KR101955390B1 - Slurry composition and method for polishing copper layer and silicon oxide layer - Google Patents
Slurry composition and method for polishing copper layer and silicon oxide layer Download PDFInfo
- Publication number
- KR101955390B1 KR101955390B1 KR1020120077254A KR20120077254A KR101955390B1 KR 101955390 B1 KR101955390 B1 KR 101955390B1 KR 1020120077254 A KR1020120077254 A KR 1020120077254A KR 20120077254 A KR20120077254 A KR 20120077254A KR 101955390 B1 KR101955390 B1 KR 101955390B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- polishing
- weight
- slurry composition
- dispersion stabilizer
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 81
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000002002 slurry Substances 0.000 title claims abstract description 35
- 239000010949 copper Substances 0.000 title claims abstract description 33
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000003381 stabilizer Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000006061 abrasive grain Substances 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- -1 organic acid compound Chemical class 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 238000007517 polishing process Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01L21/306—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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
구리막 및 실리콘산화막을 빠르고 균일하게 연마시킬 수 있는 화학 기계적 연마 슬러리 조성물 및 이를 이용한 연마 방법이 개시된다. 상기 화학 기계적 연마 슬러리 조성물은 5 내지 30 중량%의 연마 입자, 0.01 내지 5 중량%의 연마 향상제, 0.001 내지 5 중량%의 분산 안정제, 0.5 내지 5 중량%의 산화제 및 나머지 물을 포함하며, 상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 이다. 또한, 상기 연마 방법은, 5 내지 30 중량%의 연마 입자, 0.01 내지 5 중량%의 연마 향상제, 0.001 내지 5 중량%의 분산 안정제, 0.5 내지 5 중량%의 산화제, 및 나머지 물을 포함하며, 상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 인 화학 기계적 연마 슬러리 조성물을 기판에 도포하는 단계; 및 연마 패드를 상기 기판과 접촉시키고, 상기 연마 패드를 기판에 대해 이동시켜, 기판으로부터 구리막 및 실리콘산화막의 적어도 일부를 제거하는 단계를 포함한다.A chemical mechanical polishing slurry composition capable of rapidly and uniformly polishing a copper film and a silicon oxide film, and a polishing method using the same. Wherein the chemical mechanical polishing slurry composition comprises 5 to 30% by weight of abrasive particles, 0.01 to 5% by weight of a polishing improver, 0.001 to 5% by weight of a dispersion stabilizer, 0.5 to 5% by weight of an oxidizing agent, The content ratio (weight ratio) of the particles and the dispersion stabilizer is 1: 0.01 to 0.3. The polishing method may further comprise: 5 to 30 wt% of abrasive particles, 0.01 to 5 wt% of a polishing improver, 0.001 to 5 wt% of a dispersion stabilizer, 0.5 to 5 wt% of an oxidizing agent, Applying a chemical mechanical polishing slurry composition having a weight ratio of abrasive grains and a dispersion stabilizer of 1: 0.01 to 0.3 to a substrate; And contacting the polishing pad with the substrate and moving the polishing pad relative to the substrate to remove at least a portion of the copper film and the silicon oxide film from the substrate.
Description
본 발명은 구리막 및 실리콘산화막 연마 슬러리 조성물에 관한 것으로서, 더욱 상세하게는, 구리막 및 실리콘산화막을 빠르고 균일하게 연마시킬 수 있는 화학 기계적 연마 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다.
The present invention relates to a copper film and a silicon oxide film polishing slurry composition, and more particularly, to a chemical mechanical polishing slurry composition capable of rapidly and uniformly polishing a copper film and a silicon oxide film, and a polishing method using the same.
반도체 집적회로에 있어서는, 트랜지스터, 커패시터, 저항 등의 수많은 기능 요소(소자)들이 일정한 모양으로 도안된 배선에 의해 연결되어 회로를 구성한다. 집적회로는 각 세대를 거치며 소형화되고 있지만, 단순히 소자나 배선의 크기를 감소시키는 것에는 한계가 있으므로, 최근에는 각 소자를 다층으로 형성하는 다층 배선 구조에 대한 연구가 활발히 이루어지고 있다. 이와 같이 배선의 폭이 작아짐에 따라, 제조 가능성이나 회로의 신뢰성에 영향을 주는 여러 가지 문제가 발생한다. 예를 들어, 금속 배선의 선폭이 작아지면, 배선의 저항과 커패시턴스가 증가하고, 신호 전달 지연(RC time delay) 및 전압 강하를 유발하기 쉽다. 이와 같은 문제점을 해결하기 위하여, 기존의 배선 재료로 사용되는 알루미늄을 구리로 대체하는 방법이 연구되고 있다. 구리는 비저항이 낮아, 집적회로의 신호 처리 속도 및 수명을 증가시킬 수 있는 장점이 있으나, 실리콘막 내부로 확산되기 쉽고, 건식 식각이 곤란하며, 화학 기계적 연마 과정이 복잡한 단점이 있다.
