TWI379924B - - Google Patents
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- TWI379924B TWI379924B TW094145507A TW94145507A TWI379924B TW I379924 B TWI379924 B TW I379924B TW 094145507 A TW094145507 A TW 094145507A TW 94145507 A TW94145507 A TW 94145507A TW I379924 B TWI379924 B TW I379924B
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- TW
- Taiwan
- Prior art keywords
- group
- liquid
- etching
- mass
- metal
- Prior art date
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- 239000007788 liquid Substances 0.000 claims description 117
- 238000005530 etching Methods 0.000 claims description 108
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 239000004020 conductor Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 36
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000000956 alloy Substances 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 229910018487 Ni—Cr Inorganic materials 0.000 claims description 21
- -1 nitrite ions Chemical class 0.000 claims description 17
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000879 imine group Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 78
- 229910052802 copper Inorganic materials 0.000 description 70
- 239000010949 copper Substances 0.000 description 70
- 239000010410 layer Substances 0.000 description 59
- 239000010408 film Substances 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 31
- 238000004090 dissolution Methods 0.000 description 21
- 239000000758 substrate Substances 0.000 description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910000599 Cr alloy Inorganic materials 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 13
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 8
- 229940005654 nitrite ion Drugs 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- MJPVYTKZYZPIQA-UHFFFAOYSA-N 3-thiophen-2-ylpropanoic acid Chemical compound OC(=O)CCC1=CC=CS1 MJPVYTKZYZPIQA-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 206010036790 Productive cough Diseases 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 210000003802 sputum Anatomy 0.000 description 3
- 208000024794 sputum Diseases 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RZEWIYUUNKCGKA-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanol;octadecanoic acid Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCCC(O)=O RZEWIYUUNKCGKA-UHFFFAOYSA-N 0.000 description 1
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- GDSOQCSYONDNAJ-UHFFFAOYSA-N 2-thiophen-2-ylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CS1 GDSOQCSYONDNAJ-UHFFFAOYSA-N 0.000 description 1
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- UBUPCKZQZCXDAZ-UHFFFAOYSA-N C(CCCCCCCCC)N.C(C)O.C(CCCCCCCCCCC)(=O)O Chemical compound C(CCCCCCCCC)N.C(C)O.C(CCCCCCCCCCC)(=O)O UBUPCKZQZCXDAZ-UHFFFAOYSA-N 0.000 description 1
- JQVSTQIUXONSRM-UHFFFAOYSA-N C(CCCCCCCCC)N.C(C)O.C(CCCCCCCCCCCCCCCCC)(=O)O Chemical compound C(CCCCCCCCC)N.C(C)O.C(CCCCCCCCCCCCCCCCC)(=O)O JQVSTQIUXONSRM-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-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
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- RIPUKAXZALFIMA-UHFFFAOYSA-N decan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCC[NH3+] RIPUKAXZALFIMA-UHFFFAOYSA-N 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZEEJGIRESVBZPM-UHFFFAOYSA-N ethanethioic s-acid;propanoic acid Chemical compound CC(S)=O.CCC(O)=O ZEEJGIRESVBZPM-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- QSJNAFJALFWFMT-UHFFFAOYSA-N meridine Chemical group N1C=CC(=O)C2=C1C(=O)C1=NC=CC3=C(C=CC=C4)C4=NC2=C13 QSJNAFJALFWFMT-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BOWVQLFMWHZBEF-KTKRTIGZSA-N oleoyl ethanolamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCO BOWVQLFMWHZBEF-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- YFGAFXCSLUUJRG-WCCKRBBISA-M sodium;(2s)-2-amino-5-(diaminomethylideneamino)pentanoate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCCN=C(N)N YFGAFXCSLUUJRG-WCCKRBBISA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
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- 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
- C23F1/28—Acidic compositions for etching iron group metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Description
1379924 九、發明說明： 【發明所屬之技術領域】 本發明係關於，對選自Ni、Cr ' Ni-Cr合金及中至 少1種金屬進行蝕刻的蝕刻液及其補充液、以及使用其之 導體圖案形成方法。 【先前技術】 以往，印刷電路板便廣泛的用來作為電氣製品、電子 機器的配線用構件。印刷電路板係在絕緣性基材表面形成 有配線圖案的基板。其中，使用聚醯亞胺薄膜等撓性薄膜（作 為邑..彖性基材）的撓性基板，就較薄且較輕等觀點而言，除 較剛性基板具優勢之外，尚因為能彎曲而亦可使用於馬= 周邊部等可動部分，因而需求不斷增加。此外，作為液曰 模組用封裝基材，對撓性基板的需求亦不斷增加。雖: 基板的製法已知有各種製法，但是該等中就較容易形成微 細配線專觀點而言，賤鑛_雷供、土供☆ _ ^電鍍法備受矚目（例如日 2000-252625 號公報）。 n 上述錢鐘法具有下述步驟。首先，在聚酿亞胺薄 基材上，形成例如由Ni、Cr、a 、 底層，僅對該底層上構成配t Γ ° ’ Pd等所構成的 /低層上構成配線的部分進行電铲 層。在此，上述底層具有提古 ’又形成鋼 著層作用。其次，對底層 在°性的接 除，以形成由銅層與底層所禮 “去 面，一般係使用以氯化鐵A -曰的蝕刻方 孰4主成分的蝕刻液。 但疋’以氣化鐵為主W八 成刀的習知㈣液，因為對構成 底層之金屬的蝕刻速率較枵 k 因而在對底層進行蝕刻期 間，會有因上述蝕刻液而使鋼 別增/合解之虞。若銅層溶解， 配線的高度與寬度會減少， 又夕而有配線電阻增加、或發生斷 線的可能性。 【發明内容】 本發明係有鑒於此種情事 — 爿爭所凡成者，其提供，可對選 自Nl、Cr、Ni-Cr合金及Pd中至少1種金屬快速蝕刻的蝕 刻液及其補充液、以及使用其之導體圖案形成方法。 本發明的蝕刻液，係對選自Ni、Cr、Ni_Cr合金及pd 中至少1種金屬進行蝕刻的蝕刻液，其特徵在於： 該姓刻液係水溶液，其含有選自n〇、n2〇、n〇2、n〇 及該等離子中至少1種成分，以及酸成分。 23 本心月的第1補充液，係當重複使用上述本發明之姓 刻液時，添加於該㈣液中者，其特徵在於： 該補充液係水溶液’其含有選自n〇、n2〇、n〇2、no 及該等的離子中至少1種成分。 23 本發明的第2補充液’係當重複使用上述本發明之敍 刻液時’添加於該蝕刻液中者，其特徵在於： 含有化合物’其具有選自胺基、亞胺基、敌基、幾基、 石夤基及經基中$ ,卜1 # 至夕1種基，以及硫原子，且碳原子數為7 以下。 本發明的第3補充液，係當重複使用上述本發明之敍 刻液時，添加於該蝕刻液中者其特徵在於含有： 選自塞°坐及嗟唾系化合物中至少1種。 1379924 本發明之導體圖案形成方法，係斜還6 Χϊ. 1尔对遠自Ni、cr、Ni-Cr 合金及Pd中至少i種金屬進行蝕刻而形成導體圖案，其 特徵在於： 對該述金屬使用上述本發明之蝕刻液進行餘刻。 【實施方式】[Technical Field] The present invention relates to an etching solution for etching at least one metal selected from the group consisting of Ni, Cr'Ni-Cr alloy, and a replenishing liquid thereof, and a conductor using the same Pattern forming method. [Prior Art] Conventionally, printed circuit boards have been widely used as wiring members for electrical products and electronic equipment. The printed circuit board is a substrate on which a wiring pattern is formed on the surface of an insulating substrate. Among them, a flexible substrate using a flexible film such as a polyimide film (as a bismuth substrate) is thinner and lighter, and is advantageous in addition to a rigid substrate. It can be used for bending and can also be used for moving parts such as horses and peripheral parts, so the demand is increasing. In addition, as a packaging substrate for a liquid helium module, the demand for a flexible substrate is also increasing. Although various methods are known for the production method of the substrate, it is easy to form a fine wiring. In particular, the antimony ore supply and the soil supply ☆ _ ^ electroplating method are attracting attention (for example, Japanese Patent Publication No. 2000-252625) ). n The above money clock method has the following steps. First, on the polyimide-based thin substrate, for example, Ni, Cr, a, and a primer layer are formed, and only a portion of the underlayer which is formed of a wiring layer composed of t Γ ° 'Pd or the like is formed as a shovel layer. Here, the above-mentioned bottom layer has an effect of forming a steel layer. Secondly, the bottom layer is removed in order to form a copper layer and a bottom layer, and the etching layer of the main component of the etching layer of ferric chloride A - 一般 is generally used. The conventional iron (four) liquid is mainly used for the W-shaped knife. Since the etching rate of the metal constituting the underlayer is higher than 枵k, during the etching of the underlayer, the steel may be increased/combined due to the etching liquid. When the copper layer is dissolved, the height and width of the wiring are reduced, and the wiring resistance is increased or the disconnection is likely to occur. [Invention] The present invention is in view of such a situation - Provided are an etching solution capable of rapidly etching at least one metal selected from the group consisting of Nl, Cr, a Ni-Cr alloy, and Pd, and a replenishing liquid thereof, and a conductor pattern forming method using the same. The etching liquid of the present invention is selected from the group consisting of An etching solution for etching at least one metal of Ni, Cr, Ni_Cr alloy and pd, wherein: the aqueous solution of the surname is selected from the group consisting of n〇, n2〇, n〇2, n〇 and the plasma. At least 1 ingredient, and an acid component. 