WO2010093011A1 - 銅研磨用研磨剤及びそれを用いた研磨方法 - Google Patents
銅研磨用研磨剤及びそれを用いた研磨方法 Download PDFInfo
- Publication number
- WO2010093011A1 WO2010093011A1 PCT/JP2010/052069 JP2010052069W WO2010093011A1 WO 2010093011 A1 WO2010093011 A1 WO 2010093011A1 JP 2010052069 W JP2010052069 W JP 2010052069W WO 2010093011 A1 WO2010093011 A1 WO 2010093011A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- component
- acid
- abrasive
- copper
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 418
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 138
- 239000010949 copper Substances 0.000 title claims abstract description 138
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000007524 organic acids Chemical class 0.000 claims abstract description 41
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 36
- 230000001681 protective effect Effects 0.000 claims abstract description 27
- 150000001413 amino acids Chemical class 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 239000006061 abrasive grain Substances 0.000 claims abstract description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 74
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 32
- 239000012964 benzotriazole Substances 0.000 claims description 27
- 235000006408 oxalic acid Nutrition 0.000 claims description 27
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- -1 triazole compound Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 239000008119 colloidal silica Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 14
- 235000005985 organic acids Nutrition 0.000 abstract description 12
- 239000010408 film Substances 0.000 description 96
- 239000000758 substrate Substances 0.000 description 47
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 40
- 238000006386 neutralization reaction Methods 0.000 description 38
- 238000004448 titration Methods 0.000 description 36
- 239000004744 fabric Substances 0.000 description 24
- 239000004471 Glycine Substances 0.000 description 20
- 239000003082 abrasive agent Substances 0.000 description 20
- 235000001014 amino acid Nutrition 0.000 description 20
- 229940024606 amino acid Drugs 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 19
- 230000003746 surface roughness Effects 0.000 description 19
- 239000012085 test solution Substances 0.000 description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 17
- 229910000881 Cu alloy Inorganic materials 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 12
- 238000007517 polishing process Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 10
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003002 pH adjusting agent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 3
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 3
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 3
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 241000724291 Tobacco streak virus Species 0.000 description 3
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 2
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 2
- 239000004473 Threonine Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 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 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 2
- 229960000310 isoleucine Drugs 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 2
- UFSCUAXLTRFIDC-UHFFFAOYSA-N oxalosuccinic acid Chemical compound OC(=O)CC(C(O)=O)C(=O)C(O)=O UFSCUAXLTRFIDC-UHFFFAOYSA-N 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 238000009789 rate limiting process Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- JMSVCTWVEWCHDZ-UHFFFAOYSA-N syringic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1O JMSVCTWVEWCHDZ-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004474 valine Substances 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 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
- 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 description 1
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 description 1
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 1
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical compound OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 description 1
- OTOIIPJYVQJATP-BYPYZUCNSA-N (R)-pantoic acid Chemical compound OCC(C)(C)[C@@H](O)C(O)=O OTOIIPJYVQJATP-BYPYZUCNSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HMOYKDCLYCJGHG-UHFFFAOYSA-N 2-(2h-benzotriazol-4-ylmethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CC1=CC=CC2=NNN=C12 HMOYKDCLYCJGHG-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-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
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-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
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VJEFVEHNRRGNQX-UHFFFAOYSA-N 3-(benzotriazol-1-yl)propane-1,1-diol Chemical compound C1=CC=C2N(CCC(O)O)N=NC2=C1 VJEFVEHNRRGNQX-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-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
- FYTLHYRDGXRYEY-UHFFFAOYSA-N 5-Methyl-3-pyrazolamine Chemical compound CC=1C=C(N)NN=1 FYTLHYRDGXRYEY-UHFFFAOYSA-N 0.000 description 1
- QZBGOTVBHYKUDS-UHFFFAOYSA-N 5-amino-1,2-dihydropyrazol-3-one Chemical compound NC1=CC(=O)NN1 QZBGOTVBHYKUDS-UHFFFAOYSA-N 0.000 description 1
- GAHAURRLKFPBCQ-UHFFFAOYSA-N 5-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=C2NN=NC2=C1 GAHAURRLKFPBCQ-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
- 239000005711 Benzoic acid Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XFTRTWQBIOMVPK-YFKPBYRVSA-N Citramalic acid Natural products OC(=O)[C@](O)(C)CC(O)=O XFTRTWQBIOMVPK-YFKPBYRVSA-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
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AEAAPULBRBHRTM-UHFFFAOYSA-N N1(N=NC2=C1C=CC=C2)COP(OCN2N=NC1=C2C=CC=C1)=O Chemical compound N1(N=NC2=C1C=CC=C2)COP(OCN2N=NC1=C2C=CC=C1)=O AEAAPULBRBHRTM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- AAWZDTNXLSGCEK-ZHQZDSKASA-N Quinic acid Natural products O[C@H]1CC(O)(C(O)=O)C[C@H](O)C1O AAWZDTNXLSGCEK-ZHQZDSKASA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- UIAFKZKHHVMJGS-UHFFFAOYSA-N beta-resorcylic acid Natural products OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000004883 caffeic acid Nutrition 0.000 description 1
- 229940074360 caffeic acid Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- MSUOLNSQHLHDAS-UHFFFAOYSA-N cerebronic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC(O)C(O)=O MSUOLNSQHLHDAS-UHFFFAOYSA-N 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
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 1
- XFTRTWQBIOMVPK-UHFFFAOYSA-N citramalic acid Chemical compound OC(=O)C(O)(C)CC(O)=O XFTRTWQBIOMVPK-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000001785 ferulic acid Nutrition 0.000 description 1
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 1
- 229940114124 ferulic acid Drugs 0.000 description 1
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 1
- RIKMMFOAQPJVMX-UHFFFAOYSA-N fomepizole Chemical compound CC=1C=NNC=1 RIKMMFOAQPJVMX-UHFFFAOYSA-N 0.000 description 1
- 229960004285 fomepizole Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229960005219 gentisic acid Drugs 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 1
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- PCMORTLOPMLEFB-ONEGZZNKSA-N sinapic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-ONEGZZNKSA-N 0.000 description 1
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
Definitions
- the present invention relates to a polishing agent for polishing copper and a polishing method using the same.
- the present invention also relates to a high polishing rate and high smoothness after polishing, and a polishing method using the same, particularly suitable for use in a chemical mechanical polishing (CMP) process.
- CMP chemical mechanical polishing
- a general method of CMP for a metal such as a copper alloy is to apply a polishing cloth (polishing pad) on a circular polishing platen (platen), immerse the surface of the polishing cloth with a metal abrasive, and form a metal film on the substrate.
- the formed surface is pressed against the surface of the polishing cloth, and a predetermined pressure (hereinafter referred to as “polishing pressure”) is applied to the metal film from the back surface, and the polishing platen is rotated to remove the abrasive and the metal on the raised portion.
- the metal film on the raised portion is removed by mechanical friction with the film.
- a metal abrasive used in CMP generally contains an oxidizing agent and solid abrasive grains (hereinafter simply referred to as “abrasive grains”), and further contains a metal oxide dissolving agent and a protective film forming agent as required. .
- the basic mechanism of CMP using an abrasive containing an oxidizing agent is that the surface of the metal film is first oxidized by the oxidizing agent to form an oxide layer, and the oxidized layer is scraped off by the abrasive grains. It is thought to be polished.
- the oxide layer on the surface of the metal film in the groove portion of the insulating film does not touch the polishing cloth so much and the effect of scraping off by the abrasive grains is not exerted, so the metal film on the raised portion is removed with the progress of CMP.
- the surface of the substrate is flattened (for example, see Non-Patent Document 1 below).
- an abrasive that has a copper alloy film to be polished having a thickness of about 1 ⁇ m and a polishing rate of about 5000 ⁇ / min is used (for example, see Patent Document 2 below).
- Patent Document 3 discloses an abrasive capable of polishing a copper alloy film at a higher polishing rate (about 22,000 to 29000 mm / min) than before.
- Patent Document 3 Although the abrasive described in Patent Document 3 can be applied as an abrasive for TSV, there is a demand for an abrasive capable of polishing a copper alloy film smoothly at a higher polishing rate in order to improve productivity. .
- the present invention has been made in view of such circumstances, and can smoothly polish a copper film at a high polishing rate, and it is necessary to polish a thick metal film such as a high-performance wiring board or TSV.
- the purpose of the present invention is to provide a polishing agent for copper polishing that can be polished in a short time and can secure sufficient productivity, and a polishing method using the same.
- the present inventors controlled the copper film at a high polishing rate by controlling the contents of a divalent or higher inorganic acid (hereinafter simply referred to as “inorganic acid”), an amino acid, and a protective film forming agent to a predetermined amount or more. It has been found that an abrasive that can be polished smoothly is obtained. Furthermore, the present inventors control the contents of the inorganic acid, the amino acid, and the protective film forming agent to a predetermined amount or more and satisfy at least one of the following conditions (i) and (ii), thereby achieving high performance.
- inorganic acid divalent or higher inorganic acid
- amino acid amino acid
- a protective film forming agent a protective film forming agent
- abrasive capable of obtaining a high polishing rate for copper (for example, a polishing rate exceeding 30000 mm / min), which is useful for wiring board applications and TSV applications, can be obtained.
- Condition (i) The ratio of the content (mol / kg) of the inorganic acid to the content (mol / kg) of the protective film forming agent (the content of the inorganic acid / the content of the protective film forming agent) is 2.00 or more.
- the abrasive contains at least one selected from organic acids and acid anhydrides thereof.
- the present invention provides, as a first embodiment, (A) an inorganic acid, (B) an amino acid, (C) a protective film forming agent, (D) abrasive grains, (E) an oxidizing agent, F) water, the content of component (A) is 0.08 mol / kg or more, the content of component (B) is 0.20 mol / kg or more, and the content of component (C) is 0.
- a polishing slurry for copper polishing which is 0.02 mol / kg or more and the ratio of the content of the component (A) to the content of the component (C) is 2.00 or more.
- the present invention provides, as a second embodiment, (A) an inorganic acid, (B) an amino acid, (C) a protective film forming agent, (D) abrasive grains, (E) an oxidizing agent, (F) Water and at least one selected from (G) an organic acid and its acid anhydride, the content of the component (A) is 0.08 mol / kg or more, and the content of the component (B) is 0.20 mol.
- a polishing slurry for copper polishing which is not less than / kg and the content of component (C) is not less than 0.02 mol / kg.
- “copper” includes not only pure copper but also a metal containing copper (for example, copper alloy, copper oxide, and copper alloy oxide).
- the “copper polishing abrasive” refers to a metal film made of pure copper, a metal film containing copper (for example, a copper alloy film), or those metal films and other metals. An abrasive for polishing the laminated film.
- the above polishing agent for polishing copper can polish a copper film smoothly at a high polishing rate, and can be used in a short time even in applications requiring polishing of thick metal films such as high performance wiring boards and TSVs. Polishing treatment is possible and sufficient productivity can be secured. Moreover, since such a polishing slurry for copper is a pH buffer solution containing (A) an inorganic acid and (B) an amino acid having a strong dissolving action, even if copper as the object to be polished is dissolved in the polishing agent. pH fluctuation is unlikely to occur. For this reason, it is considered that a high polishing rate can be stably maintained without depending on the progress of polishing.
- the copper polishing abrasive of the first embodiment (excluding the pH adjusting agent when the copper polishing abrasive contains an acidic component such as aqueous hydrochloric acid or an alkaline component such as aqueous ammonia as a pH adjusting agent).
- the amount of potassium hydroxide required to increase the pH to 4 is preferably 0.10 mol or more per kg of polishing slurry for copper. According to such an abrasive, the copper film can be polished more smoothly at a higher polishing rate, and even in applications where a thick metal film such as a high performance wiring board or TSV needs to be polished, Polishing can be performed in a short time, and sufficient productivity can be ensured.
- the present invention provides (A) an inorganic acid, (B) an amino acid, (C) a protective film forming agent, (D) abrasive grains, (E) an oxidizing agent, ( F) water and (G) at least one selected from organic acids and acid anhydrides thereof, the content of component (A) is 0.08 mol / kg or more, and the content of component (B) is 0.
- the content of component (C) is 0.02 mol / kg or more, and the ratio of the content of component (A) to the content of component (C) is 2.00 or more.
- an abrasive for polishing copper is provided.
- the polishing abrasive for copper of the second and third embodiments is a composition obtained by removing the component (G) from the polishing abrasive for copper (the polishing abrasive for copper is an acidic component such as an aqueous hydrochloric acid solution, an aqueous ammonia solution, etc.
- the amount of potassium hydroxide required to increase the pH of the alkaline component to 4) is preferably 0.10 mol or more per kg of the composition. . According to such an abrasive, the copper film can be polished more smoothly at a higher polishing rate, and even in applications where a thick metal film such as a high performance wiring board or TSV needs to be polished, Polishing can be performed in a short time, and sufficient productivity can be ensured.
- the content of the component (G) is preferably 0.02 mol / kg or more.
- the component (G) has two carboxyl groups and an organic acid having a pKa of 2.7 or less, its acid anhydride, and three carboxyl groups.
- the organic acid is preferably at least one selected from two or more organic acids.
- organic acids having two carboxyl groups those having a pKa of 2.7 or less have a stronger interaction with the copper surface than organic acids having a pKa of more than 2.7.
- Such organic acids and acid anhydrides thereof Is considered to be highly effective in improving the polishing rate.
- the organic acid having 3 or more carboxyl groups must have 3 or more carboxyl groups even if the pKa value exceeds 2.7. Therefore, it is considered that the interaction with copper is strong and the effect of improving the polishing rate is high.
- pKa means the acid dissociation constant of the first dissociable acidic group, and is the negative common logarithm of the equilibrium constant Ka of the group.
- the component (G) is preferably at least one selected from oxalic acid, maleic acid, maleic anhydride, malonic acid, and citric acid. These (G) components significantly improve the polishing rate as compared with the case where the same amount of organic acid other than these and acid anhydride thereof are added.
- the pH of the abrasive for polishing copper of the present invention is preferably 1.5 to 4.0. In this case, it tends to have a function as a pH buffer solution, and it becomes easy to stably maintain a high polishing rate.
- the component (A) is preferably at least one selected from sulfuric acid and phosphoric acid. In this case, it is possible to make the polishing rate and smoothness more compatible.
- the copper polishing abrasive of the present invention preferably contains an amino acid having a pKa of 2 to 3 as the component (B).
