CN106435587B - 用于铜或铜合金的蚀刻溶液 - Google Patents
用于铜或铜合金的蚀刻溶液 Download PDFInfo
- Publication number
- CN106435587B CN106435587B CN201610560710.9A CN201610560710A CN106435587B CN 106435587 B CN106435587 B CN 106435587B CN 201610560710 A CN201610560710 A CN 201610560710A CN 106435587 B CN106435587 B CN 106435587B
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- Prior art keywords
- acid
- adduct
- solution
- copper
- ether
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010949 copper Substances 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 88
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 57
- 238000005530 etching Methods 0.000 title abstract description 25
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002738 chelating agent Substances 0.000 claims abstract description 41
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000004377 microelectronic Methods 0.000 claims abstract description 26
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 8
- -1 oxyimino Chemical group 0.000 claims description 69
- 150000003839 salts Chemical class 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 235000006708 antioxidants Nutrition 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 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
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 claims description 4
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical compound OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 3
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 3
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Chemical compound O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001983 poloxamer Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 2
- UINXJMGJGZQEFI-DKWTVANSSA-N (2s)-2-aminobutanedioic acid;oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)[C@@H](N)CC(O)=O UINXJMGJGZQEFI-DKWTVANSSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- QNTDTMHDTUVBGD-UHFFFAOYSA-N 1h-benzimidazole;formic acid Chemical compound OC=O.C1=CC=C2NC=NC2=C1 QNTDTMHDTUVBGD-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical compound OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- UTCHNZLBVKHYKC-UHFFFAOYSA-N 2-hydroxy-2-phosphonoacetic acid Chemical compound OC(=O)C(O)P(O)(O)=O UTCHNZLBVKHYKC-UHFFFAOYSA-N 0.000 claims description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 2
