WO2012098933A1 - Agent de polissage, procédé de polissage et procédé de fabrication d'un dispositif de circuit intégré de semi-conducteur - Google Patents
Agent de polissage, procédé de polissage et procédé de fabrication d'un dispositif de circuit intégré de semi-conducteur Download PDFInfo
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- WO2012098933A1 WO2012098933A1 PCT/JP2012/050070 JP2012050070W WO2012098933A1 WO 2012098933 A1 WO2012098933 A1 WO 2012098933A1 JP 2012050070 W JP2012050070 W JP 2012050070W WO 2012098933 A1 WO2012098933 A1 WO 2012098933A1
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- Prior art keywords
- polishing
- polished
- water
- abrasive
- integrated circuit
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 238
- 239000004065 semiconductor Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 44
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 34
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000007514 bases Chemical class 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229920005646 polycarboxylate Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000007513 acids Chemical class 0.000 description 7
- 239000003082 abrasive agent Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000006061 abrasive grain Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007517 polishing process Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- -1 nonionic Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 235000019423 pullulan Nutrition 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Definitions
- the present invention relates to an abrasive used in a manufacturing process of a semiconductor integrated circuit device, a polishing method, and a method of manufacturing a semiconductor integrated circuit device. More particularly, the present invention relates to a polishing agent and a polishing method suitable for planarizing a surface to be polished including a silicon nitride film used in a semiconductor integrated circuit device, and a method for manufacturing a semiconductor integrated circuit device using the polishing method.
- CMP chemical mechanical polishing method
- CMP is an indispensable technique for preventing the problem that a high resolution cannot be obtained.
- the CMP includes planarization of an inter-film insulating film (ILD film: Inter-Level Dielectrics), shallow trench isolation (STI), tungsten plug formation, and a multi-layer consisting of copper and a low dielectric constant film. It is used in the film wiring formation process.
- ILD film Inter-Level Dielectrics
- STI shallow trench isolation
- tungsten plug formation tungsten plug formation
- multi-layer consisting of copper and a low dielectric constant film It is used in the film wiring formation process.
- the silicon nitride film is a chemically and mechanically stable material, and flattening by CMP is difficult.
- the present invention has been made to solve these problems, and is suitable for chemically and mechanically polishing a surface to be polished including a silicon nitride film in the manufacture of a semiconductor integrated circuit device.
- An object of the present invention is to provide an abrasive and a polishing method capable of polishing on a highly flat surface.
- the present invention provides an abrasive and a polishing method for chemical mechanical polishing used for manufacturing a semiconductor integrated circuit device having the following configuration, and a method for manufacturing a semiconductor integrated circuit device.
- An abrasive for chemical mechanical polishing for polishing a surface to be polished in the manufacture of a semiconductor integrated circuit device which contains cerium oxide particles, a water-soluble polymer, a basic compound, and water.
- a polishing agent characterized in that the ratio of the water-soluble polymer to 100 parts by mass of the cerium oxide particles is 5 to 30 parts by mass, and the pH is in the range of 9.7 or more and less than 12.
- [5] The abrasive according to any one of [1] to [4], which contains the cerium oxide particles in a proportion of 0.1 to 5.0% by mass with respect to the total mass of the abrasive.
- [6] The abrasive according to any one of [1] to [5], wherein the surface to be polished includes a silicon nitride film surface.
- a polishing method for a surface to be polished in which a polishing agent is supplied to a polishing pad, the surface to be polished of a semiconductor integrated circuit device is brought into contact with the polishing pad, and polished by relative movement between the two.
- a polishing method wherein the polishing surface includes a silicon nitride film surface, and the polishing agent according to any one of [1] to [6] is used as the polishing agent.
- a method for manufacturing a semiconductor integrated circuit device comprising a step of polishing a surface to be polished by the polishing method according to [7].
- a first liquid containing cerium oxide particles, a water-soluble polymer, and water, and a second liquid containing a basic compound and water are mixed immediately before use, and [1] to [6]
- the surface to be polished when the surface to be polished is subjected to chemical mechanical polishing in the manufacture of a semiconductor integrated circuit device, the surface to be polished including the silicon nitride film is made higher.