In a semiconductor integrated circuit, a number of functional elements (elements) such as a transistor, a capacitor, and a resistor are connected to each other by a wiring patterned in a predetermined shape to form a circuit. Integrated circuits have been miniaturized through each generation, but there are limitations in simply reducing the sizes of elements and wiring. Recently, research into multilayer wiring structures for forming each element in multiple layers has been actively conducted. As the width of the wiring becomes smaller in this manner, various problems occur that affect the manufacturability and the reliability of the circuit. For example, as the line width of the metal wiring becomes smaller, the resistance and capacitance of the wiring increase, and the RC time delay and voltage drop are liable to occur. In order to solve such a problem, a method of replacing aluminum used as a conventional wiring material with copper has been studied. Copper has a low resistivity and can increase the signal processing speed and lifetime of an integrated circuit. However, copper has a disadvantage that it diffuses easily into a silicon film, is difficult to dry etch, and complicates a chemical mechanical polishing process.
이와 같이 반도체 집적회로를 형성하는 금속막, 실리콘산화막(이산화규소막) 등을 연마하기 위한 다양한 화학 기계적 연마 슬러리 조성물이 공지되어 있다. 예를 들면, 대한민국 공개특허 10-2009-0026984호는, 연마제로서 실리카, 연마 촉진제로서 유기산, 무기산, 아미노산, 킬레이트제 또는 그 염, pH 조절제, 및 탈이온수를 포함하는 절연막의 화학기계적 연마 슬러리 조성물을 개시한다. 상기 특허에 있어서, pH조절제로는 수산화칼륨이 사용되고, 실리카로는 퓸드 실리카가 사용되며, 유기산으로는 글리신이 사용되는 것이 바람직하다고 개시되어 있다. 미국 특허 공개 US 2005-0205837호는 퓸드 실리카, 수산화칼륨 등의 성분을 포함하는 실리콘 웨이퍼 연마용 조성물을 개시한다. 일본 특허 공개 H08-267356호는 퓸드 실리카 대신 콜로이달 실리카를 사용하고, 분산제로 수산화칼륨을 포함하는 실리콘 웨이퍼용 연마제를 개시한다. 미국 특허 공개 US 2002-0081865호는, 퓸드 실리카 및 pH 조절을 위하여 수산화 칼륨을 포함하는 구리막(copper layer) 및 절연막 연마용 슬러리를 개시한다. 이러한 종래의 화학 기계적 연마 슬러리 조성물은, 구성 성분에 따라, 연마 대상 금속이 달라지고, 금속막 및 실리콘산화막의 연마 속도 및 연마 속도비율도 모두 상이하다. 한편, 상기 종래 기술들에 있어서, 구리막 및 실리콘산화막을 실질적으로 동일한 속도로, 즉, 1:1 의 연마 비율로 연마하여, 구리막 및 실리콘산화막을 동시에 균일하게 평탄화하면서, 표면 결함의 발생을 억제할 수 있는 슬러리 조성물에 대하여는 개시되어 있지 않다.
Various chemical mechanical polishing slurry compositions for polishing a metal film, a silicon oxide film (silicon dioxide film), and the like that form a semiconductor integrated circuit are known. For example, Korean Patent Laid-Open No. 10-2009-0026984 discloses a chemical mechanical polishing slurry composition of an insulating film containing silica as an abrasive, an organic acid, inorganic acid, amino acid, chelating agent or salt thereof, pH adjuster and deionized water as a polishing accelerator . In the above patent, it is disclosed that potassium hydroxide is used as a pH regulator, fumed silica is used as silica, and glycine is used as an organic acid. US Patent Publication No. US 2005-0205837 discloses a composition for polishing silicon wafers containing components such as fumed silica, potassium hydroxide and the like. Japanese Patent Laid-Open No. H08-267356 discloses an abrasive for silicon wafers using colloidal silica instead of fumed silica and potassium hydroxide as a dispersing agent. US 2002-0081865 discloses a copper layer and a slurry for polishing an insulating film containing fumed silica and potassium hydroxide for pH adjustment. In such a conventional chemical mechanical polishing slurry composition, the metal to be polished varies depending on the constituent components, and the polishing rate and the polishing rate ratio of the metal film and the silicon oxide film are all different. On the other hand, in the above prior arts, the copper film and the silicon oxide film are polished at substantially the same rate, that is, at a polishing rate of 1: 1 to uniformly planarize the copper film and the silicon oxide film at the same time, There is no disclosure of a slurry composition which can be inhibited.
