TWI324362B - Cleaning solution for semiconductor substrate - Google Patents
Cleaning solution for semiconductor substrate Download PDFInfo
- Publication number
- TWI324362B TWI324362B TW092137591A TW92137591A TWI324362B TW I324362 B TWI324362 B TW I324362B TW 092137591 A TW092137591 A TW 092137591A TW 92137591 A TW92137591 A TW 92137591A TW I324362 B TWI324362 B TW I324362B
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- Taiwan
- Prior art keywords
- acid
- cleaning
- cleaning liquid
- cleaning solution
- group
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- 238000004140 cleaning Methods 0.000 title claims description 79
- 239000004065 semiconductor Substances 0.000 title claims description 19
- 239000000758 substrate Substances 0.000 title claims description 16
- 239000007788 liquid Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001231 choline Drugs 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 2
- OZXAIGIRPOOJTI-VLGMZSPHSA-N 7-hdohe Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C=C\C(O)C\C=C/CCC(O)=O OZXAIGIRPOOJTI-VLGMZSPHSA-N 0.000 claims 1
- 241001122767 Theaceae Species 0.000 claims 1
- QANDYPBZVVXLSW-UHFFFAOYSA-N acetic acid;ethanamine Chemical compound CCN.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O QANDYPBZVVXLSW-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000002950 deficient Effects 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000373 fatty alcohol group Chemical group 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000006210 lotion Substances 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 125000004437 phosphorous atom Chemical group 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- -1 polyoxypropylene dodecyl ether Polymers 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002736 nonionic surfactant Substances 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229920000090 poly(aryl ether) Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
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- 238000005530 etching Methods 0.000 description 2
