# US 2016/0237315 A1 · Dishing reducing in tungsten chemical mechanical polishing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2016/0237315 A1 - Document ID: US20160237315A1 - Status: Published application - Kind: A1 - Application number: 15/014,210 - Filed: 2016-02-03 - Published: 2016-08-18 - Earliest claimed: 2015-02-12 - Assignees: Air Products and Chemicals, Inc. - Applicants: Air Products and Chemicals, Inc. - Inventors: Matthias Stender; Blake J. Lew; Xiaobo Shi - Web page: https://patentgrep.com/patent/US20160237315A1 ## CPC - C09G 1/02: containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)} - B24B 37/20: Lapping pads for working plane surfaces - C09G 1/04: Aqueous dispersions (C09G1/02 takes precedence) - C09K 3/1445: {the coating consisting exclusively of metals} - C09K 3/1463: {Aqueous liquid suspensions} - C23F 1/26: for etching refractory metals - H10P 52/403: {of conductive or resistive materials} - C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES - 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 - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25 - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 ## Abstract This invention pertains to slurries, methods and systems that can be used in chemical mechanical planarization (CMP) of tungsten containing semiconductor device. Additives are used to reduce the dishing on large and small feature sizes (large bond pad as well as fine line structures) without retarding the tungsten removal rate. ## Claims ### Claim 1 A polishing composition comprising: 0.01 wt % to 30 wt % of abrasive; 0.01 wt % to 30 wt % of at least one oxidizing agent; 0.0005 wt % to about 10 wt % of activator; 0.1 ppm to 10,000 ppm of additive; pH adjusting agent; and remaining being water; wherein the abrasive is selected from the group consisting of colloidal silica, fumed silica, alumina, titania, ceria, zirconia, surface modified particles selected from the group consisting of activator-containing particles, composite particles, and lattice doped and inorganic oxide particles; and combinations thereof; the oxidizing agent is selected from the group consisting of peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, ammonium peroxymonosulfate; and non-per-oxy compound selected from the group consisting of ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; the activator is selected from the group consisting of (1) inorganic oxide particle with transition metal coated onto its surface; and the transition metal is selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) soluble catalyst selected from the group consisting of ammonium iron (III) oxalate trihydrate, iron(III) citrate tribasic monohydrate, iron(III) acetylacetonate and ethylenediamine tetraacetic acid, iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; the additive is selected from the group consisting of sarcosinate, sarcosinates related carboxylic compound, hydrocarbon substituted sarcosinate; organic polymer and copolymer having molecules containing ethylene oxide repeating units; ethoxylated surfactant; and combinations thereof; the pH adjusting agent is selected from the group consisting of amine, ammonium hydroxide, nitric acid, phosphoric acid, sulfuric acid, organic acid, and/or salt thereof, and combinations thereof; and pH of the composition is between 2 and 10. ### Claim 2 (depends on 1) The polishing composition of claim 1, wherein the sarcosinate is selected from the group consisting of cocoyl, lauroyl, myristoyl, oleoyl, stearoyl sarcosinate, and combinations thereof; the sarcosinates related carboxylic compound is selected from the group consisting of unsaturated salt of fatty acid selected from the group consisting of myristoleic, palmitoleic, sapienic, oleic, elaidic, vaccenic, linoleic, linoelaidic, α-linolenic, arachidocnic, eicosapentaenoic, erucic decosahexaenoic acid; and salt of saturated fatty acid selected from the group consisting of sodium, potassium, or ammonia salts of stearate, caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric and cerotic acid; and combinations thereof; the hydrocarbon substituted sarcosinate has a substituent selected from the group consisting of an alkyl, alkenyl or alkynyl, having ranging from 1 carbon atom for the alkyl substituent, 2 carbon atoms for the alkenyl, or 3 up to 24 carbon atoms for alkynyl substituent, wherein the number of double bonds for the alkenyl substituent or the number of triple bonds for the alkynyl substituent is up to 4. ### Claim 3 (depends on 1) The polishing composition of claim 1, wherein the organic polymer and copolymer have molecules containing ethylene oxide repeating units is polyoxyethylene (POE), polyethylene oxide (PEO), or polyethylene glycol (PEG); wherein the polyethylene oxide (PEO) has the general molecular structure of wherein n refers to the total numbers of the repeating unit ranging from 4 to 113636. ### Claim 4 (depends on 1) The polishing composition of claim 1, wherein the ethoxylated surfactant is selected from the group consisting of alkyl phenol ethoxylate, fatty alcohol ethoxylate, fatty amine ethoxylate, propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, and combinations thereof. ### Claim 5 (depends on 1) The polishing composition of claim 1, wherein the additive is selected from the group consisting of polyethylene oxide (PEO), oleoyl sarcosinate, N-Lauroylsarcosinate, fatty alcohol ethoxylate, fatty amine ethoxylate, propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, and