CN105220148B - Etchant and the method for manufacturing array substrate for liquid crystal display using it - Google Patents
Etchant and the method for manufacturing array substrate for liquid crystal display using it Download PDFInfo
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- CN105220148B CN105220148B CN201510342127.6A CN201510342127A CN105220148B CN 105220148 B CN105220148 B CN 105220148B CN 201510342127 A CN201510342127 A CN 201510342127A CN 105220148 B CN105220148 B CN 105220148B
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- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 150000003009 phosphonic acids Chemical class 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 39
- 239000010953 base metal Substances 0.000 claims description 35
- 238000005530 etching Methods 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- -1 cyano, thio group Chemical group 0.000 claims description 6
- 239000012212 insulator Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003643 water by type Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 106
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical group F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Disclosed herein is a kind of etchants, including：Metal layer agent, fluorine compounds, the compound of nitrogen atom, phosphonic acids, two alcohol and waters；A kind of and method manufacturing array substrate for liquid crystal display using the composition.
Description
Technical field
The method for manufacturing array substrate for liquid crystal display the present invention relates to metal layer etchant and using it.
Background technology
Flat-panel monitor screen with such as LCD, PDP and OLED especially TFT-LCD becomes larger, extensively again
It is considered as the single layer of copper or copper alloy composition, either using copper or the alloy or gold of copper alloy/other metals, other metals
The multilayer for being more than two layers for belonging to oxide, to reduce routing resistance and to improve the adhesiveness with dielectric silicon layer.For example, copper/molybdenum
Layer, copper/titanium layer or copper/molybdenum-titanium layer can be formed as the grid line of TFT-LCD and constitute the source/drain line of data line, and may have
Help expand display screen.Therefore, it is necessary to develop the composition with superior etch characteristic for etch comprising base copper
These metal layers.
As etch combination above-mentioned, usually using hydrogen peroxide and amino acids etching solution, hydrogen peroxide and
Phosphoric acid class etching solution, hydrogen peroxide and polyethylene glycols etching solution etc..
As an example, it includes water solubilityization that Korean patent application publication No. 10-2011-0031796, which is disclosed a kind of,
The etching solution for closing object, has：A) peroxide (H2O2), B) persulfate, C) soluble compound with amino and carboxyl and
Water.
Korean patent application publication No. 10-2012-0044630 discloses a kind of etching of the metal layer to contain copper
Liquid, including：Hydrogen peroxide, phosphoric acid, cyclic amine compound, sulfate, fluoboric acid and water.
Korean patent application publication No. 10-2012-0081764 discloses a kind of etching solution, including：A) ammonium hydroxide, B)
Hydrogen peroxide, C) fluorine compounds, D) polyalcohol and E) water.
However, in CD losses, gradient (taper), pattern lines degree, metal residue, the storage of the metal layer comprising base copper
It deposits in stability and pending number of sheets etc., etching solution above-mentioned cannot fully meet required in related field
Condition.
Patent document
Patent document 1：Korean patent application publication No. 10-2011-0031796
Patent document 2：Korean patent application publication No. 10-2012-0044630
Patent document 3：Korean patent application publication No. 10-2012-0081764
Invention content
Therefore, the present invention has been designed to solve the above problems, and it is an object of the present invention to provide a kind of etchings
Liquid composition, the etchant have excellent job security, bin stability, especially excellent etch-rate and
To the excellent processing capacity of a large amount of sheet materials；A kind of and method manufacturing array substrate for liquid crystal display using the composition.
In order to achieve the above object, one aspect of the present invention provides a kind of etchant, including：(A) metal
Layer oxidant；(B) fluorine compounds；(C) compound of nitrogen atom；(D) phosphonic acids；(E) glycol；(F) water.
Another aspect of the present invention provides a kind of method of manufacture array substrate for liquid crystal display, including：
A) the step of forming grid on substrate；
B) the step of forming gate insulator on the substrate comprising grid；
C) the step of forming semiconductor layer on gate insulator；
D) the step of forming source/drain on the semiconductor layer；With
E) the step of forming the pixel electrode being connect with source/drain；
Wherein, step a), d) or e) include forming metal layer and with etchant according to the present invention erosion
Metal layer is carved come the step of forming electrode.
The metal layer etchant of the present invention contains the hydrogen peroxide of low content, and therefore it has excellent work
Make safety, price competitiveness and the effect that can economically dispose the etching solution.
The metal layer of the present invention provides the ability of processing mass substrate and especially excellent storage with etchant
Stability.
