TW201619361A - 可抑制鈷之損壞的半導體元件之清洗液及利用該清洗液的半導體元件之清洗方法 - Google Patents
可抑制鈷之損壞的半導體元件之清洗液及利用該清洗液的半導體元件之清洗方法 Download PDFInfo
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- TW201619361A TW201619361A TW104132922A TW104132922A TW201619361A TW 201619361 A TW201619361 A TW 201619361A TW 104132922 A TW104132922 A TW 104132922A TW 104132922 A TW104132922 A TW 104132922A TW 201619361 A TW201619361 A TW 201619361A
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- Prior art keywords
- cobalt
- mass
- compound
- group
- tungsten
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- 238000004140 cleaning Methods 0.000 title claims abstract description 153
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 86
- 239000010941 cobalt Substances 0.000 title claims abstract description 86
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000004065 semiconductor Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 31
- 239000000463 material Substances 0.000 claims abstract description 96
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 85
- 239000010937 tungsten Substances 0.000 claims abstract description 84
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000001312 dry etching Methods 0.000 claims abstract description 66
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002978 peroxides Chemical class 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 10
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 94
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- -1 diamine compound Chemical class 0.000 claims description 34
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 16
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 150000001785 cerium compounds Chemical class 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 7
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 7
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 6
- 229910001626 barium chloride Inorganic materials 0.000 claims description 6
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 5
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 5
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
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- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- RWXZXCZBMQPOBF-UHFFFAOYSA-N 5-methyl-1H-benzimidazole Chemical compound CC1=CC=C2N=CNC2=C1 RWXZXCZBMQPOBF-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
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- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
