KR100679551B1 - Polishing fluid for metal and polishing method - Google Patents
Polishing fluid for metal and polishing method Download PDFInfo
- Publication number
- KR100679551B1 KR100679551B1 KR1020057023495A KR20057023495A KR100679551B1 KR 100679551 B1 KR100679551 B1 KR 100679551B1 KR 1020057023495 A KR1020057023495 A KR 1020057023495A KR 20057023495 A KR20057023495 A KR 20057023495A KR 100679551 B1 KR100679551 B1 KR 100679551B1
- Authority
- KR
- South Korea
- Prior art keywords
- metal
- polishing
- compound
- polishing liquid
- triazole
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 239
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 170
- 239000002184 metal Substances 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims description 44
- 239000012530 fluid Substances 0.000 title description 2
- 239000007788 liquid Substances 0.000 claims abstract description 81
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 69
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 230000004888 barrier function Effects 0.000 claims description 30
- -1 organic acid ester Chemical class 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 28
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 27
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 25
- 125000003277 amino group Chemical group 0.000 claims description 24
- 239000011229 interlayer Substances 0.000 claims description 24
- 229910052721 tungsten Inorganic materials 0.000 claims description 24
- 239000010937 tungsten Substances 0.000 claims description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 22
- 150000002739 metals Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 150000003852 triazoles Chemical group 0.000 claims description 19
- 239000006061 abrasive grain Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012964 benzotriazole Substances 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 229920003169 water-soluble polymer Polymers 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 4
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 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 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 24
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical group NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 238000007517 polishing process Methods 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001630 malic acid Substances 0.000 description 6
- 235000011090 malic acid Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
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- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 2
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
- B24D3/001—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as supporting member
- B24D3/002—Flexible supporting members, e.g. paper, woven, plastic materials
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
금속용 연마액은, 산화제, 산화금속 용해제, 금속방식제 및 물을 함유하고, 상기 금속방식제가 아미노-트리아졸 골격을 갖는 화합물 및 이미다졸 골격을 갖는 화합물의 적어도 한쪽이다. 상기 연마액을 이용하는 것에 의해, 반도체 디바이스의 배선형성공정에 있어서, 에칭속도를 낮게 유지하면서, 연마속도를 충분히 상승시키고, 금속표면의 부식과 디싱의 발생을 억제하고, 신뢰성이 높은 금속막의 매립패턴 형성을 가능하게 한다.The polishing liquid for metal contains an oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent, and water, and the metal anticorrosive agent is at least one of a compound having an amino-triazole skeleton and a compound having an imidazole skeleton. By using the polishing liquid in the wiring forming step of the semiconductor device, while maintaining the etching rate low, the polishing rate is sufficiently increased, the corrosion of the metal surface and the occurrence of dishing are suppressed, and the highly reliable metal film filling pattern Enable formation.
Description
본 발명은, 반도체 디바이스의 배선 형성공정에 적합한 금속용 연마액 및 그것을 이용한 연마방법에 관한 것이다. TECHNICAL FIELD This invention relates to the polishing liquid for metals suitable for the wiring formation process of a semiconductor device, and the polishing method using the same.
최근, 반도체 집적회로(LSI)의 고집적화, 고성능화에 수반하여 새로운 미세 가공기술이 개발되고 있다. 화학기계연마(CMP)법도 그 하나이고, LSI 제조공정, 특히 다층배선 형성공정에 있어서의 층간절연막의 평탄화, 금속 플러그 형성, 매립 배선형성에 있어서 빈번하게 이용되는 기술이다. 이 기술은, 예컨대 미국특허 No.4944836호 명세서에 개시되어 있다.Recently, new microfabrication technologies have been developed with high integration and high performance of semiconductor integrated circuits (LSI). The chemical mechanical polishing (CMP) method is one of them, and it is a technique frequently used in the planarization of the interlayer insulating film, the metal plug formation, and the buried wiring formation in the LSI manufacturing process, especially in the multilayer wiring formation process. This technique is disclosed, for example, in the specification of US Patent No.4944836.
최근, LSI를 고성능화하기 위해서, 배선재료로서 구리합금의 이용이 시도되고 있다. 그러나, 구리합금은 종래의 알루미늄 합금배선의 형성에 빈번하게 이용된 드라이에칭법에 의한 미세가공이 곤란하다. 따라서, 미리 홈을 형성하고 있는 절연막상에 구리합금 박막을 집적하여 매립하고, 홈부 이외의 구리합금 박막을 CMP에 의해 제거하여 매립 배선을 형성하는, 소위 대머신법이 주로 채용되고 있다. 이 기술은, 예컨대 일본특개평 2-278822호 공보에 개시되어 있다.In recent years, in order to improve LSI performance, the use of a copper alloy has been attempted as a wiring material. However, the copper alloy is difficult to be finely processed by the dry etching method frequently used in the formation of conventional aluminum alloy wiring. Therefore, a so-called large machine method is mainly employed in which a copper alloy thin film is integrated and buried on an insulating film in which grooves are formed in advance, and a copper alloy thin film other than the groove portion is removed by CMP to form a buried wiring. This technique is disclosed, for example, in Japanese Patent Laid-Open No. 2-278822.
금속의 CMP의 일반적인 방법은, 원형의 연마정반(플라텐)상에 연마패드를 첩 부하고, 연마패드 표면을 금속용 연마액으로 적시고, 기체의 금속막을 형성한 면을 눌러서, 그 이면으로부터 소정의 압력(연마압력 혹은 연마하중)을 가한 상태에서 연마정반을 회전시켜, 연마액과 금속막의 볼록부와의 기계적 마찰에 의해 볼록부의 금속막을 제거하는 것이다.In the general method of CMP of metal, a polishing pad is affixed on a circular polishing plate (platten), the surface of the polishing pad is soaked with a polishing liquid for metal, and the surface on which a metal film of gas is formed is pressed, and a predetermined surface is removed from the back surface. The polishing table is rotated under the application of a pressure (polishing pressure or polishing load) to remove the metal film of the convex portion by mechanical friction between the polishing liquid and the convex portion of the metal film.
CMP에 이용되는 금속용 연마액은, 일반적으로는 산화제 및 고체 지립으로 이루어져 있고, 필요에 따라 산화금속 용해제, 금속방식제가 더 첨가된다. 우선 산화에 의해 금속막 표면을 산화하고, 그 산화층을 고체 지립에 의해 깎아내는 것이 기본적인 메카니즘으로 생각되고 있다. 오목부의 금속표면의 산화층은 연마패드에 그다지 접촉하지 않아, 고체 지립에 의한 깎아내기 효과가 미치지 않으므로, CMP의 진행과 함께 볼록부의 금속층이 제거되어 기체표면은 평탄화된다. 이의 상세한 내용에 관해서는 저널ㆍ오브ㆍ일렉트로케미칼 서사이어티지(Journal of Electrochemical Society)의 제138권 11호(1991년 발행)의 3460∼3464페이지에 개시되어 있다.The polishing liquid for metals used for CMP generally consists of an oxidizing agent and a solid abrasive grain, and a metal oxide dissolving agent and a metal anticorrosive agent are further added as needed. First, the basic mechanism is considered to oxidize the surface of a metal film by oxidation and to scrape the oxide layer by solid abrasive grains. Since the oxide layer of the metal surface of the concave portion does not come into contact with the polishing pad so much, and the scraping effect caused by the solid abrasive grains is not exerted, the metal layer of the convex portion is removed and the gas surface is flattened with the progress of CMP. Details thereof are disclosed in pages 3460-3464 of Journal 138, 11 (issued in 1991) of the Journal of Electrochemical Society.
CMP에 의한 연마속도를 높이는 방법으로서 산화금속 용해제를 첨가하는 것이 유효하게 되어 있다. 고체 지립에 의해 깎아내어진 금속 산화물의 입자를 연마액에 용해시켜 버리면 고체 지립에 의한 깎아내기 효과가 증가하기 때문이라고 해석할 수 있다.It is effective to add a metal oxide solubilizer as a method of increasing the polishing rate by CMP. It can be interpreted that when the particles of the metal oxide scraped off by the solid abrasive grains are dissolved in the polishing liquid, the effect of scraping off the solid abrasive grains increases.
다만, 문제점으로서, 금속막 표면의 용해(이하, 에칭이라 한다.)를 들 수 있다. 오목부의 금속막 표면의 산화층도 에칭되어 금속막 표면이 노출하면, 산화제에 의해 금속막 표면이 더욱 산화되고, 이것이 반복되면 오목부의 금속막의 에칭이 진 행해 버려서, 평탄화 효과가 손상되는 것이 염려된다. 예컨대, 매립된 금속배선의 표면 중앙부분이 등방적으로 부식되어 접시와 같이 우묵하게 되는 현상(디싱)이 염려된다. 또한, 에칭에 의해 금속 표면의 거칠음(코로젼)도 생기는 경우가 있다.However, as a problem, melting of the surface of the metal film (hereinafter referred to as etching) may be mentioned. If the oxide layer on the metal film surface of the recess is also etched and the metal film surface is exposed, the metal film surface is further oxidized by the oxidant. If this is repeated, etching of the metal film of the recess proceeds, and the planarization effect may be impaired. For example, there is a concern that the central portion of the surface of the buried metal wiring is isotropically corroded and recessed like a dish. Moreover, the roughness (corrosion) of a metal surface may also arise by etching.
이것을 방지하기 위해서 금속방식제가 더 첨가된다. 디싱이나 연마중의 구리합금의 부식을 억제하고, 신뢰성이 높은 LSI배선을 형성하기 위해서, 글리신 등의 아미노아세트산 또는 아미드황산으로 이루어진 산화금속 용해제 및 BTA(벤조트리아졸)를 함유하는 금속용 연마액을 이용하는 방법이 제창되어 있다. 이 기술은 예컨대 일본특개평 8-83780호 공보에 기재되어 있다.In order to prevent this, a metal anticorrosive is further added. Metal polishing liquid containing BTA (benzotriazole) and a metal oxide dissolving agent composed of amino acetic acid or amide sulfuric acid, such as glycine, in order to suppress corrosion of the copper alloy during dishing and polishing and to form highly reliable LSI wiring. How to use is proposed. This technique is described, for example, in Japanese Patent Laid-Open No. 8-83780.