- the pH of the polishing slurry for copper polishing can be easily set to a desired value.
- the component (C) is preferably a triazole compound, and the triazole compound is more preferably at least one selected from benzotriazole and its derivatives.
- the polishing rate can be further improved, and an abrasive having an excellent balance between the polishing rate and the corrosion resistance can be obtained.
- the component (D) is at least one selected from colloidal silica and colloidal alumina, and the average particle size of the component (D) is preferably 100 nm or less.
- the component (E) is preferably at least one selected from hydrogen peroxide, persulfuric acid and persulfate. These components (E) are suitable as oxidizing agents because of their particularly high polishing promoting action.
- the present invention also provides a polishing method in which a metal film containing copper is polished using the above-described abrasive for polishing copper to remove at least a part of the metal film.
- the above polishing method can achieve both high polishing rate and smooth polishing, it can be suitably applied to the metal film having a maximum thickness of 5 ⁇ m or more, particularly 10 ⁇ m or more.
- the “maximum thickness of the metal film” refers to the maximum thickness of the metal film in the portion to be polished, and the thickness of the metal film in the recess when the metal film is formed on the recess in the substrate. Does not include.
- the polishing rate for the metal film can be set to 30000 mm / min or more.
- the copper polishing abrasive of the present invention exhibits a significantly faster polishing rate for copper than a normal abrasive.
- an abrasive having a polishing rate for copper exceeding 30000 mm / min can be obtained, so it is optimal for applications that polish copper in a large amount in a short time, such as high-performance wiring board applications and TSV applications.
- An abrasive for polishing copper and a polishing method using the same can be provided.
- polishing agent for copper polishing of this invention while being able to grind
- FIG. 5 is a first process diagram showing a method of using the abrasive according to one embodiment of the present invention when used for VIA-LAST.
- FIG. 6 is a second process diagram showing a method of using the abrasive according to one embodiment of the present invention when used for VIA-LAST.
- FIG. 6 is a third process diagram showing a method of using the abrasive according to one embodiment of the present invention when used for VIA-LAST.
- the polishing slurry for copper polishing (hereinafter simply referred to as “polishing agent”) according to the first embodiment of the present invention satisfies the condition (i). That is, the abrasive according to the first embodiment includes (A) an inorganic acid, (B) an amino acid, (C) a protective film forming agent, (D) abrasive grains, (E) an oxidizing agent, and (F ) Water, the content of the component (A) is 0.08 mol / kg or more, the content of the component (B) is 0.20 mol / kg or more, and the content of the component (C) is 0.00. The ratio of the content (mol / kg) of the component (A) to the content (mol / kg) of the component (C) is 2.00 or more.
- the polishing rate can be improved to some extent even when each of the component (A) or the component (B) is used alone, in this case, the effect of improving the polishing rate commensurate with the content cannot be obtained.
- polishing agent which concerns on 1st Embodiment, (A) component and (B) component are used together, and also by making those content into the said specific amount, the grinding
- the abrasive according to the first embodiment is necessary for obtaining a predetermined polishing rate improvement effect as compared with the case where the component (A) or the component (B) is used alone. It has the effect that content of (A) component and (B) component which can be reduced can be reduced.
- the use of the component (C) has the effect of suppressing the etching of copper by forming a protective film on the copper surface, but in general, the polishing rate may be suppressed. It was.
- rate is made into the high level by using together the specific amount of the said (A) component and (B) component, and using (C) component specific amount. While maintaining, the effect of suppressing the etching rate can be obtained.
- polishing agent according to the first embodiment can improve the polishing rate is not necessarily clear, but the present inventors speculate as follows. That is, a “reaction layer” containing the component (C) and copper ions is formed on the copper surface by the action of the component (C) and the component (A). Furthermore, it is considered that the component (B) is chelated to copper ions so that the reaction layer is more easily removed and polishing is promoted.
- the pH of the abrasive according to the first embodiment is preferably in the range of 1.5 to 4.0 in that the polishing rate for copper by CMP is large and the copper film is not corroded. If the pH is 1.5 or more, the surface roughness of the copper film tends to be reduced, and from the same viewpoint, the pH is more preferably 2.0 or more. When the pH is 4.0 or less, there is a tendency that the polishing rate by CMP increases to become a more practical abrasive. From the same viewpoint, the pH is more preferably 3.5 or less, and 3.0 or less. Further preferred.
- the abrasive according to the first embodiment is a pH buffer solution containing an inorganic acid as the component (A).
- Inorganic acids are generally strong acids, and if a large amount of inorganic acid is contained, the pH is lowered, and it is difficult to adjust the pH to a predetermined range (for example, a range of 1.5 to 4.0).
- the abrasive according to the first embodiment contains an amino acid as the component (B) in addition to the inorganic acid, and the abrasive is adjusted by adjusting the contents of the components (A) and (B).
- a pH buffer solution having a pH within a predetermined range for example, a range of 1.5 to 4.0
- the pH may be adjusted by the amount of constituents of the abrasive (for example, inorganic acid or amino acid) added.
- examples of such a pH adjuster include monovalent inorganic acids such as hydrochloric acid and nitric acid, bases such as ammonia, sodium hydroxide, and tetramethylammonium hydroxide. These can be used alone or in combination of two or more.
- the pH is in the desired range without including the pH adjusting agent, it is not necessary to contain the pH adjusting agent.
- the said monovalent inorganic acid as a pH adjuster is not contained in the said (A) component.
- the pH of the abrasive according to the first embodiment can be measured with a pH meter (for example, model number PH81 manufactured by Yokogawa Electric Corporation). The pH was calibrated at two points using a standard buffer (phthalate pH buffer pH: 4.01 (25 ° C.), neutral phosphate pH buffer pH 6.86 (25 ° C.)). The value after the electrode is put into an abrasive and stabilized after 2 minutes or more is adopted.
- a pH meter for example, model number PH81 manufactured by Yokogawa Electric Corporation
- the component (A) is a divalent or higher valent inorganic acid (non-monovalent inorganic acid), and any known one can be used without particular limitation.
- Divalent acids such as sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, telluric acid, tungstic acid, phosphonic acid, trivalent acids such as phosphoric acid, phosphomolybdic acid, phosphotungstic acid, vana
- a strong acid (defined as an acid having a pKa of 0 or less; the same shall apply hereinafter) is preferable in that the polishing rate by CMP is further increased.
- the strong acid include sulfuric acid, chromic acid, phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, and silicotungstic acid, and the polishing rate by CMP is further increased, and it is easier to obtain. Sulfuric acid is more preferable.
- a weak acid (defined as an acid having a pKa exceeding 0. The same shall apply hereinafter) is preferable.
- weak acids include carbonic acid, molybdic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, telluric acid, tungstic acid, phosphonic acid, phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, and vanadic acid.
- phosphoric acid is preferred. In terms of achieving both a high polishing rate and a high surface roughness, it is preferable to use the strong acid and the weak acid in combination. In this respect, a mixture of sulfuric acid and phosphoric acid is particularly preferable.
- the content of the component (A) is 0.08 mol / kg or more, preferably 0.09 mol / kg or more, more preferably 0.1 mol / kg or more with respect to the total amount of the abrasive, in terms of further excellent polishing rate. It is more preferable that The content of the component (A) is 1.0 mol / kg or less in terms of suppressing the increase in the content of the component (A) because the polishing rate tends not to increase even if the component (A) is added more than a certain amount. It is preferable that it is 0.8 mol / kg or less.
- the component (B) is an amino acid used for the purpose of adjusting pH and dissolving copper.
- a component (B) is not particularly limited as long as it is an amino acid that is slightly soluble in water.
- glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid examples thereof include at least one selected from glutamic acid, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, and oxyproline. These can be used alone or in combination of two or more.
- an amino acid having a pKa of 2 to 3 because it is easy to adjust the pH of the abrasive (for example, 1.5 to 4.0).
- glycine, alanine, valine, leucine, isoleucine, serine, threonine, methionine, aspartic acid, glutamic acid, lysine, arginine, tryptophan and the like are preferable.
- glycine is more preferable in that the effect of improving the polishing rate is high and the cost is low.
- pKa refer to the Chemical Handbook, Basic Edition II (5th revised edition, Maruzen Co., Ltd.).
- the content of the component (B) is 0.20 mol / kg or more and preferably 0.25 mol / kg or more with respect to the total amount of the abrasive in terms of further improving the polishing rate.
- the content of the component (B) is 2.0 mol / kg or less in that the increase in the content of the component (B) is suppressed because the polishing rate does not increase even when the component (B) is added in a certain amount or more. It is preferable that it is 1.8 mol / kg or less.
- the protective film forming agent as the component (C) refers to a substance having an action of forming a protective film on the copper surface, and is also a substance called an anticorrosive or an inhibitor.
- the protective film forming agent is considered to constitute a “reaction layer” that is removed during polishing, and forms a “protective film” to prevent copper from being polished. Not limited to.
- component (C) As long as it has the water solubility effective in order to exhibit the addition effect of a protective film formation agent, a conventionally well-known substance can be especially used without a restriction
- the component (C) include nitrogen-containing compounds such as quinaldic acid, anthonylic acid, salicylaldoxime, triazole compounds, imidazole compounds, pyrazole compounds, and tetrazole compounds.
- a nitrogen-containing heterocyclic compound is preferable, and a triazole compound is particularly preferable. These can be used alone or in combination of two or more.
- triazole compound examples include triazole derivatives such as 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole; benzotriazole; 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxyl (-1H-) benzotriazole, 4-carboxyl (-1H-) benzotriazole methyl ester, 4-carboxyl (-1H-) benzotriazole butyl ester, 4-carboxyl (-1H-) benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl] [1,2, 4-to Azotril-1-methyl] [2-ethylhexyl] amine, tolyltriazole, naphthotriazole, bis [(1-benzotriazo
- imidazole compound examples include 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4- Examples include methylimidazole, 2-undecylimidazole, 2-aminoimidazole and the like.
- Examples of the pyrazole compound include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole and the like.
- tetrazole compounds include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 1- (2-diaminoethyl) -5-mercaptotetrazole and the like. Can be mentioned.
- the content of the component (C) is 0.02 mol / kg or more, preferably 0.025 mol / kg or more with respect to the total amount of the abrasive, in that the surface roughness of the metal can be further reduced. More preferably, it is 0.03 mol / kg or more.
- the content of the component (C) is 0.3 mol / kg or less in terms of suppressing the increase in the content of the component (C) because the polishing rate tends not to increase even if the component (C) is added in a certain amount or more. It is preferable that it is 0.25 mol / kg or less.
- the ratio of the content (mol / kg) of the component (A) to the content (mol / kg) of the component (C) is excellent in the polishing rate. In that respect, it is 2.00 or more. Furthermore, from the viewpoint of obtaining an abrasive having an excellent polishing rate, the ratio is preferably 2.30 or more, more preferably 2.50 or more, and even more preferably 2.80 or more. The ratio is preferably 12 or less, and more preferably 10 or less, from the viewpoint of further suppressing an increase in surface roughness.
- the component (D) component is not particularly limited, and examples thereof include inorganic abrasive grains such as silica, alumina, zirconia, ceria, titania and silicon carbide, and organic abrasive grains such as polystyrene, polyacryl and polyvinyl chloride. .
- silica and alumina are preferable because the dispersion stability in the abrasive is good, and the number of scratches (scratches) generated by CMP is small, and the particle size can be easily controlled. In view of excellent polishing characteristics, colloidal silica and colloidal alumina are more preferable.
- Colloidal silica is known for its production by hydrolysis of silicon alkoxide or ion exchange of sodium silicate.
- a method for producing colloidal alumina by hydrolysis of aluminum nitrate is known.
- the said (D) component can be used individually or in combination of 2 or more types.
- abrasive grains having an average particle size of 100 nm or less are preferable in that the polishing rate is further excellent and the surface roughness after polishing is low, and colloidal silica having an average particle size of 100 nm or less and More preferred is at least one abrasive selected from colloidal alumina.
- the “average particle size” of the particles refers to the value of D50 (median diameter of volume distribution, cumulative median value) when a copper polishing abrasive is measured with a laser diffraction particle size distribution meter.
- the content of the component (D) is preferably 0.1% by mass or more with respect to the total amount of the abrasive in terms of sufficiently obtaining a physical grinding action and further increasing the polishing rate, and 0.2% by mass. % Or more is more preferable. Further, from the viewpoint of suppressing the increase in the polishing rate even when the polishing rate is saturated and the component (D) is added more than a certain amount, the component (D) is suppressed from the viewpoint of suppressing the aggregation of abrasive grains and the increase in polishing scratches.
- the content of is preferably 10% by mass or less, and more preferably 5% by mass or less.
- any oxidizing agent having an oxidizing action on copper can be used without particular limitation.
- the component (E) include hydrogen peroxide (H 2 O 2 ), persulfates such as persulfuric acid, ammonium persulfate, and potassium persulfate, periodic acid, potassium periodate, and the like. In view of further excellent speed, at least one selected from hydrogen peroxide, persulfuric acid and persulfate is preferable.
- the said oxidizing agent can be used individually or in combination of 2 or more types.
- the content of the component (E) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more with respect to the total amount of the abrasive, in that a better polishing rate is easily obtained. preferable.
- the content of the component (E) is 20% by mass or less. It is preferably 15% by mass or less.
- the oxidizing agent may reduce the stability of the polishing agent, when it is necessary to store the polishing agent for a long period (for example, one month or more), an oxidizing agent aqueous solution and an oxidizing agent other than the oxidizing agent may be used. It is preferable to store separately from the component abrasive material and mix on the polishing platen immediately before or during polishing.
- ((F) component water
- polishing agent Deionized water, ion-exchange water, ultrapure water, etc. are preferable.
- the content of the component (F) in the abrasive may be the remainder of the content of other components, and is not particularly limited as long as it is contained in the abrasive.
- the abrasive may contain, in addition to the above-described components, materials generally used for CMP abrasives such as dispersants and colorants, as long as the effects of the abrasive are not impaired.
- the abrasive according to the first embodiment includes (A) inorganic acid, (B) amino acid, (C) protective film forming agent, (D) abrasive grains, (E) oxidizing agent, and (F) water.
- the amount of potassium hydroxide required to increase the pH of the abrasive containing at least 4 to 4 is 0.10 mol or more per kg of abrasive. Is preferably added.
- the reason why the neutralization titration equivalent of inorganic acid with potassium hydroxide is specified is as follows. That is, copper contained in the metal film polished by the abrasive according to the first embodiment dissolves as cations in the abrasive when polished.
