WO2011000694A1 - Aqueous alkaline cleaning compositions and methods of their use - Google Patents
Aqueous alkaline cleaning compositions and methods of their use Download PDFInfo
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- WO2011000694A1 WO2011000694A1 PCT/EP2010/058422 EP2010058422W WO2011000694A1 WO 2011000694 A1 WO2011000694 A1 WO 2011000694A1 EP 2010058422 W EP2010058422 W EP 2010058422W WO 2011000694 A1 WO2011000694 A1 WO 2011000694A1
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- carbon atoms
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- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 238000004140 cleaning Methods 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 230000003287 optical effect Effects 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 31
- 238000012545 processing Methods 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 12
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 8
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 8
- 238000009736 wetting Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- -1 4-hydroxy-n-butyl Chemical group 0.000 claims description 30
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 26
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 238000005498 polishing Methods 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- 125000004437 phosphorous atom Chemical group 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 10
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 10
- 238000009954 braiding Methods 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- 239000013538 functional additive Substances 0.000 claims description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- 229960004889 salicylic acid Drugs 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000000018 DNA microarray Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000012789 electroconductive film Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000005304 optical glass Substances 0.000 claims description 7
- 229910052594 sapphire Inorganic materials 0.000 claims description 7
- 239000010980 sapphire Substances 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 claims description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 6
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004201 L-cysteine Substances 0.000 claims description 6
- 235000013878 L-cysteine Nutrition 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 4
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 125000004367 cycloalkylaryl group Chemical group 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 claims description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 claims description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 claims description 3
- NIQIPYGXPZUDDP-UHFFFAOYSA-N 3-aminocyclohexan-1-ol Chemical compound NC1CCCC(O)C1 NIQIPYGXPZUDDP-UHFFFAOYSA-N 0.000 claims description 3
- MNUOZFHYBCRUOD-UHFFFAOYSA-N 3-hydroxyphthalic acid Chemical compound OC(=O)C1=CC=CC(O)=C1C(O)=O MNUOZFHYBCRUOD-UHFFFAOYSA-N 0.000 claims description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 3
- IMLXLGZJLAOKJN-UHFFFAOYSA-N 4-aminocyclohexan-1-ol Chemical compound NC1CCC(O)CC1 IMLXLGZJLAOKJN-UHFFFAOYSA-N 0.000 claims description 3
- MWRVRCAFWBBXTL-UHFFFAOYSA-N 4-hydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C=C1C(O)=O MWRVRCAFWBBXTL-UHFFFAOYSA-N 0.000 claims description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 125000005215 cycloalkylheteroaryl group Chemical group 0.000 claims description 3
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- WGBBUURBHXLGFM-UHFFFAOYSA-N hexan-2-amine Chemical compound CCCCC(C)N WGBBUURBHXLGFM-UHFFFAOYSA-N 0.000 claims description 3
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 31
- 229910052802 copper Inorganic materials 0.000 description 31
- 239000010949 copper Substances 0.000 description 31
- 235000012431 wafers Nutrition 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 230000008569 process Effects 0.000 description 19
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 13
- 235000018417 cysteine Nutrition 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 230000010354 integration Effects 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 11
- 239000000356 contaminant Substances 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 230000009977 dual effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 6
- 239000013307 optical fiber Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004630 atomic force microscopy Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 2
- 235000008206 alpha-amino acids Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- WPHGSKGZRAQSGP-UHFFFAOYSA-N norcarane Chemical compound C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- 238000009987 spinning Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BEWYHVAWEKZDPP-UHFFFAOYSA-N bornane Chemical compound C1CC2(C)CCC1C2(C)C BEWYHVAWEKZDPP-UHFFFAOYSA-N 0.000 description 1
- 229930006742 bornane Natural products 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000002356 laser light scattering Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 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
- 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
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 150000004905 tetrazines Chemical class 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- 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
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- 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
- C11D7/34—Organic compounds containing sulfur
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/26—Cleaning or polishing of the conductive pattern
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
Definitions
- the present invention relates to new aqueous alkaline cleaning compositions for processing substrates useful for fabricating electrical and optical devices, in particular electrical devices, including compositions useful for surface preparation, pre-plaiting cleaning, post-etch cleaning and post-chemical mechanical polishing cleaning. Moreover, the present invention relates to new methods for processing substrates useful for fabricating electrical and optical devices, in particular electrical devices, including new methods for surface preparation, pre-plaiting cleaning, post-etch cleaning and post- chemical polishing cleaning, which new methods make use of the new aqueous alkaline cleaning compositions.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards micro machines
- DNA chips DNA chips
- micro plants and magnetic heads preferably ICs with LSI (large- scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro- conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks; requires high precision methods which involve inter alia surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-chemical polishing cleaning steps using high-purity cleaning compositions.
- the semiconductor wafers used for this purpose include a semiconductor substrate such as silicon, into which regions are patterned for the deposition of different materials having electrically insulative, conductive or semiconductive properties. In order to obtain the correct patterning, excess material used in forming the various layers on the substrates must be removed. Further, to fabricate functional and reliable ICs, it is important to have flat or planar semiconductor wafer surfaces. Thus, it is necessary to remove and/or polish certain surfaces of a semiconductor wafers during the fabrication of the ICs before carrying out the next process steps.
- CMP Chemical Mechanical Polishing or Planarization
- a chemical process such as oxidation or chelation.
- CMP involves applying a slurry, i.e. a suspension of an abrasive and an active chemistry, to a polishing pad that buffs the surface of a semiconductor wafer to achieve the removal, planarization and polishing. It is not desirable for the removal or polishing to be comprised of purely physical or purely chemical action, but rather the synergistic combination of both in order to achieve a fast uniform removal.
- the CMP slurry should also be able to preferentially remove films that comprise complex layers of metals and other materials so that highly planar surfaces can be produced for subsequent photolithography, patterning, etching and thin-film processing.
- copper is increasingly used for metal interconnects in ICs.
- the layers that must be removed and planarized include copper layers having a thickness of about 1-1.5 ⁇ m and copper seed layers having a thickness of about 0.05-0.15 ⁇ m.
- These copper layers are separated from the low-k and ultra low-k dielectric material by a layer of barrier material, typically about 5 to 30 nm thick, which prevents diffusion of copper into the low-k or ultra low-k dielectric material.
- barrier material typically about 5 to 30 nm thick, which prevents diffusion of copper into the low-k or ultra low-k dielectric material.
- the key to obtaining good uniformity across the wafer surface after polishing is to use a CMP slurry that has the correct removal selectivities for each material.
- the foregoing processing operations involving wafer substrate surface preparation, deposition, plating, etching and chemical mechanical polishing variously require cleaning operations to ensure that the ICs are free from contaminants that would otherwise deleteriously affect the function of the ICs, or even render them useless for their intended functions.
- One particularly grave issue are the residues that are left on the substrates following CMP processing.
- Such residues include CMP material and corrosion inhibitor compounds such as benzotriazole (BTA).
- BTA benzotriazole
- the copper ion concentration can exceed the maximum solubility of the copper-inhibitor complexes during CMP. Therefore, the copper-inhibitor complexes can precipitate from solution and can coagulate into a surface residue.
- these residues can stick to the surface of the polishing pad and accumulate to eventually filling the grooves in the polishing pad.
- abrasive particles and chemicals contained in the CMP slurries as well as reaction by-products can be left behind on the wafer surface.
- ultra low-k dielectric materials such as carbon-doped oxides or organic films
- the polishing of copper damascene structures containing ultra low-k dielectric materials can generate carbon-rich particles that settle on to the wafer surface.
- all these residues can also contaminate the processing tools employed in the process which come into contact with the CMP slurries.
- silicon nitride or silicon oxynitride CMP stop layers are very hydrophobic and hence are difficult to clean with water-based cleaning solutions.
- residues can cause a severe roughening of the copper metallization, which has to be avoided since this causes a poor electrical performance.
- Another residue-producing process common to IC manufacturing involves gasphase plasma etching to transfer the patterns of developed photoresist coatings to the underlying layers, which may consist of hardmask, interleval dielectric and etch-stop layers.
- Post gasphase plasma etch residues which may include chemical elements present on and in the substrate and in the plasma gases, are typically deposited on the back end of the line (BEOL) structures and, if not removed, may interfere with the subsequent silicidation and contact formation.
- metal ion-free silicates such as quaternary ammonium silicates, metal chelating agents and such as salicylic acid,
- organic solvents such as glycol ethers, and
- non-ionic surfactants such as polyoxyethylene monoalkyl ethers and alkylene glycol monoalkyl ethers.
- Example 29 discloses the solution S8 which consists of de-ionized water
- cysteine as a potential titanium residue removal enhancer.
- test results presented in the Table 28 show that cysteine has no beneficial effect in this regard.
- the American patent US 6,200,947 B1 discloses aqueous alkaline cleaning liquids containing tetraalkylammonium hydroxides and an aliphatic alcohol compound having at least one mercapto group in the molecule as metal-corrosion inhibitor.
- polar organic amines such as ethanolamine
- the American patent application US 2003/0207778 A1 , the international patent application WO 03/053602 A1 and the American patent US 7,387,964 B2 disclose aqueous alkaline copper polishing cleaning compositions containing inter alia complexing agents selected from the group consisting of unidentate alkyl amines such as ethanolamine, bidentate alkyl amines such as ethylenediamine and diethylenetriamine and tridentate amines such as triethylenetetraamine and quaternary ammonium salts such as tetramethylammonium hydroxide .
- the American patent application US 2005/0181961 A1 and the American patent US 7,435,712 B2 disclose potential aqueous alkaline cleaning compositions containing inter alia - tetraalkylammonium hydroxides as cleaning agents,
- cysteine ethylenediamine and salicylic acid as complexing agents, and/or cysteine as corrosion-inhibiting compound.
- the international patent application WO 2006/081406 A1 page 20 discloses the same aqueous alkaline cleaning compositions K and M. As follows from Table 1 , page 26, paragraph [00122] in conjunction with page 27, paragraph [00123], both compositions exhibit only a poor cleaning efficiency. Additionally, according to page 37, Example 13, paragraph [00171] in conjunction with the Figure 9, the said aqueous alkaline cleaning compositions also cause a high roughness of the treated copper surfaces. Moreover, the international patent application also discloses on page 26 the aqueous alkaline cleaning composition DF comprising inter alia ethanolamine, tetramethylammonium hydroxide and
- WO 2006/127885 A1 discloses aqueous alkaline post- CMP cleaning compositions containing inter alia amine compounds such as ethanolamine and triethylenediamine,
- polyalkylene glycol alkyl ethers such as diethylene glycol monobutyl ether as complexing agents.