그러나, 금속 방식제의 첨가에 의해, 연마속도가 저하하는 경우가 있다. 평탄화 특성을 유지하기 위해서는, 산화금속 용해제와 금속방식제의 효과의 밸런스를 취하는 것이 중요하고, 깎아낸 산화층의 입자가 효율 좋게 용해되어 CMP에 의한 연마속도가 크고, 또한 오목부의 금속막 표면의 산화층은 그다지 에칭되지 않는 것이 바람직하다.However, the polishing rate may decrease due to the addition of the metal anticorrosive. In order to maintain the planarization characteristics, it is important to balance the effects of the metal oxide dissolving agent and the metal anticorrosive agent, and the particles of the scraped oxide layer are efficiently dissolved, so that the polishing rate by CMP is high, and the oxide layer on the surface of the metal film of the concave portion. It is preferable that the silver is not etched very much.
이와 같이 산화금속 용해제와 금속 방식제를 첨가하여 화학반응의 효과를 가하는 것에 의해, CMP에 의한 연마속도가 향상함과 동시에, CMP되는 금속층 표면의 손상(대미지)도 저감되는 효과가 얻어진다.By adding a metal oxide dissolving agent and a metal anticorrosive agent in this way, and the effect of a chemical reaction, the polishing rate by CMP improves and the damage (damage) of the surface of the metal layer to be CMP is also acquired.
한편, 배선의 구리 혹은 구리합금 등의 하층에는, 층간절연막 중으로의 구리 확산방지를 위해서 배리어층으로서, 텅스텐, 질화텅스텐, 텅스텐합금 및 그 밖의 텅스텐 화합물 등의 도체막이 형성된다. 따라서, 구리 혹은 구리합금을 매립 배선 부분 이외에서는, 노출한 배리어층을 CMP에 의해 제거할 필요가 있다. 그러나, 이 들 배리어층용 도체막은, 구리 혹은 구리합금에 비하여 경도가 높기 때문에, 구리 또는 구리합금용 연마재료의 조합에서는 충분한 CMP속도가 얻어지지 않고, 배리어층을 CMP에 의해 제거하는 사이에 구리 또는 구리합금 등이 에칭되어 배선두께가 저하한다는 문제가 생긴다.On the other hand, a conductive film such as tungsten, tungsten nitride, tungsten alloy and other tungsten compounds is formed in the lower layer of the copper or copper alloy of the wiring as a barrier layer to prevent the diffusion of copper into the interlayer insulating film. Therefore, it is necessary to remove the exposed barrier layer by CMP except copper or copper alloy in the buried wiring portion. However, since the conductor film for these barrier layers has a higher hardness than copper or a copper alloy, a sufficient CMP rate cannot be obtained in a combination of copper or copper alloy abrasive materials, and copper or copper is removed during the removal of the barrier layer by CMP. The copper alloy or the like is etched to cause a problem that the wiring thickness is lowered.
본 발명은, 에칭속도를 낮게 유지하면서, 연마속도를 충분히 상승시키고, 금속 표면의 부식과 디싱의 발생을 억제하고, 신뢰성이 높은 금속막의 매립패턴형성을 가능하게 하는 금속용 연마액을 제공하는 것이다.SUMMARY OF THE INVENTION The present invention provides a polishing liquid for metal which sufficiently raises the polishing rate while keeping the etching rate low, suppresses the occurrence of corrosion and dishing on the metal surface, and enables the formation of a buried pattern of a highly reliable metal film. .
또한, 본 발명은, 에칭속도를 낮게 유지하면서, 연마속도를 충분히 상승시키고, 금속 표면의 부식과 디싱의 발생을 억제하고, 신뢰성이 높은 금속막의 매립패턴 형성을 생산성, 작업성, 수율 좋게 행할 수 있는 금속의 연마방법을 제공하는 것이다.In addition, the present invention can raise the polishing rate sufficiently while suppressing the occurrence of corrosion and dishing of the metal surface while maintaining the etching rate low, and can form a buried pattern of a highly reliable metal film with high productivity, workability and yield. It is to provide a method of polishing a metal.
발명의 개시
본 발명의 연마액은, 이하의 (1)∼(18)의 금속용 연마액 및 연마방법에 관한 것이다.
(1) 산화제, 산화금속 용해제, 금속방식제 및 물을 함유하고, 상기 금속방식제가,
트리아졸 고리의 탄소에 아미노기가 결합한 아미노-트리아졸 골격을 갖는 화합물 및
하기 일반식(I)
(일반식(I)중, R1, R2 및 R3은, 각각 독립하여 수소원자, 아미노기, 또는 C1∼C12의 알킬쇄를 나타낸다. 다만, R1, R2 및 R3의 전부가 수소원자인 경우를 제외한다.)
로 표시되는 이미다졸 골격을 갖는 화합물을 포함하는 금속용 연마액.
(2) 산화제, 산화금속 용해제, 금속방식제 및 물을 함유하고, 상기 금속방식제가,
아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물 및
하기 일반식(I)
(일반식(I)중, R1, R2 및 R3은, 각각 독립하여 수소원자, 아미노기, 또는 C1∼C12의 알킬쇄를 나타낸다. 다만, R1, R2 및 R3의 전부가 수소원자인 경우를 제외한다.)
로 표시되는 이미다졸 골격을 갖는 화합물
을 포함하는 금속용 연마액.
(3) 산화제, 산화금속 용해제, 금속방식제 및 물을 함유하고, 상기 금속방식제가
트리아졸 고리의 탄소에 아미노기가 결합한 아미노-트리아졸 골격을 갖는 화합물 및
아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물
을 포함하는 금속용 연마액.
(4) 상기 아미노-트리아졸 골격을 갖는 화합물이, 3-아미노-1,2,4-트리아졸인 상기 (1) 또는 (3) 기재의 금속용 연마액.
(5) 상기 이미다졸 골격을 갖는 화합물이, 2-메틸이미다졸, 2-에틸이미다졸, 2-(이소프로필)이미다졸, 2-프로필이미다졸, 2-부틸이미다졸, 4-메틸이미다졸, 2,4-디메틸이미다졸 및 2-에틸-4-메틸이미다졸로 이루어지는 군으로부터 선택되는 적어도 1종인 (1) 또는 (2) 기재의 금속용 연마액.
(6) 상기 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물이 1,2,3-트리아졸, 1,2,4-트리아졸, 벤조트리아졸 및 1-히드록시벤조트리아졸로 이루어지는 군으로부터 선택되는 적어도 1종인 상기 (2) 또는 (3) 기재의 금속용 연마액.
(7) 금속방식제가, 상기 아미노-트리아졸 골격을 갖는 화합물과, 상기 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물과, 상기 이미다졸 골격을 갖는 화합물을 포함하는 상기 (1)∼(6) 중 어느 하나에 기재된 금속용 연마액.
(8) 수용성 폴리머를 더 포함하는 상기 (1)∼(7) 중 어느 하나에 기재된 금속용 연마액.
(9) 수용성 폴리머가, 다당류, 폴리카본산, 폴리카본산의 에스테르, 폴리카본산의 염, 폴리아크릴아미드 및 비닐계 폴리머로 이루어지는 군으로부터 선택된 적어도 1종인 상기 (8) 기재의 금속용 연마액.
(10) 산화제가, 과산화수소, 질산, 과요오드산칼륨, 차아염소산, 과황산염 및 오존수로 이루어지는 군으로부터 선택되는 적어도 1종인 상기 (1)∼(9) 중 어느 하나에 기재된 금속용 연마액.
(11) 산화금속 용해제가, 유기산, 유기산에스테르, 유기산의 암모늄염 및 황산으로 이루어지는 군으로부터 선택되는 적어도 1종인 상기 (1)∼(10) 중 어느 하나에 기재된 금속용 연마액.
(12) 지립을 더 포함하는 상기 (1)∼(11) 중 어느 하나에 기재된 금속용 연마액.
(13) 연마되는 금속이, 구리, 구리합금, 구리산화물, 구리합금의 산화물, 탄탈 및 그 화합물, 티탄 및 그 화합물, 텅스텐 및 그 화합물로 이루어지는 군으로부터 선택되는 적어도 1종인 상기 (1)∼(12) 중 어느 하나에 기재된 금속용 연마액.
(14) 연마정반의 연마포상에 상기 (1)∼(13) 중 어느 하나에 기재된 금속용 연마액을 공급하면서, 금속막을 갖는 기체를 연마포에 압압한 상태에서 연마정반과 기체(基體)를 상대적으로 움직이는 것에 의해 금속막을 연마하는 연마방법.
(15) 금속막이, 구리, 구리합금, 구리의 산화물, 구리합금의 산화물, 탄탈 및 그 화합물, 티탄 및 그 화합물, 텅스텐 및 그 화합물로 이루어지는 군으로부터 선택되는 적어도 1종인 상기 (14) 기재의 연마방법.
(16) 2종 이상의 금속막의 적층을 연속하여 연마하는 상기 (14) 또는 (15) 기재의 연마방법.
(17) 2종 이상의 금속막의 적층 중, 처음에 연마되는 제 1의 막이 구리, 구리합금, 구리산화물, 구리합금의 산화물로부터 선택되는 1종 이상이고, 다음에 연마되는 제 2의 막이 탄탈 및 그 화합물, 티탄 및 그 화합물, 텅스텐 및 그 화합물로부터 선택되는 1종 이상인 상기 (16) 기재의 연마방법.