따라서, 본 발명의 목적은, 구리막 및 실리콘산화막을 빠르고 균일하게 연마시킬 수 있는 화학 기계적 연마 슬러리 조성물 및 연마 방법을 제공하는 것이다. 본 발명의 다른 목적은, 구리막 및 실리콘산화막을 실질적으로 동일한 속도로 연마 및 제거할 수 있는 화학 기계적 연마 슬러리 조성물 및 연마 방법을 제공하는 것이다.
It is therefore an object of the present invention to provide a chemical mechanical polishing slurry composition and a polishing method capable of rapidly and uniformly polishing a copper film and a silicon oxide film. Another object of the present invention is to provide a chemical mechanical polishing slurry composition and a polishing method capable of polishing and removing the copper film and the silicon oxide film at substantially the same rate.
상기 목적을 달성하기 위하여, 본 발명은, 5 내지 30 중량%의 연마 입자; 0.01 내지 5 중량%의 연마 향상제; 0.001 내지 5 중량%의 분산 안정제; 0.5 내지 5 중량%의 산화제; 및 나머지 물을 포함하며, 상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 인 것인, 화학 기계적 연마 슬러리 조성물을 제공한다. 또한, 본 발명은, 5 내지 30 중량%의 연마 입자, 0.01 내지 5 중량%의 연마 향상제, 0.001 내지 5 중량%의 분산 안정제, 0.5 내지 5 중량%의 산화제, 및 나머지 물을 포함하며, 상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 인 화학 기계적 연마 슬러리 조성물을 기판에 도포하는 단계; 및 연마 패드를 상기 기판과 접촉시키고, 상기 연마 패드를 기판에 대해 이동시켜, 기판으로부터 구리막 및 실리콘산화막의 적어도 일부를 제거하는 단계를 포함하는 화학 기계적 연마 방법을 제공한다.
In order to achieve the above object, the present invention provides a polishing composition comprising: 5 to 30% by weight of abrasive grains; 0.01 to 5% by weight of a polishing improver; 0.001 to 5% by weight of a dispersion stabilizer; 0.5 to 5% by weight of an oxidizing agent; And a balance of water, wherein the content ratio (weight ratio) of the abrasive particles to the dispersion stabilizer is 1: 0.01 to 0.3. The present invention also provides a polishing composition comprising 5 to 30 wt% abrasive particles, 0.01 to 5 wt% of a polishing improver, 0.001 to 5 wt% of a dispersion stabilizer, 0.5 to 5 wt% of an oxidizing agent, Applying a chemical mechanical polishing slurry composition having a weight ratio of particles and a dispersion stabilizer of 1: 0.01 to 0.3 to a substrate; And contacting the polishing pad with the substrate and moving the polishing pad relative to the substrate to remove at least a portion of the copper film and the silicon oxide film from the substrate.
본 발명에 따른 화학 기계적 연마 슬러리 조성물은 구리막 및 실리콘산화막을 빠르고 균일하게, 그리고 동일한 속도로 연마 및 제거할 수 있다.
The chemical mechanical polishing slurry composition according to the present invention can polish and remove the copper film and the silicon oxide film quickly and uniformly and at the same rate.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 화학 기계적 연마 슬러리 조성물은 구리막 및 실리콘산화막을 연마하기 위한 것으로서, 5 내지 30 중량%, 바람직하게는 8 내지 20 중량%의 연마 입자, 0.01 내지 5 중량%, 바람직하게는 0.01 내지 1 중량%의 연마 향상제, 0.001 내지 5 중량%, 바람직하게는 0.01 내지 4 중량%, 더욱 바람직하게는 0.1 내지 3.5 중량%의 분산 안정제, 0.5 내지 5 중량%, 바람직하게는 0.1 내지 4 중량%의 산화제 및 나머지 물(water)을 포함한다. 또한, 상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 이고, 바람직하게는 1 : 0.02 내지 0.2 이다. 여기서, 상기 분산 안정제의 함량비가 0.01 미만이거나 0.3을 초과하면, 구리막과 실리콘산화막의 연마 속도가 감소하거나, 구리막에 대한 실리콘산화막의 연마 속도비가 감소할 우려가 있다. 또한, 상기 연마 입자, 연마 향상제, 분산 안정제 및 산화제의 함량이 너무 작거나 많으면, 구리막 및 실리콘산화막의 연마 속도가 저하되거나, 구리막 및 실리콘산화막의 연마 속도 비율이 커지거나, 연마면에 스크래치가 발생할 우려가 있다.