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
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- 150000003333 secondary alcohols Chemical class 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
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- CCUNBJAVKGOAEV-UHFFFAOYSA-N 2,2-dihydroxy-2-phenylacetic acid;ethane-1,2-diamine Chemical compound NCCN.OC(=O)C(O)(O)C1=CC=CC=C1 CCUNBJAVKGOAEV-UHFFFAOYSA-N 0.000 description 1
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 1
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- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Chemical compound O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 1
- SFLOGVVDXPCWGR-UHFFFAOYSA-N leucopterin (keto form) Chemical compound N1C(=O)C(=O)NC2=C1C(=O)N=C(N)N2 SFLOGVVDXPCWGR-UHFFFAOYSA-N 0.000 description 1
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 description 1
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 description 1
- 235000009498 luteolin Nutrition 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- PAKISRAZZVIYMX-UHFFFAOYSA-N triazanium 2-hydroxypropane-1,2,3-tricarboxylate 2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [NH4+].[NH4+].[NH4+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PAKISRAZZVIYMX-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02065—Cleaning during device manufacture during, before or after processing of insulating layers the processing being a planarization of insulating layers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Description
I二!巧說明 [發明所屬之技術領域] 本發明係有關半導體基板用清洗液。 [先前技術] 近年來,在半導體裝置上導入Cu配線,為了該Cu配 線之形成而採用化學的機械研磨處理(CMp處理)。 所述之CMP處理為首先在平坦的含碳Si02(Si0C)等 的低介電f數的絕緣膜上形成槽、連接線孔後,用電鍍法 等將Cu成膜並將槽和連接線孔埋入,由含特殊的砂粒與 添加劑之齡漿法研磨以去除槽、連接線孔以外的Cu,使表 面平坦化,且形成配線、連接線孔。 CMP處理後之半導體基板上因附著大量由研磨淤漿 中的砂粒,研磨屑等微小的粒子狀異物,或金屬不純物等 離子狀異物,故期望開發出能同時去除粒子狀異物及離子 狀異物之清洗液β 據知像這樣的清洗液通常為例如:聚環氧乙烷壬基苯 鍵等之具苯#之非離子性界面活性劑,形成如胺基乙酸或 喹哪啶酸之金屬與配位化合物之化合物;由和含有.驗成分 所成之清洗液(參照專利文獻1 但是該清洗液在使用如Si0c疏水性的低介電常數之
絕緣膜時,會有所謂:與絕緣膜間之潤濕性差,以及在CMP 處理後,難以去除半導體基板上之粒子狀異物以及離子狀 異物之問題。 (專利文獻1):日本專利特開2002_27〇566 315377修正版 5 1324362 或烴基) 以及通式(2) CH3-(CH2)a.〇-(CbH2b〇)d-(CxH2x〇)Y-x ⑺ (式中的a、b、d、X以及y表示各自獨立之正