- the amount of the inorganic acid added is small and the polishing agent does not have a pH buffering action, it is considered that hydrogen ions are consumed due to dissolution of copper and the pH of the polishing agent is increased, resulting in a decrease in the polishing rate.
- the amount of inorganic acid in the polishing agent is equivalent to 0.10 mol / kg or more by neutralization titration with potassium hydroxide, although there are some variations depending on the polishing rate and the polishing agent flow rate during polishing.
- the amount is preferably 0.12 mol / kg or more, more preferably 0.15 mol / kg or more, and particularly preferably 0.20 mol / kg or more.
- the upper limit of the neutralization titration equivalent with potassium hydroxide can be set to, for example, 2.0 mol / kg.
- the neutralization titration equivalent of the abrasive can be determined as follows. That is, a “neutralization titration measurement test solution” having a composition obtained by removing a pH adjuster (for example, an acidic component such as an aqueous hydrochloric acid solution or an alkaline component such as an aqueous ammonia solution) from the composition of the abrasive is prepared. Next, 50 ml of the test solution is put into a beaker of about 100 ml, and a 20% strength aqueous potassium hydroxide solution is dropped while stirring at 80 rpm with a stirrer. When the pH value becomes 4.0, potassium hydroxide is added. The neutralization titration equivalent can be calculated from the added amount of the aqueous solution.
- a pH adjuster for example, an acidic component such as an aqueous hydrochloric acid solution or an alkaline component such as an aqueous ammonia solution
- the composition of the abrasive is unknown, the composition and concentration of the abrasive can be examined by ion chromatography analysis with a measurement accuracy of 10 ⁇ 8 g or more. Therefore, the test solution can be prepared from the measured value, and the neutralization titer can be measured.
- the above-mentioned abrasive can be polished at a high speed, for example, when an 8 inch (20.3 cm) disk-shaped substrate is set at a flow rate of the abrasive of around 200 ml / min.
- neutralization titration equivalent of inorganic acid with potassium hydroxide 1 kg of a test solution having a composition in which an alkali component and an organic acid described later are removed from an abrasive is prepared separately, and the pH value of this test solution is 4 Defined as the number of moles of potassium hydroxide required to increase to
- the abrasive for polishing copper (hereinafter simply referred to as “abrasive”) according to the second embodiment satisfies the condition (ii). That is, the abrasive according to the second embodiment includes (A) inorganic acid, (B) amino acid, (C) protective film forming agent, (D) abrasive grains, (E) oxidizing agent, and (F ) Water and (G) at least one selected from organic acids and acid anhydrides thereof, the content of component (A) is 0.08 mol / kg or more, and the content of component (B) is 0.00. 20 mol / kg or more, and the content of component (C) is 0.02 mol / kg or more.
- the ratio of the content (mol / kg) of the component (A) to the content (mol / kg) of the component (C) is not necessarily 2.00 or more.
- the abrasive having the ratio of 2.00 or more will be described later as an abrasive according to the third embodiment.
- the polishing rate can be improved to some extent even if the component (A), the component (B) and the component (G) are used alone or two of them can be selected and used. It is not possible to obtain an effect of improving the polishing rate commensurate with.
- polishing agent which concerns on 2nd Embodiment, combining (A) component, (B) component, and (G) component, and also making those content into the said specific amount, The polishing rate can be dramatically improved.
- the abrasive according to the second embodiment is compared with the case where the component (A), the component (B) and the component (G) are used alone or two of them are selected and used. And it has the effect that the total content of the said chemical component required in order to acquire the improvement effect of a predetermined
- polishing agent when the abrasive
- the use of the protective film forming agent as component (C) has the effect of suppressing the etching of copper by forming a protective film on the copper surface, but generally suppresses the polishing rate.
- polishing agent which concerns on 2nd Embodiment, it polishes by using together the specific amount of the said (A) component, (B) component, and (G) component, and (C) component using specific amount. While maintaining the speed at a high level, the effect of suppressing the etching speed can be obtained.
- the polishing agent according to the second embodiment can improve the polishing rate is not necessarily clear, but the present inventors speculate as follows. That is, the “reaction layer” containing the (C) component and the copper ions is formed on the copper surface by the action of the (A) component, the (C) component, and the (G) component. Furthermore, it is considered that the component (B) is chelated to copper ions so that the reaction layer is more easily removed and polishing is promoted.
- each polishing process proceeds in conjunction with other polishing processes. Therefore, even if only one type of component (A), (B), (C) and (G) is increased, the polishing process by other components becomes a bottleneck (rate-limiting process), It is considered that the polishing rate is not improved efficiently.
- each polishing process is promoted by using specific amounts of the (A) component, the (B) component, the (C) component, and the (G) component, and the polishing rate is made efficient. It is thought that it can be improved.
- polishing agent which concerns on 2nd Embodiment contains at least 1 type chosen from an organic acid and its acid anhydride as (G) component.
- the component (G) component for example, formic acid, acetic acid, glyoxylic acid, pyruvic acid, lactic acid, mandelic acid, vinyl acetic acid, 3-hydroxy entangling acid, oxalic acid, maleic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, Phthalic acid, tartaric acid, fumaric acid, malic acid, succinic acid, glutaric acid, oxaloacetic acid, citric acid, hemimellitic acid, trimellitic acid, trimesic acid, melittic acid, isocitric acid, aconitic acid, oxalosuccinic acid, propionic acid, butyric acid, Isobutyric acid, valeric acid, isovaleric acid, pi
- the component (G) at least one selected from an organic acid having two carboxyl groups and an acid anhydride having a pKa of 2.7 or less, and an organic acid having three or more carboxyl groups is preferable. .
- a higher polishing rate can be obtained by strengthening the interaction with copper and efficiently chelating with copper ions.
- the organic acid having two carboxyl groups conventionally known substances can be used without particular limitation as long as they have effective water solubility in order to exert their effects.
- the pKa of the organic acid having two carboxyl groups is 2.7 or less, preferably 2.6 or less, and more preferably 2.5 or less.
- pKa refer to the Chemical Handbook, Basic Edition II (5th revised edition, Maruzen Co., Ltd.).
- Examples of the organic acid having two carboxyl groups and having a pKa of 2.7 or less include oxalic acid, maleic acid, malonic acid, and oxaloacetic acid.
- Examples of the acid anhydride of an organic acid having two carboxyl groups and a pKa of 2.7 or less include maleic anhydride.
- these organic acids and acid anhydrides thereof oxalic acid, maleic acid, malonic acid, and maleic anhydride are preferable in that the polishing rate by CMP can be further improved.
- organic acid having three or more carboxyl groups examples include citric acid, hemimellitic acid, trimellitic acid, trimesic acid, melittic acid, isocitric acid, aconitic acid, oxalosuccinic acid and the like.
- citric acid is preferable in that not only the polishing rate of copper is further improved, but also coloring of the polishing cloth after polishing can be suppressed.
- organic acids and acid anhydrides thereof can be used alone or in combination of two or more.
- the content of the component (G) is preferably 0.02 mol / kg or more and more preferably 0.03 mol / kg or more with respect to the total amount of the polishing agent in that the polishing rate is further improved.
- the content of the component (G) is 1.0 mol / kg in that the polishing rate tends not to increase even if the component (G) is added in a certain amount or more, so that the increase in the content of the component (G) is suppressed. Or less, more preferably 0.8 mol / kg or less.
- the abrasive according to the second embodiment has an amount of potassium hydroxide required to increase the pH of the composition obtained by removing the component (G) from the abrasive to 4. It is preferable to add an inorganic acid such that the neutralization titration equivalent) is 0.10 mol or more per kg of the composition.
- polishing agent containing an organic acid can be calculated
- a pH adjuster for example, an acidic component such as a hydrochloric acid aqueous solution or an alkaline component such as an aqueous ammonia solution
- the neutralization titration equivalent can be calculated from the added amount of the aqueous solution.
- the reason for prescribing the neutralization titration equivalent of inorganic acid with potassium hydroxide and the neutralization titration equivalent of potassium hydroxide are the same as in the first embodiment.
- the abrasive for polishing copper (hereinafter simply referred to as “abrasive”) according to the third embodiment satisfies both the above conditions (i) and (ii). That is, the abrasive
- the present inventors include at least one component (G) selected from an organic acid having two carboxyl groups and a pKa of 2.7 or less, an acid anhydride thereof, and an organic acid having three or more carboxyl groups.
- an abrasive containing (A) component, (B) component, (C) component (hereinafter, the generic name of these four components is sometimes referred to as “chemical (chemical) component”), It was found that an abrasive capable of polishing copper more smoothly at a higher speed can be obtained by controlling the type and content.
- the present inventors increase the content of each of the above chemical components (for example, increase about twice or more of the conventional amount), and at least one selected from a specific organic acid and acid anhydride thereof. By using it, it discovered that the polishing rate with respect to copper improved more than expected, maintaining smoothness.
- the component (G) is selected from an organic acid having two carboxyl groups and a pKa of 2.7 or less and an acid anhydride thereof, and an organic acid having three or more carboxyl groups. It is preferable to use at least one kind.
- the other components of the abrasive according to the third embodiment are the same as those of the abrasive according to the first and second embodiments, and a description thereof will be omitted.
- the neutralization titration equivalent with potassium hydroxide is measured in the same manner as in the second embodiment.
- Abrasive storage method There is no restriction
- it may be stored as a one-component abrasive containing all of the components, and at least the components of the abrasive are mixed with each other so as to be the CMP abrasive according to each of the above embodiments (the first solution).
- additive liquid second liquid
- the first embodiment is a two-component abrasive, for example, a slurry containing (D) abrasive grains and (F) water, (A) an inorganic acid, (B) an amino acid, and (C) a protective film forming agent. And (F) an additive solution containing water.
- the polishing method according to the present embodiment is characterized in that a metal film containing copper is polished using the abrasive according to each of the above embodiments, and at least a part of the metal film is removed. More specifically, the polishing method according to the present embodiment polishes the metal film containing copper using the laminating step of laminating the metal film containing copper on the substrate and the abrasive according to each of the above embodiments. And a polishing step for removing a part of the metal film.
- the “metal film containing copper” may be a metal film made of pure copper, a metal film containing copper (for example, a copper alloy film), a laminated film of these metal films and other metals, or the like. .
- the polishing agent according to each of the above embodiments has a feature that the polishing rate for a metal film containing copper is extremely high compared to a conventional polishing agent for copper polishing. It can be particularly suitably used for polishing a thick metal film in a production process of a representative high performance / fine wiring board. More specifically, the metal film containing copper to be polished can be particularly preferably used when polishing a substrate having a thickness of, for example, 4 ⁇ m or more. Moreover, since the abrasive
- a through silicon via (TSV) forming process can be exemplified.
- TSV through silicon via
- Various methods for forming a TSV have been proposed.
- VIA-LAST in which a via is formed after an element is formed.
- a method of using the abrasive according to each of the above embodiments for VIA-LAST will be described with reference to process diagrams (schematic cross-sectional views) of FIGS.
- FIG. 1 is a schematic cross-sectional view showing a process of forming a copper layer 4 on a silicon substrate 1.
- an element 2 is formed at a predetermined position on the silicon substrate 1.
- a recess 3 for forming a through via is formed by a method such as plasma etching.
- a copper layer 4 is formed by laminating copper so as to fill the recess 3 by a method such as sputtering or electrolytic plating, thereby obtaining a substrate 100 having a structure as shown in FIG.
- FIG. 2 is a schematic cross-sectional view showing a process of polishing the substrate 100 thus formed and forming bumps 5 on one side. While supplying the above-described abrasive between the surface of the copper layer 4 in FIG. 2A and a polishing cloth (not shown), the copper layer until the element 2 is exposed as shown in FIG. 2B. 4 is polished.
- the copper layer 4 is polished by relatively moving the polishing platen and the substrate 100.
- a metal or resin brush may be used instead of the polishing cloth.
- a polishing platen that is connected to a motor or the like that can change the number of rotations and can be attached to the polishing cloth, and a holder that can hold a substrate to be polished
- a general polishing apparatus can be used.
- the polishing conditions are not limited, but the rotation speed of the polishing surface plate is preferably a low rotation of 200 rpm or less so that the substrate does not jump out.
- the pressing pressure (polishing pressure) of the substrate having the surface to be polished to the polishing cloth is preferably 1 to 100 kPa. In order to satisfy the uniformity of the CMP rate within the surface to be polished and the flatness of the pattern, More preferably, it is 5 to 50 kPa.
- an abrasive is continuously supplied to the polishing cloth with a pump or the like. Although there is no restriction
- the substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like.
- a conditioning process of the polishing cloth before polishing For example, the polishing cloth is conditioned with a liquid containing at least water using a dresser with diamond particles. Subsequently, it is preferable to perform a CMP polishing process using the polishing method according to the present embodiment, and further add a substrate cleaning process.
- bumps 5 are formed on the exposed surface portion of the copper layer 4 by a method such as electrolytic plating to obtain a substrate 200 having the bumps 5 on one side.
- Examples of the material of the bump 5 include copper.
- FIG. 3 is a schematic cross-sectional view showing a process of forming bumps 6 on the other surface.
- the surface of the silicon substrate 1 where the bumps 5 are not formed is polished by a method such as CMP to obtain a copper layer. 4 is exposed (FIG. 3B).
- bumps 6 are formed by a method similar to the method for forming bumps 5 to obtain a substrate 300 on which TSVs are formed (FIG. 3C).
- Experimental Examples 1-7 to 1-8 correspond to the first embodiment of the present invention
- Experimental Example 1-6 corresponds to the second embodiment of the present invention
- Experimental Examples 1-1 to 1-5 and 1-9 correspond to the third embodiment of the present invention.
- Example 1-1 Colloidal with an average particle size of 70 nm prepared by hydrolysis of 10 g of sulfuric acid with a concentration of 96%, 10 g of phosphoric acid with a concentration of 85%, 50 g of glycine, 10 g of benzotriazole (BTA), 10 g of oxalic acid, and tetraethoxysilane in an ammonia solution.
- 50 g of silica solid content 20%
- a 25% aqueous ammonia solution was added to adjust the pH of the solution to 2.6, and pure water was further added to make the total amount 700 g.
- Example 1-2 An abrasive 1-2 was produced in the same manner as in Example 1-1 except that 10 g of malonic acid was added instead of oxalic acid.