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- 239000012964 benzotriazole Substances 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
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- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 239000004343 Calcium peroxide Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 2
- 229910001638 barium iodide Inorganic materials 0.000 description 2
- 229940075444 barium iodide Drugs 0.000 description 2
- ARSLNKYOPNUFFY-UHFFFAOYSA-L barium sulfite Chemical compound [Ba+2].[O-]S([O-])=O ARSLNKYOPNUFFY-UHFFFAOYSA-L 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 2
- 235000019402 calcium peroxide Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical group CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CPJYFACXEHYLFS-UHFFFAOYSA-N [B].[W].[Co] Chemical compound [B].[W].[Co] CPJYFACXEHYLFS-UHFFFAOYSA-N 0.000 description 1
- FEBFYWHXKVOHDI-UHFFFAOYSA-N [Co].[P][W] Chemical compound [Co].[P][W] FEBFYWHXKVOHDI-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- MTHLBYMFGWSRME-UHFFFAOYSA-N [Cr].[Co].[Mo] Chemical compound [Cr].[Co].[Mo] MTHLBYMFGWSRME-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- NZUYJPMKCSBVLS-UHFFFAOYSA-N cadmium;hydrogen peroxide Chemical compound [Cd].OO NZUYJPMKCSBVLS-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- ZEDZJUDTPVFRNB-UHFFFAOYSA-K cerium(3+);triiodide Chemical compound I[Ce](I)I ZEDZJUDTPVFRNB-UHFFFAOYSA-K 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- OQCGPOBCYAOYSD-UHFFFAOYSA-N cobalt palladium Chemical compound [Co].[Co].[Co].[Pd].[Pd] OQCGPOBCYAOYSD-UHFFFAOYSA-N 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 239000010952 cobalt-chrome Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- IAOQICOCWPKKMH-UHFFFAOYSA-N dithieno[3,2-a:3',2'-d]thiophene Chemical compound C1=CSC2=C1C(C=CS1)=C1S2 IAOQICOCWPKKMH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- MWRJCEDXZKNABM-UHFFFAOYSA-N germanium tungsten Chemical compound [Ge].[W] MWRJCEDXZKNABM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001117 oleyl 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])=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
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- 229940093928 potassium nitrate Drugs 0.000 description 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- LCGWNWAVPULFIF-UHFFFAOYSA-N strontium barium(2+) oxygen(2-) Chemical compound [O--].[O--].[Sr++].[Ba++] LCGWNWAVPULFIF-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/30—Amines; Substituted amines ; 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