The chemical mechanical polishing slurry composition for polishing a copper film and a silicon oxide film according to the present invention comprises 5 to 30% by weight, preferably 8 to 20% by weight of abrasive grains, 0.01 to 5% by weight, preferably 0.01 to 5% A dispersion stabilizer in an amount of 0.5 to 5% by weight, preferably 0.1 to 4% by weight, based on 1% by weight of a polishing aid, 0.001 to 5% by weight, preferably 0.01 to 4% by weight, more preferably 0.1 to 3.5% An oxidant and the remainder of water. The content ratio (weight ratio) of the abrasive particles to the dispersion stabilizer is 1: 0.01 to 0.3, preferably 1: 0.02 to 0.2. Here, when the content ratio of the dispersion stabilizer is less than 0.01 or more than 0.3, the polishing rate of the copper film and the silicon oxide film may decrease or the polishing rate ratio of the silicon oxide film to the copper film may decrease. If the content of the abrasive grains, the polishing improver, the dispersion stabilizer, and the oxidizer is too small or too large, the polishing rate of the copper film and the silicon oxide film may decrease, the polishing rate ratio of the copper film and the silicon oxide film may increase, May occur.
상기 연마 입자는, 구리막 및 실리콘산화막을 물리적으로 연마하기 위한 것으로서, 콜로이달 실리카, 퓸드 실리카(Fumed silica) 등의 실리카, 알루미나, 세리아, 티타니아, 지르코니아(산화지르코늄), 젠나니아 등을 단독 또는 혼합하여 사용할 수 있고, 바람직하게는 실리카, 더욱 바람직하게는 퓸드 실리카를 사용할 수 있다.
The abrasive grains are used to physically polish the copper film and the silicon oxide film. Examples of the abrasive grains include silica such as colloidal silica and fumed silica, alumina, ceria, titania, zirconia (zirconium oxide) And silica, more preferably fumed silica, can be used.
상기 연마 향상제는, 금속막의 산화 및 연마에 의해서 발생하는 금속 이온과 결합하여 금속 착화물을 형성하는 착화제(complexing agent)의 역할을 하거나, 금속막과 결합하여 금속 - 연마 향상제의 복합물층을 형성함으로써, 금속막의 연마 속도를 증가시키는 역할을 한다. 상기 연마 향상제로는 유기 산, 유기 아민 및/또는 무기산을 사용할 수 있으며, 바람직하게는 아민(-NH2)기와 카르복실기(-COOH)를 모두 가지는 아미노산(amino acid)을 사용할 수 있다. 상기 유기 산 화합물로는 카르복실기(COOH)를 가지는 화합물을 사용할 수 있고, 예를 들면, 타르타르산, 시트르산, 락트산, 말론산, 숙신산, 아세트산, 옥살산, 폴리아크릴산, 프탈산, 포름산, 이들의 혼합물 등을 사용할 수 있다. 또한, 상기 유기 아민 화합물은 아민기(NH2, NH, N)를 포함하는 화합물로서, 예를 들면, 노닐아민, 도데실아민, 피페라진(piperazine), 이들의 혼합물 등의 탄소수 1 내지 20의 알킬아민을 사용할 수 있다. 상기 무기산으로는, 인산(phosphoric acid), 포스폰산(phosphonic acid), 아미노 황산(H3NSO3, aminosulfonic acid), 이들의 염, 이들의 혼합물 등을 사용할 수 있다. 상기 유기 산 화합물이며 동시에 유기 아민 화합물인 아미노산의 바람직한 예로는 글리신(glycine, H2NCH2COOH) 등을 예시할 수 있다. 또한, 필요에 따라, 상기 연마 향상제는 히드록시기 등의 치환기를 가질 수도 있다.