- the surface can be polished to a flat surface at high speed.
- the abrasive of the present invention is a chemical mechanical polishing abrasive for polishing a surface to be polished of a semiconductor integrated circuit device (hereinafter also simply referred to as a semiconductor device), comprising cerium oxide particles, a water-soluble polymer, And a basic compound and water, the ratio of the water-soluble polymer to 100 parts by mass of the cerium oxide particles is 5 to 30 parts by mass, and the pH is in the range of 9.7 or more and less than 12.
- the polishing agent of the present invention When the polishing agent of the present invention is used, the protrusion of the silicon nitride film can be easily removed when the surface to be polished of the semiconductor device includes the surface to be polished of the silicon nitride film. Also, the polishing rate is fast. This is because when polishing the silicon nitride film using the polishing agent of the present invention, the rate of increase in the polishing rate relative to the increase in the polishing pressure is higher in the range where the polishing pressure is higher than in the range where the polishing pressure is low. . Therefore, in the semiconductor device manufacturing process, when the polished surface of the uneven silicon nitride film is polished, the convex portion can be preferentially polished, and a highly flat polished surface can be easily formed at high speed.
- polishing agent of this invention is especially useful when the to-be-polished surface of a semiconductor device is a silicon nitride film which does not have a polishing stop layer in the lower layer. Two or more silicon nitride films may be included in one semiconductor device.
- the “surface to be polished” means an intermediate surface that appears in the process of manufacturing a semiconductor device.
- cerium oxide particles are used as the abrasive grains in the abrasive.
- a cerium oxide powder obtained by adding an alkali to a cerium (IV) ammonium nitrate aqueous solution to produce a cerium hydroxide gel, filtering, washing and firing can be preferably used.
- cerium oxide particles obtained by pulverizing and firing high-purity cerium carbonate, and further pulverizing and classifying can be preferably used, but are not particularly limited thereto.
- the cerium oxide purity of the cerium oxide particles is preferably 95% by mass or more, and the content of alkali metals and halogens is particularly preferably 10 ppm or less.
- the average particle diameter (diameter) of the cerium oxide particles is preferably 0.01 to 0.5 ⁇ m, particularly 0.02 to 0.3 ⁇ m, and more preferably 0.05 to 0.2 ⁇ m from the viewpoint of polishing characteristics and dispersion stability. . If the average particle size is too large, scratches such as scratches may easily occur on the surface to be polished of the semiconductor device (for example, the surface of the semiconductor substrate). If the average particle size is too small, not only the polishing rate may be lowered, but also the ratio of the surface area per unit volume increases, so it is easily affected by the surface condition, and depending on conditions such as pH and additive concentration Aggregates easily. When aggregation occurs, polishing scratches such as scratches are likely to occur on the surface to be polished of the semiconductor device. In this specification, the average particle diameter means a numerical value measured by a laser diffraction scattering method.
- the concentration (content ratio) of the cerium oxide particles in the polishing agent of the present invention is such that the polishing target surface of the semiconductor device, particularly the silicon nitride film surface, is polished at a high speed to a highly flat surface.
- the mass ratio of the cerium oxide particles to is preferably in the range of 0.1 to 5.0 mass%, more preferably in the range of 0.2 to 2.0 mass%.
- the abrasive of the present invention contains a water-soluble polymer.
- the water-soluble polymer refers to a water-soluble polymer in a polishing agent containing water, a polymer having a predetermined concentration and other components, when the polymer is completely dissolved in the polishing agent.
- the water-soluble polymer used in the present invention is preferably a water-soluble polymer that dissolves in pure water at 1% by mass or more, more preferably 5% by mass or more.
- water-soluble polymer examples include polycarboxylic acid, polycarboxylate, polyvinyl pyrrolidone, polyvinyl alcohol, polyalkylene oxides, polystyrene sulfonate, polystyrene sulfonate, water-soluble polysaccharide, and water-soluble polyamine. It is done.