23 1st of the heart of the month The replenishing liquid is added to the (IV) liquid when the above-mentioned surname engraving of the present invention is repeatedly used, and the replenishing liquid aqueous solution is selected from the group consisting of n〇, n2〇, n〇2, no and At least one component of the ions. 23 The second replenishing liquid of the present invention is added to the etching liquid when the above-described engraving liquid of the present invention is repeatedly used, and is characterized in that it contains a compound From the amine group, the imine group, the dibasic group, the benzyl group, the fluorenyl group, and the valence group, the group 1 and the sulfonium atom, and the number of carbon atoms is 7 or less. The third replenisher of the present invention, When the above-described etchant of the present invention is repeatedly used, the etchant is characterized in that it contains at least one selected from the group consisting of a sputum and a sputum compound. 1379924 The method for forming a conductor pattern of the present invention is The conductor is patterned by etching at least one of the metals from the Ni, Cr, Ni-Cr alloy and Pd to form a conductor pattern, wherein: the etching solution of the present invention is used for the metal described above. [Embodiment]
本發明之姓刻液，係對選自Nl、Cr、Ni_Cr合金及pd 中至少1種金屬（以下簡稱「被處理金屬」），進行钱刻者， 其係水溶液且含有：選自NO' \〇、N〇2、义〇3及該等離 子中至少i種成分（以下簡稱「含氮成分」），以及酸成分。 本發明之姓刻液係藉由具有上述構成’可對被處理金屬快 速蝕刻。因此，若使用本發明之飯刻液，從被處理金屬與 銅等其他金屬共存的被處理材，對被處理金屬進行蝕刻， 因為本發明之㈣液與被處理材的接觸時間可縮短，因而 可抑制銅等其他金屬發生溶解。故’根據本發明之蝕刻液， 可從被處理材對被處理金屬進行選擇性蝕刻。 本發明之蝕刻液之處理對象（被處理金屬）係如上述， 選自Ni、Cr、Ni_Cr合金及pd _至少i種金屬。當將N卜 Cr合金當作被處理金屬的情況時，Ni_Cr合金令的％與g 原子比並無特別限制。例如可將原子比（Ni/Cr)為卜、 1 /3等Ni Cr合金使用當作被處理金屬。根據本發明之钱刻 液除可對Ni、Cr及Ni-Cr合金快速钱刻之外，銅溶解狀 況亦極少。此外，根據本發明之蝕刻液，就算對pd亦可 快速敍X丨Pd在印刷電路板的製造方面，係使用當作化學 鍵銅的觸媒，在絕緣性基材表面上所剩餘的Pd會導致絕The surname engraving of the present invention is a solution of at least one metal selected from the group consisting of Nl, Cr, Ni_Cr alloy and pd (hereinafter referred to as "treated metal"), which is an aqueous solution and contains: selected from NO'. 〇, N〇2, 〇3, and at least one component of the plasma (hereinafter referred to as "nitrogen-containing component"), and an acid component. The surname of the present invention can be quickly etched on the metal to be treated by having the above configuration. Therefore, when the rice cooking liquid of the present invention is used, the metal to be treated which is coexisted with the metal such as copper is etched, and the contact time of the liquid of the present invention (4) and the material to be treated can be shortened. It can inhibit the dissolution of other metals such as copper. Therefore, according to the etching liquid of the present invention, the metal to be processed can be selectively etched from the material to be processed. The object to be treated (the metal to be treated) of the etching liquid of the present invention is as described above, and is selected from the group consisting of Ni, Cr, Ni_Cr alloy, and pd_at least one kind of metal. When the N-Cr alloy is regarded as the metal to be treated, the atomic ratio of % to g of the Ni_Cr alloy is not particularly limited. For example, a Ni Cr alloy having an atomic ratio (Ni/Cr) of Bu, 1 / 3 or the like can be used as the metal to be treated. In addition to the rapid engraving of Ni, Cr and Ni-Cr alloys, the copper encapsulation according to the present invention has very little copper dissolution. In addition, according to the etching liquid of the present invention, even if pd can be quickly described, X丨Pd is used in the manufacture of a printed circuit board, and a catalyst which acts as a chemical bond copper is used, and the Pd remaining on the surface of the insulating substrate causes Absolutely
7 1379924 緣性降低，且當在後續步驟中進行鍍金處料，會有在不 需要部分析出金的問題。根據本發明之钱刻液，因為可對 Pd快速蝕刻，因而亦可解決上述問題。 本發明之蝕刻液中所含的含氮成分係如上述，選自 n〇、n2o、no2、n2o3及該等離子中至少i種成分。其中， 因為亞硝酸離子在钱刻液中的濃度管理較為容易因而可 安定的維持本發明之蝕刻液的蝕刻性能。 本發明之蝕刻液中所含酸成分係例如:硫酸、鹽酸、硝 自夂、虱狀酸、有機酸等。其中，較佳為硫酸、鹽酸，尤以 合併使用硫酸與鹽酸為佳。當合併使用硫酸與鹽酸的情況 時，硫酸佔整體㈣液的比例，就從㈣速率的觀點而言， 車乂铨為1 60質里％範圍，尤以3〜3〇質量％範圍為佳以 12.5〜20質量％範圍為更佳。此外，鹽酸佔整體敍刻液的比 例，、就從敍刻速率的觀點而言，較佳為〇卜2〇質量％範圍， 、〇·5 15質里/〇範圍為佳，以7〜10質量％範圍為更佳。 調配上述各成分的方法可舉例如:預先調製含上述酸性 分的水溶液(醆性溶液)，再於該酸性溶液中溶解亞硝酸鹽， 或吹入NO氣體、n2〇氣體等含氮氣體，而添加含氮成分 的方法等。此外’亦可經依照如同上述的添加方法在水中 添加含氮成分之後，再於該等令添加上述酸性分。亞硝酸 鹽可舉例如：亞確酸納、亞石肖酸M、亞確酸卸等，該等可單 獨使用1 亦可複數種混合使用。另外，本發明之蝕刻 夜中所使用的水較佳為經去除離子性物質與雜質的水。且 體而言較佳使用諸如：離子交換水、純水、超純水等。〃 1379924 本發明之餘刻泫φ故人L ^ 〇.咖〜w錢ΓΓ 氮成分的濃度較佳為 η n 圍，尤以〇,001〜1質量％範圍為佳，以 〇.〇1〜0.5質量。/〇範圍為更佳。 質量％，會有頗難斜μ 3虱成刀的滾度少於0.0001 —a " ， +被處理金屬進行蝕刻的情況。反之， 右3虱成分的濃度超過1〇質 將趨於激烈，將I奸成 分解現象 …，法隨很度的增加而顯現出蝕 升，而有不符經濟的情況發生…卜，當使亞硝酸心 =性浴液（或水）中而調製本發明之敍刻液的情況時，較 佳將亞硝酸鹽添加成亞石肖酸離子濃度為 範圍，尤以0.001〜丨質量 里0 範圍為更佳。質以㈣為佳m〇.5質量％ 本發明之蝕刻液中’亦可更進—步含有具選自胺基、 2基、=基、幾基、續基及經基中至少i種基以及硫 :ι石厌原子數為7以下的化合物(以下簡稱「含硫化合 物m«處理金屬與銅共存的被處理材，使用習知姓 刻液對被處理金屬進行㈣，被處理金屬將與銅一起溶解 於飯刻液巾，而所轉的銅料將更加 在本發明之㈣液中含有上述含硫化合物，因二:L: 合物將捕捉㈣液中的銅離子，因而可有效的二:：： 現象。 含胺基之含硫化合物的具體例’可舉例如硫腺、二氧 化硫脲、N-甲基硫脲、二甲基硫脲、u-二乙基硫脲等。 含亞胺基之含硫化合物的具體例，可舉 含緩基之含硫化合物的具體例，可舉例如:硫::ir疏7 1379924 The edge is reduced, and when the gold plating is carried out in the subsequent steps, there is a problem that the gold is not analyzed. According to the money engraving of the present invention, the above problem can also be solved because the Pd can be quickly etched. The nitrogen-containing component contained in the etching solution of the present invention is selected from the group consisting of n〇, n2o, no2, n2o3, and at least one of the ions. Among them, since the concentration management of the nitrite ion in the money engraving liquid is relatively easy, the etching performance of the etching liquid of the present invention can be stably maintained. The acid component contained in the etching solution of the present invention is, for example, sulfuric acid, hydrochloric acid, nitrate, citric acid, organic acid or the like. Among them, sulfuric acid and hydrochloric acid are preferred, and sulfuric acid and hydrochloric acid are preferably used in combination. When sulfuric acid and hydrochloric acid are used in combination, the ratio of sulfuric acid to the total (iv) liquid is from the viewpoint of (iv) rate, and the rutting is in the range of 1 60% by mass, especially in the range of 3 to 3 % by mass. The range of 12.5 to 20% by mass is more preferable. In addition, the ratio of hydrochloric acid to the overall engraving liquid is preferably in the range of 2% by mass from the viewpoint of the characterization rate, and preferably in the range of 〇·5 15 里/〇, 7 to 10 The range of mass % is better. The method of blending the above components may, for example, preliminarily prepare an aqueous solution (an inert solution) containing the above acidic component, and then dissolving the nitrite in the acidic solution or blowing a nitrogen-containing gas such as an NO gas or an n 2 gas. A method of adding a nitrogen-containing component or the like. Further, the above-mentioned acidic component may be added after adding a nitrogen-containing component to water in accordance with the above-described addition method. The nitrite may, for example, be sodium arginate, sulphate M, or succinic acid, and the like may be used singly or in combination of plural kinds. Further, the water used in the etching night of the present invention is preferably water which removes ionic substances and impurities. It is preferably used such as ion-exchanged water, pure water, ultrapure water or the like. 