- Example 1-3 An abrasive 1-3 was produced in the same manner as in Example 1-1 except that 10 g of maleic acid was added instead of oxalic acid.
- Example 1-4 Abrasive agent 1-4 was produced in the same manner as in Experimental Example 1-1, except that 50 g of alanine was added instead of glycine.
- Example 1-5 An abrasive 1-5 was produced in the same manner as in Example 1-1 except that 50 g of serine was added instead of glycine.
- Example 1-6 An abrasive 1-6 was produced in the same manner as in Example 1-1, except that the amounts of sulfuric acid and phosphoric acid to be added were each 5 g.
- Example 1-7 Abrasive 1-7 was prepared in the same manner as in Example 1-1 except that oxalic acid was not added.
- Example 1-8 In addition to not adding oxalic acid, abrasive 1-8 was prepared in the same manner as in Example 1-1, except that the amount of sulfuric acid was increased to 20 g.
- Example 1-9 Abrasive 1-9 was produced in the same manner as in Experimental Example 1-1, except that malic acid was added instead of oxalic acid.
- Example 1-10 Abrasive X1-1 was prepared in the same manner as in Experimental Example 1-1 except that sulfuric acid and phosphoric acid were not added and the amount of oxalic acid was 30 g.
- Example 1-11 An abrasive X1-2 was produced in the same manner as in Example 1-1 except that the amount of sulfuric acid added was 1 g and the amount of phosphoric acid was 5 g.
- the neutralization titration equivalent was determined as follows. That is, 50 ml of the test solution is placed in a 100 ml beaker, and a 20% strength aqueous potassium hydroxide solution is added dropwise while stirring at 80 rpm with a stirrer. The neutralization titration equivalent was calculated from the amount.
- a substrate purchased from Advantech in which a copper film having a thickness of 20 ⁇ m was formed on a silicon substrate having a diameter of 8 inches (20.3 cm) ( ⁇ ) was prepared. Using this substrate, CMP polishing was performed while dripping the polishing agents 1-1 to 1-9 and the polishing agents X1-1 to X1-2 onto a polishing cloth affixed to a surface plate of a polishing apparatus.
- polishing conditions are as follows. Polishing equipment: Surface plate size is 600mm ( ⁇ ), Rotary type Polishing cloth: Polyurethane resin with closed cells (IC-1010, manufactured by Rohm and Haas) Polishing pressure: 32kPa Surface plate / head rotation speed: 93/87 rpm Abrasive flow rate: 200ml / min
- polishing rate The difference in film thickness before and after CMP of the substrate was calculated from the change in sheet resistance.
- a resistivity measuring device Model RT-7 manufactured by Napson Co. As a measuring device, a resistivity measuring device Model RT-7 manufactured by Napson Co. was used. As the resistance value, an average value of 77 points in the diameter direction of the wafer (excluding a portion of 5 mm from the edge) was used.
- Surface roughness (arithmetic average roughness Ra): The surface roughness of the copper film after polishing was measured with an AFM (atomic force microscope: SPA-400, manufactured by SII Nano Technology). The measurement was performed in a 5 ⁇ m ⁇ 5 ⁇ m area range at a location 50 mm away from the center of the substrate in the radial direction.
- Table 1 shows the constituents of abrasives 1-1 to 1-9 and X1-1 to X1-2, the pH of each abrasive, the neutralization titration equivalent with potassium hydroxide, and the evaluation results of the polishing test.
- the "total chemical component” in the table means the total content of the component (A), the component (B), the component (C), and the component (G).
- each of the abrasives in Experimental Examples 1-1 to 1-9 exhibited good polishing rate and surface roughness.
- the abrasive 1-1 of Experimental Example 1-1 which has a composition obtained by adding oxalic acid to the abrasive of Experimental Example 1-7, has a polishing rate while maintaining the surface roughness as compared with Experimental Example 1-7.
- the polishing agent X1-1 of Experimental Example 1-10 which has a composition obtained by replacing sulfuric acid and phosphoric acid with oxalic acid in the polishing agent of Experimental Example 1-1, maintains the surface roughness as compared with Experimental Example 1-1. However, the polishing rate was greatly reduced.
- the polishing agent 1-1 of Experimental Example 1-1 which has a composition in which a part of sulfuric acid in the polishing agent of Experimental Example 1-8 is replaced with oxalic acid, has surface roughness and polishing compared to Experimental Example 1-8. Increased speed. In Experimental Example 1-8, the speed exceeded 30000 kg / min as in Experimental Example 1-7.
- the polishing agent of Experimental Example 1-8 in which 10 g of sulfuric acid is further added to Experimental Example 1-7, has a polishing rate of 37000 g / min
- Experimental Example 1-7 in contrast, the polishing agent of Experimental Example 1-1, which was a system to which 10 g of oxalic acid was added, achieved a polishing rate of 60000 ⁇ / min. Thereby, it can confirm that combining (A) component and (G) component is effective for polishing rate improvement.
- the abrasive X1-2 of Experimental Example 1-11 in which the neutralization titration equivalent is less than 0.10 mol / kg because the amount of the component (A) is small relative to the abrasive 1-1 of Experimental Example 1-1, The polishing rate was significantly reduced as compared with Experimental Example 1-1.
- the type of component (A) and the amounts of component (A) and component (G) are the same as in Experimental Example 1-9, but Experimental Example 1-1 in which the pKa of Component (G) is 2.7 or less.
- the polishing agent 1-1 improved the polishing rate while maintaining the surface roughness as compared with Experimental Example 1-9.
- an abrasive having a polishing rate for copper of more than 30000 / min, more preferably more than 50000 / min, is optimal for use in polishing copper in a large amount in a short time, for example, TSV formation.
- Example 2-2 Abrasive agent 2--similar to Experimental Example 2-1, except that the amount of sulfuric acid was 7.7 g, the amount of phosphoric acid was 8.6 g, the amount of glycine was 30.8 g, and the amount of benzotriazole was 6.0 g. 2 was produced.
- Example 2-3 Abrasive agent 2-in the same manner as in Experimental Example 2-1, except that the amount of sulfuric acid was 10.2 g, the amount of phosphoric acid was 11.5 g, the amount of glycine was 40.5 g, and the amount of benzotriazole was 8.0 g. 3 was produced.
- Example 2-4 An abrasive 2-4 was produced in the same manner as in Experimental Example 2-1, except that 28.4 g of serine was used instead of glycine.
- Example 2-5 Abrasive X2-like in the same manner as in Experimental Example 2-1, except that the amount of sulfuric acid was 2.6 g, the amount of phosphoric acid was 2.9 g, the amount of glycine was 10.5 g, and the amount of benzotriazole was 2.0 g. 1 was produced.
- Example 2-6 Abrasive X2-2 was prepared in the same manner as in Experimental Example 2-1, except that the amount of glycine was 10.5 g and the amount of benzotriazole was 2.0 g.
- Example 2--7 Abrasive X2-like in the same manner as in Experimental Example 2-1, except that the amount of sulfuric acid was 10.2 g, the amount of phosphoric acid was 11.5 g, the amount of glycine was 10.5 g, and the amount of benzotriazole was 2.0 g. 3 was produced.
- Experimental Example 2-8) Experimental Example 2-1 except that the amount of sulfuric acid was 2.6 g, the amount of phosphoric acid was 2.9 g, the amount of benzotriazole was 2.0 g, and 36% hydrochloric acid was used instead of the aqueous ammonia solution for pH adjustment. Similarly, abrasive X2-4 was produced.
- Example 2-9 Abrasive X2-5 was prepared in the same manner as in Experimental Example 2-1, except that the amount of sulfuric acid was 2.6 g, the amount of phosphoric acid was 2.9 g, and the amount of glycine was 10.5 g.
- Example 2-10 Abrasive X2-6 was prepared in the same manner as in Experimental Example 2-1, except that the amount of sulfuric acid was 2.6 g, the amount of phosphoric acid was 2.9 g, and 36% hydrochloric acid was used instead of the aqueous ammonia solution for pH adjustment. Produced.
- Example 2-11 Abrasive X2-7 was prepared in the same manner as in Experimental Example 2-1, except that the amount of glycine was changed to 0 g.
- Example 2-12 Abrasive X2-8 was prepared in the same manner as in Experimental Example 2-1, except that the amount of glycine was 10.5 g and the amount of benzotriazole was 4.0 g.
- Example 2-13 Abrasive X2-9 was produced in the same manner as in Experimental Example 2-1, except that the amount of benzotriazole was 2.0 g.
- Example 2-14 Abrasive X2-10 was produced in the same manner as in Experimental Example 2-1, except that the amount of benzotriazole was 8.0 g.
- Test solutions for measuring neutralization titration were conducted in the same manner as in Experimental Examples 2-1 to 2-14 except that no 25% aqueous ammonia solution was added. To X2-10) were prepared. About each test liquid, the pH meter (Yokogawa Electric Corporation PH81) was used and the neutralization titration equivalent by potassium hydroxide was measured in a 25 degreeC thermostat.
- the neutralization titration equivalent was determined as follows. That is, 50 ml of the test solution is placed in a 100 ml beaker, and a 20% strength aqueous potassium hydroxide solution is added dropwise while stirring at 80 rpm with a stirrer. The neutralization titration equivalent was calculated from the amount.
- a substrate purchased from Advantech in which a copper film having a thickness of 20 ⁇ m was formed on a silicon substrate having a diameter of 8 inches (20.3 cm) ( ⁇ ) was prepared. Using this substrate, CMP polishing was performed while dripping the polishing agents 2-1 to 2-4 and the polishing agents X2-1 to X2-10 onto a polishing cloth affixed to a surface plate of a polishing apparatus.
- polishing conditions are as follows. Polishing equipment: Surface plate size is 600mm ( ⁇ ), Rotary type Polishing cloth: Polyurethane resin with closed cells (IC-1010, manufactured by Rohm and Haas) Polishing pressure: 32kPa Polishing surface plate / head rotation speed: 93/87 rpm Abrasive flow rate: 200ml / min
- polishing rate The difference in film thickness before and after CMP of the substrate was calculated from the change in sheet resistance.
- a resistivity measuring device Model RT-7 manufactured by Napson Co. was used as a measuring device.
- the average value of 77 points in the diameter direction of the wafer (excluding the 5 mm portion from the edge) was taken as the resistance value.
- Tables 2 and 3 show the constituents of the abrasives 2-1 to 2-4 and X2-1 to X2-10, the pH of each abrasive, the neutralization titration equivalent with potassium hydroxide, and the evaluation results of the polishing test. .
- the abrasive X2- of Experimental Example 2-5 in which the content of the component (A), the component (B), and the component (C) is smaller than the value of the present invention with respect to the abrasive 2-1 of Experimental Example 2-1.
- the polishing rate of 1 decreased.
- the abrasive X2-2 of Experimental Example 2-6 and Experimental Example 2-6 were the same as Experimental Example 2-5 except that only the content of component (A) was the same as that of Experimental Example 2-1.
- the polishing agent X2-3 of Experimental Example 2-7 in which the content of the component (A) was increased, although the polishing rate was slightly improved, the polishing rate was lower than that of Experimental Example 2-1. That is, it has been found that even if only the content of the component (A) is increased, the effect of improving the polishing rate is not great.
- the abrasive X2-4 and the protective film forming agent of Experimental Example 2-8 were the same as Experimental Example 2-5 except that only the content of glycine, an amino acid, was the same as that of Experimental Example 2-1.
- the polishing agent X2-5 in Experimental Example 2-9 which was the same as Experimental Example 2-5 except that only a certain benzotriazole was changed to the same content as in Experimental Example 2-1, was polished as compared with Experimental Example 2-5. The speed decreased, and the polishing speed also decreased for Experimental Example 2-1.
- the content of the component (B) and the component (C) is the same as the abrasive 2-1 of Experimental Example 2-1, but the content of the (A) component is smaller than the value of the present invention Experimental Example 2
- the polishing rate of ⁇ 10 abrasive X2-6 decreased.
- the content of the component (A) and the component (C) is the same as the abrasive 2-1 of Experimental Example 2-1, but the content of the (B) component is smaller than the value of the present invention Experimental Example 2
- the polishing rate of the polishing agent X2-7 of ⁇ 11 and the polishing agent X2-8 of Experimental Example 2-12 were decreased.
- the content of the component (A) and the component (B) is the same as the abrasive 2-1 of Experimental Example 2-1, but the content of the (C) component is smaller than the value of the present invention Experimental Example 2
- the polishing rate of ⁇ 13 abrasive X2-9 decreased.
- component (A), component (B), and component (C) are all higher than those of Experimental Example 2-5, but the content of component (A) (mol / kg) / component content of (C) The value of (mol / kg) was 1.49, and the polishing rate of the abrasive X2-10 in Experimental Example 2-14, which was lower than 2.00, was lower than that in Experimental Example 2-1.
- the polishing rates of Experimental Examples 2-6, 2-8, and 2-9 were increased or decreased as follows.
- the polishing rate increased by 3000 ⁇ / min.
- the decrease was 3000 kg / min, and only the content of the component (C) was made equivalent to that of Experimental Example 2-1.
- it decreased by 3000 kg / min.
- an abrasive exhibiting a significantly faster polishing rate than copper is obtained for copper.
- an abrasive having a polishing rate for copper exceeding 30000 mm / min is optimal for use in polishing copper in a large amount in a short time, for example, TSV formation.
- Experimental Example 3-8 corresponds to the first embodiment of the present invention
- Experimental Example 3-7 corresponds to the second embodiment of the present invention
- Experimental Examples 3-1 to 3-6, 3-9 to 3-10 correspond to the third embodiment of the present invention.
- Example 3-1 5.1 g of sulfuric acid with a concentration of 96%, 5.8 g of phosphoric acid with a concentration of 85%, 20.3 g of glycine, 4.0 g of benzotriazole (BTA), 5.4 g of oxalic acid, and colloidal with an average particle size of 70 nm as abrasive grains 50 g of silica (solid content: 20%) was added to 600 g of pure water to dissolve components other than colloidal silica. Further, a 25% aqueous ammonia solution was added to adjust the pH of the solution to 2.6, and pure water was further added to make the total amount 700 g. To this, 300 g of hydrogen peroxide solution (special grade reagent, 30% aqueous solution) was added to obtain a total amount of 1000 g of abrasive 3-1.
- BTA benzotriazole
- Example 3-2 An abrasive 3-2 was produced in the same manner as in Experimental Example 3-1, except that the content of oxalic acid was 14.0 g and the total amount of pure water was adjusted to 1000 g.