- polyalkylene oxides include polyethylene glycol, polypropylene glycol, and polyethylene glycol / polypropylene glycol copolymers.
- water-soluble polysaccharide include carboxyethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, pullulan, and dextrin.
- water-soluble polyamine examples include water-soluble polyether polyamine, water-soluble polyalkylene polyamine, polyethyleneimine, water-soluble polyvinylamine, water-soluble polyallylamine, water-soluble polylysine and water-soluble chitosan.
- the water-soluble polymer used in the present invention is preferably a polycarboxylic acid and / or a polycarboxylic acid salt.
- the polycarboxylic acid may be any water-soluble compound having a hydrocarbon main chain and a side chain having a carboxyl group (carboxylic acid group).
- a homopolymer of a monomer having an ethylenic double bond and a carboxyl group such as acrylic acid, methacrylic acid, and maleic acid.
- the homopolymer in which some or all of the carboxyl groups of such polycarboxylic acids are salts such as ammonium salts.
- Polyacrylic acid and polyacrylate are preferable from the viewpoint of price and availability.
- polycarboxylic acids and polycarboxylic acid salts are collectively referred to as polycarboxylic acids.
- the molecular weight of the polycarboxylic acids is not limited as long as the molecular weight is in the range having water solubility, but the mass average molecular weight is preferably in the range of 100 to 100,000, and preferably in the range of 100 to 20000. More preferred. When the mass average molecular weight is less than 100, the non-linearity of the polishing rate with respect to the polishing pressure described below hardly appears, and sufficient polishing performance may not be obtained. If the mass average molecular weight exceeds 100,000, even if it is water-soluble, it may adversely affect physical properties such as the fluidity of the abrasive.
- Particularly preferred polycarboxylic acids are polyacrylic acid and polyacrylic acid salt having a mass average molecular weight of 100 to 20,000.
- the content of the water-soluble polymer, preferably polycarboxylic acids, in the abrasive of the present invention is in the range of 5 to 30 parts by mass with respect to 100 parts by mass of cerium oxide contained in the abrasive.
- the content of the water-soluble polymer is appropriately set within the above range in consideration of polishing characteristics, uniformity of the abrasive slurry, the weight average molecular weight of the water-soluble polymer, and the like.
- the non-linearity means that the rate of increase of the polishing rate with respect to the increase of the polishing pressure is higher in the range where the polishing pressure is higher than in the range where the polishing pressure is low. Further, a sufficient flattening effect can be obtained in eliminating the level difference on the surface to be polished.
- the ratio of the water-soluble polymer, preferably polycarboxylic acids, to 100 parts by mass of cerium oxide contained in the abrasive is preferably in the range of 6 to 28 parts by mass, and in the range of 8 to 22 parts by mass. It is more preferable.
- the abrasive of the present invention contains a basic compound.
- the basic compound is a component that is mainly blended for the purpose of adjusting the pH of the abrasive within the range of the present invention.
- a basic compound used for pH adjustment or the like in a CMP abrasive can be used without any particular limitation.
- at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia and a quaternary ammonium salt can be exemplified.
- potassium hydroxide is particularly preferable because the amount added during pH adjustment can be reduced.
- polishing agent of this invention is an quantity from which the pH of an abrasive
- the water contained in the abrasive of the present invention is a solvent for dispersing cerium oxide particles as abrasive grains and dissolving a water-soluble polymer, a basic compound and other optional components.
- the water is not particularly limited, but it is preferable to use pure water, ultrapure water, ion-exchanged water, or the like from the viewpoint of influence on other components, mixing of impurities, and little influence on pH and the like. Since water has a function of controlling the fluidity of the abrasive of the present invention, its content can be appropriately set in accordance with the target polishing characteristics such as polishing speed and flattening characteristics.
- the pH range of the polishing agent of the present invention is pH 9.7 or more and 12.0 in consideration of polishing characteristics for the surface to be polished of a semiconductor device, particularly a silicon nitride film, specifically, non-linearity of polishing rate with respect to polishing pressure. Is less than.