(18) 표면이 오목부 및 볼록부로 이루어지는 층간절연막과, 상기 층간절연막을 표면을 따라서 피복하는 배리어층과, 상기 오목부를 충전하여 배리어층을 피복하는 배선금속층을 갖는 기판의 배선금속층을 연마하여 상기 볼록부의 배리어층을 노출시키는 제 1 연마공정과, 상기 제 1 연마공정후에, 적어도 배리어층 및 오목부의 배선금속층을 연마하여 볼록부의 층간절연막을 노출시키는 제 2 연마공정을 포함하고, 적어도 제 2 연마공정에서 상기 (1)∼(13) 중 어느 하나에 기재된 금속용 연마액을 이용하여 연마하는 연마방법.
발명을 실시하기 위한 최선의 형태
이하, 본 발명을 상세하게 설명한다.
본 발명의 금속용 연마액은, 주요 구성성분으로서 산화제, 산화금속 용해제, 금속방식제 및 물을 함유하여 이루어진다. 상기 금속방식제는, 트리아졸 고리의 탄소에 아미노기가 결합한 아미노-트리아졸 골격을 갖는 화합물(A) 및 하기 일반식(I)
(일반식(I) 중, R1, R2 및 R3은, 각각 독립하여 수소원자, 아미노기, 또는 C1∼C12의 알킬쇄를 나타낸다. 다만, R1, R2 및 R3의 전부가 수소원자인 경우를 제외한다.)
로 표시되는 이미다졸 골격을 갖는 화합물(B)를 포함하거나,
상기 화합물(B) 및 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물(C)를 포함하거나, 또는
상기 화합물(A) 및 상기 화합물(C)를 포함한다. Disclosure of Invention
The polishing liquid of the present invention relates to the polishing liquid for metals and polishing methods of the following (1) to (18).
(1) an oxidizing agent, a metal oxide solubilizer, a metal anticorrosive agent and water, wherein the metal anticorrosive agent is
A compound having an amino-triazole skeleton having an amino group bonded to a carbon of a triazole ring, and
General formula (I)
(Compound (I) of, R 1, R 2 and R 3 are, each independently represent an alkyl chain of a hydrogen atom, an amino group, or C 1~ C 12. However, all of R 1, R 2 and R 3 Except when is a hydrogen atom.)
Polishing liquid for metals containing a compound having an imidazole skeleton represented by.
(2) an oxidizing agent, a metal oxide solubilizer, a metal anticorrosive agent and water, wherein the metal anticorrosive agent is
A compound having a triazole skeleton having no amino group, and
General formula (I)
(Compound (I) of, R 1, R 2 and R 3 are, each independently represent an alkyl chain of a hydrogen atom, an amino group, or C 1~ C 12. However, all of R 1, R 2 and R 3 Except when is a hydrogen atom.)
Compound having an imidazole skeleton represented by
Polishing liquid for metal comprising a.
(3) containing an oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent and water,
A compound having an amino-triazole skeleton having an amino group bonded to a carbon of a triazole ring, and
Compounds with triazole skeletons having no amino groups
Polishing liquid for metal comprising a.
(4) The polishing liquid for metal according to the above (1) or (3), wherein the compound having an amino-triazole skeleton is 3-amino-1,2,4-triazole.
(5) The compound having the imidazole skeleton is 2-methylimidazole, 2-ethylimidazole, 2- (isopropyl) imidazole, 2-propylimidazole, 2-butylimidazole, 4 Polishing liquid for metals as described in (1) or (2) which is at least 1 sort (s) chosen from the group which consists of -methylimidazole, 2, 4- dimethyl imidazole, and 2-ethyl-4-methyl imidazole.
(6) at least a compound having a triazole skeleton having no amino group selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, benzotriazole and 1-hydroxybenzotriazole The polishing liquid for metal of said (2) or (3) description which is 1 type.
(7) In said (1)-(6) in which a metal anticorrosive agent contains the compound which has the said amino-triazole skeleton, the compound which has the triazole skeleton which does not have the said amino group, and the compound which has the said imidazole skeleton The polishing liquid for metals in any one of them.
(8) The polishing liquid for metal according to any one of (1) to (7), further comprising a water-soluble polymer.
(9) The polishing liquid for metal according to the above (8), wherein the water-soluble polymer is at least one selected from the group consisting of polysaccharides, polycarboxylic acids, esters of polycarboxylic acids, salts of polycarboxylic acids, polyacrylamides, and vinyl polymers. .
(10) The polishing liquid for metal according to any one of (1) to (9), wherein the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, nitric acid, potassium periodate, hypochlorous acid, persulfate, and ozone water.
(11) The polishing liquid for metal according to any one of the above (1) to (10), wherein the metal oxide solubilizer is at least one selected from the group consisting of organic acids, organic acid esters, ammonium salts of organic acids, and sulfuric acid.
(12) The polishing liquid for metal according to any one of the above (1) to (11), further comprising abrasive grains.
(13) The above-mentioned (1) to (1), wherein the metal to be polished is at least one selected from the group consisting of copper, copper alloys, copper oxides, oxides of copper alloys, tantalum and compounds thereof, titanium and compounds thereof, tungsten and compounds thereof. The polishing liquid for metals in any one of 12).
(14) The polishing plate and the substrate were pressed while the substrate having the metal film was pressed on the polishing cloth while the polishing liquid for metal according to any one of the above (1) to (13) was supplied onto the polishing cloth of the polishing plate. A polishing method for polishing a metal film by moving relatively.
(15) Polishing according to the above (14), wherein the metal film is at least one selected from the group consisting of copper, copper alloys, oxides of copper, oxides of copper alloys, tantalum and compounds thereof, titanium and compounds thereof, tungsten and compounds thereof. Way.
(16) The polishing method according to the above (14) or (15), wherein the lamination of two or more kinds of metal films is successively polished.
(17) Of the two or more metal films laminated, the first film to be polished first is one or more selected from oxides of copper, copper alloys, copper oxides and copper alloys, and the second film to be polished is tantalum and its The polishing method according to the above (16), which is at least one selected from a compound, titanium, the compound, tungsten, and the compound.
(18) polishing a wiring metal layer of a substrate having an interlayer insulating film having a concave portion and a convex portion, a barrier layer covering the interlayer insulating film along the surface, and a wiring metal layer filling the concave portion to cover the barrier layer; A first polishing step of exposing the barrier layer of the convex portion, and a second polishing step of exposing the interlayer insulating film of the convex portion by polishing at least the barrier layer and the wiring metal layer of the concave portion after the first polishing step, and at least the second polishing step Polishing method which grinds using the polishing liquid for metals in any one of said (1)-(13) in a process.
Best Mode for Carrying Out the Invention
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
The polishing liquid for metals of this invention contains an oxidizing agent, a metal oxide dissolving agent, a metal anticorrosive agent, and water as main components. The said metal anticorrosive agent is a compound (A) which has an amino-triazole skeleton which the amino group couple | bonded with the carbon of a triazole ring, and following General formula (I)
(Compound (I) of, R 1, R 2 and R 3 are, each independently represent an alkyl chain of a hydrogen atom, an amino group, or C 1~ C 12. However, all of R 1, R 2 and R 3 Except when is a hydrogen atom.)
A compound (B) having an imidazole skeleton represented by
The compound (B) and the compound (C) having a triazole skeleton having no amino group, or
The compound (A) and the compound (C) are included.
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이미다졸 골격을 갖는 화합물로서는, 구체적으로는, 2-메틸이미다졸, 2-에틸이미다졸, 2-이소프로필이미다졸, 2-프로필이미다졸, 2-부틸이미다졸, 4-메틸이미다졸, 2,4-디메틸이미다졸, 2-에틸-4-메틸이미다졸, 2-운데실이미다졸, 2-아미노이미다졸 등을 예시할 수 있다. 이들은 1종류 단독으로, 또는 2종류 이상 조합시켜 이용할 수 있다. 특히 2-메틸이미다졸, 2-에틸이미다졸, 2-(이소프로필)이미다졸, 2-프로필이미다졸, 2-부틸이미다졸, 4-메틸이미다졸, 2,4-디메틸이미다졸 및 2-에틸-4-메틸이미다졸로부터 선택되는 것이 바람직하다.Specifically as a compound which has an imidazole skeleton, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4- Methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-aminoimidazole and the like can be exemplified. These can be used individually by 1 type or in combination of 2 or more types. Especially 2-methylimidazole, 2-ethylimidazole, 2- (isopropyl) imidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethyl Preference is given to being selected from imidazole and 2-ethyl-4-methylimidazole.
본 발명에 있어서 아미노-트리아졸 골격을 갖는 화합물은, 트리아졸 골격의 탄소원자에 아미노기가 결합하고 있는 화합물인 것이 바람직하고, 공업적으로 생산되고 있는 것을 고려하면 3-아미노-1,2,4-트리아졸이 보다 적합하다.In the present invention, the compound having an amino-triazole skeleton is preferably a compound having an amino group bonded to a carbon atom of the triazole skeleton, and considering that it is industrially produced, 3-amino-1,2,4 -Triazole is more suitable.
본 발명의 금속용 연마액에는, 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물을, 금속방식제로서 더 함유할 수 있다.The polishing liquid for metals of this invention can further contain the compound which has a triazole skeleton which does not have an amino group as a metal anticorrosive agent.
아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물로서는, 예컨대, 1,2,3-트리아졸, 1,2,4-트리아졸, 벤조트리아졸, 1-히드록시벤조트리아졸, 1-디히드록시프로필벤조트리아졸, 2,3-디카르복시프로필벤조트리아졸, 4-히드록시벤조트리아졸, 4-카르복실(-1H-)벤조트리아졸, 4-카르복실(-1H-)벤조트리아졸메틸에스테르, 4-카르복실(-1H-)벤조트리아졸부틸에스테르, 4-카르복실(-1H-)벤조트리아졸옥틸에스테르, 5-헥실벤조트리아졸, [1,2,3-벤조트리아졸릴-1-메틸][1,2,4-트리아졸릴-1-메틸][2-에틸헥실]아민, 톨릴트리아졸, 나프토트리아졸, 비스[(1-벤조트리아졸릴)메틸]포스폰산 등을 예시할 수 있다. 이들 금속방식제는 1종류 단독으로, 또는 2종류 이상 조합시켜 이용할 수 있다.Examples of the compound having a triazole skeleton having no amino group include 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1-hydroxybenzotriazole and 1-dihydroxypropyl. Benzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) benzotriazole, 4-carboxyl (-1H-) benzotriazolemethyl ester , 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexyl benzotriazole, [1,2,3-benzotriazolyl-1 -Methyl] [1,2,4-triazolyl-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1-benzotriazolyl) methyl] phosphonic acid and the like are exemplified can do. These metal anticorrosive agents can be used individually by 1 type or in combination of 2 or more types.
