TWI710626B - Cmp slurry composition for polishing copper films and method for polishing copper films using the same - Google Patents
Cmp slurry composition for polishing copper films and method for polishing copper films using the same Download PDFInfo
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- TWI710626B TWI710626B TW108128047A TW108128047A TWI710626B TW I710626 B TWI710626 B TW I710626B TW 108128047 A TW108128047 A TW 108128047A TW 108128047 A TW108128047 A TW 108128047A TW I710626 B TWI710626 B TW I710626B
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- Prior art keywords
- weight
- slurry composition
- cmp slurry
- copper film
- polishing
- Prior art date
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- 239000002002 slurry Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 239000010949 copper Substances 0.000 title claims abstract description 71
- 238000005498 polishing Methods 0.000 title description 44
- 238000000034 method Methods 0.000 title description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 74
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- -1 imidazole compound Chemical class 0.000 claims abstract description 26
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- 238000007517 polishing process Methods 0.000 claims abstract description 8
- 238000005260 corrosion Methods 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 18
- 239000004471 Glycine Substances 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000003536 tetrazoles Chemical class 0.000 claims description 7
- 150000003852 triazoles Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims 1
- 239000012454 non-polar solvent Substances 0.000 abstract description 7
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- IPIVUPVIFPKFTG-UHFFFAOYSA-N 4-butyl-2h-benzotriazole Chemical compound CCCCC1=CC=CC2=C1N=NN2 IPIVUPVIFPKFTG-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- OKFSBQOGHYYGRZ-UHFFFAOYSA-N 4-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=CC2=C1N=NN2 OKFSBQOGHYYGRZ-UHFFFAOYSA-N 0.000 description 1
- TVOIATIUZOHKFY-UHFFFAOYSA-N 4-pentyl-2h-benzotriazole Chemical compound CCCCCC1=CC=CC2=NNN=C12 TVOIATIUZOHKFY-UHFFFAOYSA-N 0.000 description 1
- VXDLXVDZTJOKAO-UHFFFAOYSA-N 4-propyl-2h-benzotriazole Chemical compound CCCC1=CC=CC2=C1N=NN2 VXDLXVDZTJOKAO-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 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
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
本發明是有關於一種用於銅膜的CMP漿液組成物和一種使用其拋光銅膜的方法。更特定來說，本發明涉及一種用於銅膜的CMP漿液組成物，其可實現銅膜的拋光速率（polishing rate）的顯著提高和對銅膜的凹陷的抑制。相關申請的交叉引用 The present invention relates to a CMP slurry composition for copper films and a method for polishing copper films using the CMP slurry composition. More specifically, the present invention relates to a CMP slurry composition for a copper film, which can achieve a significant increase in the polishing rate of the copper film and suppression of pitting of the copper film. Cross references to related applications
本申請主張2018年8月8日在韓國智慧財產權局提交的韓國專利申請第10-2018-0092660號的權益，所述申請的全部公開內容以引用的方式併入本文中。This application claims the rights and interests of Korean Patent Application No. 10-2018-0092660 filed with the Korean Intellectual Property Office on August 8, 2018, and the entire disclosure of the application is incorporated herein by reference.
隨著半導體積體電路的高度集成和高性能，化學機械拋光（chemical mechanical polishing，CMP）作為微製造技術已受到關注。CMP通常用於層間絕緣膜的平坦化、金屬塞的形成以及嵌入式導線的形成。近來，將銅和銅合金（其具有比鋁等更低的電阻值，且因此可顯著提高積體電路的性能）用作導線的導電材料。另外，將鉭（Ta）或氮化鉭（TaN）用作用於將金屬層接合到絕緣膜（SiO2 ）的黏著層。此黏著層充當防止帶電金屬與絕緣膜之間的擴散的勢壘層。With the high integration and high performance of semiconductor integrated circuits, chemical mechanical polishing (CMP) has attracted attention as a microfabrication technology. CMP is generally used for the planarization of interlayer insulating films, the formation of metal plugs, and the formation of embedded wires. Recently, copper and copper alloys, which have a lower resistance value than aluminum or the like, and therefore can significantly improve the performance of integrated circuits, are used as conductive materials for wires. In addition, tantalum (Ta) or tantalum nitride (TaN) is used as an adhesive layer for bonding the metal layer to the insulating film (SiO 2 ). This adhesion layer serves as a barrier layer that prevents diffusion between the charged metal and the insulating film.
在半導體裝置的製造中，CMP工藝對於晶片表面的平坦化極有用處。一般來說，用於銅的CMP工藝分成兩個步驟進行。在CMP工藝的初級步驟中，由於必須去除塊狀銅膜，因此需要具有銅的高拋光速率的漿液組成物。In the manufacture of semiconductor devices, the CMP process is extremely useful for planarizing the wafer surface. Generally, the CMP process for copper is performed in two steps. In the initial step of the CMP process, since the bulk copper film must be removed, a slurry composition with a high polishing rate of copper is required.
