WO2012073909A1 - 銅配線用基板洗浄剤及び銅配線半導体基板の洗浄方法 - Google Patents
銅配線用基板洗浄剤及び銅配線半導体基板の洗浄方法 Download PDFInfo
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- WO2012073909A1 WO2012073909A1 PCT/JP2011/077436 JP2011077436W WO2012073909A1 WO 2012073909 A1 WO2012073909 A1 WO 2012073909A1 JP 2011077436 W JP2011077436 W JP 2011077436W WO 2012073909 A1 WO2012073909 A1 WO 2012073909A1
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- WO
- WIPO (PCT)
- Prior art keywords
- copper
- cleaning agent
- copper wiring
- wiring
- cleaning
- Prior art date
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- 239000010949 copper Substances 0.000 title claims abstract description 273
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 215
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000000758 substrate Substances 0.000 title claims abstract description 147
- 239000004065 semiconductor Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004140 cleaning Methods 0.000 title claims abstract description 50
- 150000001413 amino acids Chemical class 0.000 claims abstract description 61
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 48
- -1 carboxyethyl group Chemical group 0.000 claims abstract description 42
- 238000005498 polishing Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 32
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 6
- 239000012459 cleaning agent Substances 0.000 claims description 124
- 235000001014 amino acid Nutrition 0.000 claims description 61
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 claims description 38
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 30
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 20
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 19
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 19
- 239000012964 benzotriazole Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000005751 Copper oxide Substances 0.000 claims description 17
- 229910000431 copper oxide Inorganic materials 0.000 claims description 17
- 150000003863 ammonium salts Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000005750 Copper hydroxide Substances 0.000 claims description 11
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 11
- 108010077895 Sarcosine Proteins 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 7
- HSLSOCDDAXTJRW-UHFFFAOYSA-M [O-]C(C1=CC=C(C=CC=C2)C2=N1)=O.[Cu+2] Chemical compound [O-]C(C1=CC=C(C=CC=C2)C2=N1)=O.[Cu+2] HSLSOCDDAXTJRW-UHFFFAOYSA-M 0.000 claims description 7
- 239000004220 glutamic acid Substances 0.000 claims description 7
- 235000013922 glutamic acid Nutrition 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 5
- CDLNEDQJMXOTKZ-UHFFFAOYSA-N 2h-benzotriazole;copper(1+) Chemical compound [Cu+].C1=CC=CC2=NNN=C21 CDLNEDQJMXOTKZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 4
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- VDUIPQNXOQMTBF-UHFFFAOYSA-N n-ethylhydroxylamine Chemical group CCNO VDUIPQNXOQMTBF-UHFFFAOYSA-N 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 55
- 239000002184 metal Substances 0.000 abstract description 55
- 230000008569 process Effects 0.000 abstract description 22
- 239000012535 impurity Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 9
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000010828 elution Methods 0.000 abstract description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 39
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 28
- 238000005260 corrosion Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005536 corrosion prevention Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000003112 inhibitor Substances 0.000 description 16
- 239000004471 Glycine Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 150000004699 copper complex Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000007998 bicine buffer Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000006061 abrasive grain Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 description 6
- 239000007997 Tricine buffer Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- FOUZISDNESEYLX-UHFFFAOYSA-N 2-(2-hydroxyethylazaniumyl)acetate Chemical compound OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 229940043230 sarcosine Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 2
- IVCQRTJVLJXKKJ-UHFFFAOYSA-N 2-(butan-2-ylazaniumyl)acetate Chemical compound CCC(C)NCC(O)=O IVCQRTJVLJXKKJ-UHFFFAOYSA-N 0.000 description 2
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- HJOTVKSRXFESJH-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]acetic acid Chemical compound CC(C)N(C(C)C)CC(O)=O HJOTVKSRXFESJH-UHFFFAOYSA-N 0.000 description 2
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- 108010065338 N-ethylglycine Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- UNBLNSMDMBMQQF-UHFFFAOYSA-N n,n-bis(2,2-dimethylpropyl)hydroxylamine Chemical compound CC(C)(C)CN(O)CC(C)(C)C UNBLNSMDMBMQQF-UHFFFAOYSA-N 0.000 description 1
- QYTNRAKVMLCHEM-UHFFFAOYSA-N n,n-bis(2,3-dimethylbutyl)hydroxylamine Chemical compound CC(C)C(C)CN(O)CC(C)C(C)C QYTNRAKVMLCHEM-UHFFFAOYSA-N 0.000 description 1
- GOGCTRSPVDNIKE-UHFFFAOYSA-N n,n-bis(2-methylbutan-2-yl)hydroxylamine Chemical compound CCC(C)(C)N(O)C(C)(C)CC GOGCTRSPVDNIKE-UHFFFAOYSA-N 0.000 description 1
- HQBGXXRIGOMXIX-UHFFFAOYSA-N n,n-bis(2-methylbutyl)hydroxylamine Chemical compound CCC(C)CN(O)CC(C)CC HQBGXXRIGOMXIX-UHFFFAOYSA-N 0.000 description 1
- BJMHYUHEXQOMRC-UHFFFAOYSA-N n,n-bis(2-methylpentan-2-yl)hydroxylamine Chemical compound CCCC(C)(C)N(O)C(C)(C)CCC BJMHYUHEXQOMRC-UHFFFAOYSA-N 0.000 description 1
- XPXGOSPKYLSXKN-UHFFFAOYSA-N n,n-bis(2-methylpentyl)hydroxylamine Chemical compound CCCC(C)CN(O)CC(C)CCC XPXGOSPKYLSXKN-UHFFFAOYSA-N 0.000 description 1
- XFHUEIZEGRAREY-UHFFFAOYSA-N n,n-bis(2-methylpropyl)hydroxylamine Chemical compound CC(C)CN(O)CC(C)C XFHUEIZEGRAREY-UHFFFAOYSA-N 0.000 description 1
- KMRSYWCLXCQTKN-UHFFFAOYSA-N n,n-bis(3,3-dimethylbutyl)hydroxylamine Chemical compound CC(C)(C)CCN(O)CCC(C)(C)C KMRSYWCLXCQTKN-UHFFFAOYSA-N 0.000 description 1
- QSKCGBWBFNNGHW-UHFFFAOYSA-N n,n-bis(3-methylbutyl)hydroxylamine Chemical compound CC(C)CCN(O)CCC(C)C QSKCGBWBFNNGHW-UHFFFAOYSA-N 0.000 description 1
- IRQNCKMTWLHMGM-UHFFFAOYSA-N n,n-bis(4-methylpentyl)hydroxylamine Chemical compound CC(C)CCCN(O)CCCC(C)C IRQNCKMTWLHMGM-UHFFFAOYSA-N 0.000 description 1
- PRRGLBHZMSZRRW-UHFFFAOYSA-N n,n-di(butan-2-yl)hydroxylamine Chemical compound CCC(C)N(O)C(C)CC PRRGLBHZMSZRRW-UHFFFAOYSA-N 0.000 description 1
- BXCUMRWEJGRSCJ-UHFFFAOYSA-N n,n-di(cyclobutyl)hydroxylamine Chemical compound C1CCC1N(O)C1CCC1 BXCUMRWEJGRSCJ-UHFFFAOYSA-N 0.000 description 1
- QRGWVXYKHMMQJK-UHFFFAOYSA-N n,n-di(hexan-2-yl)hydroxylamine Chemical compound CCCCC(C)N(O)C(C)CCCC QRGWVXYKHMMQJK-UHFFFAOYSA-N 0.000 description 1
- ZSCCNTQVHNMLAL-UHFFFAOYSA-N n,n-di(hexan-3-yl)hydroxylamine Chemical compound CCCC(CC)N(O)C(CC)CCC ZSCCNTQVHNMLAL-UHFFFAOYSA-N 0.000 description 1