The polishing-improving agent acts as a complexing agent that binds to metal ions generated by oxidation and polishing of a metal film to form a metal complex, or forms a complex layer of a metal-polishing enhancer in combination with a metal film Thereby increasing the polishing rate of the metal film. As the polishing improver, an organic acid, an organic amine and / or an inorganic acid can be used, and preferably an amino acid having both an amine (-NH 2 ) group and a carboxyl group (-COOH) can be used. As the organic acid compound, a compound having a carboxyl group (COOH) can be used. For example, a compound having a carboxyl group (COOH) can be used, and examples thereof include tartaric acid, citric acid, lactic acid, malonic acid, succinic acid, acetic acid, oxalic acid, polyacrylic acid, phthalic acid, formic acid, . The organic amine compound is a compound containing an amine group (NH 2 , NH, N) such as nonylamine, dodecylamine, piperazine, Alkylamines can be used. Examples of the inorganic acid include phosphoric acid, phosphonic acid, H 3 NSO 3 , aminosulfonic acid, salts thereof, and mixtures thereof. Preferable examples of the organic acid compound and the organic amine compound include glycine (H 2 NCH 2 COOH) and the like. If necessary, the polishing improver may have a substituent such as a hydroxy group.
상기 분산 안정제는, 보관, 숙성 등에 의하여, 본 발명에 따른 슬러리 조성물이 겔화하거나 입자가 침전되는 현상을 억제하고 분산 안정성을 유지하기 위한 첨가제로서, 수산화암모늄(NH4OH), 수산화칼륨(KOH), 수산화나트륨(NaOH), 염산(HCl), 질산(HNO3), 황산(H2SO4), 이들의 혼합물 등의 무기 화합물을 사용하거나, 양이온성 계면활성제, 음이온성 계면활성제, 양쪽성 계면활성제, 비이온성 계면활성제, 이들의 혼합물 등의 계면 활성제를 사용할 수 있다. 상기 분산 안정제로서, 바람직하게는 상기 무기 화합물 분산 안정제를 사용할 수 있고, 더욱 바람직하게는 수산화칼륨(KOH)을 사용할 수 있다.
The dispersion stabilizer may be ammonium hydroxide (NH 4 OH), potassium hydroxide (KOH), or the like as an additive for suppressing the gelation or precipitation of the slurry composition according to the present invention by storage, aging, , sodium hydroxide (NaOH), hydrochloric acid (HCl), nitric acid (HNO 3), sulfuric acid (H 2 SO 4), using an inorganic compound such as a mixture thereof, or cationic surfactants, anionic surfactants, amphoteric A surfactant such as an active agent, a nonionic surfactant, or a mixture thereof may be used. As the dispersion stabilizer, the inorganic compound dispersion stabilizer may preferably be used, and more preferably potassium hydroxide (KOH) may be used.
본 발명의 슬러리 조성물에 사용되는 산화제는, 금속막의 표면에 산화막을 형성하여, 금속막의 연마를 촉진시키기 위한 것으로서, 상기 산화제는 웨이퍼, 기판 등의 금속층을 상응하는 산화물, 수산화물, 이온 등으로 산화시킨다. 상기 산화제로는 화학-기계적 연마 슬러리 조성물에 사용되는 통상의 산화제가 특별한 제한 없이 사용될 수 있고, 바람직하게는, 무기 또는 유기 퍼-화합물(per-compound)이 사용될 수 있다. 상기 퍼-화합물은 하나 이상의 퍼옥시기(-O-O-)를 포함하는 화합물 또는 그 자신의 가장 높은 산화 상태에 있는 원소를 포함하는 화합물을 의미한다. 상기 산화제의 구체적인 예로는, 과산화수소(H2O2), 우레아 과산화수소, 모노퍼설페이트, 디퍼설페이트, 퍼아세트산, 퍼카보네이트, 벤조일페록사이드, 퍼요오드산, 퍼요오디에이트염, 퍼브롬산, 과붕산, 과붕산염, 퍼클로로산, 퍼클로로산염, 퍼망가네이트, 퍼망가네이트염 등을 단독 또는 혼합하여 사용할 수 있고, 바람직하게는 과산화수소를 사용할 수 있다.