Further, the method for array substrate for liquid crystal display being manufactured using the etchant in the present invention can
It is manufactured with excellent drive characteristic by forming the electrode with superior etch profile on array substrate for liquid crystal display
Array substrate for liquid crystal display.
Specific implementation mode
In the following, detailed description will be given of the present invention.
The present invention relates to a kind of etchants, which is characterized in that includes：(A) metal layer agent；(B) fluorination is closed
Object；(C) compound of nitrogen atom；(D) phosphonic acids；(E) glycol；(F) water.
Metal layer agent is not particularly limited, and is typically aoxidized by hydrogen peroxide, peracetic acid, metal to be selected from
At least one of the groups of compositions such as object, nitric acid, persulfate, halogen acids, halogen acid salt ingredient.
In the following, each ingredient in the etchant to constituting the present invention is illustrated, but it is of the invention and unlimited
In these ingredients.
(A) metal layer agent
In the present invention, metal layer agent (A) is the main component for metal oxide layer, is not particularly limited,
But can be selected from compositions such as hydrogen peroxide, peracetic acid, metal oxide, nitric acid, persulfate, halogen acids, halogen acid salts
It is one or more in group, more preferably can be hydrogen peroxide.
Metal oxide refers to the metal aoxidized, for example, such as Fe3+、Cu2+Deng, and it is included in solution state
It is dissociated into Fe3+、Cu2+Deng compound and analog.Persulfate includes ammonium persulfate, over cure acid alkali metal salt, permonosulphuric acid
Hydrogen potassium complex salt (oxone) etc., and halogen acid salt includes chlorate, perchlorate, bromate, Hyperbromic acid salt etc..
In the present invention, metal layer agent is the main component of copper oxide, molybdenum or titanium.Gross weight based on the composition
The content of amount, metal layer agent is 1 weight % to 25 weight %, preferably 1 weight % to 10 weight %, more preferably 1 weight
Measure % to 5 weight %.
When the amount of metal layer agent is fallen within the above-described range, the etch-rate of copper, molybdenum and titanium is prevented to be deteriorated, Ke Yishi
The etching of existing appropriate amount, and excellent etching outline can be obtained.However, if it exceeds above range, processed layer
It will not then occur to etch or over etching occurs, and pattern loss and the function as metal line therefore may occur
Loss.
The content of metal layer agent can carry out suitable control according to the type and characteristic of oxidant.
(B) fluorine compounds
The fluorine compounds for including in the etchant of the present invention are used to etch titanium-based for removing etch residues
Metal layer.
Total weight based on the composition, the contents of fluorine compounds can be 0.1 weight % to 5 weight %, preferably 0.1
Weight % to 2 weight %.
Above range is preferably as can prevent etch residues and not cause glass substrate or lower silicon layer
Etching.
However, if it exceeds above range, stain is generated in substrate due to non-uniform etching characteristic, excessively
Etch-rate can damage lower layer, and etch-rate control may become difficult during technique.
Preferably, fluorine compounds can be the compound that can be dissociated into fluorine ion or polyatom fluorine ion.
The compound that fluorine ion or polyatom fluorine ion can be dissociated into can be selected from by hydrofluoric acid, ammonium fluoride, fluorination
Sodium, potassium fluoride, sodium bifluoride and potassium bifluoride group in one or more, and more preferably ammonium fluoride and/or hydrofluoric acid.
(C) compound of nitrogen atom
The compound of the nitrogen atom contained in the etchant of the present invention usually inhibits metal layer agent especially
It is the decomposition reaction of hydrogen peroxide, and plays the role of enhancing the etch-rate of etching solution and increase pending number of sheets.
Total weight based on the composition, the content of the compound of nitrogen atom are 1 weight % to 10 weight %, more preferably
For 1 weight % to 5 weight %.Above range be preferably as it can improve the etchant etch-rate and
Pending number of sheets.
The compound of nitrogen atom known in the art can be used without limitation, and can typically use
Compound containing amino and carboxylic acid group in molecule.
Compound in the molecule containing amino and carboxylic acid group may include contain for example between carboxylic acid and amino there are one
The a-amino acid of carbon atom, and be typically：Monovalence amino acid, such as glycine, glutamic acid, glutamine, different bright ammonia
Acid, proline, tyrosine, arginine etc.；With multivalence amino acid, such as iminodiacetic acid, nitrilotriacetic acid, ethylene glycol four
Acetic acid.
The compound of nitrogen atom can be used alone or is applied in combination with two or more.
(D) phosphonic acids
The phosphonic acids for including in the etchant of the present invention is provided with hydrionic etching solution, and can be promoted
Metal layer agent etches metal, such as copper.Further, it is combined to form phosphonic acids with the metal ion of oxidation, improves water
In solubility, and thus eliminate etching after metal layer residue.