- YHULWDKLWCOKMX-UHFFFAOYSA-N n,n-di(pentan-2-yl)hydroxylamine Chemical compound CCCC(C)N(O)C(C)CCC YHULWDKLWCOKMX-UHFFFAOYSA-N 0.000 description 1
- VHVQKDSGSCCIGS-UHFFFAOYSA-N n,n-di(pentan-3-yl)hydroxylamine Chemical compound CCC(CC)N(O)C(CC)CC VHVQKDSGSCCIGS-UHFFFAOYSA-N 0.000 description 1
- OQAIUHLITJGRMM-UHFFFAOYSA-N n,n-di(propan-2-yl)hydroxylamine Chemical compound CC(C)N(O)C(C)C OQAIUHLITJGRMM-UHFFFAOYSA-N 0.000 description 1
- PAZXUKOJTOTKBK-UHFFFAOYSA-N n,n-dibutylhydroxylamine Chemical compound CCCCN(O)CCCC PAZXUKOJTOTKBK-UHFFFAOYSA-N 0.000 description 1
- QTZCGGNOVCUAQK-UHFFFAOYSA-N n,n-dicyclohexylhydroxylamine Chemical compound C1CCCCC1N(O)C1CCCCC1 QTZCGGNOVCUAQK-UHFFFAOYSA-N 0.000 description 1
- HETSPTVTJMBTMQ-UHFFFAOYSA-N n,n-dicyclopentylhydroxylamine Chemical compound C1CCCC1N(O)C1CCCC1 HETSPTVTJMBTMQ-UHFFFAOYSA-N 0.000 description 1
- ZNAZZYNEJKNPME-UHFFFAOYSA-N n,n-dihexylhydroxylamine Chemical compound CCCCCCN(O)CCCCCC ZNAZZYNEJKNPME-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- HSZZYODJBHTPQI-UHFFFAOYSA-N n,n-dipentylhydroxylamine Chemical compound CCCCCN(O)CCCCC HSZZYODJBHTPQI-UHFFFAOYSA-N 0.000 description 1
- ZKXYINRKIDSREX-UHFFFAOYSA-N n,n-dipropylhydroxylamine Chemical compound CCCN(O)CCC ZKXYINRKIDSREX-UHFFFAOYSA-N 0.000 description 1
- JQDZCJWPDXZTEW-UHFFFAOYSA-N n,n-ditert-butylhydroxylamine Chemical compound CC(C)(C)N(O)C(C)(C)C JQDZCJWPDXZTEW-UHFFFAOYSA-N 0.000 description 1
- NTSVXMGHAIZLPZ-UHFFFAOYSA-N n-(2,2-dimethylpropyl)hydroxylamine Chemical compound CC(C)(C)CNO NTSVXMGHAIZLPZ-UHFFFAOYSA-N 0.000 description 1
- QLPNSXRLLSDPLC-UHFFFAOYSA-N n-(2,3-dimethylbutyl)hydroxylamine Chemical compound CC(C)C(C)CNO QLPNSXRLLSDPLC-UHFFFAOYSA-N 0.000 description 1
- DAQPYPPPSAQSIA-UHFFFAOYSA-N n-(2-methylbutan-2-yl)hydroxylamine Chemical compound CCC(C)(C)NO DAQPYPPPSAQSIA-UHFFFAOYSA-N 0.000 description 1
- XWCWHVVFDNCIMX-UHFFFAOYSA-N n-(2-methylbutyl)hydroxylamine Chemical compound CCC(C)CNO XWCWHVVFDNCIMX-UHFFFAOYSA-N 0.000 description 1
- PIOJVVCRHKYGJE-UHFFFAOYSA-N n-(2-methylpentan-2-yl)hydroxylamine Chemical compound CCCC(C)(C)NO PIOJVVCRHKYGJE-UHFFFAOYSA-N 0.000 description 1
- WVZXUEVWJIPVSH-UHFFFAOYSA-N n-(2-methylpentyl)hydroxylamine Chemical compound CCCC(C)CNO WVZXUEVWJIPVSH-UHFFFAOYSA-N 0.000 description 1
- WYFCDDYEWBZEMS-UHFFFAOYSA-N n-(3,3-dimethylbutyl)hydroxylamine Chemical compound CC(C)(C)CCNO WYFCDDYEWBZEMS-UHFFFAOYSA-N 0.000 description 1
- YPORECDPLSEMDE-UHFFFAOYSA-N n-(3-methylbutan-2-yl)hydroxylamine Chemical compound CC(C)C(C)NO YPORECDPLSEMDE-UHFFFAOYSA-N 0.000 description 1
- KSALNWGFDJHSPJ-UHFFFAOYSA-N n-(3-methylbutyl)hydroxylamine Chemical compound CC(C)CCNO KSALNWGFDJHSPJ-UHFFFAOYSA-N 0.000 description 1
- OJYFNTFUPCTCFI-UHFFFAOYSA-N n-(3-methylpentan-2-yl)hydroxylamine Chemical compound CCC(C)C(C)NO OJYFNTFUPCTCFI-UHFFFAOYSA-N 0.000 description 1
- LCDPHSHZYJMDOB-UHFFFAOYSA-N n-(4-methylpentyl)hydroxylamine Chemical compound CC(C)CCCNO LCDPHSHZYJMDOB-UHFFFAOYSA-N 0.000 description 1
- LHYPXHNPQLMXDH-UHFFFAOYSA-N n-butan-2-ylhydroxylamine Chemical compound CCC(C)NO LHYPXHNPQLMXDH-UHFFFAOYSA-N 0.000 description 1
- FWVWNPGJLBPKME-UHFFFAOYSA-N n-cyclobutylhydroxylamine Chemical compound ONC1CCC1 FWVWNPGJLBPKME-UHFFFAOYSA-N 0.000 description 1
- GUQRKZPMVLRXLT-UHFFFAOYSA-N n-cyclohexylhydroxylamine Chemical compound ONC1CCCCC1 GUQRKZPMVLRXLT-UHFFFAOYSA-N 0.000 description 1
- XDYRBRLMIGIKQW-UHFFFAOYSA-N n-cyclopentylhydroxylamine Chemical compound ONC1CCCC1 XDYRBRLMIGIKQW-UHFFFAOYSA-N 0.000 description 1
- WQUFNDFVLMDJKA-UHFFFAOYSA-N n-hexan-2-ylhydroxylamine Chemical compound CCCCC(C)NO WQUFNDFVLMDJKA-UHFFFAOYSA-N 0.000 description 1
- NWICVCMFTBINCD-UHFFFAOYSA-N n-hexan-3-ylhydroxylamine Chemical compound CCCC(CC)NO NWICVCMFTBINCD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- VHEBUTOUXPMMJX-UHFFFAOYSA-N n-pentan-2-ylhydroxylamine Chemical compound CCCC(C)NO VHEBUTOUXPMMJX-UHFFFAOYSA-N 0.000 description 1
- NVEFQYHCCMKEOO-UHFFFAOYSA-N n-pentan-3-ylhydroxylamine Chemical compound CCC(CC)NO NVEFQYHCCMKEOO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 description 1
- XWESXZZECGOXDQ-UHFFFAOYSA-N n-tert-butylhydroxylamine Chemical compound CC(C)(C)NO XWESXZZECGOXDQ-UHFFFAOYSA-N 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a substrate cleaning agent for copper wiring and a method for cleaning a copper wiring semiconductor substrate characterized by using the cleaning agent. More specifically, in a step of forming a semiconductor element on a semiconductor substrate such as a silicon wafer, a step of removing a residue after performing chemical mechanical polishing (CMP) on a semiconductor substrate having copper wiring or copper alloy wiring.
- CMP chemical mechanical polishing
- the present invention relates to a copper wiring substrate cleaning agent to be used, and a copper wiring semiconductor substrate cleaning method using the copper wiring substrate cleaning agent.
- CMP chemical mechanical polishing
- CMP chemical mechanical polishing
- a semiconductor substrate with metal wiring such as silicon oxide film or copper wiring to be polished is planarized using a slurry containing abrasive grains (abrasive) such as silica or alumina. It is a method to do.
- the semiconductor substrate after such a chemical mechanical polishing (CMP) process is composed of the abrasive grains (polishing agent) used in the process itself, the metal contained in the slurry, metal impurities derived from the metal wiring to be polished, Contaminated by various particles. If the semiconductor substrate is contaminated with metal impurities or particles, it will adversely affect the electrical characteristics of the semiconductor itself and reduce the reliability of the device. Therefore, the semiconductor substrate is cleaned after the chemical mechanical polishing (CMP) process. It is necessary to remove metal impurities and particles from the surface.
- CMP chemical mechanical polishing
- the copper wiring or copper alloy wiring used in the semiconductor manufacturing process has high conductivity as described above, and has high metal activity, so that it is easily oxidized (corroded) by an external oxidizing action. For this reason, there are problems such as an increase in wiring resistance or a disconnection in some cases.
- CMP chemical mechanical polishing
- copper wiring or copper alloy wiring to be polished, copper (copper alloy) residue, scratches, dishing, etc. may occur, resulting in increased wiring resistance or disconnection. May be caused.
- benzotriazoles hereinafter, benzotriazole may be abbreviated as BTA
- imidazoles hereinafter, quinaldic acids
- QCA quinaldic acid
- Such metal corrosion inhibitors include, for example, complexes with monovalent copper in copper wiring or copper alloy wiring such as copper (I) -benzotriazole coating (Cu (I) -BTA coating), or copper (II)- A copper wiring such as a quinaldic acid film (Cu (II) -QCA film) or a complex with divalent copper in a copper alloy wiring is formed.