〃 1379924 The remainder of the invention 泫φ故人L ^ 〇.咖〜w钱ΓΓ The concentration of the nitrogen component is preferably η n , especially in the range of 001 to 1% by mass, preferably 〇.〇1~0.5 quality. /〇 range is better. % of mass, there will be quite difficult to slant μ 3 虱 into a knife with a rolling degree of less than 0.0001 - a ", + the metal being etched. On the contrary, the concentration of the right 3 虱 component will be more intense than 1 〇 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the case where the nitric acid is used in the bath (or water) to prepare the engraving liquid of the present invention, it is preferred to add the nitrite to the concentration of the stannous acid ion, especially in the range of 0.001 to 丨. Better. The mass of (4) is preferably m〇.5 mass%. The etching solution of the present invention may further comprise at least one group selected from the group consisting of an amine group, a 2 group, a group, a group, a repeat group and a meridine group. And a compound of sulfur: ι stone with an atomic number of 7 or less (hereinafter referred to as "the sulfur-containing compound m« treated metal and copper coexisting material to be treated, using a conventional surname to the treated metal (4), the treated metal will be The copper is dissolved together in the rice liquid towel, and the transferred copper material will further contain the above sulfur-containing compound in the liquid of the invention (IV), because the two: L: compound will capture the copper ions in the (four) liquid, and thus can be effective Second::: Phenomenon. Specific examples of the amine-containing sulfur-containing compound include, for example, sulfur gland, sulfur dioxide dioxide, N-methylthiourea, dimethylthiourea, u-diethylthiourea, and the like. Specific examples of the amine group-containing sulfur compound include a sulfur-containing compound containing a slow group, and examples thereof include sulfur::ir
9 1379924 基乙酸硫醇基丙酸、2_硫醇基丙酸、2,2ι_硫代二甘酸、 硫代頻果酸、硫醇基號站駿、L_半胱胺酸、咐耽氨 含硫原子之羧酸、及該等的鉀鹽、鈉鹽等。含羰美之人* 化合物的具體例，可舉例如2·硫巴比妥酸等。含二：：： 硫化合物的具體例’可舉例如：2•硫醇基乙料、3^醇^ Μ確酸' 2_硫醇基苯續酸、及該等的钟鹽、納趟等。： 經基之含硫化合物的具體例，可舉例如硫二甘醇等含炉= 子之醇類等。此外，钱刻液中的上述含硫化合物之含：量 係佔整體蝕刻液例如設定在〇 〇1〜2〇質量％範圍，較佳 〇.〇5〜1〇質量％範圍，尤以〇 Η質量％範圍為佳。若含硫 化合物的含有量多於2G質量％ ’將無法期待獲得更佳效果 :有不符經濟的可能性’反之，若少於〇〇1質量％，會有 ^法獲得充分效果的可能性。另夕卜本發明之㈣液中亦 可僅含有上述含硫化合物中之1種類，亦可含有2種以上。 再者，本發明之飯刻液中，當更近-步含有選自㈣ :噻唑系化合物中至少丨種時，亦可發揮如同含有上述含 :“匕合物的情況為相同的效果。噻唑系化合物的具體例， 可舉例如:笨并噻唑、2_硫醇基苯并噻唑等。蝕刻液中的上 =化合物（選自噻唑與噻唑系化合物中至少1種）的含有 里，係佔整體蝕刻液例如〇_〇1〜20質量％範圍，較佳為 〇_〇5〜1〇質量％範圍，尤以0.1〜1質量％範圍為佳。 :者，本發明之蝕刻液中’亦可進一步含有抑制銅溶 解成分之選自节院録與烧基醇醯胺中至少1種。〒院敍的 具體例，"5ΤΓ與,. J举例如：虱化烷基二甲基节基銨等氣化苄烷銨、 1379924 溴化卞烷銨等。烷基醇醯胺的具體例，可舉例如月桂酸單 乙醇醯胺、硬脂酸單乙醇醯胺、油酸單乙醇醯胺、月桂酸 二乙醇醯胺、硬脂酸二乙醇醯胺、油酸二乙醇醯胺等脂肪 族烷基醇醯胺、芳香族烷基醇醯胺等。該等亦可為銨鹽或 鈉鹽。此外，可單獨含有丨種該等化合物，亦可含有複數9 1379924 thioacetic acid propionic acid, 2- thiol propionic acid, 2,2 ι thiodiglycolic acid, thiotrans acid, thiol group, L-cysteine, hydrazine a carboxylic acid containing a sulfur atom, and the like, a potassium salt, a sodium salt, and the like. Specific examples of the compound containing a carbonyl group are, for example, 2·thiobarbituric acid. Specific examples of the sulfur-containing compound include, for example, 2: thiol-based ethyl ester, 3-alcohol, phthalic acid, 2-thiol-benzoic acid, and the like, the clock salt, the scorpion, etc. . Specific examples of the sulfur-containing compound according to the group include, for example, an alcohol having a furnace such as thiodiglycol. In addition, the content of the above-mentioned sulfur-containing compound in the money engraving liquid is, for example, set in the range of 〇〇1 to 2〇% by mass of the entire etching liquid, preferably in the range of 〇5〇1〇% by mass, especially 〇Η The mass% range is preferred. If the content of the sulfur-containing compound is more than 2 G% by mass, it is not expected to obtain a better effect: there is a possibility of being uneconomical. On the contrary, if it is less than 〇〇1% by mass, there is a possibility that the method can obtain a sufficient effect. Further, the liquid (4) of the present invention may contain only one of the above sulfur-containing compounds, or may contain two or more kinds. Further, in the rice culturing solution of the present invention, when at least one of the thiazole-based compounds selected from the group consisting of (4) and the thiazole-based compound is contained in a more recent step, the same effect as in the case of containing the above-mentioned compound: "thiazole" may be exhibited. Specific examples of the compound include, for example, benzothiazole, 2-thiolbenzothiazole, etc. In the etchant, the upper compound (at least one selected from the group consisting of a thiazole and a thiazole compound) is contained in the etchant. The entire etching liquid is, for example, in the range of 1 to 20% by mass, preferably in the range of 〇_〇5 to 1% by mass, particularly preferably in the range of 0.1 to 1% by mass. Further, it may further contain at least one selected from the group consisting of a sulphate and a decyl decylamine which inhibits the copper-dissolved component. Specific examples of 〒院叙, "5ΤΓ和, J. For example, 虱 alkyl dimethyl benzyl group Examples of the gasification of benzalkonium chloride such as ammonium, 1379924 decyl ammonium bromide, etc. Specific examples of the alkyl alcohol decylamine include lauric acid monoethanol decylamine, stearic acid monoethanol decylamine, and oleic acid monoethanol amide. Aliphatic alkyl alcohol guanamine such as lauric acid diethanolamine, stearic acid diethanolamine or oleic acid diethanolamine Amides aromatic alkyl alcohol and the like. Such an ammonium salt or a sodium salt may also be Furthermore, such compounds may contain a single species Shu, may also contain a plurality of
種該等化合物。另夕卜上述化合物的分子量就從溶解性的 親點而言’較佳為300以下，尤以200以下為佳。另外， 當上述化合物具有脂肪族側鏈的情況時，就從溶解性的觀 點而言’較佳上述側鏈的碳數為22卩下’尤以上述側鍵 的碳數為18以下為佳。 本發明之钱刻液中，亦可進一步含有選自具石肖基之化 合物、確酸及硝酸鹽中至少丨種。該等將如同餘刻液中的 上述酸成分，可為使被處理金屬溶解的成分。具硝基之化 合物可舉例如芳香族硝化化合物等，具體而言可舉例如·硝 ，苯續酸、硝化安息香酸'硕化苯胺、硝化齡'該等的鹽Such compounds are mentioned. Further, the molecular weight of the above compound is preferably from 300 or less, more preferably from 200 or less, from the viewpoint of solubility. Further, when the compound has an aliphatic side chain, it is preferable that the carbon number of the side chain is 22 Å or less from the viewpoint of solubility, and it is particularly preferable that the number of carbon atoms of the side bond is 18 or less. The money engraving liquid of the present invention may further contain at least an anthracene selected from the group consisting of a compound having a schlossyl group, an acid and a nitrate. These may be the above-mentioned acid component in the residual liquid, and may be a component which dissolves the metal to be treated. The compound having a nitro group may, for example, be an aromatic nitrating compound, and the like, and specific examples thereof include a salt such as a nitrate, a benzoic acid, a nitrated benzoic acid, a phenylamine, and a nitrated age.
