TWI808121B - Composition for chemical mechanical polishing and polishing method - Google Patents
Composition for chemical mechanical polishing and polishing method Download PDFInfo
- Publication number
- TWI808121B TWI808121B TW108103358A TW108103358A TWI808121B TW I808121 B TWI808121 B TW I808121B TW 108103358 A TW108103358 A TW 108103358A TW 108103358 A TW108103358 A TW 108103358A TW I808121 B TWI808121 B TW I808121B
- Authority
- TW
- Taiwan
- Prior art keywords
- chemical mechanical
- polishing
- composition
- mechanical polishing
- acid
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 196
- 239000000126 substance Substances 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 82
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract description 37
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000227 grinding Methods 0.000 claims description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 16
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 6
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 abstract description 12
- 231100000331 toxic Toxicity 0.000 abstract description 6
- 230000002588 toxic effect Effects 0.000 abstract description 6
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- 238000005187 foaming Methods 0.000 description 4
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- 238000004438 BET method Methods 0.000 description 3
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- 235000001014 amino acid Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
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- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 235000011054 acetic acid Nutrition 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 235000010233 benzoic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; 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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明提供一種抑制對人體毒性強的四氧化釕的產生，並且穩定性亦優異，可對半導體基板（尤其是含釕膜的基板）進行高速研磨且可減少被研磨面的研磨損傷的化學機械研磨用組成物及使用其的研磨方法。本發明的化學機械研磨用組成物含有（A）氧化鋁修飾氧化鈦粒子、以及（B）聚(甲基)丙烯酸，且pH為7以上、13以下。The present invention provides a composition for chemical mechanical polishing that suppresses the production of ruthenium tetroxide, which is highly toxic to the human body, has excellent stability, can perform high-speed polishing on semiconductor substrates (especially substrates containing ruthenium films), and can reduce polishing damage on the surface to be polished, and a polishing method using the same. The chemical mechanical polishing composition of the present invention contains (A) alumina-modified titanium oxide particles and (B) poly(meth)acrylic acid, and has a pH of 7 or more and 13 or less.
Description
本發明是有關於一種化學機械研磨用組成物及使用其的研磨方法。 The invention relates to a composition for chemical mechanical polishing and a polishing method using the same.
隨著半導體積體電路的製造技術的提高，要求半導體元件的高積體化、高速動作。伴隨於此，半導體元件的微細電路的製造步驟中所要求的半導體基板表面的平坦性變得更加嚴格，化學機械研磨(Chemical Mechanical Polishing，CMP)成為半導體元件的製造步驟中必不可少的技術。 With the improvement of the manufacturing technology of semiconductor integrated circuits, high integration and high-speed operation of semiconductor elements are required. Along with this, the flatness of the surface of the semiconductor substrate required in the manufacturing process of the microcircuit of the semiconductor device has become more stringent, and chemical mechanical polishing (CMP) has become an indispensable technique in the manufacturing process of the semiconductor device.
CMP是一種一邊將含有研磨粒或試劑的研磨組成物供給至研磨墊上，一邊將半導體基板推壓至黏貼於壓盤上的研磨墊，使半導體基板與研磨墊相互滑動，對半導體基板進行化學及機械研磨的技術。於CMP中，可藉由利用試劑的化學反應及利用研磨粒的機械研磨來磨削半導體基板表面的凹凸而使其表面平坦化。 CMP is a technique for chemically and mechanically polishing a semiconductor substrate by supplying a polishing composition containing abrasive grains or reagents to the polishing pad, pushing the semiconductor substrate to the polishing pad attached to the platen, and sliding the semiconductor substrate and the polishing pad against each other. In CMP, the surface of the semiconductor substrate can be planarized by grinding the unevenness of the surface of the semiconductor substrate by chemical reaction of reagents and mechanical polishing by abrasive grains.
於微細化發展的半導體市場中，目前，電路線寬10nm級別的前端節點的半導體基板已成為主流。而且，為了實現電路線寬10nm級別以下的微細配線，研究了藉由對銅膜的基底施加低電阻且與銅的相容性良好的釕膜來改善銅膜的埋入性的技術。 In the miniaturized semiconductor market, at present, front-end node semiconductor substrates with a circuit line width of 10nm have become the mainstream. In addition, in order to realize fine wiring with a circuit line width of 10nm or less, a technique of improving the embedment of the copper film by applying a ruthenium film with low resistance and good compatibility with copper to the base of the copper film has been studied.
於此種背景下，研究了一種用以藉由CMP來對作為下一代半導體材料的釕膜進行平坦化的釕膜研磨用組成物(漿料)(例如，參照專利文獻1~專利文獻2)。作為此種釕膜研磨用組成物，為了提高釕膜的研磨速度，研究了併用氧化鋁或氧化鈦等研磨粒及氧化劑的漿料。 Under such a background, a ruthenium film polishing composition (slurry) for planarizing a ruthenium film as a next-generation semiconductor material by CMP has been studied (for example, refer to Patent Document 1 to Patent Document 2). As such a composition for polishing a ruthenium film, a slurry in which abrasive grains such as alumina or titanium oxide are used in combination with an oxidizing agent has been studied in order to increase the polishing rate of the ruthenium film.
[專利文獻1]日本專利特表2009-514219號公報 [Patent Document 1] Japanese Patent Application Publication No. 2009-514219
[專利文獻2]日本專利特表2010-535424號公報 [Patent Document 2] Japanese Patent Application Publication No. 2010-535424
然而，於CMP中，為了提高釕膜的研磨速度，需要使用含有高氧化力的氧化劑及/或高硬度的研磨粒的釕膜研磨用組成物。但是，於使用含有高氧化力的氧化劑的釕膜研磨用組成物的CMP中，存在容易產生對人體毒性強的四氧化釕，而阻礙生產製程的課題。另外，於使用含有高硬度的研磨粒的釕膜研磨用組成物的CMP中，存在容易於研磨後的被研磨面上產生研磨損傷的課題。 However, in CMP, in order to increase the polishing rate of the ruthenium film, it is necessary to use a ruthenium film polishing composition containing an oxidizing agent with high oxidizing power and/or abrasive grains with high hardness. However, in CMP using a composition for polishing a ruthenium film containing an oxidizing agent with high oxidizing power, ruthenium tetroxide, which is highly toxic to the human body, is likely to be generated, which hinders the production process. In addition, in CMP using a ruthenium film polishing composition containing high-hardness abrasive grains, there is a problem that polishing damage tends to occur on a surface to be polished after polishing.
進而，於使用氧化鈦粒子作為研磨粒的情況下，由於其表面是化學活性的，因此容易與水、氧、氮等進行反應而發生起泡等，從而存在容易損害生產時的操作性的課題。 Furthermore, in the case of using titanium oxide particles as abrasive grains, since the surface is chemically active, it easily reacts with water, oxygen, nitrogen, etc. to cause foaming and the like, which tends to impair workability during production.
因此，本發明的幾個形態的目的在於提供一種抑制對人體毒性強的四氧化釕的產生，並且穩定性亦優異，可對半導體基 板(尤其是含釕膜的基板)進行高速研磨且可減少被研磨面的研磨損傷的化學機械研磨用組成物及使用其的研磨方法。 Therefore, the purpose of several forms of the present invention is to provide a kind of ruthenium tetroxide that suppresses the generation of strong toxicity to human body, and stability is also excellent, can be used for semiconductor substrate. A composition for chemical mechanical polishing capable of reducing polishing damage on a surface to be polished by high-speed polishing of a plate (especially a substrate containing a ruthenium film) and a polishing method using the same.
本發明是為解決所述課題的至少一部分而成，可作為以下的形態或應用例來實現。 The present invention is made to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.
[應用例1] [Application example 1]
本發明的化學機械研磨用組成物一形態含有：(A)氧化鋁修飾氧化鈦粒子；以及(B)聚(甲基)丙烯酸，且pH為7以上、13以下。 One form of the chemical mechanical polishing composition of the present invention contains: (A) alumina-modified titanium oxide particles; and (B) poly(meth)acrylic acid, and has a pH of 7 to 13.
[應用例2] [Application example 2]
於所述應用例的化學機械研磨用組成物中，可更含有相對於化學機械研磨用組成物的總質量而為0.001質量%以上、5質量%以下的(C)氧化劑。 The chemical mechanical polishing composition of the application example may further contain (C) an oxidizing agent in an amount of not less than 0.001% by mass and not more than 5% by mass relative to the total mass of the chemical mechanical polishing composition.
[應用例3] [Application example 3]
於所述應用例的化學機械研磨用組成物中，所述(C)氧化劑可為選自過碘酸鉀、次氯酸鉀及過氧化氫中的至少一種。 In the chemical mechanical polishing composition of the application example, the (C) oxidizing agent may be at least one selected from potassium periodate, potassium hypochlorite and hydrogen peroxide.
[應用例4] [Application example 4]
於所述應用例的化學機械研磨用組成物中，可更含有(D)有機酸。 The composition for chemical mechanical polishing of the application example may further contain (D) an organic acid.
[應用例5] [Application example 5]
於所述應用例的化學機械研磨用組成物中，相對於化學機械研磨用組成物的總質量，所述(A)氧化鋁修飾氧化鈦粒子的含量可為0.1質量%以上、10質量%以下。 In the chemical mechanical polishing composition of the application example, the content of the (A) alumina-modified titanium oxide particles may be not less than 0.1 mass % and not more than 10 mass % relative to the total mass of the chemical mechanical polishing composition.
[應用例6] [Application example 6]
所述應用例的化學機械研磨用組成物可用於對包含釕膜的半導體基板進行研磨。 The composition for chemical mechanical polishing of the application example can be used to polish a semiconductor substrate including a ruthenium film.
[應用例7] [Application example 7]
本發明的研磨方法的一形態包括：使用所述應用例的化學機械研磨用組成物來對半導體基板進行研磨的步驟。 One aspect of the polishing method of the present invention includes the step of polishing a semiconductor substrate using the composition for chemical mechanical polishing of the above application example.
[應用例8] [Application example 8]
於所述應用例的研磨方法中，所述半導體基板可包含釕膜。 In the polishing method of the application example, the semiconductor substrate may include a ruthenium film.
根據本發明的化學機械研磨用組成物，可抑制對人體毒性強的四氧化釕的產生，並且穩定性亦優異，可對半導體基板、尤其是含釕膜的基板進行高速研磨且可減少被研磨面的研磨損傷。另外，根據本發明的研磨方法，藉由使用所述化學機械研磨用組成物，可對半導體基板、尤其是含釕膜的基板進行高速研磨，並且可平坦地且以高處理量進行研磨。 According to the composition for chemical mechanical polishing of the present invention, the production of ruthenium tetroxide, which is highly toxic to the human body, can be suppressed, and the stability is also excellent. It can perform high-speed polishing on semiconductor substrates, especially substrates containing ruthenium films, and can reduce polishing damage on the surface to be polished. In addition, according to the polishing method of the present invention, by using the composition for chemical mechanical polishing, a semiconductor substrate, especially a substrate containing a ruthenium film can be polished at high speed, and can be polished flat and with a high throughput.