- a complex is easier to process than copper itself, so the copper (copper alloy) residue is suppressed, and the surface of the copper wiring or copper alloy wiring is protected, thereby suppressing the occurrence of scratches and dishing. It is believed to prevent corrosion.
- a cleaning agent such as that described in Patent Documents 1, 2, and 3 is simply formed as it is from a monovalent copper and a monovalent such as a Cu (I) -BTA film formed from benzotriazole or a derivative thereof.
- CMP chemical mechanical polishing
- Cu (I ) -BTA film and other films are peeled off, elution of metallic copper cannot be sufficiently suppressed, and the action of selectively removing Cu (II) is not sufficient.
- a cleaning agent as described in Patent Document 5 is simply formed from divalent copper and quinaldic acid or a derivative thereof, and a divalent copper such as a Cu (II) -QCA film is used.
- a cleaning agent after a chemical mechanical polishing (CMP) process of a semiconductor substrate having a copper wiring or copper alloy wiring formed with a coating with a metal corrosion inhibitor, copper and metal such as a Cu (II) -QCA coating
- CMP chemical mechanical polishing
- the present invention has been made in view of the above situation.
- a monovalent such as a Cu (I) -BTA film is used.
- Copper and metal corrosion prevention film (metal corrosion prevention film layer) made of copper complex does not dissolve, and copper and metal corrosion prevention made of divalent copper complex such as Cu (II) -QCA film
- the film (metal corrosion prevention film layer) with the agent can be dissolved and removed effectively. Furthermore, even when the metal corrosion prevention film layer is insufficiently formed, the metal copper is sufficiently dissolved.
- a copper wiring substrate cleaning agent that suppresses impurities and particles such as copper hydroxide (II) and copper oxide (II) generated in the chemical mechanical polishing (CMP) process, and the copper wiring substrate Cleaning a copper wiring semiconductor substrate characterized by using a cleaning agent It is to provide a law.
- the present invention is an invention for a substrate cleaning agent for copper wiring comprising [I] an aqueous solution containing an amino acid represented by the following general formula [1] and [II] alkylhydroxylamine.
- R 1 represents a hydrogen atom, a carboxymethyl group or a carboxyethyl group
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may have a hydroxyl group. Represents a group, except that R 1 to R 3 are all hydrogen atoms.
- the present invention uses [I] a copper wiring substrate cleaning agent comprising an aqueous solution containing the amino acid represented by the above general formula [1] and [II] alkylhydroxylamine. It is a method invention.
- the substrate cleaning agent for copper wiring of the present invention is used for, for example, a cleaning process of a substrate surface on which a copper wiring or a copper alloy wiring after a chemical mechanical polishing (CMP) process is formed, and Cu (I) -BTA.
- a film of copper and a metal corrosion inhibitor (metal corrosion prevention film layer) made of a monovalent copper complex such as a film does not dissolve, and it consists of a divalent copper complex such as a Cu (II) -QCA film.
- the method for cleaning a copper wiring semiconductor substrate of the present invention is an effective method for cleaning a semiconductor substrate or the like after a chemical mechanical polishing (CMP) process, for example, which has been subjected to copper wiring or copper alloy wiring.
- CMP chemical mechanical polishing
- the present inventors have found that only a specific amino acid represented by the general formula [1] is a Cu (I) -BTA film or the like among various amino acids.
- the monovalent metal corrosion prevention film layer is not dissolved, and the divalent metal corrosion prevention film layer such as Cu (II) -QCA film can be effectively dissolved and removed. It has been found that copper hydroxide (II) and / or copper oxide (II) can be removed without corroding metallic copper even when the formation of the prevention film layer is insufficient.
- alkylhydroxylamine which is a specific reducing agent, does not interfere with the action of dissolving and removing copper hydroxide (II) and / or copper (II) oxide of a specific amino acid represented by the above general formula [1].
- the inventors have found that the effects of the present invention can be obtained only by using these specific amino acids represented by the above general formula [1] and alkylhydroxylamine in combination, and have completed the present invention.
- the substrate cleaning agent for copper wiring of the present invention comprises [I] an aqueous solution containing an amino acid represented by the following general formula [1] and [II] alkylhydroxylamine.
- R 1 represents a hydrogen atom, a carboxymethyl group or a carboxyethyl group
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms which may have a hydroxyl group. Represents a group, except that R 1 to R 3 are all hydrogen atoms.
- alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group represented by R 2 and R 3 in the amino acid represented by the general formula [1] include, for example, a methyl group and an ethyl group A linear, branched or cyclic alkyl group such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 2,3-dihydroxy-n-propyl group, 2-hydroxyisopropyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2,3-dihydroxy-n-butyl group, 2,4-dihydroxy-n-butyl group, 3,4-dihydroxy
- amino acid represented by the general formula [1] include N-methylglycine (sarcosine), N-ethylglycine, Nn-propylglycine, N-isopropylglycine, Nn-butylglycine, N- N-alkyl glycines such as isobutyl glycine, N-sec-butyl glycine, N-tert-butyl glycine, N-cyclobutyl glycine, such as N, N-dimethylglycine, N, N-diethyl glycine, N, N-di- n-propylglycine, N, N-diisopropylglycine, N, N-di-n-butylglycine, N, N-diisobutylglycine, N, N-di-sec-butylglycine, N, N-di-tert-butyl N, N-dialkyl
- amino acids represented by [I] general formula [1] in the substrate cleaning agent for copper wiring of the present invention amino acids represented by the following general formula [2] and general formula [3] are preferable.
- R 2 ′ and R 3 ′ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, provided that R 2 ′ and R 3 ′ are Excluding those that are both hydrogen atoms.
- R 1 ′ represents a carboxymethyl group or a carboxyethyl group.
- the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group represented by R 2 ′ and R 3 ′ includes R 2 in the general formula [1]. And the same alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group represented by R 3 .
- amino acid represented by the general formula [2] include N-methylglycine (sarcosine), N-ethylglycine, Nn-propylglycine, N-isopropylglycine, Nn-butylglycine, N- N-alkyl glycines such as isobutyl glycine, N-sec-butyl glycine, N-tert-butyl glycine, N-cyclobutyl glycine, such as N, N-dimethylglycine, N, N-diethyl glycine, N, N-di- n-propylglycine, N, N-diisopropylglycine, N, N-di-n-butylglycine, N, N-diisobutylglycine, N, N-di-sec-butylglycine, N, N-di-tert-butyl N, N-dialkyl
- amino acids represented by the general formula [3] include amino acids such as aspartic acid and glutamic acid.
- N-methylglycine (sarcosine), N, N-bis (2-hydroxyethyl) glycine, N- [tris (hydroxymethyl) methyl] Glycine, aspartic acid, and glutamic acid are more preferable.
- Such amino acids as compared with other amino acids according to the present invention, effectively dissolve copper oxides such as copper hydroxide (II) and copper oxide (II) without dissolving metal copper as much as possible. The effect is particularly high in terms of removal.
- the amino acids represented by the general formula [2] and the general formula [3] are formed from monovalent copper and benzotriazole or a derivative thereof, a copper (I) -benzotriazole complex (Cu (I) -BTA complex) Even if it is used for a semiconductor substrate having a copper wiring covered with (a Cu (I) -BTA film is formed), the Cu (I) -BTA complex formed on the surface of the copper wiring is not particularly dissolved. It is effective.
- N, N-bis (2-hydroxyethyl) glycine and N- [tris (hydroxymethyl) methyl] glycine do not dissolve metallic copper as much as possible, and copper (II) hydroxide, copper (II) oxide, etc. It is an excellent amino acid in that it can effectively dissolve and remove the copper oxide, and can also effectively dissolve and remove the Cu (II) -QCA complex formed on the surface of the copper wiring.
- the amino acid represented by the general formula [1] can be used singly or in combination of two or more, but the amino acid is formed from copper (II) formed from divalent copper and quinaldic acid or a derivative thereof.
- copper (II) formed from divalent copper and quinaldic acid or a derivative thereof.
- N, N-bis It is preferable to use a combination of either (2-hydroxyethyl) glycine or N- [tris (hydroxymethyl) methyl] glycine and the other amino acid represented by general formula [1].
- Etc N, N-bis (2-hydroxyethyl) glycine and N-methylglycine (sarcosine), for example, N, N-bis (2-hydroxyethyl) glycine and glutamic acid.
