KR20070059620A - Chemical mechanical polishing composition for metal circuit - Google Patents
Chemical mechanical polishing composition for metal circuit Download PDFInfo
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- KR20070059620A KR20070059620A KR1020050118665A KR20050118665A KR20070059620A KR 20070059620 A KR20070059620 A KR 20070059620A KR 1020050118665 A KR1020050118665 A KR 1020050118665A KR 20050118665 A KR20050118665 A KR 20050118665A KR 20070059620 A KR20070059620 A KR 20070059620A
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- South Korea
- Prior art keywords
- polishing composition
- polishing
- weight
- mixtures
- amine
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title abstract description 26
- 239000002184 metal Substances 0.000 title abstract description 26
- 239000000126 substance Substances 0.000 title abstract description 7
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZRUPXAZUXDFLTG-UHFFFAOYSA-N 1-aminopentan-2-ol Chemical compound CCCC(O)CN ZRUPXAZUXDFLTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims abstract description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 alkyl secondary amines Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 5
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000003945 anionic surfactant Substances 0.000 claims 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 claims 1
- 239000003623 enhancer Substances 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 7
- 238000007517 polishing process Methods 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 208000035404 Autolysis Diseases 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 239000013522 chelant Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/40—Monoamines or polyamines; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- 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)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
본 발명은 금속 배선의 화학 기계적 연마(chemical mechanical polishing: CMP) 공정에 사용될 수 있는 연마 조성물에 관한 것이다.The present invention relates to a polishing composition that can be used in a chemical mechanical polishing (CMP) process of metal wiring.
최근 반도체 소자가 고집적화 및 고성능화됨에 따라, 반도체 제조 공정에서는 기존의 알루미늄 배선이 전기저항이 낮은 구리 배선으로 대체되고 있다. 구리를 이용한 반도체 소자의 배선을 형성하기 위해서는 주로 연마 슬러리를 뿌려주면서 연마 패드(polishing pad)를 부착한 원형의 연마 정반 위에 압력을 가한 상태로 회전시켜 웨이퍼를 연마하는 화학 기계적 연마(CMP) 공정을 이용한 다머신(damascene) 또는 이중 다머신(dual-damascene) 방법이 도입되고 있다. Recently, as semiconductor devices have been highly integrated and high performance, conventional aluminum wiring has been replaced by copper wiring having low electrical resistance in the semiconductor manufacturing process. In order to form the wiring of a semiconductor device using copper, a chemical mechanical polishing (CMP) process is performed in which a wafer is polished by applying a polishing slurry while rotating the wafer under pressure under a circular polishing plate with a polishing pad attached thereto. The used damascene or dual-damascene method is introduced.
이러한 연마 공정에 사용되는 연마 슬러리는 연마제, 물, 분산제 및 첨가제가 포함되며, 이때 첨가제로는 금속 배선막을 산화시키고 에칭시키는 산화제 및 착화제와 금속의 과도한 부식을 방지하는 부식 방지제 및 pH 조절제 등이 사용된다. 이 중, 부식 방지제는 금속 배선막 표면에 부동화층 또는 용해 억제층을 형성시켜 연마 속도를 조절하여 평탄화 향상에 도움을 주는 역할을 수행하므로, 금속 배선막의 연마에 있어 특히 중요한 성분이다. The polishing slurry used in the polishing process includes an abrasive, water, a dispersant, and an additive. The additives include an oxidizing agent and a complexing agent for oxidizing and etching the metal wiring film, a corrosion inhibitor and a pH adjusting agent to prevent excessive corrosion of the metal. Used. Among these, the corrosion inhibitor forms a passivation layer or a dissolution inhibiting layer on the surface of the metal wiring film, and thus plays a role of helping to improve the planarization by adjusting the polishing rate, and thus, the corrosion inhibitor is particularly important in polishing the metal wiring film.
