CN102102206A - Metal etchant composition and etching method thereof - Google Patents
Metal etchant composition and etching method thereof Download PDFInfo
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- CN102102206A CN102102206A CN2009102606424A CN200910260642A CN102102206A CN 102102206 A CN102102206 A CN 102102206A CN 2009102606424 A CN2009102606424 A CN 2009102606424A CN 200910260642 A CN200910260642 A CN 200910260642A CN 102102206 A CN102102206 A CN 102102206A
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- fluid composition
- metal
- metal etch
- etch fluid
- molybdenum
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 147
- 239000002184 metal Substances 0.000 title claims abstract description 147
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 238000005530 etching Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 61
- 239000011733 molybdenum Substances 0.000 claims abstract description 61
- 239000010949 copper Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 18
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 14
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims description 73
- 239000000758 substrate Substances 0.000 claims description 20
- 239000003352 sequestering agent Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003851 azoles Chemical class 0.000 claims description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- 229940024606 amino acid Drugs 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PKDBCJSWQUOKDO-UHFFFAOYSA-M 2,3,5-triphenyltetrazolium chloride Chemical compound [Cl-].C1=CC=CC=C1C(N=[N+]1C=2C=CC=CC=2)=NN1C1=CC=CC=C1 PKDBCJSWQUOKDO-UHFFFAOYSA-M 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 208000006558 Dental Calculus Diseases 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229940009662 edetate Drugs 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims 2
- 229960002989 glutamic acid Drugs 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 15
- 239000000956 alloy Substances 0.000 abstract description 15
- 239000002738 chelating agent Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 42
- 238000004458 analytical method Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 229910001257 Nb alloy Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910000861 Mg alloy Inorganic materials 0.000 description 7
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940044197 ammonium sulfate Drugs 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UJKDYMOBUGTJLZ-RUCXOUQFSA-N ksc605q1h Chemical compound OC(=O)[C@@H](N)CCC(O)=O.OC(=O)[C@@H](N)CCC(O)=O UJKDYMOBUGTJLZ-RUCXOUQFSA-N 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012857 repacking Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a metal etching solution composition and an etching method thereof. The present invention provides a metal etchant composition for etching copper, copper alloy, molybdenum alloy, multilayer alloy containing copper alloy and molybdenum alloy, or copper/molybdenum multilayer metal, the metal etchant composition comprising an oxidizing agent (6 to 30 wt%), a chelating agent (0.1 to 10 wt%), a nitrogen-containing compound (0.1 to 5 wt%), an inorganic salt (0.2 to 10 wt%), and an aqueous medium, wherein the inorganic salt comprises a sulfate salt (0.1 to 5 wt%) and a phosphate salt (0.1 to 5 wt%).
Description
Technical field
The present invention relates to the metal etch fluid composition of the multiple layer metal of a kind of multilayer alloy that is used for etch copper (Cu), copper alloy (Cu alloy), molybdenum (Mo), molybdenum alloy (Mo alloy), copper alloy/molybdenum alloy or copper/molybdenum (Cu/Mo), relate in particular to a kind of method of using metal etch fluid composition etching metal.
Background technology
In the present semiconductor fabrication or the manufacturing processed of flat-panel screens, how can use chromium (Cr), molybdenum (Mo), copper (Cu), aluminium (Al), titanium metals such as (Ti) or its alloy as electro-conductive material.For the metallic conduction material is carried out efficient etch, the etchants that comprise acid (acid) and oxygenant (oxidant) that use came the multiple layer metal of chromium (Cr), aluminium (Al), titanium (Ti), molybdenum (Mo), molybdenum/aluminium (Mo/Al) or the multiple layer metal of titanium/aluminium (Ti/Al) are carried out etching more in the past.Yet, owing to will carry out etched metal species because of demand and be not quite similar, and also difference to some extent of required etching degree of carrying out, therefore, mostly industry is by selecting suitable acid and oxygenant separately at present, is aided with the concentration adjustment suitable to etching solution, to obtain best etch effect.