- the weight ratio when using either N, N-bis (2-hydroxyethyl) glycine or N- [tris (hydroxymethyl) methyl] glycine in combination with the other amino acid represented by the general formula [1] From the viewpoint of the dissolution action of Cu (II) -QCA complex and free QCA and the corrosion action of copper wiring, for example, N, N-bis (2-hydroxyethyl) glycine and other general formula [1]
- the weight ratio of the amino acids shown (N, N-bis (2-hydroxyethyl) glycine: other amino acids) is usually 99: 1 to 30:70, preferably 90:10 to 60:40, more preferably 85: 15-70: 30.
- Examples of the [II] alkylhydroxylamine in the substrate cleaning agent for copper wiring of the present invention include those represented by the following general formula [4].
- R 4 represents an alkyl group having 1 to 6 carbon atoms
- R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
- alkylhydroxylamine represented by the general formula [4] specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 4 and R 5 include, for example, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1 , 2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group Linear,
- alkylhydroxylamine represented by the general formula [4] include, for example, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine, Nn- Propylhydroxylamine, N, N-di-n-propylhydroxylamine, N-isopropylhydroxylamine, N, N-diisopropylhydroxylamine, Nn-butylhydroxylamine, N, N-di-n-butylhydroxylamine, N-isobutylhydroxylamine, N, N-diisobutylhydroxylamine, N-sec-butylhydroxylamine, N, N-di-sec-butylhydroxylamine, N-tert-butylhydroxylamine, N, N-di-tert- Butylhydroxylamine, N-cyclobutylhydroxylamine, N , N-dicyclobutylhydroxylamine, Nn-pentylhydroxyl
- alkyl hydroxylamines represented by the general formula [4] N-ethylhydroxylamine, N, N-diethylhydroxylamine, and Nn-propylhydroxylamine are preferable.
- Such an alkylhydroxylamine has a particularly excellent effect in that it hardly dissolves metallic copper and the corrosion inhibiting effect of metallic copper as compared with other alkylhydroxylamines according to the present invention.
- the substrate cleaning agent for copper wiring of the present invention is an aqueous solution and contains water as a constituent component.
- the water here is not particularly limited as long as it does not adversely affect the cleaning step after chemical mechanical polishing (CMP), for example, ordinary water, for example, purified water such as distilled water or deionized water, ultrapure water, etc. Water is preferred, and ultrapure water is particularly preferred. Since ultrapure water contains almost no impurities, it is preferably used because it hardly affects the cleaning process.
- the copper wiring board cleaning agent of the present invention includes, for example, [III] amine or ammonium salt, [IV] hydrochloric acid, sulfuric acid as a pH adjuster.
- an acid or base such as phosphoric acid or any salt selected from these may be contained within a range not impeding the effects of the present invention.
- Specific examples of [III] amine or ammonium salt mentioned here include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, tris (hydroxymethyl) aminomethane, 2- (morpholino) ethanol, etc.
- Amines such as tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline and the like.
- Specific examples of the salt with hydrochloric acid include, for example, tetramethylammonium chloride.
- specific examples of the salt with sulfuric acid include, for example, tetrabutylammonium hydrogen sulfate.
- specific examples of the salt with phosphoric acid include, for example, tetrabutylammonium phosphate.
- alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, tris (hydroxymethyl) aminomethane, and 2- (morpholino) ethanol.
- alkanolamine is a divalent copper complex formed from a divalent copper and a metal corrosion inhibitor formed on a copper wiring surface such as a Cu (II) -QCA film to be cleaned. This is preferable in that it can be dissolved and removed effectively in a shorter time.
- a semiconductor substrate having a copper wiring or a copper alloy wiring on which a film of a divalent copper and a metal corrosion inhibitor such as a Cu (II) -QCA film is formed is to be cleaned, as a pH adjuster If a phosphate buffer such as disodium hydrogen phosphate or dipotassium hydrogen phosphate is used, free QCA or Cu (II) -QCA complex may not be removed.
- a phosphate buffer such as disodium hydrogen phosphate or dipotassium hydrogen phosphate
- the substrate cleaning agent for copper wiring of the present invention is the above [I], [II], [ III] and water or those consisting only of [I], [II], [IV] and water are desirable.
- “[I], [II], [III] and water, or [I], [II], [IV] and only water” means [I], [II], [ III) and water, or [I], [II], [IV] and other components other than water are said to contain no more than an amount that may adversely affect the cleaning of the substrate having copper wiring, It does not mean to exclude the presence of trace amounts of other components.
- the substrate cleaning agent for copper wiring of the present invention is used as an alkaline solution
- a base such as [III] amine or ammonium salt
- a pH of 9 to 11 is preferred.
- a pH of 9 to 10 is more preferable.
- [IV] preferably contains an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or any salt selected from these.
- an acidic to acidic solution a pH of 4 to 7 is preferable, and a pH of 4 to 6 is more preferable.
- the weight% concentration of each component contained in the substrate cleaning agent for copper wiring of the present invention that is, the weight% concentration of [I] amino acid represented by the general formula [1] and [II] alkylhydroxylamine is described below. explain.
- the weight% concentration of the amino acid represented by the general formula [1] in the substrate cleaning agent for copper wiring of the present invention is the amino acid relative to the total weight of the cleaning agent when the cleaning agent is used as an alkaline cleaning agent.
- the weight percentage is usually from 0.001 to 6% by weight, preferably from 0.001 to 3% by weight.
- the amino acid is usually 0.001 to 3% by weight, preferably 0.001 to 1% by weight, based on the total weight of the cleaning agent.
- concentration of the amino acid used is less than 0.001% by weight, the action of dissolving and removing copper (II) hydroxide and copper (II) oxide is weak, and these may remain on the substrate.
- the concentration of an amino acid here means the total weight% concentration which added the weight% concentration of all the amino acids shown by General formula [1], and each individual case when the said amino acid is used 2 or more types. Does not mean weight percent concentration.
- the weight% concentration of [II] alkylhydroxylamine in the substrate cleaning agent for copper wiring of the present invention is the weight% of the alkylhydroxylamine relative to the total weight of the cleaning agent when the cleaning agent is used as an alkaline cleaning agent.
- the amount is usually 0.001 to 20% by weight, preferably 0.001 to 15% by weight.
- the alkylhydroxylamine is generally 0.001 to 10% by weight, preferably 0.001 to 5% by weight, based on the total weight of the cleaning agent. is there.
- the use concentration of the alkylhydroxylamine is less than 0.001% by weight, oxidation and corrosion of the copper wiring due to dissolved oxygen cannot be sufficiently suppressed.
- the use concentration is 20 as an alkaline cleaning agent. If the concentration exceeds 10% by weight, which is the concentration used as an acidic cleaning agent, there are problems such as phase separation without dissolving in water.
- the use concentration of the pH adjuster that is appropriately added to the copper wiring board cleaning agent of the present invention is the target pH as described above.
- the amount used can be adjusted within a range that does not interfere with the effect of the cleaning agent of the present invention.
- [III]% by weight of a base such as an amine or ammonium salt
- the weight percentage of the base relative to the total weight of the cleaning agent is usually 0.002 to 10 weight%, preferably 0.002 to 8 weight%.
- [IV] wt% of acid such as hydrochloric acid, sulfuric acid, phosphoric acid or any salt selected from these is usually 0.002 to 10 wt% as wt% of the acid with respect to the total weight of the detergent. It is preferably 0.002 to 6% by weight.
- the substrate cleaning agent for copper wiring of the present invention is not particularly limited as long as it can finally prepare a solution containing each component according to the present invention.
- the above general formula according to the present invention is added to water or an aqueous solution to which a pH adjusting agent such as tetramethylammonium hydroxide or monoisopropanolamine is added, for example, by removing dissolved oxygen by bubbling dry nitrogen gas or the like.
- a pH adjusting agent such as tetramethylammonium hydroxide or monoisopropanolamine
- Examples include a method in which the amino acid and alkylhydroxylamine represented by [1] are directly added and stirred to obtain a uniform aqueous solution.
- the substrate to be cleaned is a substrate to which at least copper wiring or copper alloy wiring such as copper aluminum alloy is applied.
- the target substrate include a silicon (Si) substrate, a silicon carbide (SiC) substrate, a gallium arsenide (GaAs) substrate, a gallium phosphide (GaP) substrate, an indium phosphide (InP) substrate, and the like.
- a silicon (Si) substrate is preferable.
- the substrate may contain a barrier metal that prevents diffusion of copper into the insulating film.
- the partition metal include titanium (Ti), titanium nitride (TiN), tantalum (Ta), tantalum nitride (TaN), cobalt (Co), and ruthenium (Ru). It is done.
- the substrate includes an insulator film. Examples of the insulator film include a p-TEOS thermal oxide film, silicon nitride (SiN), silicon nitride carbide (SiCN), and a low dielectric film Low-k (SiOC). , SiC) and the like.