금속방식제는, 아미노-트리아졸 골격을 갖는 화합물 및 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물의 적어도 한쪽과, 이미다졸 골격을 갖는 화합물을 병용하는 것이 보다 바람직하다. 또한, 아미노-트리아졸 골격을 갖는 화합물과 아미노기를 갖지 않는 트리아졸 골격을 갖는 화합물을 병용하는 것도 보다 바람직하다.As for a metal anticorrosive agent, it is more preferable to use together the compound which has an imidazole skeleton, and at least one of the compound which has an amino-triazole skeleton, and the compound which has a triazole skeleton which does not have an amino group. Moreover, it is more preferable to use together the compound which has an amino-triazole skeleton, and the compound which has a triazole skeleton which does not have an amino group.
본 발명에 있어서 금속방식제의 총 배합량은, 금속용 연마액의 총량에 대해서 0.001∼10중량%로 하는 것이 바람직하고, 0.01∼8중량%로 하는 것이 보다 바람직하고, 0.02∼5중량%로 하는 것이 특히 바람직하다. 이 배합량이 0.001중량% 미만에서는, 에칭의 억제가 곤란하게 되거나, 충분한 연마속도의 향상이 얻어지지 않거나 하는 경향이 있고, 10중량%를 넘으면 연마속도가 포화하거나 낮아지거나 하는 경향이 있다. 금속방식제로서 아미노-트리아졸 골격을 갖는 화합물만을 이용하는 경우는 0.05∼5중량%로 하는 것이 특히 바람직하다.In the present invention, the total amount of the metal anticorrosive agent is preferably 0.001 to 10% by weight, more preferably 0.01 to 8% by weight, more preferably 0.02 to 5% by weight based on the total amount of the metal polishing liquid. Is particularly preferred. If the blending amount is less than 0.001% by weight, the etching is difficult to be suppressed, or there is a tendency that a sufficient improvement in the polishing rate is not obtained, and when it exceeds 10% by weight, the polishing rate tends to be saturated or low. When using only the compound which has an amino-triazole skeleton as a metal anticorrosive agent, it is especially preferable to set it as 0.05 to 5 weight%.
본 발명에 있어서 산화제로서는, 과산화수소(H2O2), 질산, 과요오드산칼륨, 차아염소산, 과황산염 및 오존수 등을 들 수 있고, 그 중에서도 과산화수소가 특히 바람직하다. 이들은 1종류 단독으로, 또는 2종류 이상 조합시켜 이용할 수 있다. Examples of the oxidizing agent in the present invention include hydrogen peroxide (H 2 O 2 ), nitric acid, potassium periodate, hypochlorous acid, persulfate, ozone water, and the like, and hydrogen peroxide is particularly preferred. These can be used individually by 1 type or in combination of 2 or more types.
연마의 적용대상인 기체가 집적회로용 소자를 포함하는 실리콘 기판인 경우, 알칼리금속, 알칼리토류금속, 할로겐화물 등에 의한 오염은 바람직하지 않기 때문에, 불휘발 성분을 포함하지 않는 산화제가 바람직하다. 다만, 오존수는 조성의 시간변화가 현저하므로 과산화수소가 적절하다. 또, 기체가 반도체소자를 포함하지 않는 유리기판 등인 경우는 불휘발 성분을 포함하는 산화제이어도 상관 없다.In the case where the substrate to be applied is a silicon substrate including an integrated circuit element, contamination by alkali metals, alkaline earth metals, halides or the like is not preferable, and therefore, an oxidant containing no nonvolatile components is preferable. However, ozone water is suitable for hydrogen peroxide because the change in composition of time is remarkable. In the case where the substrate is a glass substrate or the like which does not contain a semiconductor element, it may be an oxidizing agent containing a nonvolatile component.
산화제의 배합량은, 금속용 연마액의 총량에 대해서, 0.1∼50중량%로 하는 것이 바람직하고, 0.2∼25중량%로 하는 것이 보다 바람직하고, 0.3∼15중량%로 하는 것이 특히 바람직하다. 배합량이 0.1중량% 미만에서는, 금속의 산화가 불충분하여 CMP속도가 낮아지는 경향이 있고, 50중량%를 넘으면, 연마면에 거칠음이 생기는 경향이 있다.The amount of the oxidizing agent is preferably 0.1 to 50% by weight, more preferably 0.2 to 25% by weight, and particularly preferably 0.3 to 15% by weight based on the total amount of the polishing liquid for metal. If the blending amount is less than 0.1% by weight, the oxidation of the metal is insufficient, and the CMP rate tends to be low, and when the amount exceeds 50% by weight, roughness occurs on the polished surface.
본 발명에 있어서 산화금속 용해제는, 수용성인 것이면 특별히 제한은 없고, 포름산, 아세트산, 프로피온산, 부티르산, 발레르산, 2-메틸부티르산, n-헥산산, 3,3-디메틸부티르산, 2-에틸부티르산, 4-메틸펜탄산, n-헵탄산, 2-메틸헥산산, n-옥탄산, 2-에틸헥산산, 벤조산, 글리콜산, 살리실산, 글리세린산, 옥살산, 말론산, 숙신산, 글루타르산, 아디핀산, 피메린산, 말레인산, 프탈산, 말산, 타르타르산, 시트르산 등의 유기산, 이들 유기산의 에스테르 및 이들 유기산의 암모늄염 등을 예시할 수 있다. 또한 염산, 황산, 질산 등의 무기산, 이들 무기산의 암모늄염류, 예컨대 과황산암모늄, 질산암모늄, 염화암모늄 등, 크롬산 등을 들 수 있다. 이들 중에서 특히, 효과적으로 연마할 수 있다는 점에서 포름산, 말론산, 말산, 타르타르산, 시트르산이 금속층의 CMP에 대해서 적합하다. 이들은 1종류 단독으로, 또는 2종류 이상 조합시켜 이용할 수 있다. In the present invention, the metal oxide solubilizer is not particularly limited as long as it is water-soluble. Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glycerin acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adi Examples include organic acids such as pinic acid, pimeric acid, maleic acid, phthalic acid, malic acid, tartaric acid and citric acid, esters of these organic acids, ammonium salts of these organic acids, and the like. Furthermore, inorganic acids, such as hydrochloric acid, a sulfuric acid, and nitric acid, ammonium salts of these inorganic acids, such as ammonium persulfate, ammonium nitrate, ammonium chloride, chromic acid, etc. are mentioned. Among them, formic acid, malonic acid, malic acid, tartaric acid and citric acid are suitable for CMP of the metal layer in that polishing can be effectively performed. These can be used individually by 1 type or in combination of 2 or more types.
산화금속 용해제 성분의 배합량은, 금속용 연마액의 총량에 대해서 0.001∼10중량%로 하는 것이 바람직하고, 0.01∼8중량%로 하는 것이 보다 바람직하고, 0.02∼5중량%로 하는 것이 특히 바람직하다. 이 배합량이 0.001중량% 미만으로 되면 연마속도가 극단으로 감소하는 경향이 있고, 10중량%를 넘으면, 에칭의 억제가 곤란하게 되는 경향이 있다.The amount of the metal oxide dissolving agent component is preferably 0.001 to 10% by weight, more preferably 0.01 to 8% by weight, particularly preferably 0.02 to 5% by weight based on the total amount of the metal polishing liquid. . When this compounding amount is less than 0.001% by weight, the polishing rate tends to decrease to an extreme, and when it exceeds 10% by weight, the etching is difficult to be suppressed.
본 발명의 금속용 연마액은, 수용성 폴리머를 더 포함할 수 있다. 수용성 폴리머로서는, 예컨대, 아르긴산, 펙틴산, 카르복시메틸셀룰로오스, 한천, 카드란 및 플루란 등의 다당류; 폴리아스파라긴산, 폴리글루타민산, 폴리리신, 폴리말산, 폴리메타크릴산, 폴리아미드산, 폴리말레인산, 폴리이타콘산, 폴리푸마르산, 폴리(p-스티렌카본산), 폴리아크릴산, 및 폴리글리옥실산 등의 폴리카본산; 폴리메타크릴산암모늄염, 폴리메타크릴산나트륨염, 폴리아크릴아미드, 폴리아미노아크릴아미드, 폴리아크릴산암모늄염, 폴리아크릴산나트륨염, 폴리아미드산암모늄염, 폴리아미드산나트륨염 등으로 예시되는 폴리카본산의 염 및 에스테르 및 유도체; 폴리비닐알코올, 폴리비닐피롤리돈 및 폴리아크롤레인 등의 비닐계 폴리머 등을 들 수 있다. 또한, 이들의 에스테르 및 이들의 암모늄염도 들 수 있다.The polishing liquid for metal of the present invention may further include a water-soluble polymer. As a water-soluble polymer, For example, polysaccharides, such as arginic acid, pectinic acid, carboxymethylcellulose, agar, cadmane, and pullulan; Polyaspartic acid, polyglutamic acid, polylysine, polymalic acid, polymethacrylic acid, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, and polyglyoxylic acid Polycarboxylic acid; Salts of polycarboxylic acids exemplified by polyammonium polymethacrylate salts, polymethacrylate sodium salts, polyacrylamides, polyaminoacrylamides, ammonium polyacrylate salts, sodium polyacrylate salts, ammonium polyamate salts, sodium polyamate salts, and the like. And esters and derivatives; And vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein. Moreover, these ester and these ammonium salts are also mentioned.