- aqueous alkaline cleaning or stripping compositions are susceptible to degradation when exposed to oxygen, which in turn results in darkening of the color of the compositions, with the result that sensors associated with the fabrication process tools yield erroneous outputs that can compromise the function and reliability of the tool. Additionally, such degradation involves the loss of cleaning and/or stripping power. This can become so extensive in the case of prolonged oxygen exposure that the cleaning or stripping composition has no longer a significant efficacy.
- the international patent application WO 2005/093031 A1 discloses an improved acidic chemistry for post-CMP cleaning.
- the acidic cleaning solution is in the neutral to low pH range and comprises a cleaning agent such as cysteine or salicylic acid and a corrosion- inhibiting compound such as as cysteine.
- a cleaning agent such as cysteine or salicylic acid
- a corrosion- inhibiting compound such as cysteine.
- acidic chemistry is tend to attack metallic surfaces to a much greater extent, in particular in the presence of complexing agents and oxygen. Therefore, the skilled artisan can derive nothing from the international patent application as to how he could increase the undesirably low stability of the alkaline cleaning compositions containing cysteine.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards micro machines
- DNA chips, micro plants and magnetic heads more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks, which fabrication requires high precision methods involving inter alia surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps using
- novel aqueous alkaline cleaning compositions should no longer exhibit the disadvantages of the prior art compositions such as discoloration, darkening and decomposition upon exposure to oxygen so that they can be easily prepared, stored, transported, handled and used even after prolonged storage without loss of cleaning and/or stripping power and without causing erroneous outputs of the sensors associated with the fabrication process tools, which outputs can compromise the function and reliability of the tools.
- novel aqueous alkaline cleaning compositions ought to be particularly well-suited for carrying out the above-mentioned cleaning steps, in particular, the post-CMP cleaning of semiconductor wafers during the fabrication of ICs with LSI or VLSI, in particular via the copper damascene or dual damascene process.
- novel aqueous alkaline cleaning compositions ought to remove most efficiently all kinds of residues and contaminants generated during the substrate surface preparation, deposition, plating, etching and CMP to ensure that the substrates, in particular the ICs, are free from residues and contaminants that would otherwise deleteriously affect the functions of the electrical and optical devices, in particular the ICs, or render them even useless for their intended functions. In particular, they should prevent the roughening of the copper metallization in damascene structures.
- novel aqueous alkaline cleaning compositions ought to remove most efficiently such residues and and contaminants not only from the substrates but also from the fabrication tools which are used in the various processes.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards micro machines
- DNA chips micro plants
- the novel methods for fabricating electrical and optical devices ought to involve surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps, more particularly post-etch and/or post-CMP cleaning steps, and, most particularly, post-CMP cleaning steps using the novel aqueous alkaline cleaning compositions.
- the novel methods for fabricating electrical devices ought to be particularly well-suited for the fabrication of ICs with LSI or VLSI, especially with the help of the copper damascene and dual damascene process.
- the novel methods ought to remove contaminants and residues such as particles consisting of or containing copper, copper oxide, copper-inhibitor complexes, abrasives and carbon after the CMP step from the substrate surfaces, the polishing pads and other processing tools most efficiently without scratching, etching and roughening the copper surfaces.
- novel aqueous alkaline cleaning compositions comprising
- compositions of the invention novel aqueous alkaline cleaning compositions
- novel methods for processing substrates useful for fabricating electrical and optical devices were found, the said methods making use of at least one composition of the invention in at least one process step.
- novel methods for processing substrates useful for fabricating electrical and optical devices are referred to as the "methods of the invention”.
- compositions of the invention were excellently suited for processing substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards printed circuit boards
- micro machines DNA chips
- micro plants and magnetic heads more preferably ICs with LSI (
- compositions of the invention were most excellently suited for high precision fabrication methods involving inter alia surface preparation, pre- plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps.
- the compositions of the invention themselves no longer exhibited the disadvantages of the prior art compositions such as discoloration, darkening and decomposition upon exposure to oxygen so that they could be easily prepared, stored, transported, handled and used even after prolonged storage without loss of cleaning and/or stripping power and without causing erroneous outputs of the sensors associated with the fabrication processing tools, which outputs compromised the function and reliability of the processing tools.
- compositions of the invention were most particularly well-suited for carrying out the above-mentioned cleaning steps, in particular, the post-CMP cleaning of semiconductor wafers and the fabrication of ICs with LSI or VLSI, in particular by the copper damascene or dual damascene process.
- compositions of the invention removed most efficiently all kinds of residues and contaminants generated during the substrate surface preparation, deposition, plating, etching and CMP and ensured that the substrates, in particular the ICs, were free from residues and contaminants that would have otherwise deleteriously affected the functions of the electrical and optical devices, in particular the ICs, or would have rendered them even useless for their intended functions. In particular, they prevented the scratching, etching and roughening of the copper metallization in damascene structures. Moreover, the compositions of the invention removed such residues and and contaminants most efficiently not only from the substrates but also from processing tools used in the various fabrication processes.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards micro machines
- DNA chips DNA chips
- micro plants and magnetic heads more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
- ITO indium tin oxide
- optical switching elements optical waveguides
- optical monocrystals such as the end faces of optical fibers and scintillators
- solid laser monocrystals such as the end faces of optical fibers and scintillators
- the methods of the invention were most excellently suited for the fabrication of electrical and optical devices, in particular electrical devices, which fabrication involved surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps, more particularly post-etch and/or post-CMP cleaning steps, and, most particularly, post-CMP cleaning steps.
- the methods of the invention were most particularly well-suited for the fabrication of ICs with LSI or VLSI, especially with the help of the copper damascene and dual damascene process.
- the methods of the invention removed contaminants and residues such as particles containing or consisting of copper, copper oxide, copper-inhibitor complexes, abrasives and carbon after the CMP steps from the substrate surfaces, the polishing pads and other processing tools most efficiently without scratching, etching and roughening the copper surfaces.
- the present invention relates to the compositions of the invention.
- compositions of the invention are aqueous alkaline cleaning compositions for processing substrates useful for fabricating electrical and optical devices.
- compositions of the invention contain water.
- the water content can vary broadly from competition to composition.
- Alkaline means that the compositions of the invention have a pH in the range of from 8 to 14, preferably 9 to 13 and, most preferably, 8.5 to 12.5.
- compositions of the invention comprise as the first essential component at least one, preferably one thioamino acid (A) having at least one, preferably one primary amino group and at least one, preferably one mercapto group.
- the thioamino acid (A) may be an synthetic or naturally occurring, preferably a naturally occurring amino acid. More preferably, the thioamino acid (A) is an alpha-amino acid. Even more preferably, the mercapto group of the thioamino acid (A) is in the gamma-position. Most preferably, the thioamino acid (A) is an alpha-amino acid having the mercapto group in the gamma- position.
- the thioamino acid (A) has the general formula I:
- n is an integer of 1 to 3, preferably 1 or 2. Most preferably, n equals 1.
- residues R 1 and R 2 of the general formula I are selected independently from each other from the group consisting of - hydrogen atoms; straight and branched, saturated and unsaturated, preferably saturated, substituted and unsubstituted, preferably unsubstituted aliphatic residues having 1 to 10 carbon atoms, preferably alkyl residues, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1 -methyl butyl, 2-methyl butyl, 3-methyl butyl, 1 -ethyl propyl, 1 ,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl, octyl, iso-octyl, nonyl or decyl; substituted and unsubstituted, preferably unsubstituted, saturated and unsaturated,
- the residues R 1 and R2 together form a saturated or unsaturated, preferably saturated, substituted or unsubstituted, preferably unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms is or are replaced by one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms.
- the residue R 3 of the general formula I is a single residue R 1 or R 2 or a covalent bond or bivalent group linking the carbon atom carrying the amino group and the carboxyl group to one of the residues R 1 or R 2 or to the ring formed by the residues R 1 and R 2 .
- the bivalent linking group is stable in the presence of the quaternary ammonium salt (B), which means that it does not hydrolyze or hydrolyzes only very slowly to a very small extent so that the concentration of the hydrolyzation products is so low that they do not interfere with the function of the compositions of the invention.
- the bivalent linking group is selected from the group consisting of:
- the substituted residues R 1 , R 2 and R 3 described above can contain any substituents as long as the substituents are stable in the presence of the quaternary ammonium hydroxide (B), which means that they do not hydrolyze or hydrolyze only very slowly to a very small extent and do not cause any undesired reactions which could lead to the decomposition and/or the agglomeration and/or the formation of precipitates in or of the compositions of the invention.
- the substituents are selected from the group consisting of:
- the thioamino acids (A) of the general formula I can be racemic or enantiomeric mixtures which may be equimolar or non-equimolar, or one of the respective enantiomers or diastereomers.
- At least one of the residues R 1 , R 2 and R 3 described above is a hydrogen atom. Even more preferably, all of the residues R 1 , R 2 and R 3 are hydrogen atoms.
- the thioamino acid (A) is selected from cysteine and homocysteine, in particular, cysteine, especially L-cysteine.
- compositions of the invention comprise as the second essential component at least one, preferably one quaternary ammonium hydroxide (B). More preferably, the quaternary ammonium hydroxide (B) has the general formula II:
- the residue R 1 is having the above defined meaning except hydrogen atom, whilst all the residues R 1 are the same or at least two residues R 1 are different from each other and all the residues R 1 are single residues or at least two residues R 1 form a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms are replaced by one hetero atom selected from the group of oxygen, sulfur, nitrogen and phosphorus atoms.
- the residue R 1 of the general formula Il is selected from the group consisting of straight and branched, substituted and unsubstituted, saturated aliphatic residues having 1 to 10, in particular, 1 to 4 carbon atoms.
- the quaternary ammonium hydroxide (B) of the general formula Il only contains residues R 1 which are unsubstituted and saturated, all residues R 1 are preferably the same.