- KHEVPDFAQFJIGK-UHFFFAOYSA-N 2-sulfooxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOS(O)(=O)=O KHEVPDFAQFJIGK-UHFFFAOYSA-N 0.000 claims description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- UUCQGNWZASKXNN-UHFFFAOYSA-N 3-ethylcatechol Chemical compound CCC1=CC=CC(O)=C1O UUCQGNWZASKXNN-UHFFFAOYSA-N 0.000 claims description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 2
- CUVGUPIVTLGRGI-UHFFFAOYSA-N 4-(3-phosphonopropyl)piperazine-2-carboxylic acid Chemical compound OC(=O)C1CN(CCCP(O)(O)=O)CCN1 CUVGUPIVTLGRGI-UHFFFAOYSA-N 0.000 claims description 2
- ZPCIKQLLQORQCV-UHFFFAOYSA-N 4-(4-methylphenyl)-2h-triazole Chemical compound C1=CC(C)=CC=C1C1=NNN=C1 ZPCIKQLLQORQCV-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- JXBUOZMYKQDZFY-UHFFFAOYSA-N 4-hydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1S(O)(=O)=O JXBUOZMYKQDZFY-UHFFFAOYSA-N 0.000 claims description 2
- 241001614291 Anoplistes Species 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- KVPMCFRZLDLEJW-UHFFFAOYSA-N C(C(=O)O)(=O)O.NCCC(=O)O Chemical compound C(C(=O)O)(=O)O.NCCC(=O)O KVPMCFRZLDLEJW-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
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- 239000001294 propane Substances 0.000 description 1
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- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/02—Bonding areas ; Manufacturing methods related thereto
- H01L24/03—Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76885—By forming conductive members before deposition of protective insulating material, e.g. pillars, studs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/03—Manufacturing methods
- H01L2224/034—Manufacturing methods by blanket deposition of the material of the bonding area
- H01L2224/0346—Plating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/02—Bonding areas; Manufacturing methods related thereto
- H01L2224/03—Manufacturing methods
- H01L2224/036—Manufacturing methods by patterning a pre-deposited material
- H01L2224/0361—Physical or chemical etching
- H01L2224/03614—Physical or chemical etching by chemical means only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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Abstract
本发明涉及用于铜或铜合金的蚀刻溶液。更具体而言,本发明提供了一种用于从微电子装置选择性蚀刻铜或铜合金的溶液,其中所述装置同时包括铜或铜合金和含镍材料,所述溶液是用于铜或铜合金的蚀刻溶液,其包含在分子中具有酸基团的螯合剂、过氧化氢和在分子中具有氧化乙烯链的表面活性剂。
Description