그 중에서도 다당류, 폴리카본산, 폴리카본산의 에스테르, 폴리카본산의 염, 폴리아크릴아미드 및 비닐계 폴리머로 이루어지는 군으로부터 선택된 적어도 1종이 바람직하고, 구체적으로는 펙틴산, 한천, 폴리말산, 폴리메타크릴산, 폴리아크릴산, 폴리아크릴아미드, 폴리비닐알코올 및 폴리비닐피롤리돈, 그들의 에스테르 및 그들의 암모늄염이 바람직하다. 다만, 적용하는 기체가 반도체 집적회로용 실리콘 기판 등의 경우는 알칼리금속, 알칼리토류금속, 할로겐화물 등에 의한 오염은 바람직하지 않기 때문에, 산 또는 그 암모늄염이 바람직하다. 또, 기체가 유리기판 등인 경우는 그것에 한정되지 않는다.Among them, at least one selected from the group consisting of polysaccharides, polycarboxylic acids, esters of polycarboxylic acids, salts of polycarboxylic acids, polyacrylamides and vinyl polymers is preferable, and specifically, pectinic acid, agar, polymalic acid, poly Preference is given to methacrylic acid, polyacrylic acid, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone, their esters and their ammonium salts. However, when the substrate to be applied is a silicon substrate for a semiconductor integrated circuit or the like, contamination with alkali metals, alkaline earth metals, halides or the like is not preferable, and therefore an acid or an ammonium salt thereof is preferable. Incidentally, the case where the base is a glass substrate or the like is not limited thereto.
수용성 폴리머의 배합량은, 연마액의 총량에 대해서 0∼10중량%로 하는 것이 바람직하고, 0.01∼8중량%가 보다 바람직하고, 0.02∼5중량%가 특히 바람직하다. 이 배합량이 10중량%를 넘으면 연마속도가 저하하는 경향이 있다.It is preferable to make the compounding quantity of a water-soluble polymer into 0 to 10 weight% with respect to the total amount of polishing liquid, 0.01 to 8 weight% is more preferable, 0.02 to 5 weight% is especially preferable. When this compounding quantity exceeds 10 weight%, there exists a tendency for a grinding | polishing speed to fall.
수용성 폴리머의 중량평균 분자량(GPC측정, 표준 폴리스티렌 환산)은 500 이상으로 하는 것이 바람직하고, 1,500 이상으로 하는 것이 보다 바람직하고, 5,000 이상으로 하는 것이 특히 바람직하다. 중량평균 분자량의 상한은 특별히 규정하는 것은 아니지만, 용해성의 관점으로부터 500만 이하가 바람직하다. 중량평균 분자량이 500 미만에서는 높은 연마속도가 발현하지 않는 경향이 있다. 본 발명에서는, 중량평균 분자량이 500 이상인 적어도 1종의 수용성 폴리머를 이용하는 것이 바람직하다.The weight average molecular weight (GPC measurement, standard polystyrene conversion) of the water-soluble polymer is preferably 500 or more, more preferably 1,500 or more, and particularly preferably 5,000 or more. Although the upper limit of a weight average molecular weight is not specifically prescribed, 5 million or less are preferable from a viewpoint of solubility. If the weight average molecular weight is less than 500, the high polishing rate tends not to be expressed. In this invention, it is preferable to use at least 1 type of water-soluble polymer whose weight average molecular weight is 500 or more.
본 발명의 연마액은, 지립을 함유하여도 좋다. LSI 등의 구리 또는 구리합금 배선의 절연막층으로서 이산화규소막이 이용되는데, 이 경우 배리어층인 탄탈 등의 연마에 이어서, 본 발명의 연마액으로 이산화규소막을 연마하는 경우에는, 지립을 함유하는 것이 바람직하다.The polishing liquid of the present invention may contain abrasive grains. A silicon dioxide film is used as an insulating film layer of copper or copper alloy wiring such as LSI. In this case, when polishing the silicon dioxide film with the polishing liquid of the present invention, followed by polishing of tantalum or the like as a barrier layer, it is preferable to contain abrasive grains. Do.
본 발명에 있어서 지립으로서는, 실리카, 알루미나, 지르코니아, 세리아, 티타니아, 게르마니아, 탄화규소 등의 무기물 지립, 폴리스티렌, 폴리아크릴, 폴리염화비닐 등의 유기물 지립의 어느 하나이어도 좋지만, 실리카, 알루미나, 세리아, 티타니아, 지르코니아, 게르마니아로부터 선택된 1종 이상인 것이 바람직하다. 더욱이, 연마액중에서의 분산안정성이 양호하고, CMP에 의해 발생하는 연마손상(스크래치)의 발생 수가 적은, 평균 입경이 150nm 이하의 콜로이달 실리카, 콜로이달 알루미나가 바람직하다. 여기에서, 평균입경은, 배리어층의 연마속도가 보다 크게 되는 100nm 이하가 보다 바람직하고, 70nm 이하가 더욱 바람직하다. 콜로이달 실리카는 실리콘알콕시드의 가수분해 또는 규산나트륨의 이온교환에 의한 제조방법이 알려져 있고, 콜로이달 알루미나는 질산알루미늄의 가수분해에 의한 제조방법이 알려져 있다.In the present invention, the abrasive may be any one of inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania, germania, silicon carbide, and organic abrasive grains such as polystyrene, polyacryl, and polyvinyl chloride, but silica, alumina, ceria, It is preferable that it is at least one selected from titania, zirconia, and germania. Furthermore, colloidal silica and colloidal alumina having an average particle diameter of 150 nm or less, which have good dispersion stability in the polishing liquid and a low number of polishing damages (scratches) generated by CMP, are preferable. Here, the average particle diameter is more preferably 100 nm or less, more preferably 70 nm or less, in which the polishing rate of the barrier layer becomes larger. Colloidal silica is known to be produced by hydrolysis of silicon alkoxide or ion exchange of sodium silicate, and colloidal alumina is known to be produced by hydrolysis of aluminum nitrate.
지립을 배합하는 경우, 지립의 농도는, 연마액 총 중량에 대해서, 0.01∼20.0중량%가 바람직하고, 0.05∼15.0중량%가 보다 바람직하고, 0.1∼8.0중량%가 가장 바람직하다. 지립 농도가 0.01중량% 미만에서는, 지립을 첨가하는 효과가 나타나지 않고, 20.0중량%를 초과하여 첨가하면, 지립이 응집하기 쉬워질 뿐만 아니라, 연마속도에 차이가 나타나지 않기 때문이다.In the case of blending the abrasive grains, the concentration of the abrasive grains is preferably 0.01 to 20.0% by weight, more preferably 0.05 to 15.0% by weight, and most preferably 0.1 to 8.0% by weight based on the total weight of the polishing liquid. If the abrasive concentration is less than 0.01% by weight, the effect of adding the abrasive grains does not appear, and if the abrasive grains are added in excess of 20.0% by weight, the abrasive grains tend to aggregate and the difference in polishing speed does not appear.
본 발명의 금속용 연마액에는, 상술한 재료 이외에 필요에 따라서, 계면활성제 등의 분산제, 빅토리아퓨어블루 등의 염료, 프탈로시아닌그린 등의 안료 등의 착색제 등을 0.01∼1중량% 정도, 보다 바람직하게는 0.1∼0.8중량% 정도 함유시켜도 좋다. 또, 물의 배합량은 잔부로 좋고, 함유되어 있으면 특별히 제한은 없다.In the polishing liquid for metals of the present invention, in addition to the materials described above, dispersing agents such as surfactants, dyes such as Victoria Pure Blue, coloring agents such as pigments such as phthalocyanine green, and the like, are more preferably 0.01 to 1% by weight. You may contain about 0.1 to 0.8 weight%. Moreover, the compounding quantity of water is good as remainder and there is no restriction | limiting in particular if it contains.
본 발명을 적용하는 피연마막인 금속막으로서는, 구리, 구리합금, 구리산화물, 구리합금의 산화물(이하, 구리 및 그 화합물이라 한다.), 탄탈, 질화탄탈, 탄탈합금 등(이하, 탄탈 및 그 화합물이라 한다.), 티탄, 질화티탄, 티탄합금 등(이하, 티탄 및 그 화합물이라 한다.), 텅스텐, 질화텅스텐, 텅스텐합금 등(이하, 텅스텐 및 그 화합물이라 한다.) 등을 예시할 수 있고, 공지의 스퍼터법, 도금법에 의해 성막할 수 있다. 더욱이, 금속막은, 2종 이상의 상기 금속을 조합시킨 적층막이어도 좋다.Examples of the metal film to be polished to which the present invention is applied include copper, copper alloys, copper oxides, oxides of copper alloys (hereinafter referred to as copper and compounds thereof), tantalum, tantalum nitride, tantalum alloys, and the like (hereinafter, tantalum and Titanium, titanium nitride, titanium alloy and the like (hereinafter referred to as titanium and its compounds), tungsten, tungsten nitride, tungsten alloy and the like (hereinafter referred to as tungsten and its compounds), and the like. The film can be formed by a known sputtering method or a plating method. Furthermore, the metal film may be a laminated film obtained by combining two or more kinds of the above metals.
상기 적층막으로서는, 상층(처음에 연마되는 제 1의 막)이 구리 및 그 화합물로부터 선택되고, 하층(계속하여 연마되는 제 2의 막)이 탄탈 및 그 화합물, 티탄 및 그 화합물, 텅스텐 및 그 화합물로부터 선택되는 것을 예시할 수 있다.As the laminated film, the upper layer (the first film to be first polished) is selected from copper and the compound, and the lower layer (the second film to be polished subsequently) is tantalum and the compound, titanium and the compound, tungsten and the It can illustrate what is chosen from a compound.