Answer the trend of flat-panel screens to large sizeization, for the impedance that reduces lead to promote the speed that signal transmits, simplify the structure dress manufacturing processed of drive IC simultaneously, therefore, adopting lower copper or the other materials of resistance ratio aluminium is inevitable development trend as conductor material.In with the application of copper as conductor material, owing to adopt the manufacturing processed of dry etching (dry etch) will produce not volatile compound, cause residual easily and be unfavorable for follow-up manufacturing processed operation, therefore, at present industry adopt more the manufacturing processed of wet etching (wet etch) think in response to.Moreover, separately with copper as conductor material, can influence the yield of product again because the sticking power between copper and the other materials (for example: glass baseplate, silicon nitride (siliconnitride) and amorphous silicon (amorphous silicon)) is not good, so, also just arise at the historic moment by solving the not good problem of product yield as the mode of conductor material to wrap copper bearing multiple layer metal.
Although can solve the not good defective of portioned product yield to wrap copper bearing multiple layer metal really as conductor material, yet also still there are many improved problems for the treatment of in such mode.Multiple layer metal with copper/molybdenum is an example, and alternative on the market etching solution still has the unmanageable problem of etch effect that difference causes of selecting ratio because of the rate of etch of copper and molybdenum at present.Moreover the wet etching mode that present industry is habitually practised also causes the multiple layer metal critical dimension loss (critical dimension loss) of copper/molybdenum excessive easily, and oblique angle (taper angle) is more than or equal to the situations of 90 degree.In addition, the residual phenomenon of molybdenum (as shown in Figure 1) also takes place on the substrate easily, and the situation (as shown in Figure 2) that the molybdenum layer undercutting takes place after the etching, all this kind all remains further to be improved.
In order to solve aforesaid problems, the etchant of at present existing multiple multiple layer metal at copper, copper alloy and copper/molybdenum is proposed successively, for example Taiwan patent announcement case is I231275 number and No. 480611, and the etchant that proposed for No. 200916605 of Taiwan patent disclosure case.Yet, in the aforementioned etchant that discloses, must add the composition of fluorine-containing (fluorine), for example: hydrofluoric acid (hydrofluoric aicd), Neutral ammonium fluoride (ammonium fuoride), Sodium Fluoride (sodium fluoride), Potassium monofluoride (potassiumfuoride), ammonium bifluoride (ammonium bifluoride), potassium hydrogen fluoride (potassiumbifluoride) or sodium bifluoride (sodium bifluoride), just can avoid producing the residual problem of molybdenum.But more and more paying attention under the trend of environmental protection and industrial safety now, relevant dealer wishes to reduce the use of fluorine-containing composition invariably in the middle of its manufacturing processed, its reason is the existing manufacturing processed equipment of the unavoidable necessary repacking of the use of fluorine-containing composition, increased the cost of making virtually, moreover, owing to use fluorine-containing composition in the manufacturing processed, therefore, except manufacturing processed originally, also additionally increased the cost of handling fluoride waste, and thereby improved the risk of industrial safety.In addition, glass baseplate, silicon nitride (silicon nitride) and amorphous silicon (amorphous silicon) in the fluorine-containing corrosion TFT-LCD of the one-tenth branch panel material, thereby cause yield loss, and product heavy industry (rework) back generating material corrosion default (defect).
Moreover the etching solution that Taiwan patent announcement case is disclosed for I231275 number comprises the organic acid in order to etch copper.Yet organic acid concentration is higher, and the rate of etch of molybdenum is lower, and molybdenum is residual also more difficult to be removed, and therefore, is unfavorable for follow-up manufacturing processed operation.
Because existing etchant still has many defectives, thereby has limited the use of existing etchant, in view of this, industry still demands solving the metal etch fluid composition of above-mentioned problems urgently at present.
Summary of the invention
The invention provides new metal etch fluid composition, it need not comprise that organic acid gets final product etch copper, and it is minimum that the residual degree of molybdenum is dropped to, and need not comprise that also fluorine-containing composition, can be with the molybdenum residue removal to increase the rate of etch to molybdenum.
Because the present invention can overcome the existing existing many shortcomings of etchant effectively, and can prolong the work-ing life (life time) of etchant simultaneously, therefore, the present invention is a kind of etchant that has industry development value in fact.
In one embodiment of the invention, the metal etch fluid composition is provided, it comprises: oxygenant, sequestrant (chelating agent), nitrogenous compound, inorganic salt and aqueous medium, and metal etch fluid composition of the present invention the example of etched metal comprise the multilayer alloy of copper, copper alloy, molybdenum, molybdenum alloy, copper alloy/molybdenum alloy and the multiple layer metal of copper/molybdenum.