10:基體 10: matrix
12:氧化矽膜 12: Silicon oxide film
14:配線用槽 14: Groove for wiring
16:釕膜 16: Ruthenium film
18:銅膜 18: copper film
42:漿料供給噴嘴 42: Slurry supply nozzle
44:漿料(化學機械研磨用組成物) 44: Slurry (composition for chemical mechanical polishing)
46:研磨布 46: Grinding cloth
48:轉盤 48: turntable
50:半導體基板 50:Semiconductor substrate
52:載架頭 52: carrier head
54:水供給噴嘴 54: Water supply nozzle
56:修整器 56: Dresser
100:被處理體 100: object to be processed
200:研磨裝置 200: grinding device
圖1是示意性地表示適合使用本實施方式的研磨方法的被處理體的剖面圖。 FIG. 1 is a schematic cross-sectional view showing an object to be processed to which the polishing method of this embodiment is suitable.
圖2是示意性地表示第一研磨步驟結束時的被處理體的剖面圖。 Fig. 2 is a cross-sectional view schematically showing the object to be processed at the end of the first polishing step.
圖3是示意性地表示第二研磨步驟結束時的被處理體的剖面圖。 Fig. 3 is a cross-sectional view schematically showing the object to be processed at the end of the second polishing step.
圖4是示意性地表示化學機械研磨裝置的立體圖。 Fig. 4 is a perspective view schematically showing a chemical mechanical polishing device.
以下，對本發明的較佳實施方式進行詳細說明。再者，本發明並不限定於下述實施方式，亦包含在不變更本發明的主旨的範圍內所實施的各種變形例。 Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modification examples implemented in the range which do not change the summary of this invention are included.
於本說明書中，使用「~」而記載的數值範圍是包含「~」的前後所記載的數值作為下限值及上限值的含義。另外，本說明書中的「(甲基)丙烯酸~」是包括「丙烯酸~」及「甲基丙烯酸~」兩者的概念。 In this specification, the numerical range described using "~" is the meaning which includes the numerical value described before and after "~" as a lower limit and an upper limit. In addition, "(meth)acryl~" in this specification is a concept including both "acryl~" and "methacryl~".
1.化學機械研磨用組成物 1. Composition for chemical mechanical polishing
本實施方式的化學機械研磨用組成物含有(A)氧化鋁修飾氧化鈦粒子及(B)聚(甲基)丙烯酸，且pH為7以上、13以下。以下，對本實施方式的化學機械研磨用組成物中所含的各成分進行詳細說明。 The chemical mechanical polishing composition of the present embodiment contains (A) alumina-modified titanium oxide particles and (B) poly(meth)acrylic acid, and has a pH of 7 or more and 13 or less. Hereinafter, each component contained in the chemical mechanical polishing composition of the present embodiment will be described in detail.
1.1.(A)氧化鋁修飾氧化鈦粒子 1.1. (A) Al2O3-modified TiO2 particles
本實施方式的化學機械研磨用組成物含有(A)氧化鋁修飾 氧化鈦粒子。於本發明中，所謂「(A)氧化鋁修飾氧化鈦粒子」，是指氧化鈦粒子的至少一部分的外層由氧化鋁(alumina)被覆的粒子。 The chemical mechanical polishing composition of this embodiment contains (A) alumina modified Titanium oxide particles. In the present invention, "(A) alumina-modified titania particles" refers to particles in which at least a part of the outer layer of the titania particles is coated with alumina.
此種(A)氧化鋁修飾氧化鈦粒子於pH為7以上、13以下的範圍內，動(Zata)電位的絕對值比未經氧化鋁修飾的氧化鈦粒子大，粒子彼此的靜電斥力更大，因此認為於化學機械研磨用組成物中的分散性提高。其結果，可抑制(A)氧化鋁修飾氧化鈦粒子的凝聚，因此可在減少半導體基板(尤其是含釕膜的基板)的研磨損傷的同時進行高速研磨。另外，氧化鈦粒子的表面是化學活性的，因此有容易與水、氧、氮等進行反應的一面，但(A)氧化鋁修飾氧化鈦粒子中，氧化鋁被覆於氧化鈦粒子的表面，因此變為化學惰性，可降低與水、氧、氮等的反應性。藉此，於化學機械研磨用組成物中不易發生起泡，因此生產時的操作性提高。 Such (A) alumina-modified titanium oxide particles have a greater absolute value of kinetic (Zata) potential than titanium oxide particles not modified with alumina in the pH range of 7 or more and 13 or less, and the electrostatic repulsion between the particles is larger. Therefore, it is considered that the dispersibility in the composition for chemical mechanical polishing is improved. As a result, aggregation of (A) alumina-modified titanium oxide particles can be suppressed, and thus high-speed polishing can be performed while reducing polishing damage to semiconductor substrates (especially substrates containing a ruthenium film). In addition, the surface of titanium oxide particles is chemically active, so it is easy to react with water, oxygen, nitrogen, etc., but in (A) alumina-modified titanium oxide particles, aluminum oxide is coated on the surface of titanium oxide particles, so it becomes chemically inert and can reduce reactivity with water, oxygen, nitrogen, etc. Thereby, foaming is less likely to occur in the composition for chemical mechanical polishing, so the workability at the time of production is improved.
(A)氧化鋁修飾氧化鈦粒子的製造方法並無特別限制，例如可藉由以下方法來製造。 (A) The method for producing alumina-modified titanium oxide particles is not particularly limited, and can be produced, for example, by the following method.
首先，一邊攪動氧化鈦粒子一邊加入水中來進行漿料化。此時，將氧化鈦粒子的濃度調整為100g/L~300g/L。接著，一邊加入鋁酸鈉水溶液、硫酸鋁水溶液、氯化鋁水溶液等鋁鹽水溶液，一邊同時加入硫酸、鹽酸、硝酸等酸或者氫氧化鈉水溶液、氨水等鹼，對該漿料進行保持pH為5~8的操作。藉由該操作，使氧化鋁被覆於氧化鈦粒子的表面，但為使該狀態穩定化，理想的是至少攪拌30分鐘以上。其後，藉由通常公知的方法進行過濾、清 洗、乾燥，其後進行粉碎。乾燥溫度可設為室溫至200℃以下的溫度，乾燥時間可以水分成為10%以下的方式適宜地選擇。 First, the titanium oxide particles were added to water while agitating the particles to form a slurry. At this time, the concentration of the titanium oxide particles is adjusted to 100 g/L to 300 g/L. Next, while adding an aluminum salt solution such as an aqueous solution of sodium aluminate, an aqueous solution of aluminum sulfate, or an aqueous solution of aluminum chloride, an acid such as sulfuric acid, hydrochloric acid, or nitric acid or an alkali such as an aqueous solution of sodium hydroxide or ammonia is added simultaneously to maintain the pH of the slurry at 5 to 8. By this operation, alumina is coated on the surface of the titanium oxide particles, but in order to stabilize this state, it is desirable to stir for at least 30 minutes or more. Thereafter, filter and clean by a generally known method Washed, dried, and then pulverized. The drying temperature can be set to a temperature from room temperature to 200° C. or lower, and the drying time can be appropriately selected so that the water content becomes 10% or lower.
所述鋁鹽水溶液較佳以如下方式添加：相對於氧化鈦粒子100質量份，以氧化鋁換算計而較佳成為1質量份~50質量份，更佳成為2質量份~30質量份，尤佳成為3質量份~15質量份。 The aluminum salt aqueous solution is preferably added in such a manner that it is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and most preferably 3 to 15 parts by mass, in terms of alumina, relative to 100 parts by mass of titanium oxide particles.
關於所述製造方法中所使用的氧化鈦粒子，可使用金紅石(rutile)型、銳鈦礦(Anatase)型、無定形及該些的混合物中的任一者，較佳為金紅石型。 As the titanium oxide particles used in the production method, any of rutile type, anatase type, amorphous type and mixture thereof can be used, preferably rutile type.
即便欲使氧化鈦粒子分散於化學機械研磨用組成物中，但氧化鈦粒子彼此會凝聚而容易變得分散性不良，(A)氧化鋁修飾氧化鈦粒子於pH為7以上、13以下的化學機械研磨用組成物中易分散，其穩定性亦優異。作為其理由，認為在於：於pH為7以上、13以下的化學機械研磨用組成物中，(A)氧化鋁修飾氧化鈦粒子的動電位變大，因此藉由粒子彼此的靜電斥力，分散性提高。 Even if it is intended to disperse the titanium oxide particles in the chemical mechanical polishing composition, the titanium oxide particles tend to aggregate with each other and tend to have poor dispersibility. The (A) alumina-modified titanium oxide particles are easily dispersed in a chemical mechanical polishing composition with a pH of 7 or more and 13 or less, and their stability is also excellent. The reason for this is considered to be that in the chemical mechanical polishing composition with a pH of 7 or more and 13 or less, the zeta potential of (A) alumina-modified titanium oxide particles increases, so that the dispersibility improves due to the electrostatic repulsion between the particles.
就此種觀點而言，pH為7以上、13以下的化學機械研磨用組成物中的(A)氧化鋁修飾氧化鈦粒子的動電位的絕對值較佳為25mV以上，更佳為30mV以上，尤佳為35mV以上。於處於所述pH區域的化學機械研磨用組成物中，若(A)氧化鋁修飾氧化鈦粒子的動電位的絕對值為25mV以上，則(A)氧化鋁修飾氧化鈦粒子的分散性提高，並且可在減少半導體基板(尤其是含釕膜的基板)的研磨損傷的同時進行高速研磨。 From this point of view, the absolute value of the kinetic potential of (A) alumina-modified titanium oxide particles in the chemical mechanical polishing composition having a pH of 7 to 13 is preferably at least 25 mV, more preferably at least 30 mV, and most preferably at least 35 mV. In the composition for chemical mechanical polishing in the above pH range, if the absolute value of the zeta potential of (A) alumina-modified titanium oxide particles is 25 mV or more, the dispersibility of (A) alumina-modified titanium oxide particles is improved, and high-speed polishing can be performed while reducing polishing damage of semiconductor substrates (especially substrates containing a ruthenium film).
(A)氧化鋁修飾氧化鈦粒子的平均粒徑較佳為10nm以上、300nm以下，更佳為20nm以上、200nm以下，尤佳為25nm以上、150nm以下。若為具有所述範圍的平均粒徑的(A)氧化鋁修飾氧化鈦粒子，則可獲得充分的研磨速度，並且可獲得不發生粒子的沈澱．分離的、穩定性優異的化學機械研磨用組成物，因此可達成良好的性能。再者，關於(A)氧化鋁修飾氧化鈦粒子的平均粒徑，可藉由如下方式求出：針對將作為原料的氧化鋁修飾氧化鈦粒子組成物的一部分加以乾燥而獲得的試樣，例如使用流動式比表面積自動測定裝置(島津製作所股份有限公司製造，「微型測量流動吸附II2300(micrometricsFlowSorbII2300)」)，藉由布厄特(Brunauer-Emmett-Teller，BET)法來測定比表面積，根據其測定值而算出。 (A) The average particle diameter of the alumina-modified titanium oxide particles is preferably not less than 10 nm and not more than 300 nm, more preferably not less than 20 nm and not more than 200 nm, especially preferably not less than 25 nm and not more than 150 nm. If it is (A) alumina-modified titanium oxide particles having an average particle diameter within the above range, a sufficient polishing rate can be obtained, and particle precipitation does not occur. A composition for chemical mechanical polishing that is separated and excellent in stability, and therefore can achieve good performance. Furthermore, the average particle diameter of (A) alumina-modified titania particles can be obtained by measuring the specific surface area of a sample obtained by drying a part of the alumina-modified titania particle composition as a raw material, for example, by the Brunauer-Emmett-Teller (BET) method using a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, "micrometrics Flow Sorb II 2300 (micrometrics Flow Sorb II 2300)"). The surface area is calculated from the measured value.