本申请为国际申请日2011年8月16日、国际申请号PCT/US2011/047927于2013年2月18日进入中国国家阶段、申请号201180039954.8、发明名称“用于铜或铜合金的蚀刻溶液”的分案申请。相关申请的交叉引用
本申请要求2010年8月16日提交的题为“用于铜或铜合金的蚀刻溶液”(EtchingSolution for Copper or Copper Alloy)的日本专利申请号2010-181485和2011年8月11日提交的题为“用于铜或铜合金的蚀刻溶液”(Etching Solution for Copper or CopperAlloy)的日本专利申请号2011-175477的优先权,两者在此以其全文引为参考。
技术领域
本发明涉及从微电子基板蚀刻铜或铜合金的溶液,更具体来说涉及从具有由铜或铜合金和镍制成的电极例如凸块的微电子基板选择性蚀刻铜或铜合金的溶液。
背景技术
在微电子装置中,发展了元件的微型化和高度集成以便提高它们的性能并减小尺寸。不利的是,在半导体装置中,微型化技术正接近它们的极限。尽管正越来越多地使用具有三维结构例如引线接合、倒装芯片、凸块等的装置,但仍然需要更高度的集成。
已经开发了通过形成穿透硅的细小通孔,并用导电材料例如铜填充所述通孔来形成电极的技术(TSV技术)。通常情况下,在TSV技术中使用铜作为电极的情形中,在硅基板(1)中提供开口,然后在开口的内壁上形成氧化硅层(2)(即低k介电层)和钛、钽等的金属阻挡层(3)。随后,通过金属有机化学气相沉积法或物理气相沉积法形成铜晶种层(4)(图1)。接下来,使用抗蚀剂树脂(5)在铜晶种层上形成电极的部分以外的部分上形成保护膜(图2)。将金属例如铜(6)埋置在未形成保护膜的部分中,以形成凸块。不利的是,如果铜未被保护,表面氧化现象将降低连接可靠性。因此,通常情况下,分别层压镍层(7)以及金、或者锡与银的合金的焊料层(8)(图3)。然后,通过移除抗蚀剂树脂来形成凸块(9)(图4)。
铜晶种层和金属阻挡层不仅形成在硅基板的开口内,而且形成在硅基板表面上,并且即使在抗蚀剂树脂被移除后仍保留。因此,剩余的铜晶种层和金属阻挡层必须通过蚀刻溶液移除(图5和6)。其中,作为湿法蚀刻铜晶种层的方法,使用由酸和氧化剂构成的蚀刻溶液、即硫酸和过氧化氢的混合溶液的方法被广泛使用(日本专利申请公开号2000-286531和2009-120870)。使用含有氯化铜或氯化铁的蚀刻溶液的方法,也已广为人知(日本专利申请公开号2008-285720)。不利的是,这些蚀刻方法不仅蚀刻在电子基板中形成的铜晶种层,而且由于用于形成凸块的镍也被蚀刻而使凸块变形。
因此,在本技术领域中,对于能够从同时包括铜或铜合金和含镍材料的微电子装置,相对于含镍材料而选择性蚀刻铜或铜合金的溶液,仍存在需求。
发明内容
总的来说,本发明涉及溶液,所述溶液能够在从包括铜或铜合金和含镍材料的微电子基板蚀刻铜或铜合金的步骤中选择性蚀刻铜或铜合金。
一方面,描述了一种从同时包括铜或铜合金和含镍材料的微电子装置选择性蚀刻铜或铜合金的溶液,所述溶液包含在分子中具有酸基团的螯合剂(A)、过氧化氢(B)和在分子中具有氧化乙烯链的表面活性剂(C)。所述溶液还包含选自至少一种溶剂(D)、至少一种抗腐蚀组分(E)、至少一种抗氧化剂(F)和至少一种碱性化合物(G)的至少一种组分。
另一方面,描述了一种生产微电子装置的方法,所述方法包括使用溶液从所述微电子装置选择性蚀刻铜或铜合金,其中所述装置同时包括铜或铜合金和含镍材料,其中所述溶液包含在分子中具有酸基团的螯合剂(A)、过氧化氢(B)和在分子中具有氧化乙烯链的表面活性剂(C)。所述溶液还包含选自至少一种溶剂(D)、至少一种抗腐蚀组分(E)、至少一种抗氧化剂(F)和至少一种碱性化合物(G)的至少一种组分。
从后面的公开内容和权利要求书,本发明的其他方面、特征和实施方案将更充分显现。
附图说明
图1是具有开口的硅基板(1)的剖视图,其中氧化硅层(2)、金属阻挡层(3)和铜晶种层(4)被层压在开口的内壁上。
图2是在图1的硅基板上施加抗蚀剂树脂(5)并形成保护膜后硅基板的剖视图。
图3是在图2的硅基板上进一步层压金属铜(6)、镍(7)和金(8)后硅基板的剖视图。
图4是从图3的硅基板移除抗蚀剂树脂后硅基板的剖视图。
图5是从图4的硅基板移除铜晶种层后基板的剖视图。
图6是从图5的硅基板移除金属阻挡层后硅基板的剖视图。
具体实施方式
在本文中描述了一种用于从微电子装置选择性蚀刻铜或铜合金的溶液,其中所述铜或铜合金相对于含镍材料被选择性移除。此外,还描述了使用所述溶液从微电子装置基本上移除铜或铜合金的方法,其中所述铜或铜合金相对于同时存在的含镍材料被选择性移除。
为了易于指称,“微电子装置”是指半导体基板、平板显示器、相变存储装置、太阳能板和其他产品,包括被制造用于微电子、集成电路或计算机芯片应用的太阳能基板、光伏器件和微机电系统(MEMS)。应该理解,术语“微电子装置”不意味着以任何方式进行限制,并且包括最终将变成微电子装置或微电子组件的任何基材。
正如本文中所定义,“铜或铜合金”是指铜(0)或铜与至少一种其他组分例如锌、锡、铝、硅、镍、磷、铁、锰、铍、钴、铅及其组合的混合物(合金)。专业技术人员将会理解,经历过某些表面反应例如氧化的铜或铜合金,仍被认为是用于本发明的目的的铜或铜合金。铜的实例包括通过化学气相沉积法(CVD方法)、物理气相沉积法(PVD方法)、原子层沉积法(ALD方法)和电镀法形成的铜。
正如本文中所定义,术语“金属阻挡层”是指在本技术领域中用于密封金属线路例如铜互连系统,以最小化所述金属例如铜扩散到介电材料中的任何材料。优选的阻挡层材料包括钽、钛、钌、铪、钨和其他耐熔金属及其氮化物和硅化物。