- the substrate cleaning agent for copper wiring of the present invention it is preferable to use it for a cleaning step after chemical mechanical polishing (CMP) treatment of a substrate having a copper wiring, that is, as a cleaning agent after Cu-CMP.
- CMP chemical mechanical polishing
- the substrate cleaning agent for copper wiring of the present invention is used as a cleaning agent after the chemical mechanical polishing (CMP) step, not only the abrasive grains (polishing agent) used in the chemical mechanical polishing (CMP) step, but also chemical mechanical polishing ( Impurities derived from copper wiring or copper alloy wiring such as copper hydroxide (II) and / or copper oxide (II) generated during the CMP process and various particles can be effectively removed.
- the substrate cleaning agent for copper wiring according to the present invention is a copper wiring or copper alloy wiring having a surface formed from monovalent copper and benzotriazole or a derivative thereof, among the substrates having copper wiring or copper alloy wiring. It is preferably used for a semiconductor substrate having a wiring covered with a Cu (II) -QCA complex formed from (I) -BTA complex or divalent copper and quinaldic acid or a derivative thereof.
- a semiconductor substrate having copper wiring or copper alloy wiring is treated with an abrasive containing benzotriazole or a derivative thereof (for example, benzotriazole-containing SiO 2 slurry), the surface of the copper wiring or copper alloy wiring on the substrate is monovalent.
- the surface of the copper wiring or the copper alloy wiring is covered with a monovalent copper complex formed from copper and benzotriazole or a derivative thereof, that is, a Cu (I) -BTA complex or a complex thereof.
- the substrate cleaning agent for copper wiring of the present invention can be obtained by removing copper (II) hydroxide and / or oxidation without removing the monovalent copper complex film on the surface of the copper wiring such as Cu (I) -BTA complex. Impurities derived from copper wiring or copper alloy wiring such as copper (II) can be effectively removed.
- the copper wiring substrate cleaning agent of the present invention is suitable for cleaning a semiconductor substrate having a wiring in which the surface of a copper wiring or a copper alloy wiring is treated with benzotriazole or a derivative thereof.
- a semiconductor substrate having copper wiring or copper alloy wiring is treated with an abrasive containing quinaldic acid or a derivative thereof (for example, quinaldic acid-containing SiO 2 slurry)
- the copper wiring or copper alloy wiring surface on the substrate is divalent.
- the surface of the copper wiring or the copper alloy wiring is covered with a divalent copper complex formed of copper and quinaldic acid or a derivative thereof, that is, a Cu (II) -QCA complex or a complex thereof.
- the substrate cleaning agent for copper wiring of the present invention removes the film of the divalent copper complex on the surface of the copper wiring such as Cu (II) -QCA complex, and at the same time, copper (II) hydroxide and / or copper oxide. Impurities derived from copper wiring or copper alloy wiring such as (II) can also be effectively removed.
- the surface of the copper wiring after the film of the divalent copper complex is removed is protected by a monovalent copper oxide such as copper oxide (I).
- the substrate cleaning agent for copper wiring of the present invention is suitable for cleaning a semiconductor substrate having a wiring in which the surface of a copper wiring or a copper alloy wiring is treated with quinaldic acid or a derivative thereof.
- the copper wiring semiconductor substrate cleaning method of the present invention uses [I] a copper wiring substrate cleaning agent comprising an aqueous solution containing the amino acid represented by the above general formula [1] and [II] alkylhydroxylamine.
- a copper wiring substrate cleaning agent comprising an aqueous solution containing the amino acid represented by the above general formula [1] and [II] alkylhydroxylamine.
- the method for cleaning a copper wiring semiconductor substrate of the present invention is characterized by using the substrate cleaning agent for copper wiring of the present invention, and the cleaning method itself is not particularly limited.
- each component relating to the substrate cleaning agent for copper wiring of the present invention is prepared within a predetermined concentration range by the above-described preparation method.
- cleaning is achieved by immersing the substrate as described above in the copper wiring substrate cleaning agent of the present invention.
- a method usually employed in this field such as a spin (dropping) method or a spraying (spray) method can be applied to the cleaning method, and there is no particular limitation.
- any of a batch type in which a plurality of substrates are processed at a time and a single wafer type in which a plurality of substrates are processed one by one may be used.
- the cleaning temperature at the time of cleaning in the method for cleaning a copper wiring semiconductor substrate of the present invention is not particularly limited as long as it is a cleaning temperature generally used in this field, and in particular, cleaning may be performed at 15 to 30 ° C. preferable. Further, the cleaning time at the time of cleaning is not particularly limited as long as it is usually performed in this field, but it is preferable to perform the cleaning in 15 to 120 seconds from the viewpoint that the substrate can be cleaned efficiently. .
- Example 1 and Comparative Example 1 Immersion experiment using a substrate cleaning agent for copper wiring 8 inches of Sematech 845 (copper wiring, barrier metal TaN, oxide film TEOS; manufactured by Sematech Co., Ltd.) with a polishing slurry containing benzotriazole (BTA).
- a wafer that was polished and then washed with pure water was purchased.
- the wafer was immersed in a 1% benzotriazole (BTA) aqueous solution for 1 hour to form a Cu (I) -BTA film on the surface of the copper wiring, and then rinsed with pure water using a single wafer cleaning machine (multi-spinner manufactured by Kaijo). Spin dried. Next, the substrate was cut into pieces of about 2 cm ⁇ 2 cm to obtain an evaluation substrate.
- BTA benzotriazole
- Various complexing agents (chelating agents) and various reducing agents shown in Tables 1 and 2 were added to 1% each, and the pH was adjusted to 9 or 6 with tetramethylammonium hydroxide (TMAH) or sulfuric acid. 10 mL of each aqueous solution (cleaning agent) was prepared. Next, the evaluation substrate was placed in the aqueous solution (cleaning agent) and immersed for 1 hour while stirring. Thereafter, the evaluation substrate is taken out from the aqueous solution (cleaning agent), rinsed with running water for 1 minute, dried with nitrogen gas, stored in a clean room with a humidity of 50% and 23 ° C. for one day, and field emission scanning electrons.
- TMAH tetramethylammonium hydroxide
- the degree of corrosion of the copper wiring surface was observed with a microscope (FE-SEM) (manufactured by Hitachi High-Technologies; S-4800).
- the results at pH 9 are shown in Table 1, and the results at pH 6 are shown in Table 2.
- surface corresponds to the board
- “-” in the table means that it has not been carried out.
- TMAH tetramethylammonium hydroxide
- Example 3 and Comparative Example 3 Copper (II) oxide dissolution experiment 50 mg of copper (II) oxide (99.99%; manufactured by Wako Pure Chemical Industries, Ltd.) powder was weighed and prepared in a 200 mL polyethylene beaker in advance. Next, various complexing agents (chelating agents) and various reducing agents shown in Table 4 were added so that each would be 1%, and an aqueous solution (cleaning agent) adjusted to pH 9 with tetramethylammonium hydroxide (TMAH). The 25 mL solution was put into the polyethylene beaker in which 50 mg of the copper (II) oxide powder was weighed, and stirred for 10 minutes to dissolve the copper (II) oxide.
- TMAH tetramethylammonium hydroxide
- the copper wiring board cleaning agent of the present invention that is, the complexing agent represented by the general formula [1] according to the present invention.
- the specific amino acid and the copper wiring board cleaning agent of the present invention which has selected alkylhydroxylamine as the reducing agent, suppresses corrosion on the copper wiring, and does not dissolve the copper metal. It was clarified that it can be dissolved and removed effectively. That is, from the results of Example 1, it was found that the substrate cleaning agent for copper wiring of the present invention did not corrode the copper wiring, and from the results of Example 2, it was found that elution of copper from the copper plate was suppressed. .
- the substrate cleaning agent for copper wiring of the present invention can effectively dissolve and remove copper (II) oxide. Furthermore, from the results of Experimental Example 1, when the amino acid represented by the general formula [1] according to the present invention is used, the zeta potential of silica shows a negative value. It was found that a cleaning agent capable of effectively removing the abrasive grains (polishing agent) from the substrate without attaching the grains (polishing agent) to the substrate was obtained.
- Example 4 and Comparative Example 5 Dissolution experiment of copper (II) -quinaldic acid complex (Cu (II) -QCA complex) and free quinaldic acid (QCA) After adding 200 ⁇ L of 0.1 M copper sulfate (CuSO 4 ) aqueous solution, stirring was performed to prepare an aqueous solution in which the Cu (II) -QCA complex and free QCA were suspended. Subsequently, 1000 ⁇ L of ultrapure water and 400 ⁇ L of 0.2M solutions of various amino acids shown in Table 6 adjusted to pH 9.7 with tetramethylammonium hydroxide (TMAH) were added to the above suspensions, respectively. The degree of suspension was visually confirmed.