就以高速對半導體基板進行研磨的觀點而言，相對於化學機械研磨用組成物的總質量，(A)氧化鋁修飾氧化鈦粒子的含量較佳為0.1質量%以上，更佳為0.3質量%以上，尤佳為0.5質量%以上。就減少被研磨面的研磨損傷的產生的觀點而言，(A)氧化鋁修飾氧化鈦粒子的含量較佳為10質量%以下，更佳為5質量%以下，尤佳為3質量%以下。 From the viewpoint of polishing a semiconductor substrate at high speed, the content of (A) alumina-modified titanium oxide particles is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, and especially preferably at least 0.5% by mass, based on the total mass of the composition for chemical mechanical polishing. From the viewpoint of reducing the occurrence of grinding damage on the surface to be polished, the content of (A) alumina-modified titanium oxide particles is preferably at most 10% by mass, more preferably at most 5% by mass, and most preferably at most 3% by mass.
1.2.(B)聚(甲基)丙烯酸 1.2.(B) Poly(meth)acrylic acid
本實施方式的化學機械研磨用組成物含有(B)聚(甲基)丙烯酸。(B)聚(甲基)丙烯酸具有吸附於半導體基板(尤其是含釕膜的基板)的表面而減少研磨摩擦的功能。藉此，可更有效地減少 被研磨面的研磨損傷的產生。 The chemical mechanical polishing composition of the present embodiment contains (B) poly(meth)acrylic acid. (B) Poly(meth)acrylic acid has a function of reducing polishing friction by being adsorbed on the surface of a semiconductor substrate (especially a substrate containing a ruthenium film). In this way, it is possible to more effectively reduce Occurrence of grinding damage on the ground surface.
再者，本發明中的「(B)聚(甲基)丙烯酸」是指於分子內具有源自丙烯酸或甲基丙烯酸的重複單元的高分子化合物。作為此種(B)聚(甲基)丙烯酸，可列舉：聚丙烯酸、聚甲基丙烯酸、聚丙烯酸鈉、聚甲基丙烯酸鈉，以及丙烯酸/馬來酸共聚物鹽、甲基丙烯酸/馬來酸共聚物鹽、丙烯酸/磺酸系單體共聚物、甲基丙烯酸/磺酸系單體共聚物等共聚物。該些中，就極力防止半導體基板的金屬污染的觀點而言，較佳為聚丙烯酸、聚甲基丙烯酸。 In addition, "(B) poly(meth)acrylic acid" in this invention means the polymer compound which has a repeating unit derived from acrylic acid or methacrylic acid in a molecule|numerator. Examples of such (B) poly(meth)acrylic acid include polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, and copolymers such as acrylic acid/maleic acid copolymer salts, methacrylic acid/maleic acid copolymer salts, acrylic acid/sulfonic acid monomer copolymers, and methacrylic acid/sulfonic acid monomer copolymers. Among these, polyacrylic acid and polymethacrylic acid are preferable from the viewpoint of preventing metal contamination of the semiconductor substrate as much as possible.
(B)聚(甲基)丙烯酸的重量平均分子量(Mw)較佳為1,000以上、1,500,000以下，更佳為10,000以上、500,000以下，尤佳為30,000以上、100,000以下。若(B)聚(甲基)丙烯酸的重量平均分子量為所述範圍內，則(B)聚(甲基)丙烯酸容易吸附於半導體基板(尤其是含釕膜的基板)，從而進一步減少研磨摩擦。其結果，使用具有所述範圍內的重量平均分子量的(B)聚(甲基)丙烯酸而得的化學機械研磨用組成物可更有效地減少被研磨面的研磨損傷的產生。再者，本說明書中的「重量平均分子量(Mw)」是指藉由凝膠滲透層析法(Gel Penetration Chromatography，GPC)所測定的聚乙二醇換算的重量平均分子量。 (B) The weight average molecular weight (Mw) of poly(meth)acrylic acid is preferably from 1,000 to 1,500,000, more preferably from 10,000 to 500,000, particularly preferably from 30,000 to 100,000. If the weight average molecular weight of the (B) poly(meth)acrylic acid is within the above range, the (B) poly(meth)acrylic acid is easily adsorbed to a semiconductor substrate (especially a substrate containing a ruthenium film), thereby further reducing polishing friction. As a result, the chemical mechanical polishing composition using (B) poly(meth)acrylic acid having a weight average molecular weight within the above range can more effectively reduce the occurrence of polishing damage on the surface to be polished. In addition, "weight average molecular weight (Mw)" in this specification means the weight average molecular weight of polyethylene glycol conversion measured by gel permeation chromatography (Gel Penetration Chromatography, GPC).
就有效地獲得減少被研磨面的研磨損傷的產生這一效果的觀點而言，相對於化學機械研磨用組成物的總質量，(B)聚(甲基)丙烯酸的含量較佳為0.001質量%以上，更佳為0.003質量%以上，尤佳為0.01質量%以上。就抑制被研磨面的研磨損傷的產生， 並且以充分的研磨速度進行研磨的觀點而言，(B)聚(甲基)丙烯酸的含量較佳為1質量%以下，更佳為0.5質量%以下，尤佳為0.1質量%以下。 From the viewpoint of effectively obtaining the effect of reducing the occurrence of polishing damage on the surface to be polished, the content of (B) poly(meth)acrylic acid is preferably at least 0.001% by mass, more preferably at least 0.003% by mass, and especially preferably at least 0.01% by mass, based on the total mass of the chemical mechanical polishing composition. In order to suppress the occurrence of grinding damage on the surface to be ground, And from the viewpoint of polishing at a sufficient polishing rate, the content of (B) poly(meth)acrylic acid is preferably at most 1% by mass, more preferably at most 0.5% by mass, and most preferably at most 0.1% by mass.
另外，(B)聚(甲基)丙烯酸的含量相對於(A)氧化鋁修飾氧化鈦粒子的含量的比([(B)聚(甲基)丙烯酸的含量/(A)氧化鋁修飾氧化鈦粒子的含量]×100)較佳為0.1%~15%，更佳為0.5%~10%。若(B)聚(甲基)丙烯酸的含量相對於(A)氧化鋁修飾氧化鈦粒子的含量的比處於所述範圍，則會抑制被研磨面的研磨損傷的產生，並且有時會更有效地獲得使研磨速度提高的作用效果。 In addition, the ratio of the content of (B) poly(meth)acrylic acid to the content of (A) alumina-modified titanium oxide particles ([(B) content of poly(meth)acrylic acid/(A) content of alumina-modified titanium oxide particles]×100) is preferably 0.1% to 15%, more preferably 0.5% to 10%. When the ratio of the content of (B) poly(meth)acrylic acid to the content of (A) alumina-modified titanium oxide particles is in the above range, the occurrence of grinding damage on the surface to be polished can be suppressed, and the effect of increasing the polishing rate can be more effectively obtained in some cases.
再者，(B)聚(甲基)丙烯酸的含量亦依存於(B)聚(甲基)丙烯酸的重量平均分子量(Mw)，但較佳為以使化學機械研磨用組成物的黏度不足10mPa．s的方式進行調整。若化學機械研磨用組成物的黏度不足10mPa．s，則容易以高速對半導體基板(尤其是含釕膜的基板)進行研磨，且因黏度適當而可將化學機械研磨用組成物穩定地供給至研磨布上。 Furthermore, the content of (B) poly(meth)acrylic acid also depends on the weight average molecular weight (Mw) of (B) poly(meth)acrylic acid, but it is preferable to make the viscosity of the composition for chemical mechanical polishing less than 10mPa. s to adjust. If the viscosity of the composition for chemical mechanical polishing is less than 10mPa. s, it is easy to polish the semiconductor substrate (especially the substrate containing the ruthenium film) at high speed, and the composition for chemical mechanical polishing can be stably supplied to the polishing cloth due to the appropriate viscosity.
1.3.(C)氧化劑 1.3. (C) Oxidizing agent
本實施方式的化學機械研磨用組成物亦可於不在CMP步驟中將釕膜氧化而生成四氧化釕的範圍內，含有(C)氧化劑。藉由含有(C)氧化劑，會對釕等金屬進行氧化而促進與研磨液成分的錯合反應，藉此可於被研磨面製作出脆弱的改質層，因此具有容易進行研磨的效果。 The chemical mechanical polishing composition of the present embodiment may contain (C) an oxidizing agent within a range in which the ruthenium film is not oxidized in the CMP step to form ruthenium tetroxide. By containing (C) oxidizing agent, metals such as ruthenium will be oxidized to promote the complexation reaction with the components of the polishing liquid, whereby a fragile modified layer can be produced on the surface to be polished, so it has the effect of easy polishing.
作為(C)氧化劑，例如可列舉：過硫酸銨、過硫酸鉀、過氧化氫、硝酸鐵、硝酸鈰銨(diammonium cerium nitrate)、次氯酸鉀、臭氧、過碘酸鉀、過氧乙酸等。該些氧化劑中，就抑制四氧化釕的產生的觀點而言，較佳為選自過碘酸鉀、次氯酸鉀及過氧化氫中的至少一種，更佳為過氧化氫。該些(C)氧化劑可單獨使用一種，亦可組合兩種以上來使用。 Examples of the (C) oxidizing agent include ammonium persulfate, potassium persulfate, hydrogen peroxide, iron nitrate, diammonium cerium nitrate, potassium hypochlorite, ozone, potassium periodate, peracetic acid and the like. Among these oxidizing agents, from the viewpoint of suppressing the generation of ruthenium tetroxide, at least one selected from potassium periodate, potassium hypochlorite, and hydrogen peroxide is preferred, and hydrogen peroxide is more preferred. These (C) oxidizing agents may be used alone or in combination of two or more.
於含有(C)氧化劑的情況下，就防止釕等金屬的氧化變得不充分而研磨速度下降的觀點而言，相對於化學機械研磨用組成物的總質量，(C)氧化劑的含量較佳為0.001質量%以上，更佳為0.005質量%以上，尤佳為0.01質量%以上。就防止因釕的過度氧化而產生四氧化釕的觀點而言，(C)氧化劑的含量較佳為5質量%以下，更佳為3質量%以下，尤佳為1質量%以下。 When the (C) oxidizing agent is contained, the content of the (C) oxidizing agent is preferably at least 0.001% by mass, more preferably at least 0.005% by mass, and most preferably at least 0.01% by mass, based on the total mass of the chemical mechanical polishing composition, from the viewpoint of preventing insufficient oxidation of metals such as ruthenium and a decrease in the polishing rate. From the viewpoint of preventing the generation of ruthenium tetroxide due to excessive oxidation of ruthenium, the content of the (C) oxidizing agent is preferably at most 5% by mass, more preferably at most 3% by mass, and most preferably at most 1% by mass.