正如本文中所定义的,“低k介电材料”是指在层状微电子装置中用作介电材料的任何材料,其中所述材料具有低于约3.5的介电常数。优选情况下,低k介电材料包括低极性材料例如含硅有机聚合物、含硅杂合有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和掺碳氧化物(CDO)玻璃。应该认识到,低k介电材料可以具有不同密度和不同孔隙度。
“基本上不含”在本文中被定义为小于2wt.%、优选小于1wt.%、更优选小于0.5wt.%、最优选小于0.1wt.%。
当在本文中使用时,“约”打算是指所陈述值的±5%。
当在本文中使用时,“相对于含镍材料选择性蚀刻铜或铜合金”是指铜或铜合金相对于含镍材料的移除速率为至少100:1、更优选至少1000:1、还更优选至少10000:1、最优选至少100000:1。
正如本文中所定义,“基本上不含”是指以组合物的总重量计,少于所述组合物的约2wt.%、更优选少于1wt.%、还更优选少于0.1wt.%、最优选为0wt%。
本文描述的组合物可以体现在广泛的各种特定配方中,正如后文中更充分描述的。
在所有这样的组合物中,其中所述组合物的特定组分参照包括零值下限的重量百分率范围进行讨论,应该理解,在组合物的各种特定实施方案中这样的组分可能存在或不存在,并且在这样的组分存在的情形中,它们可以以使用这样的组分的组合物的总重量计,低至0.001wt.%的浓度存在。
一方面,描述了一种溶液,所述溶液从其上具有铜或铜合金材料的微电子装置蚀刻所述铜或铜合金材料,其中所述溶液相对于含镍材料选择性蚀刻铜或铜合金。该溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)和至少一种在分子中具有氧化乙烯链的表面活性剂(C)。在另一个实施方案中,该溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)和至少一种溶剂(D)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)和至少一种抗腐蚀组分(E)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)和至少一种抗氧化剂(F)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)、至少一种抗腐蚀组分(E)和至少一种抗氧化剂(F)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)和至少一种碱性化合物(G)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)、至少一种抗腐蚀组分(E)和至少一种碱性化合物(G)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)、至少一种抗氧化剂(F)和至少一种碱性化合物(G)。在另一个实施方案中,溶液可以包含、其组成为、或者其基本组成为至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、至少一种溶剂(D)、至少一种抗腐蚀组分(E)、至少一种抗氧化剂(F)和至少一种碱性或酸性化合物(G)。
正如在本文中所述,添加在分子中具有酸基团的螯合剂(A)或其盐以提高铜或铜合金的蚀刻速率。优选情况下,在分子中具有酸基团的螯合剂(A)具有两个以上的官能团,至少一个所述官能团是酸基团。考虑到的其他官能团包括中性羟基或酚羟基。螯合剂(A)中的酸基团的实例包括羧基、膦酸基、磺酸基、磷酸基、硫酸基、硝酸基和硼酸基。例如,螯合剂(A)可以包括含有两个以上的羧基作为酸基团的有机酸或其盐(A1)、包括两个以上的膦酸基作为酸基团的有机酸或其盐(A2)、包括两个以上的磺酸基作为酸基团的有机酸或其盐(A3)、以及包括一个以上的羧基和一个以上的膦酸基作为酸基团的有机酸或其盐(A4)。螯合剂(A)可以是包括仅仅一个羧基、一个膦酸基或一个磺酸基作为酸基团的螯合剂(A5),只要所述螯合剂在分子中具有表现出螯合效应的羟基即可。应该认识到,如果存在一种以上的螯合剂,设想的是A1、A2、A3、A4和A5螯合剂的任意组合。
本文设想的A1螯合剂包括但不限于乙二胺四乙酸、二亚乙基三胺五乙酸、三亚乙基四胺六乙酸、羟乙基乙二胺三乙酸、二羟乙基乙二胺四乙酸、次氮基三乙酸、羟乙基亚氨基二乙酸、β-丙氨酸二乙酸、天冬氨酸二乙酸、甲基甘氨酸二乙酸、亚氨基二琥珀酸、丝氨酸二乙酸、羟基亚氨基二琥珀酸、酒石酸、柠檬酸、均苯四酸、苯并多羧酸、环戊烷四羧酸、其盐及其组合。
A2螯合剂包括但不限于甲基二膦酸、氨基三(亚甲基膦酸)、1-羟基亚乙基-1,1-二膦酸(HEDP)、乙二胺四(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、丙二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、三亚乙基四胺六(亚甲基膦酸)、三氨基三乙基胺六(亚甲基膦酸)、反式-1,2-环己烷二胺四(亚甲基膦酸)、乙二醇醚二胺四(亚甲基膦酸)、四亚乙基五胺七(亚甲基膦酸)、其盐及其组合。
A3螯合剂包括但不限于甲二磺酸、乙二磺酸、苯酚二磺酸、萘二磺酸、哌嗪-1,4-双(2-乙磺酸)、其盐及其组合。
A4螯合剂包括但不限于膦酰乙酸、2-羟基-2-膦酰乙酸、羧基膦酸、3-膦酰基丙酸、4-(3-膦酰基丙基)-2-哌嗪甲酸、其盐及其组合。
A5螯合剂包括但不限于乳酸、水杨酸、没食子酸、2-羟乙基膦酸、2-羟基乙磺酸、其盐及其组合。