- TMAH tetramethylammonium hydroxide
- Example 5 and Comparative Example 6 Dissolution experiment of copper (II) -quinaldic acid complex (Cu (II) -QCA complex) and free quinaldic acid (QCA) After adding 200 ⁇ L of 0.1 M copper sulfate (CuSO 4 ) aqueous solution, stirring was performed to prepare an aqueous solution in which the Cu (II) -QCA complex and free QCA were suspended.
- Cu (II) -QCA complex copper sulfate
- QCA free quinaldic acid
- the substrate cleaning agent for copper wiring according to the present invention is a Cu (II) -QCA complex formed from divalent copper and quinaldic acid or a derivative thereof.
- the amino acids represented by the general formula [1] according to the present invention at least N, N-bis (2-hydroxyethyl) glycine ( It has been found desirable to use an amino acid comprising any one of Bicine) and N- [Tris (hydroxymethyl) methyl] glycine (Tricine).
- Example 5 and Comparative Example 6 the Cu (II) -QCA complex and the free QCA were mixed with any one of Bicine and Tricine and other amino acids rather than with glutamic acid alone or sarcosine alone. It was found that the dissolution and removal ability of was excellent. In addition, when either Bicine or Tricine is mixed with other amino acids, the Cu (II) -QCA complex and free are equivalent to Bicine alone or Tricine alone or more by adjusting the weight ratio. It was found that the dissolution and removal ability of QCA was excellent.
- At least one of Bicine and Tricine is used as a component of the cleaning agent. Clarified that it is desirable to do.
- Examples 9 to 11 Immersion experiment using a substrate cleaning agent for copper wiring 8 inches of Sematech 845 (copper wiring, barrier metal TaN, oxide film TEOS; manufactured by Sematech) was polished with a polishing slurry containing benzotriazole (BTA). Thereafter, a wafer cleaned with pure water was purchased. The wafer was rinsed with methanol (MeOH), then immersed in an isopropanol (IPA) solution for 30 seconds, and further rinsed with pure water for 10 seconds. Next, the rinsed wafer was immersed in a 0.1 M dilute sulfuric acid aqueous solution for 30 seconds, rinsed with running water with pure water, washed with isopropanol (IPA) in that order, and then dried with nitrogen gas.
- IPA isopropanol
- the wafer was immersed in a slurry containing 1% quinaldic acid (QCA) containing 0.07% aqueous hydrogen peroxide for 30 seconds to form a Cu (II) -QCA film on the surface of the copper wiring, and then single wafer cleaning Rinsed with pure water and spin-dried with a machine (multi spinner manufactured by Kaijo). Next, the substrate was cut into pieces of about 2 cm ⁇ 2 cm to obtain an evaluation substrate.
- QCA quinaldic acid
- II 0.07% aqueous hydrogen peroxide
- the substrate cleaning agent for copper wiring of the present invention was formed from a Cu (II) -QCA complex formed from divalent copper and quinaldic acid or a derivative thereof.
- monoisopropanolamine is used as a base for adjusting the pH to be alkaline rather than an alkylammonium salt such as tetramethylammonium hydroxide (TMAH). It was found that the alkanolamine such as can dissolve and remove the Cu (II) -QCA complex in a shorter time.
- alkanolamine which is an organic solvent-based basic substance
- alkylammonium salt which is a water-soluble basic substance.
- the copper wiring substrate cleaning agent of the present invention has no adverse effect on the copper wiring, and copper (II) hydroxide and copper oxide (II) produced in the chemical mechanical polishing (CMP) process. It has been clarified that it is an excellent cleaning agent that can effectively remove impurities such as silica) and abrasive grains (polishing agent) such as silica used in the CMP process.
- the substrate cleaning agent for copper wiring of the present invention does not adversely affect the film (metal corrosion prevention film layer) of monovalent copper and metal corrosion inhibitor such as Cu (I) -BTA film, Since the film (metal corrosion prevention film layer) of divalent copper and metal corrosion inhibitor such as Cu (II) -QCA film can be removed, the copper wiring on which such a metal corrosion prevention film layer is formed Or it was clarified that it is a cleaning agent suitable for cleaning a semiconductor substrate having a copper alloy wiring.
- the substrate cleaning agent for copper wiring of the present invention can be used as a cleaning agent for a semiconductor substrate having a copper wiring or a copper alloy wiring after a chemical mechanical polishing (CMP) step, that is, a cleaning agent after Cu-CMP.
- CMP chemical mechanical polishing
- it is a cleaning agent suitable for a semiconductor substrate having a copper wiring or a copper alloy wiring having a metal corrosion prevention film layer formed on the surface thereof.
- the copper wiring semiconductor substrate cleaning method of the present invention is an effective method for cleaning, for example, a semiconductor substrate after a chemical mechanical polishing (CMP) process, which has been subjected to copper wiring or copper alloy wiring, and particularly on the surface thereof.
- CMP chemical mechanical polishing
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Abstract
Description
本発明の銅配線用基板洗浄剤は、〔I〕下記一般式[1]で示されるアミノ酸及び〔II〕アルキルヒドロキシルアミンを含む水溶液からなるものである。