另外，(C)氧化劑的含量相對於(A)氧化鋁修飾氧化鈦粒子的含量的比([(C)氧化劑的含量/(A)氧化鋁修飾氧化鈦粒子的含量]×100)較佳為1%~200%，更佳為2%~150%。若(C)氧化劑的含量相對於(A)氧化鋁修飾氧化鈦粒子的含量的比處於所述範圍，則會抑制釕的過度氧化，並且有時會更有效地獲得更容易進行對釕膜的研磨的作用效果。 In addition, the ratio of the content of the (C) oxidizing agent to the content of the (A) alumina-modified titanium oxide particles ([(C) content of the oxidizing agent/(A) content of the alumina-modified titanium oxide particles]×100) is preferably 1% to 200%, more preferably 2% to 150%. When the ratio of the content of the (C) oxidizing agent to the content of the (A) alumina-modified titanium oxide particles is within the above range, excessive oxidation of ruthenium is suppressed, and the effect of easier polishing of the ruthenium film may be more effectively obtained.
1.4.(D)有機酸 1.4. (D) Organic acids
本實施方式的化學機械研磨用組成物含有(D)有機酸。藉由含有(D)有機酸，可更高速地對含釕膜的基板進行研磨。 The chemical mechanical polishing composition of the present embodiment contains (D) an organic acid. By containing (D) the organic acid, the substrate containing the ruthenium film can be polished at a higher speed.
(D)有機酸並無特別限定，且只要為CMP領域中已知 作為螯合劑或蝕刻劑的有機酸，則並無特別限定。作為(D)有機酸，例如可列舉：硬脂酸、月桂酸、乳酸、酒石酸、富馬酸、乙醇酸、鄰苯二甲酸、馬來酸、甲酸、乙酸、草酸、檸檬酸、蘋果酸、丙二酸、戊二酸、琥珀酸、苯甲酸、喹啉酸、2-喹啉甲酸、胺基磺酸(amidosulfuric acid)；甘胺酸、丙胺酸、天冬胺酸、麩胺酸、離胺酸、精胺酸、芳香族胺基酸及雜環型胺基酸等胺基酸。該些中，若考慮到抑制四氧化釕的產生及提高(A)氧化鋁修飾氧化鈦粒子的分散性等，則較佳為二羧酸類，更佳為二羧酸中選自馬來酸及丙二酸中的至少一種。該些有機酸可單獨使用一種，亦可組合兩種以上來使用。 (D) The organic acid is not particularly limited, and as long as it is known in the field of CMP The organic acid used as a chelating agent or an etchant is not particularly limited. (D) Organic acids include, for example, stearic acid, lauric acid, lactic acid, tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid, acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, succinic acid, benzoic acid, quinolinic acid, 2-quinolinic acid, amidosulfuric acid; glycine, alanine, aspartic acid, glutamic acid, lysine, Amino acids such as arginine, aromatic amino acids and heterocyclic amino acids. Among these, in view of suppressing the generation of ruthenium tetroxide and improving the dispersibility of (A) alumina-modified titanium oxide particles, etc., dicarboxylic acids are preferred, and at least one dicarboxylic acid selected from maleic acid and malonic acid is more preferred. These organic acids may be used alone or in combination of two or more.
另外，(D)有機酸可為所述有機酸的鹽，亦可與化學機械研磨用組成物中另行添加的鹼反應而成為所述有機酸的鹽。作為此種鹼，可列舉：氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫等鹼金屬的氫氧化物、四甲基氫氧化銨(Tetramethyl Ammonium Hydroxide，TMAH)、膽鹼等有機鹼化合物、及氨等。 In addition, (D) the organic acid may be a salt of the organic acid, or may react with a base separately added to the chemical mechanical polishing composition to form a salt of the organic acid. Examples of such a base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, organic base compounds such as tetramethyl ammonium hydroxide (TMAH), choline, and ammonia.
於含有(D)有機酸的情況下，就對包含釕等金屬的半導體基板進行高速研磨的觀點而言，相對於化學機械研磨用組成物的總質量，(D)有機酸的含量較佳為0.001質量%以上，更佳為0.003質量%以上，尤佳為0.005質量%以上。就防止四氧化釕的產生的觀點而言，(D)有機酸的含量較佳為15質量%以下，更佳為10質量%以下，尤佳為5質量%以下。 When the (D) organic acid is contained, the content of the (D) organic acid is preferably at least 0.001% by mass, more preferably at least 0.003% by mass, and especially preferably at least 0.005% by mass, based on the total mass of the composition for chemical mechanical polishing, from the viewpoint of high-speed polishing of a semiconductor substrate containing a metal such as ruthenium. From the viewpoint of preventing the generation of ruthenium tetroxide, the content of (D) the organic acid is preferably at most 15% by mass, more preferably at most 10% by mass, and most preferably at most 5% by mass.
1.5.其他添加劑 1.5. Other additives
本實施方式的化學機械研磨用組成物不僅含有作為主要的液狀介質的水，而且亦可視需要含有含氮雜環化合物、界面活性劑、無機酸及其鹽、(B)聚(甲基)丙烯酸以外的水溶性高分子等。 The chemical mechanical polishing composition of the present embodiment contains not only water as the main liquid medium, but also nitrogen-containing heterocyclic compounds, surfactants, inorganic acids and salts thereof, (B) water-soluble polymers other than poly(meth)acrylic acid, and the like as needed.
<水> <water>
本實施方式的化學機械研磨用組成物含有水作為主要的液狀介質。作為水，並無特別限制，但在用於化學機械研磨用組成物的情況下，可較佳地使用純水。水只要作為所述化學機械研磨用組成物的構成材料的剩餘部分來調配即可，關於水的含量，並無特別限制。 The chemical mechanical polishing composition of this embodiment contains water as a main liquid medium. The water is not particularly limited, but when used in a composition for chemical mechanical polishing, pure water can be preferably used. Water may be prepared as the remainder of the constituent materials of the chemical mechanical polishing composition, and the content of water is not particularly limited.
<含氮雜環化合物> <Nitrogen-containing heterocyclic compound>
本實施方式的化學機械研磨用組成物亦可含有含氮雜環化合物。藉由含有含氮雜環化合物，可抑制釕等金屬的過度蝕刻，且防止腐蝕等研磨後的表面粗糙。 The chemical mechanical polishing composition of this embodiment may also contain a nitrogen-containing heterocyclic compound. By containing the nitrogen-containing heterocyclic compound, excessive etching of metals such as ruthenium can be suppressed, and surface roughness after polishing such as corrosion can be prevented.
含氮雜環化合物是具有至少一個氮原子且包含選自五員雜環及六員雜環中的至少一種的雜環的有機化合物。作為所述雜環，可列舉：吡咯結構、咪唑結構、***結構等五員雜環；吡啶結構、嘧啶結構、噠嗪結構、吡嗪結構等六員雜環。該雜環亦可形成稠環。具體而言，可列舉：吲哚結構、異吲哚結構、苯并咪唑結構、苯并***結構、喹啉結構、異喹啉結構、喹唑啉結構、噌啉結構、酞嗪結構、喹噁啉結構、吖啶結構等。具有此種結構的雜環化合物中，較佳為具有吡啶結構、喹啉結構、苯并咪唑結構、苯并***結構的雜環化合物。 The nitrogen-containing heterocyclic compound is an organic compound having at least one nitrogen atom and including at least one heterocyclic ring selected from five-membered heterocyclic rings and six-membered heterocyclic rings. Examples of the heterocyclic ring include five-membered heterocyclic rings such as pyrrole structure, imidazole structure, and triazole structure, and six-membered heterocyclic rings such as pyridine structure, pyrimidine structure, pyridazine structure, and pyrazine structure. The heterocyclic ring may also form a condensed ring. Specifically, indole structure, isoindole structure, benzimidazole structure, benzotriazole structure, quinoline structure, isoquinoline structure, quinazoline structure, cinnoline structure, phthalazine structure, quinoxaline structure, acridine structure, etc. are mentioned. Among heterocyclic compounds having such structures, heterocyclic compounds having a pyridine structure, quinoline structure, benzimidazole structure, and benzotriazole structure are preferable.
作為含氮雜環化合物的具體例，可列舉：氮丙啶、吡啶、嘧啶、吡咯啶、哌啶、吡嗪、三嗪、吡咯、咪唑、吲哚、喹啉、異喹啉、苯并異喹啉、嘌呤、喋啶、***、***啶(triazolidine)、苯并***、羧基苯并***等，進而可列舉具有該些的骨架的衍生物。該些中，較佳為選自苯并***及***中的至少一種。該些含氮雜環化合物可單獨使用一種，亦可組合兩種以上來使用。 Specific examples of nitrogen-containing heterocyclic compounds include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinoline, isoquinoline, benzisoquinoline, purine, pteridine, triazole, triazolidine, benzotriazole, carboxybenzotriazole, and the like, and derivatives having these skeletons are further exemplified. Among these, at least one selected from benzotriazole and triazole is preferable. These nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
於含有含氮雜環化合物的情況下，相對於化學機械研磨用組成物的總質量，含氮雜環化合物的含量較佳為0.05質量%~2質量%，更佳為0.1質量%~1質量%。 When the nitrogen-containing heterocyclic compound is contained, the content of the nitrogen-containing heterocyclic compound is preferably 0.05% by mass to 2% by mass, more preferably 0.1% by mass to 1% by mass, relative to the total mass of the chemical mechanical polishing composition.
<界面活性劑> <Surfactant>
本實施方式的化學機械研磨用組成物亦可含有(B)聚(甲基)丙烯酸以外的界面活性劑。界面活性劑中，除了具有對化學機械研磨用組成物賦予適度的黏性的效果以外，有時可抑制釕等金屬的過度蝕刻，且防止腐蝕等研磨後的表面粗糙。 The chemical mechanical polishing composition of this embodiment may contain (B) a surfactant other than poly(meth)acrylic acid. Among the surfactants, in addition to the effect of imparting moderate viscosity to the chemical mechanical polishing composition, it may suppress excessive etching of metals such as ruthenium and prevent surface roughness after polishing such as corrosion.
界面活性劑並無特別限制，可列舉陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑等。作為陰離子性界面活性劑，例如可列舉：脂肪酸皂、烷基醚羧酸鹽等羧酸鹽；烷基苯磺酸鹽、烷基萘磺酸鹽、α-烯烴磺酸鹽等磺酸鹽；高級醇硫酸酯鹽、烷基醚硫酸鹽、聚氧乙烯烷基苯基醚硫酸鹽等硫酸鹽；全氟烷基化合物等含氟系界面活性劑等。作為陽離子性界面活性劑，例如可列舉脂肪族胺鹽及脂肪族銨鹽等。作為非離子性界面活性劑，例如可列舉乙炔乙二醇、乙炔乙二醇環氧乙烷加成物、 乙炔醇等具有三鍵的非離子性界面活性劑；聚乙二醇型界面活性劑等。該些界面活性劑可單獨使用一種，亦可組合兩種以上來使用。 The surfactant is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, and the like. Examples of anionic surfactants include fatty acid soaps and carboxylates such as alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates; sulfates such as higher alcohol sulfates, alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates; and fluorine-containing surfactants such as perfluoroalkyl compounds. As a cationic surfactant, an aliphatic amine salt, an aliphatic ammonium salt, etc. are mentioned, for example. Examples of nonionic surfactants include acetylene glycol, acetylene glycol ethylene oxide adducts, Nonionic surfactants with triple bonds such as acetylene alcohol; polyethylene glycol-type surfactants, etc. These surfactants may be used alone or in combination of two or more.