本發明的一個目標是提供一種可提高銅膜的拋光速率的用於銅膜的CMP漿液組成物。An object of the present invention is to provide a CMP slurry composition for copper films that can increase the polishing rate of copper films.
本發明的另一目標是提供一種可通過抑制銅膜的凹陷來提高拋光表面的平坦度的用於銅膜的CMP漿液組成物。Another object of the present invention is to provide a CMP slurry composition for a copper film that can improve the flatness of a polished surface by suppressing the depression of the copper film.
根據本發明的一個方面，一種用於銅膜的CMP漿液組成物包含：選自極性溶劑和非極性溶劑當中的至少一種；金屬氧化物磨料（metal oxide abrasive）；甘氨酸；組氨酸；以及咪唑化合物。According to one aspect of the present invention, a CMP slurry composition for a copper film includes: at least one selected from a polar solvent and a non-polar solvent; a metal oxide abrasive (metal oxide abrasive); glycine; histidine; and imidazole Compound.
在一個實施例中，咪唑化合物可包含由式1表示的化合物：In one embodiment, the imidazole compound may include a compound represented by Formula 1:
[式1]
其中R1 是氫、C1 到C10 烷基或C6 到C20 芳基；且R2 、R3 以及R4 各自獨立地是氫、C1 到C10 烷基、C6 到C20 芳基或鹵素原子。Wherein R 1 is hydrogen, C 1 to C 10 alkyl, or C 6 to C 20 aryl; and R 2 , R 3 and R 4 are each independently hydrogen, C 1 to C 10 alkyl, C 6 to C 20 Aryl or halogen atom.
在一個實施例中，咪唑化合物可包含選自咪唑和甲基咪唑當中的至少一種。In one embodiment, the imidazole compound may include at least one selected from imidazole and methylimidazole.
在一個實施例中，甘氨酸和組氨酸可以0.02重量%到10重量%的總量存在於CMP漿液組成物中。In one embodiment, glycine and histidine may be present in the CMP slurry composition in a total amount of 0.02% to 10% by weight.
在一個實施例中，CMP漿液組成物可更包含腐蝕抑制劑。In one embodiment, the CMP slurry composition may further include a corrosion inhibitor.
在一個實施例中，腐蝕抑制劑可以0.001重量%到5重量%的量存在於CMP漿液組成物中。In one embodiment, the corrosion inhibitor may be present in the CMP slurry composition in an amount of 0.001% to 5% by weight.
在一個實施例中，腐蝕抑制劑可包含選自三唑和四唑當中的至少一種。In one embodiment, the corrosion inhibitor may include at least one selected from triazole and tetrazole.
在一個實施例中，CMP漿液組成物可具有5到9的pH。In one embodiment, the CMP slurry composition may have a pH of 5-9.
根據本發明的另一方面，一種拋光銅膜的方法包含：使用根據本發明的用於銅膜的CMP漿液組成物來拋光銅膜。According to another aspect of the present invention, a method of polishing a copper film includes polishing the copper film using the CMP slurry composition for a copper film according to the present invention.
本發明提供一種可提高銅膜的拋光速率的用於銅膜的CMP漿液組成物。The present invention provides a CMP slurry composition for copper films that can increase the polishing rate of copper films.
本發明提供一種可通過抑制銅膜的凹陷來提高所拋光表面的平坦度的用於銅膜的CMP漿液組成物。The present invention provides a CMP slurry composition for a copper film that can improve the flatness of a polished surface by suppressing the depression of the copper film.
拋光半導體裝置的方法包含用於拋光銅膜（銅線）的初級拋光工藝，以及用於同時拋光銅膜、反擴散膜以及絕緣層的二級拋光工藝。在初級拋光工藝中，經由拋光快速去除銅膜。在本文中，銅膜可包含由純銅或銅合金構成的膜。The method of polishing a semiconductor device includes a primary polishing process for polishing a copper film (copper wire), and a secondary polishing process for simultaneously polishing a copper film, an anti-diffusion film, and an insulating layer. In the primary polishing process, the copper film is quickly removed through polishing. Here, the copper film may include a film composed of pure copper or copper alloy.
根據本發明的一個方面，銅膜的拋光速率可通過將咪唑化合物摻入到包含甘氨酸和組氨酸的用於銅膜的CMP漿液組成物中來顯著地提高。另外，根據本發明的一個方面，銅膜的拋光速率的顯著提高和對凹陷的抑制二者可通過將咪唑化合物和腐蝕抑制劑摻入到包含甘氨酸和組氨酸的用於銅膜的CMP漿液組成物中來實現。According to an aspect of the present invention, the polishing rate of a copper film can be significantly improved by incorporating an imidazole compound into a CMP slurry composition for a copper film containing glycine and histidine. In addition, according to one aspect of the present invention, both the significant increase in the polishing rate of the copper film and the suppression of pitting can be achieved by incorporating an imidazole compound and a corrosion inhibitor into a CMP slurry for a copper film containing glycine and histidine. In the composition.