기존 연마 조성물에는 부식 방지제로 벤조트리아졸(BTA)과 같은 아졸계 화합물을 주로 사용해 왔는데, 이러한 벤조트리아졸 등은 구리 등의 금속과 리간드 반응을 형성하여 금속 배선 표면에 너무 강력한 부식 보호막을 형성함으로써 연마시 에칭을 저해할 뿐 아니라 연마 속도도 크게 저하시키는 문제점이 있으며, 연마 후 배선막 표면에 유기물이나 연마입자가 잔존될 수 있는 소지가 많다. Conventional polishing compositions have mainly used azole compounds such as benzotriazole (BTA) as corrosion inhibitors. These benzotriazoles form ligand reactions with metals such as copper to form a very strong corrosion protective film on the surface of the metal wiring. There is a problem that not only inhibits etching during polishing but also greatly decreases the polishing speed, and there are many cases in which organic matter or abrasive particles may remain on the wiring film surface after polishing.
한편, 연마 조성물의 pH가 산성 영역에 있는 경우 금속막 연마시 금속의 부식이 너무 과도하게 일어나는 문제점이 있어, 금속의 부식 및 에칭을 적절히 제어할 수 있는 연마 조성물이 필요하다.On the other hand, when the pH of the polishing composition is in an acidic region, there is a problem that corrosion of the metal is excessively excessive when the metal film is polished, and a polishing composition capable of appropriately controlling corrosion and etching of the metal is required.
이에, 본 발명의 목적은 금속 배선막의 부식 및 에칭을 효율적으로 제어함으로써 우수한 연마 속도로 연마 공정을 수행할 수 있는 연마 조성물을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a polishing composition capable of performing a polishing process at an excellent polishing rate by efficiently controlling corrosion and etching of a metal wiring film.
상기 목적에 따라, 본 발명에서는 연마제, 아민계 착화제, 및 부식 방지제로서 친수성기를 갖는 비이온성 또는 양이온성 계면활성제 또는 이들의 혼합물을 포함하며, 6 내지 10 범위의 pH 값을 갖는, 금속 배선용 화학기계적 연마 조성물을 제공한다.According to the above object, the present invention includes a nonionic or cationic surfactant having a hydrophilic group or a mixture thereof as an abrasive, an amine complexing agent, and a corrosion inhibitor, and has a pH value in the range of 6 to 10, metal wiring chemistry Provide a mechanical polishing composition.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 연마 조성물은 착화제로서 아민계 화합물 및 부식 방지제로서 친수성기를 갖는 비이온성 또는 양이온성 계면활성제를 포함하는 것을 특징으로 한다.The polishing composition of the present invention is characterized in that it comprises an amine compound as a complexing agent and a nonionic or cationic surfactant having a hydrophilic group as a corrosion inhibitor.
본 발명의 연마 조성물은 금속 이온에 대한 착화제로서 아민계 화합물을 포함하며, 상기 아민계 화합물은 금속 이온과 효과적으로 착화물을 형성할 뿐만 아니라 조성물의 pH 범위를 중성 내지 약염기성, 예컨대 6 내지 10으로 유지하여 금속의 과도한 부식을 억제하는 역할을 한다. 이러한 아민계 화합물은 또한 베리어 막으로 사용되는 탄탈륨 및 탄탈 나이트라이드에 대한 연마 선택비가 우수하여, 금속 연마 공정시 과연마에 의한 디싱(dishing) 및 에로젼(erosion) 발생을 감소시킬 수 있다.The polishing composition of the present invention comprises an amine compound as a complexing agent for metal ions, which not only effectively forms a complex with the metal ions, but also the pH range of the composition is neutral to weakly basic, such as 6 to 10. It keeps it to prevent excessive corrosion of metal. These amine compounds also have excellent polishing selectivity for tantalum and tantalum nitride used as barrier films, which can reduce the occurrence of dishing and erosion by overpolishing in the metal polishing process.