combinations thereof; ### Claim 6 (depends on 1) The polishing composition of claim 1 comprises colloidal silica; iron coated silica particle or ammonium iron (III) oxalate trihydrate; hydrogen peroxide; one selected from the group consisting of propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, oleoyl sarcosinate, N-Lauroylsarcosinate, and combination thereof, and the pH is between 6 and 8. ### Claim 7 (depends on 1) The polishing composition of claim 1 further comprises biocide ranging from 0.0001 wt % to 0.03 wt %. ### Claim 8 (depends on 1) The polishing composition of claim 1 further comprises at least one selected from the group consisting of surfactant; stabilizing and passivating agent; dispersion agent; chelator; film-forming anticorrosion agent; a polish enhancement agent; and combinations thereof. ### Claim 9 A system for chemical mechanical planarization, comprising: a semiconductor substrate comprising at least one surface containing tungsten; a polishing pad; and a polishing composition comprising: 0.01 wt % to 30 wt % of abrasive; 0.01 wt % to 30 wt % of at least one oxidizing agent; 0.0005 wt % to about 10 wt % of activator; 0.1 ppm to 10,000 ppm of additive; pH adjusting agent; and remaining being water; wherein the abrasive is selected from the group consisting of colloidal silica, fumed silica, alumina, titania, ceria, zirconia, surface modified particles selected from the group consisting of activator-containing particles, composite particles, and lattice doped and inorganic oxide particles; and combinations thereof; the oxidizing agent is selected from the group consisting of peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, ammonium peroxymonosulfate; and non-per-oxy compound selected from the group consisting of ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; the activator is selected from the group consisting of (1) inorganic oxide particle with transition metal coated onto its surface; and the transition metal is selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) soluble catalyst selected from the group consisting of ammonium iron (III) oxalate trihydrate, iron(III) citrate tribasic monohydrate, iron(III) acetylacetonate and ethylenediamine tetraacetic acid, iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; the additive is selected from the group consisting of sarcosinate and related carboxylic compound, hydrocarbon substituted sarcosinate; organic polymer and copolymer having molecules containing ethylene oxide repeating units; ethoxylated surfactant; and combinations thereof; the pH adjusting agent is selected from the group consisting of amine, ammonium hydroxide, nitric acid, phosphoric acid, sulfuric acid, organic acid, and/or salt thereof, and combinations thereof; and pH of the composition is between 2 and 10; wherein the at least one surface containing tungsten is in contact with the polishing pad and the polishing composition. ### Claim 10 (depends on 9) The system of claim 9, wherein the sarcosinate is selected from the group consisting of cocoyl, lauroyl, myristoyl, oleoyl, stearoyl sarcosinate, and combinations thereof; the sarcosinates related carboxylic compound is selected from the group consisting of unsaturated salt of fatty acid selected from the group consisting of myristoleic, palmitoleic, sapienic, oleic, elaidic, vaccenic, linoleic, linoelaidic, α-linolenic, arachidocnic, eicosapentaenoic, erucic decosahexaenoic acid; and salt of saturated fatty acid selected from the group consisting of sodium, potassium, or ammonia salts of stearate, caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric and cerotic acid; and combinations thereof; the hydrocarbon substituted sarcosinate has a substituent selected from the group consisting of an alkyl, alkenyl or alkynyl, having ranging from 1 carbon atom for the alkyl substituent, 2 carbon atoms for the alkenyl, or 3 up to 24 carbon atoms for alkynyl substituent, wherein the number of double bonds for the alkenyl substituent or the number of triple bonds for the alkynyl substituent is up to 4. ### Claim 11 (depends on 9) The system of claim 9, wherein the organic polymer and copolymer having molecules containing ethylene oxide repeating units is polyoxyethylene (POE), polyethylene oxide (PEO), or polyethylene glycol (PEG); wherein the polyethylene oxide (PEO) has the general molecular structure of wherein n refers to the total numbers of the repeating unit ranging from 4 to 113636. ### Claim 12 (depends on 9) The system of claim 9, wherein the ethoxylated surfactant is selected from the group consisting of alkyl phenol ethoxylate, fatty alcohol ethoxylate, fatty amine ethoxylate, propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, and combinations thereof. ### Claim 13 (depends on 9) The system of claim 9, wherein the polishing composition comprises colloidal silica; iron coated silica particle or ammonium iron (III) oxalate trihydrate; hydrogen peroxide; one selected from the group consisting of propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, oleoyl sarcosinate, N-Lauroylsarcosinate, and combination thereof, and the pH is between 6 and 8. ### Claim 14 (depends on 9) The system of claim 9, wherein the polishing composition further comprises at least one selected from the group consisting of biocide ranging from 0.0001 wt % to 0.03 wt %; surfactant; stabilizing and passivating agent; dispersion agent; chelator; film-forming anticorrosion agent; a polish enhancement