen peroxide; about 0.05% to about 5% by weight at least one amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof; about 5 ppm to about 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof; about 0.05% to about 5% by weight a corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; l-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof; and water; wherein the particulate material has a particle size in the range of about 4 nm to about 1000 nm; the composition has a pH in a range between about 3.5 and about 9; and the composition facilitates removal of the copper from the wafer surface while maintaining a rate of removal of copper to stop layer of at least 50:1. ### Claim 9 (depends on 8) The composition of claim 8 wherein the amino acid is aminoacetic acid. ### Claim 10 (depends on 8) The composition of claim 8 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof. ### Claim 11 (depends on 8) The composition of claim 8 wherein the composition maintains a rate of removal of copper to stop layer of at least 100:1. ### Claim 12 (depends on 8) The composition of claim 8 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm. ### Claim 13 (depends on 8) The composition of claim 8 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 100 ppm. ### Claim 14 (depends on 8) The composition of claim 8 wherein the particulate material has a particle size in the range of about 4 nm to about 400 nm. ### Claim 15 A chemical mechanical planarization (CMP) system for polishing a wafer, comprising 1) the wafer having at least one surface comprising copper laying above a stop layer; 2) a polishing pad; 3) a CMP composition consisting essentially of: a) an oxidizing agent; b) about 0.05% to about 5% by weight at least one amino acid selected from the group consisting of aminoacetic acid, serine, glutamine, L-alanine, DL-alanine, iminoacetic acid, asparagine, aspartic acid, valine, sarcosine, and mixtures thereof; c) about 5 ppm to about 700 ppm by weight particulate material selected from the group consisting of fumed silica, colloidal silica, fumed alumina, colloidal alumina, cerium oxide, titanium dioxide, zirconium oxide, polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof; d) about 0.05% to about 5% by weight a corrosion inhibitor selected from the group consisting of 1,2,3-triazole; 1,2,4-triazole; 4-amino-4H-1,2,4-triazole; benzotriazole; 1,2,3-benzotriazole; 5-methylbenzotriazole; l-hydroxybenzotriazole; 4-hydroxybenzotriazole and combinations thereof; and e) water; wherein the particulate material has a particle size in the range of about 4 nm to about 1000 nm; the composition has a pH in a range between about 3.5 and about 9; and the composition facilitates removal of the copper from the surface of the wafer while maintaining a rate of removal of copper to stop layer of at least 50:1; wherein the copper is in contact with the polishing pad and the CMP composition; and the CMP composition facilitates removal of copper while maintaining a rate of removal of copper to stop layer of at least 50:1. ### Claim 16 (depends on 15) The system of claim 15 wherein the oxidizing agent is hydrogen peroxide and the amino acid is aminoacetic acid. ### Claim 17 (depends on 15) The system of claim 15 wherein the particulate material is selected from the group consisting of polystyrene, polymethyl methacrylate, mica, hydrated aluminum silicate, and mixtures thereof. ### Claim 18 (depends on 15) The system of claim 15 having a pH in a range between about 3.5 and about 9. ### Claim 19 (depends on 15) The system of claim 15 having a pH of about 6.6 and the particulate material has a concentration in the range of about 5 ppm to about 400 ppm. ### Claim 20 (depends on 15) The composition of claim 15 wherein the oxidizing agent is hydrogen peroxide; the amino acid is aminoacetic acid; and the corrosion inhibitor is 1,2,4-triazole.