In metal etch fluid composition of the present invention, the example of employed oxygenant comprises hydrogen peroxide (hydrogen peroxide), ammonium persulphate (ammonium persulfate), Sodium Persulfate (sodium persulfate; Na
2S
2O
8), hydrogen persulfate sodium (sodium hydrogen persulfate; NaHSO
5), Potassium Persulphate (potassium persulfate; K
2S
2O
8), potassium hydrogen persulfate (potassium hydrogen persulfate; KHSO
5), with and composition thereof, and the ratio of oxygenant accounts for 6 to 30 weight % (wt%) with total restatement of metal etch fluid composition.
Moreover, sequestrant used in the present invention comprises amino acid, and amino acid whose example comprises Beta Alanine (alanine), L-glutamic acid (glutamic acid), glycine (glycine), Gelucystine (cystine), l-asparagine (asparagine), ethylenediamine tetraacetic acid (EDTA) (ethylenediaminetetraacetic acid, EDTA-4H), edetate (EDTA-salt), imino-acetic acid (iminodiacetic acid, IDA), nitrilotriacetic acid (nitrilotriacetic acid, NTA), the nitrilotriacetic acid derivative, with and composition thereof, and the ratio of sequestrant accounts for 0.1 to 10 weight % with total restatement of metal etch fluid composition.
In addition, nitrogenous compound used in the present invention comprises azole compounds (azole), and the example of azole compounds comprises benzotriazole (benzotriazole, BTA), triphenyltetrazolium chloride (triphenyltetrazolium chloride, TTC), amino tetrazole (aminotetrazole), imidazoles, pyrazoles,
Azoles, azimido-toluene (tolyltriazole, TTA), with and composition thereof, and the ratio of nitrogenous compound accounts for 0.1 to 5 weight % with total restatement of metal etch fluid composition.
Then, inorganic salt used in the present invention comprise vitriol (sulfate) and phosphoric acid salt (phosphate) both, in the present invention, various vitriol and phosphoric acid salt all can use, and it is without particular limitation, and the ratio of inorganic salt accounts for 0.2 to 10 weight % with total restatement of metal etch fluid composition.
In one embodiment of the invention, the example of vitriol comprises ammonium sulfate (ammoniumsulfate), sodium sulfate (sodium sulfate), vitriolate of tartar (potassium sulfate), sal enixum (potassium bisulfate), with and composition thereof, phosphatic example then comprises Secondary ammonium phosphate (diammonium hydrogen phosphate), primary ammonium phosphate (ammoniumdihydrogen phosphate), Sodium phosphate dibasic (disodium hydrogen phosphate), SODIUM PHOSPHATE, MONOBASIC (sodium dihydrogen phosphate), dipotassium hydrogen phosphate (dipotassiumhydrogen phosphate), potassium primary phosphate (potassium dihydrogen phosphate), with and composition thereof, and vitriol and phosphatic ratio respectively account for 0.1 to 5 weight % with total restatement of metal etch fluid composition.
The example of the aqueous medium of metal etch fluid composition of the present invention can be deionized water.
In one embodiment of the invention, oxygenant act as the etching molybdenum, and copper is oxidized to cupric oxide.Moreover because the existence to impurity is quite responsive in the manufacturing processed of electronic industry, therefore, oxygenant must have certain purity, does not repeat them here.In addition, cross when low, also certainly will influence etched speed, even cause etching to carry out cmpletely when the concentration of oxygenant.
In the present invention, etched speed is controlled in acting as of sequestrant, is example with copper bearing single or multiple lift metal, but free free cupric ion in the sequestrant chelating etchant is used the stability that improves oxygenant, and reduces the rate of decomposition of oxygen.
In the present invention, acting as of nitrogenous compound suppresses contingent lateral erosion in the etch process, and especially copper lateral erosion is to reduce critical dimension loss (critical dimension loss, or abbreviation CD Loss).
In the present invention, inorganic salt comprise phosphoric acid salt and vitriol, and wherein, phosphatic mainly acting as controlled oblique angle (taper angle), and prolongs the work-ing life of etchant; Then for suppressing lateral erosion, especially molybdenum lateral erosion takes place with the phenomenon of avoiding undercutting (undercut) in the main effect of vitriol.In addition, the use of vitriol also can make the operation concentration of oxygenant be improved, and increases etched efficient, and prolongs the work-ing life (life time) of oxygenant.In one embodiment of the invention, vitriol also can solve the residual problem of molybdenum.