- Example 3-3 An abrasive 3-3 was prepared in the same manner as in Experimental Example 3-1, except that 7.0 g of maleic acid was used instead of 5.4 g of oxalic acid and the amount of pure water added was adjusted to 1000 g.
- Example 3-4 Abrasive 3-4 was prepared in the same manner as in Experimental Example 3-1, except that 5.9 g of maleic anhydride was used instead of 5.4 g of oxalic acid, and the amount of pure water added was adjusted to 1000 g.
- Example 3-5 An abrasive 3-5 was prepared in the same manner as in Experimental Example 3-1, except that 6.2 g of malonic acid was used instead of 5.4 g of oxalic acid, and the total amount of pure water was adjusted to 1000 g by adjusting the amount of pure water added.
- Example 3-6 Abrasive 3-6 was prepared in the same manner as in Experimental Example 3-1, except that 11.5 g of citric acid was used instead of 5.4 g of oxalic acid, and the total amount of pure water was adjusted to 1000 g.
- Example 3-7 Abrasive 3-7 was prepared in the same manner as in Experimental Example 3-1, except that the content of benzotriazole was 7.9 g and the amount of pure water was adjusted to a total amount of 1000 g.
- Example 3-8) Abrasive 3-8 was prepared in the same manner as in Experimental Example 3-1, except that oxalic acid was not added and the amount of pure water was adjusted to a total amount of 1000 g.
- Example 3-9 Abrasive 3-9 was prepared in the same manner as in Experimental Example 3-1, except that 9.0 g of tartaric acid was used instead of 5.4 g of oxalic acid and the total amount of pure water was adjusted to 1000 g.
- Example 3-10 Abrasive 3-10 was prepared in the same manner as in Experimental Example 3-1, except that malic acid was replaced with oxalic acid of 5.4 g and the amount of pure water was adjusted to 8.0 g and the total amount was adjusted to 1000 g.
- an abrasive X3-3 was produced.
- Abrasive X3-4 was produced in the same manner as in Experimental Example 3-11 except that the content of benzotriazole was 4.0 g and the total amount of pure water was adjusted to 1000 g by adjusting the amount of pure water added.
- An abrasive X3-5 was prepared in the same manner as in Experimental Example 3-11 except that 5.4 g of oxalic acid was further added as an organic acid, and the amount of pure water added was adjusted to a total amount of 1000 g.
- Test solutions for neutralization titration measurement were conducted in the same manner as in Experimental Examples 3-1 to 3-15 except that an organic acid and a 25% aqueous ammonia solution were not added.
- X3-1 to X3-5 were prepared. About each test liquid, the pH meter (Yokogawa Electric Corporation PH81) was used and the neutralization titration equivalent by potassium hydroxide was measured in a 25 degreeC thermostat.
- the neutralization titration equivalent was determined as follows. That is, 50 ml of the test solution is placed in a 100 ml beaker, and a 20% strength aqueous potassium hydroxide solution is added dropwise while stirring at 80 rpm with a stirrer. The neutralization titration equivalent was calculated from the amount.
- a substrate made by Global Net Co., Ltd. was prepared by forming a copper film having a thickness of 20 ⁇ m on a silicon substrate having a diameter of 12 inches (30.5 cm) ( ⁇ ). Using this substrate, CMP polishing was performed while dripping the polishing agents 3-1 to 3-10 and the polishing agents X3-1 to X3-5 onto a polishing cloth affixed to a surface plate of a polishing apparatus.
- polishing machine Polishing machine for CMP (product name: Reflexion, manufactured by Applied Materials)
- Polishing cloth Expanded polyurethane resin with closed cells (trade name: IC-1010, manufactured by Rohm and Haas) Polishing pressure: 32kPa Surface plate / head rotation speed: 60/55 rpm Abrasive flow rate: 300ml / min
- the polishing rate was calculated as follows. First, using a metal film thickness measuring instrument VR-120 (trade name) manufactured by Hitachi Kokusai Electric Engineering Co., Ltd., sheet resistance was measured at each of 81 locations on the copper film surface in the diameter direction of the substrate, and CMP Average values were calculated before and after polishing. And it converted from the difference of the average value before and behind grinding
- Tables 4 and 5 show the evaluation results of the constituents of abrasives 3-1 to 3-10 and abrasives X3-1 to X3-5, pH of each abrasive, neutralization titration equivalent with potassium hydroxide, and polishing rate. Shown in
- the polishing agent X3-2 is the same as the polishing agent X3-1 except that the content of the component (A) is the same as that of the polishing agent 3-1, and a slight polishing rate relative to the polishing agent X3-1. Although the improvement was observed, the polishing rate decreased with respect to the abrasive 3-1.
- the content of the component (B) is the same as that in the abrasive 3-1, and the same as that of the abrasive X3-1 except that the substance used for pH adjustment was changed. -1 and polishing agent X3-1, the polishing rate decreased.
- the content of the component (C) was the same as that in the abrasive X3-1 except that the content of the component (C) was the same as that in the abrasive 3-1, and the abrasive 3-1 and the abrasive X3-1 In contrast, the polishing rate decreased.
- the content of the component (G) was the same as that of the abrasive X3-1 except that the content of the component (G) was the same as that of the abrasive 3-1, but the polishing rate was higher than that of the abrasive 3-1. Declined.
- the polishing rate is 3000 ⁇ / min compared with the polishing agent X3-1. Increased.
- the polishing agent X3-3 that is the same as the polishing agent X3-1 except that the content of the component (B) is the same as that of the polishing agent 3-1, the polishing rate is 3000 min / min compared with the polishing agent X3-1. Diminished.
- the polishing rate is 3000 ⁇ / min compared with the polishing agent X3-1. Diminished.
- the polishing agent X3-5 that is the same as the polishing agent X3-1 except that the content of the component (D) is the same as that of the polishing agent 3-1, the polishing rate is 7000 ⁇ / min compared with the polishing agent X3-1. Increased.
- the polishing rate for the abrasive X3-1 when the contents of the component (A), the component (B), the component (C), and the component (G) are all equal to the abrasive 3-1, the polishing rate for the abrasive X3-1.
- the amount of increase is normally expected to be about 4000 kg / min, which is the sum of the increase / decrease of the polishing rate of the polishing agents X3-2 to X3-5 with respect to the polishing agent X3-1.
- the polishing rate of the abrasive 3-1 is increased by 23000 ⁇ / min with respect to the abrasive X3-1, and the contents of the components (A), (B), (C) and (D) are simultaneously increased.
- the polishing rate is improved by setting the content of the component (A) (mol / kg) / the content of the component (C) (mol / kg) to 2.00 or more while keeping within the predetermined range of the present invention. It was confirmed that the effect was high.
- the content of the component (A), the component (B) and the component (C) is within the predetermined range of the present invention, the content of the component (A) (mol / kg) / the content of the component (C) ( The polishing rate of the abrasive 3-1 was improved with respect to the abrasive 3-7 having a mol / kg) of less than 2.00.
- the content of the component (A), the component (B), and the component (C) is about twice that of the abrasive X3-1, but the abrasive 3-8 that does not contain the component (G) is polished.
- Agent 3-1 improved the polishing rate.
- the abrasive 3-9 containing tartaric acid having a pKa of 2.82 and the abrasive 3-10 containing malic acid having a pKa of 3.46 were used.
- the polishing rate was improved with the abrasive 3-1.
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
条件(i)保護膜形成剤の含有量(mol/kg)に対する無機酸の含有量(mol/kg)の比率(無機酸の含有量/保護膜形成剤の含有量)が、2.00以上であること。
条件(ii)研磨剤中に有機酸及びその酸無水物から選ばれる少なくとも一種を含むこと。
本発明の第1実施形態に係る銅研磨用研磨剤(以下、単に「研磨剤」という。)は、前記条件(i)を満たす。すなわち、第1実施形態に係る研磨剤は、(A)無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水とを含み、(A)成分の含有量が0.08mol/kg以上であり、(B)成分の含有量が0.20mol/kg以上であり、(C)成分の含有量が0.02mol/kg以上であり、(C)成分の含有量(mol/kg)に対する(A)成分の含有量(mol/kg)の比率が2.00以上である。
第1実施形態に係る研磨剤のpHは、CMPによる銅に対する研磨速度が大きく、銅膜に腐食を生じさせないという点で、1.5~4.0の範囲であることが好ましい。pHが1.5以上であると、銅膜の表面粗さを低減しやすくなる傾向があり、同様の観点から、pHは2.0以上がより好ましい。pHが4.0以下であると、CMPによる研磨速度が増加してより実用的な研磨剤となる傾向があり、同様の観点から、pHは3.5以下がより好ましく、3.0以下が更に好ましい。
(A)成分は、二価以上の無機酸(一価でない無機酸)であり、公知のものを特に制限なく使用することができ、例えば、硫酸、クロム酸、炭酸、モリブデン酸、硫化水素、亜硫酸、チオ硫酸、セレン酸、テルル酸、亜テルル酸、タングステン酸、ホスホン酸等の二価の酸、リン酸、リンモリブデン酸、リンタングステン酸、バナジン酸等の三価の酸、ケイモリブデン酸、ケイタングステン酸、ピロリン酸、トリポリリン酸等の四価以上の酸などが挙げられる。これらは単独で又は二種類以上を組み合わせて使用することができる。