等肖酉夂鹽可舉例如：確酸錢、硝酸鈉、硝酸卸 '硝酸鐵、 硝酸鎳等。 本發明之蝕刻液中，配合需要亦可進一步含有各種添 加劑。添加劑可舉例如·提升對被處理材濕潤性的界面活性 dJ、將本發明之钱刻液造杆哈冷土卩大^ J成進仃噴塗法時防止起泡現象的消泡 劑、防止銅變色的防鏽劑等。 本發明之敍刻液的佶用古、土 # ρ α 饮的便用方法並無特別限制，可採用諸 如：浸潰法、喷塗法等。此外， 此外上述蝕刻液的使用溫度通常 設定為20〜65°C範圍。另外，舍估田么 乃卜*使用蝕刻裝置進行蝕刻時， 2如T在將上述㈣液的所有成分調製成既定組成之後， Γ應給㈣裝置，亦可將上述㈣液的各μ個別供應 =刻裝置，然後在蝕刻裝置内將上述各成分進行混合而 :成既定組成’亦可將上述蝕刻液成分之其中—部分預 蝕Γΐ混合再供應給钱刻裝置，然後再將其他成分供應給 ―:1 :置，並將上述蝕刻液的各成分進行混合而調製成既 2、·且成。另外，當將上述蝕刻液的各成分供應給蝕刻裝置 日…上述各成分的濃度並無特別限制’例如可將高濃度的 2各成分供應給_裝置’再於㈣裝置内利用水進行 稀釋，而調製成既定濃度。 本發明之第i補充液，係當重複使用上述本發明之餘 刻液時，添加於該银刻液中者，其係水溶液且含有選自N〇、 =、n〇2、N2〇3及該等離子中至少、（種成分（即上述含氮 :)。利用上述補充液’就算上述敍刻液中的含氮成分漠 :降低，藉由在適當時機將該補充液添加於上述钱刻液 了維持上述钱刻液的敍刻性能。 上述補充液例如藉由使上述含氮成分溶解於 ==即可輕易的調製。特別係當上述含氮成分為使 子的情況時，因為亞硝酸離子將安定的存在於 =鹼性水溶液中，因而可安定的維持上述補充液令的 述3乳成分（亞硝酸離子）濃度。上述補充液 ，例如0.1〜75質量%，較佳一質量%，尤 貝里％為佳。若上述含氮成分的濃度小於〇丨 4±· 4- 只里 /〇 局月 t* 維持本發明之敍刻液的敍刻性能’將有必須大量添加上述 12 1379924 補充液的可能性。 上述補充液的添加量係隨最初在蝕刻液中所含上述含 氮成刀的s、所姓刻金屬的種類與厚度、添加時機等因素 而異。例如當敍刻液的餘刻速率低於既定速率時只要在 钱刻液中添加上述補充液，直到飯刻液中的上述含氮成分 f度達能獲得必要韻刻速率的濃度即可。另外，上述「既 疋速率」ϋ無特別限冑，只要經考慮生產#等因素之後再 適當設定即可。 本發明之第2補充液係含有··具選自胺基、亞胺基、羧 基、羰基、績基及經基中至少、i種基，以及硫原子，且碳 原子數為7以下的化合物（含硫化合物）。若重複使用含有 上述含硫化合物的本.發明之㈣液’因為上述㈣液中的 上述含硫化合物將消耗’因而會有銅溶解的抑制力降低之 可月&性。此種情況下，名：Μ定μ、+，、士 ㈣况下#將上述補充液添加於上述蝕刻液 中’可將上述含硫化合物的含有量保持於適當範圍，因而 可維持銅溶解的抑制力。此情況時的上述補充液添加量將 隨上述姓刻液中的上述含硫化合物含有量而異例如添加 成上述飯刻液中的上述含硫化合物含有量，佔上述整體钱 刻液例如〇·〇卜2〇質量％範圍，較佳GG5〜iGff% 尤以（MM質量％範圍為佳。另外，上述補充液中的 含硫化合物含有量係在能將上述蝕刻液中的上述 物含有量維持於適當範圍内的前提下，並無特別限：，： :佔，述整體補充液的0.5〜95質量％範圍，較佳〇 f %範圍’尤以1〜15質量％範圍為佳。 13 解 8 月之第2補充液係例如利用使上述含硫化合物溶 ^性溶液或驗性溶液^可調製。特別係較佳使 低τ液，因為將不致使本發明之钱刻液中的酸濃度降 外’本發明之第2補充液t ’亦可添加諸如上述含 、安定性提升劑、卩面活性劑、消泡劑、防鏽劑 寻添加劑。 之第3補充液，係含有選自噻唑與噻唑系化合 物中至少 1 4ώ 〇 種。該補充液係當重複使用含有選自噻唑與噻 系化口物中至少1種的本發明之蝕刻液時，所添加的補 政果、調製方法等均如上述本發明的第2補充液。 人本發明的導體圖案形成方法，係對選自Ni、Cr、Ni_Cr 口金及Pd中至少1種金屬(即上述被處理金屬)進行蝕刻， 日而形成導體圖案’其特徵在於:對被處理金屬使用上述本發 月之蝕刻液進行蝕刻。根據本發明的導體圖案形成方法， 為女上it可對被處理金屬快速钱刻，因而例如可從被處 理金屬與銅等其他金屬共存的被處理材中，對被處理金屬 進行選擇性餘刻。 上述導體圖案可舉例如配線圖案、焊墊圖案、或該等 的組合等。導體圖案的層構成，可舉例如由Ni、Cr、Ni-Cr 合金或Pd所構成的底層 '以及在該底層上所形成的銅層。 另外’依據本發明導體圖案形成方法所形成的導體圖案， 除上述被處理金屬與銅等其他金屬共存的導體圖案之外， 尚可為例如上述被處理金屬，即選自Ni、Cr、Ni-Cr合金 及Pd中至少1種金屬所構成的導體圖案。 1379924 本發明導體圖案形成方法的具體例，可舉例如下述方 法。 (a) 在絕緣性基材上形成底層的⑷、d 合金 層再於其上形成抗鍍膜，接著再利用鑛銅僅在構成導體 圖案的部分處形成鋼層，然後將抗鍵膜去除後再使該等 與本發明之蝕刻液接觸而將未形成銅層部分的底層溶解， 而形成導體圖案。 (b) 在絕緣性基材上形成底層的Ni、Cr或Ni_Cr合金 層^再於其上形成銅層，接著再將構成導體圖案的部分利 用抗钱膜被覆然後使該等接觸及銅#刻丨，而將未被抗 蝕臈被覆部分的銅進行蝕刻，接著再使該等與本發明之蝕 d液接觸將經上述銅蝕刻而裸露出的底層溶解，而形成 導體圖案。 經對絕緣性基材上賦予化學鍍觸媒（Pd)之後便進行 化學鍍銅，接著進行電鍍銅，然後將構成導體圖案的部分 覆蓋著抗蝕膜，接著再使該等接觸及銅蝕刻液，而對未被 抗蝕膜所覆蓋部分的銅（化學鍍銅層及鍍銅層）進行蝕刻， 再使S玄等與本發明之蝕刻液接觸，而將經上述銅蝕刻所裸 路出在絕緣性基材上剩餘的化學鍍觸媒（pd)去除，而形成 導體圖案。 上述任一情況下，使用本發明之蝕刻液進行蝕刻時的 姓刻方法並無特別限制，可採取諸如浸潰法、喷塗法等方 法進行蝕刻。根據本發明導體圖案形成方法，當上述（3)或 (b)的情況時’就算將構成底層的Ni、Cr或Ni-Cr合金層 15 1379924 厚度增厚（例如達〇.1/im以上的厚度），仍可在使構成導體 圖案的銅層形狀幾乎無產生變化的情況下，迅速的將底層 溶解。此外，就算上述（c)的情況，仍可在使構成導體圖案 的銅層形狀幾乎無產生變化的情況下，迅速的去除絕緣性 基材上所剩餘的化學鑛觸媒（Pd)。 再者，當重複如上述的蝕刻時，於重複使用本發明之 蝕刻液的情況下，本發明之蝕刻液中的含氮成分減少而導 致蝕刻液的蝕刻速率降低之虞。在此種情況下，較佳將上 述本發明補充液添加於上述蝕刻液中，在將依上述蝕刻液 所進行被處理金屬的蝕刻速率維持於既定速率以上的情況 下，對被處理金屬進行蝕刻。藉此，可維持上述蝕刻液的 蝕刻性能，因而可不需要頻繁更換上述蝕刻液，能以低成 本形成導體圖案。 其··人’本發明之導體圖案形成方法之一實施形態參照 圖式進行説明。如第1A〜1C圖及第2A〜2C圖所示，其係 說明本發明之導體圖案形成方法之一實施形態的各步驟截 面圖。 首先，如第1A圖所示，在由聚醯亞胺薄膜所構成的 絕緣性基材1〇上，利用濺鍍形成由]^_&合金層所構成的 底層1 1。絕緣性基材10及底層1 1厚度係例如可分別設定 為20〜5〇μηι及0.005〜o.ipm範圍。 其次’如第1B圖所示’在底層n上形成鋼層12。銅 層12之形成方法可舉例如：經利用濺鍍形成〇 2〜〇坫爪厚 度的銅薄膜層之後，再於該銅薄骐層上形成例如2〜i〇^m 1379924 厚度之鍍銅層的方法。 接著，如第1C圖所示，在銅層丨2上將構成導體圖案 的。p刀利用抗蝕膜13被覆。抗蝕膜13的形成方法可舉例 如.在銅層12上貼合乾膜光阻之後，再使用周知光微影法 對乾膜光阻進行圖案化處理的方法。 其次，使用如含有氯化銅或氣化鐵的銅蝕刻液，對未 被抗蝕膜13所被覆的銅層12a進行蝕刻，如第2a圖所示 將銅層12圖案化。 μ 接著，如第2Β圖所示，例如使用氫氧化鈉水溶液等 剝離液將抗蝕膜13剝離後，使用本發明之蝕刻液將經上 述銅蝕刻而裸露出的底層lla溶解。藉此而獲得如第2c 圖所示由配線圖案所構成的導體圖案1。 (實施例） 以下’針對本發明之蝕刻液的實施例，合併比較例進 行説明。另外，本發明並不僅侷限於下述實施例。 (蝕刻液之調製） 將表1所示成分混合，而調製成實施例1〜8的蝕刻液。 此外’將表2所示成分混合，而調製成比較例1〜3的蝕刻 液。另外’實施例5與8的蝕刻液係將除氧化氮（NO)以外 的成分混合後’再對該混合溶液丨kg吹入3公升No氣體 而調製成。 (Ni-Cr合金之敍刻） 準備在聚醯亞胺薄膜上經利用濺鍍法形成Ni-Cr合金 膜的被處理材。該被處理材係聚醯亞胺薄膜及Ni-Cr合金Such as the Xiaoyan salt can be exemplified by: acid, sodium nitrate, nitric acid, 'iron nitrate, nickel nitrate, and the like. The etching liquid of the present invention may further contain various additives as needed. The additive may, for example, be an interfacial activity dJ for improving the wettability of the material to be treated, a defoaming agent for preventing foaming during the spraying method, and a copper preventing agent for preventing the foaming phenomenon. Color-changing rust inhibitors, etc. The method for using the ancient and soil #ρα beverages of the immersion liquid of the present invention is not particularly limited, and examples thereof include a dipping method, a spray method, and the like. Further, the use temperature of the above etching liquid is usually set to a range of 20 to 65 °C. In addition, when the etched device is used for etching, 2, for example, T, after all the components of the above (4) liquid are prepared into a predetermined composition, the device may be supplied to the device (4), or the respective (μ) liquid may be supplied separately. = engraving device, and then mixing the above components in the etching device: into a predetermined composition 'may also partially-pre-etch and mix the above-mentioned etching liquid components to the money engraving device, and then supply other components to ―:1: Set, and mix the components of the above etching liquid to prepare both. Further, when the components of the etching liquid are supplied to the etching apparatus, the concentration of each of the above components is not particularly limited. For example, two components of the high concentration can be supplied to the device, and then diluted with water in the device. It is modulated to a predetermined concentration. The ith replenishing liquid of the present invention is added to the silver engraving liquid when the remnant of the present invention is repeatedly used, and is an aqueous solution containing N 〇, =, n 〇 2, N 2 〇 3 and At least (the above-mentioned nitrogen-containing component) of the plasma. The above-mentioned replenishing liquid is used to reduce the nitrogen-containing component in the above-mentioned engraving liquid, and the replenishing liquid is added to the above-mentioned money engraving liquid at an appropriate timing. The replenishing performance of the above-described money engraving liquid is maintained. The replenishing liquid can be easily prepared by, for example, dissolving the nitrogen-containing component in ==, especially when the nitrogen-containing component is a meson, because of the nitrite ion. The stability is maintained in the = alkaline aqueous solution, so that the concentration of the third milk component (nitrite ion) of the above-mentioned replenishing liquid can be stably maintained. The above-mentioned replenishing liquid is, for example, 0.1 to 75% by mass, preferably 1% by mass, particularly The Berry% is better. If the concentration of the above nitrogen-containing component is less than 〇丨4±·4- only 里/〇局月** maintains the characterization performance of the etchant of the present invention', it will be necessary to add a large amount of the above 12 1379924 supplement The possibility of liquid. The amount of the above supplement It is different from the s of the above-mentioned nitrogen-containing knives contained in the etching solution, the type and thickness of the metal to be engraved, the timing of addition, etc. For example, when the residual rate of the engraving liquid is lower than the predetermined rate, it is only in the money. The above-mentioned replenishing liquid is added to the engraving liquid until the concentration of the above-mentioned nitrogen-containing component in the rice engraving liquid reaches a concentration at which the necessary rhythm rate can be obtained. In addition, the above-mentioned "carrying rate" is not particularly limited as long as production is