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Abstract
根據本發明可提供一種清洗液,其將具有 (1)含鈷或鈷合金之材料、或(2)含鈷或鈷合金及鎢之材料與低介電常數膜(Low-k膜)的半導體元件的表面的乾蝕刻殘渣予以除去;含有鹼金屬化合物0.001~7質量%、過氧化物0.005~35質量%、防蝕劑0.005~10質量%、鹼土類金屬化合物0.000001~1質量%及水。
Description
本發明係關於一種於半導體元件的製造步驟中,至少可以抑制低介電常數層間絕緣膜與(1)含鈷或鈷合金的材料、或(2)含鈷或鈷合金及鎢的材料之損壞,並除去存在於半導體元件表面的乾蝕刻殘渣的清洗液,以及使用該清洗液之半導體元件的清洗方法。
高度積體化的半導體元件的製造一般會採取如下之一系列的步驟:通常係於矽晶圓等的元件上形成成為導電用配線素材的金屬膜等的導電薄膜,或以進行導電薄膜間的絕緣為目的之層間絕緣膜之後,於其表面均勻地塗佈光阻設置感光層,並對此實施選擇性的曝光・顯像處理,製作所希望的光阻圖案。接下來藉由將此光阻圖案作為光罩,對層間絕緣膜實施乾蝕刻處理,而於該薄膜形成所希望的圖案。接著,將光阻圖案及利用乾蝕刻處理而產生的殘渣物(以下稱為「乾蝕刻殘渣」)等利用氧氣電漿進行灰化,之後,使用清洗液等完全除去。
近年來,設計規則微型化在進步,信號傳輸的延遲已逐漸主導了高速運算處理的極限。因此,導電用配線素材由鋁過渡到電阻較低的銅,而層間絕緣膜由氧化矽膜向低介電常數膜(相對介電常數比3小的膜。以下稱為「Low-k膜」)的過渡正在進行。但,依配線微型化的進行,因流過配線的電流密度增大而導致容易發生銅的電遷移。因此,有人報告使用鈷作為代替銅的高信賴性配線材料的技術,或導入鈷合金作為帽蓋金屬以防止銅的電遷移的技術。又,於0.2μm以下的圖案,膜厚1μm的光阻中的圖案的深寬比(光阻膜厚除以光阻線寬的比)太大,會發生圖案崩塌等的問題。為了解決此問題有時會使用硬式光罩法:係將含有鈦或矽的膜(以下稱為「硬式光罩」)插入於實際上欲形成的圖案膜與光阻膜之間,並暫時將光阻圖案以乾蝕刻法轉寫於硬式光罩,之後,將此硬式光罩作為蝕刻光罩,利用乾蝕刻法將圖案轉寫於實際欲形成的膜。此方法可以變更蝕刻硬式光罩時的氣體與蝕刻實際欲形成的膜時的氣體,因可以選擇於蝕刻硬式光罩時採取和光阻有選擇比之氣體、於蝕刻實際的膜時採取和硬式光罩有選擇比之氣體,故有可以用薄的光阻形成圖案的優點。又,與基板進行連接的接觸插塞(contact plug)中使用含鎢材料。
以氧氣電漿除去乾蝕刻殘渣的情況,會發生Low-k膜、鈷及鈷合金、障壁金屬(barrier metal)及障壁絕緣膜曝露於氧氣電漿等而受到損壞,且電性質顯著劣化之問題。因此,於使用Low-k膜的半導體元件的製造中,尋求一種於抑制Low-k膜、鈷及鈷合金、障壁金屬及障壁絕緣膜的損壞,同時與氧氣電漿步驟同等程度地除去乾蝕刻殘渣的方法。進而為了使用於露出接觸插塞的層,會有也需要抑制含鎢材料損壞的情況。又,使用硬式光罩的情況,也必須抑制對含有硬式光罩的材料的損壞。
專利文獻1中,有人提出使用苯并三唑等之防止鈷的腐蝕之方法。但是,此方法無法令人滿意地抑制鈷的損壞(參照比較例6、9)。
專利文獻2中,有人提出使用5-胺基-1H-四唑與1-羥基苯并三唑的組合之防止鈷的腐蝕之方法。不過,此方法無法令人滿意地抑制鈷的損壞(參照比較例7、10)。
專利文獻3中,有人提出使用銅(II)離子與苯并三唑等,於鈷上形成抗腐蝕膜之防止鈷的腐蝕之方法,但此方法無法令人滿意地抑制鈷的損壞(參照比較例8、11)。
專利文獻4中,有人提出使用4-胺基-1,2,4-三唑或聚伸乙亞胺之防止鎢的腐蝕之方法。不過此方法無法令人滿意地抑制含鎢材料的損壞(參照比較例6、7、8)。
專利文獻5中,有人提出使用4級銨鹽或吡啶、聯吡啶、咪唑鹽之防止鎢的腐蝕之方法。但是,此方法無法令人滿意地抑制含鎢材料的損壞(參照比較例9、10、11)。
專利文獻6中,有人提出利用含有磷酸、鹽酸、1~4級銨、胺基酸型界面活性劑與水的清洗液的配線形成方法。但是,因此清洗液無法令人滿意地將殘渣予以除去,且無法令人滿意地抑制鈷的損壞,故不能使用於本目的(參照比較例12)。
專利文獻7中,有人提出利用含有氧化劑、4級銨氫氧化物、烷醇胺、鹼金屬氫氧化物與水的清洗液的配線形成方法。但是,此清洗液無法令人滿意地抑制含鎢材料的損壞,而不能使用於本目的(參照比較例13)。
專利文獻8中,有人提出利用含有氧化劑、胺、4級銨氫氧化物或鹼金屬氫氧化物、有機溶劑、介面活性劑與水的清洗液的配線形成方法。但是,此清洗液無法令人滿意地抑制鎢的損壞,而不能使用於本目的(參照比較例14)。
專利文獻9中,有人提出利用含有氟化合物、金屬抗腐蝕劑、鈍化劑與水的清洗液的配線形成方法,但因此清洗液不能將殘渣充分除去,且無法令人滿意地抑制Low-k膜的損壞,故不能使用於本目的(參照比較例15)。 【先前技術文獻】 【專利文獻】
【專利文獻1】日本特開2011-91248號公報 【專利文獻2】日本特開2012-182158號公報 【專利文獻3】日本特開平6-81177號公報 【專利文獻4】日本特開2001-026890號公報 【專利文獻5】日本特開2008-285508號公報 【專利文獻6】日本特開2003-316028號公報 【專利文獻7】日本特開2009-75285號公報 【專利文獻8】日本特開2009-231354號公報 【專利文獻9】日本特開2013-533631號公報
【發明所欲解決之問題】
本發明的目的係提供一種於半導體元件的製造步驟中,至少能抑制Low-k膜、與含鈷或鈷合金材料的損壞,並除去被處理物表面的乾蝕刻殘渣的清洗液,及使用該清洗液之清洗方法。 此外,本發明的另一個目的係提供一種於半導體元件的製造步驟中,至少能抑制Low-k膜、與含鈷或鈷合金材料以及鎢材料的損壞,並除去被處理物表面的乾蝕刻殘渣的清洗液,及使用該清洗液的清洗方法。 【解決問題之方式】