致,b與X 互為不同。X表示氫原子或烴基)所示之非離 哪卞界面活性 劑。 通式(1)或(2)中之1以及a表示為正數,較 卞人ΙΞΕ马8至18, 以8至11為更佳,又以9至11為最佳。 ’ 1及3不滿8或超過18時,與低介電常數之絕
濕性變差,粒子狀異物之去除性有降低之傾向,特、U 過18時,因為了加強親油基之作用而在水溶 2 以溶解之傾向。 甲支仔有難 又X為氫原子或烴基,作為烴基可舉 基等。 ”马甲基、乙 通式⑴中,m表示為正數之2或3,而以2為佳。 η表示為正數,較佳為4至2(),以5至1〇更佳。 η不滿4時,在水溶液之溶解性有惡化傾 2〇時,與低介電常數的絕緣膜 、'’超過 、…。、心 啄犋之潤濕性有惡化之傾向。 通式⑺表示正數,b通常為2。
又d通常為1至20’較佳為1至1〇。如H 時,.盥低介啻片批认你* 主10。如d超過2〇 ^低"“數的絕緣膜之_財惡化之傾向。 在通式(2)中’ x以及表 較佳為3至5,以3為更#正數4通常為3至1〇, 以3為更佳。父如 解性有惡化之傾向。 時’在水中之溶 315377修正版 7 1324362 又,y通常為1至10,較佳為1至5。如丫超過1〇時, 與低介電常數的絕緣膜之潤濕性有惡化之傾向。 通式(2)所示之非離子界面活性劑為2種環氧化物聚合 的形態,其聚合形態並無特別限制’有無規共聚、嵌段共 聚等各種形態。在無規共聚物時,通式(2)中之d以及y係 成為分子鏈中之重覆單元(CbHuO)以及(CxH2X〇)的各自總 數。 " 另外,末端之X亦可與(CbH2b〇)以及(CxH2X〇)之任一 者之重覆單元結合。 在通式⑴以及⑺所示之非離子界面活性劑中,親油基 (chhcha以及CHHCH2)a部分)之起始原料為一級醇叫 以及a係以9至11者為佳。即使親油基中總碳數
12,以二級醇作為起始原料之非離子界面活性劑,如下述 通式(4)或(5) ,L 通式(4) (CH3-(CH2)4)2CH-0-(CmH2m0)n-X ⑷ 通式(5) (CH3-(CH2)4)2CH-〇.(CbH2bO)d-(CxH2x〇)Y.x ⑺ (…小^以及又與上述同樣^斤示之非離子! 面活性劑,耗提高與低介電常數的絕緣膜之潤濕性,^ 是對於粒子狀異物之去除並不完全。 _ 通式(1)或(2)中所示之非離子界 叫/石性劑可舉例為, 環氧乙烷癸醚、聚環氧乙烷十二峻、 $ 取卢丄 心裱巩乙烷十六醚、 1¾乳乙烧十八醚、聚環氧乙烷聚氧 乳化丙烯癸醚 '聚環挛 315377修正版 8 缔十六喊、 =聚氧化丙烯十二醚、聚環氧乙烷聚氧化丙 tJ衣氧乙貌聚氧化丙埽十八趟等。 在這當中,最好使用聚環氧乙 ,φ w _ 展氧乙烷十 、’聚裱氧乙烷聚氧化丙烯癸醚,聚環氧乙烷聚氧化丙 烯十二。 在非離子界面活性劑(通式(1)以及(2)的總和)之清洗 液中/辰度較佳$ 0.0001至!重量%,以〇 〇〇1至1重量% 為更佳。 ,不滿0.0001重量%時,與低介電常數之絕緣膜之潤濕 性有惡化之傾肖’超過i重量%時,清洗液之起泡性加劇 清洗時的作業性有惡化之傾向。 整合劑係只要能去除金屬者則並無特別限制,可擧例 為選自聚胺基羧酸類、聚羧酸類、具膦酸基之化合物類、 經酸類、酚類、雜環化合物類以及罩酚酮類群中之至少一 種。在此所說的〈類〉通常為含該化合物之鹽或衍生物.。 聚胺基羧酸類可擧例為乙二胺四乙酸(EDTA : Ethylenediamine tetraacetic acid),反式 _1,2_環己二胺四乙 酸(CyDTA . trans-l,2-Diaminocyclohexan-N,N,N,,N,-tetraacetic acid)、三乙酸胺(ΝΤΑ : Nitrilotriacetic acid), 一乙樓二胺五乙酸(DTPA : Diet+hylene triamine pentaacetic acid)、N-(2-羥乙基)_ 乙二胺 _n,N,,N’·三乙酸(EDTA-OH) 等。 其中較佳為乙二胺四乙酸(EDTA)。 聚羧酸類可擧例為乙二酸、丙二酸、丁二酸 '戊二酸、 9 315377修正版 1324362 曱基丙二酸、2 -幾基酪酸以及該等之敍鹽等。 其中以使用乙二酸及乙二酸録為較佳。 具有膦酸基之化合物類可舉例為乙二胺四乙膦酸、乙 二胺二亞甲膦酸、氮川叁(亞甲膦酸)、丨_羥基亞乙基二膦 酸等。其中以使用1-羥基亞乙基二膦酸為較佳。 經缓酸類可拳例為葡糖酸、酒石酸、檸檬酸等。 其中適合使用檸檬酸 '檸檬酸銨。 紛類可擧例為苯酚、曱酚 '乙基苯酚、第三丁醇、f 氧苯紛、兒茶酚、間苯二酚、對苯二酚、4-甲基鄰苯二酚、 2 -甲基對苯二酚、焦掊酚、3,4-二羥基苯甲酸、沒食子酸、 2,3,4-三羥基苯曱酸、2,4_二羥基_6_甲基苯甲酸、乙二胺二 鄰經基本乙酸[丑0011八:£1:11)^16116(11〇1111116-1^,1^-(11(。