상기 아민계 화합물로는 암모늄 하이드록사이드, 헥실아민, 피페라진, t-부틸아민, 다이프로필아민, 프로필아민, 다이에탄올아민, 트라이에탄올아민, 에틸렌다이아민, N,N-다이에틸에탄올아민, n-프로필에탄올아민 등이 사용될 수 있으며, 함량은 연마 조성물 중량 대비 0.01 내지 5 중량% 범위가 바람직하다. 아민계 화합물 함량이 5 중량%를 초과하는 경우 디싱이 발생할 수 있으며, 0.01 중량% 미만인 경우에는 연마속도에 있어서 불리해진다.Examples of the amine compound include ammonium hydroxide, hexylamine, piperazine, t-butylamine, dipropylamine, propylamine, diethanolamine, triethanolamine, ethylenediamine, N, N-diethylethanolamine, n-propylethanolamine and the like may be used, and the content is preferably in the range of 0.01 to 5% by weight based on the weight of the polishing composition. Dishes may occur when the amine compound content exceeds 5% by weight, and when the amine compound content is less than 0.01% by weight, disadvantageous in polishing rate.
본 발명에서는 부식 방지제로 친수성기를 갖는 비이온성 또는 양이온성 계면 활성제를 사용하는데, 기존 벤조트리아졸(BTA) 등의 부식 방지제가 금속 표면에 금속과의 리간드 반응에 의해 매우 강력한 부식 보호막을 형성하는 것과는 달리, 암모늄계 또는 착화제와 유사한 아민계 화합물을 선택함으로써 흡착에 의한 자기 조립막(self assembled monolayer)을 형성하게 하는 것이 바람직하다. 이와 같이, 흡착에 의해 형성된 조립막은 구리 등 금속의 부식을 효과적으로 억제할 수 있는 우수한 보호막 역할을 할 뿐만 아니라, 쉽게 제거될 수 있어 유기물 잔존 및 그에 따른 연마 속도 저하 등의 문제점을 해소시킬 수 있다.In the present invention, a nonionic or cationic surfactant having a hydrophilic group is used as a corrosion inhibitor, except that a conventional corrosion inhibitor such as benzotriazole (BTA) forms a very strong corrosion protection film by ligand reaction with a metal on a metal surface. Alternatively, it is preferable to select a amine compound similar to an ammonium-based or complexing agent to form a self assembled monolayer by adsorption. As such, the granulated film formed by adsorption not only serves as an excellent protective film that can effectively suppress corrosion of metals such as copper, and can be easily removed, thereby eliminating problems such as remaining organic material and a decrease in polishing rate.
본 발명에서 사용가능한 비이온성 계면활성제로는 알킬 2차 아민, 알킬 3차 아민, 알킬 프로판다이아민, 알킬 에틸렌 다이아민, 알킬 다이에틸렌 트라이아민, 알킬 트라이에틸렌 테트라아민, 알킬 테트라에틸렌 펜트아민, 알킬이미다졸린 하이드록시에틸아민, 알킬이미다졸린 에틸렌다이아민, 폴리아민 및 이들의 혼합물을 들 수 있으며, 특히 수용해도가 0.001 중량% 이상인 것이 바람직하다. 또한, 양이온성 계면활성제로는 4차 암모늄, 아민, 이미다졸, 및 이들로부터 유도된 염, 예컨대 메틸폴리옥시에틸렌 암모늄 클로라이드, 세틸트라이메틸 암모늄 브로마이드, 세틸트라이메틸 암모늄 클로라이드, 도데실 다이메틸아민 하이드로클로라이드 및 이들의 혼합물을 들 수 있으며, 수용해도를 고려해 탄소수가 10 미만인 것이 바람직하다.Nonionic surfactants usable in the present invention include alkyl secondary amines, alkyl tertiary amines, alkyl propanediamines, alkyl ethylene diamines, alkyl diethylene triamines, alkyl triethylene tetraamines, alkyl tetraethylene pentamines, alkyls Imidazoline hydroxyethylamine, alkylimidazoline ethylenediamine, polyamines and mixtures thereof, and particularly preferably those having a water solubility of at least 0.001% by weight. In addition, cationic surfactants include quaternary ammonium, amines, imidazoles, and salts derived therefrom such as methylpolyoxyethylene ammonium chloride, cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride, dodecyl dimethyl Amine hydrochlorides and mixtures thereof, preferably having less than 10 carbon atoms in view of water solubility.