根據本發明可以解決上述課題。即本發明系如下所述。 <1> 一種清洗液,其將具有低介電常數膜(Low-k膜)與(1)含鈷或鈷合金之材料、或(2)含鈷或鈷合金及鎢之材料的半導體元件的表面的乾蝕刻殘渣予以除去;含有鹼金屬化合物0.001~7質量%、過氧化物0.005~35質量%、防蝕劑0.005~10質量%、鹼土類金屬化合物0.000001~1質量%及水。 <2> 如上述<1>中記載之清洗液,其中,該鹼金屬化合物係選自於由氫氧化鋰、硫酸鋰、碳酸鋰、碳酸氫鋰、硝酸鋰、氟化鋰、氯化鋰、溴化鋰、碘化鋰、乙酸鋰、氫氧化鈉、硫酸鈉、碳酸鈉、碳酸氫鈉、硝酸鈉、氟化鈉、氯化鈉、溴化鈉、碘化鈉、乙酸鈉、氫氧化鉀、硫酸鉀、碳酸鉀、碳酸氫鉀、硝酸鉀、氟化鉀、氯化鉀、溴化鉀、碘化鉀、乙酸鉀、氫氧化銫、硫酸銫、碳酸銫、碳酸氫銫、硝酸銫、氟化銫、氯化銫、溴化銫、碘化銫、及乙酸銫構成之群組中之至少1種以上。 <3> 如上述<1>或<2>中記載之清洗液,其中,該過氧化物係選自於由過氧化氫、過氧化脲、間氯過氧苯甲酸、第三丁基過氧化氫、過乙酸、二第三丁基過氧化物、過氧化苯甲醯、過氧化丙酮、過氧化甲乙酮、六亞甲基三過氧化物、及異丙苯過氧化氫構成之群組中之至少1種以上。 <4> 如上述<1>至<3>中記載之任一項之清洗液,其中,該防蝕劑係選自於由二胺化合物、烷醇胺化合物、吡唑化合物、咪唑化合物、及三唑化合物構成之群組中之至少1種以上。 <5> 如上述<4>中記載之清洗液,其中,該二胺化合物係選自於由1,2-丙二胺、1,3-丙二胺、及1,4-丁二胺構成之群組中之至少1種以上。 <6> 如上述<4>中記載之清洗液,其中,該烷醇胺化合物係選自於由2-胺基乙醇、2-甲胺基乙醇、1-胺基-2-丙醇、及1-胺基-3-丙醇構成之群組中之至少1種以上。 <7> 如上述<4>中記載之清洗液,其中,該吡唑化合物係選自於由吡唑、及3,5-二甲基吡唑構成之群組中之至少1種以上。 <8> 如上述<4>中記載之清洗液,其中,該咪唑化合物係選自於由1-甲基咪唑、1-乙烯基咪唑、及5-甲基苯并咪唑構成之群組中之至少1種以上。 <9> 如上述<4>中記載之清洗液,其中,該三唑化合物係選自於由1,2,4-三唑、1,2,3-三唑、及5-甲基-1H-苯并三唑構成之群組中之至少1種以上。 <10> 如上述<1>至<9>中任一項記載之清洗液,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鋇化合物構成之群組中之至少1種以上。 <11> 一種清洗方法,係清洗半導體元件而將該半導體元件表面之乾蝕刻殘渣予以除去,該半導體元件係於具有低介電常數膜(Low-k膜)與(1)含鈷或鈷合金之材料、或(2)含鈷或鈷合金及鎢之材料之基板上形成硬遮罩圖案,然後將此硬遮罩圖案作為遮罩,對該低介電常數膜(Low-k膜)施以乾蝕刻處理而得;其特徵為:使用如上述<1>至<10>中任一項記載之清洗液。 【發明之效果】
根據本發明的清洗液以及使用其的清洗方法,於半導體元件的製造步驟中,至少可抑制低介電常數層間絕緣膜與(1)含鈷或鈷合金的材料或(2)含鈷或鈷合金及鎢的材料的損壞,並除去被處理物表面上的乾蝕刻殘渣,能以高成品率製造高精度、高品質的半導體元件。
本發明的清洗液係使用於製造半導體元件的清洗步驟,此時,能令人充分滿意地清洗.除去乾蝕刻殘渣,且至少可以抑制Low-k膜與(1)含鈷或鈷合金的材料、或(2)含鈷或鈷合金及鎢的材料的損壞。本發明的清洗液可以對具有含鈷或鈷合金材料的半導體元件使用,也可以對具有含鈷或鈷合金及鎢的材料的半導體元件使用。鈷或鈷合金與鎢兩者皆具有的情況,鈷或鈷合金與鎢不必含於構成一個半導體元件的同一層中,分別含有於構成一個半導體元件的個別的層中即可。根據本發明,因利用一份清洗液,對含鈷或鈷合金的層可以防止鈷或鈷合金腐蝕,對含鎢的其他的層也可以防止鎢的腐蝕,故便利性極佳。適用於本發明的清洗液的半導體元件若含有(1)鈷或鈷合金、或(2)鈷或鈷合金及鎢即可,也可以含有該等以外的金屬。
作為於本發明的清洗液中含有的鹼金屬化合物,例如可以列舉氫氧化鋰、硫酸鋰、碳酸鋰、碳酸氫鋰、硝酸鋰、氟化鋰、氯化鋰、溴化鋰、碘化鋰、乙酸鋰、氫氧化鈉、硫酸鈉、碳酸鈉、碳酸氫鈉、硝酸鈉、氟化鈉、氯化鈉、溴化鈉、碘化鈉、乙酸鈉、氫氧化鉀、硫酸鉀、碳酸鉀、碳酸氫鉀、硝酸鉀、氟化鉀、氯化鉀、溴化鉀、碘化鉀、乙酸鉀、氫氧化銫、硫酸銫、碳酸銫、碳酸氫銫、硝酸銫、氟化銫、氯化銫、溴化銫、碘化銫以及乙酸銫。 該等之中,以氫氧化鋰、碳酸鋰、氫氧化鈉、氫氧化鉀、硫酸鉀、碳酸鉀、碳酸氫鉀、硝酸鉀、氟化鉀、氯化鉀、溴化鉀、碘化鉀、乙酸鉀以及碳酸銫為佳。 該等的鹼金屬化合物可以單獨或組合兩種以上摻合。
本發明的清洗液中含有的鹼金屬化合物的濃度範圍係0.001~7質量%,以0.005~5質量%為佳,以0.01~4.5質量%更佳,0.1~3質量%特佳。於上述範圍內的話,可以有效地除去乾蝕刻殘渣。濃度範圍比7質量%更大的情況會有造成Low-k膜損壞之虞。
本發明的清洗液中含有的過氧化物係具有(-O-O-)的結構的化合物(O係氧原子)。過氧化物的具體例係過氧化氫、過氧化脲、間氯過氧苯甲酸、第三丁基過氧化氫、過乙酸、二第三丁基過氧化物、過氧化苯甲醯、過氧化丙酮、過氧化甲乙酮、六甲亞基三過氧化物、異丙苯過氧化氫等,但並不限定於該等過氧化物。該等之中,以過氧化氫、間氯過氧苯甲酸及第三丁基過氧化氫更佳。又,該等可以單獨或組合兩種以上進行摻合。
無機過氧化物因與水反應,並於清洗液中產生過氧化氫,故實質上與過氧化氫相當。因此,為了使清洗液中產生過氧化氫也可以添加無機過氧化物。無機過氧化物的具體例係過氧化鋰、過氧化鉀、過氧化鈉、過氧化銣、過氧化銫、過氧化鈹、過氧化鎂、過氧化鈣、過氧化鍶、過氧化鋇、過氧化鋅、過氧化鎘、過氧化銅,但並不限定於該等無基過氧化物。