- the quaternary ammonium hydroxide (B) of the general formula Il contains residues R 1 which are a substituted and saturated, it is preferred that only one of the residues R 1 is substituted.
- the quaternary ammonium hydroxide (B) of the general formula Il contains methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 2- hydroxyethyl, 2- and 3-hydroxypropyl and/or 4-hydroxy-n-butyl groups, in particular, methyl and/or 2-hydroxyethyl groups.
- TMAH tetramethylammonium hydroxide
- TMAH tetramethylammonium hydroxide
- choline especially TMAH
- compositions of the invention contain as the third essential componentat least one chelating and/or corrosion inhibiting agent (C) selected from the group consisting of aliphatic and cycloaliphatic amines having at least two, preferably two primary amino groups, aliphatic and cycloaliphatic amines having at least one, preferably one hydroxy group, and aromatic compounds having at least one, preferably one acid group, in particular at least one, preferably one carboxylic acid group, and at least one, preferably one hydroxy group.
- C chelating and/or corrosion inhibiting agent
- the aliphatic amine (C) having at least two primary amino groups is selected from the group consisting ethylenediamine, propylenediamine, n-butylenediamine, diethylenetriamine, dipropylenetriamine, di-n-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, and tri-n-butylenetetraamine, more preferably ethylenediamine and triethylenetetraamine, most preferably ethylenediamine.
- the cycloaliphatic amine (C) is selected from the group consisting of 1 ,2-, 1 ,3- and 1 ,4-diamino cyclohexane;
- the aliphatic amine (C) having at least one hydroxy group is selected from the group consisting of ethanolamine, diethanolamine and triethanolamine, most preferably ethanolamine.
- the cycloaliphatic amine (C) having at least one hydroxy group is selected from the group consisting of 2-, 3- and 4-hydroxy cyclohexylamine.
- the aromatic compound (C) having at least one, preferably one carboxylic acid group and at least one, preferably one hydroxy group is selected from the group consisting of salicylic acid, 3- and 4-hydroxy phthalic acid, 2-hydroxy terephthalic acid, and 3-, 4-, 5- and 6-hydroxy salicylic acid, most preferably salicylic acid.
- the chelating and/or corrosion inhibiting agent (C) is selected from the group consisting of ethylenediamine, triethylenetetraamine, ethanolamine and salicylic acid.
- compositions of the invention comprise as the fourth essential component at least one, preferably one organic solvent (D) having wetting properties and melting point below 0 0 C.
- a solvent having wetting properties comprises a hydrophilic and a hydrophobic structural element so that the solvent is capable of lowering the surface tension of solids and liquids.
- any organic solvent (D) having the above-mentioned properties can be used, as long as it is not decomposed by water or causes the decomposition and/or precipitation and/or agglomeration of one of the components of the compositions of the invention.
- the organic solvent (D) is selected from the group consisting of polyalkylene glycol mono ethers. More preferably, the polyalkylene glycol mono ether (D) is of the general formula III: HO-(-R 4 -O-) m -R 1 (III), wherein the variables and the index have the following meaning: m integer of from 2 to 6, preferably 2 to 4, more preferably 2 or 3 and most preferably 2; R 1 as defined above, except hydrogen atom; and
- R 4 alkylene group having 2 to 4, preferably 2 or 3 and, most preferably, 2 carbon atoms.
- the polyalkylene glycol mono ether (D) of the general formula (III) is selected from the group consisting of diethylene glycol monomethyl, monoethyl, mononpropyl and mono-n-butyl ether, most preferably diethylene glycol mono-n-butyl ether.
- compositions of the invention can contain at least one functional additive (E) which is different from the essential components (A), (B), (C) and (D).
- the functional additive (E) is selected from the group consisting of corrosion inhibitors, bases, titanium residue removal enhancers, organic solvents, alcohols having at least one mercapto group, complexing or chelating agents, surfactants and metal free silicates.
- compositions of the invention can contain the essential components (A), (B), (C) and (D) and optionally (E) in broadly varying amounts.
- the compositions of the invention can be highly concentrated solutions which contain only small amounts of water.
- compositions of the invention are diluted or highly diluted aqueous compositions, i.e., they contain more than 50% by weight, more preferably more than 75% by weight and, most preferably, more than 90% by weight of water, each weight percentage being based on a complete weight of a composition of the invention.
- compositions of the invention contain
- component (A) 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight and, most preferably, 1 to 2% by weight of the component (B);
- the amounts of the optional functional additive or additives (E) can also vary broadly. Preferably, the customary amounts known from the prior art cited above are used.
- compositions of the invention can be prepared by customary and standard mixing processes and mixing apparatuses such as agitated vessels, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used for carrying out the mixing of the components of the compositions in the desired amounts.
- compositions of the invention are excellently suited for the methods of the invention.
- compositions of the invention are also excellently suited for cleaning all kinds of processing tools such as polishing pads, sensors, nozzles, pipes and/or structural features of the equipment used, which tools come into contact with other processing liquids used in fabricating electrical or optical devices.
- the main purpose of the methods of the invention is the processing of substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
- ICs semiconductor integrated circuits
- liquid crystal panels organic electroluminescent panels
- printed circuit boards micro machines
- DNA chips micro plants and magnetic heads
- optical glasses such as photo-masks, lenses and pris
- the methods of the invention involve surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps, in particular post-CMP cleaning steps.
- the methods of the invention are particularly well-suited for the processing of substrates useful for fabricating ICs with LSI or VLSI, in particular in the back end of the line processing (BEOL).
- the methods of the invention are most particularly well-suited for the post-CMP cleaning of semiconductor wafers in the fabrication of ICs with LSI or VLSI, in particular by the copper damascene or dual damascene process.
- a typical equipment for the CMP consists of a rotating platen which is covered with a polishing pad.
- the wafer is mounted on a carrier or chuck with its upper side down facing the polishing pad.
- the carrier secures the wafer in the horizontal position.
- This particular arrangement of polishing and holding device is also known as the hard-platen design.
- the carrier may retain a carrier pad which lies between the retaining surface of the carrier and the surface of the wafer which is not being polished. This pad can operate as a cushion for the wafer.
- the larger diameter platen is also generally horizontally positioned and presents a surface parallel to that of the wafer to be polished. Its polishing pad contacts the wafer surface during the planarization process.
- the CMP agent (A) in particular, the CMP agent of the invention is applied onto the polishing pad as a continuous stream or in dropwise fashion.
- Both the carrier and the platen are caused to rotate around their respective shafts extending perpendicular from the carrier and the platen.
- the rotating carrier shaft may remain fixed in position relative to the rotating platen or may oscillate horizontally relative to the platen.
- the direction of rotation of the carrier typically, though not necessarily, is the same as that of the platen.
- the speeds of rotation for the carrier and the platen are generally, though not necessarily, set at different values.
- the temperature of the platen is set at temperatures between 10 and 70 0 C.
- the surface of the semiconductor wafer is contacted with a composition of the invention for a time and a temperature sufficient to clean the unwanted contaminants and residues from the substrate surface.
- the substrate is rinsed to remove the composition of the invention and the contaminants and residues and dried to remove any excess solvents or rinsing agents.
- the methods of the invention use a bath or a spray application to expose the substrate to the composition.
- Bath or spray cleaning times are generally one minute to 30 minutes, preferably 5 minutes to 20 minutes.
- Bath or spray cleaning temperatures are generally 10 0 C to 90°C, preferably 20 0 C to 50°C.
- megasonics and ultrasonic, preferably megasonics cleaning methods can also be applied.
- the rinse times are generally 10 seconds to 5 minutes at room temperature, preferably 30 seconds to 2 minutes at room temperature.
- deionized water is used to rinse the substrates.
- the drying of the substrates substrates can be accomplished using any combination of air-evaporation, heat, spinning or pressurized gas.
- the preferred drying technique is spinning under a filtered inert gas flow, such as nitrogen, for a period of time until the substrate is dry.
- Examples 1 and 2 and Comparative Experiment C1 The Preparation of Aqueous Alkaline Cleaning Compositions Containing L-Cysteine (Examples 1 and 2) and Not Containing L-Cysteine (Comparative Experiment C1 )
- the aqueous alkaline cleaning compositions of the examples 1 and 2 and the comparative experiment C1 were prepared by mixing their ingredients and homogenizing the resulting mixtures.
- the Table 1 summarizes their compositions.
- Table 1 The Compositions of the Aqueous Alkaline Cleaning Compositions
- composition of the example 1 was used for the example 3; the composition of the example 2 was used for the example 4; and the composition of the comparative experiment C1 was used for the comparative experiment C2.
- etching rates were measured by the 4-point probe (Napson) method and confirmed by the atomic force microscopy (AFM).
- ECD electroless copper deposit
- the cleaning efficacy of the aqueous alkaline cleaning compositions was tested as follows. ECD copper wafer pieces were contaminated with CMP agents containing silica particles having a mean primary particle diameter of 30 nm as measured with the laser light scattering method. Thereafter, the contaminated ECD copper wafer pieces were treated with the compositions of the example 1 or 2 and, for purposes of comparison, with deionized water for one minute each. Thereafter, the surfaces of the treated ECD copper wafer pieces were checked for particle residues by scanning electron microscopy (SEM).
- SEM scanning electron microscopy
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Abstract
Aqueous alkaline cleaning composition comprising (A) at least one thioamino acid having at least one primary amino group and at least one mercapto group, (B) at least one quaternary ammonium hydroxide, (C) at least one chelating and/or corrosion inhibiting agent selected from the group consisting of aliphatic and cycloaliphatic amines having at least two primary amino groups, aliphatic and cycloaliphatic amines having at least one hydroxy group, and aromatic compounds having at least one acid group and at least one hydroxy group, (D) at least one organic solvent having wetting properties and a melting point below 0°C; and a method for processing substrates useful for fabricating electrical and optical devices making use of the said aqueous alkaline cleaning composition.