Use metal etch fluid composition of the present invention to carry out etch process, at least has following plurality of advantages: (1) Control Critical size penalty, in one embodiment of the invention, metal etch fluid composition of the present invention especially the may command critical dimension loss one-sided 0.5 to 1 micron (μ m) only arranged; (2) control the oblique angle, in one embodiment of the invention, metal etch fluid composition of the present invention especially the may command oblique angle between 25 ° to 60 °; (3) operating temperature range is big, although metal etch fluid composition of the present invention can obtain preferable operating effect between 25 ℃ to 30 ℃, yet, in the middle of 20 ℃ to 40 ℃ environment, still can not influence the normal running of metal etch fluid composition of the present invention; (4) metal etch fluid composition of the present invention does not have fluorine-containing composition, therefore, metal etch fluid composition of the present invention there is no the anxiety of etching glass base material, silicon nitride and amorphous silicon, takes into account product yield, safety and environmental protection simultaneously, and the risk of defective takes place behind the reduction heavy industry; (5) the pH value of metal etch fluid composition of the present invention is preferably between 2 to 4 between 2 to 7, is slightly acidic, therefore helps the stable of oxygenant, thereby avoids the decay of oxygenant; And (6) in specific embodiments more of the present invention, and metal etch fluid composition of the present invention can prevent the residual of molybdenum effectively.
Based on above-mentioned various advantages, in another embodiment of the present invention, a kind of purposes of metal etch fluid composition is provided, comprise and be used to prepare flat-panel screens (flat panel display, abbreviation FPD), colored filter (color filter), touch panel (touch panel), Organic Light Emitting Diode (OLED), Electronic Paper (E-paper), MEMS (micro electro mechanical system) (Micro ElectroMechanical System, abbreviation MEMS), unicircuit (integrated circuit is called for short IC) or encapsulation (package).
In another embodiment of the present invention, provide the method for etching metal, having comprised: formed metal level on substrate; Form patterned protective layer on metal level; And use metal etch fluid composition etch metal layers of the present invention, wherein, the example of patterned protective layer comprises photoresistance.
According to engraving method of the present invention, the example of metal level comprises the multilayer alloy of copper, copper alloy, molybdenum, molybdenum alloy, copper alloy/molybdenum alloy and the multiple layer metal of copper/molybdenum.Moreover the example of substrate used in the present invention comprises glass substrate, silicon wafer substrate, polyimide substrate or Resins, epoxy copper clad laminate.
Description of drawings
Fig. 1 shows with behind the scanning electron microscope analysis, still has molybdenum to residue on the substrate through the multiple layer metal of overetched copper/molybdenum;
Fig. 2 shows with behind the scanning electron microscope analysis, through the phenomenon of the multiple layer metal generation molybdenum layer undercutting of overetched copper/molybdenum;
Fig. 3 shows that use metal etch fluid composition of the present invention carries out etched schema;
Fig. 4 shows the synoptic diagram of the board structure of the multiple layer metal that contains copper metal layer and molybdenum layer;
Fig. 5 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 2 the one-sided critical dimension loss of the etched multiple layer metal that contains copper metal layer and molybdenum layer less than 1 micron (μ m), and the oblique angle is about 30 °;
Fig. 6 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 2 the etched multiple layer metal that contains copper metal layer and molybdenum layer there is no molybdenum and residue on the substrate;
Fig. 7 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 7 the one-sided critical dimension loss of the etched multiple layer metal that contains copper metal layer and molybdenum layer less than 1 micron, and the oblique angle is about 53 °;
Fig. 8 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 7 the etched multiple layer metal that contains copper metal layer and molybdenum layer there is no molybdenum and residue on the substrate;
Fig. 9 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 11 the one-sided critical dimension loss of the etched multiple layer metal that contains copper metal layer and molybdenum layer less than 1 micron, and the oblique angle is about 60 °;
Figure 10 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 11 the etched multiple layer metal that contains copper metal layer and molybdenum layer there is no molybdenum and residue on the substrate;
Figure 11 shows the synoptic diagram of the board structure of the molybdenum that contains individual layer;
Figure 12 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 3 the one-sided critical dimension loss of molybdenum of etched individual layer less than 0.5 micron, and the oblique angle is about 45 °;
Figure 13 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 3 the molybdenum of etched individual layer there is no molybdenum and residue on the substrate;
Figure 14 shows the synoptic diagram of the board structure of the multilayer alloy that contains molybdenum niobium alloy and copper-magnesium alloy;
Figure 15 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 7 the one-sided critical dimension loss of the etched multilayer alloy that contains molybdenum niobium alloy and copper-magnesium alloy less than 1 micron, and the oblique angle is about 58 °; And
Figure 16 shows with behind the scanning electron microscope analysis, through the metal etch fluid composition of embodiments of the invention 7 the etched multilayer alloy that contains molybdenum niobium alloy and copper-magnesium alloy there is no the molybdenum niobium alloy and residue on the substrate.