considered. It is sufficient to set the factor # and the like. The second replenishing liquid of the present invention contains a group selected from an amine group, an imine group, a carboxyl group, a carbonyl group, a mercapto group, and at least a group, and a sulfur atom. And a compound having a carbon number of 7 or less (sulfur-containing compound). If the above-mentioned (four) liquid containing the above-mentioned sulfur-containing compound is repeatedly used, the above sulfur-containing compound in the above (iv) liquid will be consumed, and thus copper is dissolved. In this case, the name: Μ定μ, +, 士(四)下# Adding the above-mentioned replenishing solution to the above etching solution', the content of the above-mentioned sulfur-containing compound can be Keep in the proper range, thus The amount of the above-mentioned replenishing liquid to be added in the above-mentioned engraving liquid varies depending on the content of the sulfur-containing compound in the above-mentioned engraving liquid, and is added to the content of the sulfur-containing compound in the above-mentioned rice engraving liquid, for example, The whole money engraving liquid is, for example, 〇·〇卜2〇% by mass, preferably GG5 to iGff%, particularly preferably (MM mass% is in a range. Further, the sulfur compound content in the above replenishing liquid is based on the above etching liquid In the premise that the content of the above-mentioned substance is maintained within an appropriate range, there is no particular limitation: :: occupies a range of 0.5 to 95% by mass of the total replenishing liquid, preferably 〇f % range 'especially 1 to 15 masses The range of % is preferred. 13 The second replenishing solution in August is prepared by, for example, using the sulfur-containing compound solution or the test solution. In particular, it is preferred to use a low τ liquid because it will not cause the present invention. The acid concentration in the money engraving liquid is reduced. The second replenishing liquid t' of the present invention may also be added with additives such as the above-mentioned inclusion, stability improving agent, kneading surfactant, antifoaming agent and antirust agent. The third replenisher contains at least 14 ώ species selected from the group consisting of thiazole and thiazole compounds. In the replenishing liquid, when the etching liquid of the present invention containing at least one selected from the group consisting of a thiazole and a thiolated mouth is repeatedly used, the added fruit, the preparation method, and the like are the second replenishing liquid of the present invention. In the method of forming a conductor pattern according to the present invention, at least one metal selected from the group consisting of Ni, Cr, Ni_Cr gold, and Pd (that is, the metal to be treated) is etched to form a conductor pattern in a day, which is characterized in that the metal to be processed is Etching is performed using the above-described etching solution of the present month. According to the conductor pattern forming method of the present invention, it is possible for the metal to be processed to be quickly burned, so that, for example, the metal to be treated may be selectively treated from the processed metal in which the metal to be treated and other metals coexist. . The conductor pattern may be, for example, a wiring pattern, a pad pattern, or a combination thereof. The layer structure of the conductor pattern may, for example, be a bottom layer ' composed of Ni, Cr, a Ni-Cr alloy or Pd, and a copper layer formed on the underlayer. Further, the conductor pattern formed by the conductor pattern forming method of the present invention may be, for example, the above-mentioned metal to be processed, that is, selected from the group consisting of Ni, Cr, Ni-, in addition to the conductor pattern in which the metal to be treated and other metals such as copper coexist. A conductor pattern composed of at least one metal of a Cr alloy and Pd. 1379924 A specific example of the method for forming a conductor pattern of the present invention is exemplified by the following method. (a) forming a (4), d alloy layer on the insulating substrate and then forming a plating resist thereon, and then using the ore copper to form a steel layer only at a portion constituting the conductor pattern, and then removing the anti-bond film These layers are brought into contact with the etching liquid of the present invention to dissolve the underlayer in which the copper layer portion is not formed, thereby forming a conductor pattern. (b) forming a bottom layer of Ni, Cr or Ni_Cr alloy on the insulating substrate and then forming a copper layer thereon, and then coating the portion constituting the conductor pattern with the anti-money film and then making the contact and copper Then, the copper which is not covered by the anti-corrosion coating is etched, and then the underlying layer which is exposed by the copper etching is dissolved by contacting the etching liquid of the present invention to form a conductor pattern. After the electroless plating catalyst (Pd) is applied to the insulating substrate, electroless copper plating is performed, followed by electroplating copper, and then the portion constituting the conductor pattern is covered with the resist film, and then the contact and copper etching liquid are further applied. And etching copper (electroless copper plating layer and copper plating layer) which is not covered by the resist film, and then contacting S Xuan et al. with the etching liquid of the present invention, and leaving the bare copper through the copper etching The electroless plating catalyst (pd) remaining on the insulating substrate is removed to form a conductor pattern. In any of the above cases, the method of etching the etching using the etching solution of the present invention is not particularly limited, and etching may be carried out by a method such as a dipping method or a spraying method. According to the conductor pattern forming method of the present invention, in the case of the above (3) or (b), the thickness of the Ni, Cr or Ni-Cr alloy layer 15 1379924 constituting the underlayer is increased (for example, 达〇.1/im or more). The thickness) can be quickly dissolved in the case where the shape of the copper layer constituting the conductor pattern hardly changes. Further, even in the case of the above (c), the chemical mineral catalyst (Pd) remaining on the insulating substrate can be quickly removed without causing a change in the shape of the copper layer constituting the conductor pattern. Further, when the etching as described above is repeated, in the case where the etching liquid of the present invention is repeatedly used, the nitrogen-containing component in the etching liquid of the present invention is reduced to cause a decrease in the etching rate of the etching liquid. In this case, it is preferable that the replenishing liquid of the present invention is added to the etching liquid, and the metal to be treated is etched while maintaining the etching rate of the metal to be treated according to the etching liquid at a predetermined rate or higher. . Thereby, the etching performance of the etching liquid can be maintained, so that it is not necessary to frequently replace the etching liquid, and the conductor pattern can be formed at a low cost. The embodiment of the conductor pattern forming method of the present invention will be described with reference to the drawings. As shown in Figs. 1A to 1C and Figs. 2A to 2C, a cross-sectional view showing each step of an embodiment of