The oxidizing agent used in the slurry composition of the present invention is for oxidizing the metal film by forming an oxide film on the surface of the metal film. The oxidizing agent oxidizes a metal layer such as a wafer or a substrate with a corresponding oxide, hydroxide or ion . As the oxidizing agent, a conventional oxidizing agent used in the chemical-mechanical polishing slurry composition may be used without particular limitation, and preferably, an inorganic or organic per-compound may be used. The per-compound means a compound comprising at least one peroxy group (-OO-) or a compound comprising an element in its highest oxidation state. Specific examples of the oxidizing agent include hydrogen peroxide (H 2 O 2 ), urea hydrogen peroxide, monopersulfate, dipersulfate, peracetic acid, percarbonate, benzoyl peroxide, periodic acid, peroiodic acid, perbromic acid, perboric acid , Perborate, perchloric acid, perchlorate, peranganate, peranganate, and the like can be used singly or in combination, and hydrogen peroxide can be preferably used.
본 발명에 따른 슬러리 조성물은, 필요에 따라, 부식 방지제 등의 첨가제를 더욱 포함할 수 있다. 상기 부식 방지제는, 금속막의 부식을 방지하기 위한 것으로서, 화학-기계적 연마 슬러리 조성물에 사용되는 통상의 부식 방지제가 특별한 제한 없이 사용될 수 있다. 상기 부식 방지제는 질소 함유 고리(cyclic) 화합물, 요소, 티오요소 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다. 상기 질소 함유 고리 화합물의 구체적인 예로는, 트리아졸, 벤조트리아졸, 이미다졸, 벤즈이미다졸, 벤조티아졸 등을 예시할 수 있고, 이들은, 필요에 따라, 히드록시기, 아미노기, 이미노기, 카르복시기, 머캅토기, 니트로기, 알킬기 등의 치환기를 가질 수 있다. 본 발명에 따른 슬러리 조성물은, 발명의 목적 및 효과를 달성하는 한도 내에서, pH 조절제 등의 통상적인 다른 첨가제를 더욱 포함할 수 있다.
The slurry composition according to the present invention may further contain an additive such as a corrosion inhibitor if necessary. The corrosion inhibitor is used to prevent corrosion of the metal film. Conventional corrosion inhibitors used in the chemical-mechanical polishing slurry composition may be used without any particular limitation. The corrosion inhibitor may be selected from the group consisting of nitrogen containing cyclic compounds, urea, thiourea, and mixtures thereof. Specific examples of the nitrogen-containing cyclic compound include triazole, benzotriazole, imidazole, benzimidazole, benzothiazole and the like, and they may be substituted with a hydroxyl group, an amino group, an imino group, A nitro group, an alkyl group, and the like. The slurry composition according to the present invention may further contain other conventional additives such as a pH adjusting agent to the extent that the objects and effects of the invention are achieved.
본 발명에 따른 슬러리 조성물은, 공지된 임의의 방법으로 제조될 수 있고, 예를 들면, 연마 입자, 연마 향상제 및 분산 안정제를 탈이온수, 증류수 등의 수성매질(이하, 필요에 따라, 단순히 "물"이라 한다)에 필요한 농도로 첨가한 다음, 산화제 또는 산화제 수용액을 상기 수성 매질에 원하는 농도로 첨가하여, 본 발명의 조성물을 제조할 수 있다. 본 발명의 조성물을 구성하는 각 성분은, 웨이퍼의 연마 공정 직전에 혼합되어 연마 공정에 사용될 수도 있고, 혼합 후 소정의 시간이 경과된 후 연마 공정에 사용될 수도 있으며, 1 이상의 성분을 포함하는 2이상의 포장(package) 단위로 제공된 후, 연마 공정 직전에 상기 2 이상의 포장 단위에 포함된 성분들을 혼합하여 사용할 수도 있다.
The slurry composition according to the present invention can be prepared by any known method and can be produced, for example, by dispersing the abrasive particles, the polishing improver and the dispersion stabilizer in an aqueous medium such as deionized water and distilled water (hereinafter, Quot;), and then adding an oxidizing agent or an oxidizing agent aqueous solution to the aqueous medium at a desired concentration, the composition of the present invention can be prepared. Each component constituting the composition of the present invention may be mixed immediately before the polishing process of the wafer and used in the polishing process, or may be used in the polishing process after a predetermined time has elapsed after the mixing, and two or more It is also possible to use a mixture of the components contained in the two or more packaging units just before the polishing process after being provided in a package unit.