銅膜の表面粗さを更に低減できるという点では、弱酸(pKaが0を超える酸と定義する。以下同じ)が好ましい。弱酸としては、具体的には、炭酸、モリブデン酸、硫化水素、亜硫酸、チオ硫酸、セレン酸、テルル酸、亜テルル酸、タングステン酸、ホスホン酸、リン酸、ピロリン酸、トリポリリン酸、バナジン酸が挙げられ、リン酸が好ましい。
研磨速度と表面粗さとを更に高度に両立できる点では、上記強酸と上記弱酸とを組み合わせて使用することが好ましく、この観点で、硫酸及びリン酸の混合物が特に好ましい。
(B)成分は、pHを調整し、かつ銅を溶解させる目的で使用されるアミノ酸である。このような(B)成分としては、わずかでも水に溶解するアミノ酸であれば特に制限はなく、例えば、グリシン、アラニン、バリン、ロイシン、イソロイシン、セリン、トレオニン、システイン、シシチン、メチオニン、アスパラギン酸、グルタミン酸、リシン、アルギニン、フェニルアラニン、チロシン、ヒスチジン、トリプトファン、プロリン、オキシプロリンから選択される少なくとも一種が挙げられる。これらは単独で又は二種類以上を組み合わせて使用することができる。
(C)成分である保護膜形成剤とは、銅表面に対して保護膜を形成する作用を有する物質をいい、防食剤やインヒビターとも呼ばれる物質である。ただし、上述のように保護膜形成剤は、研磨進行時に除去される「反応層」を構成していると考えられ、必ずしも銅が研磨されるのを防ぐための「保護膜」を形成するものに限られない。
(D)成分としては、特に制限はなく、例えば、シリカ、アルミナ、ジルコニア、セリア、チタニア、炭化珪素等の無機物砥粒、ポリスチレン、ポリアクリル、ポリ塩化ビニル等の有機物砥粒を挙げることができる。これらの(D)成分の中でも、研磨剤中での分散安定性が良く、CMPにより発生する研磨傷(スクラッチ)の発生数が少ない点で、シリカ及びアルミナが好ましく、粒径の制御が容易であり、研磨特性により優れる点で、コロイダルシリカ、コロイダルアルミナがより好ましい。コロイダルシリカは、シリコンアルコキシドの加水分解又は珪酸ナトリウムのイオン交換による製造方法が知られている。コロイダルアルミナは、硝酸アルミニウムの加水分解による製造方法が知られている。上記(D)成分は単独で又は二種類以上を組み合わせて使用することができる。
(E)成分としては、銅に対する酸化作用を有する酸化剤であれば特に制限なく使用することができる。(E)成分としては、例えば、過酸化水素(H2O2)、過硫酸、過硫酸アンモニウム、過硫酸カリウム等の過硫酸塩、過ヨウ素酸、過ヨウ素酸カリウム等が挙げられ、その中でも研磨速度に更に優れる点で過酸化水素、過硫酸及び過硫酸塩から選択される少なくとも一種が好ましい。上記酸化剤は単独で又は二種類以上組み合わせて使用することができる。
研磨剤の媒体である(F)成分としては、特に制限されないが、脱イオン水、イオン交換水、超純水等が好ましい。研磨剤における(F)成分の含有量は、他の構成成分の含有量の残部でよく、研磨剤中に含有されていれば特に限定されない。
適用される基板や用途によっては、銅に対する更に高い研磨速度(例えば50000Å/minを超えるような研磨速度)が求められる場合がある。このような場合、第1実施形態に係る研磨剤は、(A)無機酸、(B)アミノ酸、(C)保護膜形成剤、(D)砥粒、(E)酸化剤及び(F)水を少なくとも含む研磨剤のpHを4まで増加させるために要する水酸化カリウムの量(無機酸の水酸化カリウムによる中和滴定等量)が、研磨剤1kg当たり0.10mol以上となるように無機酸を添加することが好ましい。
第2実施形態に係る銅研磨用研磨剤(以下、単に「研磨剤」という。)は、前記条件(ii)を満たす。すなわち、第2実施形態に係る研磨剤は、(A)無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水と、(G)有機酸及びその酸無水物から選ばれる少なくとも一種とを含み、(A)成分の含有量が0.08mol/kg以上であり、(B)成分の含有量が0.20mol/kg以上であり、(C)成分の含有量が0.02mol/kg以上である。
第2実施形態に係る研磨剤は、(G)成分として有機酸及びその酸無水物から選ばれる少なくとも一種を含有する。(G)成分としては、例えば、ギ酸、酢酸、グリオキシル酸、ピルビン酸、乳酸、マンデル酸、ビニル酢酸、3-ヒドロキシ絡酸、シュウ酸、マレイン酸、マロン酸、メチルマロン酸、ジメチルマロン酸、フタル酸、酒石酸、フマル酸、リンゴ酸、コハク酸、グルタル酸、オキサロ酢酸、クエン酸、ヘミメリト酸、トリメリト酸、トリメシン酸、メリト酸、イソクエン酸、アコニット酸、オキサロコハク酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、イソ吉草酸、ピバル酸、カプロン酸、オクタン酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、アクリル酸、プロピオール酸、メタクリル酸、クロトン酸、イソクロトン酸、安息香酸、ケイヒ酸、イソフタル酸、テレフタル酸、フランカルボン酸、チオフェンカルボン酸、ニコチン酸、イソニコチン酸、グリコール酸、サリチル酸、クレオソート酸、バニリン酸、シリング酸、ピロカテク酸、レソルシル酸、ゲンチジン酸、プロカテク酸、オルセリン酸、没食子酸、タルトロン酸、ロイシン酸、メバロン酸、パントイン酸、リシノール酸、リシネライジン酸、セレブロン酸、シトラマル酸、キナ酸、シキミ酸、マンデル酸、ベンジル酸、アトロラクチン酸,メリロト酸、フロレト酸、クマル酸、ウンベル酸、カフェー酸、フェルラ酸、イソフェルラ酸、シナピン酸等の有機酸、及び、無水マレイン酸、無水プロピオン酸、無水コハク酸、無水フタル酸等の有機酸の酸無水物から選ばれる少なくとも一種が挙げられる。なお、(G)成分としては(B)成分のアミノ酸を除く。
適用される基板や用途によっては、銅に対する更に高い研磨速度(例えば50000Å/minを超えるような研磨速度)が求められる場合がある。このような場合、第2実施形態に係る研磨剤は、研磨剤から(G)成分を除いた組成物のpHを4まで増加させるために要する水酸化カリウムの量(無機酸の水酸化カリウムによる中和滴定等量)が、前記組成物1kg当たり0.10mol以上となるように無機酸を添加することが好ましい。
第3実施形態に係る銅研磨用研磨剤(以下、単に「研磨剤」という。)は、前記条件(i)及び(ii)の両方を満たす。すなわち、第3実施形態に係る研磨剤は、(A)無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水と、(G)有機酸及びその酸無水物から選ばれる少なくとも一種とを含み、(A)成分の含有量が0.08mol/kg以上であり、(B)成分の含有量が0.20mol/kg以上であり、(C)成分の含有量が0.02mol/kg以上であり、(C)成分の含有量に対する(A)成分の含有量の比率が2.00以上である。
上記各実施形態に係る研磨剤の保存方法に特に制限はない。例えば、構成成分を全て含む1液式研磨剤として保存しても良く、互いに混合して上記各実施形態に係るCMP研磨剤となるように該研磨剤の構成成分を少なくともスラリー(第1の液)と添加液(第2の液)とに分ける2液式研磨剤として保存しても良い。上記第1実施形態が2液式研磨剤の場合、例えば、(D)砥粒及び(F)水を含有するスラリーと、(A)無機酸、(B)アミノ酸、(C)保護膜形成剤及び(F)水を含有する添加液とに分けられる。(E)酸化剤は、スラリーと添加液とを混合する際に添加される。スラリーと添加剤とを混合せずに保管すると、研磨剤の保存安定性を向上させることが可能であり、研磨速度の低下を更に抑制し安定した研磨速度で研磨することが可能である。
本実施形態に係る研磨方法は、上記各実施形態に係る研磨剤を用いて銅を含む金属膜を研磨し、金属膜の少なくとも一部を除去することを特徴とする。本実施形態に係る研磨方法は、より具体的には、基板上に、銅を含む金属膜を積層する積層ステップと、上記各実施形態に係る研磨剤を用いて銅を含む金属膜を研磨し、当該金属膜の一部を除去する研磨ステップ、を有することを特徴とする。ここで、「銅を含む金属膜」とは、純銅からなる金属膜、銅を含む金属膜(例えば銅合金膜)、又はそれらの金属膜と他の金属との積層膜等であってもよい。
また、研磨剤を所定の圧力で吹きつけることで研磨しても良い。
(研磨剤の作製)
以下、実験例1-1~1-11の研磨剤について説明する。なお、実験例1-7~1-8は、本発明の上記第1実施形態に相当し、実験例1-6は、本発明の上記第2実施形態に相当し、実験例1-1~1-5、1-9は、本発明の上記第3実施形態に相当する。
濃度96%の硫酸10g、濃度85%のリン酸10g、グリシン50g、ベンゾトリアゾール(BTA)10g、シュウ酸10g、及びテトラエトキシシランのアンモニア溶液中での加水分解により作製した平均粒径70nmのコロイダルシリカ(固形分20%)50gを水550gに加えて、コロイダルシリカ以外の成分を溶解させた。さらに25%のアンモニア水溶液を添加して液のpHを2.6に調整した後、純水をさらに加えて全量を700gとした。これに、過酸化水素水(試薬特級、30%水溶液)300gを加えて、全量1000gの研磨剤1-1を得た。
(実験例1-2)
シュウ酸の代わりにマロン酸を10g添加した以外は実験例1-1と同様にして研磨剤1-2を作製した。
(実験例1-3)
シュウ酸の代わりにマレイン酸を10g添加した以外は実験例1-1と同様にして研磨剤1-3を作製した。
(実験例1-4)
グリシンの代わりにアラニンを50g添加した以外は実験例1-1と同様にして研磨剤1-4を作製した。
(実験例1-5)
グリシンの代わりにセリンを50g添加した以外は実験例1-1と同様にして研磨剤1-5を作製した。
(実験例1-6)
添加する硫酸とリン酸の量をそれぞれ5gとした以外は実験例1-1と同様にして研磨剤1-6を作製した。
(実験例1-7)
シュウ酸を加えないこと以外は実験例1-1と同様にして研磨剤1-7を作製した。
(実験例1-8)
シュウ酸を加えないことに加えて、硫酸の量を20gに増量した以外は実験例1-1と同様にして研磨剤1-8を作製した。
(実験例1-9)
シュウ酸の代わりにリンゴ酸を添加したこと以外は実験例1-1と同様にして研磨剤1-9を作製した。
硫酸及びリン酸を加えず、シュウ酸の量を30gとした以外は実験例1-1と同様にして研磨剤X1-1を作製した。
(実験例1-11)
添加する硫酸の量を1g、リン酸の量を5gとした以外は実験例1-1と同様にして研磨剤X1-2を作製した。
上記研磨剤1-1~1-9、X1-1~X1-2のpHを横河電機株式会社製の型番PH81を用いて測定した。表1に記載のpHはこの測定値である。
有機酸及び25%のアンモニア水溶液を添加しないこと以外は実験例1-1~1-11と同様にして、中和滴定量測定用の試験液(試験液1-1~1-9及び試験液X1-1~X1-2)を作製した。それぞれの試験液について、pHメータ(横河電機株式会社製 PH81)を使用し、25℃の恒温水槽中で、水酸化カリウムによる中和滴定等量を測定した。なお、実験例1-10については、シュウ酸及びアンモニア水を添加しない状態でのpHが4.0を超えていたため、中和滴定量を0(mol/kg)とした。
直径8インチ(20.3cm)(φ)サイズのシリコン基板上に厚み20μmの銅膜を製膜した基板(アドバンテック社より購入)を用意した。この基板を使用し、上記研磨剤1-1~1-9及び研磨剤X1-1~X1-2を、研磨装置の定盤に貼り付けた研磨布に滴下しながら、CMP研磨を行った。
研磨装置:定盤寸法は直径600mm(φ)、ロータリータイプ
研磨布:独立気泡を持つ発泡ポリウレタン樹脂(IC-1010、ロームアンドハース社製)
研磨圧力:32kPa
定盤/ヘッド回転速度:93/87rpm
研磨剤流量:200ml/min
上述のようにして研磨した基板について、CMPによる銅の研磨速度(以下、単に「研磨速度」という)及び表面粗さを測定した。
研磨速度:基板のCMP前後での膜厚差をシート抵抗変化から換算して求めた。測定装置はナプソン社製抵抗率測定器Model RT-7を用いた。なお、抵抗値としては、ウエハの直径方向77点(エッジから5mm部分除外)の平均値を用いた。
表面粗さ(算術平均粗さRa):研磨後の銅膜表面粗さをAFM(原子間力顕微鏡:SPA-400,エスアイアイナノテクノロジー社製)で測定した。測定は基板中央部から半径方向に50mm離れた箇所において、5μm×5μmの面積範囲で行った。
実験例1-7の研磨剤にシュウ酸を加えた組成である実験例1-1の研磨剤1-1は、実験例1-7と比較して表面粗さが維持されつつ、研磨速度が向上した。
実験例1-1の研磨剤において硫酸及びリン酸をシュウ酸に置き換えた組成である実験例1-10の研磨剤X1-1は、実験例1-1と比較して、表面粗さは維持したものの、研磨速度は大幅に低下した。
実験例1-8の研磨剤において硫酸の一部をシュウ酸に置き換えた組成である実験例1-1の研磨剤1-1は、実験例1-8と比較して、表面粗さ及び研磨速度が向上した。実験例1-8は、実験例1-7と同様に30000Å/minを上回る速度であった。
また、研磨速度に着目すると、実験例1-7に対して10gの硫酸を更に追加した実験例1-8の研磨剤では、研磨速度が37000Å/minであるのに対し、実験例1-7に対して10gのシュウ酸を加えた系である実験例1-1の研磨剤では、研磨速度が60000Å/minを達成した。これにより、(A)成分と(G)成分を組み合わせることが研磨速度向上に有効であることが確認できる。
一方、(A)成分の種類、(A)成分及び(G)成分の量は実験例1-9と同じであるが、(G)成分のpKaが2.7以下である実験例1-1の研磨剤1-1は、実験例1-9と比較して表面粗さが維持されつつ、研磨速度が向上した。
(研磨剤の作製)
以下、実験例2-1~2-14の研磨剤について説明する。なお、実験例2-1~2-4は、本発明の上記第1実施形態に相当する。
濃度96%の硫酸5.1g、濃度85%のリン酸5.8g、グリシン20.3g、ベンゾトリアゾール(BTA)4.0g、及び、砥粒としてテトラエトキシシランのアンモニア溶液中での加水分解により作製した平均粒径70nmのコロイダルシリカ(固形分20%)50gを純水600gに加えて、コロイダルシリカ以外の成分を溶解させた。更に25%のアンモニア水溶液を添加して液のpHを2.6に調整した後、純水を更に加えて全量を700gとした。これに、過酸化水素水(試薬特級、30%水溶液)300gを加えて、全量1000gの研磨剤2-1を得た。
硫酸の量を7.7g、リン酸の量を8.6g、グリシンの量を30.8g、ベンゾトリアゾールの量を6.0gとした以外は実験例2-1と同様にして研磨剤2-2を作製した。
(実験例2-3)
硫酸の量を10.2g、リン酸の量を11.5g、グリシンの量を40.5g、ベンゾトリアゾールの量を8.0gとした以外は実験例2-1と同様にして研磨剤2-3を作製した。
(実験例2-4)
グリシンのかわりにセリンを28.4g用いた以外は実験例2-1と同様にして研磨剤2-4を作製した。
硫酸の量を2.6g、リン酸の量を2.9g、グリシンの量を10.5g、ベンゾトリアゾールの量を2.0gとした以外は実験例2-1と同様にして研磨剤X2-1を作製した。
(実験例2-6)
グリシンの量を10.5g、ベンゾトリアゾールの量を2.0gとした以外は実験例2-1と同様にして研磨剤X2-2を作製した。
(実験例2-7)
硫酸の量を10.2g、リン酸の量を11.5g、グリシンの量を10.5g、ベンゾトリアゾールの量を2.0gとした以外は実験例2-1と同様にして研磨剤X2-3を作製した。
(実験例2-8)
硫酸の量を2.6g、リン酸の量を2.9g、ベンゾトリアゾールの量を2.0gとし、pH調整にアンモニア水溶液にかえて36%の塩酸を使用した以外は実験例2-1と同様にして研磨剤X2-4を作製した。
(実験例2-9)
硫酸の量を2.6g、リン酸の量を2.9g、グリシンの量を10.5gとした以外は実験例2-1と同様にして研磨剤X2-5を作製した。
(実験例2-10)
硫酸の量を2.6g、リン酸の量を2.9gとし、pH調整にアンモニア水溶液にかえて36%の塩酸を使用した以外は実験例2-1と同様にして研磨剤X2-6を作製した。
(実験例2-11)
グリシンの量を0gとした以外は実験例2-1と同様にして研磨剤X2-7を作製した。
(実験例2-12)
グリシンの量を10.5g、ベンゾトリアゾールの量を4.0gとした以外は実験例2-1と同様にして研磨剤X2-8を作製した。
(実験例2-13)
ベンゾトリアゾールの量を2.0gとした以外は実験例2-1と同様にして研磨剤X2-9を作製した。
(実験例2-14)
ベンゾトリアゾールの量を8.0gとした以外は実験例2-1と同様にして研磨剤X2-10を作製した。
上記研磨剤2-1~2-4、X2-1~X2-10のpHを横河電機株式会社製の型番PH81を用いて測定した。表2,3に記載のpHはこの測定値である。
25%のアンモニア水溶液を添加しないこと以外は実験例2-1~2-14と同様にして、中和滴定量測定用の試験液(試験液2-1~2-4及び試験液X2-1~X2-10)を作製した。それぞれの試験液について、pHメータ(横河電機株式会社製 PH81)を使用し、25℃の恒温水槽中で、水酸化カリウムによる中和滴定等量を測定した。
直径8インチ(20.3cm)(φ)サイズのシリコン基板上に20μm厚さの銅膜を製膜した基板(アドバンテック社より購入)を用意した。この基板を使用し、上記研磨剤2-1~2-4及び研磨剤X2-1~X2-10を、研磨装置の定盤に貼り付けた研磨布に滴下しながら、CMP研磨を行った。
研磨装置:定盤寸法は直径600mm(φ)、ロータリータイプ
研磨布:独立気泡を持つ発泡ポリウレタン樹脂(IC-1010、ロームアンドハース社製)
研磨圧力:32kPa
研磨定盤/ヘッド回転速度:93/87rpm
研磨剤流量:200ml/min
上述のようにして研磨した基板について、CMPによる銅の研磨速度(以下、単に「研磨速度」という。)及び表面粗さを測定した。
研磨速度:基板のCMP前後での膜厚差をシート抵抗変化から換算して求めた。測定装置はナプソン社製抵抗率測定器Model RT-7を用いた。ウエハの直径方向77点(エッジから5mm部分除外)の平均値を抵抗値とした。
表面粗さ(算術平均粗さRa):研磨後の銅膜の表面粗さをAFM(原子間力顕微鏡:SPA-400、エスアイアイナノテクノロジー社製)で測定した。測定は、基板中央から半径方向に50mm離れた箇所において、5μm×5μmの面積範囲で行った。
(A)成分の含有量のみを実験例2-1と同含有量とした以外は実験例2-5と同様にした実験例2-6の研磨剤X2-2、及び、実験例2-6の(A)成分の含有量を増した実験例2-7の研磨剤X2-3については、若干の研磨速度の向上は見られたものの実験例2-1に対して研磨速度は低下した。つまり、(A)成分の含有量のみを増しても研磨速度の向上効果は大きくないことが分かった。
実験例2-1の研磨剤2-1に対して(A)成分、(C)成分の含有量は同じであるが、(B)成分の含有量が本発明の値よりも小さい実験例2-11の研磨剤X2-7、実験例2-12の研磨剤X2-8の研磨速度は低下した。
実験例2-1の研磨剤2-1に対して(A)成分、(B)成分の含有量は同じであるが、(C)成分の含有量が本発明の値よりも小さい実験例2-13の研磨剤X2-9の研磨速度は低下した。
実験例2-1と実験例2-6、2-8、2-9の関係から(A)成分、(B)成分、(C)成分のうち1成分のみの含有量を同程度にし、他の成分の含有量が本発明の値より小さい場合は、研磨速度が不充分であることが分かる。
実験例2-1と実験例2-10~2-14の関係から(A)成分、(B)成分、(C)成分のうち2成分の含有量を同程度にし、他の成分の含有量が本発明の値より小さい場合は、研磨速度が不充分であることが分かる。
以上の結果より同時に(A)成分、(B)成分、(C)成分の3成分を一定量以上にすることで効率良く研磨速度を向上させることができることが分かる。
(研磨剤の作製)
以下、実験例3-1~3-15の研磨剤について説明する。なお、実験例3-8は、本発明の上記第1実施形態に相当し、実験例3-7は、本発明の上記第2実施形態に相当し、実験例3-1~3-6、3-9~3-10は、本発明の上記第3実施形態に相当する。