Description
Aqueous Alkaline Cleaning Compositions and Methods of Their Use Field of the Invention The present invention relates to new aqueous alkaline cleaning compositions for processing substrates useful for fabricating electrical and optical devices, in particular electrical devices, including compositions useful for surface preparation, pre-plaiting cleaning, post-etch cleaning and post-chemical mechanical polishing cleaning. Moreover, the present invention relates to new methods for processing substrates useful for fabricating electrical and optical devices, in particular electrical devices, including new methods for surface preparation, pre-plaiting cleaning, post-etch cleaning and post- chemical polishing cleaning, which new methods make use of the new aqueous alkaline cleaning compositions.
Description of the Prior Art
The fabrication of electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; preferably ICs with LSI (large- scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro- conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks; requires high precision methods which involve inter alia surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-chemical polishing cleaning steps using high-purity cleaning compositions.
Particular care has to be taken in the fabrication of ICs with LSI or VLSI. The semiconductor wafers used for this purpose include a semiconductor substrate such as silicon, into which regions are patterned for the deposition of different materials having electrically insulative, conductive or semiconductive properties.
In order to obtain the correct patterning, excess material used in forming the various layers on the substrates must be removed. Further, to fabricate functional and reliable ICs, it is important to have flat or planar semiconductor wafer surfaces. Thus, it is necessary to remove and/or polish certain surfaces of a semiconductor wafers during the fabrication of the ICs before carrying out the next process steps.
Chemical Mechanical Polishing or Planarization (CMP) is a process in which material is removed from a substrate surface, as for example, the surface of a semiconductor wafer, and the surface is polished (planarized) by coupling a physical process such as abrasion with a chemical process such as oxidation or chelation. In its most rudimentary form, CMP involves applying a slurry, i.e. a suspension of an abrasive and an active chemistry, to a polishing pad that buffs the surface of a semiconductor wafer to achieve the removal, planarization and polishing. It is not desirable for the removal or polishing to be comprised of purely physical or purely chemical action, but rather the synergistic combination of both in order to achieve a fast uniform removal. In the fabrication of ICs, the CMP slurry should also be able to preferentially remove films that comprise complex layers of metals and other materials so that highly planar surfaces can be produced for subsequent photolithography, patterning, etching and thin-film processing. Nowadays, copper is increasingly used for metal interconnects in ICs. In the copper damascene or dual damascene process commonly used for the metallization of circuitry in the semiconductor fabrication, the layers that must be removed and planarized include copper layers having a thickness of about 1-1.5 μm and copper seed layers having a thickness of about 0.05-0.15 μm. These copper layers are separated from the low-k and ultra low-k dielectric material by a layer of barrier material, typically about 5 to 30 nm thick, which prevents diffusion of copper into the low-k or ultra low-k dielectric material. The key to obtaining good uniformity across the wafer surface after polishing is to use a CMP slurry that has the correct removal selectivities for each material. The foregoing processing operations involving wafer substrate surface preparation, deposition, plating, etching and chemical mechanical polishing variously require cleaning operations to ensure that the ICs are free from contaminants that would otherwise deleteriously affect the function of the ICs, or even render them useless for their intended functions.
One particularly grave issue are the residues that are left on the substrates following CMP processing. Such residues include CMP material and corrosion inhibitor compounds such as benzotriazole (BTA). Thus, the copper ion concentration can exceed the maximum solubility of the copper-inhibitor complexes during CMP. Therefore, the copper-inhibitor complexes can precipitate from solution and can coagulate into a surface residue. Moreover, these residues can stick to the surface of the polishing pad and accumulate to eventually filling the grooves in the polishing pad. Additionally, abrasive particles and chemicals contained in the CMP slurries as well as reaction by-products can be left behind on the wafer surface. Furthermore, the polishing of copper damascene structures containing ultra low-k dielectric materials such as carbon-doped oxides or organic films can generate carbon-rich particles that settle on to the wafer surface. Of course, all these residues can also contaminate the processing tools employed in the process which come into contact with the CMP slurries. To make matters worse these ultra low-k dielectric materials as well as silicon carbide, silicon nitride or silicon oxynitride CMP stop layers are very hydrophobic and hence are difficult to clean with water-based cleaning solutions.
All these residues can cause a severe roughening of the copper metallization, which has to be avoided since this causes a poor electrical performance. Another residue-producing process common to IC manufacturing involves gasphase plasma etching to transfer the patterns of developed photoresist coatings to the underlying layers, which may consist of hardmask, interleval dielectric and etch-stop layers. Post gasphase plasma etch residues, which may include chemical elements present on and in the substrate and in the plasma gases, are typically deposited on the back end of the line (BEOL) structures and, if not removed, may interfere with the subsequent silicidation and contact formation.
In order to ameliorate these problems at least to a certain extent, aqueous alkaline cleaning and stripping compositions containing quaternary ammonium hydroxides had been developed and were disclosed in the prior art.
Thus, the American patent US 6,465,403 B1 discloses aqueous alkaline compositions for stripping or cleaning semiconductor wafer substrates which contain inter alia - bases such as quaternary ammonium hydroxides,
metal ion-free silicates such as quaternary ammonium silicates,
metal chelating agents and such as salicylic acid,
organic solvents such as glycol ethers, and
non-ionic surfactants such as polyoxyethylene monoalkyl ethers and alkylene glycol monoalkyl ethers.
Moreover, Example 29, column 47, line 10 to column 49, line 8 in conjunction with the Table 28 discloses the solution S8 which consists of de-ionized water,
- tetramethylammonium silicate,
tetramethylammonium hydroxide,
trans-(1 ,2-cyclohexylenenitrilo)-tetraacetic acid, and
cysteine as a potential titanium residue removal enhancer. However, the test results presented in the Table 28 show that cysteine has no beneficial effect in this regard.
The American patent US 6,200,947 B1 discloses aqueous alkaline cleaning liquids containing tetraalkylammonium hydroxides and an aliphatic alcohol compound having at least one mercapto group in the molecule as metal-corrosion inhibitor.
The international patent application WO 01/95381 A2 and the American patent US 6,492,308 B1 disclose a post-CMP cleaning solution comprising inter alia - quaternary ammonium hydroxides,
polar organic amines such as ethanolamine, and
ethylenediamine as corrosion inhibitor.
The American patent application US 2003/0207778 A1 , the international patent application WO 03/053602 A1 and the American patent US 7,387,964 B2 disclose aqueous alkaline copper polishing cleaning compositions containing inter alia complexing agents selected from the group consisting of unidentate alkyl amines such as ethanolamine, bidentate alkyl amines such as ethylenediamine and diethylenetriamine and tridentate amines such as triethylenetetraamine and quaternary ammonium salts such as tetramethylammonium hydroxide .
The American patent application US 2005/0181961 A1 and the American patent US 7,435,712 B2 disclose potential aqueous alkaline cleaning compositions containing inter alia - tetraalkylammonium hydroxides as cleaning agents,
cysteine, ethylenediamine and salicylic acid as complexing agents, and/or cysteine as corrosion-inhibiting compound.
The American patent application US 2006/0166847 A1 , page 5, paragraphs [0082] and [0083] discloses the aqueous alkaline cleaning composition K containing inter alia ethanolamine,
tetramethylammonium hydroxide and
cysteine; and the aqueous cleaning composition M containing inter alia ethanolamine,
tetramethylammonium hydroxide and
- ethylenediamine.
However, as can be taken from page 8, Table 1 in conjunction with paragraph [0161], both compositions exhibit only a poor cleaning efficiency. Moreover, according to page 12, Example 13, paragraph [0198] in conjunction with the Figure 9, the said aqueous alkaline cleaning compositions also cause a high roughness of the treated copper surfaces.
The international patent application WO 2006/081406 A1 , page 20 discloses the same aqueous alkaline cleaning compositions K and M. As follows from Table 1 , page 26, paragraph [00122] in conjunction with page 27, paragraph [00123], both compositions exhibit only a poor cleaning efficiency. Additionally, according to page 37, Example 13, paragraph [00171] in conjunction with the Figure 9, the said aqueous alkaline cleaning compositions also cause a high roughness of the treated copper surfaces. Moreover, the international patent application also discloses on page 26 the aqueous alkaline cleaning composition DF comprising inter alia ethanolamine,
tetramethylammonium hydroxide and
diethylene glycol hexyl ether.
However, no application properties are disclosed.
The international patent application WO 2006/127885 A1 discloses aqueous alkaline post- CMP cleaning compositions containing inter alia amine compounds such as ethanolamine and triethylenediamine,
- quaternary ammonium salts and
polyalkylene glycol alkyl ethers such as diethylene glycol monobutyl ether as complexing agents.
Page 19 of the international patent application specifically mentions the formulations AM and AQ both containing inter alia ethanolamine,
tetramethylammonium hydroxide and
diethylene glycol hexyl ether.
However, no experimental details are disclosed.
The prior art aqueous alkaline cleaning or stripping compositions are susceptible to degradation when exposed to oxygen, which in turn results in darkening of the color of the compositions, with the result that sensors associated with the fabrication process tools yield erroneous outputs that can compromise the function and reliability of the tool. Additionally, such degradation involves the loss of cleaning and/or stripping power. This can become so extensive in the case of prolonged oxygen exposure that the cleaning or stripping composition has no longer a significant efficacy.
The prior art discussed above does not offer any hints as to how these problems may be resolved. In particular, it appears that ingredients such as cysteine, ethylenediamine, ethanolamine or polyalkylene glycol ethers at best offer no advantages if they are not altogether disadvantageous as demonstrated by the international patent application WO 2006/081406 A1 or the American patent application US 2006/0166847 A1 discussed above.
As regards cysteine, it is well known in the art that this compound is easily oxidized (cf., for example, Shayne C. Gad, Handbook of Pharmaceutical Biotechnology, John Wiley and Sons, 2007, page 328). Moreover, traces of heavy metals in particular iron and copper can decompose cysteine (cf. Rompp Online 2009, "L-cysteine"). Consequently, one would even less so expect that aqueous alkaline cleaning compositions could ameliorate the problems described above.
The international patent application WO 2005/093031 A1 discloses an improved acidic chemistry for post-CMP cleaning. The acidic cleaning solution is in the neutral to low pH range and comprises a cleaning agent such as cysteine or salicylic acid and a corrosion- inhibiting compound such as as cysteine. However, such acidic chemistry is tend to attack metallic surfaces to a much greater extent, in particular in the presence of complexing agents and oxygen. Therefore, the skilled artisan can derive nothing from the international patent application as to how he could increase the undesirably low stability of the alkaline cleaning compositions containing cysteine.