最优选的螯合剂是来自于A1、A2或A3的螯合剂,最优选为来自于A2的螯合剂。在分子中具有酸基团的螯合剂(A)的含量,以溶液的总重量计优选为约0.1至约50wt.%,更优选为约0.5至约30wt.%,最优选为约1至约20wt.%。
包含过氧化氢(B)以提高铜或铜合金的蚀刻速率。可以使用过氧化氢的水性溶液作为过氧化氢(B)。根据纯度,其含量以溶液的总重量计优选为约0.05至约20wt.%、更优选约0.1至约10wt.%、最优选约0.2至约5wt.%。
在分子中具有氧化乙烯链的表面活性剂(C)包括非离子型表面活性剂例如烷基胺的环氧乙烷(EO)加合物(C1)、一元醇的EO加合物(C2)、多元醇的EO加合物(C3)、环氧乙烷环氧丙烷共聚物(C4)、烷基酚的EO加合物(C5)和脂肪酸的EO加合物(C6),通过修饰烷基醇的EO加合物的末端而制备的阴离子型表面活性剂(C7)、通过修饰烷基酚的EO加合物的末端而制备的阴离子型表面活性剂(C8)及其任意组合。烷基胺的EO加合物(C1)的实例包括辛胺的EO加合物和月桂胺的EO加合物。一元醇的EO加合物(C2)的实例包括聚氧乙烯辛基醚、聚氧乙烯月桂基醚和聚氧乙烯硬脂基醚的EO加合物。多元醇的EO加合物(C3)的实例包括蔗糖的EO加合物、山梨糖醇的EO加合物、季戊四醇的EO加合物和山梨糖醇单月桂酸酯的EO加合物。环氧乙烷-环氧丙烷共聚物(C4)的实例包括聚氧化丙二醇的环氧乙烷加合物和聚氧化乙二醇的环氧丙烷加合物。待添加的环氧乙烷的摩尔数为1至300,待添加的环氧丙烷的摩尔数为1至300。使用环氧乙烷-环氧丙烷共聚物(C4)作为组分(C)特别有用,因为它具有作为消泡剂的效果。烷基酚的EO加合物(C5)的实例包括聚氧乙烯壬基苯基醚和聚氧乙烯辛基苯基醚。脂肪酸的EO加合物(C6)的实例包括聚乙二醇单硬脂酸酯、聚乙二醇二硬脂酸酯、聚乙二醇单油酸酯和聚乙二醇二油酸酯。通过修饰烷基醇的EO加合物的末端而制备的阴离子型表面活性剂(C7)的实例,包括通过用有机酸修饰一元醇的EO加合物(C2)而制备的阴离子型表面活性剂,例如聚氧乙烯辛基醚乙酸(盐)、聚氧乙烯月桂基醚乙酸(盐)、聚氧乙烯辛基醚磺基琥珀酸(盐)、聚氧乙烯月桂基醚磺基琥珀酸(盐)、聚氧乙烯辛基醚硫酸酯(盐)和聚氧乙烯月桂基醚硫酸酯(盐)。通过修饰烷基酚的EO加合物的末端而制备的阴离子型表面活性剂(C8)的实例,包括通过用有机酸修饰烷基酚的EO加合物(C5)而制备的阴离子型表面活性剂,例如聚氧乙烯壬基苯基醚硫酸酯(盐)和聚氧乙烯辛基苯基醚硫酸酯(盐)。优选情况下,在分子中具有氧化乙烯链的表面活性剂(C)中存在的EO的摩尔数为1至20,优选为2至15。在分子中具有氧化乙烯链的表面活性剂(C)中,从铜或铜合金的蚀刻速率相对于含镍材料的蚀刻速率的比率以及晶片的高度可润湿性的观点来看,优选的是烷基胺的EO加合物(C1)、环氧乙烷环氧丙烷共聚物(C4)和通过修饰烷基醇的EO加合物的末端而制备的阴离子型表面活性剂(C7)。从较低金属杂质的观点来看,更优选的是烷基胺的EO加合物(C1)。从消泡效果的观点来看,更优选的是环氧乙烷-环氧丙烷共聚物(C4)。
从铜或铜合金的蚀刻速率的观点来看,分子中具有酸基团的螯合剂(A)的重量与过氧化氢(B)的重量比(A)/(B)优选为1至30,更优选为2至20,特别优选为3至10。此外,分子中具有酸基团的螯合剂(A)的重量与表面活性剂(C)的重量比(A)/(C)优选为1至100,更优选为2至50,特别优选为5至30。
溶剂(D)包括但不限于水、醇类、二醇醚类、醚类、酯类、酮类、碳酸酯类、酰胺类及其组合。醇类的实例包括甲醇、乙醇、异丙醇、正丙醇、正己醇、正辛醇、2-乙基己醇、环己醇、乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、四氢糠醇和甘油。二醇醚类的实例包括丙二醇单甲醚、丙二醇单甲醚乙酸酯、乙二醇单甲醚、乙二醇单甲醚乙酸酯、乙二醇单甲醚丙酸酯、乙二醇单丁醚和乙二醇单丁醚乙酸酯。醚类的实例包括二乙醚、二异丙基醚、二丁醚、四氢呋喃和1,4-二氧六环。酯类的实例包括乳酸乙酯、3-甲氧基丙酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯和γ-丁内酯。酮类的实例包括丙酮、甲基乙基酮、甲基异丙基酮、甲基异丁基酮、甲基戊基酮、环戊酮和环己酮。碳酸酯的实例包括碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯和碳酸丙烯酯。酰胺类的实例包括N,N-二甲基乙酰胺和N,N-二甲基甲酰胺。水是优选的溶剂。
为了保护布线金属,在需要时可以向溶液添加至少一种抗腐蚀组分(E),例如三唑类、咪唑类、硫醇化合物和糖醇。三唑类的实例包括苯并三唑、邻甲苯基三唑、间甲苯基三唑、对甲苯基三唑、羧基苯并三唑、1-羟基苯并三唑、硝基苯并三唑和二羟基丙基苯并三唑。咪唑类的实例包括咪唑、苯并咪唑、苯并咪唑甲酸、咪唑-2-甲酸、咪唑-4-甲酸、咪唑-2-羧基醛、咪唑-4-羧基醛和4-咪唑二硫代甲酸。硫醇化合物的实例包括巯基噻唑、巯基乙醇和硫代甘油。糖醇的实例包括赤藓糖醇、苏糖醇、阿拉伯糖醇、木糖醇、核糖醇、甘露糖醇、山梨糖醇、麦芽糖醇和肌醇。
为了保护布线金属,在需要时可以向溶液添加抗氧化剂(F)。抗氧化剂的实例包括酚类例如儿茶素、生育酚、儿茶酚、甲基儿茶酚、乙基儿茶酚、叔丁基儿茶酚、没食子酸、没食子酸甲酯和没食子酸丙酯、3-羟基黄酮和抗坏血酸。