(実験例3-1)
濃度96%の硫酸5.1g、濃度85%のリン酸5.8g、グリシン20.3g、ベンゾトリアゾール(BTA)4.0g、シュウ酸5.4g、及び、砥粒として平均粒径70nmのコロイダルシリカ(固形分20%)50gを純水600gに加えて、コロイダルシリカ以外の成分を溶解させた。更に25%のアンモニア水溶液を添加して液のpHを2.6に調整した後、純水を更に加えて全量を700gとした。これに、過酸化水素水(試薬特級、30%水溶液)300gを加えて、全量1000gの研磨剤3-1を得た。
シュウ酸の含有量を14.0gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-2を作製した。
(実験例3-3)
シュウ酸5.4gの代わりにマレイン酸7.0gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-3を作製した。
(実験例3-4)
シュウ酸5.4gの代わりに無水マレイン酸5.9gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-4を作製した。
(実験例3-5)
シュウ酸5.4gの代わりにマロン酸6.2gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-5を作製した。
(実験例3-6)
シュウ酸5.4gの代わりにクエン酸11.5gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-6を作製した。
(実験例3-7)
ベンゾトリアゾールの含有量を7.9gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-7を作製した。
(実験例3-8)
シュウ酸を添加せず、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-8を作製した。
(実験例3-9)
シュウ酸5.4gの代わりに酒石酸9.0gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-9を作製した。
(実験例3-10)
シュウ酸5.4gの代わりにリンゴ酸8.0gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-1と同様にして研磨剤3-10を作製した。
濃度96%の硫酸2.6g、濃度85%のリン酸2.9g、グリシン10.2g、ベンゾトリアゾール2.0g、砥粒として平均粒径70nmのコロイダルシリカ(固形分20%)50gを水600gに加えて、コロイダルシリカ以外の成分を溶解させた。更に25%のアンモニア水溶液を添加して液のpHを2.6に調整した後、純水を更に加えて全量を700gとした。これに、過酸化水素水(試薬特級、30%水溶液)300gを加えて、全量1000gの研磨剤X3-1を得た。
(実験例3-12)
硫酸の含有量を5.1gとし、リン酸の含有量を5.8gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-11と同様にして研磨剤X3-2を作製した。
(実験例3-13)
グリシンの含有量を20.3gとし、pH調整にアンモニア水溶液にかえて36%の塩酸を使用し、純水の添加量を調整して全量1000gとしたこと以外は実験例3-11と同様にして研磨剤X3-3を作製した。
(実験例3-14)
ベンゾトリアゾールの含有量を4.0gとし、純水の添加量を調整して全量1000gとしたこと以外は実験例3-11と同様にして研磨剤X3-4を作製した。
(実験例3-15)
有機酸としてシュウ酸を5.4g更に加え、純水の添加量を調整して全量1000gとしたこと以外は実験例3-11と同様にして研磨剤X3-5を作製した。
上記研磨剤3-1~3-10、X3-1~X3-5のpHを横河電機株式会社製の型番PH81を用いて測定した。表4,5に記載のpHはこの測定値である。
有機酸及び25%のアンモニア水溶液を添加しないこと以外は実験例3-1~3-15と同様にして、中和滴定量測定用の試験液(試験液3-1~3-10及び試験液X3-1~X3-5)を作製した。それぞれの試験液について、pHメータ(横河電機株式会社製 PH81)を使用し、25℃の恒温水槽中で、水酸化カリウムによる中和滴定等量を測定した。
直径12インチ(30.5cm)(φ)サイズのシリコン基板上に厚さ20μmの銅膜を製膜した基板(グローバルネット社製)を用意した。この基板を使用し、上記研磨剤3-1~3-10及び研磨剤X3-1~X3-5を、研磨装置の定盤に貼り付けた研磨布に滴下しながら、CMP研磨を行った。
研磨装置:CMP用研磨機(アプライドマテリアルズ製、商品名:Reflexion)
研磨布:独立気泡を持つ発泡ポリウレタン樹脂(商品名:IC-1010、ロームアンドハース社製)
研磨圧力:32kPa
定盤/ヘッド回転速度:60/55rpm
研磨剤流量:300ml/min
Claims (19)
- (A)二価以上の無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水とを含み、
前記(A)成分の含有量が0.08mol/kg以上であり、
前記(B)成分の含有量が0.20mol/kg以上であり、
前記(C)成分の含有量が0.02mol/kg以上であり、
前記(C)成分の含有量に対する前記(A)成分の含有量の比率が2.00以上である、銅研磨用研磨剤。 - pHを4まで増加させるために要する水酸化カリウムの量が銅研磨用研磨剤1kg当たり0.10mol以上である、請求項1に記載の銅研磨用研磨剤。
- (A)二価以上の無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水と、(G)有機酸及びその酸無水物から選ばれる少なくとも一種とを含み、
前記(A)成分の含有量が0.08mol/kg以上であり、
前記(B)成分の含有量が0.20mol/kg以上であり、
前記(C)成分の含有量が0.02mol/kg以上である、銅研磨用研磨剤。 - (A)二価以上の無機酸と、(B)アミノ酸と、(C)保護膜形成剤と、(D)砥粒と、(E)酸化剤と、(F)水と、(G)有機酸及びその酸無水物から選ばれる少なくとも一種とを含み、
前記(A)成分の含有量が0.08mol/kg以上であり、
前記(B)成分の含有量が0.20mol/kg以上であり、
前記(C)成分の含有量が0.02mol/kg以上であり、
前記(C)成分の含有量に対する前記(A)成分の含有量の比率が2.00以上である、銅研磨用研磨剤。 - 銅研磨用研磨剤から前記(G)成分を除いた組成物のpHを4まで増加させるために要する水酸化カリウムの量が、前記組成物1kg当たり0.10mol以上である、請求項3又は4に記載の銅研磨用研磨剤。
- 前記(G)成分の含有量が0.02mol/kg以上である、請求項3~5のいずれか一項に記載の銅研磨用研磨剤。
- 前記(G)成分が、カルボキシル基を2つ有しかつpKaが2.7以下である有機酸及びその酸無水物並びにカルボキシル基を3つ以上有する有機酸から選択される少なくとも一種である、請求項3~6のいずれか一項に記載の銅研磨用研磨剤。
- 前記(G)成分がシュウ酸、マレイン酸、無水マレイン酸、マロン酸及びクエン酸から選択される少なくとも一種である、請求項3~7のいずれか一項に記載の銅研磨用研磨剤。
- pHが1.5~4.0である、請求項1~8のいずれか一項に記載の銅研磨用研磨剤。
- 前記(A)成分が硫酸及びリン酸から選択される少なくとも一種である、請求項1~9のいずれか一項に記載の銅研磨用研磨剤。
- 前記(B)成分としてpKaが2~3のアミノ酸を含む、請求項1~10のいずれか一項に記載の銅研磨用研磨剤。
- 前記(C)成分がトリアゾール化合物である、請求項1~11のいずれか一項に記載の銅研磨用研磨剤。
- 前記トリアゾール化合物がベンゾトリアゾール及びその誘導体から選択される少なくとも一種である、請求項12に記載の銅研磨用研磨剤。
- 前記(D)成分がコロイダルシリカ及びコロイダルアルミナから選択される少なくとも一種であり、該(D)成分の平均粒径が100nm以下である、請求項1~13のいずれか一項に記載の銅研磨用研磨剤。
- 前記(E)成分が過酸化水素、過硫酸及び過硫酸塩から選択される少なくとも一種である、請求項1~14のいずれか一項に記載の銅研磨用研磨剤。
- 請求項1~15のいずれか一項に記載の銅研磨用研磨剤を用いて銅を含む金属膜を研磨し、前記金属膜の少なくとも一部を除去する、研磨方法。
- 前記金属膜の最大厚みが5μm以上である、請求項16に記載の研磨方法。
- 前記金属膜の最大厚みが10μm以上である、請求項16に記載の研磨方法。
- 前記金属膜に対する研磨速度が30000Å/min以上である、請求項16~18のいずれか一項に記載の研磨方法。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127005402A KR101400585B1 (ko) | 2009-02-16 | 2010-02-12 | 구리 연마용 연마제 및 이를 이용한 연마 방법 |
KR1020117019004A KR101153510B1 (ko) | 2009-02-16 | 2010-02-12 | 구리 연마용 연마제 및 이를 이용한 연마 방법 |
CN201080007580.7A CN102318042B (zh) | 2009-02-16 | 2010-02-12 | 铜研磨用研磨剂和使用了其的研磨方法 |
SG2011048501A SG172829A1 (en) | 2009-02-16 | 2010-02-12 | Polishing agent for copper polishing and polishing method using same |
US13/201,529 US8889555B2 (en) | 2009-02-16 | 2010-02-12 | Polishing agent for copper polishing and polishing method using same |
JP2010550557A JP4930641B2 (ja) | 2009-02-16 | 2010-02-12 | 銅研磨用研磨剤及びそれを用いた研磨方法 |
US13/412,893 US8859429B2 (en) | 2009-02-16 | 2012-03-06 | Polishing agent for copper polishing and polishing method using same |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-032635 | 2009-02-16 | ||
JP2009032635 | 2009-02-16 | ||
JP2009121144 | 2009-05-19 | ||
JP2009-121144 | 2009-05-19 | ||
JP2009290563 | 2009-12-22 | ||
JP2009-290563 | 2009-12-22 | ||
JPPCT/JP2010/050806 | 2010-01-22 | ||
PCT/JP2010/050806 WO2010092865A1 (ja) | 2009-02-16 | 2010-01-22 | 研磨剤及び研磨方法 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/201,529 A-371-Of-International US8889555B2 (en) | 2009-02-16 | 2010-02-12 | Polishing agent for copper polishing and polishing method using same |
US13/412,893 Continuation US8859429B2 (en) | 2009-02-16 | 2012-03-06 | Polishing agent for copper polishing and polishing method using same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010093011A1 true WO2010093011A1 (ja) | 2010-08-19 |
Family
ID=42561851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/052069 WO2010093011A1 (ja) | 2009-02-16 | 2010-02-12 | 銅研磨用研磨剤及びそれを用いた研磨方法 |
Country Status (7)
Country | Link |
---|---|
US (2) | US8889555B2 (ja) |
JP (2) | JP4930641B2 (ja) |
KR (2) | KR101153510B1 (ja) |
CN (3) | CN102703027A (ja) |
SG (2) | SG172829A1 (ja) |
TW (1) | TWI535834B (ja) |
WO (1) | WO2010093011A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013545277A (ja) * | 2010-10-04 | 2013-12-19 | インターナショナル・ビジネス・マシーンズ・コーポレーション | フィンfetデバイスの製造のための化学機械平坦化プロセス |
US20140131615A1 (en) * | 2011-07-04 | 2014-05-15 | Mitsubishi Gas Chemical Company, Inc. | Etching solution for copper or a compound comprised mainly of copper |
WO2017208667A1 (ja) * | 2016-06-03 | 2017-12-07 | 富士フイルム株式会社 | 研磨液、及び化学的機械的研磨方法 |
US10858585B2 (en) | 2018-01-03 | 2020-12-08 | Ecolab Usa Inc. | Benzotriazole derivatives as corrosion inhibitors |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8845915B2 (en) | 2009-02-16 | 2014-09-30 | Hitachi Chemical Company, Ltd. | Abrading agent and abrading method |
CN102703027A (zh) * | 2009-02-16 | 2012-10-03 | 日立化成工业株式会社 | 铜研磨用研磨剂的应用 |
KR101380098B1 (ko) * | 2009-07-16 | 2014-04-01 | 히타치가세이가부시끼가이샤 | 팔라듐 연마용 cmp 연마액 및 연마 방법 |
JP5533889B2 (ja) | 2010-02-15 | 2014-06-25 | 日立化成株式会社 | Cmp研磨液及び研磨方法 |
KR102137293B1 (ko) * | 2012-08-30 | 2020-07-23 | 히타치가세이가부시끼가이샤 | 연마제, 연마제 세트 및 기체의 연마 방법 |
JP6222907B2 (ja) * | 2012-09-06 | 2017-11-01 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
KR101526006B1 (ko) | 2012-12-31 | 2015-06-04 | 제일모직주식회사 | 구리 연마용 cmp 슬러리 조성물 및 이를 이용한 연마 방법 |
KR102225154B1 (ko) | 2013-06-12 | 2021-03-09 | 쇼와덴코머티리얼즈가부시끼가이샤 | Cmp용 연마액 및 연마 방법 |
JP6366308B2 (ja) * | 2014-03-12 | 2018-08-01 | 株式会社ディスコ | 加工方法 |
JP6405776B2 (ja) * | 2014-08-07 | 2018-10-17 | 日立化成株式会社 | タングステン用研磨剤、研磨剤用貯蔵液及び研磨方法 |
EP3237563B1 (en) * | 2014-12-22 | 2019-02-20 | Basf Se | Use of a chemical mechanical polishing (cmp) composition for polishing of cobalt and / or co-balt alloy comprising substrates |
CN108621033B (zh) * | 2017-03-21 | 2020-04-07 | 中芯国际集成电路制造(上海)有限公司 | 研磨垫的研磨方法 |
KR102190916B1 (ko) * | 2018-08-31 | 2020-12-15 | 씨제이제일제당 주식회사 | 점착 조성물, 및 이의 제조방법 |
US20200102475A1 (en) * | 2018-09-28 | 2020-04-02 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mecahnical polishing composition and method of polishing silcon dioxide over silicon nitiride |
TWI749287B (zh) * | 2019-01-22 | 2021-12-11 | 達興材料股份有限公司 | 酸性過氧化氫水溶液組成物 |
US10781343B2 (en) * | 2019-01-24 | 2020-09-22 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Acid polishing composition and method of polishing a substrate having enhanced defect inhibition |
CN110064973A (zh) * | 2019-03-21 | 2019-07-30 | 林德谊 | 一种铜或铜合金的表面抛光处理工艺 |
ES2837489B2 (es) * | 2019-12-31 | 2022-02-28 | Primalchit Solutions S L | Mezcla de componentes organicos no polimericos con capacidad retardante de llama, metodo de preparacion y uso |
CA3110390A1 (en) * | 2021-02-25 | 2022-08-25 | Sixring Inc. | Modified sulfuric acid and uses thereof |
WO2023034131A1 (en) * | 2021-09-01 | 2023-03-09 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions and methods of using the same |
CN113981450A (zh) * | 2021-10-28 | 2022-01-28 | 兰溪市同力铝业股份有限公司 | 一种铝合金氧化工艺用二酸化抛物及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006302968A (ja) * | 2005-04-15 | 2006-11-02 | Hitachi Chem Co Ltd | 磁性金属膜および絶縁材料膜複合材料用研磨材および研磨方法 |