Objects of the Invention It was an object of the present invention to provide novel aqueous alkaline cleaning compositions for processing substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips, micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks, which fabrication requires high precision methods involving inter alia surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps using high-purity cleaning compositions.
In particular, the novel aqueous alkaline cleaning compositions should no longer exhibit the disadvantages of the prior art compositions such as discoloration, darkening and decomposition upon exposure to oxygen so that they can be easily prepared, stored,
transported, handled and used even after prolonged storage without loss of cleaning and/or stripping power and without causing erroneous outputs of the sensors associated with the fabrication process tools, which outputs can compromise the function and reliability of the tools.
The novel aqueous alkaline cleaning compositions ought to be particularly well-suited for carrying out the above-mentioned cleaning steps, in particular, the post-CMP cleaning of semiconductor wafers during the fabrication of ICs with LSI or VLSI, in particular via the copper damascene or dual damascene process.
The novel aqueous alkaline cleaning compositions ought to remove most efficiently all kinds of residues and contaminants generated during the substrate surface preparation, deposition, plating, etching and CMP to ensure that the substrates, in particular the ICs, are free from residues and contaminants that would otherwise deleteriously affect the functions of the electrical and optical devices, in particular the ICs, or render them even useless for their intended functions. In particular, they should prevent the roughening of the copper metallization in damascene structures.
Moreover, the novel aqueous alkaline cleaning compositions ought to remove most efficiently such residues and and contaminants not only from the substrates but also from the fabrication tools which are used in the various processes.
It was another object of the invention to provide novel methods for processing substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks, which novel methods make use of the novel aqueous alkaline cleaning compositions. In particular, the novel methods for fabricating electrical and optical devices, in particular electrical devices, ought to involve surface preparation, pre-plaiting cleaning, post-etch
cleaning and/or post-CMP cleaning steps, more particularly post-etch and/or post-CMP cleaning steps, and, most particularly, post-CMP cleaning steps using the novel aqueous alkaline cleaning compositions. The novel methods for fabricating electrical devices ought to be particularly well-suited for the fabrication of ICs with LSI or VLSI, especially with the help of the copper damascene and dual damascene process. Regarding the copper damascene and dual damascene process, the novel methods ought to remove contaminants and residues such as particles consisting of or containing copper, copper oxide, copper-inhibitor complexes, abrasives and carbon after the CMP step from the substrate surfaces, the polishing pads and other processing tools most efficiently without scratching, etching and roughening the copper surfaces.
Summary of the Invention
Accordingly, the novel aqueous alkaline cleaning compositions were found, comprising
(A) at least one thioamino acid having at least one primary amino group and at least one mercapto group,
(B) at least one quaternary ammonium hydroxide,
(C) at least one chelating and/or corrosion inhibiting agent selected from the group consisting of aliphatic and cycloaliphatic amines having at least two primary amino groups, aliphatic and cycloaliphatic amines having at least one hydroxy group, and aromatic compounds having at least one acid group and at least one hydroxy group,
(D) at least one organic solvent having wetting properties and a melting point below 00C.
Hereinafter the novel aqueous alkaline cleaning compositions are referred to as the "compositions of the invention".
Moreover, the novel methods for processing substrates useful for fabricating electrical and optical devices were found, the said methods making use of at least one composition of the invention in at least one process step. Hereinafter the novel methods for processing substrates useful for fabricating electrical and optical devices are referred to as the "methods of the invention".
Advantages of the Invention In view of the prior art discussed above, it was surprising and could not be expected by the skilled artisan that the objects underlying the present invention could be solved by the compositions and the methods of the invention.
It was particularly surprising that the compositions of the invention were excellently suited for processing substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
It was even more surprising that the compositions of the invention were most excellently suited for high precision fabrication methods involving inter alia surface preparation, pre- plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps. The compositions of the invention themselves no longer exhibited the disadvantages of the prior art compositions such as discoloration, darkening and decomposition upon exposure to oxygen so that they could be easily prepared, stored, transported, handled and used even after prolonged storage without loss of cleaning and/or stripping power and without causing erroneous outputs of the sensors associated with the fabrication processing tools, which outputs compromised the function and reliability of the processing tools.
The compositions of the invention were most particularly well-suited for carrying out the above-mentioned cleaning steps, in particular, the post-CMP cleaning of semiconductor wafers and the fabrication of ICs with LSI or VLSI, in particular by the copper damascene or dual damascene process.
The compositions of the invention removed most efficiently all kinds of residues and contaminants generated during the substrate surface preparation, deposition, plating, etching and CMP and ensured that the substrates, in particular the ICs, were free from residues and contaminants that would have otherwise deleteriously affected the functions of the electrical and optical devices, in particular the ICs, or would have rendered them even useless for their intended functions. In particular, they prevented the scratching, etching and roughening of the copper metallization in damascene structures. Moreover, the compositions of the invention removed such residues and and contaminants most efficiently not only from the substrates but also from processing tools used in the various fabrication processes.
It was most particularly surprising that the methods of the invention were most excellently suited for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks. In particular, the methods of the invention were most excellently suited for the fabrication of electrical and optical devices, in particular electrical devices, which fabrication involved surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps, more particularly post-etch and/or post-CMP cleaning steps, and, most particularly, post-CMP cleaning steps.
The methods of the invention were most particularly well-suited for the fabrication of ICs with LSI or VLSI, especially with the help of the copper damascene and dual damascene process. Regarding the copper damascene and dual damascene process, the methods of the invention removed contaminants and residues such as particles containing or consisting of copper, copper oxide, copper-inhibitor complexes, abrasives and carbon after the CMP steps from the substrate surfaces, the polishing pads and other processing tools most efficiently without scratching, etching and roughening the copper surfaces.
Detailed Description of the Invention
In its broadest aspect the present invention relates to the compositions of the invention.
The compositions of the invention are aqueous alkaline cleaning compositions for processing substrates useful for fabricating electrical and optical devices.
"Aqueous" means that the compositions of the invention contain water. The water content can vary broadly from competition to composition.
"Alkaline" means that the compositions of the invention have a pH in the range of from 8 to 14, preferably 9 to 13 and, most preferably, 8.5 to 12.5.
The compositions of the invention comprise as the first essential component at least one, preferably one thioamino acid (A) having at least one, preferably one primary amino group and at least one, preferably one mercapto group. The thioamino acid (A) may be an synthetic or naturally occurring, preferably a naturally occurring amino acid. More preferably, the thioamino acid (A) is an alpha-amino acid. Even more preferably, the mercapto group of the thioamino acid (A) is in the gamma-position. Most preferably, the thioamino acid (A) is an alpha-amino acid having the mercapto group in the gamma- position.
Most particularly preferably, the thioamino acid (A) has the general formula I:
HS-[-C(-R1)(-R2)-]n-C(-R3)(-NH2)-COOH (I). In the general formula I the index n is an integer of 1 to 3, preferably 1 or 2. Most preferably, n equals 1.
The residues R1 and R2 of the general formula I are selected independently from each other from the group consisting of - hydrogen atoms; straight and branched, saturated and unsaturated, preferably saturated, substituted and unsubstituted, preferably unsubstituted aliphatic residues having 1 to 10 carbon atoms, preferably alkyl residues, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1 -methyl butyl, 2-methyl butyl, 3-methyl butyl, 1 -ethyl propyl, 1 ,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl, octyl, iso-octyl, nonyl or decyl; substituted and unsubstituted, preferably unsubstituted, saturated and unsaturated, preferably saturated cycloalkyl residues having 3 to 8 carbon atoms, in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and residues derived from by bicyclo[2.2.1]cycloheptane or norcarane; substituted and unsubstituted, preferably unsubstituted, saturated and unsaturated, preferably saturated alkylcycloalkyl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the cycloalkyl group is having from 3 to 8 carbon atoms, in particular residues derived from methyl-, ethyl-, propyl-, isopropyl- or butyl-substituted cyclopropane, cyclobutane or cyclohexane, pinane or bornane, which alkylcycloalkyl residues may be linked to the basic structure of the thioamino acid (A) of the general formula I via a carbon atom of the alkyl group or via a carbon atom of the cycloalkyl group; substituted and unsubstituted, preferably unsubstituted aryl residues having from 6 to 16 carbon atoms, in particular phenyl or naphthyl or residues derived from anthracene or phenanthrene; substituted and unsubstituted, preferably unsubstituted alkylaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the aryl group is having from 6 to 16 carbon atoms, in particular methyl-, ethyl-, propyl-, isopropyl- or butyl- substituted phenyl or naphthyl or residues derived from methyl-, ethyl-, propyl-, isopropyl- or butyl-substituted anthracene or phenanthrene which alkylaryl
residues may be linked to the basic structure of the thioamino acid (A) of the general formula I via a carbon atom of the alkyl group or via a carbon atom of the aryl group; - substituted and unsubstituted, preferably unsubstituted cycloalkylaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms and the aryl group is having from 6 to 16 carbon atoms, in particular cyclopropyl-, cyclobutyl-, cyclopentyh cyclohexyl-substituted phenyl, which cycloalkylaryl residues may be linked to the basic structure of the thioamino acid (A) of the general formula I via a carbon atom of the cycloalkyl group or via a carbon atom of the aryl group; substituted and unsubstituted, preferably unsubstituted heteroaryl residues having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms, in particular residues derived from furane, xanthene, thiophene, pyrrole, imidazole, triazoles, tetrazole, pyridine, pyridazine, pyrimidine, pyrazene, triazines, tetrazines, indole, quinoline, isoquinoline, purine or phosphinine; substituted and unsubstituted, preferably unsubstituted alkylheteroaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms, in particular the alkyl groups described hereinbefore, and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms, in particular the heteroaryl groups as described hereinbefore, which alkylheteroaryl residues may be linked to the basic structure of the thioamino acid (A) via a carbon atom of the alkyl group or via a carbon atom of the heteroaryl group; substituted and unsubstituted, preferably unsubstituted cycloalkylheteroaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms, in particular the cycloalkyl groups as described hereinbefore, and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms, in particular the heteroaryl groups as described herein before; and - substituted and unsubstituted, preferably unsubstituted arylheteroaryl residues wherein the aryl group is having from 6 to 16 carbon atoms, in particular the aryl
groups as described hereinbefore, and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms, in particular the heteroaryl groups as described herein before. Alternatively, the residues R1 and R2 together form a saturated or unsaturated, preferably saturated, substituted or unsubstituted, preferably unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms is or are replaced by one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms.