이러한 부식 방지제는 본 발명의 연마 조성물 중량 대비 0.001 내지 1 중량%의 양으로 사용하는 것이 바람직하며, 사용량이 1 중량%를 초과하게 되면 연마속도가 감소되고 계면활성제 분자간의 셀(micelle)이 형성되어 자기 조립막 형성이 불 리해진다. Such a corrosion inhibitor is preferably used in an amount of 0.001 to 1% by weight based on the weight of the polishing composition of the present invention, and when the amount is more than 1% by weight, the polishing rate is reduced and the cells between the surfactant molecules are formed. Self-assembled film formation is called.
아울러, 본 발명의 연마 조성물은 부식 방지제로 상기 비이온성 또는 양이온성 계면활성제에 종래에 사용되던 아졸계 화합물을 추가로 혼합시켜 사용할 수 있다. 상기 아졸계 화합물로는 벤조트리아졸, 트리아졸, 아미노트라이졸 및 이미다졸 등이 있으며, 비이온성 또는 양이온성 계면활성제:아졸계 화합물의 혼합 중량비는 1:0.1 내지 1:10 범위일 수 있다. In addition, the polishing composition of the present invention can be used by further mixing the azole compound used in the conventional nonionic or cationic surfactant as a corrosion inhibitor. The azole compound includes benzotriazole, triazole, aminotriazole, imidazole, and the like, and the mixing weight ratio of the nonionic or cationic surfactant: azole compound may range from 1: 0.1 to 1:10.
이외에도, 본 발명의 연마 조성물은 제 2 착화제로서 에틸렌다이아민테트라아세트산(EDTA), 하이드록시에틸렌다이포스폰산(HEDP), 1,2-사이클로헥산다이아미노테트라아세트산(CDTA), 다이에틸렌트라이아미노펜타아세트산(DTPA), 트라이에탄올아민(TEA), 다이에틸렌트라이아민 펜타메틸렌포스폰산(DTPMP), 나이트릴로트라이아세트산(NTA) 또는 이들의 혼합물과 같은 아민계 또는 인산계 킬레이트 화합물을 추가로 포함할 수 있으며, 이때 함량은 연마 조성물 중량 대비 0.01 내지 1 중량%가 바람직하다. 이들 착화제는 금속 이온에 대한 착화반응을 더욱 촉진시킬 뿐만 아니라, 염기성 영역에서 산화제인 과산화수소의 자기분해 반응을 억제하여 연마 슬러리의 사용한계 시간을 증가시킬 수 있다. In addition, the polishing composition of the present invention is ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediphosphonic acid (HEDP), 1,2-cyclohexanediaminotetraacetic acid (CDTA), diethylenetriaminophen as the second complexing agent. Amine or phosphate chelate compounds such as diacetic acid (DTPA), triethanolamine (TEA), diethylenetriamine pentamethylenephosphonic acid (DTPMP), nitrilotriacetic acid (NTA) or mixtures thereof In this case, the content is preferably 0.01 to 1% by weight based on the weight of the polishing composition. These complexing agents not only promote the complexing reaction to the metal ions, but also inhibit the autolysis of hydrogen peroxide as an oxidizing agent in the basic region, thereby increasing the service life of the polishing slurry.
본 발명에 따른 연마 조성물은 통상의 방법에 따라 제조할 수 있으며, 바람직하게는 연마제를 밀링하면서 물을 처리하는 습식 밀링 공정 후 상기의 착화제와 부식방지제, 및 산화제, pH 조절제 등의 기타 첨가제를 추가로 포함시켜 슬러리로 제조될 수 있다. The polishing composition according to the present invention may be prepared according to a conventional method, and preferably, after the wet milling process of treating water while milling the abrasive, the complexing agent and the corrosion inhibitor, and other additives such as an oxidizing agent and a pH adjusting agent may be used. It can be further included to prepare a slurry.
