TW200526769A - Compositions and methods for polishing copper - Google Patents
Compositions and methods for polishing copper Download PDFInfo
- Publication number
- TW200526769A TW200526769A TW093133218A TW93133218A TW200526769A TW 200526769 A TW200526769 A TW 200526769A TW 093133218 A TW093133218 A TW 093133218A TW 93133218 A TW93133218 A TW 93133218A TW 200526769 A TW200526769 A TW 200526769A
- Authority
- TW
- Taiwan
- Prior art keywords
- weight
- polishing
- acid
- composition
- salt
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- 239000010949 copper Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000001913 cellulose Substances 0.000 claims abstract description 10
- 229920002678 cellulose Polymers 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 25
- -1 guanidine ions Chemical class 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 claims 7
- 210000003462 vein Anatomy 0.000 claims 3
- 230000001629 suppression Effects 0.000 claims 2
- 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 1
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- YEFJHNZIYIHXJQ-UHFFFAOYSA-N [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Os+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YEFJHNZIYIHXJQ-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- CNUNWZZSUJPAHX-UHFFFAOYSA-N guanidine nitrate Chemical compound NC(N)=N.O[N+]([O-])=O CNUNWZZSUJPAHX-UHFFFAOYSA-N 0.000 claims 1
- 150000007857 hydrazones Chemical class 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 238000007517 polishing process Methods 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 8
- 239000008139 complexing agent Substances 0.000 abstract description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000012530 fluid Substances 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 235000019260 propionic acid Nutrition 0.000 description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003082 abrasive agent Substances 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229920000591 gum Polymers 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000010418 carrageenan Nutrition 0.000 description 2