본 발명의 금속용 연마액을 이용하는 것에 의해 상기의 2종 이상의 금속막의 적층막을 연속하여 연마할 수 있다. 환언하면, 금속막마다 연마액을 변경하는 수고를 덜 수 있다.By using the metal polishing liquid of the present invention, the laminated film of the two or more metal films described above can be continuously polished. In other words, the effort of changing the polishing liquid for each metal film can be saved.
본 발명의 제 1의 연마방법은, 연마정반의 연마포상에 상기 금속용 연마액을 공급하면서, 피연마막인 금속막을 갖는 기체를 연마포에 압압한 상태에서, 연마정반과 기체를 상대적으로 움직이는 것에 의해 피연마막인 금속막을 연마하는 연마방법이다. 연마하는 장치로서는, 금속층을 갖는 기체를 유지하는 홀더와, 연마포(연마패드)를 첩부할 수 있고, 회전수가 변경 가능한 모터 등이 부착되어 있는 연마정반을 갖는 일반적인 연마장치가 사용될 수 있다.In the first polishing method of the present invention, the polishing plate and the gas are relatively moved while the substrate having the metal film as the polishing film is pressed onto the polishing cloth while the polishing liquid for metal is supplied onto the polishing cloth of the polishing plate. This is a polishing method for polishing a metal film as a to-be-polished film. As the apparatus for polishing, a general polishing apparatus having a holder holding a base having a metal layer, and a polishing table on which a polishing cloth (polishing pad) can be attached, and which has a motor or the like capable of changing the rotation speed can be used.
연마포로서는, 일반적인 부직포, 발포 폴리우레탄, 다공질 불소수지 등을 사용할 수 있고, 특별히 제한이 없다. 연마조건에는 제한은 없지만, 연마정반의 회전속도는 기체가 튀어 나가지 않도록 200rpm 이하의 저회전이 바람직하다. 피연마막을 갖는 기체의 연마포로의 누르는 압력(연마압력)은 1∼100kPa가 바람직하고, CMP 속도의 웨이퍼 면내 균일성 및 패턴의 평탄성을 만족하기 위해서는, 5∼50kPa가 보다 바람직하다.As the polishing cloth, a general nonwoven fabric, a foamed polyurethane, a porous fluorocarbon resin, or the like can be used, and there is no particular limitation. Although there is no restriction | limiting in grinding | polishing conditions, The rotation speed of a grinding | polishing table is preferable low rotation of 200 rpm or less so that a gas may not protrude. The pressing pressure (polishing pressure) of the substrate having the polishing film to the polishing cloth is preferably 1 to 100 kPa, and more preferably 5 to 50 kPa in order to satisfy the in-plane uniformity of the CMP speed and the flatness of the pattern.
연마방법은, 연마정반과 기체를 상대적으로 움직이게 하는 것이면, 피연마막이나 연마장치에 따라 적절하게 선택할 수 있다. 예컨대, 연마정반을 회전시키는 것 이외에, 홀더를 회전이나 요동시키는 연마방법, 연마정반을 유성회전시키는 연마방법, 벨트상의 연마포를 장척방향의 한쪽 방향으로 직선상으로 움직이는 연마방법 등을 들 수 있다. 또, 홀더는 고정, 회전, 요동의 어느 상태이어도 좋다.The polishing method can be appropriately selected in accordance with the polishing film and the polishing apparatus as long as the polishing table and the substrate are relatively moved. For example, in addition to rotating the polishing table, a polishing method for rotating or oscillating the holder, a polishing method for planetary rotation of the polishing table, a polishing method for moving the belt-shaped polishing cloth in a straight line in one direction in the long direction, and the like can be given. . The holder may be in any of the states of fixing, rotation, and swinging.
연마하고 있는 사이, 연마포 표면과 기체의 피연마면과의 사이에는 금속용 연마액을 펌프 등으로 연속적으로 공급한다. 이 공급량에 제한은 없지만, 연마포의 표면이 항상 연마액으로 덮여 있는 것이 바람직하다.While polishing, the polishing liquid for metal is continuously supplied between the surface of the polishing cloth and the surface to be polished of the substrate by a pump or the like. Although this supply amount is not limited, it is preferable that the surface of the polishing cloth is always covered with the polishing liquid.
연마 종료후의 기체는, 유수중에서 잘 세정후, 스핀드라이 등을 이용하여 기체상에 부착한 물방울을 흩어 떨어뜨려 건조시키는 것이 바람직하다.It is preferable to dry the gas after completion | finish of grinding | polishing after disperse | distributing the water droplet which adhered to the base | substrate using spin-drying etc. after wash | cleaning well in flowing water.
본 발명의 금속용 연마액 및 이 연마액을 이용하는 연마방법은, 금속의 연마속도가 충분히 높고, 또한 에칭속도가 작기 때문에, 생산성이 높고, 금속표면의 부식 및 디싱이 작기 때문에, 미세화, 박막화, 치수정밀도, 전기특성이 우수하고, 신뢰성이 높은 반도체 디바이스 및 기기의 제조에 적합하다.The polishing liquid for metal of the present invention and the polishing method using the polishing liquid have high productivity because the polishing rate of the metal is sufficiently high and the etching rate is small, so that the productivity is high and the corrosion and dishing of the metal surface are small. It is suitable for the manufacture of semiconductor devices and devices with excellent dimensional accuracy and electrical characteristics and high reliability.
즉 본 발명의 제 2의 연마방법은, 표면이 오목부 및 볼록부로 이루어지는 층간절연막과, 상기 층간절연막을 표면을 따라서 피복하는 배리어층과, 상기 오목부를 충전하여 배리어층을 피복하는 배선금속층을 갖는 기판의 배선금속층을 연마하여 상기 볼록부의 배리어층을 노출시키는 제 1 연마공정과, 상기 제 1 연마공정 후에, 적어도 배리어층 및 오목부의 배선 금속층을 연마하여 볼록부의 층간절연막을 노출시키는 제 2 연마공정을 포함하고, 적어도 제 2 연마공정에서 본 발명의 금속용 연마액을 이용하여 연마하는 연마방법이다.That is, the second polishing method of the present invention has an interlayer insulating film whose surface is formed with concave portions and convex portions, a barrier layer covering the interlayer insulating film along the surface, and a wiring metal layer filling the concave portion and covering the barrier layer. A first polishing step of polishing the wiring metal layer of the substrate to expose the barrier layer of the convex portion; and a second polishing step of exposing the interlayer insulating film of the convex portion by polishing at least the barrier layer and the wiring metal layer of the concave portion after the first polishing step. And a polishing method for polishing using the polishing liquid for metal of the present invention in at least a second polishing step.
층간절연막으로서는, 실리콘계 피막이나 유기 폴리머막을 들 수 있다. 실리콘계 피막으로서는, 이산화규소, 플루오로실리케이트글래스, 트리메틸실란이나 디메톡시디메틸실란을 출발원료로 하여 얻어지는 오르가노실리케이트글래스, 실리콘옥시나이트라이드, 수소화 실세스퀴옥산 등의 실리카계 피막이나 실리콘카바이드 및 실리콘나이트라이드를 들 수 있다. 또한, 유기 폴리머막으로서는, 전체 방향족계 저유전율 층간절연막을 들 수 있다. 특히, 오르가노실리케이트글래스가 바람직하다. 이들 막은, CVD법, 스핀코트법, 딥코트법, 또는 스프레이법 등에 의해 성막된다.Examples of the interlayer insulating film include a silicon film and an organic polymer film. Examples of the silicone coating include silica-based coatings such as silicon dioxide, fluorosilicate glass, trimethylsilane and dimethoxydimethylsilane as starting materials, silica-based coating films such as silicon oxynitride and hydrogenated silsesquioxane, silicon carbide and silicon. Nitrides. Moreover, as an organic polymer film, a wholly aromatic low dielectric constant interlayer insulation film is mentioned. In particular, organosilicate glass is preferable. These films are formed by a CVD method, a spin coat method, a dip coat method, a spray method, or the like.
배리어층은 층간절연막 중으로의 구리 등의 금속 확산방지, 및 절연막과 금속과의 밀착성 향상을 위해서 형성된다. 배리어층은, 텅스텐 및 텅스텐화합물, 탄탈 및 탄탈화합물, 티탄 및 티탄화합물 중에서 선택되는 적어도 1종인 것이 바람직하고, 1종의 조성으로 이루어진 단층구조이어도, 2종 이상의 조성으로 이루어진 적층구조이어도 좋다.The barrier layer is formed to prevent diffusion of metals such as copper into the interlayer insulating film and to improve adhesion between the insulating film and the metal. The barrier layer is preferably at least one selected from tungsten and tungsten compounds, tantalum and tantalum compounds, titanium and titanium compounds, and may be a single layer structure composed of one kind of composition or a laminated structure composed of two or more kinds of compositions.
배선금속층으로서는, 구리 및 그 화합물, 텅스텐, 텅스텐합금, 은, 금 등의 금속이 주성분인 층을 들 수 있다. 이들 중, 구리 및 그 화합물로부터 선택되는 적어도 1종을 포함하는 층을 연마하는 것이 바람직하다. 배선금속층은 공지의 스퍼터법, 도금법에 의해 배리어층의 위에 성막할 수 있다.As a wiring metal layer, the layer whose main components are metals, such as copper and its compound, tungsten, a tungsten alloy, silver, and gold, are mentioned. Among these, it is preferable to grind the layer containing at least 1 sort (s) chosen from copper and its compound. The wiring metal layer can be formed on the barrier layer by a known sputtering or plating method.
이하, 본 발명의 연마방법의 실시태양을, 반도체 디바이스 제조공정에 있어서 배선층의 형성에 따라서 설명한다.Hereinafter, an embodiment of the polishing method of the present invention will be described in accordance with the formation of the wiring layer in the semiconductor device manufacturing process.