於含有界面活性劑的情況下，相對於化學機械研磨用組成物的總質量，界面活性劑的含量較佳為0.001質量%以上、5質量%以下，更佳為0.001質量%以上、3質量%以下，尤佳為0.01質量%以上、1質量%以下。 When a surfactant is contained, the content of the surfactant is preferably at least 0.001% by mass and not more than 5% by mass, more preferably at least 0.001% by mass and not more than 3% by mass, and most preferably at least 0.01% by mass and not more than 1% by mass, relative to the total mass of the chemical mechanical polishing composition.
<無機酸及其鹽> <Inorganic acid and its salt>
本實施方式的化學機械研磨用組成物亦可含有無機酸及其鹽。藉由含有無機酸及其鹽，有時對釕等金屬的研磨速度會進一步提高。作為無機酸，例如較佳為選自鹽酸、硝酸、硫酸及磷酸中的至少一種。作為無機酸的鹽，可為所述無機酸的鹽，亦可由化學機械研磨用組成物中另行添加的鹼與所述無機酸來形成鹽。作為此種鹼，可列舉氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫等鹼金屬的氫氧化物；四甲基氫氧化銨(TMAH)、膽鹼等有機鹼化合物及氨等。 The chemical mechanical polishing composition of this embodiment may also contain an inorganic acid and a salt thereof. The polishing rate of metals such as ruthenium may be further increased by containing an inorganic acid and its salt. As the inorganic acid, for example, at least one selected from hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid is preferable. The salt of the inorganic acid may be a salt of the above-mentioned inorganic acid, or a salt may be formed from a base separately added to the composition for chemical mechanical polishing and the above-mentioned inorganic acid. Examples of such a base include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; organic base compounds such as tetramethylammonium hydroxide (TMAH), choline, and ammonia.
於含有無機酸及其鹽的情況下，相對於化學機械研磨用組成物的總質量，無機酸及其鹽的含量較佳為3質量%~8質量%，更佳為3質量%~6質量%。 When the inorganic acid and its salt are contained, the content of the inorganic acid and its salt is preferably 3% by mass to 8% by mass, more preferably 3% by mass to 6% by mass relative to the total mass of the chemical mechanical polishing composition.
<其他水溶性高分子> <Other water-soluble polymers>
本實施方式的化學機械研磨用組成物亦可含有(B)聚(甲基)丙烯酸以外的水溶性高分子。藉由含有(B)聚(甲基)丙烯酸以外 的水溶性高分子，有時可進一步提高(B)聚(甲基)丙烯酸的功能(即，吸附於半導體基板(尤其是含釕膜的基板)的表面而減少研磨摩擦的功能)。作為此種水溶性高分子，可列舉：聚(甲基)丙烯醯胺、聚乙烯基醇、聚乙烯基吡咯啶酮、聚乙烯亞胺、聚乙烯基甲基醚、聚烯丙基胺、羥基乙基纖維素等。 The chemical mechanical polishing composition of the present embodiment may contain (B) water-soluble polymers other than poly(meth)acrylic acid. By containing (B) poly(meth)acrylic acid other than The water-soluble polymer can sometimes further improve the function of (B) poly(meth)acrylic acid (that is, the function of adsorbing on the surface of a semiconductor substrate (especially a substrate containing a ruthenium film) to reduce abrasive friction). Examples of such water-soluble polymers include poly(meth)acrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyvinylmethyl ether, polyallylamine, and hydroxyethylcellulose.
1.6.pH 1.6.pH
本實施方式的化學機械研磨用組成物的pH為7~13，較佳為8~12.5，更佳為9~11。若pH為7以上，則化學機械研磨用組成物中的(A)氧化鋁修飾氧化鈦粒子的動電位的絕對值變大，分散性提高，因此可在減少半導體基板(尤其是含釕膜的基板)的研磨損傷的同時進行高速研磨。另外，若pH為13以下，則生產時的操作性提高。另一方面，若pH不足7，則化學機械研磨用組成物中的(A)氧化鋁修飾氧化鈦粒子的動電位的絕對值變小，分散性劣化而發生凝聚，因此研磨速度降低，並且容易產生研磨缺陷。 The pH of the composition for chemical mechanical polishing in this embodiment is 7-13, preferably 8-12.5, more preferably 9-11. If the pH is 7 or more, the absolute value of the zeta potential of (A) alumina-modified titanium oxide particles in the composition for chemical mechanical polishing becomes large, and the dispersibility improves, so that high-speed polishing can be performed while reducing polishing damage of a semiconductor substrate (especially a substrate containing a ruthenium film). Moreover, when pH is 13 or less, workability at the time of production improves. On the other hand, if the pH is less than 7, the absolute value of the zeta potential of the (A) alumina-modified titanium oxide particles in the chemical mechanical polishing composition decreases, the dispersibility deteriorates and aggregation occurs, so the polishing rate decreases and polishing defects are likely to occur.
再者，本實施方式的化學機械研磨用組成物的pH例如可藉由添加氫氧化鉀、乙二胺、TMAH(四甲基氫氧化銨)、氨等來進行調整，可使用該些的一種以上。 Furthermore, the pH of the chemical mechanical polishing composition of this embodiment can be adjusted by adding potassium hydroxide, ethylenediamine, TMAH (tetramethylammonium hydroxide), ammonia, etc., and one or more of these can be used.
於本發明中，pH是指氫離子指數，其值可使用市售的pH計(例如，堀場製作所股份有限公司製造的桌上型pH計)來測定。 In the present invention, pH means a hydrogen ion index, and its value can be measured using a commercially available pH meter (for example, a desktop pH meter manufactured by Horiba Seisakusho Co., Ltd.).
1.7.用途 1.7. Purpose
如上所述，本實施方式的化學機械研磨用組成物於含釕膜的 基板的CMP中，抑制對人體毒性強的四氧化釕的產生，並且穩定性優異，可對含釕膜的基板進行高速研磨，且可減少被研磨面的研磨損傷。因此，本實施方式的化學機械研磨用組成物於對銅膜的基底施加作為下一代半導體材料的釕膜而成的半導體基板中，作為用以對含釕膜的基板進行化學機械研磨的研磨材料而較佳。 As described above, the chemical mechanical polishing composition of the present embodiment is applied to the ruthenium-containing film. In the CMP of the substrate, the production of ruthenium tetroxide, which is highly toxic to the human body, is suppressed, and the stability is excellent, and the substrate containing the ruthenium film can be polished at high speed, and the polishing damage of the polished surface can be reduced. Therefore, the composition for chemical mechanical polishing of this embodiment is suitable as an abrasive for chemical mechanical polishing of a substrate containing a ruthenium film in a semiconductor substrate obtained by applying a ruthenium film as a next-generation semiconductor material on a copper film base.
1.8.化學機械研磨用組成物的製備方法 1.8. Preparation method of composition for chemical mechanical polishing
本實施方式的化學機械研磨用組成物可藉由使所述各成分溶解或分散於水等液狀介質中來製備。溶解或分散的方法並無特別限制，只要可均勻地進行溶解或分散，則可應用任意方法。另外，關於所述各成分的混合順序或混合方法，亦無特別限制。 The chemical mechanical polishing composition of the present embodiment can be prepared by dissolving or dispersing the above components in a liquid medium such as water. The method of dissolution or dispersion is not particularly limited, and any method can be applied as long as the dissolution or dispersion can be performed uniformly. In addition, there is no particular limitation on the mixing order or mixing method of the above-mentioned components.
另外，本實施方式的化學機械研磨用組成物亦可作為濃縮型的原液來製備，於使用時利用水等液狀介質進行稀釋來使用。 In addition, the composition for chemical mechanical polishing according to the present embodiment can also be prepared as a concentrated stock solution and diluted with a liquid medium such as water before use.
2.研磨方法 2. Grinding method
本實施方式的研磨方法包括使用所述化學機械研磨用組成物對半導體基板進行研磨的步驟。所述化學機械研磨用組成物於對表面含有釕的基板進行化學機械研磨時，可抑制對人體毒性強的四氧化釕的發生，並且穩定性優異，可對所述表面含有釕的基板進行高速研磨且可減少被研磨面的研磨損傷。因此，本實施方式的研磨方法適合於對在銅膜的基底施加作為下一代半導體材料的釕膜而成的半導體基板進行研磨的情況。以下，使用圖式，對本實施方式的研磨方法的一具體例進行詳細說明。 The polishing method of this embodiment includes the step of polishing a semiconductor substrate using the composition for chemical mechanical polishing. The composition for chemical mechanical polishing can suppress the generation of ruthenium tetroxide, which is highly toxic to the human body, when performing chemical mechanical polishing on a substrate containing ruthenium on the surface, and has excellent stability, can perform high-speed polishing on the substrate containing ruthenium on the surface, and can reduce polishing damage on the surface to be polished. Therefore, the polishing method of the present embodiment is suitable for polishing a semiconductor substrate obtained by applying a ruthenium film, which is a next-generation semiconductor material, under a copper film. Hereinafter, a specific example of the polishing method of this embodiment will be described in detail using the drawings.
2.1.被處理體 2.1. Object to be processed
圖1是示意性地表示適合使用本實施方式的研磨方法的被處理體的剖面圖。被處理體100經過以下的步驟(1)至步驟(4)而形成。 FIG. 1 is a schematic cross-sectional view showing an object to be processed to which the polishing method of this embodiment is suitable. The object to be processed 100 is formed through the following steps (1) to (4).
(1)首先，如圖1所示，準備基體10。基體10例如可包括矽基板及形成於其上的氧化矽膜。進而，亦可對基體10形成(未圖示)電晶體等功能器件。其次，使用熱氧化法於基體10之上形成作為絕緣膜的氧化矽膜12。 (1) First, as shown in FIG. 1 , a substrate 10 is prepared. The base body 10 may include, for example, a silicon substrate and a silicon oxide film formed thereon. Furthermore, functional devices such as transistors may be formed (not shown) on the base body 10 . Next, a silicon oxide film 12 as an insulating film is formed on the substrate 10 by thermal oxidation.
(2)繼而，對氧化矽膜12進行圖案化。將所獲得的圖案作為遮罩，藉由光微影法於氧化矽膜12形成配線用槽14。 (2) Next, the silicon oxide film 12 is patterned. Using the obtained pattern as a mask, grooves 14 for wiring are formed in the silicon oxide film 12 by photolithography.
(3)繼而，於氧化矽膜12的表面及配線用槽14的內壁面形成釕膜16。釕膜16例如可藉由使用釕前驅物的化學氣相成長法(Chemical Vapour Deposition，CVD)或原子層堆積法(Atomic Layer Deposition，ALD)、或者濺鍍等物理氣相堆積法(Physical Vapor Deposition，PVD)來形成。 (3) Next, the ruthenium film 16 is formed on the surface of the silicon oxide film 12 and the inner wall surface of the wiring groove 14 . The ruthenium film 16 can be formed by, for example, Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) using a ruthenium precursor, or Physical Vapor Deposition (PVD) such as sputtering.