- 239000000679 carrageenan Substances 0.000 description 2
- 229920001525 carrageenan Polymers 0.000 description 2
- 229940113118 carrageenan Drugs 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
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- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
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- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
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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
- C09G1/04—Aqueous dispersions
-
- 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
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror 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
- H01L21/302—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)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
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200526769 九、發明說明: 【發明所屬之技術領域】 本發明係關於半導體晶圓材料之化學機械平坦化 (CMP),更特定言之,CMP組合物及在介電體與屏障材料存 在下自半導體晶圓抛光銅交連之方法。 【先前技術】 一般而言,半導體晶圓具有矽晶圓及含多溝渠(其排列形 成介電層内之電路交連圖案)之介電層。圖案排列通常具有 金屬鑲嵌結構或雙重金屬鑲嵌結構。屏障層覆蓋圖案化介 電層且金屬層覆蓋屏障層。金屬層具有至少足以以金屬充 填圖案溝渠而形成電路叉連之厚度。 CMP法經常包括多拋光步驟。例如,第一步驟自底下之 屏障介電層去除金屬層。第一步驟拋光去除金屬層,而在 具有提供電路交連平面之充填金屬溝渠之晶圓上留下光滑 平坦表面,其使拋光表面平坦。第一步驟拋光以起初高速 去除過量叉連金屬,如銅。在第一步驟去除後,第二步驟 拋光可去除殘留在半導體晶圓上之屏障。此第二步驟拋光 自底下之半導體晶圓介電層去除屏障而在介電層上提供平 坦之拋光表面。 不幸地,涉及聚胺甲酸酯拋光墊與半導體晶圓(其上含金 屬交連)之拋光區高磨擦可造成拋光區振動。此振動造成大 聲之黏滯-滑動事件,其在全部第一步驟拋光循環中持續而 使技術員無法工作。此外,此問題可嚴重到晶圓載具受損, 及來自載具之碎片污染拋光區,在晶圓表面上造成不欲之 96930.doc 200526769 刮痕。
Tsuchiya等人(美國專利第6,585,56S號)揭示一種用於拋 光銅降低振動之漿液,其係藉由各以5對70之比例混合三唑 化合物與笨并二峻化合物。然而,加入苯并三峻導致銅拋 光速率降低,及過量之苯并三唑增加振動噪音。此外,一 些製造者已修改其拋光參數,如降低施加壓力。然而,這 些修改通常造成降低之去除速率及生產力。 因此,所需為有效地以降低噪音程度拋光銅交連之改良 拋光組合物及方法。特別地,需要在銅交連拋光時降低噪 音程度而不有害地影響拋光速率之組合物及方法。 【發明内容】 在第一態樣中,本發明提供一種可用於在半導體晶圓上 拋光銅之水性組合物,其包含1至15重量%之氧化劑、〇· 1 至1重量%之非鐵質金屬抑制劑、〇·〇5至3重量%之非鐵質金 屬錯合劑、0.01至5重量%之羧酸聚合物、〇·〇ι至5重量%之 改質纖維素、0.0001至2重量%之具陽離子與陰離子成分之 鹽、其餘為水,此鹽降低來自晶圓與拋光墊間振動之噪音 程度。 