Embodiment
Below be by particular specific embodiment explanation the specific embodiment of the present invention, the general technical staff of the technical field of the invention can understand other advantages of the present invention and effect by the content that this specification sheets disclosed, so the present invention is not limited to the embodiment in the following example.
Embodiment 1 to 20: the preparation of etchant and use
Shown in the step 110 of Fig. 3, preparation contains the etchant of the weight percent concentration that the composition shown in the table 1 and table 2 put down in writing, and wherein, employed aqueous medium is a deionized water.Subsequently, shown in the step 120 of Fig. 3, the temperature with etchant in Water Tank with Temp.-controlled is adjusted to default 30 ℃.
Then, use known in the technical field of the invention vapour deposition process, as shown in Figure 4, on glass substrate 20, form the multiple layer metal 30 contain molybdenum layer 31 and copper metal layer 32 in regular turn, wherein, the thickness of formed multiple layer metal 30 be 2150 to
And wherein, the thickness of molybdenum layer 31 be 150 to
And the thickness of copper metal layer 32 be 2000 to
Or as shown in figure 11, on glass substrate 20, form the molybdenum 50 of individual layer respectively, wherein, the thickness of the molybdenum 50 of formed individual layer be 1000 to
Or as shown in figure 14, on glass substrate 20, form the multilayer alloy 60 contain molybdenum niobium alloy (Mo-Nb alloy) 61 and copper-magnesium alloy (Cu-Mg alloy) 62 in regular turn, wherein, the thickness of formed molybdenum niobium alloy 61 be 150 to
And the thickness of copper-magnesium alloy 62 be 2000 to
Must benly be, the thickness of each metal level/alloy layer only be exemplary explanation at this, and the general technical staff of the technical field of the invention can do suitable adjustment according to actual demand, not as limit.
Then, on the copper-magnesium alloy 62 of the molybdenum 50 of the copper metal layer 32 of multiple layer metal 30, individual layer or multilayer alloy 60, form patterned protective layer 40 respectively.Then, shown in the step 130 of Fig. 3, use the aforementioned metal etch fluid composition of finishing through preparation, metal level or alloy layer are carried out metal etch in the mode of soaking (dip) or sprinkling (spray).For example, with embodiment 1 to 20 prepared arbitrary etchant multiple layer metal shown in Figure 4 30 is carried out etching, its etching period is about 120 seconds; Or the molybdenum 50 of individual layer shown in Figure 11 is carried out etching with the prepared etchant of embodiment 3, its etching period is about 130 seconds; Or multilayer alloy shown in Figure 14 60 is carried out etching with embodiment 7 prepared etchants, its etching period is about 110 seconds.Being understandable that, only is exemplary explanation in this listed etching period, can be because of the kind and the thickness of metal level, and user's specific demand and do suitable adjustment, not as limit.
Subsequently, shown in the step 140 and step 150 of Fig. 3, use film thickness measuring instrument to measure the rate of etch of metal etch fluid composition respectively to metal level, and after using scanning electron microscope analysis to handle through the metal etch fluid composition, the situation of critical dimension loss, oblique angle, metal level undercutting and metal residual.
By scanning electronic microscope the multiple layer metal 30 after handling through the prepared etchants of embodiment 2,7 and 11, the molybdenum 50 and the multilayer alloy 60 after embodiment 7 prepared etchants are handled of individual layer after embodiment 3 prepared etchants are handled are analyzed.The result respectively shown in Fig. 6,8,10,13 and 16, use metal etch fluid composition of the present invention to handle after, the situation of metal residual does not take place.