在需要时,可以向溶液添加碱性或酸性化合物(G)作为pH调节剂。碱性化合物可以是氨、胺类、四烷基氢氧化铵类和含氮杂环化合物。胺类的实例包括脂肪胺类、烷醇胺类、亚烷基二胺类、多亚烷基多胺类、芳香胺类、脂环族胺类和胍。脂肪胺类的实例包括甲胺、乙胺、丙胺、异丙胺、丁胺、己胺、二甲胺、乙基甲基胺、丙基甲基胺、丁基甲基胺、二乙胺、丙基乙基胺、二异丙基胺、三甲胺、乙基二甲基胺、二乙基甲基胺、三乙胺、三正丙基胺和三正丁基胺。烷醇胺类的实例包括单乙醇胺、二乙醇胺、三乙醇胺、二甲基氨基乙醇、二乙基氨基乙醇、2-氨基-2-甲基-1-丙醇、N-(氨基乙基)乙醇胺、N,N-二甲基-2-氨基乙醇和2-(2-氨基乙氧基)乙醇。亚烷基二胺类的实例包括乙二胺、丙二胺、三亚甲基二胺、四亚甲基二胺和六亚甲基二胺。多亚烷基多胺类的实例包括二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、六亚甲基七胺、亚氨基双丙基胺、双(六亚甲基)三胺和五亚乙基六胺。芳香胺类的实例包括苯胺、苯二胺、甲苯二胺、苯二甲胺、亚甲基二苯胺、二苯基醚二胺、萘二胺和蒽二胺。脂环族胺类的实例包括异佛尔酮二胺、亚环己基二胺、哌嗪、N-氨基乙基哌嗪和1,4-二氨基乙基哌嗪。四烷基氢氧化铵类的实例包括四甲基氢氧化铵、四乙基氢氧化铵和胆碱。含氮杂环化合物的实例包括吡咯、咪唑、吡唑、噁唑、噻唑、吡啶、嘧啶、哒嗪、吡嗪、联吡啶和菲咯啉。
酸性化合物可以是无机酸例如硫酸、盐酸、硝酸和氢氟酸,以及有机酸例如乙酸。为了使蚀刻速率稳定,添加无机酸或其盐也是有效的。
在优选实施方案中,pH在约0至约5、更优选约1至约4、最优选约2至约3的范围内。
在需要时可以向溶液添加消泡剂。消泡剂的实例包括硅酮消泡剂、长链醇消泡剂、脂肪酸酯消泡剂和金属皂消泡剂。上述的环氧乙烷环氧丙烷共聚物(C4)可以用作消泡剂。
本文所述的溶液可用于以下应用,所述应用包括但不限于移除铜或铜合金、优选相对于含镍材料选择性移除铜或铜合金。此外,考虑到了本文所述的溶液可用于清洁和保护金属(例如含铜)产品,包括但不限于微电子装置、装饰金属、金属引线接合、印刷线路板和使用金属或金属合金的其他电子包装。
在特别优选实施方案中,溶液包含、其组成为、或其基本组成为HEDP、月桂胺的EO加合物、过氧化氢和水。
在另一个优选实施方案中,本文所述的溶液还包括铜。铜可以溶解和/或悬浮在溶液中。
本发明的溶液基本上不含磨料、氟化物源、氟化碳化合物、双胍化合物、丝氨酸、组氨酸和天冬氨酸及其任意组合。此外,使用本文所描述的组分浓度,溶液不能形成树脂材料或聚合物材料。
溶液可以通过简单地加入相应成分并混合至均匀状况来容易地配制。此外,可将溶液容易地配制成单包装制剂或多部分制剂,所述多部分制剂在使用的时间点处或之前进行混合,例如多部分制剂的各个部分可以在工具处或工具上游的储存罐中进行混合。相应组分的浓度可以以溶液的特定倍数而广泛变化,即更稀或更浓,并且应该认识到,本文描述的溶液可以各不相同并可选地包含、其组成为、或其基本组成为与本文公开内容相符的成分的任意组合。
相应地,另一方面涉及一种试剂盒,其在一个或多个容器中包含适合于形成本文所述溶液的一种或多种组分。试剂盒可以在一个或多个容器中包括至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、任选至少一种溶剂(D)、任选至少一种抗腐蚀组分(E)、任选至少一种抗氧化剂(F)和任选至少一种碱性或酸性化合物(G),用于在实验室或使用地点处与溶剂组合。可选地,试剂盒可以在第一容器中包括至少一种在分子中具有酸基团的螯合剂(A)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、任选至少一种溶剂(D)、任选至少一种抗腐蚀组分(E)、任选至少一种抗氧化剂(F)和任选至少一种碱性或酸性化合物(G),以及在第二容器中包含过氧化氢(B),用于在实验室或使用地点处彼此组合并与其他溶剂组合。试剂盒的容器必须适合于储存和运输所述溶液,例如容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。
在本文所述溶液用于从其上具有铜和铜合金的微电子装置选择性移除铜和铜合金的应用中,典型地将溶液与装置在约10℃至约100℃、优选约20℃至约80℃范围内的温度下接触优选约30秒至约10分钟的时间。这样的接触时间和温度是示例性的,并且可以使用在方法的广泛实践中有效地相对于含镍材料选择性蚀刻铜或铜合金的任何其他适合的时间和温度条件。
在蚀刻应用中,将溶液以任何适合的方式施加到其上具有铜或铜合金的微电子装置的表面,例如通过将溶液喷洒在装置表面上,通过将包含铜或铜合金的装置浸渍或浸泡在溶液中(在静态或动态溶液体积中),通过将装置与其上吸收有溶液的另一种材料例如衬垫或纤维状吸收性涂覆元件相接触,通过将包含铜或铜合金的装置与循环的溶液相接触,或者通过能够使溶液与其上具有铜或铜合金的微电子装置相接触的任何其他适合的手段、方式或技术。所述应用可以在分批或单个晶片装置中,用于动态或静态清洁。有利的是,本文描述的溶液,凭借其与可能存在于微电子装置结构上并暴露于溶液的其他含镍材料相比对铜或铜合金的选择性,以高效和高选择性方式实现了铜或铜合金的移除。
在获得所需蚀刻作用后,如在本发明溶液的给定最终应用中可能是理想且有效的,可以通过例如漂洗、清洗或其他移除步骤,将溶液从以前施加有它的微电子装置上容易地移除。例如,装置可以用包含去离子水的漂洗溶液漂洗和/或干燥(例如甩干、N2、蒸气干燥等)。
另一方面涉及制造制品,其包含清洁溶液、微电子装置晶片、铜或铜合金材料以及含镍材料,其中溶液包含至少一种在分子中具有酸基团的螯合剂(A)、过氧化氢(B)、至少一种在分子中具有氧化乙烯链的表面活性剂(C)、任选至少一种溶剂(D)、任选至少一种抗腐蚀组分(E)、任选至少一种抗氧化剂(F)和任选至少一种碱性或酸性化合物(G)。.