the conductor pattern forming method of the present invention will be described. First, as shown in Fig. 1A, a primer layer 11 composed of an alloy layer is formed by sputtering on an insulating substrate 1 made of a polyimide film. The thickness of the insulating base material 10 and the underlayer 1 1 can be set, for example, in the range of 20 to 5 〇 μηι and 0.005 to 0.1 μm, respectively. Next, a steel layer 12 is formed on the bottom layer n as shown in Fig. 1B. The copper layer 12 may be formed by, for example, forming a copper thin film layer having a thickness of 〇2 to 〇坫2 by sputtering, and then forming a copper plating layer having a thickness of, for example, 2 to 〇m 1379924 on the copper thin layer. Methods. Next, as shown in Fig. 1C, a conductor pattern is formed on the copper layer 丨2. The p-blade is covered with the resist film 13. The method of forming the resist film 13 can be, for example, a method in which a dry film photoresist is bonded to the copper layer 12, and then the dry film photoresist is patterned by a well-known photolithography method. Next, the copper layer 12a not covered by the resist film 13 is etched using a copper etching solution containing copper chloride or iron carbide, and the copper layer 12 is patterned as shown in Fig. 2a. μ Next, as shown in Fig. 2, the resist film 13 is peeled off using, for example, a stripping solution such as an aqueous sodium hydroxide solution, and then the underlayer 11a exposed by the above-described copper etching is dissolved using the etching liquid of the present invention. Thereby, the conductor pattern 1 composed of the wiring pattern as shown in Fig. 2c is obtained. (Examples) Hereinafter, the examples of the etching liquid of the present invention will be described with reference to comparative examples. Further, the present invention is not limited to the following embodiments. (Preparation of Etching Liquid) The components shown in Table 1 were mixed to prepare the etching liquids of Examples 1 to 8. Further, the components shown in Table 2 were mixed to prepare an etching solution of Comparative Examples 1 to 3. Further, the etching liquids of Examples 5 and 8 were mixed with components other than nitrogen oxide (NO), and then 3 liters of No gas was blown into the mixed solution 丨kg to prepare. (Synthesis of Ni-Cr alloy) A material to be processed for forming a Ni-Cr alloy film by a sputtering method on a polyimide film is prepared. The treated material is a polyimide film and a Ni-Cr alloy
17 137992417 1379924
膜厚度分別為5〇μιη與0.1/im ’且Ni-Cr合金膜的Ni與Cr 原子比（>^/〇)為88/12。然後，將該被處理材浸漬於表1 與表2所示各蝕刻液（4(TC )中，利用螢光X射線分析裝置 進行測定，測量直到聚醯亞胺薄膜表面未檢測出Ni與G 的時間(N“Cr合金溶解時間)。結果如表i與表2所示。此Γ 外’參照資料係將長4〇mm、寬4〇mm、厚35仰、重〇Μ 的銅泊’在表1與纟2所示各姓刻液（40°C)中，浸潰與上 述溶解時間為相同的時間，$用浸潰前後的碉 銅溶解量。結果如表1與表2括弧内所示。 調查 (pd之蝕刻） 準備在環氧樹脂含潰玻璃纖維布基材上賦予化學鍍觸 的=的破處理材。在該被處理材上基材每lm2附著2〇呵 液_=二=材浸潰於表1與表2所示各'刻 測量直到基材= = 果如表1與表此外二=間^結 ㈣，t，浸潰與上述溶解時丄=二 用浸潰前後的重晋#““ 為相冋的時間’利 括弧内所示 調查銅溶解量。結果如表1與表2 1379924 (表1)The film thicknesses were 5 〇 μηη and 0.1/im ′, respectively, and the Ni-Cr atomic ratio (>^/〇) of the Ni-Cr alloy film was 88/12. Then, the material to be treated was immersed in each of the etching liquids (4 (TC) shown in Tables 1 and 2, and measured by a fluorescent X-ray analyzer, and was measured until no Ni and G were detected on the surface of the polyimide film. The time (N "Cr alloy dissolution time". The results are shown in Table i and Table 2. This ' outside 'reference data system will be 4 〇 mm long, 4 〇 mm wide, 35 thick, and heavy copper berth' In each of the engraved liquids (40 ° C) shown in Tables 1 and 2, the dissolution time was the same as the above dissolution time, and the amount of bismuth copper dissolved before and after the immersion was used. The results are shown in Table 1 and Table 2 in parentheses. Investigate (etching of pd) Prepare a cracked material that gives an electroless plating touch on an epoxy resin-containing glass fiber cloth substrate. On the substrate to be treated, the substrate is attached to each lm2. Two = material impregnated in Table 1 and Table 2 shown in each 'inscription until the substrate = = fruit as shown in Table 1 and Table 2 = between ^ (4), t, impregnation and above dissolution 丄 = two with impregnation Before and after the re-introduction #" "for the time of the opposite", the copper dissolved amount was investigated in the brackets. The results are shown in Table 1 and Table 2 1379924 (Table 1)
" —____ 組成 Ni-Cr合金溶解時間 (銅箔重量變化） Pd溶解時間 (銅箔重量變化） 實施例1 鹽酸(氣化氫-- 硫酸:20質量％ 離子):0.1議 20 秒(0.03g) 30 秒(0.03g) 實施例2 鹽酸(氯化氫):2〇質量0/0 硫酸:20質量％ 亞硝酸鈉(亞硝酸離子):〇丨質晉％ 硫代水楊酸:0.001質量％ 離子交換水:剩餘 20 秒(O.OOg) 30 秒(O.OOg) 實施例3 鹽酸(氣化氫):20質量％ 硫酸:20質量％ 亞硝酸納(亞硝酸離子Η皙景％ 噻唑:0.01質量％ 離子交換水:剩餘 20 秒(0_00g) 30 秒(O.OOg) 實施例4 鹽酸(氣化氫):20質量％ 硫酸:10質量％ 亞硝酸納(亞硝酸離子):0.01質量〇/〇 苯并噻唑:0.3質量％ 離子交換水:剩餘 30 秒(O.OOg) 60 秒(O.OOg) 實施例5 鹽酸(氣化氫):2〇質量％ 硫酸:20質量％ 氧化氮(NO):溶液每1kg為3公升 /S-硫醇基丙酸:0.3質量％ 離子交換水:剩餘 20 秒(O.OOg) 30 秒(O.OOg) 實施例6 鹽酸(氣化氫):20質量％ 硫酸:10質量％ 亞琐酸經(亞硝酸離子):0.01質量％ 笨并噻唑:0.1質量％ 石-硫醇基丙酸:0.1質量％ 離子交換水:剩餘 30 秒(〇.〇〇g) 50 秒(O.OOg) 實施例7 鹽酸(氣化氫):10質量％ 硫酸:20質量％ 亞硝酸鉀(亞硝酸離子):1質量％ 2-硫醇基乙磺酸鈉:0.05質量。/〇 離子交換水:剩餘 20 秒(O.OOg) 30 秒(O.OOg) 實施例8 鹽酸(氣化氫):20質量％ 硫酸:20質量％ 氧化氮(NO):溶液每1kg為3公升 2-硫醇基乙磺酸鈉·〇·〇1質量％ 硫代水楊酸:0.01質量％ 離子交換水:剿餘 20 秒(O.OOg) 30 秒(O.OOg) 19 1379924 (表2) 組成 Ni-Cr合金溶解時間 (销箔重量變化） Pd溶解時間 (銅箔重量變化） 比較例1 鹽酸(氣化氫):10質量％ 硫酸:20質量％ 硫脉:1質量％ 離子交換水:剩餘 300秒(0.01 g) 300秒以上(0.01 g) 比較例2 鹽酸(氯化氫):5質量％ 氯化鐵:30質量％ 離子交換水:剩餘 180 秒(0.48g) 30 秒(〇.〇8g) 比較例3 鹽酸(氣化氫):5質量〇/〇 硫酸:5質量％ 離子交換水:剩餘 600秒以上(0.3g以上） 600秒以上(〇.3g以上） 如表1所示’使用本發明之蝕刻液的實施例1〜8，Ni_ Cr合金與Pd可迅速溶解，且幾乎未發現到銅箔的溶解。 相對於此’表2所示比較例丨〜3，Ni_Cr合金與Pd的溶解 時間將拉長’結果比較例2與比較例3在相較於實施例1〜8 之下’銅箔在触刻液中的溶解量增加。 再者’經使用上述實施例2的蝕刻液以上述條件重複 進行Ni-Cr合金的钱刻處理，最初的Ni_cr合金溶解時間 雖為20秒’但是經重覆使用之後，上述溶解時間將達3〇〇 秒而降低姓刻速率。在此將亞硝酸鈉溶解於離子交換水中 的補充液（含亞硝酸離子6〇質量％)，對蝕刻液每1公升添 加17毫升’然後再進行蝕刻。如此，Ni_Cr合金的溶解時 間成為當初溶解時間之2〇秒，已恢復蝕刻速率。 再者’針對上述補充液添加前後在蝕刻液中的亞硝酸 20 ⑧ 離子濃度，以下述方法進行。 P，^ '、里。測$方法，係首先取樣 既疋里的钱刻液，在該樣太 mn 令添加格里斯試劑（含有磺胺與 鄰（1-萘基）乙烯二胺的試劑）， 7 I至恤中放置5〜10分鐘（在 此期間將變色為紅紫色）。1 '、人針對该樣本測量520〜550nm 搞i二光吸M MW預先知道亞确酸離子濃度之標準 樣本的上述吸光度進行比較，並進行濃度換算。結果，上 =充液添加前⑼-Cr合金溶解時間為繼秒）的亞硝酸離 ^農度係0.0_5質量％，上述補充液添加後（Νι心合金 冷解時間為20秒）的亞確酸離子濃度為〇 〇ι質量％。 (噻唑含有量之調整） 再者’為觀察蝕刻液中的噻唑影響而進行以下的實驗。 將實施例3的银刻液（1〇〇g)保持於啊中在該敍刻 液中將上述已形成Nl_Cr合金膜的被處理材浸潰【分鐘。 其次’將上述被處理材從银刻液中取出’將長4〇醜、寬 * :厚35/rni、重0.50g的銅箔’在上述蝕刻液)中 又項1 π鐘’利H潰前後的重量變化調查銅的溶解量。 =此操作為i循環，經重複進行3G週期，發現第3〇片銅 备將減夕0.03g的銅。在此時候，經測量上述蝕刻液中的 塞坐3有量，結果減少至〇 〇〇2質量％(初始値』質量 )在此於噻唑含有量已減少的上述蝕刻液中，添加在經 離子交換水中溶解鹽酸（氯化氫）2〇質量％、硫酸2〇質量％ 及噻唑1質量0/〇的補充液（ig)。藉此，蝕刻液中的噻唑含 有量將為0.01質量％。然後，在該蝕刻液中如同上述浸潰 銅名’結果銅箔的重量變化為0 〇〇g。 1379924 (冷-硫醇基丙酸含有量之調整） 再者’為觀察蝕刻液中的万-硫醇基丙酸影響而進行以 . 下的實驗。 . 使用實施例5的蝕刻液（l〇〇g)，重複進行如同上述實 施例3之蝕刻液相同的浸潰處理3〇週期。結果發現第3〇 片銅/1如同上述將減少〇 〇 3 g的銅。在此時候，經測量上 述實施例5之蝕刻液中的万_硫醇基丙酸含有量，結果減少 至〇.005質量％(初始値：〇.3質量％)。在此於点·硫醇基丙酸 含有置已減少的上述蝕刻液中，添加經在離子交換水中溶 解鹽酸（氣化氫）2〇質量％、硫酸2〇質量％及召_硫醇基丙酸 2〇貝里％的補充液（l.6g)。藉此蝕刻液中的s·硫醇基丙酸 3有里將為0.3質量％。然後，在該蝕刻液中如同上述般 的將銅箔次潰，結果銅箔的重量變化為〇.〇〇g。 (導體圖案形成方法） 其次，針對本發明導體圖案形成方法的實施例，合併 鲁比較例進行說明。另外，本發明並不僅限於下述實施例。 首先，如同上述實施例中對Ni_Cr合金進行蝕刻時所 使用被處理材的相同被處理材。其次，在該被處理材的 N^Cr合金臈（底層）上，經利用濺鍍形成〇 2〜〇邛爪厚度的 銅j膜層之後，再於該鋼薄膜層上形成錄銅層，而形成由 銅薄膜層與鑛銅層所構成的銅層（合計厚度鄭⑷。 八人對該銅層上將構成導體圖案的部分利用抗蝕膜 被覆。抗蝕膜係在銅層上貼附著厚度15_的乾膜光阻， 再使用周知的光微影法，對上述乾膜光阻進行圖案化處 22 ⑧ 1379924 而形成等間隔線=15μηι/ΐ5#ηι(線寬為l5ym,線與線間 的間隔為1 5 // m)的線圖案。 接著，使用含有氯化銅的銅蝕刻液（4(rc ),對未被抗 钱膜所被覆的銅層，依喷壓〇 15MPa的條件進行飯刻而去 除之後，再噴淋3質量％的氫氧化鈉水溶液而將抗蝕膜剝 離。 ^然後，在上述實施例2的蝕刻液（40。〇中，將經剝離 抗蝕膜後的被處理材一邊搖晃一邊浸潰，直到經上述銅蝕 刻所裸露出的Ni-Cr合金膜溶解為止。此時的Νί·&合金 膜溶解時間（即蝕刻時間）為2〇秒。另外，Ni_Cr合金膜是 否已去除之事’係、利用金屬顯微鏡對配線間的聚酿亞胺^ 膜表面放大400倍觀察而進行確認。藉此可獲得由如上述 第2C圖所示配線圖案構成的導體圖案（實施例9)。 再者，比較例4與比較例5係除分別使用上述比較例 1與上述比較#j 2 6^刻液及姓刻時間 <彳，其餘均以如 上述實施例9相同的條件形成導體圖案。另外，比較例的 Ni-Cr合金膜溶解時間（即蝕刻時間），在比較例4中為3㈧ 秒’比較例5則為180秒。 表3所示係上述實施例 合金膜去除前後的銅層高度 度W i (參照第2 C圖）、銅層 配線間距。