And by the result shown in Fig. 5,7,9,12 and 15 as can be known, the one-sided critical dimension loss of the multiple layer metal 30 after the etching, the molybdenum 50 of individual layer and multilayer alloy 60 is slight, and the bevel angle is between 25 ° to 60 °, and molybdenum layer 31, the molybdenum 50 of individual layer or the situation that undercutting does not all take place molybdenum niobium alloy 61.For example, Fig. 5 show through the metal etch fluid composition of embodiments of the invention 2 the one-sided critical dimension loss of the etched multiple layer metal 30 that contains copper metal layer and molybdenum layer less than 1 micron (μ m), and the oblique angle is about 30 °; Fig. 7 show through the metal etch fluid composition of embodiments of the invention 7 the one-sided critical dimension loss of the etched multiple layer metal 30 that contains copper metal layer and molybdenum layer less than 1 micron, and the oblique angle is about 53 °; Fig. 9 show through the metal etch fluid composition of embodiments of the invention 11 the one-sided critical dimension loss of the etched multiple layer metal 30 that contains copper metal layer and molybdenum layer less than 1 micron, and the oblique angle is about 60 °; Figure 12 show through the metal etch fluid composition of embodiments of the invention 3 the one-sided critical dimension loss of molybdenum 50 of etched individual layer less than 0.5 micron, and the oblique angle is about 45 °; And Figure 15 show through the metal etch fluid composition of embodiments of the invention 7 the one-sided critical dimension loss of the etched multilayer alloy 60 that contains molybdenum niobium alloy and copper-magnesium alloy less than 1 micron, and the oblique angle is about 58 °.Above-mentioned result shows the etch effect of metal etch fluid composition excellence of the present invention once more.
Moreover, put in order as following table 2 and table 3 with the rate of etch that film thickness measuring instrument is measured, wherein, the calculation formula of rate of etch is as follows:
Rate of etch=etch depth
/ etching period (minute).
By shown in table 2 and the table 3 as can be known, metal etch fluid composition of the present invention has splendid rate of etch.Therefore, under the operating unit of identical metal etch fluid composition, metal etch fluid composition of the present invention can be handled more etching metal simultaneously, thereby improves the efficient of manufacturing processed, and reduces the cost of making.
Table 1
Table 2
Table 3
Employed in the above-described embodiments oxygenant, sequestrant, nitrogenous compound, vitriol and phosphoric acid salt only are that the method for metal etch fluid composition of the present invention and etching metal thereof is described illustratively, but not are used to limit the present invention.The general technical staff of the technical field of the invention all can be under spirit of the present invention and category; the above embodiments are modified and change; in addition; more can suitably replace and adjust the kind and the concentration of oxygenant, sequestrant, nitrogenous compound, vitriol, phosphoric acid salt and aqueous medium according to its needs, so protection scope of the present invention should be put down in writing as claims.
Claims (20)
1. metal etch fluid composition, it comprises oxygenant, sequestrant, nitrogenous compound, inorganic salt and aqueous medium.
2. metal etch fluid composition according to claim 1, wherein, described oxygenant be selected from by hydrogen peroxide, ammonium persulphate, Sodium Persulfate, hydrogen persulfate sodium, Potassium Persulphate, potassium hydrogen persulfate, and composition thereof form one in the group.
3. metal etch fluid composition according to claim 1, wherein, the ratio of described oxygenant accounts for 6 to 30 weight % with total restatement of described metal etch fluid composition.
4. metal etch fluid composition according to claim 1, wherein, described sequestrant comprises amino acid.
5. metal etch fluid composition according to claim 4, wherein, described amino acid be selected from by L-Ala, L-glutamic acid, glycine, Gelucystine, l-asparagine, ethylenediamine tetraacetic acid (EDTA), edetate, imino-acetic acid, nitrilotriacetic acid, nitrilotriacetic acid derivative, and composition thereof form one in the group.
6. metal etch fluid composition according to claim 1, wherein, the ratio of described sequestrant accounts for 0.1 to 10 weight % with total restatement of described metal etch fluid composition.
7. metal etch fluid composition according to claim 1, wherein, described nitrogenous compound comprises azole compounds.
8. metal etch fluid composition according to claim 7, wherein, described azole compounds be selected from by benzotriazole, triphenyltetrazolium chloride, amino tetrazole, imidazoles, pyrazoles,
Azoles, azimido-toluene, and composition thereof form one in the group.
9. metal etch fluid composition according to claim 1, wherein, the ratio of described nitrogenous compound accounts for 0.1 to 5 weight % with total restatement of described metal etch fluid composition.
10. metal etch fluid composition according to claim 1, wherein, described inorganic salt comprise vitriol and phosphoric acid salt.
11. metal etch fluid composition according to claim 10, wherein, described vitriol be selected from by ammonium sulfate, sodium sulfate, vitriolate of tartar, sal enixum, and composition thereof form one in the group.