(4)繼而，藉由化學蒸鍍法或電鍍法，堆積膜厚10,000Å~15,000Å(此處，「Å」是指0.1nm)的銅膜18。作為銅膜18的材料，不僅可使用純度高的銅，亦可使用含有銅的合金。作為含有銅的含金中的銅含量，較佳為95質量%以上。 (4) Next, a copper film 18 having a film thickness of 10,000 Å to 15,000 Å (here, "Å" means 0.1 nm) is deposited by chemical vapor deposition or electroplating. As the material of the copper film 18, not only high-purity copper but also an alloy containing copper can be used. The copper content in the copper-containing gold is preferably 95% by mass or more.
2.2.研磨方法 2.2. Grinding method
2.2.1.第一研磨步驟 2.2.1. First grinding step
圖2是示意性地表示第一研磨步驟結束時的被處理體100的剖面圖。如圖2所示，第一研磨步驟是使用銅膜用的化學機械研 磨用組成物對銅膜18進行研磨直至露出釕膜16為止的步驟。 FIG. 2 is a cross-sectional view schematically showing the object 100 at the end of the first polishing step. As shown in Figure 2, the first grinding step is to use chemical mechanical grinding for copper film. A step of polishing the copper film 18 with the composition until the ruthenium film 16 is exposed.
2.2.2.第二研磨步驟 2.2.2. Second grinding step
圖3是示意性地表示第二研磨步驟結束時的被處理體100的剖面圖。如圖3所示，第二研磨步驟是使用所述化學機械研磨用組成物對釕膜16及銅膜18進行研磨直至露出氧化矽膜12為止的步驟。於第二研磨步驟中使用所述化學機械研磨用組成物，因此抑制對人體毒性強的四氧化釕的產生，並且可對釕膜進行高速研磨，且可減少被研磨面的研磨損傷。 FIG. 3 is a cross-sectional view schematically showing the object 100 at the end of the second polishing step. As shown in FIG. 3 , the second polishing step is a step of polishing the ruthenium film 16 and the copper film 18 using the composition for chemical mechanical polishing until the silicon oxide film 12 is exposed. The composition for chemical mechanical polishing is used in the second polishing step, so the production of ruthenium tetroxide, which is highly toxic to the human body, can be suppressed, and the ruthenium film can be polished at high speed, and the polishing damage of the polished surface can be reduced.
2.3.化學機械研磨裝置 2.3. Chemical mechanical grinding device
於所述第一研磨步驟及第二研磨步驟中，例如可使用圖4所示般的研磨裝置200。圖4是示意性地表示研磨裝置200的立體圖。所述第一研磨步驟及第二研磨步驟是藉由自漿料供給噴嘴42供給漿料(化學機械研磨用組成物)44，且一邊使貼附有研磨布46的轉盤48旋轉，一邊將保持著半導體基板50的載架頭(carrier head)52抵接來進行。再者，圖4亦一併示出了水供給噴嘴54及修整器(dresser)56。 In the first grinding step and the second grinding step, for example, a grinding device 200 as shown in FIG. 4 can be used. FIG. 4 is a perspective view schematically showing the polishing device 200 . The first polishing step and the second polishing step are performed by supplying the slurry (chemical mechanical polishing composition) 44 from the slurry supply nozzle 42, and bringing the carrier head 52 holding the semiconductor substrate 50 into contact with the turntable 48 on which the polishing cloth 46 is attached while rotating. Furthermore, FIG. 4 also shows a water supply nozzle 54 and a dresser 56 together.
載架頭52的研磨負荷可於0.7psi~70psi的範圍內選擇，較佳為1.5psi~35psi。另外，轉盤48及載架頭52的轉速可於10rpm~400rpm的範圍內適當選擇，較佳為30rpm~150rpm。自漿料供給噴嘴42供給的漿料(化學機械研磨用組成物)44的流量可於10mL/分~1,000mL/分的範圍內選擇，較佳為50mL/分~400mL/分。 The grinding load of the carrier head 52 can be selected within the range of 0.7psi~70psi, preferably 1.5psi~35psi. In addition, the rotation speed of the turntable 48 and the carrier head 52 can be appropriately selected within the range of 10 rpm to 400 rpm, preferably 30 rpm to 150 rpm. The flow rate of the slurry (chemical mechanical polishing composition) 44 supplied from the slurry supply nozzle 42 can be selected within the range of 10 mL/min to 1,000 mL/min, preferably 50 mL/min to 400 mL/min.
作為市售的研磨裝置，例如可列舉荏原製作所公司製造的型號「EPO-112」、「EPO-222」；藍邁斯特(Lapmaster)SFT公司製造的型號「LGP-510」、「LGP-552」；應用材料(Applied Material)公司製造的型號「米拉(Mirra)」、「瑞福興(Reflexion)」；G & P科技(TECHNOLOGY)公司製造的型號「POLI-400L」；AMAT公司製造的型號「瑞福興(Reflexion)LK」等。 Examples of commercially available grinding devices include models "EPO-112" and "EPO-222" manufactured by Ebara Seisakusho; models "LGP-510" and "LGP-552" manufactured by Lapmaster SFT; models "Mirra" and "Reflexion" manufactured by Applied Materials; POLI-400L”; model “Reflexion LK” manufactured by AMAT, etc.
3.實施例 3. Example
以下，藉由實施例對本發明進行說明，但本發明並不受該些實施例的任何限定。再者，本實施例中的「份」及「%」只要無特別說明則為質量基準。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited by these examples. In addition, "part" and "%" in this Example are mass basis unless otherwise indicated.
3.1.包含研磨粒的水分散體的製備 3.1. Preparation of aqueous dispersions containing abrasive particles
<氧化鈦粒子A的製備> <Preparation of Titanium Oxide Particles A>
藉由常規方法對硫酸氧鈦溶液進行水解，於進行過濾清洗後的含水二氧化鈦濾餅(二氧化鈦水合物)35kg(以TiO2換算計為10kg)中，一邊攪拌一邊投入48%氫氧化鈉水溶液40kg，之後進行加熱，以95℃~105℃的溫度範圍攪拌2小時。繼而，對此漿料進行過濾，並進行清洗，藉此獲得經鹼處理的二氧化鈦水合物。對此水合物濾餅加入水進行漿料化，調整為TiO2換算濃度110g/L。一邊攪拌此漿料，一邊添加35%鹽酸，製成pH7.0。 The titanyl sulfate solution was hydrolyzed by a conventional method, and 40 kg of a 48% sodium hydroxide aqueous solution was added to 35 kg (10 kg in conversion of TiO 2 ) of the hydrated titanium dioxide filter cake (titanium dioxide hydrate) after filtration and washing, while stirring, and then heated, and stirred at a temperature range of 95° C. to 105° C. for 2 hours. Next, this slurry was filtered and washed to obtain alkali-treated titanium dioxide hydrate. Water was added to the hydrate filter cake to make slurry, and the concentration was adjusted to 110 g/L in terms of TiO 2 . While stirring this slurry, 35% hydrochloric acid was added to adjust the pH to 7.0.
繼而，將所述漿料加熱至50℃，於此溫度下一邊攪拌一邊以4分鐘添加35%鹽酸12.5kg，使添加鹽酸後的漿料中的鹽酸濃度以100%HCl換算計成為40g/L。鹽酸添加速度設為每TiO2 換算1kg為0.11kg/分。於添加鹽酸後，繼而進行漿料的加熱，以100℃進行2小時的熟化。對熟化後的漿料添加氨水，中和為pH=6.5。進行過濾、水洗，於乾燥後，利用流體能量研磨機進行粉碎，獲得金紅石型氧化鈦粒子A。 Next, the slurry was heated to 50° C., and 12.5 kg of 35% hydrochloric acid was added for 4 minutes while stirring at this temperature, so that the concentration of hydrochloric acid in the slurry after the addition of hydrochloric acid was 40 g/L in terms of 100% HCl. The hydrochloric acid addition rate was 0.11 kg/min per 1 kg of TiO 2 converted. After adding hydrochloric acid, heating of the slurry was performed successively, and aging was performed at 100 degreeC for 2 hours. Ammonia water is added to the aged slurry to neutralize to pH=6.5. Filtration, washing with water, and drying were carried out, followed by pulverization with a fluid energy mill to obtain rutile-type titanium oxide particles A.
針對上述中所製備的金紅石型氧化鈦粒子A，使用流動式比表面積自動測定裝置(島津製作所股份有限公司製造，「微型測量流動吸附II2300(micrometricsFlowSorbII2300)」)，藉由BET法來測定比表面積，根據其測定值而算出平均粒徑，結果求出為139nm。 For the rutile-type titanium oxide particles A prepared above, the specific surface area was measured by the BET method using a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, "micrometrics Flow Sorb II 2300"), and the average particle diameter was calculated from the measured value, which was found to be 139 nm.
<氧化鋁被覆氧化鈦粒子B的製備> <Preparation of alumina-coated titanium oxide particles B>
使用上述中所製備的氧化鈦粒子A，將以TiO2換算計為200g/L的水分散液800mL加熱至60℃並攪拌30分鐘。繼而，加入18%鋁酸鈉水溶液32mL(以Al2O3換算計，相對於TiO2而為5%)，同時加入30%稀硫酸30mL，將該漿料的pH保持為5~6達10分鐘，同時進行中和，然後攪拌30分鐘。對其進行過濾、清洗，並於110℃下進行24小時乾燥後加以粉碎，獲得氧化鋁被覆金紅石型氧化鈦粒子B。 Using the titanium oxide particles A prepared above, 800 mL of an aqueous dispersion liquid of 200 g/L in terms of TiO 2 was heated to 60° C. and stirred for 30 minutes. Next, 32 mL of an 18% sodium aluminate aqueous solution (5% relative to TiO 2 in terms of Al 2 O 3 ) was added, and 30 mL of 30% dilute sulfuric acid was added at the same time, and the pH of the slurry was kept at 5 to 6 for 10 minutes while neutralizing and stirring for 30 minutes. This was filtered, washed, dried at 110°C for 24 hours, and then pulverized to obtain alumina-coated rutile-type titanium oxide particles B.
針對上述中所製備的氧化鋁被覆金紅石型氧化鈦粒子B，使用流動式比表面積自動測定裝置(島津製作所股份有限公司製造，「微型測量流動吸附II2300(micrometricsFlowSorbII2300)」)，藉由BET法來測定比表面積，根據其測定值而算出平均粒徑，結果求出為142nm。 For the alumina-coated rutile-type titanium oxide particles B prepared above, the specific surface area was measured by the BET method using a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, "micrometrics Flow Sorb II 2300"), and the average particle diameter was calculated from the measured value, which was found to be 142 nm.