本發明的清洗液中所含的過氧化物的濃度範圍係0.005~35質量%,以0.01~30質量%為佳,以0.1~25質量%更佳,以0.5~6質量%特佳。濃度範圍未達0.005質量%會有無法除去乾蝕刻殘渣的情況。另一方面,濃度範圍比35質量%大的情況,會有造成含鎢材料、或硬式光罩損壞的情況。
作為本發明的清洗液中所含的防蝕劑,例如可以列舉1,2-丙二胺、1,3-丙二胺、1,4-丁二胺等的二胺化合物;2-胺基乙醇、2-甲胺基乙醇、1-胺基-2-丙醇、1-胺基-3-丙醇等的烷醇胺化合物;吡唑、3,5-二甲基吡唑等的吡唑化合物;1-甲基咪唑、1-乙烯基咪唑、5-甲基苯并咪唑等的咪唑化合物;1,2,4-三唑、1,2,3-三唑、4-胺基-1,2,4-三唑、5-甲基-1H-苯并三唑等的三唑化合物。 該等之中,以1,2-丙二胺、1,4-丁二胺、2-胺基乙醇、1-胺基-2-丙醇、吡唑、1-甲基咪唑、1,2,4-三唑及5-甲基-1H-苯并三唑更佳。 該等的防蝕劑可以單獨或組合兩種以上進行摻合。
本發明的清洗液中所含的防蝕劑的濃度範圍係0.005~10質量%,以0.008~8質量%為佳,0.01~5質量%更佳,0.01~3質量%特佳。於上述範圍內的話,可以抑制鈷的損壞。
作為本發明的清洗液中所含的鹼土類金屬化合物,可以列舉鈣化合物、鍶化合物以及鋇化合物。作為該等鈣化合物、鍶化合物以及鋇化合物的具體例,可以列舉氫氧化鈣、硫酸鈣、亞硫酸鈣、碳酸鈣、碳酸氫鈣、硝酸鈣、氟化鈣、氯化鈣、溴化鈣、碘化鈣、氧化鈣、過氧化鈣、硫化鈣、乙酸鈣、氫氧化鍶、硫酸鍶、亞硫酸鍶、碳酸鍶、碳酸氫鍶、硝酸鍶、氟化鍶、氯化鍶、溴化鍶、碘化鍶、氧化鍶、過氧化鍶、硫化鍶、乙酸鍶、氫氧化鋇、硫酸鋇、亞硫酸鋇、碳酸鋇、碳酸氫鋇、硝酸鋇、氟化鋇、氯化鋇、溴化鋇、碘化鋇、氧化鋇、過氧化鋇、硫化鋇、乙酸鋇,但並不限於該等化合物。 該等之中,以氫氧化鈣、碳酸鍶、氫氧化鋇、硝酸鋇、硫酸鋇、碳酸鋇、碳酸氫鋇以及氯化鋇更佳,以氫氧化鋇、硝酸鋇以及氯化鋇特佳。 該等的鹼土類金屬化合物可以單獨或組合兩種以上進行摻合。
本發明的清洗液所含的鹼土類金屬化合物的濃度範圍係0.000001~1質量%,以0.000001~0.5質量%為佳,0.00001~0.1質量%更佳,0.00075~0.075質量%特佳。於上述範圍內的話,可以有效地除去乾蝕刻殘渣。濃度範圍未達0.000001質量%會有造成鎢損壞的情況。 本發明者們係初次發現:清洗液中所含的鹼土類金屬化合物會對含鎢材料表現出抗腐蝕效果。其機制尚未明瞭,但可推測係鹼土類金屬化合物會吸附於鎢的表面,並防止清洗液中所含的過氧化氫等的過氧化物或鹼侵蝕鎢。
本發明的清洗液中,依需要於不損及本發明的目的範圍內,也可以摻合習知半導體用清洗液中所使用的鹼性化合物。例如可以添加4級銨氫氧化物、氨、有機胺、銣化合物、鈹化合物、鎂化合物等。但是,能使用的鹼性化合物並不限於該等。
本發明的清洗液中,於不損及本發明的目的範圍內,也可以摻合習知半導體用清洗液中所使用的添加劑。例如可以列舉螯合劑、介面活性劑、消泡劑等作為添加劑。
使用本發明的清洗液的溫度係10~80℃,以20~70℃的範圍為佳,可以依據蝕刻的條件、或使用的半導體元件適當地選擇。本發明的清洗方法可因應需要而合併使用超音波。 使用本發明的清洗液的時間係0.2~60分鐘的範圍,可以依據蝕刻的條件、或使用的半導體元件適當地選擇。作為使用本發明的清洗液後之沖洗液,可以使用如酒精的有機溶劑,但僅以水沖洗也已足夠。
本發明的清洗液適用的半導體元件及顯示元件係包含矽,非晶矽、多晶矽、玻璃等的基板材料;氧化矽、氮化矽、碳化矽以及該等的衍生物等的絕緣材料;鈷、鈷合金、鎢、鈦-鎢等的材料;鎵-砷、鎵-磷、銦-磷、銦-砷、銦-鋁-砷等的化合物半導體;氧化鉻等的氧化物半導體等。
作為一般的Low-k膜,會使用羥基矽倍半氧烷(HSQ)系或甲基矽倍半氧烷(MSQ)系的OCD(商品名,東京應化工業公司製)、摻碳氧化矽(SiOC)系的Black Diamond(商品名,Applied Materials公司製)、Aurora(商品名,ASM International公司製)、Coral(商品名,Novellus Systems公司製)以及無機系的Orion(商品名,Trikon Tencnlogies公司製),但Low-k膜並不限定於該等產品。
本發明的清洗液所適用的半導體元件也可含有障壁金屬、障壁絕緣膜及/或硬式光罩。 作為一般的障壁金屬,可使用鉭、氮化鉭、鈦、氮化鈦、釕、錳、鎂及該等的氧化物。障壁金屬並不限定於該等。
作為一般的障壁絕緣膜,可以使用氮化矽、碳化矽、氮碳化矽。障壁絕緣膜並不限定於該等。
作為一般的硬式光罩,可以使用矽、鈦、鋁、鉭或任何該等的氧化物、氮化物或碳化物。 作為本發明的清洗液適用的半導體元件中所含的硬式光罩,以含有10原子%以上的鈦的材料為佳。該鈦的原子組成百分比係以15原子%以上為佳、20原子%以上更加、25原子%以上再更佳,30原子%以上特佳。鈦系材料的具體例為氧化鈦、氮化鈦、鈦、矽化鈦等,以氧化鈦、氮化鈦以及鈦為佳。該等材料也可以將2種以上疊層使用。硬式光罩並不限定於該等材料。 本發明中,鈦的含量可利用X射線光電子光譜法(XPS)的離子濺射法,藉由測量成為目標的含鈦材料的鈦原子的構成比而檢測之。有時會有因含鈦材料的表面附近受到氧化,而使氧原子的構成比較材料內部為高的情況。因此,鈦與氧的原子的構成比成為定值前,可以利用離子濺射對含鈦材料的表面進行蝕刻,測量因離子濺射而露出的含鈦材料內部的鈦原子的構成比。作為測量裝置,可以使用全自動XPS分析裝置K-Alpha(Thermo Fisher Scientific有限公司製)。
本發明的清洗液適用的半導體元件中含有的含鎢材料係含有10原子%以上的鎢的材料,該鎢的原子組成百分比以15原子%以上為佳,20原子%以上更佳,25原子%以上再更佳,30原子%以上特佳。含鎢材料的具體例有氧化鎢、氮化鎢、鎢、矽化鎢等,以氧化鎢、氮化鎢以及鎢為佳。但,含鎢材料若為含10原子%以上的鎢的材料,則不限定於該等材料。 本發明中,鎢的含量可以利用如前述的XPS的離子濺射法,藉由測量成為目標的含鎢材料的鎢原子的構成比檢測之。作為測量裝置,可以使用全自動XPS分析裝置K-Alpha(Thermo Fisher Scientific有限公司製)。