우선, 실리콘의 기판상에 이산화규소 등의 층간절연막을 적층한다. 다음에, 레지스트층 형성, 에칭 등의 공지의 수단에 의해, 층간절연막 표면에 소정 패턴의 오목부(기판 노출부)를 형성하여 볼록부와 오목부로 이루어지는 층간절연막으로 한다. 이 층간절연막상에, 표면의 요철을 따라 층간절연막을 피복하는 텅스텐 등의 배리어층을 증착 또는 CVD 등에 의해 성막한다. 더욱이, 상기 오목부를 충전하도록 배리어층을 피복하는 구리 등의 배선금속층을 증착, 도금 또는 CVD 등에 의해 형성한다.First, an interlayer insulating film such as silicon dioxide is laminated on a silicon substrate. Next, by a known means such as resist layer formation or etching, recesses (substrate exposed portions) of a predetermined pattern are formed on the surface of the interlayer insulating film to form an interlayer insulating film composed of convex portions and recesses. On this interlayer insulating film, a barrier layer such as tungsten that coats the interlayer insulating film along the unevenness of the surface is formed by vapor deposition or CVD. Further, a wiring metal layer such as copper covering the barrier layer to fill the recess is formed by vapor deposition, plating or CVD.
(제 1 연마공정) 다음에, 이 반도체 기판을 연마장치에 고정하고, 표면의 배선금속층을 피연마면으로 하여, 연마액을 공급하면서 연마한다. 이것에 의해, 층간절연막 볼록부의 배리어층이 기판 표면에 노출하고, 층간절연막 오목부에 상기 금속층이 남겨진 소망의 도체 패턴이 얻어진다.(1st polishing process) Next, this semiconductor substrate is fixed to a polishing apparatus, and it polishes, supplying polishing liquid, making the wiring metal layer of a surface into a to-be-polished surface. As a result, a desired conductor pattern in which the barrier layer of the interlayer insulating film convex portion is exposed to the substrate surface and the metal layer is left in the interlayer insulating film concave portion is obtained.
(제 2 연마공정) 다음에, 상기 도체 패턴을 피연마면으로 하여, 적어도, 상기 노출하고 있는 배리어층 및 오목부의 배선금속층을, 본 발명의 연마액을 공급하면서 연마한다. 볼록부의 배리어층의 아래의 층간절연막이 전부 노출하고, 오목부에 배선층으로 되는 상기 금속층이 남겨지고, 볼록부와 오목부와의 경계에 배리어층의 단면이 노출한 소망의 패턴이 얻어진 시점에서 연마를 종료한다. 연마종료시의 보다 우수한 평탄성을 확보하기 위해서, 추가로, 오버연마(예컨대, 제 2 연마공정에서 소망의 패턴을 얻을때 까지의 시간이 100초인 경우, 이 100초의 연마에 더해서 50초 추가하여 연마하는 것을 오버연마 50%라 한다.)하여 볼록부의 층간절연막의 일부를 포함하는 깊이까지 연마하여도 좋다.(Second Polishing Step) Next, at least the exposed barrier layer and the wiring metal layer of the concave portion are polished while supplying the polishing liquid of the present invention, with the conductor pattern serving as the surface to be polished. The interlayer insulating film below the barrier layer of the convex portion is exposed completely, and the metal layer serving as the wiring layer is left in the concave portion, and polishing is obtained when a desired pattern is obtained in which the cross section of the barrier layer is exposed at the boundary between the convex portion and the concave portion. To exit. In order to ensure better flatness at the end of polishing, in addition, if the time required for overpolishing (for example, 100 seconds until the desired pattern is obtained in the second polishing step) is further added, polishing is performed in addition to the polishing of 100 seconds for 50 seconds. It is referred to as 50% over-polishing) to a depth including a part of the interlayer insulating film of the convex portion.
제 2 연마공정에서는, 본 발명의 제 1의 연마방법과 같이 기판의 피연마면을 연마포에 압압한 상태에서 연마포와 기판을 상대적으로 움직이게 하여 피연마면을 연마하는 연마방법 이외에, 금속제 또는 수지제의 블러쉬를 접촉시키는 방법, 연마액을 소정의 압력으로 뿜어서 부착시키는 연마방법을 들 수 있다.In the second polishing step, as in the first polishing method of the present invention, in addition to the polishing method of polishing the surface to be polished by relatively moving the polishing cloth and the substrate while the surface to be polished is pressed against the polishing cloth, And a polishing method in which a resin-made blush is brought into contact with each other, and a polishing liquid is sprayed and attached at a predetermined pressure.
제 1 연마공정 및 제 2 연마공정 중, 적어도 제 2 연마공정에서 본 발명의 연마액을 이용하여 연마한다. 제 1 및 제 2 연마공정에서 계속하여, 본 발명의 연마액을 사용하여 연마하여도 좋다. 이 경우, 제 1 연마공정과 제 2 연마공정과의 사이는, 특히 피연마면의 세정공정이나 건조공정 등을 행할 필요는 없지만, 연마정반이나 연마포의 교환이나, 가공하중 등을 변경시키기 위해서 정지시켜도 좋다. 제 1 연마공정 및 제 2 연마공정에서 사용하는 본 발명의 연마액은 동일 조성이어도 다른 조성이어도 좋지만, 동일 조성의 연마액이면, 제 1 연마공정으로부터 제 2 연마공정으로 정지시키지 않고 연속하여 연마를 계속할 수 있으므로, 생산성이 우수하다.Among the first polishing step and the second polishing step, polishing is performed using the polishing liquid of the present invention at least in the second polishing step. Subsequent to the first and second polishing steps, the polishing liquid of the present invention may be used for polishing. In this case, in particular, it is not necessary to perform the cleaning step or the drying step of the surface to be polished between the first polishing step and the second polishing step, but in order to change the polishing table, the polishing cloth, or change the processing load. You may stop it. The polishing liquid of the present invention used in the first polishing process and the second polishing process may have the same composition or different compositions, but if the polishing liquid of the same composition is used, polishing is continuously performed without stopping from the first polishing process to the second polishing process. Since it can continue, productivity is excellent.
이와 같이 하여 형성된 금속배선의 위에, 더욱이, 층간절연막, 배리어층 및 배선금속층을 형성하고, 이것을 연마하여 반도체기판 전면에 걸쳐 평활한 면으로 하여 제 2층째의 금속배선을 형성한다. 이 공정을 소정수 반복하는 것에 의해, 소망의 배선층 수를 갖는 반도체 디바이스를 제조할 수 있다.On the metal wiring thus formed, an interlayer insulating film, a barrier layer and a wiring metal layer are further formed and polished to form a second metal wiring with a smooth surface over the entire surface of the semiconductor substrate. By repeating this process a predetermined number, a semiconductor device having a desired number of wiring layers can be manufactured.
이하, 실시예에 의해 본 발명을 설명한다. 본 발명은 이들의 실시예에 의해 한정되는 것은 아니다.
[실시예 1∼4, 6∼11, 참고예 1, 2 및 비교예 1, 2]
(금속용 연마액 제작방법)
금속용 연마액은, 총량에 대해서 말산 0.15중량%, 수용성 폴리머(아크릴계 중합체, 중량평균 분자량 : 약 1만) 0.15중량%, 표 1 및 표 2에 나타내는 아미노트리아졸 화합물 0.2중량%, 아미노트리아졸 화합물 이외의 금속방식제로서 표 1 및 표 2에 나타내는 벤조트리아졸 0.2중량% 및/또는 이미다졸 화합물 0.05중량%, 과산화수소수 9중량%, 잔부를 물로 하여 혼합하여 조제했다.
얻어진 금속용 연마액을 이용하여 이하의 조건에서 에칭 및 CMP 연마하고, 평가했다. 표 1에 구리기체에 대한 CMP의 연마속도, 에칭속도를, 표 2에 텅스텐 기체에 대한 연마속도, 에칭속도를 병기한다.
(연마조건)
구리기체 : 두께 1500nm의 구리금속을 퇴적한 실리콘 기판
텅스텐기체 : 두께 600nm의 텅스텐 화합물을 퇴적한 실리콘 기판
연마액 공급량 : 15cc/분
연마패드 : 발포 폴리우레탄 수지(로델사제 형식번호 IC1000)
연마압력 : 29.4kPa(300gf/㎠)
기체와 연마정반과의 상대속도 : 45m/min, 연마정반 회전속도 : 75rpm
(평가항목)
연마속도 : 각 막의 연마 전후에서의 막두께 차이를 전기저항치로부터 환산하여 구하였다.
에칭속도 : 각각의 기체를 교반한 금속용 연마액(실온, 25℃, 교반 600rpm)에 침지하고, 침지 전후의 금속층 막두께 차이를 전기저항치로부터 환산하여 구하였다.
[실시예 13∼20, 참고예 3∼6 및 비교예 3]
(금속용 연마액 제작방법)
금속용 연마액은 총량에 대해서 말산 0.15중량%, 수용성 폴리머(아크릴계 중합체, 중량평균 분자량 : 약 1만) 0.15중량%, 표 3에 나타내는 이미다졸 화합물 0.2중량%, 표 3에 나타내는 벤조트리아졸 또는 3-아미노-1,2,4-트리아졸 0.2중량%, 과산화수소수 9중량%, 잔부를 물로 하여 혼합하여 조제했다.
얻어진 금속용 연마액을 이용하여 실시예 1과 동일하게 에칭 및 CMP연마하여, 평가했다. 에칭속도를 표 3에 병기한다.Hereinafter, an Example demonstrates this invention. This invention is not limited by these Examples.
[Examples 1-4, 6-11, Reference Examples 1 and 2 and Comparative Examples 1 and 2]
(Method of manufacturing polishing liquid for metal)
As for the polishing liquid for metals, 0.15 weight% of malic acid, 0.15 weight% of water-soluble polymers (acrylic-type polymer, weight average molecular weight: about 10,000), 0.2 weight% of aminotriazole compounds shown in Table 1 and Table 2, aminotriazole As metal anticorrosive agents other than a compound, 0.2 weight% of benzotriazole and / or 0.05 weight% of imidazole compounds shown in Table 1 and Table 2, 9 weight% of hydrogen peroxide, and remainder were mixed and prepared.