agent; and combinations thereof. ### Claim 15 A polishing method for chemical mechanical planarization of a semiconductor substrate comprising at least one surface containing tungsten, comprising the steps of: contacting the at least one surface containing tungsten with a polishing pad; delivering a polishing composition to the surface, the polishing composition comprising: 0.01 wt % to 30 wt % of abrasive; 0.01 wt % to 30 wt % of at least one oxidizing agent; 0.0005 wt % to about 10 wt % of activator; 0.1 ppm to 10,000 ppm of additive; pH adjusting agent; and remaining being water; wherein the abrasive is selected from the group consisting of colloidal silica, fumed silica, alumina, titania, ceria, zirconia, surface modified particles selected from the group consisting of activator-containing particles, composite particles, and lattice doped and inorganic oxide particles; and combinations thereof; the oxidizing agent is selected from the group consisting of peroxy compound selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, propaneperoxoic acid, substituted or unsubstituted butaneperoxoic acid, hydroperoxy-acetaldehyde, potassium periodate, ammonium peroxymonosulfate; and non-per-oxy compound selected from the group consisting of ferric nitrite, KClO4, KBrO4, KMnO4; and combinations thereof; the activator is selected from the group consisting of (1) inorganic oxide particle with transition metal coated onto its surface; and the transition metal is selected from the group consisting of Fe, Cu, Mn, Co, Ce, and combinations thereof; (2) soluble catalyst selected from the group consisting of ammonium iron (III) oxalate trihydrate, iron(III) citrate tribasic monohydrate, iron(III) acetylacetonate and ethylenediamine tetraacetic acid, iron (III) sodium salt hydrate; (3) a metal compound having multiple oxidation states selected from the group consisting of Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, V; and combinations thereof; the additive is selected from the group consisting of sarcosinate and related carboxylic compound, hydrocarbon substituted sarcosinate; organic polymer and copolymer having molecules containing ethylene oxide repeating units; ethoxylated surfactant; and combinations thereof; the pH adjusting agent is selected from the group consisting of amine, ammonium hydroxide, nitric acid, phosphoric acid, sulfuric acid, organic acid, and/or salt thereof, and combinations thereof; and pH of the composition is between 2 and 10; and C) polishing the at least one surface containing tungsten with the polishing composition. ### Claim 16 (depends on 15) The polishing method of claim 15, wherein the sarcosinate is selected from the group consisting of cocoyl, lauroyl, myristoyl, oleoyl, stearoyl sarcosinate, and combinations thereof; the sarcosinates related carboxylic compound is selected from the group consisting of unsaturated salt of fatty acid selected from the group consisting of myristoleic, palmitoleic, sapienic, oleic, elaidic, vaccenic, linoleic, linoelaidic, α-linolenic, arachidocnic, eicosapentaenoic, erucic decosahexaenoic acid; and salt of saturated fatty acid selected from the group consisting of sodium, potassium, or ammonia salts of stearate, caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric and cerotic acid; and combinations thereof; the hydrocarbon substituted sarcosinate has a substituent selected from the group consisting of an alkyl, alkenyl or alkynyl, having ranging from 1 carbon atom for the alkyl substituent, 2 carbon atoms for the alkenyl, or 3 up to 24 carbon atoms for alkynyl substituent, wherein the number of double bonds for the alkenyl substituent or the number of triple bonds for the alkynyl substituent is up to 4. ### Claim 17 (depends on 15) The polishing method of claim 15, wherein the organic polymer and copolymer having molecules containing ethylene oxide repeating units is polyoxyethylene (POE), polyethylene oxide (PEO), or polyethylene glycol (PEG); wherein the polyethylene oxide (PEO) has the general molecular structure of wherein n refers to the total numbers of the repeating unit ranging from 4 to 113636. ### Claim 18 (depends on 15) The polishing method of claim 15, wherein the ethoxylated surfactant is selected from the group consisting of alkyl phenol ethoxylate, fatty alcohol ethoxylate, fatty amine ethoxylate, propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, and combinations thereof. ### Claim 19 (depends on 15) The polishing method of claim 15, wherein the polishing composition comprises colloidal silica; iron coated silica particle or ammonium iron (III) oxalate trihydrate; hydrogen peroxide; one selected from the group consisting of propylene glycol (PPG)-ethylene glycol (PEG) block copolymer, polyether silicone surfactant, oleoyl sarcosinate, N-Lauroylsarcosinate, and combination thereof, and the pH is between 6 and 8. ### Claim 20 (depends on 19) The polishing method of claim 19, wherein the semiconductor substrate further comprising at least one surface containing TEOS; and the ratio of the removal rates of tungsten (WRR) to TEOS (TEOSRR) is greater than 60. ### Claim 21 (depends on 15) The polishing method of claim 15, wherein the polishing composition further comprises at least one selected from the group consisting of biocide ranging from 0.0001 wt % to 0.03 wt %; surfactant; stabilizing and passivating agent; dispersion agent; chelator; film-forming anticorrosion agent; a polish enhancement agent; and combinations thereof.