作為本發明的清洗液適用的半導體元件中含有的含鈷合金材料的具體例,可以列舉鈷鎢磷、鈷鎢硼、鈷鉻、鈷鉻鉬、鈷鐵、鈷鈮鋯、鈷鋁、鈷鎳、鈷鈦、鐵鎳鈷、鈷鈀等,但並不限定於該等材料。
【實施例】 接著,利用實施例及比較例對本發明進行更具體的說明。但是,本發明不因該等實施例而有任何的限制。
(SEM觀察) 測量設備:使用日立High Technologies股份有限公司製,超高解析場發射型掃描式電子顯微鏡SU9000,以倍率10萬倍進行觀察。 判定: I. 乾蝕刻殘渣的除去狀態 E:完全地除去乾蝕刻殘渣。 P:乾蝕刻殘渣的除去並不足夠。 E判定為合格。 II. 含鎢材料的損壞 E:與清洗前相比看不出含鎢材料的變化。 G:含鎢材料的表面看得見些微粗糙。 P:含鎢材料上看得見大洞。 E與G判定為合格。 III. 鈷的損壞 E:與清洗前相比看不出鈷的變化。 P:與清洗前相比看得見鈷的變化。 E判定為合格。 IV. Low-k膜的損壞 E:與清洗前相比看不出Low-k膜的變化。 G:Low-k膜略有凹陷。 P:Low-k膜有大凹陷。 E與G判定為合格。 V. 硬式光罩的損壞 E:與清洗前相比看不出硬式光罩的變化。 P:可以看見硬式光罩剝離或形狀的變化。 E判定為合格。
[實施例1~27] 試驗中,使用具有圖1及圖2所表示的層的半導體元件。為了除去乾蝕刻殘渣1,將半導體元件以表2中所表示的溫度、時間,浸漬於表1中記載的清洗液,之後,實施利用超純水之沖洗、利用乾燥氮氣噴射之乾燥。藉由以SEM觀察清洗後的半導體元件,判斷乾蝕刻殘渣1的除去狀態與含鎢材料3、鈷4、Low-k膜2及硬式光罩6的損壞。試驗中使用的硬式光罩6係氧化鈦,且含有30原子%的鈦。又,試驗中使用的含鎢材料係氧化鎢,且含有40原子%的鎢。 另外,鈦與鎢的含量如上所述,利用X射線光電子光譜法(XPS)的離子濺射法進行測量。作為測量裝置,均使用全自動XPS分析裝置K-Alpha(Thermo Fisher Scientific有限公司製)。
可得知:使用表2中表示的本發明的清洗液的實施例1~27可防止含鎢材料3、鈷4、Low-k膜2及硬式光罩6的損壞,同時將乾蝕刻殘渣1完全地除去。又、在任何實施例中、均未看見障壁金屬7及障壁絕緣膜5的損壞。
[比較例1(無鹼金屬化合物)] 以含有過氧化氫6質量%、1,2,4-三唑1質量%、硝酸鋇0.001質量%以及水92.999質量%的清洗液(表3、清洗液2A)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。無法除去乾蝕刻殘渣1。雖然可以防止Low-k膜2、硬式光罩6及含鎢材料3的損壞,但於鈷4看見損壞。因此可得知:2A的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low- k膜與含鈷或鈷合金的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例2(無過氧化物)] 以含有氫氧化鉀0.6質量%、1,2,4-三唑1質量%、硝酸鋇0.001質量%以及水98.399質量%的清洗液(表3、清洗液2B)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。無法除去乾蝕刻殘渣1。雖然可以防止Low-k膜2、硬式光罩6及含鎢材料3的損壞,但於鈷4看見損壞。因此可得知:2B的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷或鈷合金的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例3(無防蝕劑)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、硝酸鋇0.001質量%以及水93.399質量%的清洗液(表3、清洗液2C)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1且可以防止Low-k膜2、硬式光罩6及含鎢材料3的損壞。但於鈷4看見損壞。因此可得知:2C的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷或鈷合金的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例4(無鹼土類金屬化合物)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、1,2,4-三唑1質量%以及水92.4質量%的清洗液(表3、清洗液2D)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1且可以防止Low-k膜2與鈷4的損壞。但於含鎢材料3與硬式光罩6看見損壞。因此可得知:2D的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)以及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例5(無鹼土類金屬化合物)] 以含有氫氧化鉀0.01質量%、過氧化氫0.01質量%、1,2,4-三唑1質量%以及水98.98質量%的清洗液(表3、清洗液2E)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2及鈷4的損壞。但於含鎢材料3與硬式光罩6看見損壞。