- hydroxyphenyl)acetic acid]、N,N_ 雙(2-羥苄基)乙二胺 -N,N-2 乙酸[HBED : N,N-bis(2-hydroxybenzyl) ethylenediaminc-N,N-2acetic acid]、乙二胺二經甲基苯乙酸 [EDDHMA . Ethylenediamine dihydroxy methyl phenyl acetic acid]等 ° 其中以使用兒茶酚、乙二胺二鄰羥基苯乙酸[EDDHA] 為較佳》 雜環化合物可擧例為8-喹啉酚、2-甲基-8-喹啉酚、喹 啉二醇、1-(2-吡啶基偶氮)_2_萘酚、2-氨基-4,6,7-蝶啶三 醇、5,7,3’,4’-四羥基黃酮[木犀草素]、3,3,-雙[队仏雙(羥 曱基)胺甲基]螢光素[鈣黃綠素]、2,3-羥基吡啶等。 其中適合使用8 -喹琳盼。 10 315377修正版 6-異丙基罩盼酮等。 罩酚酮類可擧例如罩酚綱 其中適合使用罩酚嗣。 在螯合劑之清洗液中的濃度較佳為〇 〇〇〇〇1至】〇重量 % ’較佳為0.0001至1重量% 。 如未滿o.ooool重詈%時,數人+丨 更里/0時,螯合劑的金屬去除性能降 低’超過10重量科,在清洗液中之溶解性降低。 螯合劑促進劑係為更有效地螯合半導體基板上附著之 金屬不純物而添加的。 螯合促進劑通常為酸性化合物、或驗性化合物及其趟 等。酸性化合物可例擧如氟化物或其鹽,鹼性化合物例擧 如氫氧化物。 在此,氟化物或其鹽可例擧如氫氟酸,氟化鉀,氟化 鈉,氟化銨等。 其中適合使用氟化銨。 在此氫氧化物例擧如:具有氫氧基之化合物,具體而 言為氫氧化納、氫氧化卸、氫氧化錄等之無機化合物;氣 氧化四甲銨、膽鹼等之四級銨的氫氧化物;單乙醇胺、二 乙醇胺、二乙醇胺、2-甲胺基乙醇、2·乙胺基乙醇' N—甲 一乙醇胺' 二甲胺基乙醇' 2气2_胺基乙氧基)乙醇、丨_胺基 -2-丙醇、.單丙醇胺、二丁醇胺等的烷醇胺類等。 其中從不使半導體基板(矽晶圓)表面污染到金屬的角 度來看’適合使用氫氧化銨,氫氧化四曱銨,膽鹼等不含 金屬之化合物。 餐合促進劑較佳以由含有氫氧化物與氟化物或其鹽所 31 «77修正版 1324362 成者。只含有氫氧化物’或氟化物或其鹽所成者,其效果 並無法充分發揮’而包括兩者的螯合促進劑因可提高螯合 劑的金屬去除性而佳。 清洗液中的氟化物或其鹽濃度較佳為〇.〇〇〇1至4〇〇/〇, 更佳為0.0 1至5重量〇/〇。 不滿0.0001重量%時,其金屬去除性降低,超過4〇 重量%時,則不僅提高不了金屬去除性反而使基底之低介 電常數的絕緣膜膜質變差。 去除性降低,超 緣膜膜質變差。 清洗液中的氫氧化物濃度較佳為〇 〇〇〇1至3〇重量 %,較佳為0.001至i重量%。未滿〇 〇〇〇1重量%時,金屬 超過3 0重量%時,則基底之低介電常數的絕 對於氫氧化物與氟化物或其鹽之濃度關係,係以氫氧. 化物之濃度在氟化物的濃度以下者為佳。 ^氫氡化物的濃度高於氟化物的濃度時,基雇之低介電 常數的絕緣臈膜質會惡化。 除去低介電常數絕緣膜外露 狀異物、離子狀異物為目的 發明之清洗液中又以合古厶 本發明之清洗液,係在製造半導體裝置的過
’例如··苯并三唑' 二0坐 '甲本三唾、4-尹基味唾、 之半導體基板(晶圓)上之粒子 ’因有Cu配繞夕卜霞,私I、,士 315377修正版 12 1324362 5-赵甲基·4-甲基咪唑、3_胺基三唑等。 又,金屬防蝕劑較佳含有具有至少丨個疏基,該皲基 鍵結的碳原子與羥基鍵結的碳原子鄰接且碳數為2以上 的脂肪族醇系化合物。 金屬之防蝕劑可例擧如硫甘油,硫甘醇等。 本發明之清洗液較佳的ρΗ為7至12,更理想為7至 9。pH未滿7(酸性)時,不僅對於微粒子的去除性降低,而 且在清洗中由Cu與障礙金屬間的電池效應而產生腐蝕。 本發明之清洗液對於低介電常數的絕緣膜外露之半導 體基板(晶圓)上之粒子狀異物及離子狀異物有顯著的去除 性。 ’、 低介電常數之絕緣膜可例擧如FSG(含F之Si〇2:), SiOC(含碳之SiOO,SiON(含氮之Si〇2)的無機系;曱基矽 倍半氧烧(MSQ : Methylsilsesquioxane)、氫碎倍半氧统 (HSQ : hydrogen silsesquioxane)、甲基化氫矽倍半氧烷 (MHSQ · Methylation hydrogen silsesquioxane)等聚有機石夕 氣烧系,聚芳基謎(PAE : polyarylether) '二乙埽石夕氧烧_ 雙-本弁環丁稀(BCB : divinylsiloxane-Bis-benzocyclobutene)等的芳香族系;絲(Silk)、多孔絲等有機 膜系等。在此所述之低介電常數的絕緣膜係指表示比介電 常數為3.0以下的值。 本發明之清洗液無論在低介電常數的絕緣膜的種類 或其成膜方法上均可使用,特別是對於SiOC、MSQ、PAE(聚 芳基醚)等絕緣膜很有效,故使用在這些絕緣膜上較佳。 