在第二態樣中,本發明提供一種自半導體晶圓拋光銅之 方法,其包含使晶圓接觸拋光組合物,此晶圓含銅,此拋 光組合物包含1至15重量%之氧化劑、〇. 1至1重量%之非鐵 質金屬抑制劑、0.05至3重量。/〇之非鐵質金屬錯合劑、〇.〇1 至5重量%之羧酸聚合物、〇.〇1至5重量。之改質纖維素、 0.0001至2重量%之鹽、其餘為水,及以拋光墊將晶圓拋光, 96930.doc 200526769 此鹽降低來自晶圓與拋光墊間振動之噪音程度。 【實施方式】 此組合物及方法提供意料外之來自銅交連拋光時造成之 振動之深音私度降低。本發明之組合物利用加入鹽或其混 合物而有效地降低來自晶圓上之銅交連第一步·驟拋光時之 振動之噪音程度。此外,加入鹽有利地減少晶圓之剩餘拋 光時間。雖然本發明對銅交連特別有用,本水性拋光組合 物亦I疋供增強之其他金屬交連拋光,如鋁、鎳、鐵、鋼、 鈹、鋅、鈦、鉻等。 為了本說明書之目的,「鹽」係定義為在分別之先前反 應、或在其中使用鹽之最終混合物中原處,由酸與鹼或金 屬與酸之反應產生之化合物。因此,此鹽包括陽離子成分 與陰離子成分。陽離子成分可實質上為任何不因欲拋光金 屬表面上之無電極電鍍而沈積之游離元素。此鹽之較佳陽 離子成分為元素週期表(IUPAC版本)第ΙΑ、IIA、ΙΠΑ、丨VA、 及IVB族之游離元素,及鋅、鈽、鐵(2 +或3+)、銨、與胍離 子。所示族之重金屬通常由於成本及污染因素而不利。氧 結基Zr02+為較佳之陽離子。此鹽之陰離子成分較佳為包括 氣離子、溴離子、碘離子、硝酸基、磷酸基、聚磷酸基、 硫酸基、碳酸基、與全氯酸基離子。 較佳之水性拋光組合物可使用至少一種包含以下之鹽調 配·氣化鋁、硝酸氧锆、硫酸氧鍺、硝酸鈽、硝酸鋁、溴 化鋁、碘化鋁、氯化鋁、氯化氧锆、氯化錫、全氣酸鋁、 氯化鎂、氯化鋅、全氯酸鎂、氯化鐵、氯化鉀、硫酸鉀、 96930.doc 200526769 硝酸胍、硫酸胍、碳酸胍、氯化銨、確酸錄、鱗酸按等。 有利地’本發明之拋光組合物之鹽成分以有效降低抛光 區嗓音程度之量存^此拋光組合物之水成分主要為用於 懸浮固體成分之懸浮劑及作為鹽成分之溶劑。如果需要, 則可將此拋光組合物製備成濃縮形式且藉由加入水至所需 濃度而稀釋使I據信即使是殘量之鹽存在於此拋光組合 物對於拋光銅仍有效。使用組合物之約〇 〇〇〇1至約2重量% 之鹽得到令人滿意之噪音程度降低及可接受之拋光效率。 鹽成分之較佳範圍為組合物之約0 00丨至約丨重量%。最佳 為’鹽成分為組合物之約〇·〇!重量0/〇。 由於鹽通常溶於使用之水中,鹽之粒度並不重要。然而, 鹽粒度希望為小到足以快速地溶於水中。此外,許多種這 些鹽較佳為水合形式以防止在與水接觸時分解。混合鹽或 鹽組合與水之溫度、鹽或鹽組合對水之加入速率、及混合 參數(如鹽或鹽組合與水形成拋光組合物之混合速率)通常 依照此業界且為熟悉此技藝者所已知。 此外,拋光組合物鹽可原處產生。可將適當之酸與鹼加 入水性組合物,例如,可將Mg(〇H)2組合hn〇3而形成 Mg(N〇3)2與水。或者,鹽可藉由加入金屬與酸而原處產生, 例如’粉狀鋅金屬加氫氯酸形成Znci2。 有利地,此新穎拋光組合物含約001至5重量%之羧酸聚 合物。較佳為,此組合物含約〇.〇5至2重量%之羧酸聚合物。 亦較佳為,此組合物具有約2〇,〇〇〇至ι,5〇〇,〇〇〇之數量平均 分子量。此外,可使用較高或較低數量平均分子量羧酸聚 96930.doc 200526769 合物之摻合物。上述聚合物之數量平均分子量係藉GpC(凝 膠穿透層析術)測定。 羧酸聚合物係由不飽和單羧酸與不飽和二羧酸形成。典 型不飽和單叛酸單體含3至6個碳原子且包括丙晞酸、寡聚 丙烯酸、甲基丙晞酸、巴豆酸、與乙晞基乙酸。典型不飽 和二羧酸含4至8個碳原子及包括其酐且為,例如,順丁缔 二酸、順丁稀二酸Sf、反丁烯二酸、戊二酸、伊康酸、伊 康酸酐、與環己晞二羧酸。此外,亦可使用上述酸之水溶 性鹽。 特別有用為具有約20,000至150,000,較佳為25,000至 75,000,而且更佳為25,000至40,000之分子量之「聚(甲基) 丙晞酸」。在此使用之名詞「聚(甲基)丙埽酸」係定義為丙 烯酸之聚合物或甲基丙晞酸之聚合物。不同數量平均分子 量聚(甲基)丙晞酸之摻合物特佳。在這些聚(甲基)丙烯酸之 摻合物或混合物中,將數量平均分子量為20,000至1〇〇,〇〇〇 而且較佳為20,000至40,000之較低數量平均分子量聚(甲 基)丙晞酸、與數量平均分子量為150,000至1,500,000而且 較佳為200,000至300,〇 00之較高數量平均分子量聚(甲基) 丙晞酸組合使用。