The residue R3 of the general formula I is a single residue R1 or R2 or a covalent bond or bivalent group linking the carbon atom carrying the amino group and the carboxyl group to one of the residues R1 or R2 or to the ring formed by the residues R1 and R2. The bivalent linking group is stable in the presence of the quaternary ammonium salt (B), which means that it does not hydrolyze or hydrolyzes only very slowly to a very small extent so that the concentration of the hydrolyzation products is so low that they do not interfere with the function of the compositions of the invention.
Preferably, the bivalent linking group is selected from the group consisting of:
-O-, -C(O)-, -C(S)-, -C(O)-O-, -0-C(O)-O-, -0-C(S)-O-;
-NR1-, =N-, -N=N-, -NR1-C(O)-, -NR1-NR1-C(O)-, -NR1-NR1-C(S)-, -0-C(O)-NR1-,
-0-C(S)-NR1-, -NR1-C(O)-NR1-, -NR1-C(S)-NR1-;
-S-, -S(O)-, -S(O)2-, -0-S(O)2-, and -NR1-S(O)2-, wherein the residue R1 is having the above-described meaning.
Generally, the substituted residues R1, R2 and R3 described above can contain any substituents as long as the substituents are stable in the presence of the quaternary ammonium hydroxide (B), which means that they do not hydrolyze or hydrolyze only very slowly to a very small extent and do not cause any undesired reactions which could lead to the decomposition and/or the agglomeration and/or the formation of precipitates in or of the compositions of the invention. Preferably, the substituents are selected from the group consisting of:
-OR1, -C(O)-R1, -COOR1, -SO3R1, -P(O)2R1, -N(-R1)2,
-NR1-C(O)(-R1)2;
-F, -Cl, -CN and -NO2; wherein the residue R1 is having the above-described meaning.
Additional examples for thioamino acids (A) of the general formula I are known from the international patent application WO 02/22568, page 13, line 9, to page 16, line 12.
The thioamino acids (A) of the general formula I can be racemic or enantiomeric mixtures which may be equimolar or non-equimolar, or one of the respective enantiomers or diastereomers.
More preferably, at least one of the residues R1, R2 and R3 described above is a hydrogen atom. Even more preferably, all of the residues R1, R2 and R3 are hydrogen atoms.
Therefore, most preferably, the thioamino acid (A) is selected from cysteine and homocysteine, in particular, cysteine, especially L-cysteine.
The compositions of the invention comprise as the second essential component at least one, preferably one quaternary ammonium hydroxide (B). More preferably, the quaternary ammonium hydroxide (B) has the general formula II:
N(-R1)4 + OH- (II). In the general formula II, the residue R1 is having the above defined meaning except hydrogen atom, whilst all the residues R1 are the same or at least two residues R1 are different from each other and all the residues R1 are single residues or at least two residues R1 form a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms are replaced by one hetero atom selected from the group of oxygen, sulfur, nitrogen and phosphorus atoms.
More preferably, the residue R1 of the general formula Il is selected from the group consisting of straight and branched, substituted and unsubstituted, saturated aliphatic residues having 1 to 10, in particular, 1 to 4 carbon atoms.
In the case that the quaternary ammonium hydroxide (B) of the general formula Il only contains residues R1 which are unsubstituted and saturated, all residues R1 are preferably the same. In the case that the quaternary ammonium hydroxide (B) of the general formula Il contains residues R1 which are a substituted and saturated, it is preferred that only one of the residues R1 is substituted.
Particularly preferably, the quaternary ammonium hydroxide (B) of the general formula Il contains methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 2- hydroxyethyl, 2- and 3-hydroxypropyl and/or 4-hydroxy-n-butyl groups, in particular, methyl and/or 2-hydroxyethyl groups.
Most particularly preferably, tetramethylammonium hydroxide (TMAH) and/or choline, especially TMAH, is or are used.
The compositions of the invention contain as the third essential componentat least one chelating and/or corrosion inhibiting agent (C) selected from the group consisting of aliphatic and cycloaliphatic amines having at least two, preferably two primary amino groups, aliphatic and cycloaliphatic amines having at least one, preferably one hydroxy group, and aromatic compounds having at least one, preferably one acid group, in particular at least one, preferably one carboxylic acid group, and at least one, preferably one hydroxy group. Preferably, the aliphatic amine (C) having at least two primary amino groups is selected from the group consisting ethylenediamine, propylenediamine, n-butylenediamine, diethylenetriamine, dipropylenetriamine, di-n-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, and tri-n-butylenetetraamine, more preferably ethylenediamine and triethylenetetraamine, most preferably ethylenediamine.
Preferably, the cycloaliphatic amine (C) is selected from the group consisting of 1 ,2-, 1 ,3- and 1 ,4-diamino cyclohexane;
Preferably, the aliphatic amine (C) having at least one hydroxy group is selected from the group consisting of ethanolamine, diethanolamine and triethanolamine, most preferably ethanolamine.
Preferably, the cycloaliphatic amine (C) having at least one hydroxy group is selected from the group consisting of 2-, 3- and 4-hydroxy cyclohexylamine. Preferably, the aromatic compound (C) having at least one, preferably one carboxylic acid group and at least one, preferably one hydroxy group is selected from the group consisting of salicylic acid, 3- and 4-hydroxy phthalic acid, 2-hydroxy terephthalic acid, and 3-, 4-, 5- and 6-hydroxy salicylic acid, most preferably salicylic acid. Particularly preferably, the chelating and/or corrosion inhibiting agent (C) is selected from the group consisting of ethylenediamine, triethylenetetraamine, ethanolamine and salicylic acid.
The compositions of the invention comprise as the fourth essential component at least one, preferably one organic solvent (D) having wetting properties and melting point below 00C.
As is known and the art, a solvent having wetting properties comprises a hydrophilic and a hydrophobic structural element so that the solvent is capable of lowering the surface tension of solids and liquids.
Generally, any organic solvent (D) having the above-mentioned properties can be used, as long as it is not decomposed by water or causes the decomposition and/or precipitation and/or agglomeration of one of the components of the compositions of the invention.
Preferably, the organic solvent (D) is selected from the group consisting of polyalkylene glycol mono ethers. More preferably, the polyalkylene glycol mono ether (D) is of the general formula III: HO-(-R4-O-)m-R1 (III), wherein the variables and the index have the following meaning: m integer of from 2 to 6, preferably 2 to 4, more preferably 2 or 3 and most preferably 2;
R1 as defined above, except hydrogen atom; and
R4 alkylene group having 2 to 4, preferably 2 or 3 and, most preferably, 2 carbon atoms.
More preferably, the polyalkylene glycol mono ether (D) of the general formula (III) is selected from the group consisting of diethylene glycol monomethyl, monoethyl, mononpropyl and mono-n-butyl ether, most preferably diethylene glycol mono-n-butyl ether.
Optionally, the compositions of the invention can contain at least one functional additive (E) which is different from the essential components (A), (B), (C) and (D). Preferably, the functional additive (E) is selected from the group consisting of corrosion inhibitors, bases, titanium residue removal enhancers, organic solvents, alcohols having at least one mercapto group, complexing or chelating agents, surfactants and metal free silicates.
Such functional additives (E) are described, for example, in the American patents US 6,465,403 B1 , column 7, line 1 to column 8, line 65; US 6,200,947 B1 , column 2, lines 29 to 40, US 6,194,366 B1 , column 3, lines 55 to 60, and US 6,492,308 B1 , column 3, lines 1 to 9, and the American patent application US 2005/0181961 A1 , page 2, paragraph [0019].
The compositions of the invention can contain the essential components (A), (B), (C) and (D) and optionally (E) in broadly varying amounts. Thus, the compositions of the invention can be highly concentrated solutions which contain only small amounts of water.
Preferably, the compositions of the invention are diluted or highly diluted aqueous compositions, i.e., they contain more than 50% by weight, more preferably more than 75% by weight and, most preferably, more than 90% by weight of water, each weight percentage being based on a complete weight of a composition of the invention.
More preferably, the compositions of the invention contain
0.5 to 5% by weight, even more preferably 0.75 to 3% by weight and, most preferably, 1 to 2% by weight of the component (A)
0.1 to 5% by weight, even more preferably 0.5 to 3% by weight and, most preferably, 1 to 2% by weight of the component (B);
0.1 to 5% by weight, even more preferably 0.5 to 3% by weight and, most preferably, 0.75 to 2% by weight of the component (C); and
1 to 10 % by weight, even more preferably 2 to 7.5% by weight and, most preferably, 3 to 7.5% by weight of the component (D); the weight percentages being based on the complete weight of a composition of the invention .
The amounts of the optional functional additive or additives (E) can also vary broadly. Preferably, the customary amounts known from the prior art cited above are used.
The compositions of the invention can be prepared by customary and standard mixing processes and mixing apparatuses such as agitated vessels, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used for carrying out the mixing of the components of the compositions in the desired amounts.
The compositions of the invention are excellently suited for the methods of the invention.
Moreover, the compositions of the invention are also excellently suited for cleaning all kinds of processing tools such as polishing pads, sensors, nozzles, pipes and/or structural features of the equipment used, which tools come into contact with other processing liquids used in fabricating electrical or optical devices.
The main purpose of the methods of the invention however is the processing of substrates useful for fabricating electrical devices, in particular, semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; more preferably ICs with LSI (large-scale integration) or VLSI (very-large-scale integration); as well as optical devices, in particular, optical glasses such as photo-masks, lenses and prisms; inorganic electro-conductive films such as indium tin oxide (ITO); optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals such as the end faces of
optical fibers and scintillators; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
It is essential that the methods of the invention make use of at least one composition of the invention in at least one process step.
Preferably, the methods of the invention involve surface preparation, pre-plaiting cleaning, post-etch cleaning and/or post-CMP cleaning steps, in particular post-CMP cleaning steps.