본 발명에 따른 슬러리 조성물은, 반도체 집적회로의 제조에 있어서, 구리 및 실리콘산화막의 연마에 특히 유용하다. 본 발명의 슬러리 조성물을 이용하여, 웨이퍼, 유리 등의 기판에 형성된 구리막 및 실리콘산화막을 연마하는 방법으로는 통상의 다양한 화학 기계적 연마 방법이 사용될 수 있다. 예를 들면, 본 발명의 슬러리 조성물을 기판에 도포하고, 연마 패드를 기판과 접촉시키고, 연마 패드를 기판에 대해 이동시켜, 기판으로부터 구리막 및 실리콘산화막의 적어도 일부를 제거할 수 있다. 본 발명에 따른 슬러리 조성물에 있어서, 연마 입자(연마제)인 실리카와 분산 안정제인 수산화칼륨(KOH)의 함량비(중량비)를 1 : 0.01 내지 0.3으로 설정함으로써, 금속막(특히, 구리막) 및 실리콘산화막(실리콘산화막)을 동일한 속도로, 즉, 구리막 : 실리콘산화막을 대략 1 : 1, 예를 들면, 1 : 0.9 내지 1.3의 연마 속도 비율로 연마시킬 수 있고, 또한 구리막과 실리콘산화막의 연마 속도를 향상시킬 수 있다.
The slurry composition according to the present invention is particularly useful for polishing copper and silicon oxide films in the manufacture of semiconductor integrated circuits. Various conventional chemical mechanical polishing methods can be used as a method of polishing the copper film and the silicon oxide film formed on a substrate such as a wafer or a glass using the slurry composition of the present invention. For example, the slurry composition of the present invention can be applied to a substrate, the polishing pad can be brought into contact with the substrate, and the polishing pad can be moved relative to the substrate to remove at least a portion of the copper film and the silicon oxide film from the substrate. In the slurry composition according to the present invention, by setting the content ratio (weight ratio) of silica as abrasive particles (abrasive) to potassium hydroxide (KOH) as a dispersion stabilizer at 1: 0.01 to 0.3, It is possible to polish the silicon oxide film (silicon oxide film) at the same rate, that is, the copper film: silicon oxide film at a polishing rate ratio of about 1: 1, for example, 1: 0.9 to 1.3, The polishing rate can be improved.
이하, 구체적인 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples. The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention.
[실시예 1~10, 비교예 1~2] 화학-기계적 연마 슬러리 조성물의 제조 및 평가 [Examples 1 to 10, Comparative Examples 1 and 2] Preparation and evaluation of chemical-mechanical polishing slurry compositions
연마 입자, 분산 안정제 및 연마 향상제의 종류와 함량에 따른 화학-기계적 연마 슬러리 조성물의 성능을 평가하기 위하여, 하기 표 1에 나타낸 함량(중량%)의 연마 입자(실리카), 분산 안정제(KOH) 및 연마 향상제(Glycine), 3.5 중량%의 산화제(H2O2) 및 나머지 물(deionized water)을 포함하는 슬러리 조성물(실시예 1~10, 비교예 1~2)을 제조하였다.In order to evaluate the performance of the chemical-mechanical polishing slurry composition according to the kind and content of the abrasive grains, the dispersion stabilizer and the polishing improver, abrasive grains (silica), dispersion stabilizer (KOH) and Slurry compositions (Examples 1 to 10, Comparative Examples 1 to 2) containing a polishing agent (Glycine), 3.5 wt% of an oxidizing agent (H2O2) and deionized water were prepared.