本発明の銅配線半導体基板の洗浄方法は、〔I〕上記一般式[1]で示されるアミノ酸及び〔II〕アルキルヒドロキシルアミンを含む水溶液からなる銅配線用基板洗浄剤を用いることを特徴とするものである。すなわち、本発明の銅配線半導体基板の洗浄方法は、本発明の銅配線用基板洗浄剤を用いることを特徴とするものであり、洗浄方法自体は特に限定されない。
ベンゾトリアゾール(BTA)含有の研磨スラリーで8インチのセマテック845(銅配線、バリアメタルTaN、酸化膜TEOS;セマテック社製)を研磨し、その後、純水洗浄したウエハを購入した。そのウエハを1%ベンゾトリアゾール(BTA)水溶液に1時間浸漬し、銅配線表面にCu(I)-BTA皮膜を形成させた後、枚葉式洗浄機(カイジョー製マルチスピナー)で純水リンス、スピン乾燥した。次いで当該基板を2cm×2cm程度に細片化し、評価基板とした。
レアメタリック社製の銅板(純度4N)を2cm×2cm程度に細片化し、アセトン洗浄で脱脂した後、0.5Nの硫酸水溶液に1時間浸漬し表面の酸化物を除去した。その後、窒素ガスで脱気した純水でリンスし、窒素ガスで乾燥させた。次いでこの銅板を、表3に示す各種錯化剤(キレート剤)と各種還元剤とが各々1%となるように添加し、テトラメチルアンモニウムヒドロキシド(TMAH)でpHを9に調整した水溶液(洗浄剤)の各10mL溶液中に、直ちに投入した。当該水溶液(洗浄剤)を攪拌しながら15分間浸漬した後、該銅板を取り出して水溶液(洗浄剤)中に溶出した金属銅濃度を、溶存酸素によって酸化銅(II)に酸化した銅を指標として、誘電結合プラズマ発光分光分析装置(ICP-AES)(SII製;SPS-3100HV)で定量した。その結果を表3に示す。なお、表中の太字枠内の組成のものが本発明の銅配線用基板洗浄剤(実施例2)に該当し、その他のものは、比較のための洗浄剤(比較例2)に該当する。また、表中の「-」は未実施であることを意味する。
酸化銅(II)(99.99%;和光純薬工業株式会社製)粉末50mgを秤量し、予め200mLのポリエチレン製ビーカーに用意した。次いで表4に示す各種錯化剤(キレート剤)と各種還元剤とが各々1%となるように添加し、テトラメチルアンモニウムヒドロキシド(TMAH)でpHを9に調整した水溶液(洗浄剤)の25mL溶液を、上記酸化銅(II)粉末50mgが秤量された上記ポリエチレン製ビーカーにそれぞれ投入し、10分間攪拌して酸化銅(II)を溶解させた。その後、0.2μmの水系用のフィルターで未溶解の酸化銅(II)を除去し、ろ過後の洗浄剤中に溶解している銅濃度を誘電結合プラズマ発光分光分析装置(ICP-AES)(SII製;SPS-3100HV)で定量した。その結果を表4に示す。なお、表中の太字枠内の組成のものが本発明の銅配線用基板洗浄剤(実施例3)に該当し、その他のものは、比較のための洗浄剤(比較例3)に該当する。また、表中の「-」は未実施であることを意味する。
遠沈管に0.5%SiO2水溶液を1mL入れ、表5に示す各種錯化剤(キレート剤)を投入し、テトラメチルアンモニウムヒドロキシド(TMAH)でpHを調整すると共に、ゼータ電位の測定時に、錯化剤(キレート剤)の濃度が0.2Mになるように調整した水溶液とした。銅イオンを添加した場合は、硫酸銅(CuSO4)水溶液を用い、ゼータ電位の測定時に硫酸銅(CuSO4)の濃度も0.2Mになるように投入した。なお、pHは必ず測定前に調整し、テトラメチルアンモニウムヒドロキシド(TMAH)でpHが9となるようにした(測定機器:シスメックス製 ゼータサイザーμV)。その結果を表5に示す。なお、表中の太字枠内の組成のものが本発明の銅配線用基板洗浄剤に係る一般式[1]で示されるアミノ酸を含有するもの(実験例1)に該当し、その他のものは比較例4に該当する。また、表中の「-」は未実施であることを意味する。
キナルジン酸(QCA)及び水酸化カリウム含有の研磨スラリー1000μLに、0.1M硫酸銅(CuSO4)水溶液を200μL添加後、攪拌してCu(II)-QCA錯体及び遊離QCAを懸濁させた水溶液を用意した。次いで超純水1000μL及びテトラメチルアンモニウムヒドロキシド(TMAH)でpH9.7に調整した表6に示す各種アミノ酸の0.2M溶液400μLを、上記した懸濁液にそれぞれ添加し、添加後の溶液の懸濁度合いを目視確認した。その後、それぞれの溶液に85%ジエチルヒドロキシルアミン水溶液を50μL添加し、2分後の溶液の懸濁度合いを目視確認した。その結果を表6に示す。なお、表中の太字枠内の組成のものが実施例4に該当し、その他のものは、比較例5に該当する。
キナルジン酸(QCA)及び水酸化カリウム含有の研磨スラリー1000μLに、0.1M硫酸銅(CuSO4)水溶液を200μL添加後、攪拌してCu(II)-QCA錯体及び遊離QCAを懸濁させた水溶液を用意した。次いで超純水1000μL及び水酸化カリウムでpH9.7に調整した、(A)N,N-ビス(2-ヒドロキシエチル)グリシン(Bicine)単独、グルタミン酸単独又はこれら2種類のアミノ酸を任意の割合で混合した0.2M溶液400μL、あるいは(B)N,N-ビス(2-ヒドロキシエチル)グリシン(Bicine)単独、N-メチルグリシン(サルコシン)単独又はこれら2種類のアミノ酸を任意の割合で混合した0.2M溶液400μLを、上記懸濁液にそれぞれ添加し、添加後の溶液の懸濁度合いを目視確認した。その結果を表7に示す。なお、表中の太字枠内の組成比と目視観察の結果が実施例5に該当し、その他のものは、比較例6に該当する。
キナルジン酸(QCA)及び水酸化カリウム含有の研磨スラリー200μLに、0.1M硫酸銅(CuSO4)水溶液を40μL添加後、攪拌してCu(II)-QCA錯体及び遊離QCAを懸濁させた水溶液を用意した。次いで表8に示す組成比の各洗浄剤の30倍希釈溶液1000μLを、上記した懸濁液にそれぞれ添加し、添加直後からの溶液の懸濁度合いの経時変化を目視観察した。その結果を表8に示す。
ベンゾトリアゾール(BTA)含有の研磨スラリーで8インチのセマテック845(銅配線、バリアメタルTaN、酸化膜TEOS;セマテック社製)を研磨し、その後、純水洗浄したウエハを購入した。該ウエハをメタノール(MeOH)でリンスした後、イソプロパノール(IPA)溶液に30秒間浸漬し、更に純水で10秒間リンスした。次いでリンス後のウエハを0.1M希硫酸水溶液に30秒間浸漬し、純水による流水リンス、イソプロパノール(IPA)で順に洗浄後、窒素ガスで乾燥させた。そのウエハを、0.07%過酸化水素水溶液を含む1%キナルジン酸(QCA)含有スラリーに30秒間浸漬し、銅配線表面にCu(II)-QCA皮膜を形成させた後、枚葉式洗浄機(カイジョー製マルチスピナー)で純水リンス、スピン乾燥した。次いで当該基板を2cm×2cm程度に細片化し、評価基板とした。
Claims (27)
- 前記銅配線が、1価の銅とベンゾトリアゾール又はその誘導体とから形成される、銅(I)-ベンゾトリアゾール錯体で皮覆されたものである、請求項1に記載の洗浄剤。
- 前記銅配線が、2価の銅とキナルジン酸又はその誘導体とから形成される、銅(II)-キナルジン酸錯体で皮覆されたものである、請求項1に記載の洗浄剤。
- 前記基板が、化学機械研磨(CMP)後のものである、請求項1に記載の洗浄剤。
- 水酸化銅(II)及び酸化銅(II)の少なくともいずれかを除去するためのものである、請求項2に記載の洗浄剤。
- 銅(II)-キナルジン酸錯体と、水酸化銅(II)及び酸化銅(II)の少なくともいずれかとを除去するためのものである、請求項3に記載の洗浄剤。
- 前記水溶液のpHが、9~11の範囲である、請求項1に記載の洗浄剤。
- 前記水溶液のpHが、4~7の範囲である、請求項1に記載の洗浄剤。
- 更に〔III〕アミン又はアンモニウム塩を含む、請求項1に記載の洗浄剤。
- 更に〔IV〕塩酸、硫酸、リン酸又はこれらから選ばれるいずれかの塩を含む、請求項1に記載の洗浄剤。
- 前記〔I〕、〔II〕、〔III〕及び水のみからなる、請求項9に記載の洗浄剤。
- 前記〔I〕、〔II〕、〔IV〕及び水のみからなる、請求項10に記載の洗浄剤。
- 前記〔I〕一般式[1]で示されるアミノ酸の重量%が0.001~6重量%、前記〔II〕アルキルヒドロキシルアミンの重量%が0.001~20重量%、並びに前記〔III〕アミン又はアンモニウム塩の重量%が0.002~10重量%である、請求項9に記載の洗浄剤。
- 前記〔I〕一般式[1]で示されるアミノ酸の重量%が0.001~3重量%、前記〔II〕アルキルヒドロキシルアミンの重量%が0.001~10重量%、並びに前記〔IV〕塩酸、硫酸、リン酸又はこれらから選ばれるいずれかの塩の重量%が0.002~10重量%であって、前記銅配線が、1価の銅とベンゾトリアゾール又はその誘導体とから形成される、銅(I)-ベンゾトリアゾール錯体で皮覆されたものである、請求項10に記載の洗浄剤。
- 前記〔I〕一般式[1]で示されるアミノ酸が、N-メチルグリシン、N,N-ビス(2-ヒドロキシエチル)グリシン、N-[トリス(ヒドロキシメチル)メチル]グリシン、アスパラギン酸及びグルタミン酸から選ばれるものである、請求項2に記載の洗浄剤。
- 前記〔I〕一般式[1]で示されるアミノ酸の1種が、N,N-ビス(2-ヒドロキシエチル)グリシン及びN-[トリス(ヒドロキシメチル)メチル]グリシンから選ばれるものである、請求項3に記載の洗浄剤。
- 前記〔II〕アルキルヒドロキシルアミンが、N-エチルヒドロキシルアミン、N,N-ジエチルヒドロキシルアミン、N-n-プロピルヒドロキシルアミンから選ばれるものである、請求項1に記載の洗浄剤。
- 前記〔III〕アミン又はアンモニウム塩が、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、トリス(ヒドロキシメチル)アミノメタン、2-(モルホリノ)エタノール、テトラメチルアンモニウムヒドロキシド及びコリンから選ばれるものである、請求項9に記載の洗浄剤。
- 請求項1に記載の洗浄剤を用いることを特徴とする銅配線半導体基板の洗浄方法。
- 前記銅配線半導体基板が、ベンゾトリアゾール又はその誘導体を含有する溶液で処理されたものである、請求項21に記載の洗浄方法。
- 前記銅配線半導体基板が、キナルジン酸又はその誘導体を含有する溶液で処理されたものである、請求項21に記載の洗浄方法。
- 前記銅配線半導体基板が、化学機械研磨(CMP)後のものである、請求項21に記載の洗浄方法。
- 水酸化銅(II)及び酸化銅(II)の少なくともいずれかを除去するためのものである、請求項22に記載の洗浄方法。
- 銅(II)-キナルジン酸錯体と、水酸化銅(II)及び酸化銅(II)の少なくともいずれかとを除去するためのものである、請求項23に記載の洗浄方法。
- 15~30℃で洗浄する、請求項21に記載の洗浄方法。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014168166A1 (ja) | 2013-04-10 | 2014-10-16 | 和光純薬工業株式会社 | 金属配線用基板洗浄剤および半導体基板の洗浄方法 |
WO2015068823A1 (ja) | 2013-11-08 | 2015-05-14 | 和光純薬工業株式会社 | 半導体基板用洗浄剤および半導体基板表面の処理方法 |
WO2021230026A1 (ja) * | 2020-05-11 | 2021-11-18 | 株式会社ダイセル | 洗浄剤組成物及び化学的機械的研磨用組成物 |
WO2024095926A1 (ja) * | 2022-10-31 | 2024-05-10 | 東京応化工業株式会社 | 洗浄液、及び基板の洗浄方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6751015B2 (ja) * | 2013-03-15 | 2020-09-02 | キャボット マイクロエレクトロニクス コーポレイション | 銅の化学的機械的平坦化後のための水性清浄化組成物 |