<二氧化矽粒子水分散體的製備> <Preparation of Aqueous Dispersion of Silica Particles>
針對四甲氧基矽烷1522.2g、甲醇413.0g的混合液，將液溫保持為35℃並花費55分鐘滴加至純水787.9g、26%氨水786.0g、甲醇12924g的混合液中，獲得以水、甲醇為液狀介質的二氧化矽溶膠。將此二氧化矽溶膠於常壓下加熱濃縮至5000mL，獲得二氧化矽粒子分散體。 For the mixed solution of 1522.2 g of tetramethoxysilane and 413.0 g of methanol, keep the liquid temperature at 35°C and spend 55 minutes to add dropwise to the mixed solution of 787.9 g of pure water, 786.0 g of 26% ammonia water, and 12924 g of methanol to obtain a silica sol with water and methanol as the liquid medium. The silica sol was heated and concentrated to 5000 mL under normal pressure to obtain a silica particle dispersion.
針對上述中所製備的二氧化矽粒子，使用流動式比表面積自動測定裝置(島津製作所股份有限公司製造，「微型測量流動吸附II2300(micrometricsFlowSorbII2300)」)，藉由BET法來測定比表面積，根據其測定值而算出平均粒徑，結果求出為142nm。 For the silica particles prepared above, the specific surface area was measured by the BET method using a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, "micrometrics FlowSorb II2300"), and the average particle diameter was calculated from the measured value, which was found to be 142 nm.
3.2.化學機械研磨用組成物的製備及動電位的測定 3.2. Preparation of composition for chemical mechanical polishing and measurement of zeta potential
於聚乙烯製容器中，以成為表1~表3所示的組成的方式添加各成分，進而視需要加入氨，以成為表1~表3所示的pH的方式進行調整，並以全部成分的合計量成為100質量份的方式以純水進行調整，藉此製備各實施例及各比較例的化學機械研磨用組成物。 In a container made of polyethylene, each component was added so as to have the composition shown in Tables 1 to 3, and ammonia was added as needed, and the pH was adjusted to be the pH shown in Tables 1 to 3, and the total amount of all the components was adjusted with pure water so that it became 100 parts by mass, thereby preparing chemical mechanical polishing compositions for each example and each comparative example.
另外，使用超音波方式粒度分佈．動電位測定裝置(分散技術(Dispersion Technology)公司製造，型號「DT-1200」)，測定上述中所獲得的化學機械研磨用組成物中所含的研磨粒的表面電荷(動電位)。將其結果一併示於表1~表3中。 In addition, particle size distribution using ultrasonic method. A potentiodynamic measuring device (manufactured by Dispersion Technology, model "DT-1200") measured the surface charge (dynamic potential) of the abrasive grains contained in the chemical mechanical polishing composition obtained above. The results are shown in Tables 1 to 3 together.
3.3.評價方法 3.3. Evaluation method
3.3.1.研磨速度評價 3.3.1. Grinding speed evaluation
使用上述中所獲得的化學機械研磨用組成物，以直徑8吋的帶釕膜50nm的晶圓為被研磨體，以下述研磨條件進行30秒的化學機械研磨試驗。 Using the composition for chemical mechanical polishing obtained above, a wafer with a diameter of 8 inches and a 50 nm ruthenium film was used as the object to be polished, and a chemical mechanical polishing test was carried out for 30 seconds under the following polishing conditions.
<研磨條件> <Grinding conditions>
．研磨裝置：G & P科技(TECHNOLOGY)公司製造，型號「POLI-400L」 ． Grinding device: Manufactured by G & P TECHNOLOGY, model "POLI-400L"
．研磨墊：富士紡績公司製造，「多硬質聚胺基甲酸酯墊；H800-typel(3-1S)775」 ． Polishing pad: "Multi-rigid polyurethane pad; H800-typel(3-1S)775" manufactured by Fuji Industries
．化學機械研磨用組成物供給速度：100mL/分 ． Supply rate of composition for chemical mechanical polishing: 100mL/min
．壓盤轉速：100rpm ． Platen speed: 100rpm
．研磨頭轉速：90rpm ． Grinding head speed: 90rpm
．研磨頭按壓壓力：2psi ． Grinding head pressing pressure: 2psi
．研磨速度(Å/分)=(研磨前的膜的厚度-研磨後的膜的厚度)/研磨時間 ． Grinding speed (Å/min) = (thickness of the film before grinding - thickness of the film after grinding) / grinding time
再者，釕膜的厚度是藉由電阻率測定機(NPS公司製造，型號「Σ-5」)，以直流4探針法對電阻進行測定，並根據此片電阻值及釕的體積電阻率而由下述式算出。 In addition, the thickness of the ruthenium film was measured by the DC 4-probe method with a resistivity measuring machine (manufactured by NPS Corporation, model "Σ-5"), and calculated from the following formula based on the sheet resistance value and the volume resistivity of ruthenium.
膜的厚度(Å)=[釕膜的體積電阻率(Ω．m)÷片電阻值(Ω/sq)]×1010 Membrane thickness (Å) = [volume resistivity of ruthenium membrane (Ω.m) ÷ sheet resistance value (Ω/sq)] × 10 10
研磨速度的評價基準如下。將釕膜的研磨速度及其評價 結果一併示於表1~表3。 The evaluation criteria of the polishing rate are as follows. The grinding speed of ruthenium film and its evaluation The results are shown in Table 1~Table 3 together.
(評價基準) (evaluation criteria)
．於研磨速度為300Å/分以上的情況下，研磨速度大，因此，能夠容易地確保實際的半導體研磨中與其他材料膜的研磨的速度平衡，是實用性的，由此判斷為良好，標記為「A」。 ． When the polishing speed is 300 Å/min or more, the polishing speed is high, so it is practical to easily ensure the speed balance with the polishing of other material films in actual semiconductor polishing, so it is judged as good and marked as "A".
．於研磨速度不足300Å/分的情況下，研磨速度小，因此，實用困難，而判斷為不良，標記為「B」。 ． When the polishing speed is less than 300 Å/min, the polishing speed is low, so it is difficult to put it to practical use, and it is judged as defective, and "B" is indicated.
3.3.2.缺陷評價 3.3.2. Defect evaluation
針對作為被研磨體的直徑12吋的帶釕膜的晶圓，以下述條件進行1分鐘的研磨。 A 12-inch-diameter wafer with a ruthenium film was polished under the following conditions for 1 minute.
<研磨條件> <Grinding conditions>
．研磨裝置：AMAT公司製造，型號「瑞福興(Reflexion)LK」 ． Grinding device: Manufactured by AMAT, model "Reflexion LK"
．研磨墊：富士紡績公司製造，「多硬質聚胺基甲酸酯墊；H800-typel(3-1S)775」 ． Polishing pad: "Multi-rigid polyurethane pad; H800-typel(3-1S)775" manufactured by Fuji Industries
．化學機械研磨用組成物供給速度：300mL/分 ． Supply rate of composition for chemical mechanical polishing: 300mL/min
．壓盤轉速：100rpm ． Platen speed: 100rpm
．研磨頭轉速：90rpm ． Grinding head speed: 90rpm
．研磨頭按壓壓力：2psi ． Grinding head pressing pressure: 2psi
針對上述中進行了研磨的帶釕膜的晶圓，使用缺陷檢查裝置(科磊(KLA Tencor)公司製造，型號「表面掃描SP1(Surfscan SP1)」)，對90nm以上的大小的缺陷總數進行計數。評價基準如下。將每晶圓的缺陷總數及其評價結果一併示於表1~表3。 For the wafer with the ruthenium film polished above, the total number of defects with a size of 90 nm or more was counted using a defect inspection device (manufactured by KLA Tencor, model "Surfscan SP1"). The evaluation criteria are as follows. The total number of defects per wafer and their evaluation results are shown in Tables 1 to 3.
(評價基準) (evaluation criteria)
．將每晶圓的缺陷總數不足500個的情況判斷為良好，於表中記載為「A」。 ． The case where the total number of defects per wafer was less than 500 was judged to be good, and described as "A" in the table.
．將每晶圓的缺陷總數為500個以上的情況判斷為不良，於表中記載為「B」。 ． When the total number of defects per wafer was 500 or more, it was judged as defective, and described as "B" in the table.
3.3.3.化學機械研磨用組成物的起泡試驗 3.3.3. Foaming test of composition for chemical mechanical polishing
將表1~表3所記載的化學機械研磨用組成物5mL放入至透明塑膠容器(亞速旺(ASONE)製造，10mL苯乙烯棒瓶)中，加蓋密閉，靜置一天。一天後，藉由目視對容器壁面上附著的起泡的數量進行計數。化學機械研磨用組成物的起泡試驗的評價基準如下。將起泡的個數及其評價結果一併示於表1~表3。 Put 5 mL of the composition for chemical mechanical polishing described in Table 1 to Table 3 into a transparent plastic container (manufactured by ASONE, 10 mL styrene stick bottle), seal it with a cap, and let it stand for a day. One day later, the number of blisters adhered to the container wall was counted visually. The evaluation criteria of the foaming test of the chemical mechanical polishing composition are as follows. The number of blisters and their evaluation results are shown in Tables 1 to 3 together.
(評價基準) (evaluation criteria)
．於起泡數不足3個的情況下，氣體的產生少，因此是實用性的，由此判斷為良好，標記為「A」。 ． When the number of bubbles is less than 3, the generation of gas is small, so it is practical, and it is judged to be good from this, and it is marked as "A".
．於起泡數為3個以上的情況下，氣體的產生多，因此是非實用性的，由此判斷為不良，標記為「B」。 ． When the number of bubbles is 3 or more, since there are many gas generation, it is impractical, it is judged as defective, and it is marked as "B".
3.3.4.腐蝕評價 3.3.4. Corrosion evaluation
將所述帶釕膜50nm的晶圓切割為1cm×1cm，製成金屬晶圓試驗片。針對此試驗片，藉由掃描式電子顯微鏡以倍率50,000倍預先對表面進行觀察。分別將各實施例及各比較例的化學機械研磨用組成物50mL放入至聚乙烯容器中，並保持為25℃，將金屬晶圓試驗片(1cm×1cm)浸漬60分鐘，以流水進行10秒鐘的 清洗，並使其乾燥，之後，藉由掃描式電子顯微鏡以倍率50,000倍對表面的腐蝕狀態進行觀察，以以下的基準進行評價。將其結果一併示於表1~表3。 The 50 nm wafer with the ruthenium film was cut into 1 cm×1 cm to make a metal wafer test piece. With respect to this test piece, the surface was observed in advance with a scanning electron microscope at a magnification of 50,000 times. Put 50 mL of the chemical mechanical polishing composition of each example and each comparative example into a polyethylene container, and keep it at 25° C., immerse a metal wafer test piece (1 cm × 1 cm) for 60 minutes, and carry out 10 seconds in running water. After cleaning and drying, the state of corrosion on the surface was observed with a scanning electron microscope at a magnification of 50,000 times, and the following criteria were used for evaluation. The results are shown in Tables 1 to 3 together.
(評價基準) (evaluation criteria)
A：與浸漬前相比，未確認到因腐蝕導致的表面的形狀變化。 A: Compared with before immersion, the shape change of the surface by corrosion was not recognized.
B：與浸漬前相比，同時存在被腐蝕了的部位與未被腐蝕的部位。 B: Corroded parts and uncorroded parts exist at the same time compared with before immersion.
C：與浸漬前相比，整個面被腐蝕。 C: Compared with before dipping, the whole surface is corroded.
3.4.評價結果 3.4. Evaluation Results
於表1~表3中示出各實施例及各比較例的化學機械研磨用組成物的組成以及各評價結果。 Tables 1 to 3 show the composition of the chemical mechanical polishing composition of each example and each comparative example and each evaluation result.