(Glycine)Abrasion improver
(Glycine)
(KOH)Dispersion stabilizer
(KOH)
함량비Silica: KOH
Content ratio
두산 세미콘테크사(DOOSAN SEMICON TECH)의 Unipla 211 연마 장비(Polisher)에 연마 패드를 부착하고, 구리막(Cu) 및 실리콘산화막(PETEOS (Tetraethylortho silicate)막)이 형성된 웨이퍼(wafer, 크기: 8 인치)를 장착하였다. 다음으로, 상기 슬러리 조성물(실시예 1 ~ 10, 비교예 1~2)을 200 ml/min의 속도로 상기 웨이퍼로 공급하면서, 24 rpm의 압반(platen) 속도, 97 rpm의 선두(head) 속도, 2.1 psi의 하중압력으로 1분 동안(polishing time) 구리막(Cu) 및 실리콘산화막(PETEOS)을 연마하였다. 구리막 및 실리콘산화막의 연마속도(Removal Rate, 단위: Angstrom(Å)/min, 이하 R/R)를 각각 저항 측정기(CMT-2000, 4-point probe, ㈜창민 Tech.) 및 엘립소미터(Ellipsometer)로 측정하였으며, 그 결과를 하기 표 2에 나타내었다A wafer (size: 8 inches) on which a polishing pad was attached to a Unipla 211 polishing machine of Doosan Semiconductor TECH and a copper film (Cu) and a silicon oxide film (PETEOS (Tetraethylortho silicate) film) ). Next, while supplying the slurry composition (Examples 1 to 10, Comparative Examples 1 and 2) to the wafer at a rate of 200 ml / min, a platen speed of 24 rpm, a head speed of 97 rpm , Copper film (Cu) and silicon oxide film (PETEOS) were polished at a load pressure of 2.1 psi for 1 minute (polishing time). (CMT-2000, 4-point probe, Changmin Tech.) And ellipsometer ()) were used to measure the polishing rate (removal rate, unit: Angstrom Ellipsometer), and the results are shown in Table 2 below
상기 표 2에 나타낸 바와 같이, 실리카 : 분산 안정제의 함량비가 1 : 0.01 ~ 0.3 의 범위(실시예 1 ~ 10)에서는 구리막 : 실리콘산화막이 대략 1 : 1의 비율(연마율)로 연마되는 반면, 상기 분산 안정제의 함량비가 0.01 미만이거나(비교예 1), 0.3을 초과하는(비교예 2) 경우, 실리콘산화막의 연마율이 급격히 감소된다. 상기 결과는, 분산 안정제의 함량이 작으면, 연마 입자의 분산성이 불충분한 반면, 분산 안정제의 함량이 너무 많으면, 연마 입자(실리카)를 용해시켜, 실리콘산화막의 연마율이 오히려 저하되기 때문인 것으로 판단된다.As shown in Table 2, the copper film: silicon oxide film is polished at a ratio (polishing rate) of about 1: 1 in the range of the silica: dispersion stabilizer content ratio of 1: 0.01 to 0.3 (Examples 1 to 10) , The polishing rate of the silicon oxide film is drastically reduced when the content ratio of the dispersion stabilizer is less than 0.01 (Comparative Example 1) or more than 0.3 (Comparative Example 2). The above results indicate that when the content of the dispersion stabilizer is small, the dispersibility of the abrasive particles is insufficient, while when the content of the dispersion stabilizer is too large, the abrasive particles (silica) are dissolved to lower the polishing rate of the silicon oxide film .
Claims (7)
0.01 내지 5 중량%의 연마 향상제;
0.001 내지 5 중량%의 수산화암모늄, 수산화칼륨, 수산화나트륨, 염산, 질산, 황산 및 이들의 혼합물로 이루어진 군으로부터 선택되는 분산 안정제;
0.5 내지 5 중량%의 산화제; 및
나머지 물을 포함하며,
상기 연마 입자와 분산 안정제의 함량비(중량비)는 1 : 0.01 내지 0.3 인 것인, 화학 기계적 연마 슬러리 조성물5 to 30% by weight of abrasive grains;
0.01 to 5% by weight of a polishing improver;
From 0.001 to 5% by weight of a dispersion stabilizer selected from the group consisting of ammonium hydroxide, potassium hydroxide, sodium hydroxide, hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof;
0.5 to 5% by weight of an oxidizing agent; And
The remaining water,
Wherein the content ratio (weight ratio) of the abrasive particles to the dispersion stabilizer is 1: 0.01 to 0.3; and the chemical mechanical polishing slurry composition
연마 패드를 상기 기판과 접촉시키고, 상기 연마 패드를 기판에 대해 이동시켜, 기판으로부터 구리막 및 실리콘산화막의 적어도 일부를 제거하는 단계를 포함하는 화학 기계적 연마 방법.A dispersion stabilizer selected from the group consisting of 5 to 30 wt% abrasive particles, 0.01 to 5 wt% abrasive enhancer, 0.001 to 5 wt% ammonium hydroxide, potassium hydroxide, sodium hydroxide, hydrochloric acid, nitric acid, sulfuric acid, , 0.5 to 5% by weight of an oxidizing agent, and the balance of water, wherein the weight ratio of the abrasive particles to the dispersion stabilizer is 1: 0.01 to 0.3; And
Contacting the polishing pad with the substrate, moving the polishing pad relative to the substrate, and removing at least a portion of the copper film and the silicon oxide film from the substrate.
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