根據本發明的CMP漿液組成物包含：選自極性溶劑和非極性溶劑當中的至少一種；金屬氧化物磨料；甘氨酸；組氨酸；以及咪唑化合物。現將詳細地描述根據本發明的CMP漿液組成物的各個組分。The CMP slurry composition according to the present invention includes: at least one selected from a polar solvent and a non-polar solvent; a metal oxide abrasive; glycine; histidine; and an imidazole compound. Each component of the CMP slurry composition according to the present invention will now be described in detail.
選自極性溶劑和非極性溶劑當中的至少一種用以在用金屬氧化物磨料拋光銅膜時減小摩擦力。選自極性溶劑和非極性溶劑當中的至少一種可包含水（例如超純水或去離子水）、有機胺、有機醇、有機醇胺、有機醚、有機酮等。優選地，選自極性溶劑和非極性溶劑當中的至少一種是超純水或去離子水。選自極性溶劑和非極性溶劑當中的至少一種可以餘量存在於CMP漿液組成物中。At least one selected from the group consisting of polar solvents and non-polar solvents is used to reduce friction when polishing the copper film with metal oxide abrasives. At least one selected from polar solvents and non-polar solvents may include water (for example, ultrapure water or deionized water), organic amines, organic alcohols, organic alcohol amines, organic ethers, organic ketones, and the like. Preferably, at least one selected from a polar solvent and a non-polar solvent is ultrapure water or deionized water. At least one selected from a polar solvent and a non-polar solvent may be present in the CMP slurry composition in the balance.
金屬氧化物磨料可在高拋光速率下拋光銅膜。具體來說，金屬氧化物磨料可包含由下述者所組成的群組中選出的至少一種：二氧化矽、氧化鋁、二氧化鈰、二氧化鈦以及氧化鋯。優選地，金屬氧化物磨料是二氧化矽。Metal oxide abrasives can polish copper films at high polishing rates. Specifically, the metal oxide abrasive may include at least one selected from the group consisting of silica, alumina, ceria, titania, and zirconia. Preferably, the metal oxide abrasive is silicon dioxide.
金屬氧化物磨料可以是球形顆粒或非球形顆粒，且可具有10奈米到150奈米（例如20奈米到70奈米）的平均粒徑（D50）。在此範圍內，金屬氧化物磨料可提供用於銅膜（其為本文中的拋光目標）的充足拋光速率，不產生刮痕，且可提高銅膜的拋光表面的平坦度。如本文中所使用，“平均粒徑（D50）”是所屬領域中已知的典型粒徑計量，且是指在磨料顆粒的重量累積分佈中對應於50重量%的粒徑。The metal oxide abrasive may be spherical particles or non-spherical particles, and may have an average particle diameter (D50) of 10 nanometers to 150 nanometers (for example, 20 nanometers to 70 nanometers). Within this range, the metal oxide abrasive can provide a sufficient polishing rate for the copper film (which is the polishing target herein), does not produce scratches, and can improve the flatness of the polished surface of the copper film. As used herein, "average particle size (D50)" is a typical particle size measurement known in the art, and refers to the particle size corresponding to 50% by weight in the cumulative weight distribution of abrasive particles.
金屬氧化物磨料可以0.001重量%到20重量%的量，具體地以0.01重量%到10重量%的量，更具體地以0.01重量%到5重量%的量，又更具體地以0.01重量%到1重量%的量存在於CMP漿液組成物中。在此範圍內，金屬氧化物磨料可提供用於銅膜的充足拋光速率，不產生刮痕，且可提高組成物的分散穩定性。舉例來說，金屬氧化物磨料可以0.001重量%、0.005重量%、0.01重量%、0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%、10重量%、11重量%、12重量%、13重量%、14重量%、15重量%、16重量%、17重量%、18重量%、19重量%或20重量%的量存在於CMP漿液組成物中。The metal oxide abrasive may be in an amount of 0.001% by weight to 20% by weight, specifically in an amount of 0.01% by weight to 10% by weight, more specifically in an amount of 0.01% by weight to 5% by weight, and more specifically in an amount of 0.01% by weight. It is present in the CMP slurry composition in an amount of up to 1% by weight. Within this range, the metal oxide abrasive can provide a sufficient polishing rate for the copper film, does not produce scratches, and can improve the dispersion stability of the composition. For example, the metal oxide abrasive can be 0.001% by weight, 0.005% by weight, 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09 Weight%, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight , 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16 The amount of weight %, 17 weight %, 18 weight %, 19 weight% or 20 weight% is present in the CMP slurry composition.