一般而言,較低數量平均分子量聚(甲基) 丙烯酸對較高數量平均分子量聚(甲基)丙烯酸之重量。/〇比 例為約10:1至1:10,較佳為4:1至1:4,而且更佳為2:1至1:2。 較佳摻合物包含1:1重量比例之數量平均分子量為約30,000 之聚丙烯酸與數量平均分子量為約250,000之聚丙烯酸。 此外,可使用含共聚物與三聚物之羧酸,其中羧酸成分 96930.doc -10- 200526769 包含聚合物之5-75重量。/〇。典型之此種聚合物為(甲基)丙締 酸與丙烯醯胺或甲基丙烯醯胺之聚合物;(甲基)丙婦酸與 苯乙缔及其他乙烯基芳族單體之聚合物;(甲基)丙婦酸烷 酯(丙烯酸或甲基丙缔酸之酯)與單或二羧酸(如丙締酸或甲 基丙烯酸或伊康酸)之聚合物;具有取代基(如_素(即, 氯、氟、溴)、硝基、氰基、烷氧基、自烷基、羧基、胺基、 胺基:fe基)之經取代乙晞基芳族單體與不飽和單或二羧酸 及(甲基)丙晞酸燒酿之聚合物;含氮環之單乙埽不飽和單 體(如乙缔基吡啶、烷基乙埽基吡啶、乙烯基丁内醯胺、乙 烯基己内醯胺)與不飽和單或二羧酸之聚合物;缔烴(如丙 晞、異丁烯、或具有10至20個碳原子之長鏈烷基烯烴)與不 飽和單或二羧酸之聚合物;乙烯醇酯(如乙酸乙烯酯與硬 脂酸乙晞酯)或齒乙晞(如氟乙缔、a乙缔、氟亞乙烯)或乙 烯腈(如丙稀腈與甲基丙烯腈)與不飽和單或二羧酸之聚合 物;燒基中具有個碳原子之(甲基)㈣酸燒酉旨與不^ 和單羧酸(如丙晞酸或甲基丙晞酸)之聚合物。其僅為可用於 本發明之新穎拋光組合物之各種聚合物之一些實例。亦可 使用可生物降解、可光降解、或可藉其他方法降解之聚合 物。可生物降解之組合物之實例為含聚(丙埽酸酿共2_氯基 丙晞酸甲酯)段之聚丙烯酸聚合物。 有利地,溶液含1至15重量%之氧化劑。更佳為’氧化劑 為5至10重量%之範圍。此氧化劑對於幫助溶液去除在低pH 範圍形成〈氧化銅膜特別有效。此氧化劑可為許?種氧化 化合物之至少-種,如過氧化氫(H2Q2)、單過硫酸基、破 96930.doc 200526769 酸基、過酞酸鎂、過氧酷酸盘Α ώ Α # /、具他又過氧酸、過硫酸基、 溴酸基、過碘酸基、硝酸基、鐵 病息師鹽、Μη (ni)、Mn (IV) 與Μη (VI)鹽、銀鹽、銅鹽 、 路孤鉛鹽、ΐ素次氯酸基、 及其混合物。此外,使用g仆流丨乂 用乳化劑化合物之混合物經常為有 利的。在拋光漿液含不安定氣化杳 疋虱化劑(如過氧化氫)時,恰在使 用時將氧化劑混合至組合物中經常最有利。 此外/合液;0· 1至1 .〇重1 %之抑制劑,以藉靜態蚀刻或 其他去除機構控制銅交連去除速率。調整抑制劑濃度因保 護金屬免於靜態蚀刻而調整交連金屬去除速率。有利地, 溶液含0.2至0.50重量%之抑制劑。抑制劑可包括抑制劑混 合物。唑抑制劑對銅與銀交連特別有效。典型唑抑制劑包 括苯并三唑(BTA)、氫硫基苯并三唑(MBT)、甲苯基三唑、 與咪吐。BTA為對銅與銀特別有效之抑制劑。 除了抑制劑,此組合物有利地含〇 〇5至3重量%之非鐵質 金屬錯合劑。此錯合劑防止因溶解非鐵質金屬交連而形成 之金屬離子沈澱。或者,此組合物含〇·丨至丨重量%之非鐵質 金屬錯合劑。錯合劑之實例包括乙酸、檸檬酸、乙醯乙酸 乙酯、羥乙酸、乳酸、羥丁二酸、草酸、柳酸、二乙基二 硫胺甲酸鈉、琥珀酸、酒石酸、硫乙醇酸、甘胺酸、丙胺 天冬胺酸、乙一*胺、丙 <—胺、丙二酸、戊二酸、3 -基丁酸、丙酸、醜酸、異酞酸、3-經基柳酸、3,5-二幾基柳 酸、五倍子酸、葡萄糖酸、兒茶酚、五倍子酚、單寧酸, 包括其鹽及混合物。有利地,此錯合劑選自乙酸、檸檬酸、 乙醯乙酸乙酯、羥乙酸、乳酸、羥丁二酸、草酸、及其混 96930.doc 12 200526769 合物組成之群組。最有利為此錯合劑為羥丁二酸。 此外,本發明之拋光組合物含001至5 〇重量%之改質纖 維素。較佳為,此組合物含〇1至3重量%之改質纖維素。加 入改質纖維素(例%,幾甲基纖維素)對抛光組合物提供意料 外之凹狀扭曲研磨值降低。例示改質纖維素為陰離子膠, 如瓜爾膠阿拉伯膠、印度樹膠、梧桐膠、果膠、角豆膠、 只耆膠、羅望子膠、鹿角菜苷膠、與黃原膠丨變性澱粉; 可經孤電子對供予結合之改質含㈣合物;I鱗酸基以結 合表面之聚合物;纟可因疏水性結合表面之疏水性改質基 之聚合物;含氫鍵形成基以結合表面之聚合物,及其修改 與組合。 此組合物及方法提供意料外之來自銅交連拋光時造成之 振動之噪音程度降低。本發明之不磨損拋光組合物或流體 利用加入鹽或其混合物而有效地降低來自晶圓上之銅交連 第一步驟拋光時之振動之噪音程度。此外,加入鹽有利地 減少曰Εί圓之剩餘拋光時間。此水性組合物包含氧化劑、抑 制劑、錯合劑、聚合物與鹽、其餘為水。此外,相較於習 知拋光組合物,本組合物提供鋼電路之凹狀扭曲研磨之大 幅減少。此新穎之拋光組合物提供無常由拋光造成之刮痕 及其他缺陷之實質上平坦表面。