下面讨论的示例性实施例将更充分地显示本发明的特征和优点。
实施例1
通过将表1中示出的螯合剂(A)、过氧化氢(B)、表面活性剂(C)和水(D)在聚丙烯制成的容器中混合,获得了本文所述的溶液和比较用溶液。
表1中的符号对应于下列化合物:
HEDP:60%1-羟亚乙基-1,1-二膦酸水性溶液
EDA:1,2-乙二磺酸二水合物
NTMPA:次氮基三亚甲基膦酸
(C-1):8Mol月桂胺的EO加合物
(C-2):2.5Mol月桂醇的EO加合物的硫酸酯钠盐
(C-3):聚氧化丙二醇的EO加合物(约10至约50mol的环氧丙烷,优选约31mol环氧丙烷;约30至约60mol的环氧丙烷,优选约45mol的环氧丙烷)
(C'-1):硬脂基三甲基氯化铵
作为性能评估,通过下述方法评估了铜的蚀刻时间和镍的蚀刻性能(蚀刻量)。
铜的蚀刻时间通过下述方法来评估:
(1)将硅基板如图4所示进行加工,将生产的晶片(铜晶种层的厚度为1μm)切割成15-mm的正方形,以制备测试样片。使用扫描电子显微镜(SEM;Hitachi High-TechnologiesCorporation,S-4800)观察通过将晶片切割成1cm正方形而制备的测试样片的横截面。凸块的宽度约为30μm,凸块的高度约为8μm。铜晶种层的厚度为1μm。
(2)将在实施例1至7和比较例1至5中制备的每种蚀刻溶液置于由聚丙烯制成的容器中并搅拌。将测试样片分别浸泡在蚀刻溶液中。
(3)目测观察浸泡在蚀刻溶液中的测试样片的表面,并测量直至铜晶种层的整个表面上铜的光泽消失为止的时间(例如,图5中的(3):直至可以看见钛层的整个表面)。
优选情况下,直至铜的光泽消失为止的时间优选不超过10分钟。对于其中光泽在60分钟后未消失的测试样片来说,在60分钟后停止浸泡,并且评估在表1中显示为“>60”。
按照下述方法确定被蚀刻的镍的量。使用SEM,在铜晶种层被蚀刻之前和铜晶种层被蚀刻之后获取测试样片的侧表面的照片,以便可以确定镍层待被腐蚀的程度及其待被腐蚀的宽度。从摄影图像,测量蚀刻铜晶种层之前测试样片的镍层(图4中的7)的宽度A1(μm)和蚀刻之后测试样片的镍层的宽度A2(μm)。如果蚀刻之前和之后镍层的宽度之间的差值A1-A2小于1.0μm,它用○表示;如果所述差值不小于1.0μm,它用×表示。
在表1中可以看出,在实施例1至5中,铜晶种层被快速蚀刻,而没有观察到镍部分的蚀刻。也就是说,在移除铜晶种层期间,所需的凸块可以形成并且不被降解。
另一方面,在不包含本文所述的分子中具有氧化乙烯链的表面活性剂(C)的比较例1和比较例2中,铜晶种层被快速蚀刻,但是镍也被蚀刻,产生变形的凸块。结果,晶片不能被使用。此外,在使用硫酸代替螯合剂(A)的比较例3中,铜晶种层被快速蚀刻,但是镍也被蚀刻,产生变形的凸块。结果,晶片不能被使用。在不包含螯合剂(A)的比较例4中,铜晶种层和镍都未被蚀刻。在不包含过氧化氢(B)的比较例5中,铜晶种层和镍都未被蚀刻。
尽管在本文中已参考示例性实施方案和特征对本发明进行了各种公开,但应该认识到并未打算用上文中所描述的实施方案和特征来限制本发明,并且根据本文的公开内容,其他变化、修改和其他实施方案将自然而然出现在本技术领域的普通专业人员面前。因此,本发明应该被广泛地解释为涵盖了在所提出的权利要求书的精神和范围之内的所有这样的变化、修改和可选实施方案。
Claims (15)
1.一种用于从同时包括铜或铜合金和含镍材料的微电子装置选择性蚀刻铜或铜合金的溶液,所述溶液包含在分子中具有酸基团的螯合剂(A)、过氧化氢(B)和在分子中具有氧化乙烯链的表面活性剂(C),其中所述螯合剂(A)包含选自以下的有机酸:乙二胺四乙酸、二亚乙基三胺五乙酸、三亚乙基四胺六乙酸、羟乙基乙二胺三乙酸、二羟乙基乙二胺四乙酸、次氮基三乙酸、羟乙基亚氨基二乙酸、β-丙氨酸二乙酸、天冬氨酸二乙酸、甲基甘氨酸二乙酸、亚氨基二琥珀酸、丝氨酸二乙酸、羟基亚氨基二琥珀酸、酒石酸、柠檬酸、均苯四酸、苯并多羧酸、环戊烷四羧酸、甲基二膦酸、氨基三(亚甲基膦酸)、1-羟基亚乙基-1,1-二膦酸(HEDP)、乙二胺四(亚甲基膦酸)、六亚甲基二胺四(亚甲基膦酸)、丙二胺四(亚甲基膦酸)、二亚乙基三胺五(亚甲基膦酸)、三亚乙基四胺六(亚甲基膦酸)、三氨基三乙基胺六(亚甲基膦酸)、反式-1,2-环己烷二胺四(亚甲基膦酸)、乙二醇醚二胺四(亚甲基膦酸)、四亚乙基五胺七(亚甲基膦酸)、甲二磺酸、乙二磺酸、苯酚二磺酸、萘二磺酸、哌嗪-1,4-双(2-乙磺酸)、膦酰乙酸、2-羟基-2-膦酰乙酸、羧基膦酸、3-膦酰基丙酸、4-(3-膦酰基丙基)-2-哌嗪甲酸、乳酸、水杨酸、没食子酸、2-羟乙基膦酸、2-羟基乙磺酸、其盐及其组合,
其中pH在0至5的范围内。
2.权利要求1的溶液,其中所述表面活性剂(C)包含烷基胺的环氧乙烷(EO)加合物(C1)、一元醇的EO加合物(C2)、多元醇的EO加合物(C3)、环氧乙烷环氧丙烷共聚物(C4)、烷基酚的EO加合物(C5)、脂肪酸的EO加合物(C6)、通过修饰烷基醇的EO加合物的末端而制备的阴离子型表面活性剂(C7)、通过修饰烷基酚的EO加合物的末端而制备的阴离子型表面活性剂(C8)及其任意组合。
3.权利要求1的溶液,其中所述表面活性剂(C)包含烷基胺的环氧乙烷加合物。