JP2007103485A (ja) * | 2005-09-30 | 2007-04-19 | Fujifilm Corp | 研磨方法及びそれに用いる研磨液 |
JP2007150264A (ja) * | 2005-10-27 | 2007-06-14 | Hitachi Chem Co Ltd | 有機絶縁材料膜及び銅膜複合材料用研磨材及び研磨方法 |
JP2008270826A (ja) * | 2008-06-02 | 2008-11-06 | Hitachi Chem Co Ltd | 研磨液及び研磨方法 |
Family Cites Families (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4954142A (en) | 1989-03-07 | 1990-09-04 | International Business Machines Corporation | Method of chemical-mechanical polishing an electronic component substrate and polishing slurry therefor |
US5575885A (en) * | 1993-12-14 | 1996-11-19 | Kabushiki Kaisha Toshiba | Copper-based metal polishing solution and method for manufacturing semiconductor device |
US6217416B1 (en) | 1998-06-26 | 2001-04-17 | Cabot Microelectronics Corporation | Chemical mechanical polishing slurry useful for copper/tantalum substrates |
EP1137056B1 (en) * | 1998-08-31 | 2013-07-31 | Hitachi Chemical Company, Ltd. | Abrasive liquid for metal and method for polishing |
JP4053165B2 (ja) * | 1998-12-01 | 2008-02-27 | 株式会社フジミインコーポレーテッド | 研磨用組成物およびそれを用いた研磨方法 |
JP4164941B2 (ja) * | 1999-05-27 | 2008-10-15 | 日立化成工業株式会社 | 金属用研磨液及び研磨方法 |
TWI296006B (ja) * | 2000-02-09 | 2008-04-21 | Jsr Corp | |
TWI268286B (en) | 2000-04-28 | 2006-12-11 | Kao Corp | Roll-off reducing agent |
US6551935B1 (en) * | 2000-08-31 | 2003-04-22 | Micron Technology, Inc. | Slurry for use in polishing semiconductor device conductive structures that include copper and tungsten and polishing methods |
EP1211024A3 (en) * | 2000-11-30 | 2004-01-02 | JSR Corporation | Polishing method |
US7128825B2 (en) * | 2001-03-14 | 2006-10-31 | Applied Materials, Inc. | Method and composition for polishing a substrate |
US7160432B2 (en) * | 2001-03-14 | 2007-01-09 | Applied Materials, Inc. | Method and composition for polishing a substrate |
US20040159050A1 (en) * | 2001-04-30 | 2004-08-19 | Arch Specialty Chemicals, Inc. | Chemical mechanical polishing slurry composition for polishing conductive and non-conductive layers on semiconductor wafers |
JP3899456B2 (ja) | 2001-10-19 | 2007-03-28 | 株式会社フジミインコーポレーテッド | 研磨用組成物およびそれを用いた研磨方法 |
WO2003094216A1 (fr) * | 2002-04-30 | 2003-11-13 | Hitachi Chemical Co., Ltd. | Fluide de polissage et procede de polissage |
US6803353B2 (en) * | 2002-11-12 | 2004-10-12 | Atofina Chemicals, Inc. | Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents |
US7300601B2 (en) * | 2002-12-10 | 2007-11-27 | Advanced Technology Materials, Inc. | Passivative chemical mechanical polishing composition for copper film planarization |
US20040175942A1 (en) * | 2003-01-03 | 2004-09-09 | Chang Song Y. | Composition and method used for chemical mechanical planarization of metals |
US7736405B2 (en) * | 2003-05-12 | 2010-06-15 | Advanced Technology Materials, Inc. | Chemical mechanical polishing compositions for copper and associated materials and method of using same |
TW200427827A (en) * | 2003-05-30 | 2004-12-16 | Sumitomo Chemical Co | Metal polishing composition |
KR20070104479A (ko) * | 2003-06-06 | 2007-10-25 | 어플라이드 머티어리얼스, 인코포레이티드 | 전도성 물질을 폴리싱하기 위한 폴리싱 조성물 및 방법 |
US7186653B2 (en) * | 2003-07-30 | 2007-03-06 | Climax Engineered Materials, Llc | Polishing slurries and methods for chemical mechanical polishing |
JP4707311B2 (ja) | 2003-08-08 | 2011-06-22 | 花王株式会社 | 磁気ディスク用基板 |
US20050090104A1 (en) * | 2003-10-27 | 2005-04-28 | Kai Yang | Slurry compositions for chemical mechanical polishing of copper and barrier films |
TWI288046B (en) * | 2003-11-14 | 2007-10-11 | Showa Denko Kk | Polishing composition and polishing method |
TW200521217A (en) * | 2003-11-14 | 2005-07-01 | Showa Denko Kk | Polishing composition and polishing method |
US7390744B2 (en) | 2004-01-29 | 2008-06-24 | Applied Materials, Inc. | Method and composition for polishing a substrate |
JP5412706B2 (ja) * | 2005-11-01 | 2014-02-12 | 日立化成株式会社 | 銅膜及び絶縁材料膜用研磨材及び研磨方法 |
JP2007270826A (ja) * | 2006-03-07 | 2007-10-18 | Denso Corp | 燃料ポンプ |
JPWO2007138975A1 (ja) * | 2006-05-31 | 2009-10-08 | 旭硝子株式会社 | 研磨剤組成物および研磨方法 |
JP2008181955A (ja) * | 2007-01-23 | 2008-08-07 | Fujifilm Corp | 金属用研磨液及びそれを用いた研磨方法 |
JP2008186898A (ja) | 2007-01-29 | 2008-08-14 | Nissan Chem Ind Ltd | 研磨用組成物 |
JP2008235481A (ja) * | 2007-03-19 | 2008-10-02 | Nippon Chem Ind Co Ltd | 半導体ウエハ研磨用組成物、その製造方法、及び研磨加工方法 |
JP2008270584A (ja) * | 2007-04-23 | 2008-11-06 | Nippon Chem Ind Co Ltd | 半導体ウエハ研磨用組成物及び研磨加工方法 |
KR101472617B1 (ko) * | 2007-07-30 | 2014-12-15 | 히타치가세이가부시끼가이샤 | 금속용 연마액 및 연마 방법 |
JP5275595B2 (ja) * | 2007-08-29 | 2013-08-28 | 日本化学工業株式会社 | 半導体ウエハ研磨用組成物および研磨方法 |
WO2009047203A1 (en) * | 2007-10-08 | 2009-04-16 | Basf Se | ETCHANT COMPOSITIONS AND ETCHING METHOD FOR METALS Cu/Mo |
CN102703027A (zh) * | 2009-02-16 | 2012-10-03 | 日立化成工业株式会社 | 铜研磨用研磨剂的应用 |
KR101666516B1 (ko) * | 2009-11-27 | 2016-10-17 | 삼성전자주식회사 | 구리 식각용 조성물 및 이를 이용한 반도체 장치의 제조방법 |
-
2010
- 2010-02-12 CN CN2012101356086A patent/CN102703027A/zh active Pending
- 2010-02-12 KR KR1020117019004A patent/KR101153510B1/ko not_active IP Right Cessation
- 2010-02-12 SG SG2011048501A patent/SG172829A1/en unknown
- 2010-02-12 US US13/201,529 patent/US8889555B2/en active Active
- 2010-02-12 SG SG2014002869A patent/SG196817A1/en unknown
- 2010-02-12 CN CN201210135053.5A patent/CN102690605B/zh not_active Expired - Fee Related
- 2010-02-12 KR KR1020127005402A patent/KR101400585B1/ko active IP Right Grant
- 2010-02-12 WO PCT/JP2010/052069 patent/WO2010093011A1/ja active Application Filing
- 2010-02-12 TW TW099104840A patent/TWI535834B/zh active
- 2010-02-12 CN CN201080007580.7A patent/CN102318042B/zh not_active Expired - Fee Related
- 2010-02-12 JP JP2010550557A patent/JP4930641B2/ja active Active
-
2011
- 2011-11-25 JP JP2011257827A patent/JP5472271B2/ja active Active
-
2012
- 2012-03-06 US US13/412,893 patent/US8859429B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006302968A (ja) * | 2005-04-15 | 2006-11-02 | Hitachi Chem Co Ltd | 磁性金属膜および絶縁材料膜複合材料用研磨材および研磨方法 |
JP2007103485A (ja) * | 2005-09-30 | 2007-04-19 | Fujifilm Corp | 研磨方法及びそれに用いる研磨液 |
JP2007150264A (ja) * | 2005-10-27 | 2007-06-14 | Hitachi Chem Co Ltd | 有機絶縁材料膜及び銅膜複合材料用研磨材及び研磨方法 |
JP2008270826A (ja) * | 2008-06-02 | 2008-11-06 | Hitachi Chem Co Ltd | 研磨液及び研磨方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013545277A (ja) * | 2010-10-04 | 2013-12-19 | インターナショナル・ビジネス・マシーンズ・コーポレーション | フィンfetデバイスの製造のための化学機械平坦化プロセス |
US20140131615A1 (en) * | 2011-07-04 | 2014-05-15 | Mitsubishi Gas Chemical Company, Inc. | Etching solution for copper or a compound comprised mainly of copper |
US9644274B2 (en) * | 2011-07-04 | 2017-05-09 | Mitsubishi Gas Chemical Company, Inc. | Etching solution for copper or a compound comprised mainly of copper |
WO2017208667A1 (ja) * | 2016-06-03 | 2017-12-07 | 富士フイルム株式会社 | 研磨液、及び化学的機械的研磨方法 |
JPWO2017208667A1 (ja) * | 2016-06-03 | 2019-05-16 | 富士フイルム株式会社 | 研磨液、及び化学的機械的研磨方法 |
US10858585B2 (en) | 2018-01-03 | 2020-12-08 | Ecolab Usa Inc. | Benzotriazole derivatives as corrosion inhibitors |
Also Published As
Publication number | Publication date |
---|---|
CN102703027A (zh) | 2012-10-03 |
KR101153510B1 (ko) | 2012-06-11 |
US8859429B2 (en) | 2014-10-14 |
JPWO2010093011A1 (ja) | 2012-08-16 |
KR20110112429A (ko) | 2011-10-12 |
JP5472271B2 (ja) | 2014-04-16 |
TW201035301A (en) | 2010-10-01 |
SG196817A1 (en) | 2014-02-13 |
US8889555B2 (en) | 2014-11-18 |
JP2012104835A (ja) | 2012-05-31 |
US20120160804A1 (en) | 2012-06-28 |
KR20120037509A (ko) | 2012-04-19 |
CN102318042B (zh) | 2015-07-01 |
CN102318042A (zh) | 2012-01-11 |
JP4930641B2 (ja) | 2012-05-16 |
CN102690605A (zh) | 2012-09-26 |
CN102690605B (zh) | 2015-01-21 |
TWI535834B (zh) | 2016-06-01 |
KR101400585B1 (ko) | 2014-05-27 |
SG172829A1 (en) | 2011-08-29 |
US20120024818A1 (en) | 2012-02-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5472271B2 (ja) | 銅研磨用研磨剤及びそれを用いた研磨方法 | |
JP5516734B2 (ja) | 銅研磨用研磨液及びそれを用いた研磨方法 | |
KR20120023712A (ko) | Cmp 연마액 및 연마 방법 | |
JP5880524B2 (ja) | 研磨剤及び研磨方法 | |
JP2013004660A (ja) | 銅研磨用研磨剤及びそれを用いた研磨方法 | |
WO2011077973A1 (ja) | 銅研磨用研磨剤及びそれを用いた研磨方法 | |
JP6379764B2 (ja) | 研磨液及び研磨方法 | |
JP2018157164A (ja) | 研磨用組成物、研磨用組成物の製造方法、研磨方法および半導体基板の製造方法 | |
JP2012028516A (ja) | 銅研磨用研磨液及びそれを用いた研磨方法 | |
TWI833935B (zh) | 研磨用組合物、研磨方法及基板之製造方法 | |
JP2013004670A (ja) | 金属用研磨液及び金属用研磨液を用いた研磨方法 | |
JP2015028968A (ja) | 化学機械研磨用水系分散体および化学機械研磨方法、ならびに化学機械研磨用水系分散体調製用キット | |
JP2022028258A (ja) | 研磨剤、2液式研磨剤及び研磨方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080007580.7 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10741288 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2010550557 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13201529 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20117019004 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10741288 Country of ref document: EP Kind code of ref document: A1 |