The methods of the invention are particularly well-suited for the processing of substrates useful for fabricating ICs with LSI or VLSI, in particular in the back end of the line processing (BEOL). The methods of the invention are most particularly well-suited for the post-CMP cleaning of semiconductor wafers in the fabrication of ICs with LSI or VLSI, in particular by the copper damascene or dual damascene process.
As is known in the art, a typical equipment for the CMP consists of a rotating platen which is covered with a polishing pad. The wafer is mounted on a carrier or chuck with its upper side down facing the polishing pad. The carrier secures the wafer in the horizontal position. This particular arrangement of polishing and holding device is also known as the hard-platen design. The carrier may retain a carrier pad which lies between the retaining surface of the carrier and the surface of the wafer which is not being polished. This pad can operate as a cushion for the wafer.
Below the carrier, the larger diameter platen is also generally horizontally positioned and presents a surface parallel to that of the wafer to be polished. Its polishing pad contacts the wafer surface during the planarization process. During the CMP process of the invention, the CMP agent (A), in particular, the CMP agent of the invention is applied onto the polishing pad as a continuous stream or in dropwise fashion.
Both the carrier and the platen are caused to rotate around their respective shafts extending perpendicular from the carrier and the platen. The rotating carrier shaft may remain fixed in position relative to the rotating platen or may oscillate horizontally relative to the platen. The direction of rotation of the carrier typically, though not necessarily, is
the same as that of the platen. The speeds of rotation for the carrier and the platen are generally, though not necessarily, set at different values.
Customarily, the temperature of the platen is set at temperatures between 10 and 700C.
For further details reference is made to the international patent application WO 2004/063301 A1 , in particular page 16, paragraph [0036] to page 18, paragraph [0040] in conjunction with the figure 1. After the CMP step, the surface of the semiconductor wafer is contacted with a composition of the invention for a time and a temperature sufficient to clean the unwanted contaminants and residues from the substrate surface. Optionally, the substrate is rinsed to remove the composition of the invention and the contaminants and residues and dried to remove any excess solvents or rinsing agents.
Preferably, the methods of the invention use a bath or a spray application to expose the substrate to the composition. Bath or spray cleaning times are generally one minute to 30 minutes, preferably 5 minutes to 20 minutes. Bath or spray cleaning temperatures are generally 100C to 90°C, preferably 200C to 50°C. However, megasonics and ultrasonic, preferably megasonics cleaning methods can also be applied.
If required, the rinse times are generally 10 seconds to 5 minutes at room temperature, preferably 30 seconds to 2 minutes at room temperature. Preferably, deionized water is used to rinse the substrates.
If required, the drying of the substrates substrates can be accomplished using any combination of air-evaporation, heat, spinning or pressurized gas. The preferred drying technique is spinning under a filtered inert gas flow, such as nitrogen, for a period of time until the substrate is dry.
Examples
Examples 1 and 2 and Comparative Experiment C1 The Preparation of Aqueous Alkaline Cleaning Compositions Containing L-Cysteine (Examples 1 and 2) and Not Containing L-Cysteine (Comparative Experiment C1 )
The aqueous alkaline cleaning compositions of the examples 1 and 2 and the comparative experiment C1 were prepared by mixing their ingredients and homogenizing the resulting mixtures. The Table 1 summarizes their compositions.
Table 1 : The Compositions of the Aqueous Alkaline Cleaning Compositions
(Balance: Water)
b) ethylenediamine;
c) diethylene glycol monobutyl ether.
Examples 3 and 4 and Comparative Experiment C2
The Etching Rates of the Aqueous Alkaline Compositions of the Examples 1 and 2 (Examples 3 and 4) and of the Comparative Experiment C1 (Comparative Experiment C2)
The composition of the example 1 was used for the example 3; the composition of the example 2 was used for the example 4; and the composition of the comparative experiment C1 was used for the comparative experiment C2.
The etching rates were measured by the 4-point probe (Napson) method and confirmed by the atomic force microscopy (AFM).
To this end, pieces of electroless copper deposit (ECD) wafers were immersed in the various aqueous alkaline cleaning compositions at room temperature for 1 hour (4-point probe measurements) or 1 minute (AFM measurements). Thereafter, the ECD wafers were taken from the compositions, rinsed with water and dried in a nitrogen streamactual temperature. Whereas the ECD wafers of the examples 3 and 4 were not etched and showed no change in their surface roughness, the ECD wafers of the comparative
experiment C1 showed an etching rate of 17.9 A/minute (1.79 nm/minute) and a significant increase of their surface roughness.
Examples 5 and 6 and Comparative Experiment C3
The Cleaning Efficacy of the Aqueous Alkaline Cleaning Compositions of the Examples 1 and 2 (Examples 5 and 6) in Comparison with Deionized Water (Comparative Experiment C3) The composition of the example 1 was used for the example 5; and the composition of the example 2 was used for the example 6. Deionized water was used for the comparative experiment C3.
The cleaning efficacy of the aqueous alkaline cleaning compositions was tested as follows. ECD copper wafer pieces were contaminated with CMP agents containing silica particles having a mean primary particle diameter of 30 nm as measured with the laser light scattering method. Thereafter, the contaminated ECD copper wafer pieces were treated with the compositions of the example 1 or 2 and, for purposes of comparison, with deionized water for one minute each. Thereafter, the surfaces of the treated ECD copper wafer pieces were checked for particle residues by scanning electron microscopy (SEM).
Whereas the surfaces of the ECD copper wafer pieces treated with the compositions of the examples 1 and 2 were free from silica particles, the surfaces of the ECD copper wafer pieces treated with deionized water were still covered with considerable amounts of silica particles.
Claims
1. Aqueous alkaline cleaning composition comprising (A) at least one thioamino acid having at least one primary amino group and at least one mercapto group,
(B) at least one quaternary ammonium hydroxide, (C) at least one chelating and/or corrosion inhibiting agent selected from the group consisting of aliphatic and cycloaliphatic amines having at least two primary amino groups, aliphatic and cycloaliphatic amines having at least one hydroxy group, and aromatic compounds having at least one acid group and at least one hydroxy group,
(D) at least one organic solvent having wetting properties and a melting point below 00C.
2. The aqueous alkaline cleaning compositions according to claim 1 , wherein the amino acid (A) has the general formula I:
HS-[-C(-R1)(-R2)-]n-C(-R3)(-NH2)-COOH (I), wherein the index and the variables have the following meaning: n integer of 1 to 3;
R1 and R2 selected independently from each other from the group consisting of
- hydrogen atoms;
straight and branched; saturated and unsaturated, substituted and unsubstituted aliphatic residues having 1 to 10 carbon atoms;
substituted and unsubstituted, saturated and unsaturated cycloalkyl residues having 3 to 8 carbon atoms; substituted and unsubstituted, saturated and unsaturated alkylcycloalkyl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the cycloalkyl group is having from 3 to 8 carbon atoms;
- substituted and unsubstituted aryl having from 6 to 16 carbon atoms;
substituted and unsubstituted alkylaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the arylgroup is having from 6 to 16 carbon atoms;
- substituted and unsubstituted cycloalkylaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms and the arylgroup is having from 6 to 16 carbon atoms;
substituted and unsubstituted heteroaryl residues having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms;
substituted and unsubstituted alkyl heteroaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the heteroaryl group is having having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms;
substituted and unsubstituted cycloalkylheteroaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms
substituted and unsubstituted arylheteroaryl residues wherein the aryl group is having from 6 to 16 carbon atoms and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms or, alternatively,
R1 and R2 together forming a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms is or are replaced by one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms;
R3 single residue R1 or R2 or covalent bond or bivalent group linking the carbon atom carrying the amino group and the carboxyl group to one of the residues R1 or R2 or to the ring formed by the residues R1 and R2.
3. The aqueous alkaline cleaning composition according to claim 2, wherein the thioamino acid (A) is a racemic or an enantiomeric mixture or one of the respective enantiomers or diastereomers.
4. The aqueous alkaline cleaning composition according to claim 3, wherein at least one of the residues R1, R2 and R3 is a hydrogen atom.
5. The aqueous alkaline cleaning composition according to claim 4, wherein all the the residues R1, R2 and R3 of the thioamino acid (A) are hydrogen atoms.
6. The aqueous alkaline cleaning composition according to claim 5, wherein the thioamino acid (A) is L-cysteine.
7. The aqueous alkaline cleaning composition according to claim 1 , wherein the quaternary ammonium hydroxide (B) has the general formula II: N(-RV OH- (II), wherein the residue R1 is having the above defined meaning except hydrogen atom, whilst all the residues R1 are the same or at least two residues R1 are different from each other and all the residues R1 are single residues or at least two residues R1 form a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms are replaced by one hetero atom selected from the group of oxygen, sulfur, nitrogen and phosphorus atoms.
8. The aqueous alkaline cleaning composition according to claim 7, wherein the residue R1 of the general formula (II) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 2- hydroxyethyl, 2- and 3-hydroxypropyl and 4-hydroxy-n-butyl.
9. The aqueous alkaline cleaning composition according to claim 8, wherein the residue R1 of the general formula (II) is methyl.
10. The aqueous alkaline cleaning composition according to claim 1 , wherein the aliphatic amine (C) having at least two primary amino groups is selected from the group consisting of ethylenediamine, propylenediamine, n-butylenediamine, diethylenetriamine, dipropylenetriamine, di-n-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, and tri-n-butylenetetraamine; the cycloaliphatic amine (C) is selected from the group consisting of 1 ,2-, 1 ,3- and 1 ,4- diamino cyclohexane; the aliphatic amine (C) having at least one hydroxy group is selected from the group consisting of ethanolamine, diethanolamine and triethanolamine; the cycloaliphatic amine (C) having at least one hydroxy group is selected from the group consisting of 2-, 3- and 4-hydroxy cyclohexylamine; and the aromatic compound (C) having at least one acid group and at least one hydroxy group is selected from the group consisting of salicylic acid, 3- and 4- hydroxy phthalic acid, 2-hydroxy terephthalic acid, and 3-, 4-, 5- and 6-hydroxy salicylic acid.
1 1. The aqueous alkaline cleaning composition according to claim 1 , wherein the organic solvent (D) having wetting properties and a melting point below 00C is selected from the group consisting of polyalkylene glycol mono ethers.