Using the obtained polishing liquid for metals, etching and CMP polishing were performed on the following conditions, and it evaluated. Table 1 shows the polishing rate and etching rate of CMP for copper gas, and Table 2 shows the polishing rate and etching rate for tungsten gas.
(Polishing condition)
Copper gas: Silicon substrate on which a copper metal with a thickness of 1500 nm is deposited
Tungsten gas: Silicon substrate on which a tungsten compound with a thickness of 600 nm is deposited
Polishing fluid supply amount: 15cc / min
Polishing Pad: Foamed Polyurethane Resin (Model No. IC1000, Made by Rodel Corporation)
Polishing Pressure: 29.4kPa (300gf / ㎠)
Relative speed between gas and polishing table: 45m / min, Polishing table rotation speed: 75rpm
(Evaluation item)
Polishing rate: The film thickness difference before and after polishing of each film was calculated from the electrical resistance value.
Etching rate: Each gas was immersed in a stirred metal polishing liquid (room temperature, 25 ° C, stirring 600rpm), and the metal layer film thickness difference before and after immersion was calculated in terms of electric resistance.
[Examples 13-20, Reference Examples 3-6, and Comparative Example 3]
(Method of manufacturing polishing liquid for metal)
The polishing liquid for metals is 0.15% by weight of malic acid, 0.15% by weight of a water-soluble polymer (acrylic polymer, weight average molecular weight: about 10,000), 0.2% by weight of the imidazole compound shown in Table 3, benzotriazole shown in Table 3, or the like. 0.2% by weight of 3-amino-1,2,4-triazole, 9% by weight of hydrogen peroxide and the balance were mixed with water to prepare.
Using the obtained polishing liquid for metals, it etched and CMP-polished similarly to Example 1, and evaluated. Etch rates are listed in Table 3.
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실시예 1∼4, 참고예 1은 구리의 연마속도가 어느 경우에도 130nm/min 이상이고, 비교예 1과 비교하여 개선되어 있다. 한편, 에칭속도에 관해서도 비교예와 비교하여 충분히 낮은 값이었다.
실시예 6∼11, 참고예 2는 텅스텐의 연마속도가 어느 경우에도 80nm/min 이상이고, 비교예 2와 비교하여 개선되어 있다. 한편, 에칭속도에 관해서도 비교예와 비교하여 충분히 낮은 값이었다.
실시예 13∼20은 구리의 에칭속도가 어느 경우에도 0.5nm/min 이하이고, 비교예 3과 비교하여 크게 개선되어 있다. 한편, 텅스텐에 있어서도 비교예와 비교하여 충분히 낮은 값이었다. 참고예 3∼6도, 텅스텐에 있어서 충분히 낮아, 실용 레벨이었다.
또한, 실시예 13∼20, 참고예 3∼6에서 구리, 텅스텐의 연마속도는 각각 100nm/min, 20nm/min 이상이고, 충분히 실용레벨이었다.
In Examples 1 to 4 and Reference Example 1, the polishing rate of copper was 130 nm / min or more in all cases, and improved compared with Comparative Example 1. On the other hand, the etching rate was also sufficiently low compared with the comparative example.
In Examples 6 to 11 and Reference Example 2, the polishing rate of tungsten was 80 nm / min or more in all cases, and improved compared with Comparative Example 2. On the other hand, the etching rate was also sufficiently low compared with the comparative example.
In Examples 13 to 20, the etching rate of copper was 0.5 nm / min or less in all cases, and greatly improved compared with Comparative Example 3. On the other hand, also in tungsten, it was a sufficiently low value compared with a comparative example. Reference examples 3-6 were also low enough in tungsten, and were a practical use level.
In Examples 13 to 20 and Reference Examples 3 to 6, the polishing rates of copper and tungsten were 100 nm / min and 20 nm / min or more, respectively, and were sufficiently practical.
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[실시예 25]Example 25
말산 0.15중량%, 수용성 폴리머(아크릴계 중합체, 중량평균 분자량 : 약 1만) 0.15중량%, 3-아미노-1,2,4-트리아졸 0.3중량%, 벤조트리아졸 0.14중량%, 2,4-디메틸이미다졸 0.05중량%, 지립(콜로이달 실리카, 1차 입경 30nm) 0.4중량% 및 과산화수소수 9중량%, 잔부를 물로 하여 혼합하여 금속용 연마액을 조제했다.0.15% by weight of malic acid, 0.15% by weight of water-soluble polymer (acrylic polymer, weight average molecular weight: about 10,000), 0.3% by weight of 3-amino-1,2,4-triazole, 0.14% by weight of benzotriazole, 2,4- 0.05% by weight of dimethylimidazole, 0.4% by weight of abrasive grains (colloidal silica, primary particle diameter of 30 nm), 9% by weight of hydrogen peroxide and the balance were mixed with water to prepare a polishing liquid for metal.
이산화실리콘 중에 깊이 0.5∼100㎛의 홈을 형성하고, 공지의 방법에 의해 배리어층으로서 두께 50nm의 텅스텐층을 형성하고, 그 상층에 구리막을 1.0㎛ 형성한 실리콘 기판을 준비했다. 기판 표면 전면에서 이산화실리콘의 볼록부가 노출할 때까지 상기 연마액에 의해 실시예 1과 동일한 연마조건에서 연마를 행하였다. 연마시간은 2분이고, 약 500nm/min 이상의 연마속도가 얻어졌다. 다음에, 촉침식 단차계로 배선금속부 폭 100㎛, 절연막부 폭 100㎛가 서로 번갈아 늘어선 스트라이프상 패턴부의 표면 형상으로부터, 절연막부에 대한 배선금속부의 막감소량을 구한 바 70nm이고, 충분히 실용적인 값이었다.A silicon substrate in which a groove having a depth of 0.5 to 100 µm was formed in silicon dioxide, a tungsten layer having a thickness of 50 nm was formed as a barrier layer by a known method, and 1.0 µm of a copper film was formed on the upper layer. The polishing liquid was polished under the same polishing conditions as in Example 1 until the convex portions of silicon dioxide were exposed on the entire surface of the substrate surface. The polishing time was 2 minutes, and a polishing rate of about 500 nm / min or more was obtained. Next, the film reduction amount of the wiring metal portion relative to the insulating film portion was determined from the surface shape of the stripe pattern portion in which the width of the wiring metal portion 100 μm and the insulating film portion width 100 μm were alternately arranged with a tactile step system. .
[실시예 26]Example 26
말산 0.15중량, 수용성 폴리머(아크릴계 중합체, 중량평균 분자량 : 약 1만) 0.15중량%, 3-아미노-1,2,4-트리아졸 0.3중량%, 벤조트리아졸 0.14중량%, 2,4-디메틸이미다졸 0.05중량%, 과산화수소수 9중량%, 잔부를 물로 하여 혼합하여 연마액을 조제했다.Malic acid 0.15 weight, Water-soluble polymer (acrylic polymer, weight average molecular weight: about 10,000) 0.15 weight%, 3-amino-1,2,4-triazole 0.3 weight%, benzotriazole 0.14 weight%, 2,4-dimethyl A polishing liquid was prepared by mixing imidazole 0.05% by weight, hydrogen peroxide solution 9% by weight and the balance as water.
이 연마액을 이용한 것 이외에는 실시예 1과 동일하게 하여, 에칭을 행하였다. 이때의 에칭속도는, 구리에서는 0.37nm/min, 텅스텐에서는 0.49nm/min이었다.Etching was performed in the same manner as in Example 1 except that the polishing liquid was used. The etching rate at this time was 0.37 nm / min in copper and 0.49 nm / min in tungsten.
실시예 25에서 사용한 것과 동일한 실리콘 기판을 표면 전면에서 이산화실리콘의 볼록부가 노출할때까지 상기 연마액에 의해 실시예 1과 동일한 연마조건에서 연마를 행하였다. 연마시간은 3분이고, 약 350nm/min 이상의 연마속도가 얻어졌다. 다음에, 촉침식 단차계로 배선금속부 폭 100㎛, 절연막부 폭 100㎛가 서로 번갈아 늘어선 스트라이프상 패턴부의 표면 형상으로부터, 절연막부에 대한 배선금속부의 막 감소량을 구한 바 50nm이고, 충분히 실용적인 값이었다.The same silicon substrate as used in Example 25 was polished under the same polishing conditions as in Example 1 with the polishing liquid until the convex portions of silicon dioxide were exposed on the entire surface. The polishing time was 3 minutes, and a polishing rate of about 350 nm / min or more was obtained. Next, the film reduction amount of the wiring metal portion with respect to the insulating film portion was calculated from the surface shape of the stripe pattern portion in which the width of the wiring metal portion 100 μm and the insulating film portion 100 μm were alternately arranged with a tactile step system. .
본 발명의 금속용 연마액은, 에칭속도를 낮게 유지하면서, 연마속도를 충분히 상승시키고, 금속 표면의 부식과 디싱의 발생을 억제하고, 신뢰성이 높은 금속막의 매립패턴 형성을 가능하게 하는 것이다.The metal polishing liquid of the present invention is capable of sufficiently increasing the polishing rate, suppressing corrosion of the metal surface and occurrence of dishing while maintaining a low etching rate, and making it possible to form a buried pattern of a highly reliable metal film.
본 발명의 연마방법은, 에칭속도를 낮게 유지하면서, 연마속도를 충분히 상승시키고, 금속 표면의 부식과 디싱의 발생을 억제하고, 신뢰성이 높은 금속막의 매립패턴 형성을 생산성, 작업성, 수율 양호하게 행할 수 있는 것이다.According to the polishing method of the present invention, while maintaining the etching rate low, the polishing rate is sufficiently increased, the corrosion of the metal surface and the occurrence of dishing are suppressed, and the formation of a buried pattern of a highly reliable metal film is improved in productivity, workability and yield. It can be done.
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