13 315377修正版 〜又’本發明之清洗液不僅可以單獨使用,也可以在不 破壞本發明目的之範圍内與其他藥液混合使用。 其他藥液可例舉如陰離子系、陽離子系、非離子系的 各種界面活性劑、分散劑、金屬防#劑、雙氧水等。 又,為了抑制由界面活性劑所引起的氣泡性亦可加入 消泡劑。 消泡劑可擧例為聚石夕氧貌系,聚㈣,特殊非離子系, 脂肪酸I系等的消泡劑;甲醇、乙醇、卜丙醇、2_丙醇、 2_f基-1·丙醇、丙_、f基乙酮等水溶性有機化合物等。 使用本發明的清洗液之半導體基板(聚矽氧烷晶圓等) 之清=方法可例舉如將晶圓直接浸潰於清洗液的浸潰清洗 法;浸潰清洗法上並用超音波照射的方法;將清洗液嘴到 基板表面的嗔霧清洗法;一邊將清洗液喷射一邊用刷子清 洗之噴刷清洗法;且喷刷清洗法並用超音波照射的方法等。 又’清洗時亦可加熱清洗液。 其次,說明有關在半導體裝置的製造上清洗低介電常 數絕緣膜外露的晶圓之使用本發明清洗液的清洗例❶ 首先’如第1圖(a),形成電晶體等元件的半導體基板 (無圖示)上形成氧化矽膜丨,氮化矽膜2後,為了保護低介 电常數絕緣膜3、低介電常數絕緣膜而形成罩層膜(例Si〇2 膜)4。其次,利用習知的蝕刻處理形成槽後,如第1圖(b) 形成柵攔金屬膜5以及鋼膜6,利用習知之CMP處理研磨 銅膜與障礙金屬膜形成銅配線。之後,如第1圖(c)所示, 去除由研磨引起的附著於表面的研磨屑、研磨劑中的於漿 14 315377修正版 (SlUrry)成分、金屬不純物等。然而,如以CMP處理在晶 圓面内均勻地研磨眸,故丁入 τ 雖不會使低介電常數絕緣膜外露於 表面’但在不均勻時’則如第i圖卜2)所示,罩層的一部 刀由研磨去掉有時會使低介電常數絕緣膜外露於表面。 如此if况以以往之清洗液則難以清洗外露之低介電常數 絕緣膜,然而本發明之清洗液卻適用。 又,在寬幅的配線上易於碟形下陷(dishing),清洗後 鋼配線上形成罩層7,更在其上形成低介電常數絕緣膜8 時如第1圖(e)所示’ Cu配線之中央部的凹部反映到上 層之低介電常數絕緣膜8 ’使表面變得不平坦。因此,如 低介電常數絕緣膜8成凹形時,在下一步處理之蝕刻法上 因可能產生焦點不聚的問題,故有必要使低介f常數絕緣 膜由CMP處理使平坦化。本發明之清洗液亦可適用於清洗 如此之低介電常數絕緣臈以CMp處理研磨後之表面上的 異物。 本發明之清洗液對於CMP處理後之半導體基板上的 粒子狀〃物離子狀異物有顯著去除性,特別是可適用於 表面顯示疏水性白勺低介電常數絕緣膜所露出表面的清洗。 以下,由貫施例詳細說明本發明,但本發明並非只限 於該等之實施例。 實施例1 根據表1之組成調整清洗液i或清洗液2。使用此清 洗液1、2,預先在表面上設置以污染之微粒子以及金屬不 純物的低介電常數絕緣膜之丄種Si〇c膜成膜之晶圓,使 315377修正版 15 li'24362 用刷子清洗裝置清洗時之殘留微粒子數以及殘留金屬不純 物濃度同樣示於表1。 且,清洗前的SiOC膜晶圓上的微粒子污染採用浸潰 於CuCMP用淤漿中的方法,使膜表面上污染淤漿中的砂 粒粒子。清洗前的污染微粒子為3 000個/片。又,金屬不 純物實際上係以CuCMP研磨Cu膜時使外露的si〇c膜上 污染金屬,清洗前的金屬污染量在〇11為5xi〇12at〇ms/ [表1] 聚環氧乙
1為11,m為.2,η為8,Χ為氫原子之通式(1)所示之 非離子性界面活性劑 *2 a為ll,b為2’^為10,乂為3,丫為卜父為氫原子 之通式2所不之界面活性劑 如表1所示,經由本發明之清洗液清洗,便可去除 SiOC膜上的微粒子以及Cu不純物甚至程度達到了半導體 315377修正版 16 1324362 裝置製造所需的水平。 膏施例2,比鮫例1、2 與實施例1同樣的方法使用微粒子污染的Si〇c膜與 刷洗機’以表2所示之清洗液(改變清洗液中的界面活性劑 的種類)清洗’比較微粒子的去除性。其結果示於表2。又, 各清洗液之SiOC膜之潤濕性由測定清洗液與Si〇c膜之接 觸角來做比較。 [表2] 聚環氧乙烧十二鱗*1
實施例比Γ]_例~T 清洗液 1清洗液3清洗液1 0.1% 高級醇(Softanol)70*3 乙二酸銨 _ 羥基乙烷二膦酸 0.1% 0.1% 〇".0!% 0.1% 0.1%