甘氨酸和組氨酸用以螯合在銅膜拋光期間產生的氧化銅。甘氨酸和組氨酸可以0.02重量%到10重量%（具體地1重量%到5重量%）的總量存在於CMP漿液組成物中。在此範圍內，甘氨酸和組氨酸可根據漿液的分散穩定性和所拋光銅膜的表面特徵提供良好特性且可結合咪唑化合物來提高銅膜的拋光速率。舉例來說，甘氨酸和組氨酸可以0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%、5重量%、6重量%、7重量%、8重量%、9重量%或10重量%的總量存在於CMP漿液組成物中。Glycine and histidine are used to chelate copper oxide generated during polishing of the copper film. Glycine and histidine may be present in the CMP slurry composition in a total amount of 0.02% to 10% by weight (specifically 1% to 5% by weight). Within this range, glycine and histidine can provide good characteristics according to the dispersion stability of the slurry and the surface characteristics of the polished copper film, and can combine with imidazole compounds to increase the polishing rate of the copper film. For example, glycine and histidine can be 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt The total amount of %, 7%, 8%, 9% or 10% by weight is present in the CMP slurry composition.
甘氨酸可以0.01重量%到5重量%的量，具體地以0.05重量%到5重量%的量，更具體地以0.1重量%到5重量%的量存在於CMP漿液組成物中。在此範圍內，甘氨酸可在拋光速率、漿液的分散穩定性以及所拋光銅膜的表面特徵方面提供良好特性。舉例來說，甘氨酸可以0.01重量%、0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%或5重量%的量存在於CMP漿液組成物中。Glycine may be present in the CMP slurry composition in an amount of 0.01% to 5% by weight, specifically in an amount of 0.05% to 5% by weight, more specifically in an amount of 0.1% to 5% by weight. Within this range, glycine can provide good characteristics in terms of polishing rate, dispersion stability of the slurry, and surface characteristics of the polished copper film. For example, glycine can be 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight, It is present in an amount of 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, or 5% by weight In the CMP slurry composition.
組氨酸可以0.01重量%到5重量%的量，具體地以0.05重量%到5重量%的量，更具體地以0.1重量%到5重量%的量存在於CMP漿液組成物中。在此範圍內，組氨酸可在拋光速率、漿液的分散穩定性以及所拋光銅膜的表面特徵方面提供良好特性。舉例來說，組氨酸可以0.01重量%、0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%或5重量%的量存在於CMP漿液組成物中。Histidine may be present in the CMP slurry composition in an amount of 0.01% to 5% by weight, specifically in an amount of 0.05% to 5% by weight, more specifically in an amount of 0.1% to 5% by weight. Within this range, histidine can provide good characteristics in terms of polishing rate, dispersion stability of the slurry, and surface characteristics of the polished copper film. For example, histidine can be 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight %, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, or 5% by weight The amount is present in the CMP slurry composition.
如上文所描述，在包含於CMP漿液組成物（其包含甘氨酸和組氨酸）中時，咪唑化合物可顯著地提高銅膜的拋光速率。咪唑化合物可以0.001重量%到5重量%的量，具體地以0.005重量%到1重量%的量，更具體地以0.01重量%到0.5重量%的量存在於根據本發明的CMP漿液組成物中。在此範圍內，咪唑化合物可顯著地提高銅膜的拋光速率。舉例來說，咪唑化合物可以0.001重量%、0.005重量%、0.01重量%、0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%或5重量%的量存在於CMP漿液組成物中。As described above, when included in the CMP slurry composition (which includes glycine and histidine), the imidazole compound can significantly increase the polishing rate of the copper film. The imidazole compound may be present in the CMP slurry composition according to the present invention in an amount of 0.001% by weight to 5% by weight, specifically in an amount of 0.005% by weight to 1% by weight, more specifically in an amount of 0.01% by weight to 0.5% by weight . Within this range, the imidazole compound can significantly increase the polishing rate of the copper film. For example, the imidazole compound may be 0.001% by weight, 0.005% by weight, 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight , 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4 The amount of wt% or 5 wt% is present in the CMP slurry composition.
咪唑化合物可包含具有經取代或未經取代的咪唑基的單分子化合物。在本文中，術語“單分子化合物”可指由一個咪唑分子組成的化合物，而不是通過聚合一或多種咪唑化合物而獲得的寡聚物或聚合物。The imidazole compound may include a single molecule compound having a substituted or unsubstituted imidazole group. As used herein, the term "monomolecular compound" may refer to a compound composed of one imidazole molecule, rather than an oligomer or polymer obtained by polymerizing one or more imidazole compounds.
咪唑化合物可包含由式1表示的化合物：The imidazole compound may include a compound represented by Formula 1:
[式1]
其中R1 是氫、C1 到C10 烷基或C6 到C20 芳基，且R2 、R3 以及R4 各自獨立地是氫、C1 到C10 烷基、C6 到C20 芳基或鹵素原子。Where R 1 is hydrogen, C 1 to C 10 alkyl or C 6 to C 20 aryl, and R 2 , R 3 and R 4 are each independently hydrogen, C 1 to C 10 alkyl, C 6 to C 20 Aryl or halogen atom.