12. The aqueous alkaline cleaning composition according to claim 11 , wherein the polyalkylene glycol mono ether (C) is of the general form III:
HO-(-R4-O-)m-R1 (III), wherein the variables and the index have the following meaning: m integer of from 2 to 6; R1 as defined above, except hydrogen atom; and R4 alkylene group having 2 to 4 carbon atoms.
13. The aqueous alkaline cleaning composition according to claim 12, wherein the polyalkylene glycol mono ether (D) of the general formula III is selected from the group consisting of diethylene glycol monomethyl, monoethyl, mononpropyl and mono-n-butyl ether.
14. The aqueous alkaline cleaning composition according to claim 1 containing - 0.5 to 5% by weight of the component (A)
0.1 to 5% by weight of the component (B);
0.1 to 5% by weight of the component (C); and
1 to 10 % by weight of the component (D); the weight percentages being based on the complete weight of the aqueous alkaline cleaning composition.
15. Aqueous alkaline cleaning composition according to claim 1 furthermore comprising at least one functional additive (E) which is different from the components (A), (B), (C) and (D).
16. The aqueous alkaline cleaning composition according to claim 15, wherein the functional additive (E) is selected from the group consisting of corrosion inhibitors, bases, titanium residue removal enhancers, organic solvents, alcohols having at least one mercapto group, complexing or chelating agents, surfactants and metal free silicates.
17. A method for processing substrates useful for fabricating electrical and optical devices, said method comprising the process step of contacting the substrate surface at least once with at least one aqueous alkaline cleaning composition comprising (A) at least one thioamino acid having at least one primary amino group and at least one mercapto group,
(B) at least one quaternary ammonium hydroxide,
(C) at least one chelating and/or corrosion inhibiting agent selected from the group consisting of aliphatic and cycloaliphatic amines having at least two primary amino groups, aliphatic and cycloaliphatic amines having at least one hydroxy group, and aromatic compounds having at least one acid group and at least one hydroxy group,
(D) at least one organic solvent having wetting properties and a melting point below 00C.
18. The method according to claim 17, wherein the thioamino acid (A) has the general formula I:
HS-[-C(-R1)(-R2)-]n-C(-R3)(-NH2)-COOH (I), wherein the index and the variables have the following meaning: n integer of 1 to 3
R1 and R2 selected independently from each other from the group consisting of hydrogen atoms;
straight and branched; saturated and unsaturated, substituted and unsubstituted aliphatic residues having 1 to 10 carbon atoms;
- substituted and unsubstituted, saturated and unsaturated cycloalkyl residues having 3 to 8 carbon atoms;
substituted and unsubstituted, saturated and unsaturated alkylcycloalkyl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the cycloalkyl group is having from 3 to 8 carbon atoms; substituted and unsubstituted aryl residues having from 6 to 16 carbon atoms;
substituted and unsubstituted alkylaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the arylgroup is having from 6 to 16 carbon atoms;
substituted and unsubstituted cycloalkylaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms and the arylgroup is having from 6 to 16 carbon atoms;
- substituted and unsubstituted heteroaryl residues having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms;
substituted and unsubstituted alkyl heteroaryl residues wherein the alkyl group is having from 1 to 4 carbon atoms and the heteroaryl group is having having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms;
substituted and unsubstituted cycloalkylheteroaryl residues wherein the cycloalkyl group is having from 3 to 8 carbon atoms and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms
substituted and unsubstituted arylheteroaryl residues wherein the aryl group is having from 6 to 16 carbon atoms and the heteroaryl group is having at least one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms or, alternatively;
R1 and R2 together forming a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms are replaced by one hetero atom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus atoms; R3 single residue R1 or R2 or covalent bond or bivalent group linking the carbon atom carrying the amino group and the carboxyl group to one of the residues R1 or R2 or to the ring formed by the residues R1 and R2.
19. The method according to claim 18, wherein the thioamino acid (A) is a racemic or an enantiomeric mixture or one of the respective enantiomers or diastereomers.
20. The method according to claim 19, wherein at least one of the residues R1, R2 and R3 is a hydrogen atom.
21. The method according to claim 20, wherein all the the residues R1, R2 and R3 of the thioamino acid (A) are hydrogen atoms.
22. The method according to claim 21 , wherein the thioamino acid (A) is L-cysteine.
23. The method according to claim 17, wherein the quaternary ammonium hydroxide (B) has the general formula II:
N(-RV OH- (II), wherein the residue R1 is having the above defined meaning except hydrogen atom, whilst all the residues R1 are the same or at least two residues R1 are different from each other and all the residues R1 are single residues or at least two residues R1 form a saturated or unsaturated, substituted or unsubstituted ring having 3 to 6 carbon atoms, wherein no carbon atom or 1 or 2 carbon atoms are replaced by one hetero atom selected from the group of oxygen, sulfur, nitrogen and phosphorus atoms.
24. The method according to claim 23, wherein the residue R1 of the general formula (II) is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 2-hydroxyethyl, 2- and 3-hydroxypropyl and
4-hydroxy-n-butyl.
25. The method according to claim 24, wherein the residue R1 of the general formula (II) is methyl.
26. The method according to claim 17, wherein the aliphatic amine (C) having at least two primary amino groups is selected from the group consisting of ethylenediamine, propylenediamine, n-butylenediamine, diethylenetriamine, dipropylenetriamine, di-n-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, and tri-n-butylenetetraamine; the cycloaliphatic amine (C) is selected from the group consisting of 1 ,2-, 1 ,3- and 1 ,4-diamino cyclohexane; the aliphatic amine (c) having at least one hydroxy group is selected from the group consisting of ethanolamine, diethanolamine and triethanolamine; the cycloaliphatic amine (C) having at least one hydroxy group is selected from the group consisting of 2-, 3- and 4-hydroxy cyclohexylamine; and the aromatic compound (C) having at least one acid group and at least one hydroxy group is selected from the group consisting of salicylic acid, 3- and 4-hydroxy phthalic acid, 2-hydroxy terephthalic acid, and 3-, 4-, 5- and 6-hydroxy salicylic acid.
27. The method according to claim 17, wherein the organic solvent (D) having wetting properties and a melting point below 00C is selected from the group consisting of polyalkylene glycol mono ethers.
28. The method according to claim 27, wherein the polyalkylene glycol mono ether (D) is of the general form III:
HO-(-R4-O-)m-R1 (III), wherein the variables and the index have the following meaning: m integer of from 2 to 6;
R1 as defined above, except hydrogen atom; and R4 alkylene group having 2 to 4 carbon atoms.
29. The method according to claim 28, wherein the polyalkylene glycol mono ether (D) of the general formula (III) is selected from the group consisting of diethylene glycol monomethyl, monoethyl, mononpropyl and mono-n-butyl ether.
30. The method according to claim 17 containing
0.5 to 5% by weight of the component (A)
0.1 to 5% by weight of the component (B);
0.1 to 5% by weight of the component (C); and
1 to 10 % by weight of the component (D); the weight percentages being based on a complete weight of the aqueous cleaning composition.
31. Aqueous method according to claim 17 furthermore comprising at least one functional additive (E) which is different from the components (A), (B), (C) and (D).
32. The method according to claim 31 , wherein the functional additive (E) is selected from the group consisting of corrosion inhibitors, bases, titanium residue removal enhancers, organic solvents, alcohols having at least one mercapto group, complexing or chelating agents, surfactants and metal free silicates.
33. The method according to claim 17, wherein the process step is at least one surface preparation step, pre-plaiting cleaning step, post-etch cleaning step or post-chemical polishing cleaning step.
34. The method according to claim 33, wherein the electrical devices are semiconductor integrated circuits (ICs); liquid crystal panels; organic electroluminescent panels; printed circuit boards; micro machines; DNA chips; micro plants and magnetic heads; and the optical devices are optical glasses; inorganic electro-conductive films; optical integrated circuits; optical switching elements; optical waveguides; optical monocrystals; solid laser monocrystals; sapphire substrates for blue laser LEDs; semiconductor monocrystals; and glass substrates for magnetic disks.
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US22180709P | 2009-06-30 | 2009-06-30 | |
US61/221,807 | 2009-06-30 |
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WO2011000694A1 true WO2011000694A1 (en) | 2011-01-06 |
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Cited By (4)
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---|---|---|---|---|
WO2012011020A2 (en) | 2010-07-19 | 2012-01-26 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
US8969275B2 (en) | 2009-06-30 | 2015-03-03 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
US9184057B2 (en) | 2011-03-18 | 2015-11-10 | Basf Se | Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less |
US9458415B2 (en) | 2012-02-06 | 2016-10-04 | Basf Se | Post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid |
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US5989353A (en) * | 1996-10-11 | 1999-11-23 | Mallinckrodt Baker, Inc. | Cleaning wafer substrates of metal contamination while maintaining wafer smoothness |
US20070225186A1 (en) * | 2006-03-27 | 2007-09-27 | Matthew Fisher | Alkaline solutions for post CMP cleaning processes |
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2010
- 2010-06-16 WO PCT/EP2010/058422 patent/WO2011000694A1/en active Application Filing
- 2010-06-30 TW TW099121539A patent/TW201114889A/en unknown
Patent Citations (2)
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US5989353A (en) * | 1996-10-11 | 1999-11-23 | Mallinckrodt Baker, Inc. | Cleaning wafer substrates of metal contamination while maintaining wafer smoothness |
US20070225186A1 (en) * | 2006-03-27 | 2007-09-27 | Matthew Fisher | Alkaline solutions for post CMP cleaning processes |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8969275B2 (en) | 2009-06-30 | 2015-03-03 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
WO2012011020A2 (en) | 2010-07-19 | 2012-01-26 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
US8927476B2 (en) | 2010-07-19 | 2015-01-06 | Basf Se | Aqueous alkaline cleaning compositions and methods of their use |
US9184057B2 (en) | 2011-03-18 | 2015-11-10 | Basf Se | Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less |
US9458415B2 (en) | 2012-02-06 | 2016-10-04 | Basf Se | Post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid |
EP3385363A1 (en) | 2012-02-06 | 2018-10-10 | Basf Se | A post chemical-mechanical-polishing (post-cmp) cleaning composition comprising a specific sulfur-containing compound and a sugar alcohol or a polycarboxylic acid |
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