[表1]
表1~表3中的各成分分別使用了下述商品或試劑。 For each component in Tables 1 to 3, the following products or reagents were used, respectively.
<研磨粒> <Abrasive grains>
．氧化鈦粒子A：上述中所製作的金紅石型氧化鈦粒子A ． Titanium oxide particles A: Rutile-type titanium oxide particles A produced above
．氧化鈦粒子B：上述中所製作的氧化鋁被覆金紅石型氧化鈦粒子B ． Titanium oxide particles B: alumina-coated rutile-type titanium oxide particles B produced above
．二氧化矽粒子：上述中所製作的二氧化矽粒子水分散體 ． Silica particles: the aqueous dispersion of silica particles prepared above
<聚(甲基)丙烯酸> <Poly(meth)acrylic acid>
．聚(甲基)丙烯酸A：東亞合成股份有限公司製造，商品名「朱麗馬(Jurymer)AC-10L」，重量平均分子量(Mw)=50,000 ． Poly(meth)acrylic acid A: manufactured by Toa Gosei Co., Ltd., trade name "Jurymer (Jurymer) AC-10L", weight average molecular weight (Mw)=50,000
．聚(甲基)丙烯酸B：東亞合成股份有限公司製造，商品名「朱麗馬(Jurymer)AC-10P」，重量平均分子量(Mw)=9,000 ． Poly(meth)acrylic acid B: manufactured by Toa Gosei Co., Ltd., trade name "Jurymer (Jurymer) AC-10P", weight average molecular weight (Mw)=9,000
．聚(甲基)丙烯酸C：東亞合成股份有限公司製造，商品名「朱麗馬(Jurymer)AC-10H」，重量平均分子量(Mw)=800,000 ． Poly(meth)acrylic acid C: manufactured by Toa Gosei Co., Ltd., trade name "Jurymer (Jurymer) AC-10H", weight average molecular weight (Mw)=800,000
<氧化劑> <Oxidizing agent>
．過氧化氫：富士軟片和光純藥工業股份有限公司製造，商品名「過氧化氫」，30質量%過氧化氫水(各表中的過氧化氫的含量表示的是進行了過氧化氫換算的含量，而非30質量%過氧化氫水的含量) ． Hydrogen peroxide: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "hydrogen peroxide", 30% by mass hydrogen peroxide water (the content of hydrogen peroxide in each table represents the content converted from hydrogen peroxide, not the content of 30% by mass hydrogen peroxide water)
．過碘酸鉀：富士軟片和光純藥工業股份有限公司製造，商品名「過碘酸鉀」 ． Potassium periodate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "potassium periodate"
．次氯酸鉀：關東化學股份有限公司製造，商品名「次氯酸鉀溶液」 ． Potassium hypochlorite: manufactured by Kanto Chemical Co., Ltd., trade name "potassium hypochlorite solution"
<有機酸> <Organic acid>
．丙二酸：富士軟片和光純藥工業股份有限公司製造，商品名「丙二酸」 ． Malonic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "malonic acid"
．馬來酸：富士軟片和光純藥工業股份有限公司製造，商品名「馬來酸」 ． Maleic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "maleic acid"
．硬脂酸：富士軟片和光純藥工業股份有限公司製造，商品名「硬脂酸」 ． Stearic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "stearic acid"
．月桂酸：富士軟片和光純藥工業股份有限公司製造，商品名「月桂酸」 ． Lauric acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "lauric acid"
<其他添加劑> <Other additives>
．苯并***：富士軟片和光純藥工業股份有限公司製造，商品名「1H-苯并***」，含氮雜環化合物 ． Benzotriazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "1H-benzotriazole", a nitrogen-containing heterocyclic compound
．1,2,4-***：東京化成工業股份有限公司製造，商品名「1,2,4-Triazole」，含氮雜環化合物 ． 1,2,4-Triazole: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "1,2,4-Triazole", nitrogen-containing heterocyclic compound
．乙炔二醇系非離子性界面活性劑：日信化學工業股份有限公司製造，商品名「薩非諾爾(Surfynol)485」，界面活性劑 ． Acetylene glycol-based nonionic surfactant: manufactured by Nissin Chemical Industry Co., Ltd., trade name "Surfynol (Surfynol) 485", surfactant
．十二烷基苯磺酸鈉：東京化成工業股份有限公司製造，商品名「Sodium Dodecylbenzenesulfonate」，界面活性劑 ． Sodium dodecylbenzenesulfonate: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Sodium Dodecylbenzenesulfonate", surfactant
．烯基琥珀酸二鉀：花王股份有限公司製造，商品名「拉特姆(LATEMUL)ASK」，界面活性劑 ． Dipotassium alkenyl succinate: manufactured by Kao Co., Ltd., trade name "LATEMUL ASK", surfactant
．聚乙烯基吡咯啶酮(K30)：日本觸媒股份有限公司製造，商品名「聚乙烯基吡咯啶酮K-30」，水溶性高分子 ． Polyvinylpyrrolidone (K30): manufactured by Nippon Shokubai Co., Ltd., trade name "polyvinylpyrrolidone K-30", water-soluble polymer
於實施例1~實施例17中，可知：藉由使用氧化鋁被覆氧化鈦粒子B作為研磨粒，化學機械研磨用組成物的穩定性優異，可對半導體基板(尤其是含釕膜的基板)進行高速研磨，且可減少被研磨面的研磨損傷。 In Examples 1 to 17, it can be seen that by using alumina-coated titanium oxide particles B as abrasive grains, the stability of the composition for chemical mechanical polishing is excellent, semiconductor substrates (especially substrates containing ruthenium films) can be polished at high speed, and the grinding damage of the polished surface can be reduced.
比較例1是使用含有未經氧化鋁被覆的氧化鈦粒子A作為研磨粒、且不含有聚(甲基)丙烯酸的化學機械研磨用組成物的示例。於此情況下，於氧化鈦粒子A的表面確認到因與過氧化氫的反應而形成的大量的起泡。另外，於缺陷評價中，確認到因使用未經氧化鋁被覆的氧化鈦粒子A而形成的大量的缺陷。 Comparative Example 1 is an example of using a chemical mechanical polishing composition containing titanium oxide particles A not coated with alumina as abrasive grains and not containing poly(meth)acrylic acid. In this case, a large number of foams formed by the reaction with hydrogen peroxide were confirmed on the surface of the titanium oxide particle A. In addition, in the defect evaluation, a large number of defects formed by using the titanium oxide particles A not coated with alumina were confirmed.
比較例2是使用含有氧化鋁被覆氧化鈦粒子B作為研磨粒、且不含有聚(甲基)丙烯酸的化學機械研磨用組成物的示例。於此情況下，可抑制氧化鋁被覆氧化鈦粒子B的表面上的與過氧化氫的反應，從而穩定。然而，無法獲得由聚(甲基)丙烯酸帶來的被研磨面的摩擦減少效果，於被研磨面的表面確認到雖較比較例1少但仍為大量的缺陷。 Comparative Example 2 is an example of using a composition for chemical mechanical polishing that contains alumina-coated titanium oxide particles B as abrasive grains and does not contain poly(meth)acrylic acid. In this case, the reaction with hydrogen peroxide on the surface of the alumina-coated titanium oxide particle B can be suppressed and stabilized. However, the friction-reducing effect of the polished surface by poly(meth)acrylic acid could not be obtained, and a large number of defects were confirmed on the surface of the polished surface although it was smaller than that of Comparative Example 1.
比較例3是使用含有未經氧化鋁被覆的氧化鈦粒子A作為研磨粒、且含有聚(甲基)丙烯酸的化學機械研磨用組成物的示例。於此情況下，與比較例1同樣地，亦於氧化鈦粒子A的表面確認到因與過氧化氫的反應而形成的大量的起泡。另外可知，於使用未經氧化鋁被覆的氧化鈦粒子A的情況下，於被研磨面的表面會產生大量的缺陷。 Comparative Example 3 is an example of using a chemical mechanical polishing composition containing titanium oxide particles A not coated with alumina as abrasive grains and poly(meth)acrylic acid. In this case, similarly to Comparative Example 1, a large number of foams formed by the reaction with hydrogen peroxide were confirmed on the surface of the titanium oxide particles A. Moreover, when using the titanium oxide particle A which is not coated with alumina, it turns out that many defects generate|occur|produce on the surface of the surface to be polished.
比較例4及比較例5是使用含有氧化鋁被覆氧化鈦粒子 B作為研磨粒、且含有聚(甲基)丙烯酸、但pH不足7的化學機械研磨用組成物的示例。於此情況下，氧化鋁被覆氧化鈦粒子B的動電位的絕對值變小，導致該些粒子彼此凝聚，因此釕膜的研磨速度變小，於被研磨面的表面確認到大量的缺陷。 Comparative Example 4 and Comparative Example 5 use titanium oxide particles containing alumina B is an example of a chemical mechanical polishing composition having abrasive grains, containing poly(meth)acrylic acid, and having a pH of less than 7. In this case, the absolute value of the zeta potential of the alumina-coated titanium oxide particles B decreases, causing these particles to aggregate together, so the polishing rate of the ruthenium film decreases, and many defects are confirmed on the surface to be polished.
比較例6是使用含有二氧化矽粒子作為研磨粒、且含有聚(甲基)丙烯酸的化學機械研磨用組成物的示例。於此情況下可知：關於被研磨面的表面缺陷或漿料穩定性並無問題，但釕膜的研磨速度顯著降低。 Comparative Example 6 is an example of using a chemical mechanical polishing composition containing silica particles as abrasive grains and poly(meth)acrylic acid. In this case, it can be seen that there is no problem with respect to surface defects on the surface to be polished or slurry stability, but the polishing rate of the ruthenium film is significantly reduced.
自以上結果得知：根據本發明的化學機械研磨用組成物，化學機械研磨用組成物的穩定性優異，可對半導體基板(尤其是含釕膜的基板)進行高速研磨，且可減少被研磨面的研磨損傷。 From the above results, it is known that according to the composition for chemical mechanical polishing of the present invention, the composition for chemical mechanical polishing has excellent stability, can perform high-speed polishing on a semiconductor substrate (especially a substrate containing a ruthenium film), and can reduce polishing damage on the surface to be polished.
本發明不限定於所述實施方式，可進行各種變形。例如，本發明包括與實施方式中說明的構成實質上相同的構成(例如功能、方法及結果相同的構成，或目的及效果相同的構成)。另外，本發明包括將實施方式中說明的構成的非本質部分進行了替換的構成。另外，本發明包括發揮與實施方式中說明的構成相同的作用效果的構成或可達成相同目的之構成。另外，本發明包括對實施方式中說明的構成附加公知技術所得的構成。 The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes substantially the same configurations as those described in the embodiments (for example, configurations with the same functions, methods, and results, or configurations with the same purpose and effects). In addition, this invention includes the structure which replaced the non-essential part of the structure demonstrated in embodiment. In addition, the present invention includes configurations that exhibit the same effects as the configurations described in the embodiments, or configurations that can achieve the same purpose. In addition, the present invention includes configurations obtained by adding known techniques to the configurations described in the embodiments.
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