優選地，R1 是氫或甲基。優選地，R2 、R3 以及R4 各自獨立地是氫或C1 到C10 烷基。舉例來說，咪唑化合物可包含：咪唑；以及甲基咪唑，例如1-甲基咪唑、2-甲基咪唑以及4-甲基咪唑。Preferably, R 1 is hydrogen or methyl. Preferably, R 2 , R 3 and R 4 are each independently hydrogen or C 1 to C 10 alkyl. For example, the imidazole compound may include: imidazole; and methylimidazole, such as 1-methylimidazole, 2-methylimidazole, and 4-methylimidazole.
CMP漿液組成物可更包含腐蝕抑制劑。The CMP slurry composition may further contain corrosion inhibitors.
腐蝕抑制劑用以抑制在銅膜拋光期間的凹陷。腐蝕抑制劑可包含選自三唑和四唑當中的至少一種。根據本發明的CMP漿液組成物可提高銅膜的拋光速率，且可通過包含咪唑化合物（其為二唑）和選自三唑和四唑當中的至少一種作為腐蝕抑制劑來抑制銅膜的凹陷，以提高所拋光表面的平坦度。Corrosion inhibitors are used to suppress depressions during polishing of the copper film. The corrosion inhibitor may include at least one selected from triazole and tetrazole. The CMP slurry composition according to the present invention can increase the polishing rate of the copper film, and can suppress the depression of the copper film by including an imidazole compound (which is a diazole) and at least one selected from triazole and tetrazole as a corrosion inhibitor , To improve the flatness of the polished surface.
三唑可包含由式2或式3表示的化合物：The triazole may include a compound represented by Formula 2 or Formula 3:
[式2]
其中R5 和R6 可各自獨立地是氫、未經取代的C1 到C10 烷基、未經取代的C6 到C10 芳基、氨基（-NH2）、磺酸基、羧酸基、經氨基取代的C1 到C10 烷基、經氨基取代的C6 到C10 芳基、經羧酸基取代的C6 到C10 芳基或經磺酸基取代的C6 到C10 芳基，或可彼此連接以形成未經取代的C4 到C10 芳基或經取代的C4 到C10 芳基；且R7 是氫或羥基，以及Wherein R 5 and R 6 may each independently be hydrogen, unsubstituted C 1 to C 10 alkyl, unsubstituted C 6 to C 10 aryl, amino (-NH2), sulfonic acid group, carboxylic acid group , an amino group substituted by a C 1 to C 10 alkyl, amino-substituted C 6 to C 10 aryl group, a carboxylic acid group substituted by a C 6 to C 10 aryl group, or a sulfonic acid group substituted with a C 6 to C 10 Aryl groups, or may be connected to each other to form an unsubstituted C 4 to C 10 aryl group or a substituted C 4 to C 10 aryl group; and R 7 is hydrogen or a hydroxyl group, and
[式3]
其中R8 和R9 各自獨立地是氫、未經取代的C1 到C10 烷基、未經取代的C6 到C10 芳基、氨基（-NH2 ）、磺酸基、羧酸基、經氨基取代的C1 到C10 烷基、經氨基取代C6 到C10 芳基、經羧酸基取代的C6 到C10 芳基或經磺酸基取代的C6 到C10 芳基；且R10 是氫或羥基。Wherein R 8 and R 9 are each independently hydrogen, unsubstituted C 1 to C 10 alkyl, unsubstituted C 6 to C 10 aryl, amino (-NH 2 ), sulfonic acid group, carboxylic acid group , an amino group substituted by a C 1 to C 10 alkyl, amino-substituted C 6 to C 10 aryl group, a carboxylic acid group substituted by a C 6 to C 10 aryl group, or a sulfonic acid substituted aromatic C 6 to C 10 And R 10 is hydrogen or hydroxyl.
舉例來說，三唑可包含：苯並三唑化合物，所述苯並三唑化合物包含苯並三唑、甲基苯並三唑（甲苯基三唑）（例如5-甲基苯並三唑和4-甲基苯並三唑）、乙基苯並三唑、丙基苯並三唑、丁基苯並三唑、戊基苯並三唑、己基苯並三唑以及羥基苯並三唑；1,2,4-三唑；以及1,2,3-三唑。CMP漿液組成物可包含三唑本身或其鹽。For example, the triazole may include: a benzotriazole compound, the benzotriazole compound includes benzotriazole, tolyltriazole (tolyltriazole) (such as 5-methylbenzotriazole) And 4-methylbenzotriazole), ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole and hydroxybenzotriazole ; 1,2,4-triazole; and 1,2,3-triazole. The CMP slurry composition may contain triazole itself or its salt.