如表3所示，比 於Ni-Cr合金的蝕刻速率， 間銅層幾乎全被去除，而無 9與比較例4、5中，將 H(參照第2C圖）、銅層頂部寬 基部寬度wz(參照第2C圖）及 較例5因為銅的蝕刻速率較快 因而在將Ni-Cr合金膜去除期 法形成導體圖案。此外，若將 1379924 實施例9與比較例4進行比較，經所獲得導體圖案的形狀 而言雖幾乎無差異可言，但是就Ni-Cr合金膜的溶解時間 H (即蝕刻時間）而言，比較例4將為300秒，而實施例9則 • 為2〇秒。由此結果得知，根據本發明的導體圖案形成方 法’可迅速的將Ni-Cr合金膜去除。 (表3) 銅層高度Η (μιη) 銅層頂部寬度w, (㈣ 銅層基部寬度w2 im) 配線間距 (μηα) 實施例9 去除前 8 13 15 30 去除後 7.98 12.97 14.97 30 比較例4 去除前 8 13 15 30 去除後 7.97 12.98 14.97 30 比較例5 去除前 8 13 15 30 去除後 — 0 1 30 【圖式簡單說明】 φ 第1 A〜C圖係說明本發明之導體圖案形成方法一實施 形態的各步驟戴面圖。 第2Λ〜C圖係說明本發明之導體圖案形成方法一實施 形態的各步驟戴面圖。 【主要元件符號說明】 1 導體圖案 10 絕緣性基材 11' 11a 底層 1 2、1 2 a 銅層 24 1379924 13 抗蝕膜 Η 銅層高度 w, 銅層頂部寬度 w2 銅層基部寬度" —____ Composition Ni-Cr alloy dissolution time (copper foil weight change) Pd dissolution time (copper foil weight change) Example 1 Hydrochloric acid (hydrogenation gas - sulfuric acid: 20 mass% ion): 0.1 to 20 seconds (0.03 g) 30 seconds (0.03g) Example 2 Hydrochloric acid (hydrogen chloride): 2 〇 mass 0 / 0 Sulfuric acid: 20% by mass Sodium nitrite (nitrite ion): bismuth bismuth thiosalicylic acid: 0.001% by mass Ion exchange water: remaining 20 seconds (O.OOg) 30 seconds (O.OOg) Example 3 Hydrochloric acid (hydrogenated hydrogen): 20% by mass Sulfuric acid: 20% by mass Sodium nitrite (nitrite ion % % thiazole: 0.01% by mass ion-exchanged water: 20 seconds remaining (0_00g) 30 seconds (O.OOg) Example 4 Hydrochloric acid (hydrogenated hydrogen): 20% by mass Sulfuric acid: 10% by mass Sodium nitrite (nitrite ion): 0.01 mass 〇 /〇 Benzothiazole: 0.3% by mass Ion-exchanged water: 30 seconds remaining (O.OOg) 60 seconds (0.00 g) Example 5 Hydrochloric acid (hydrogenated hydrogen): 2% by mass Sulfuric acid: 20% by mass Nitric oxide ( NO): 3 liters per Skg of solution / thiol-propionic acid: 0.3% by mass Ion-exchanged water: 20 seconds remaining (O.OOg) 30 seconds (O.OOg) Example 6 Hydrochloric acid (hydrogenated hydrogen): 20% by mass sulfuric acid: 10% by mass Acid (nitrite ion): 0.01% by mass Stupid thiazole: 0.1% by mass Stone-thiol propionic acid: 0.1% by mass Ion-exchanged water: 30 seconds remaining (〇.〇〇g) 50 seconds (O.OOg) Example 7 Hydrochloric acid (hydrogenated hydrogen): 10% by mass Sulfuric acid: 20% by mass Potassium nitrite (nitrite ion): 1% by mass Sodium 2-thiol ethanesulfonate: 0.05 mass. / hydrazine ion exchange water: remaining 20 seconds (O.OOg) 30 seconds (O.OOg) Example 8 Hydrochloric acid (hydrogenated hydrogen): 20% by mass Sulfuric acid: 20% by mass Nitric oxide (NO): 3 liters of 2-thiol B per 1 kg of solution Sodium sulfonate·〇·〇1% by mass Thiosalicylic acid: 0.01% by mass Ion-exchanged water: 20 seconds remaining (O.OOg) 30 seconds (O.OOg) 19 1379924 (Table 2) Composition of Ni-Cr alloy Dissolution time (change in pin foil weight) Pd dissolution time (change in weight of copper foil) Comparative Example 1 Hydrochloric acid (hydrogenated hydrogen): 10% by mass Sulfuric acid: 20% by mass Sulfur veins: 1% by mass Ion exchanged water: 300 seconds remaining (0.01 g) 300 seconds or more (0.01 g) Comparative Example 2 Hydrochloric acid (hydrogen chloride): 5 mass% Ferric chloride: 30 mass% Ion-exchanged water: 180 seconds remaining (0.48 g) 30 seconds (〇.〇8 g) Comparative Example 3 Hydrochloric acid (Gas hydrogenation): 5 mass 〇 / 〇 sulfuric acid: 5 mass % ion-exchanged water: 600 seconds or more (0.3 g or more) remaining 600 seconds or more (〇.3g or more) As shown in Table 1 'Examples 1 to 8 using the etching liquid of the present invention, Ni_Cr alloy and Pd can be quickly dissolved And almost no dissolution of the copper foil was found. In contrast to the comparative example 丨3 shown in Table 2, the dissolution time of the Ni_Cr alloy and Pd will be elongated. [Results Comparative Example 2 and Comparative Example 3 are in comparison with Examples 1 to 8] The amount of dissolution in the liquid increases. Furthermore, the etching process of the Ni-Cr alloy was repeated using the etching solution of the above Example 2 under the above conditions, and the initial Ni_cr alloy dissolution time was 20 seconds', but after repeated use, the above dissolution time would be 3 Decrease the rate of surnames in leap seconds. Here, sodium nitrite was dissolved in ion-exchanged water (6 〇 mass% of nitrite ions), and 17 ml of etchant was added per liter of ‘and then etched. Thus, the dissolution time of the Ni_Cr alloy becomes 2 sec seconds of the initial dissolution time, and the etching rate has been restored. Further, the concentration of nitrous acid 20 8 in the etching solution before and after the addition of the above-mentioned replenishing liquid was carried out in the following manner. P, ^ ', in. To measure the $ method, first sample the money engraving solution in the sputum, and add the Gris reagent (reagent containing sulfonamide and o-(1-naphthyl)ethylenediamine) to the sample. ~10 minutes (will change to reddish purple during this period). 1 ', the person measured 520~550nm for this sample, and the second absorbance M MW knows the standard absorbance of the sample. The above absorbance is compared and the concentration is converted. As a result, the nitrous acid (the dissolution time of the (9)-Cr alloy before the liquid filling is sec.) is 0.0_5 mass%, and the above-mentioned replenishing liquid is added (the cold solution time of the Νι heart alloy is 20 seconds). The acid ion concentration was 〇〇 by mass%. (Adjustment of thiazole content) The following experiment was conducted to observe the influence of thiazole in the etching solution. The silver etchant (1 〇〇g) of Example 3 was held in the immersion liquid, and the above-mentioned material to which the Nl_Cr alloy film had been formed was immersed in [minutes]. Next, 'take the above-mentioned material to be taken out from the silver engraving liquid'. The copper foil with a length of 4 〇 ug, width *: thickness 35/rni, weight 0.50g in the above etching liquid) is again 1 π clock 'li H collapse The weight change before and after was investigated for the amount of copper dissolved. = This operation is an i-cycle. After repeating the 3G cycle, it is found that the third copper piece will be reduced by 0.03g of copper. At this time, the amount of the plug 3 in the etching liquid is measured, and as a result, it is reduced to 2% by mass (initial 値 mass), and the etchant having a reduced thiazole content is added to the ion. A replenishing solution (ig) in which hydrochloric acid (hydrogen chloride) 2% by mass, 2% by mass of sulfuric acid, and thiazole 1 mass 0/〇 are dissolved in the exchange water. Thereby, the thiazole content in the etching solution will be 0.01% by mass. Then, in the etching solution, the weight change of the copper foil was 0 〇〇g as in the above-mentioned impregnated copper name. 1379924 (Adjustment of the content of cold-thiol propionic acid) In addition, the experiment was carried out to observe the influence of 10,000-thiol propionic acid in the etching solution. Using the etching liquid (10 g) of Example 5, the same immersion treatment as in the above-described Example 3 was repeated for 3 〇 cycles. As a result, it was found that the third sheet of copper/1 as described above would reduce 〇 3 g of copper. At this time, the content of 10,000-thiol propionic acid in the etching liquid of the above Example 5 was measured, and as a result, it was reduced to 005005 mass% (initial 値: 3.3 mass%). Here, in the above-mentioned etching liquid containing a reduced amount of thiol-propionic acid, the amount of hydrochloric acid (hydrogenated hydrogen) dissolved in ion-exchanged water is increased by 2% by mass, 2% by mass of sulfuric acid, and thiol-propionate is added. Acid 2 〇 里 % % of the supplement (l. 6g). Thereby, s·thiol propionic acid 3 in the etching solution will have a mass ratio of 0.3% by mass. Then, in the etching solution, the copper foil was broken as described above, and as a result, the weight of the copper foil was changed to 〇.