此化合物在含其餘為水之溶液中於廣泛?11範圍有效。此 /谷液之可用pH擴展為2至5。此外,此溶液有利地依賴其餘 去離子水限制附帶雜質。本發明之拋光流體ipH較佳為2.8 至4.2,更佳為2.6至3.8之pH。用以調整本發明組合物之pH 96930.doc -13- 200526769 <酸為,例如,硝酸、硫酸、氫氯酸、磷酸等。用以調整 本發明組合物之pH之例示鹼為,例如,氫氧化銨與氫氧化 奸0 此外’此拋光組合物可視情況地含〇至3重量%之磨料以 利於金屬層去除。在此範圍内,希望使磨料以大於或等於 〇·〇1重量%之量存在。在此範圍内亦希望為小於或等於丨重 量%之量。 為了防止過量金屬凹狀扭曲研磨及介電腐蝕,磨料具有 小於或等於50奈米(nm)之平均粒度。為了本說明書之目 的,粒度指磨料之平均粒度。更佳為,希望使用平均粒度 小於或等於40 nm之膠體磨料。此外,平均粒度小於或等於 30 nm之膠體矽石有利地發生最小介電腐蝕及金屬凹狀扭 曲研磨。將膠體磨料之大小降至小於或等於3〇nm趨於改良 拋光組合物之選擇性,但是亦趨於降低去除速率。此外, 較佳膠體磨料可包括添加劑,如分散劑、界面活性劑與緩 衝劑,以改良膠體磨料之安定性。_種此種膠體磨料為得 自法國Puteaux之Clariam s.a·之膠體矽石。亦可使用其他 之磨料,包括發煙、沈澱、黏聚者等。 拋光組合物可包括用於「機械」去除金屬交連層之磨料。 磨料之實例包括無機氧化物、無減氧化物、金屬硼化物、 金屬碳化物、金屬氮化物、聚合物顆粒、及包含以上至少 之一之混合物。適當之無機氧化物包括,例如,矽石(si〇2)、 氧化銘(A12〇3)、氧化锆(Zr〇2)、氧化鈽(Ce〇2)、氧化錳 (Mn〇2)、或包含以上氧化物至少之一之組合。如果需要, 96930.doc 14 200526769 亦可利用每些無機氧化物之改質形式,如塗聚合物無機氧 ^物顆粒與播機塗覆顆粒。適當之金屬碳化物、硼化物與 氮^包括’例如,碳切、氮切、料(sicN)、碳化 领、敌化鶴、碳化锆、硼化銘、碳化起、碳化鈥、或包含 以上金屬碳化物、硼化物與氮化物至少之一之組合。如果 需要,亦可使用鑽石作為磨料。替代性磨料亦包括聚合顆 粒及塗覆聚合顆粒。如果使用,較佳之磨料為矽石。 本發明之組合物可應用於任何含導電性金屬(如銅、鋁、 •烏鉑免金、或銀)之半導體晶圓;屏障或襯塾膜,如 纽、氮化起、鈥、或氮化鈇;及底下之介電層。為了本說 明書之目的,名詞介電指介電常數!^之半導電材料,其包括 低k及超低k介電材料。此組合物及方法優於防止多晶圓組 成之腐蝕,例如,多孔性與非多孔性低]^介電體、有機與無 機低k介電體、有機矽酸鹽玻璃(〇SG)、氟矽酸鹽玻璃 (FSG)、摻碳氧化物(CDO)、正矽酸四乙酯(TE〇s)、及衍生 自TEOS之矽石。 實例 在實例中,數值表示本發明之實例且字母表示比較例。 所有之實例溶液含〇.30重量%之BTA、〇.22重量%之龜丁二 酸、0.15重里%之致甲基纖維素(CMC)、〇.〇9重量❶/。之聚丙 晞酸(30k)/0_09重量%之聚丙缔酸(25〇k)之摻合物、及9〇〇 重量%之過氧化氫。 實例1 此實驗測自半導體晶圓抛光剩餘銅時之噪音程度 96930.doc -15 · 200526769 (dB)。特別地,此測試測定在第一步驟(第2平台)拋光操作 時加入鹽或其混合物對噪音程度之影響。使用Appned Materials,Inc.之Mirra 200毫米拋光機將樣品平坦化,其在 約3 psi (20.7 kPa)之向下力條件下及80 cC/分鐘之拋光溶液 流速、33 RPM之平台速度與61 RPM之載具速度,使用 1C 1 010TM聚胺甲酸醋拋光塾(R〇(jei,inc )。以硝酸調整,拋 光落液具有3.4之pH。所有之溶液含去離子水。噪音程度係 以 Extech Instruments,Inc·測音計測量,其具有 30-130 dB (+/- 1·5 dB)分貝範圍。機器之背景噪音測為75-77 dB。不 欲噪音實測為約94 dB或更高分貝之程度。 表1 第二平台拋光之噪音程度結果 測試 添加物 重量% 噪音程度(dB) A 無 -- 95.0-99.0 1 硝酸抑 0.1 90.0-93.4 2 硝酸鉀/氯化鉀 0.1/0.1 85.0-90.0 3 氫氣酸胍 0.01 86.1-86.6 4 硝酸胍 0.01 86.6-86.9 5 硫酸胍 0.01 87.1-87.4 6 碳酸胍 0.01 87.4-87.7 如表1所描述,因將鹽或其混合物加入本發明之對照拋光 流體’ p呆音程度顯著地降低。