- the pH is less than 9.7, the polishing rate for the silicon nitride film is slow, and when it is 12.0 or more, a sufficient polishing rate cannot be obtained.
- the pH is made into the range of 9.8 or more and less than 11.6, it is preferable at the point from which the said grinding
- the above polishing characteristics are, for example, the low pressure when the relationship between the polishing pressure and the polishing rate when the polishing pressure on the surface to be polished is changed is plotted on the graph with the polishing rate as the vertical axis and the polishing pressure as the horizontal axis.
- the ratio of the slope of the polishing rate between the high pressure side and the high pressure side can be evaluated as an index. More specifically, in the above graph, the slope on the low pressure side and the slope on the high pressure side are obtained with a specific polishing pressure as a boundary, and the ratio (slope on the high pressure side) / (slope on the low pressure side) is the ratio. Can be defined as an indicator.
- the polishing pressure that becomes the boundary between the low pressure side and the high pressure side depends on the polishing conditions, but when the silicon nitride film is polished under general polishing conditions using a general polishing apparatus, It can be appropriately selected from the range of 5 to 45 kPa.
- the index that is, (the inclination on the high pressure side) / (the inclination on the low pressure side) is 1.8 or more. This value is more preferably 2.0 or more, and still more preferably 2.3 or more.
- the abrasive of the present invention contains the above-mentioned cerium oxide particles, water-soluble polymer, basic compound and water as essential components in the above-mentioned predetermined amounts, but other components may optionally coexist.
- a typical example is a dispersant for maintaining good dispersibility of the cerium oxide particles.
- anionic, nonionic, cationic surfactants and the like can be used as the dispersant.
- anionic, nonionic, and cationic surfactants include alkylbenzene sulfonic acid, polyvinyl pyrrolidone, and water-soluble polyamine.
- the abrasive of the present invention does not necessarily have to be supplied to the polishing process as a mixture of all the above-mentioned constituent components. Only when supplying it to a grinding
- It can also be divided into a liquid containing cerium oxide particles, optionally a dispersant, a water-soluble polymer and water, and a liquid containing a basic compound and water. Further, the two liquids divided by other division methods may be mixed and used by appropriately adjusting the ratio.
- the first liquid containing cerium oxide particles, a water-soluble polymer and water, and the second liquid containing a basic compound and water are mixed before use, and the above-described abrasive of the present invention. From the viewpoint of the dispersibility of the abrasive, it is preferable to prepare and use this as an abrasive.
- the content ratio of at least the cerium oxide particles and the water-soluble polymer in the first liquid is set as described above. It is the ratio of the invention.
- the ratio which mixes a 1st liquid and a 2nd liquid is adjusted so that pH may become the range of the said invention in the obtained abrasive
- the polishing agent is supplied to the polishing pad, and the semiconductor device A method of polishing a surface to be polished, including the surface to be polished of the silicon nitride film, by bringing the surface to be polished and a polishing pad into contact with each other by relative movement between them is preferable.
- the polishing agent of the present invention when used, the polishing surface including the silicon nitride film has non-linearity in the polishing rate with respect to the polishing pressure. Become.
- polishing agent and polishing method of this invention are especially useful when the to-be-polished surface of a semiconductor device is a silicon nitride film which does not have a polishing stop layer in the lower layer.
- FIG. 1 is a diagram showing an example of a polishing apparatus that can be used in the polishing method of the present invention.
- the polishing apparatus 10 includes a polishing head 2 that holds a semiconductor device 1 including a silicon nitride film, a polishing surface plate 3, a polishing pad 4 attached to the surface of the polishing surface plate 3, and an abrasive agent on the polishing pad 4. And an abrasive supply pipe 6 for supplying 5.
- the polishing apparatus used in the polishing method of the present invention is not limited to such a structure.
- the polishing head 2 may move linearly as well as rotationally. Further, the polishing surface plate 3 and the polishing pad 4 may be as large as or smaller than the semiconductor device 1. In that case, it is preferable that the entire polishing surface of the semiconductor device can be polished by relatively moving the polishing head 2 and the polishing surface plate 3. Furthermore, the polishing surface plate 3 and the polishing pad 4 do not have to perform a rotational motion, and may be, for example, a belt type that moves in one direction.