4.权利要求1的溶液,其中所述表面活性剂(C)包含选自以下的物质:辛胺的环氧乙烷(EO)加合物、月桂胺的EO加合物、聚氧乙烯辛基醚的EO加合物、聚氧乙烯月桂基醚的EO加合物、聚氧乙烯硬脂基醚的EO加合物、蔗糖的EO加合物、山梨糖醇的EO加合物、季戊四醇的EO加合物、山梨糖醇单月桂酸酯的EO加合物、聚氧化丙二醇的环氧乙烷加合物、聚氧化乙二醇的环氧丙烷加合物、聚氧乙烯壬基苯基醚的EO加合物、聚氧乙烯辛基苯基醚的EO加合物、聚乙二醇单硬脂酸酯的EO加合物、聚乙二醇二硬脂酸酯的EO加合物、聚乙二醇单油酸酯的EO加合物、聚乙二醇二油酸酯的EO加合物、聚氧乙烯辛基醚乙酸(盐)、聚氧乙烯月桂基醚乙酸(盐)、聚氧乙烯辛基醚磺基琥珀酸(盐)、聚氧乙烯月桂基醚磺基琥珀酸(盐)、聚氧乙烯辛基醚硫酸酯(盐)、聚氧乙烯月桂基醚硫酸酯(盐)、聚氧乙烯壬基苯基醚硫酸酯(盐)、聚氧乙烯辛基苯基醚硫酸酯(盐)及其组合。
5.权利要求1的溶液,其中所述表面活性剂(C)包含辛胺的环氧乙烷(EO)加合物、月桂胺的EO加合物或其组合。
6.权利要求1的溶液,其中所述螯合剂(A)的重量与过氧化氢(B)的重量比(A)/(B)为1至30。
7.权利要求1的溶液,其中所述螯合剂(A)的重量与所述表面活性剂(C)的重量比(A)/(C)为1至100。
8.权利要求1的溶液,其还包含至少一种溶剂(D)。
9.权利要求8的溶液,其中所述至少一种溶剂包含选自以下的物质:水、甲醇、乙醇、异丙醇、正丙醇、正己醇、正辛醇、2-乙基己醇、环己醇、乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、四氢糠醇、甘油、丙二醇单甲醚、丙二醇单甲醚乙酸酯、乙二醇单甲醚、乙二醇单甲醚乙酸酯、乙二醇单甲醚丙酸酯、乙二醇单丁醚、乙二醇单丁醚乙酸酯、二乙醚、二异丙基醚、二丁醚、四氢呋喃、1,4-二氧六环、乳酸乙酯、3-甲氧基丙酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、γ-丁内酯、丙酮、甲基乙基酮、甲基异丙基酮、甲基异丁基酮、甲基戊基酮、环戊酮、环己酮、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺及其组合。
10.权利要求8的溶液,其中所述至少一种溶剂包含水。
11.权利要求1的溶液,其还包含选自至少一种抗腐蚀组分(E)、至少一种抗氧化剂(F)和至少一种碱性化合物(G)的至少一种组分。
12.权利要求11的溶液,其包含选自以下的至少一种抗腐蚀组分(E):苯并三唑、邻甲苯基三唑、间甲苯基三唑、对甲苯基三唑、羧基苯并三唑、1-羟基苯并三唑、硝基苯并三唑、二羟基丙基苯并三唑、咪唑、苯并咪唑、苯并咪唑甲酸、咪唑-2-甲酸、咪唑-4-甲酸、咪唑-2-羧基醛、咪唑-4-羧基醛、4-咪唑二硫代甲酸、巯基噻唑、巯基乙醇、硫代甘油、赤藓糖醇、苏糖醇、阿拉伯糖醇、木糖醇、核糖醇、甘露糖醇、山梨糖醇、麦芽糖醇和肌醇。
13.权利要求11的溶液,其包含选自以下的至少一种抗氧化剂(F):儿茶素、生育酚、儿茶酚、甲基儿茶酚、乙基儿茶酚、叔丁基儿茶酚、没食子酸、没食子酸甲酯、没食子酸丙酯、3-羟基黄酮和抗坏血酸。
14.权利要求11的溶液,其包含选自以下的至少一种碱性化合物(G):甲胺、乙胺、丙胺、异丙胺、丁胺、己胺、二甲胺、乙基甲基胺、丙基甲基胺、丁基甲基胺、二乙胺、丙基乙基胺、二异丙基胺、三甲胺、乙基二甲基胺、二乙基甲基胺、三乙胺、三正丙基胺、三正丁基胺、单乙醇胺、二乙醇胺、三乙醇胺、二甲基氨基乙醇、二乙基氨基乙醇、2-氨基-2-甲基-1-丙醇、N-(氨基乙基)乙醇胺、N,N-二甲基-2-氨基乙醇、2-(2-氨基乙氧基)乙醇、乙二胺、丙二胺、三亚甲基二胺、四亚甲基二胺、六亚甲基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、六亚甲基七胺、亚氨基双丙基胺、双(六亚甲基)三胺、五亚乙基六胺、苯胺、苯二胺、甲苯二胺、苯二甲胺、亚甲基二苯胺、二苯基醚二胺、萘二胺、蒽二胺、异佛尔酮二胺、亚环己基二胺、哌嗪、N-氨基乙基哌嗪、1,4-二氨基乙基哌嗪、四甲基氢氧化铵、四乙基氢氧化铵、胆碱、吡咯、咪唑、吡唑、噁唑、噻唑、吡啶、嘧啶、哒嗪、吡嗪、联吡啶和菲咯啉。
15.一种生产微电子装置的方法,所述方法包括使用溶液从微电子装置选择性蚀刻铜或铜合金,其中所述装置同时包括铜或铜合金和含镍材料,其中所述溶液是权利要求1至14任一项的溶液。
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JP2012062572A (ja) | 2012-03-29 |
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SG10201506427XA (en) | 2015-10-29 |
SG187857A1 (en) | 2013-03-28 |
CN103080382A (zh) | 2013-05-01 |
CN103080382B (zh) | 2016-08-17 |
JP6101421B2 (ja) | 2017-03-22 |
WO2012024300A3 (en) | 2012-05-31 |
TWI565834B (zh) | 2017-01-11 |
KR101809302B1 (ko) | 2017-12-14 |
WO2012024300A2 (en) | 2012-02-23 |
TW201213613A (en) | 2012-04-01 |
KR20170140420A (ko) | 2017-12-20 |
CN106435587A (zh) | 2017-02-22 |
US10570522B2 (en) | 2020-02-25 |
US20130270217A1 (en) | 2013-10-17 |
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