1為11,Π1為2, η為8’ X為氫原子的通式⑴所示之 非離子性界面活性劑 日本催化劑公司製造第二級高級醇乙醇鹽 使用親油基碳數為12的第二級醇,以爪為2,“ 7, 為風原子的通式⑷對應之非離子性界面活性劑。 如表2所示’不含界面活性劑的比較例2上因與si〇c 膜潤濕性差而幾乎未能去 , 此去除被拉子。雖然一方面加入界面 活性劑以改善潤渴性 仁在比較例1之界面活性劑中,微 315377修正版 17 粒子去除性差,、爭4 還達不到半導體裝置製造上所需的水平。 預備如表1 所不組成的清洗液,其中,將氧化矽膜晶 圓》X、/貝兩分鐘。复彡纟 v 具後’分析晶圓表面殘留的金屬附著量。 先月〗的氧化石夕膜晶圓在轉速200rpm的旋轉塗膜機 上方疋轉其表面滴入含lppm之Fe、A1的超純水40ml, 使氧化梦表面上污染金屬以使用。清洗前的金屬附著量^ *1 為 49〇Xl〇1〇at〇ms/cm2 ’ A1 為 34〇xl〇i〇atoms/cm2。 [表3] "- 實施例2 比較例1 比較例4 '聚環氧乙燒十二喊*1 二酸铵 — 清洗液1 清洗液5 清洗液6 ___0^1% 0.1% 0.1% 0.1% 0.1% 羥基乙烷二膦酸 0.01% 0.01% nh4oh 0.05% nh4f 0.4% Fe 附著量(xl 〇luat〇ms/ cm2) 6 86 460 A1 附著量〔xit)lvatoms/ cm2) 9 320 330 1為11,m為2, η為8, X為氫原子的通式(1)所示之 非離子界面活性劑 由表3所不結果,清洗液丨顯示良好的金屬去除性能, 而在不含螯合劑以及螯合促進劑之比較例4、不含螯合促 進劑之比較例3中,均未能得到良好的金屬去除性能。 實施例4至5,比較例5 g_ ή 由表4之組成所調整之各種界面活性劑溶解於清洗液 315377修正版 18 1324362 6至9 ’測定與低介電常數骐之間的接觸角。其結果示於表 4。又,在此狀態下的界面活性劑的溶解性由目視以液體的 混濁狀態來評價。且,使用ΡΑΕ臈以作為低介電常數膜, 清洗液之界面活性劑濃度為0.1 %。 [表4]
界面活性劑 聚環氧乙烷 十二醚*1 0.1% N-520*5 0.1% 實施例5 清洗液2 聚€氧乙烷 氧丙烧十二&1*4 0.1% EH-6*6 0.1% —0.1% 乙二酸銨 羥基乙烷二膦酸 0.1% 0.01% 0.1% 0.01% 0.1% 0.01% 0.01% νη4οη nh4f
1為為2,„為8]為氯原子的通 之 非離子性界面活性劑 * 4 a為11 ’ b為2,d為1〇,y為 (2)所示之非離子性界面活性劑。 *5 ’ X為氫原子的通式 月木油脂公司製造之聚環氧 ,通式⑴中,吸_仰2)1之親油基相當於壬基苯, ⑺為2,n為20,X為氫原子的界面活性劑。 *6 青木油脂公司製造之聚環氧乙烧2_乙基己_ 3J5377修正版 19 在通式(1)中,CH^CHA之親油基相當於2_乙基己 基,m為2,n為6,X為氫原子的界面活性劑。 a如表4所示,通式(1)以及(2)所示之界面活性劑與低介 申數膜之間的潤濕性良好。—方面即使係、與通式⑴類似 =界面活性劑’在使用親油基之結構不同者時,與低介電 1數之接觸角增大、潤濕性變差’而且觀察到有因不溶於 Θ洗液中而所謂白色渾濁的現象P (發明效果) CMP處理後之半 顯著的去除性。 由本發明可提供一種清洗液,其對於 導體基板上之粒子狀異物及離子狀異物有 [圖示簡單說明] 聲置^ "Ja)至(f)係表示為使用本發明清洗液之半導體 裝置之製造處理其中—例之處理剖面圖。 牛導體 件符號說明] 氧化矽膜 Λ 1 氮化矽膜 低介電常數絕緣膜 4、7 罩層膜 障礙金屬膜 . 0 銅膜
315377修正版 20
Claims (1)
- 丄J厶HJVJ厶 第92137591號專利申請案 ” ,. (99 年 1 月 27 日') 7,如申請專利範圍笫 电、〆 第1項或第5項之清洗液,其中,螯合 劑係選自聚胺基羧酸 類、聚竣酸類、具有膦酸基之化合 物類、經酸類、私 、 類、雜環化合物類以及罩酚酮類群中 之至少一種者。 8.如申請專利範圍第 乐7項之 >月洗液,其中,螯合劑係選自 乙一胺四乙酸、乙-缺 T 心’乙二酸銨、1-羥基亞乙基二膦 檬酸、檸檬酸錢、兒茶盼、乙.二胺二鄰經基苯乙 9 2 HDHA V’啉酚、以及罩酚酮群中之至少-種者。 .請專利範圍第1項或第5項之清洗液,其中,螯入 :進劑含有氫氧化物、氟化物以及氟化物之鹽中之心 任一種。 10.如申請專利範圍 人人 乐"項之/月洗液,其中,氫氧化物為不 3金屬之化合物者。 專利範圍第10項之清洗液,其中,氨氧化物為 k自虱乳化銨,虱氧化四曱基銨以及膽鹼組成之群中 至少一種者。 12.如申請專利範圍第9項之清洗液,其中,氟化物或其鹽 為氫氟酸或氟化敍。 13·如申請專利範圍第1項或第5項之清洗液,其更含有金 屬防钱劑。 k如申請專利範圍第13項之清洗液,其中,金屬防餘劑 為分子内至少含有氮原子、氧原子、磷原子、硫原子中 之一種的有機化合物。 W如申請專利範圍第14項之清洗液,其中,金屬防餘劑 315377修正版 22 1324362 第92137591號專利申請案 (99年1月27日) 為分子内至少具有1個唑基之化合物。 16. 如申請專利範圍第14項之清洗液,其中,金屬防蝕劑 為含有至少1個酼基的脂肪醇,且其中毓基鍵結的碳原 子係與羥基鍵結的碳原子鄰接之化合物。 17. 如申請專利範圍第1項或第5項之清洗液,係pH為7 以上者。 18. —種申請專利範圍第1項或第5項之清洗液之用途,係 製造半導體裝置用,係清洗外露於半導體基板上的低介 電常數的絕緣膜。 23 315377修正版