- the polishing conditions of the polishing apparatus 10 are not particularly limited, but by applying a load to the polishing head 2 and pressing it against the polishing pad 4, the polishing pressure can be further increased and the polishing rate can be improved.
- the polishing pressure is preferably about 0.5 to 50 kPa, and more preferably about 3 to 40 kPa from the viewpoint of polishing surface uniformity of the semiconductor device 1 at the polishing speed, flatness, and prevention of polishing defects such as scratches.
- the rotation speed of the polishing surface plate 3 and the polishing head 2 is preferably about 50 to 500 rpm, but is not limited thereto.
- the amount of the abrasive 5 supplied is appropriately adjusted and selected depending on the material constituting the surface to be polished, the composition of the abrasive, each of the above polishing conditions, etc. For example, when polishing a wafer having a diameter of 200 mm, A supply amount of about 100 to 300 ml / min is preferable.
- the polishing pad 4 may be made of a general nonwoven fabric, foamed polyurethane, porous resin, non-porous resin, or the like. Further, in order to promote the supply of the polishing agent 5 to the polishing pad 4 or to collect a certain amount of the polishing agent 5 on the polishing pad 4, the surface of the polishing pad 4 has a lattice shape, a concentric circle shape, a spiral shape, or the like. Groove processing may be performed.
- the pad conditioner may be brought into contact with the surface of the polishing pad 4 to perform polishing while conditioning the surface of the polishing pad 4.
- the convex portion of the surface to be polished is preferentially polished, and the surface to be polished is highly flattened.
- the surface can be formed easily and at high speed. Therefore, in manufacturing a semiconductor device using the polishing method of the present invention, the cost can be reduced and the throughput can be improved.
- Examples 1 to 9 are examples, and examples 10 to 17 are comparative examples.
- “%” means mass% unless otherwise specified.
- Examples 1 to 17 According to the composition shown in Table 1, cerium oxide particles, water, ammonium polyacrylate as a water-soluble polymer, and potassium hydroxide as a basic compound are weighed (however, Example 15 does not contain ammonium polyacrylate) ), And mixed to prepare the abrasives of Examples 1 to 17. The components used for the preparation of the abrasive were all the same in each example, and the following physical properties of cerium oxide particles and ammonium polyacrylate were used.
- Cerium oxide particles purity 99%, average particle size 0.2 ⁇ m (by laser scattering diffractometer (trade name: LA-920, manufactured by Horiba, Ltd.))
- Ammonium polyacrylate mass average molecular weight (Mw) 5000
- Mw mass average molecular weight
- Polishing characteristics The following tests were conducted using the abrasives obtained in the above examples to evaluate the polishing characteristics.
- Polishing pad 2 membrane pads IC-1400 K-groove (Rohm and Haas) Polishing pad conditioning: MEC100-PH3.5L (Mitsubishi Materials Corporation) Number of rotations of polishing platen: 127 rpm (common to all examples) Number of revolutions of polishing head: 123 rpm (common to all examples) Polishing pressure (P): About each example, it carried out on 4 conditions of 13.8 kPa, 20.7 kPa, 27.6 kPa, and 34.5 kPa.
- Example 2 shows representative graphs of Examples and Comparative Examples (Example: Example 2, Example 8, Comparative Example: Example 11, Example 16). The results are shown in Table 2.
- the index of inclination 2 / inclination 1 the larger the value, the more the convex portion can be selectively polished with respect to the unevenness of the surface to be polished, and the better the polishing characteristics.
- the indices of the inclination 2 / inclination 1 are both 2.3 or more, and the surface to be polished of the silicon nitride film In the range where the polishing pressure is high, it can be seen that the rate of increase in the polishing rate relative to the increase in the polishing pressure is higher in each stage and the polishing performance is higher than in the range where the polishing pressure is low.
- all of the polishing agents of Examples 10 to 17 which are comparative examples have an index of the inclination 2 / inclination 1 of 1.5 or less, and the convex portions are preferentially given to the polished surface of the silicon nitride film. It can be seen that polishing characteristics are low and high planarization is not easy.