12. metal etch fluid composition according to claim 10, wherein, described phosphoric acid salt be selected from by Secondary ammonium phosphate, primary ammonium phosphate, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, dipotassium hydrogen phosphate, potassium primary phosphate, and composition thereof form one in the group.
13. metal etch fluid composition according to claim 1, wherein, the ratio of described inorganic salt accounts for 0.2 to 10 weight % with total restatement of described metal etch fluid composition.
14. metal etch fluid composition according to claim 10, wherein, the ratio of described vitriol and described phosphoric acid salt respectively accounts for 0.1 to 5 weight % with total restatement of described metal etch fluid composition.
15. metal etch fluid composition according to claim 1, wherein, described aqueous medium is a deionized water.
16. metal etch fluid composition according to claim 1, wherein, described metal comprises the multilayer alloy of copper, copper alloy, molybdenum, molybdenum alloy, copper alloy/molybdenum alloy or the multiple layer metal of copper/molybdenum.
17. the method for an etching metal comprises:
Form metal level on substrate;
Form patterned protective layer on this metal level; And
Use is according to each this metal level of described metal etch fluid composition etching in the claim 1 to 16.
18. method according to claim 17, wherein, described metal level comprises the multilayer alloy of copper, copper alloy, molybdenum, molybdenum alloy, copper alloy/molybdenum alloy or the multiple layer metal of copper/molybdenum.
19. method according to claim 17, wherein, described substrate comprises glass substrate, silicon wafer substrate, polyimide substrate or Resins, epoxy copper clad laminate.
20. the purposes according to each described metal etch fluid composition in the claim 1 to 16, it is used to prepare flat-panel screens, colored filter, touch panel, Organic Light Emitting Diode, Electronic Paper, MEMS (micro electro mechanical system), unicircuit or encapsulation.
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| CN102912350A (en) * | 2012-07-24 | 2013-02-06 | 友达光电股份有限公司 | etching solution and method for forming patterned multi-layer metal layer |
| CN102912350B (en) * | 2012-07-24 | 2015-07-01 | 友达光电股份有限公司 | Etching solution and method for forming patterned multi-layer metal layer |
| CN103924243A (en) * | 2013-01-11 | 2014-07-16 | 上海飞凯光电材料股份有限公司 | Etching solution composition |
| CN109136925A (en) * | 2013-10-02 | 2019-01-04 | 易安爱富科技有限公司 | Copper and molybdenum contain the etchant of film |
| CN104513983A (en) * | 2013-10-07 | 2015-04-15 | 易安爱富科技有限公司 | Etching liquid composition for copper-and-molybdenum-containing film |
| CN104513983B (en) * | 2013-10-07 | 2018-09-04 | 易安爱富科技有限公司 | Copper and molybdenum contain the etchant of film |
| CN106255777A (en) * | 2014-04-25 | 2016-12-21 | 松下知识产权经营株式会社 | Comprise the multilayer film etching solution of molybdenum and copper, etching concentrated solution and engraving method |
| WO2015162934A1 (en) * | 2014-04-25 | 2015-10-29 | パナソニックＩｐマネジメント株式会社 | Etching solution for multi-layer film containing molybdenum and copper, etching concentrate, and etching method |
| JP2015209568A (en) * | 2014-04-25 | 2015-11-24 | パナソニックＩｐマネジメント株式会社 | Etching liquid and etching concentrated liquid for multilayer film containing molybdenum and copper and etching method |
| CN106255777B (en) * | 2014-04-25 | 2018-03-20 | 松下知识产权经营株式会社 | Multilayer film etching solution comprising molybdenum and copper, etching concentrate and engraving method |
| CN105220148A (en) * | 2014-06-27 | 2016-01-06 | 东友精细化工有限公司 | Etchant and use it to manufacture the method for array substrate for liquid crystal display |
| CN107075693B (en) * | 2014-11-18 | 2019-07-12 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, using the composition engraving method and extend the composition service life method |