〇〇g. (Conductor pattern forming method) Next, an embodiment of the conductor pattern forming method of the present invention will be described with reference to a comparative example. Further, the present invention is not limited to the following embodiments. First, the same processed material of the material to be treated used for etching the Ni_Cr alloy as in the above embodiment. Next, on the N^Cr alloy crucible (underlayer) of the material to be processed, after forming a copper j film layer having a thickness of 〇2 to 〇邛2 by sputtering, a copper layer is formed on the steel film layer, and A copper layer composed of a copper thin film layer and a mineralized copper layer is formed (total thickness Zheng (4). Eight people on the copper layer are covered with a resist pattern on the copper layer. The resist film is adhered to the copper layer. 15_ dry film photoresist, using the well-known photolithography method, the above-mentioned dry film photoresist is patterned at 22 8 1379924 to form an equally spaced line = 15μηι / ΐ 5 # ηι (line width is l5ym, line and line A line pattern with a spacing of 1 5 // m). Next, using a copper etching solution (4(rc ) containing copper chloride, the copper layer not covered by the anti-money film is subjected to a pressure of 15 MPa. After the meal was removed and removed, a 3 mass% sodium hydroxide aqueous solution was sprayed to peel off the resist film. Then, in the etching liquid (40 in the above-mentioned Example 2, after the resist film was peeled off) The material to be treated is immersed while being shaken until the Ni-Cr alloy film exposed by the copper etching is dissolved. The 溶解ί·& alloy film dissolution time (ie, etching time) is 2 〇 seconds. In addition, whether the Ni_Cr alloy film has been removed, the metal film is used to magnify the surface of the polyaniline film in the wiring room by 400 times. Further, it was confirmed that a conductor pattern composed of the wiring pattern as shown in the above FIG. 2C was obtained (Example 9). Further, Comparative Example 4 and Comparative Example 5 were used in addition to the above Comparative Example 1 and the above comparison # j 2 6^ etchant and surname time < 彳, the rest of the conductor pattern was formed under the same conditions as in the above-mentioned Example 9. In addition, the dissolution time (ie, etching time) of the Ni-Cr alloy film of the comparative example was compared in the comparative example. In the case of 4, it is 3 (eight) seconds, and in Comparative Example 5, it is 180 seconds. Table 3 shows the copper layer height W i (see FIG. 2 C) before and after the removal of the alloy film of the above embodiment, and the copper layer wiring pitch. It is shown that the interlayer copper layer is almost completely removed compared to the etching rate of the Ni-Cr alloy, and in the case of No. 9 and Comparative Examples 4 and 5, H (see FIG. 2C) and the width of the top of the copper layer are wide wz (see the 2C) and Comparative Example 5, because the etching rate of copper is faster, the Ni-Cr is combined. The film removal period method forms a conductor pattern. Further, when 1379924 Example 9 is compared with Comparative Example 4, there is almost no difference in the shape of the obtained conductor pattern, but the dissolution time of the Ni-Cr alloy film is H. (i.e., etching time), Comparative Example 4 would be 300 seconds, and Example 9 would be 2 seconds. From this result, it was found that the conductor pattern forming method according to the present invention can rapidly introduce Ni-Cr alloy. Film removal. (Table 3) Copper layer height μ (μιη) Copper layer top width w, ((4) Copper layer base width w2 im) Wiring pitch (μηα) Example 9 Removal before 8 13 15 30 Removal 7.98 12.97 14.97 30 Comparison Example 4 Before removal 8 13 15 30 After removal 7.97 12.98 14.97 30 Comparative Example 5 Before removal 8 13 15 30 After removal - 0 1 30 [Simple diagram] φ 1A to C diagram illustrates the formation of the conductor pattern of the present invention Method 1 is a step view of each step of the embodiment. Fig. 2 is a plan view showing the steps of the embodiment of the conductor pattern forming method of the present invention. [Main component symbol description] 1 Conductor pattern 10 Insulating substrate 11' 11a Underlayer 1 2, 1 2 a Copper layer 24 1379924 13 Resist film Η Copper layer height w, Copper layer top width w2 Copper layer base width
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| JP2005013007 | 2005-01-20 |
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| TW094145507A TW200626750A (en) | 2005-01-20 | 2005-12-21 | Etching liquid, refilling liquid, and forming method of conductor pattern using it |
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| JP (1) | JP4580331B2 (en) |
| KR (1) | KR100927068B1 (en) |
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| JP2008106354A (en) * | 2006-09-25 | 2008-05-08 | Mec Kk | Metal removing solution and metal removing method using the same |
| JP5432139B2 (en) * | 2008-06-27 | 2014-03-05 | 帝人株式会社 | Communication sheet structure |
| KR101243847B1 (en) * | 2011-08-18 | 2013-03-20 | 주식회사 이엔에프테크놀로지 | Method for etching cu/mo alloy film with etching capacity of etching solution improved |
| CN103107085B (en) * | 2013-01-31 | 2016-02-10 | 电子科技大学 | A kind of dry etch process of NiCr film |
| KR101324678B1 (en) * | 2013-06-20 | 2013-11-04 | 주식회사 에이씨엠 | Seed etchant comprising metal halogen compounds |
| KR101475892B1 (en) * | 2013-07-29 | 2014-12-23 | 주식회사 에이씨엠 | Seed Etchant for Wiring with High Aspect Ratio |
| CN106245030A (en) * | 2016-09-14 | 2016-12-21 | 佛山科学技术学院 | The chemical decoating liquid of a kind of palladium-nickel alloy coating strip and strip method |
| CN111334298B (en) * | 2020-02-26 | 2021-10-01 | 江阴润玛电子材料股份有限公司 | Molybdenum-aluminum-molybdenum and ITO/Ag/ITO compatible etching solution and preparation method thereof |
| CN112064028B (en) * | 2020-09-14 | 2022-09-16 | 深圳市志凌伟业光电有限公司 | Etching liquid for composite copper film structure |
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| JP3711650B2 (en) * | 1996-09-12 | 2005-11-02 | 旭硝子株式会社 | Patterning method for transparent conductive film and substrate with transparent electrode |
| US6117795A (en) * | 1998-02-12 | 2000-09-12 | Lsi Logic Corporation | Use of corrosion inhibiting compounds in post-etch cleaning processes of an integrated circuit |
| JP2001140084A (en) * | 1999-08-27 | 2001-05-22 | Mec Kk | Etching solution for nickel or nickel alloy |
| JP3454765B2 (en) * | 1999-12-07 | 2003-10-06 | 住友大阪セメント株式会社 | Precious metal catalyst removal solution |
| KR100319161B1 (en) * | 2000-02-15 | 2001-12-29 | 한의섭 | Selective etching solution for chromium metal layer |
| JP2003155586A (en) | 2001-11-16 | 2003-05-30 | Sumitomo Chem Co Ltd | Cleaning solution for electronic part |
| JP4241018B2 (en) * | 2002-12-06 | 2009-03-18 | メック株式会社 | Etching solution |
| JP2004277576A (en) | 2003-03-17 | 2004-10-07 | Daikin Ind Ltd | Method for preparing solution for etching or cleaning |
| JP4418916B2 (en) * | 2004-06-09 | 2010-02-24 | 奥野製薬工業株式会社 | Etching composition |
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| KR100927068B1 (en) | 2009-11-13 |
| CN1819748A (en) | 2006-08-16 |
| JP2006229196A (en) | 2006-08-31 |
| CN1819748B (en) | 2012-11-14 |
| KR20060084809A (en) | 2006-07-25 |
| TW200626750A (en) | 2006-08-01 |
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