- the polishing agent and polishing method of the present invention are used for chemical mechanical polishing (for CMP) for polishing a silicon nitride film polished surface of a semiconductor integrated circuit device having a silicon nitride film in the manufacture of a semiconductor integrated circuit device.
- CMP chemical mechanical polishing
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
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- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
L'invention concerne un agent de polissage et un procédé de polissage qui sont avantageux pour un polissage chimique et mécanique d'une surface à polir qui comprend un film de nitrure de silicium et avec lesquels une surface ayant une planéité élevée peut être polie avec une vitesse supérieure dans la fabrication d'un dispositif de circuit intégré de semi-conducteur. L'agent de polissage pour un polissage chimique et mécanique d'une surface à polir dans la fabrication d'un dispositif de circuit intégré de semi-conducteur est caractérisé en ce qu'il contient des particules d'oxyde de cérium, un polymère soluble dans l'eau, un composé basique et de l'eau, le rapport du polymère soluble dans l'eau par rapport à 100 parties en masse des particules d'oxyde de cérium étant de 5 à 30 parties en masse et le pH se situant dans la plage de 9,7 à moins de 12. Le procédé de polissage consiste à fournir un agent de polissage à un tampon de polissage, à amener le tampon de polissage et la surface à polir du dispositif de circuit intégré de semi-conducteur en contact l'un avec l'autre et à polir la surface à polir par le déplacement relatif entre les deux, la surface à polir comprenant une surface de film de nitrure de silicium et l'agent de polissage décrit ci-dessus étant utilisé.
Applications Claiming Priority (2)
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JP2011009831 | 2011-01-20 | ||
JP2011-009831 | 2011-04-27 |
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WO2012098933A1 true WO2012098933A1 (fr) | 2012-07-26 |
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PCT/JP2012/050070 WO2012098933A1 (fr) | 2011-01-20 | 2012-01-05 | Agent de polissage, procédé de polissage et procédé de fabrication d'un dispositif de circuit intégré de semi-conducteur |
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TW (1) | TW201237129A (fr) |
WO (1) | WO2012098933A1 (fr) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005048125A (ja) * | 2003-07-31 | 2005-02-24 | Hitachi Chem Co Ltd | Cmp研磨剤、研磨方法及び半導体装置の製造方法 |
JP2006019740A (ja) * | 2004-06-30 | 2006-01-19 | Dongjin Semichem Co Ltd | 化学的機械的研磨スラリー組成物 |
WO2006098141A1 (fr) * | 2005-03-16 | 2006-09-21 | Asahi Glass Company, Limited | Abrasif pour dispositif de circuit integre a semi-conducteurs, procede pour polir ledit dispositif et procede de fabrication dudit dispositif |
JP2010153576A (ja) * | 2008-12-25 | 2010-07-08 | Asahi Glass Co Ltd | 半導体集積回路装置用研磨剤、研磨方法および半導体集積回路装置の製造方法 |
-
2012
- 2012-01-05 WO PCT/JP2012/050070 patent/WO2012098933A1/fr active Application Filing
- 2012-01-11 TW TW101101141A patent/TW201237129A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005048125A (ja) * | 2003-07-31 | 2005-02-24 | Hitachi Chem Co Ltd | Cmp研磨剤、研磨方法及び半導体装置の製造方法 |
JP2006019740A (ja) * | 2004-06-30 | 2006-01-19 | Dongjin Semichem Co Ltd | 化学的機械的研磨スラリー組成物 |
WO2006098141A1 (fr) * | 2005-03-16 | 2006-09-21 | Asahi Glass Company, Limited | Abrasif pour dispositif de circuit integre a semi-conducteurs, procede pour polir ledit dispositif et procede de fabrication dudit dispositif |
JP2010153576A (ja) * | 2008-12-25 | 2010-07-08 | Asahi Glass Co Ltd | 半導体集積回路装置用研磨剤、研磨方法および半導体集積回路装置の製造方法 |
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