四唑可包含由式4表示的化合物：The tetrazole may include a compound represented by formula 4:
[式4]
其中R1 是氫、未經取代的C1 到C10 烷基、未經取代的C6 到C10 芳基、氨基（-NH2 ）；磺酸基、羧酸基、經氨基取代的C1 到C10 烷基；經氨基取代的C6 到C10 芳基；經羧酸基取代的C6 到C10 芳基或經磺酸基取代的C6 到C10 芳基。Wherein R 1 is hydrogen, unsubstituted C 1 to C 10 alkyl, unsubstituted C 6 to C 10 aryl, amino (-NH 2 ); sulfonic acid, carboxylic acid, C substituted by amino 1 to C 10 alkyl group; amino substituted by C 6 to C 10 aryl group; a carboxylic acid group substituted by a C 6 to C 10 aryl group, or a sulfonic acid group is substituted to C 6 C 10 aryl group.
舉例來說，四唑可包含選自下述者當中的至少一種：5-氨基四唑、5-甲基四唑以及5-苯基四唑。CMP漿液組成物可包含四唑本身或其鹽。For example, the tetrazole may include at least one selected from the group consisting of 5-aminotetrazole, 5-methyltetrazole, and 5-phenyltetrazole. The CMP slurry composition may contain tetrazole itself or its salt.
腐蝕抑制劑可以0.001重量%到5重量%的量，具體地以0.005重量%到1重量%的量，更具體地以0.01重量%到0.1重量%的量存在於CMP漿液組成物中。在此範圍內，腐蝕抑制劑可抑制銅膜在銅膜拋光期間的凹陷，同時提高銅膜的拋光速率。舉例來說，腐蝕抑制劑可以0.001重量%、0.005重量%、0.01重量%、0.02重量%、0.03重量%、0.04重量%、0.05重量%、0.06重量%、0.07重量%、0.08重量%、0.09重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%或5重量%的量存在於CMP漿液組成物中。The corrosion inhibitor may be present in the CMP slurry composition in an amount of 0.001% to 5% by weight, specifically in an amount of 0.005% to 1% by weight, more specifically in an amount of 0.01% to 0.1% by weight. Within this range, the corrosion inhibitor can suppress the depression of the copper film during the polishing of the copper film, while increasing the polishing rate of the copper film. For example, the corrosion inhibitor can be 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt %, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, The amount of 4% by weight or 5% by weight is present in the CMP slurry composition.
CMP漿液組成物可更包含氧化劑。氧化劑通過使銅膜氧化來促進銅膜的拋光，且通過使銅膜的表面平滑化來提供所拋光表面的表面粗糙度方面的所需特性。The CMP slurry composition may further include an oxidizing agent. The oxidizing agent promotes polishing of the copper film by oxidizing the copper film, and provides desired characteristics in terms of surface roughness of the polished surface by smoothing the surface of the copper film.
氧化劑可包含由下述者所組成的群組中選出的至少一種：無機過化合物（inorganic per-compound）、有機過化合物（organic per-compound）、溴酸或其鹽、硝酸或其鹽、氯酸或其鹽、鉻酸或其鹽、碘酸或其鹽、鐵或其鹽、銅或其鹽、稀土金屬氧化物、過渡金屬氧化物以及重鉻酸鉀。在本文中，“過化合物（per-compound）”是指含有至少一個過氧化基（-O-O-）或含有處於最高氧化態的元素的化合物。優選地，氧化劑是過化合物。過化合物的實例可包含由下述者所組成的群組中選出的至少一種：過氧化氫、過碘酸鉀、過硫酸鈣以及鐵氰化鉀。優選地，氧化劑是過氧化氫。The oxidizing agent may include at least one selected from the group consisting of: inorganic per-compound, organic per-compound, bromic acid or its salt, nitric acid or its salt, chlorine Acid or its salt, chromic acid or its salt, iodic acid or its salt, iron or its salt, copper or its salt, rare earth metal oxide, transition metal oxide, and potassium dichromate. As used herein, "per-compound" refers to a compound containing at least one peroxide group (-O-O-) or an element in the highest oxidation state. Preferably, the oxidizing agent is a per compound. Examples of per-compounds may include at least one selected from the group consisting of hydrogen peroxide, potassium periodate, calcium persulfate, and potassium ferricyanide. Preferably, the oxidizing agent is hydrogen peroxide.
氧化劑可以0.01重量%到5重量%的量，具體地以0.05重量%到3重量%的量，更具體地以0.1重量%到2重量%的量存在於CMP漿液組成物中。在此範圍內，氧化劑可改善對銅線的拋光選擇性。舉例來說，氧化劑可以0.01重量%、0.05重量%、0.1重量%、0.2重量%、0.3重量%、0.4重量%、0.5重量%、0.6重量%、0.7重量%、0.8重量%、0.9重量%、1重量%、2重量%、3重量%、4重量%或5重量%的量存在於CMP漿液組成物中。The oxidizing agent may be present in the CMP slurry composition in an amount of 0.01% to 5% by weight, specifically in an amount of 0.05% to 3% by weight, more specifically in an amount of 0.1% to 2% by weight. Within this range, the oxidizing agent can improve the polishing selectivity of the copper wire. For example, the oxidant may be 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, An amount of 1% by weight, 2% by weight, 3% by weight, 4% by weight, or 5% by weight is present in the CMP slurry composition.