EP3209815B1 (en) | 2014-10-21 | 2021-12-29 | CMC Materials, Inc. | Corrosion inhibitors and related compositions and methods |
CN107075310B (zh) | 2014-10-21 | 2019-04-02 | 嘉柏微电子材料股份公司 | 钴凹陷控制剂 |
WO2016065060A1 (en) * | 2014-10-21 | 2016-04-28 | Cabot Microelectronics Corporation | Cobalt polishing accelerators |
US9944828B2 (en) | 2014-10-21 | 2018-04-17 | Cabot Microelectronics Corporation | Slurry for chemical mechanical polishing of cobalt |
KR20170134925A (ko) * | 2016-05-27 | 2017-12-07 | 세메스 주식회사 | 기판 처리 장치 및 기판 처리 방법 |
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KR102245577B1 (ko) * | 2017-05-02 | 2021-04-28 | 주식회사 이엔에프테크놀로지 | Cmp-후 세정액 조성물 |
US10832917B2 (en) | 2017-06-09 | 2020-11-10 | International Business Machines Corporation | Low oxygen cleaning for CMP equipment |
CN113921383B (zh) | 2021-09-14 | 2022-06-03 | 浙江奥首材料科技有限公司 | 一种铜表面钝化组合物、其用途及包含其的光刻胶剥离液 |
CN114806693B (zh) * | 2022-05-27 | 2023-04-14 | 三象聚合物(湖北)有限公司 | 一种用于电火花线放电切割的高环保水性组合物 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09153472A (ja) * | 1995-11-30 | 1997-06-10 | Toshiba Corp | 半導体装置の製造装置および製造方法 |
JP2001517863A (ja) | 1997-09-23 | 2001-10-09 | アーチ・スペシャルティ・ケミカルズ・インコーポレイテッド | 半導体基板から残留物を除去する方法 |
JP2002299300A (ja) * | 2001-03-30 | 2002-10-11 | Kaijo Corp | 基板処理方法 |
JP2002359223A (ja) | 2001-05-30 | 2002-12-13 | Shibaura Mechatronics Corp | 洗浄液 |
WO2005040325A1 (en) | 2003-10-25 | 2005-05-06 | Unilever Plc | Detergent component |
JP2005217114A (ja) | 2004-01-29 | 2005-08-11 | Kao Corp | 銅配線用残渣洗浄剤 |
JP2006063201A (ja) | 2004-08-27 | 2006-03-09 | Sanyo Chem Ind Ltd | 洗浄剤 |
JP2010177702A (ja) * | 2004-03-19 | 2010-08-12 | Air Products & Chemicals Inc | 化学的機械的平坦化後用のアルカリ性洗浄組成物 |
JP2010535422A (ja) * | 2007-08-02 | 2010-11-18 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | マイクロ電子デバイスから残渣を除去するための非フッ化物含有組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69333877T2 (de) * | 1992-07-09 | 2006-06-14 | Ekc Technology Inc | Reinigungsmittelzusammensetzung, das einem Redox Aminverbindung enthält |
US6825156B2 (en) * | 2002-06-06 | 2004-11-30 | Ekc Technology, Inc. | Semiconductor process residue removal composition and process |
JP2003041385A (ja) * | 2001-07-27 | 2003-02-13 | Ajinomoto Co Inc | 金属表面保護膜形成剤及びその使用 |
US7435712B2 (en) * | 2004-02-12 | 2008-10-14 | Air Liquide America, L.P. | Alkaline chemistry for post-CMP cleaning |
CN101525563B (zh) * | 2008-03-03 | 2011-04-13 | 盟智科技股份有限公司 | 用于后研磨清洁剂的腐蚀抑制剂 |
US7825079B2 (en) * | 2008-05-12 | 2010-11-02 | Ekc Technology, Inc. | Cleaning composition comprising a chelant and quaternary ammonium hydroxide mixture |
US8361237B2 (en) * | 2008-12-17 | 2013-01-29 | Air Products And Chemicals, Inc. | Wet clean compositions for CoWP and porous dielectrics |
-
2011
- 2011-11-28 US US13/990,328 patent/US20130261040A1/en not_active Abandoned
- 2011-11-28 SG SG2013042007A patent/SG190444A1/en unknown
- 2011-11-28 CN CN201180057321XA patent/CN103228775A/zh active Pending
- 2011-11-28 EP EP20110845260 patent/EP2647693A4/en not_active Withdrawn
- 2011-11-28 KR KR1020137016793A patent/KR20130129997A/ko not_active Application Discontinuation
- 2011-11-28 WO PCT/JP2011/077436 patent/WO2012073909A1/ja active Application Filing
- 2011-11-28 JP JP2012546869A patent/JPWO2012073909A1/ja not_active Withdrawn
- 2011-11-29 TW TW100143675A patent/TW201231642A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09153472A (ja) * | 1995-11-30 | 1997-06-10 | Toshiba Corp | 半導体装置の製造装置および製造方法 |
JP2001517863A (ja) | 1997-09-23 | 2001-10-09 | アーチ・スペシャルティ・ケミカルズ・インコーポレイテッド | 半導体基板から残留物を除去する方法 |
JP2002299300A (ja) * | 2001-03-30 | 2002-10-11 | Kaijo Corp | 基板処理方法 |
JP2002359223A (ja) | 2001-05-30 | 2002-12-13 | Shibaura Mechatronics Corp | 洗浄液 |
WO2005040325A1 (en) | 2003-10-25 | 2005-05-06 | Unilever Plc | Detergent component |
JP2005217114A (ja) | 2004-01-29 | 2005-08-11 | Kao Corp | 銅配線用残渣洗浄剤 |
JP2010177702A (ja) * | 2004-03-19 | 2010-08-12 | Air Products & Chemicals Inc | 化学的機械的平坦化後用のアルカリ性洗浄組成物 |
JP2006063201A (ja) | 2004-08-27 | 2006-03-09 | Sanyo Chem Ind Ltd | 洗浄剤 |
JP2010535422A (ja) * | 2007-08-02 | 2010-11-18 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | マイクロ電子デバイスから残渣を除去するための非フッ化物含有組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2647693A4 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2014168166A1 (ja) | 2013-04-10 | 2014-10-16 | 和光純薬工業株式会社 | 金属配線用基板洗浄剤および半導体基板の洗浄方法 |
KR20150143627A (ko) | 2013-04-10 | 2015-12-23 | 와코 쥰야꾸 고교 가부시키가이샤 | 금속배선용 기판 세정제 및 반도체 기판의 세정방법 |
WO2015068823A1 (ja) | 2013-11-08 | 2015-05-14 | 和光純薬工業株式会社 | 半導体基板用洗浄剤および半導体基板表面の処理方法 |
KR20160083885A (ko) | 2013-11-08 | 2016-07-12 | 와코 쥰야꾸 고교 가부시키가이샤 | 반도체 기판용 세정제 및 반도체 기판 표면의 처리방법 |
US9862914B2 (en) | 2013-11-08 | 2018-01-09 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for semiconductor substrates and method for processing semiconductor substrate surface |
WO2021230026A1 (ja) * | 2020-05-11 | 2021-11-18 | 株式会社ダイセル | 洗浄剤組成物及び化学的機械的研磨用組成物 |
WO2024095926A1 (ja) * | 2022-10-31 | 2024-05-10 | 東京応化工業株式会社 | 洗浄液、及び基板の洗浄方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201231642A (en) | 2012-08-01 |
CN103228775A (zh) | 2013-07-31 |
JPWO2012073909A1 (ja) | 2014-05-19 |
EP2647693A4 (en) | 2014-05-28 |
US20130261040A1 (en) | 2013-10-03 |
SG190444A1 (en) | 2013-06-28 |
EP2647693A1 (en) | 2013-10-09 |
KR20130129997A (ko) | 2013-11-29 |
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