鹽加入將來自接觸晶圓之拋 光墊振動之噪音程度降至至少低於94 dB。將〇· 1至〇·〇 1重量 %之鹽加入對照拋光流體提供93 4至85 間之降低噪音程 度。特別地,將0.1重量%之硝酸鉀(測試丨)加入對照拋光流 200526769 體將噪音程度降至90-93.4 dB之間。比較下,無鹽加入之抛 光流體(測試A)產生95-99 dB之間之不可接受噪音程度。〇 i 重量%之硝酸鹽與Ο·!重量%之氯化鉀之混合物(測試2)亦將 噪音程度降至85-90 dB。鉀鹽混合物提供85 dB之最低噪音 程度。此外,將均為〇.〇1重量%之各種胍(測試弘6)加入對照 拋光流體,而且這些實例拋光流體提供約861(氫氣酸胍) 至約87.7 dB(碳酸胍)之噪音程度降低。應注意,討論之嗓 音程度為以上定義之實例測試條件。噪音程度可隨測試參 數改變而不同。 測試2 在此測試中,測量剩餘銅清除之拋光時間。利用如實例 之相同拋光條件,將測試樣品在第二平台上拋光,而且利 用Applied Materials之’’Mirra"終點系統測量終點。在τΐ, 底下之屏障層(Ta或TaN)穿越銅層,及在T2,殘留極少或無 剩餘銅。測試拋光流體1及2含〇.〇1重量%之硝酸胍。 表2 第二平台拋光之剩餘拋光時間結果 測試 T1(秒) T2(秒) Τ2-Τ1(秒) A 118 175 57 B 113 175 62 1 115 150 35 2 97 131 34 如表2所描述,將鹽加入對照拋光流體減少去除剩餘銅之 抛光時間。特別地,加入0.01重量%之硝酸胍(測試丨及?)將 去除剩餘銅之拋光時間各減少至35及34秒。比較下,未加 96930.doc 200526769 入鹽之拋光流體(測試A及B)各需要57及62秒去除剩餘銅。 換言之,拋光時間減少至少38%。 此溶液及方法提供意料外之銅交連時噪音程度降低。本 發明之拋光流體利用加入鹽或其混合物而有效地將來自晶 圓上銅交連之第一步驟拋光時之振動之噪音程度降至至少 低於94 dB。此外,加入鹽有利地將晶圓之剩餘拋光時間減 少至少38%。此水性組合物包含氧化劑、抑制劑、錯合劑、 聚合物與鹽、其餘為水。 96930.doc 18 -
Claims (1)
- 200526769 十、申請專利範圍: 1. -種可詩在半導體晶圓上拋光銅之水性組合物,宜包 =1至15重量%之氧化劑—重量%之非鐵質金屬抑制 .05至3重量%之非鐵質金屬錯合劑、0.01至5重量% 之,酸聚合物、㈣1至5重量%之改質纖維素、0.0001至2 重量%之具陽離子與陰離子成分之鹽、其餘為水,該鹽降 低來自晶圓與拋光墊間振動之噪音程度。 2·如請求項!之組合物,其中陽離子成分包含選自包含元素 週期表第IA、IIA、IIIA、!VA、及TVB族之群組之離子化 元素,辞、鈽、鐵、銨、與胍離子。 3·如請求項1之組合物,其中陰離子成分係選自包含氯離 子/臭離子、蛾離子、硝,酉复基、麟酸基、聚碟酸基、硫 酸基、碳酸基、與全氣酸基離子之群組。 4·如請求項1之組合物,其中鹽係選自包含以下之群組:氣 化鋁硝酸氧锆、硫酸氧錯、硝酸鈽、硝酸鋁、溴化鋁、 峨化鋁氯化鋁、氣化氧锆、氣化錫、全氣酸鋁、氣化 鎂、氣化鋅、全氣酸鎂、氣化鐵、氣化鉀、硫酸鉀、氫 氣SiL胍、硝酸脈、硫酸脈、碳酸脈、氣化銨、硝酸銨、 與磷酸銨。 5 ·如研求項1之組合物,其中羧酸聚合物包含聚(甲基)丙烯 酸之播合物’該摻合物包含具有數量平均分子量為20,000 至1 〇〇,000之第一聚合物、及至少一種具有數量平均分子 $為200,000至1,5〇〇〇〇〇之第二聚合物。 6.如請求項5之組合物,其中第一聚合物為具有數量平均分 96930.doc 200526769 子量為30,〇〇〇之聚丙烯酸,及第二聚合物為具有數量平均 分子量為250,000之聚丙烯酸,該第一與第二聚合物係以 1 ·· 1重量比例存在。 7. 8. 9. 10. 如請求項1之組合物,其中改質纖維素為羧甲基纖維素。 如請求項1之組合物,其中溶液具有小於5之?11。 一種自半導體晶圓拋光鋼之方法,其包括: 使晶圓接觸拋光組合物,該晶圓含銅,該拋光組合物 包含1至15重量%之氧化劑、〇·ι至1重量%之非鐵質金屬抑 制>丨0·05至3重量%之非鐵質金屬錯合劑、〇·〇1至5重量 %之羧酸聚合物、〇.〇1至5重量%之改質纖維素、〇 〇〇〇1至 2重量。/〇之鹽、其餘為水;及 以拋光墊將晶圓拋光,該鹽降低來自晶圓與拋光墊間 振動之噪音程度。 长項9之方法’其中該鹽減少銅之剩餘拋光時間。 96930.doc 200526769 七、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無) 96930.doc