| WO2016080383A1 (en) * | 2014-11-18 | 2016-05-26 | 関東化學株式会社 | Etchant composition for multilayered metal film of copper and molybdenum, method of etching using said composition, and method for prolonging life of said composition |
| US10655231B2 (en) | 2014-11-18 | 2020-05-19 | Kanto Kagaku Kabushiki Kaisha | Etchant composition for multilayered metal film of copper and molybdenum, method of etching using said composition, and method for prolonging life of said composition |
| CN107075693A (en) * | 2014-11-18 | 2017-08-18 | 关东化学株式会社 | Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method |
| JP2016098386A (en) * | 2014-11-18 | 2016-05-30 | 関東化學株式会社 | Copper-molybdenum metal laminated film etching liquid composition, etching method using the composition, and method for elongating service life of composition |
| CN104480469A (en) * | 2014-12-12 | 2015-04-01 | 江阴润玛电子材料股份有限公司 | Novel TFT copper-molybdenum laminated film etching liquid composition and etching method |
| CN105887089A (en) * | 2015-02-13 | 2016-08-24 | 关东鑫林科技股份有限公司 | Etching liquid composition and etching method using the same |
| CN107316836B (en) * | 2016-04-25 | 2023-08-01 | 东友精细化工有限公司 | Etching liquid composition, array substrate for display device and manufacturing method thereof |
| CN107316836A (en) * | 2016-04-25 | 2017-11-03 | 东友精细化工有限公司 | Etchant, array substrate for display device and its manufacture method |
| CN107630219A (en) * | 2016-07-19 | 2018-01-26 | 东友精细化工有限公司 | The manufacture method of metal film etchant and array substrate for display device |
| CN107630219B (en) * | 2016-07-19 | 2020-01-24 | 东友精细化工有限公司 | Metal film etching solution composition and method for manufacturing array substrate for display device |
| KR102707568B1 (en) | 2016-12-09 | 2024-09-19 | 동우 화인켐 주식회사 | Etching solution composition, etching method using thereof and preparing method of an array substrate for display using the same |
| CN108220963A (en) * | 2016-12-09 | 2018-06-29 | 东友精细化工有限公司 | The manufacturing method of multilayer film etchant, engraving method and array substrate |
| KR20180066764A (en) * | 2016-12-09 | 2018-06-19 | 동우 화인켐 주식회사 | Etching solution composition, etching method using thereof and preparing method of an array substrate for display using the same |
| CN108203830A (en) * | 2016-12-16 | 2018-06-26 | 东进世美肯株式会社 | Metal wire etchant |
| CN108203830B (en) * | 2016-12-16 | 2023-02-28 | 东进世美肯株式会社 | Metal wire etching liquid composition |
| CN108359987A (en) * | 2017-01-26 | 2018-08-03 | 易案爱富科技有限公司 | Etch combination |
| CN108570679A (en) * | 2017-03-10 | 2018-09-25 | 东友精细化工有限公司 | The preparation method and array substrate of etchant, array substrate for display device |
| CN108950556A (en) * | 2017-05-19 | 2018-12-07 | 东友精细化工有限公司 | Etchant |
| CN108950556B (en) * | 2017-05-19 | 2020-10-02 | 东友精细化工有限公司 | Etching liquid composition |
| CN109112539A (en) * | 2017-06-23 | 2019-01-01 | 东友精细化工有限公司 | Etchant |
| CN109778190A (en) * | 2017-11-10 | 2019-05-21 | 深圳市华星光电技术有限公司 | A kind of Cu-MoTi etching solution |
| WO2020042223A1 (en) * | 2018-08-31 | 2020-03-05 | 深圳市华星光电技术有限公司 | Etching solution composition for copper/molybdenum film layer |
| CN110592604A (en) * | 2019-10-18 | 2019-12-20 | 沈阳永清环保科技有限公司 | A kind of environment-friendly bright pickling agent and preparation method thereof |
| CN114438495A (en) * | 2020-11-03 | 2022-05-06 | 宣城亨旺新材料有限公司 | Metal etching solution and metal etching method |
| CN112410789A (en) * | 2020-11-04 | 2021-02-26 | Tcl华星光电技术有限公司 | Metal wiring etching solution composition and application thereof |
| CN114457335A (en) * | 2022-02-15 | 2022-05-10 | 江西省科学院应用物理研究所 | A kind of copper-iron-carbon alloy metallographic etchant and using method thereof |
| CN114457335B (en) * | 2022-02-15 | 2023-10-27 | 江西省科学院应用物理研究所 | Metallographic etchant for copper-iron-carbon alloy and use method thereof |
| WO2023198163A1 (en) * | 2022-04-15 | 2023-10-19 | 三井化学株式会社 | Metal member and manufacturing method therefor, etching solution, and metal-resin complex and manufacturing method for metal-resin complex |
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