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CN1639846A (zh) * | 2002-01-28 | 2005-07-13 | 三菱化学株式会社 | 半导体器件用基板的清洗液及清洗方法 |
WO2006125462A1 (en) * | 2005-05-25 | 2006-11-30 | Freescale Semiconductor, Inc | Cleaning solution for a semiconductor wafer |
DE102006000882A1 (de) * | 2006-01-04 | 2007-07-05 | Henkel Kgaa | Reinigung gesägter Siliciumscheiben |
US7374621B2 (en) * | 2006-02-09 | 2008-05-20 | Hitachi Global Storage Technologies Netherlands Bv | System and method for cleaning chemistry and processing during thin film magnetic head wafer fabrication |
US7772128B2 (en) * | 2006-06-09 | 2010-08-10 | Lam Research Corporation | Semiconductor system with surface modification |
US9058975B2 (en) * | 2006-06-09 | 2015-06-16 | Lam Research Corporation | Cleaning solution formulations for substrates |
WO2008023215A1 (en) * | 2006-08-23 | 2008-02-28 | Freescale Semiconductor, Inc. | Post chemical mechanical polishing rinse formulation |
US20100273330A1 (en) * | 2006-08-23 | 2010-10-28 | Citibank N.A. As Collateral Agent | Rinse formulation for use in the manufacture of an integrated circuit |
DE102007058829A1 (de) * | 2007-12-06 | 2009-06-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Textur- und Reinigungsmedium zur Oberflächenbehandlung von Wafern und dessen Verwendung |
US7700535B1 (en) * | 2009-01-12 | 2010-04-20 | Ppt Research | Wafer/Ingot cleaning in wire saw cutting comprising an ethoxylated alcohol/polyalkylsiloxane mixture |
US8366954B2 (en) | 2009-01-13 | 2013-02-05 | Avantor Performance Materials, Bv | Solution for increasing wafer sheet resistance and/or photovoltaic cell power density level |
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US8148311B2 (en) | 2009-10-24 | 2012-04-03 | Wai Mun Lee | Composition and method for cleaning semiconductor substrates comprising an alkyl diphosphonic acid |
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JP6066552B2 (ja) | 2011-12-06 | 2017-01-25 | 関東化學株式会社 | 電子デバイス用洗浄液組成物 |
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