CMP漿液組成物可具有5到9（具體地6到8）的pH。在此範圍內，CMP漿液組成物可提供對銅膜的良好防腐蝕性。舉例來說，CMP漿液組成物可具有5、6、7、8或9的pH。The CMP slurry composition may have a pH of 5 to 9 (specifically 6 to 8). Within this range, the CMP slurry composition can provide good corrosion resistance to the copper film. For example, the CMP slurry composition may have a pH of 5, 6, 7, 8, or 9.
CMP漿液組成物可更包含將CMP漿液組成物的pH值調整在上述範圍內的pH調節劑。pH調節劑可包含：無機酸，例如硝酸、磷酸、氫氯酸以及硫酸中的至少一種；以及有機酸，例如pKa為6或小於6的有機酸，例如乙酸和檸檬酸中的至少一種。或者，pH調節劑可包含鹼，例如由下述者所組成的群組中選出的至少一種：氫氧化鉀、氫氧化鈉以及氫氧化銨；碳酸鈉以及碳酸鉀。The CMP slurry composition may further include a pH adjuster for adjusting the pH of the CMP slurry composition within the above range. The pH adjuster may include: inorganic acids, such as at least one of nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid; and organic acids, such as organic acids with a pKa of 6 or less, such as at least one of acetic acid and citric acid. Alternatively, the pH adjuster may include a base, such as at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and ammonium hydroxide; sodium carbonate and potassium carbonate.
CMP漿液組成物可更包含所屬領域中已知的典型添加劑，例如界面活性劑（surfactant）、分散劑、改質劑以及表面活性劑（surface active agent）。The CMP slurry composition may further include typical additives known in the art, such as surfactants, dispersants, modifiers, and surface active agents.
根據本發明的拋光銅膜的方法包含：使用根據本發明的用於銅膜的CMP漿液組成物來拋光銅膜。The method of polishing a copper film according to the present invention includes polishing the copper film using the CMP slurry composition for a copper film according to the present invention.
接下來，將參考一些實例更詳細地描述本發明。應理解，這些實例只是出於說明而提供，並且不應以任何方式解釋為限制本發明。Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and should not be construed as limiting the present invention in any way.
實例和比較例中所使用的各個組分的細節如下：The details of each component used in the examples and comparative examples are as follows:
金屬氧化物磨料：具有25奈米的平均粒徑（D50）的二氧化矽（DVSTS027，納爾科公司（Nalco Company））Metal oxide abrasive: Silica (DVSTS027, Nalco Company) with an average particle size (D50) of 25 nm
pH調節劑：硝酸或氫氧化鉀。 [實例1]pH regulator: nitric acid or potassium hydroxide. [Example 1]
將0.1重量%的金屬氧化物磨料、1.2重量%的甘氨酸、0.4重量%的組氨酸、0.2重量%的咪唑以及作為腐蝕抑制劑的0.02重量%的苯並三唑與餘量的超純水混合，由此製備CMP漿液組成物，其中前述組分的量是以組成物的總重量計。接著，使用硝酸或氫氧化鉀將漿液組成物的pH調整為7.0。 [實例2到實例4]Combine 0.1% by weight of metal oxide abrasive, 1.2% by weight of glycine, 0.4% by weight of histidine, 0.2% by weight of imidazole, 0.02% by weight of benzotriazole as a corrosion inhibitor, and the balance of ultrapure water By mixing, a CMP slurry composition is prepared, wherein the amounts of the foregoing components are based on the total weight of the composition. Next, the pH of the slurry composition was adjusted to 7.0 using nitric acid or potassium hydroxide. [Example 2 to Example 4]
除了將甘氨酸、組氨酸以及咪唑的量更改為如表1中所列且將腐蝕抑制劑的種類和量（單位：重量%）更改為如表1中所列之外，以與實例1中相同的方式製備漿液組成物。 [實例5]Except that the amounts of glycine, histidine, and imidazole are changed to those listed in Table 1, and the type and amount of corrosion inhibitors (unit: wt%) are changed to those listed in Table 1, they are the same as those in Example 1. The slurry composition was prepared in the same manner. [Example 5]
將0.1重量%的金屬氧化物磨料、0.7重量%的甘氨酸、0.4重量%的組氨酸、0.2重量%的咪唑以及作為腐蝕抑制劑的0.02重量%的苯並三唑與餘量的超純水混合，由此製備CMP漿液組成物，其中前述組分的量是以組成物的總重量計。接著，使用硝酸或氫氧化鉀將漿液組成物的pH調整為7.0。 [比較例1]Combine 0.1% by weight of metal oxide abrasive, 0.7% by weight of glycine, 0.4% by weight of histidine, 0.2% by weight of imidazole, 0.02% by weight of benzotriazole as a corrosion inhibitor, and the balance of ultrapure water Mixing, thereby preparing a CMP slurry composition, wherein the amounts of the foregoing components are based on the total weight of the composition. Next, the pH of the slurry composition was adjusted to 7.0 using nitric acid or potassium hydroxide. [Comparative Example 1]
除了不包括咪唑之外，以與實例1中相同的方式製備漿液組成物。 [比較例2]A slurry composition was prepared in the same manner as in Example 1, except that imidazole was not included. [Comparative Example 2]
除了使用聚乙烯基咪唑替代咪唑之外，以與實例1中相同的方式製備漿液組成物。 [比較例3]A slurry composition was prepared in the same manner as in Example 1, except that polyvinylimidazole was used instead of imidazole. [Comparative Example 3]
除了使用聚乙烯吡咯啶酮替代咪唑之外，以與實例1中相同的方式製備漿液組成物。A slurry composition was prepared in the same manner as in Example 1, except that polyvinylpyrrolidone was used instead of imidazole.