因此可得知:2E的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例6(專利文獻1、4中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、苯并三唑0.1質量%、聚伸乙亞胺(分子量1800)0.01質量%以及水93.29質量%的清洗液(表3、清洗液2F)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2F的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例7(專利文獻2、4中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、5-胺基-1H-四唑0.1質量%、1-羥基苯并三唑0.1質量%、4-胺基-1,2,4-三唑0.01質量%以及水93.19質量%的清洗液(表3、清洗液2G)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2G的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例8(專利文獻3、4中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、苯并三唑0.102質量%、硫酸銅5水合物0.125質量%、4-胺基-1,2,4-三唑0.01質量%以及水93.163質量%的清洗液(表3、清洗液2H)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2H的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例9(專利文獻1、5中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、苯并三唑0.1質量%、Ethoquad O/12[油醯基雙(2-羥乙基)甲基銨-雙(三氟甲烷磺醯)醯亞胺](LION有限公司製)0. 001質量%以及水93.299質量%的清洗液(表3、清洗液2I)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2I的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例10(專利文獻2、5中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、5-胺基-1H-四唑0.1質量%、1-羥基苯并三唑0.1質量%、Ethoquad O/12[油醯基雙(2-羥乙基)甲基銨-雙(三氟甲烷磺醯)醯亞胺](LION有限公司製)0.001質量%以及水93.199質量%的清洗液(表3、清洗液2J)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2J的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例11(專利文獻3、5中記載的發明)] 以含有氫氧化鉀0.6質量%、過氧化氫6質量%、苯并三唑0.102質量%、硫酸銅5水合物0.125質量%、Ethoquad O/12[油醯基雙(2-羥乙基)甲基銨-雙(三氟甲烷磺醯)醯亞胺](LION有限公司製)0.001質量%以及水93.172質量%的清洗液(表3、清洗液2K)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。可以除去乾蝕刻殘渣1,並防止Low-k膜2的損壞。但,於含鎢材料3、鈷4及硬式光罩6看見損壞。因此可得知:2K的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例12(專利文獻6中記載的發明)] 以含有磷酸1.35質量%、鹽酸1質量%、氫氧化四甲銨5質量%、十二烷二胺乙基甘胺酸鈉0.01質量%以及水92.64質量%的清洗液(表3、清洗液2L)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。無法除去乾蝕刻殘渣1。雖然可以防止Low-k膜2、硬式光罩6及含鎢材料3的損壞,但於鈷4看見損壞。因此可得知:2L的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例13(專利文獻7中記載的發明)] 以含有氫氧化四甲銨12質量%、過氧化氫5質量%、氫氧化鉀2質量%、三乙醇胺35質量%以及水46質量%的清洗液(表3、清洗液2M)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。無法除去乾蝕刻殘渣1。雖然可以防止Low-k膜2、硬式光罩6及鈷4的損壞,但於含鎢材料3看見損壞。因此可得知:2M的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例14(專利文獻8中記載的發明)] 以含有氫氧化鉀2.6質量%、過氧化氫0.9質量%、正高碘酸2質量%、乙二胺0.03質量%、二伸乙三胺0.01質量%、Surfynol 465[於2,4,7,9-四甲基-5-癸炔-4,7-二醇加成65mol%的環氧乙烷而得的組成物](Air Products Japan股份有限公司製) 0.02質量%、十六烷基三甲基氯化銨0.02質量%、N-甲基吡咯啶酮10質量%以及水84.42質量%的清洗液(表3、清洗液2N)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。雖然可以防止Low-k膜2、硬式光罩6及鈷4的損壞,但無法除去乾蝕刻殘渣1,且於含鎢材料3看見損壞。因此可得知:2N的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例15(專利文獻9中記載的發明)] 以含有苯并三唑0.1質量%、1,2,4-三唑0.1質量%、氟化銨5質量%、硼酸1質量%以及水93.8質量%的清洗液(表3、清洗液2O)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。雖然可以防止硬式光罩6、含鎢材料3及鈷4的損壞,但無法除去乾蝕刻殘渣1,且於Low-k膜2看見損壞。因此可得知:2O的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