연마제는 연마 대상과의 기계적인 마찰로 연마를 수행하는 역할을 한다. 이 러한 연마제로는 통상적인 평균입경 50 내지 300 ㎚의 금속 산화물로, 예를 들면 알루미나(Al2O3), 퓸드 실리카 또는 콜로이달 실리카(SiO2), 마그네시아(MgO2), 지르코니아(ZrO2), 세리아(CeO2), 티타니아(TiO2) 및 산화 텅스텐(WO3) 등을 사용할 수 있으며, 연마 조성물 중량 대비 0.1 내지 30 중량%, 바람직하게는 0.3 내지 5 중량% 범위로 사용할 수 있다.The abrasive serves to perform polishing by mechanical friction with the polishing object. Such abrasives are conventional metal oxides having an average particle diameter of 50 to 300 nm, for example alumina (Al 2 O 3 ), fumed silica or colloidal silica (SiO 2 ), magnesia (MgO 2 ), zirconia (ZrO 2). ), Ceria (CeO 2 ), titania (TiO 2 ), tungsten oxide (WO 3 ), and the like, and may be used in an amount ranging from 0.1 to 30 wt%, preferably 0.3 to 5 wt%, based on the weight of the polishing composition.
산화제는 연마 대상인 금속 배선막이 그에 상응하는 산화물, 수산화물 또는 이온으로 산화되도록 하여 연마를 돕는 역할을 한다. 본 발명의 연마 조성물에 사용될 수 있는 산화제는 특별히 한정되지는 않으나, 예를 들면 CMP 공정에 통상적으로 사용되는 과산화수소(H2O2)가 바람직하며, 연마 조성물 중량 대비 0.1 내지 5 중량% 범위로 사용될 수 있다.The oxidant serves to assist the polishing by causing the metal wiring film to be oxidized to be oxidized to a corresponding oxide, hydroxide or ion. The oxidizing agent that can be used in the polishing composition of the present invention is not particularly limited, but for example, hydrogen peroxide (H 2 O 2 ) which is commonly used in a CMP process is preferable, and is used in the range of 0.1 to 5% by weight based on the weight of the polishing composition. Can be.
아울러, 본 발명의 연마 조성물은 연마 선택비를 더욱 극대화시키기 위해, 질산 암모늄, 황산 암모늄 및 이들의 혼합물로부터 선택되는 암모늄계 연마선택비 향상제를 추가로 포함할 수 있으며, 연마 조성물 중량 대비 0.01 내지 1 중량% 범위로 사용될 수 있다.In addition, the polishing composition of the present invention may further include an ammonium-based polishing selectivity improving agent selected from ammonium nitrate, ammonium sulfate, and mixtures thereof, in order to further maximize the polishing selectivity. It can be used in the weight percent range.
이렇게 얻어진 본 발명의 연마 조성물은 금속 배선막의 부식과 에칭을 적절히 제어하여 연마를 수행할 수 있어, 디싱 및 에로젼 등을 감소시킴은 물론 연마 효율이 우수하므로, 반도체 제조시 금속 배선의 평판화를 위한 화학 기계적 연마 공정에 유용하게 활용될 수 있다. The polishing composition of the present invention thus obtained can perform polishing by appropriately controlling the corrosion and etching of the metal wiring film, thereby reducing dishing and erosion and the like, and having excellent polishing efficiency. It can be usefully used in the chemical mechanical polishing process for.
본 발명에 따른 연마 조성물은 아민계 착화제 및 부식 방지제로서의 비이온성 또는 양이온성 계면활성제를 포함함으로써, 연마 공정시 중성 내지 약알칼리성의 pH 범위를 유지하고, 금속 표면에 부드러운 부식 방지 보호막을 형성하여 금속의 부식과 에칭을 효과적으로 제어하고 연마속도를 우수하게 유지시킬 수 있으므로, 반도체 소자 제조시 금속막의 평판화를 위한 화학 기계적 연마 공정에 유용하게 활용될 수 있다.The polishing composition according to the present invention includes an amine-based complexing agent and a nonionic or cationic surfactant as a corrosion inhibitor, thereby maintaining a neutral to weakly alkaline pH range during the polishing process, and forming a soft anti-corrosion protective film on the metal surface. Since the corrosion and etching of the metal can be effectively controlled and the polishing rate can be maintained well, it can be usefully used in the chemical mechanical polishing process for flattening the metal film during semiconductor device manufacturing.
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