在實例和比較例中製備的每一個CMP漿液組成物均以下列特性評估：Each CMP slurry composition prepared in the Examples and Comparative Examples was evaluated with the following characteristics:
（1）銅膜的拋光速率（單位：Å/20秒）：使用200毫米MIRRA拋光機（應用材料（Applied Materials，AMAT）公司），在工作臺旋轉速度（table rotation speed）為93轉/分鐘、磁頭旋轉速度為87轉/分鐘、拋光壓力為1.5磅/平方英寸、漿液進料速率為150毫升/分鐘且拋光持續時間為60秒的條件下拋光銅膜。此處，使用IC1010墊（羅德爾公司（Rodel Co., Ltd））作為拋光墊。基於電阻值轉換的拋光前後的厚度差來計算拋光速率。(1) The polishing rate of the copper film (unit: Å/20 seconds): using a 200 mm MIRRA polishing machine (Applied Materials (AMAT) company), the table rotation speed (table rotation speed) is 93 revolutions per minute , The head rotation speed is 87 revolutions/min, the polishing pressure is 1.5 psig, the slurry feed rate is 150 ml/min, and the polishing duration is 60 seconds to polish the copper film. Here, IC1010 pad (Rodel Co., Ltd) was used as the polishing pad. The polishing rate is calculated based on the thickness difference before and after polishing converted from the resistance value.
（2）凹陷（單位：奈米）：在與（1）中相同的拋光條件下執行圖案評估。在銅和氧化物膜的寬度為100微米的區域中測量凹陷。(2) Depression (unit: nanometer): Perform pattern evaluation under the same polishing conditions as in (1). The depression was measured in an area where the width of the copper and oxide film was 100 microns.
表1
根據表1中所顯示的結果，可看出根據本發明的CMP漿液組成物對於銅線具有非常高的拋光速率，同時顯著地抑制凹陷。According to the results shown in Table 1, it can be seen that the CMP slurry composition according to the present invention has a very high polishing rate for copper wires while significantly suppressing pits.
相反，與包含相同量的組氨酸和甘氨酸的實例1的CMP漿液組成物相比，不含咪唑化合物的比較例1的CMP漿液組成物對於銅線具有相當低的拋光速率。另外，與包含相同量的組氨酸和甘氨酸的實例1的CMP漿液組成物相比，包含聚乙烯基咪唑而非咪唑化合物的比較例2的CMP漿液組成物對於銅線也具有相當低的拋光速率。此外，包含聚乙烯吡咯啶酮而非咪唑化合物的比較例3的CMP漿液組成物具有低拋光速率且在抑制凹陷方面展現不良特性。In contrast, compared with the CMP slurry composition of Example 1 containing the same amounts of histidine and glycine, the CMP slurry composition of Comparative Example 1, which does not contain an imidazole compound, has a relatively low polishing rate for copper wires. In addition, compared with the CMP slurry composition of Example 1 containing the same amount of histidine and glycine, the CMP slurry composition of Comparative Example 2 containing polyvinylimidazole instead of an imidazole compound also had a relatively low polishing rate for copper wires. rate. In addition, the CMP slurry composition of Comparative Example 3 containing polyvinylpyrrolidone instead of the imidazole compound has a low polishing rate and exhibits poor characteristics in suppressing pitting.
應理解，所屬領域的技術人員可在不脫離本發明的精神和範圍的情況下作出各種修改、變化、更改以及等效實施例。It should be understood that those skilled in the art can make various modifications, changes, alterations and equivalent embodiments without departing from the spirit and scope of the present invention.
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