[比較例16] 以含有氫氧化鉀1.2質量%、氫氧化四甲銨16.5質量%、甘油30質量%、過氧化氫0.009質量%以及水52.291質量%的清洗液(表3、清洗液2P)清洗具有圖1及圖2所表示的層的半導體元件,清洗條件與評估結果顯示於表4。雖然可以防止硬式光罩6、含鎢材料3及鈷4的損壞,但無法除去乾蝕刻殘渣1,且於Low-k膜2看見損壞。因此可得知:2P的清洗液無法用於本發明的標的,即於半導體元件的製造步驟中,至少抑制Low-k膜與含鈷(或鈷合金)及鎢的材料的損壞,並除去被處理物表面的乾蝕刻殘渣之目的。
【表1】
KOH:氫氧化鉀 K2
CO3
:碳酸鉀 KNO3
:硝酸鉀 Li2
CO3
:碳酸鋰 LiOH:氫氧化鋰 NaOH:氫氧化鈉 Cs2
Co3
:碳酸銫 mCPBA:間氯過氧苯甲酸 TBHP:第三丁基過氧化氫 1,2,4-TAZ:1,2,4-三唑 Ba(NO3
)2
:硝酸鋇 Ca(OH)2
:氫氧化鈣 SrCO3
:碳酸鍶 BaSO4
:硫酸鋇
【表2】
除去狀態I:乾蝕刻殘渣1的除去狀態 損壞II:含鎢材料3的損壞 損壞III:鈷4的損壞 損壞IV:Low-k膜2的損壞 損壞V:硬式光罩6的損壞
【表3】
Ethoquad O/12:[油醯基雙(2-羥乙基)甲基銨-雙(三氟甲烷磺醯)醯亞胺](LION有限公司製) Surfynol 465:[於2,4,7,9-四甲基-5-癸炔-4,7-二醇加成65mol%的環氧乙烷而得的組成物](Air Products Japan有限公司製)
【表4】
除去狀態I:乾蝕刻殘渣1的除去狀態 損壞II:含鎢材料3的損壞 損壞III:鈷4的損壞 損壞IV:Low-k膜2的損壞 損壞V:硬式光罩6的損壞 【產業上利用性】
根據本發明的清洗液及清洗方法,於半導體元件的製造步驟中,至少可以抑制Low-k膜與(1)含鈷或鈷合金的材料,或者(2)含鈷或鈷合金及鎢的材料的損壞,並除去被處理物的表面的乾蝕刻殘渣,且能以高成品率製造高精度、高品質的半導體元件,於產業上係有用的。
1‧‧‧乾蝕刻殘渣
2‧‧‧Low-k膜
3‧‧‧含鎢材料
4‧‧‧鈷
5‧‧‧障壁絕緣膜
6‧‧‧硬式光罩
7‧‧‧障壁金屬
8‧‧‧銅
2‧‧‧Low-k膜
3‧‧‧含鎢材料
4‧‧‧鈷
5‧‧‧障壁絕緣膜
6‧‧‧硬式光罩
7‧‧‧障壁金屬
8‧‧‧銅
【圖1】表示除去乾蝕刻殘渣前的半導體元件中之具有含硬式光罩之鈷帽蓋金屬結構的層的一例之概略剖面圖。 【圖2】表示除去乾蝕刻殘渣前的半導體元件中之具有含鎢材料的層的一例的概略剖面圖。
1‧‧‧乾蝕刻殘渣
2‧‧‧Low-k膜
4‧‧‧鈷
5‧‧‧障壁絕緣膜
6‧‧‧硬式光罩
7‧‧‧障壁金屬
8‧‧‧銅
Claims (11)
- 一種清洗液,其將具有低介電常數膜(Low-k膜)與(1)含鈷或鈷合金之材料、或(2)含鈷或鈷合金及鎢之材料的半導體元件的表面的乾蝕刻殘渣予以除去, 含有鹼金屬化合物0.001~7質量%、過氧化物0.005~35質量%、防蝕劑0.005~10質量%、鹼土類金屬化合物0.000001~1質量%及水。
- 如申請專利範圍第1項之清洗液,其中,該鹼金屬化合物係選自於由氫氧化鋰、硫酸鋰、碳酸鋰、碳酸氫鋰、硝酸鋰、氟化鋰、氯化鋰、溴化鋰、碘化鋰、乙酸鋰、氫氧化鈉、硫酸鈉、碳酸鈉、碳酸氫鈉、硝酸鈉、氟化鈉、氯化鈉、溴化鈉、碘化鈉、乙酸鈉、氫氧化鉀、硫酸鉀、碳酸鉀、碳酸氫鉀、硝酸鉀、氟化鉀、氯化鉀、溴化鉀、碘化鉀、乙酸鉀、氫氧化銫、硫酸銫、碳酸銫、碳酸氫銫、硝酸銫、氟化銫、氯化銫、溴化銫、碘化銫、及乙酸銫構成之群組中之至少1種以上。
- 如申請專利範圍第1或2項之清洗液,其中,該過氧化物係選自於由過氧化氫、過氧化脲、間氯過氧苯甲酸、第三丁基過氧化氫、過乙酸、二第三丁基過氧化物、過氧化苯甲醯、過氧化丙酮、過氧化甲基乙基酮、六亞甲基三過氧化物、及異丙苯過氧化氫構成之群組中之至少1種以上。
- 如申請專利範圍第1或2項之清洗液,其中,該防蝕劑係選自於由二胺化合物、烷醇胺化合物、吡唑化合物、咪唑化合物、及三唑化合物構成之群組中之至少1種以上。
- 如申請專利範圍第4項之清洗液,其中,該二胺化合物係選自於由1,2-丙二胺、1,3-丙二胺、及1,4-丁二胺構成之群組中之至少1種以上。
- 如申請專利範圍第4項之清洗液,其中,該烷醇胺化合物係選自於由2-胺基乙醇、2-甲胺基乙醇、1-胺基-2-丙醇、及1-胺基-3-丙醇構成之群組中之至少1種以上。
- 如申請專利範圍第4項之清洗液,其中,該吡唑化合物係選自於由吡唑、及3,5-二甲基吡唑構成之群組中之至少1種以上。
- 如申請專利範圍第4項之清洗液,其中,該咪唑化合物係選自於由1-甲基咪唑、1-乙烯基咪唑、及5-甲基苯并咪唑構成之群組中之至少1種以上。
- 如申請專利範圍第4項之清洗液,其中,該三唑化合物係選自於由1,2,4-三唑、1,2,3-三唑、及5-甲基-1H-苯并三唑構成之群組中之至少1種以上。
- 如申請專利範圍第1或2項之清洗液,其中,該鹼土類金屬化合物係選自於由鈣化合物、鍶化合物、及鋇化合物構成之群組中之至少1種以上。
- 一種清洗方法,係清洗半導體元件而將該半導體元件表面之乾蝕刻殘渣予以除去,該半導體元件係於具有低介電常數膜(Low-k膜)與(1)含鈷或鈷合金之材料、或(2)含鈷或鈷合金及鎢之材料之基板上形成硬遮罩圖案,然後將此硬遮罩圖案作為遮罩,對該低介電常數膜(Low-k膜)施以乾蝕刻處理而得; 其特徵為: 使用如申請專利範圍第1至10項中任一項之清洗液。
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