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US6162268A (en) * | 1999-05-03 | 2000-12-19 | Praxair S. T. Technology, Inc. | Polishing slurry |
US6443812B1 (en) * | 1999-08-24 | 2002-09-03 | Rodel Holdings Inc. | Compositions for insulator and metal CMP and methods relating thereto |
US6258140B1 (en) * | 1999-09-27 | 2001-07-10 | Fujimi America Inc. | Polishing composition |
US6293848B1 (en) * | 1999-11-15 | 2001-09-25 | Cabot Microelectronics Corporation | Composition and method for planarizing surfaces |
JP3768402B2 (ja) * | 2000-11-24 | 2006-04-19 | Necエレクトロニクス株式会社 | 化学的機械的研磨用スラリー |
US6582633B2 (en) * | 2001-01-17 | 2003-06-24 | Akzo Nobel N.V. | Process for producing objects |
US6632259B2 (en) * | 2001-05-18 | 2003-10-14 | Rodel Holdings, Inc. | Chemical mechanical polishing compositions and methods relating thereto |
US6821897B2 (en) * | 2001-12-05 | 2004-11-23 | Cabot Microelectronics Corporation | Method for copper CMP using polymeric complexing agents |
US6620215B2 (en) * | 2001-12-21 | 2003-09-16 | Dynea Canada, Ltd. | Abrasive composition containing organic particles for chemical mechanical planarization |
JP4560294B2 (ja) * | 2002-03-25 | 2010-10-13 | ローム アンド ハース エレクトロニック マテリアルズ シーエムピー ホウルディングス インコーポレイテッド | タンタルバリア除去溶液 |
-
2003
- 2003-11-13 US US10/712,446 patent/US20050104048A1/en not_active Abandoned
-
2004
- 2004-11-01 TW TW093133218A patent/TW200526769A/zh unknown
- 2004-11-04 EP EP04256808A patent/EP1533352A1/en not_active Withdrawn
- 2004-11-12 KR KR1020040092500A patent/KR20050046620A/ko not_active Application Discontinuation
- 2004-11-12 CN CN200410092968.8A patent/CN1629238A/zh active Pending
- 2004-11-15 JP JP2004330000A patent/JP2005191544A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
KR20050046620A (ko) | 2005-05-18 |
US20050104048A1 (en) | 2005-05-19 |
EP1533352A1 (en) | 2005-05-25 |
JP2005191544A (ja) | 2005-07-14 |
CN1629238A (zh) | 2005-06-22 |
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