The content of total weight based on the composition, phosphonic acids is 0.01 weight % to 10 weight %, preferably 0.01 weight
Measure % to 1 weight %.When the amount of phosphonic acids meets above range, expected function can be executed, because can be to avoid by phosphonic acids
Caused by metal layer over etching and lower layer's corrosion risk, and it will not cause the etch-rate of copper metal layer due to phosphonic acids
Content is too small and the problem of decline.
In the present invention, phosphonic acids (D) can be one kind in the group being made of following chemical formula 1 and chemical formula 2
Or it is a variety of：
[chemical formula 1]
[chemical formula 2]
In chemical formula 1 to chemical formula 2 above, n is 1 to 4 integer, and
R is organic group, can be identical or different from each other, and is the alkyl, alkenyl, alkynes of C1~C20 linear chain or branched chains
Base, aryl or aralkyl；And
The alkyl, alkenyl, alkynyl, aryl or aralkyl can include select free hydroxyl, carbonyl, carboxyl, epoxy group,
One kind in the group that ether, amino, nitro, cyano, thio group, silicyl, sulfo group, phosphate radical, halogenation base ,-O- and-N- are formed
Or it is a variety of, and may include one or more functional groups, but it can be without being limited thereto.
The example for the compound that n is 1 in chemical formula 1 above is preferably the change of following chemical formula 3 to chemical formula 10
Close object.
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
The example for the compound that n is 2 in chemical formula 1 above is preferably the change of following chemical formula 11 to chemical formula 13
Close object.
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
The example for the compound that n is 3 in chemical formula 1 above is preferably the compound of following chemical formula 14.
[chemical formula 14]
The example for the compound that n is 4 in chemical formula 1 above is preferably the compound of following chemical formula 15.
[chemical formula 15]
The example of compound is preferably compound of the following chemical formula 16 to chemical formula 17 in chemical formula 2 above.
[chemical formula 16]
[chemical formula 17]
(E) glycol
The glycol for including in the etchant of the present invention, which is used to pass through, surrounds the metal ion for melting out etching solution simultaneously
And inhibit the decomposition reaction of metal layer agent by inhibiting the activity of metal ion.If reducing metal ion like this
Activity, can reliably execute processing while using etching solution, and also improve the pending sheet material for substrate
Number.
The content of total weight based on the composition, glycol is 0.1 weight % to 10 weight %, preferably 1 weight % to 5
Weight %.
If the content of glycol is less than 0.1 weight %, it may have the problem of etch uniformity reduces.Further
Ground, when it is more than 10 weight %, the shortcomings that may causing to generate a large amount of foams.
As glycol, ingredient known in the art can be used without any restrictions, particularly preferably uses polyethylene glycol.
As polyethylene glycol, there are the addition polymers of the ethylene oxide of hydroxyl or ether using end, but it preferably has extremely
A few hydroxyl.Further, molecular weight is more preferably 1000 hereinafter, so that suppression solution excess stickiness rises.
(F) water
There is no particular limitation for the water for including in the etchant of the present invention, but preferably refers to deionized water, and
And more preferably it is more than the semiconductor technology deionized water of 18M Ω/cm using resistivity value.
The composition can be made to add up to 100 weight % containing the water content of surplus.
In addition to the ingredient being previously mentioned, etchant of the invention can further contain etching conditioning agent, surface is lived
More than one in property agent, chelating agent, corrosion inhibitor and pH adjusting agent.
The ingredient for constituting the etchant of the present invention is preferably needed with semiconductor technology purity.
The etchant of the present invention can be preferred for etch copper base metal layer, molybdenum base metal layer, titanium-based metal layer
Or the multilayer being made of them.
Copper base metal layer refers to layers of copper or copper alloy layer, and molybdenum base metal layer refers to molybdenum layer or Mo alloy, and titanium-based is golden
It refers to titanium layer or titanium alloy layer to belong to layer.
Multilayer includes for example：The bilayer of molybdenum base metal layer/copper base metal layer, copper base metal layer are lower layer and molybdenum base metal
Layer is upper layer；The bilayer of copper base metal layer/molybdenum base metal layer, Mo layer is lower layer and copper base metal layer is upper layer；It is copper-based
The bilayer of metal layer/molybdenum base and titanium-based metal layer；And the multilayer more than three layers, copper base metal layer and molybdenum base metal layer layer each other
It is folded, such as molybdenum base metal layer/copper base metal layer/molybdenum base metal layer or copper base metal layer/molybdenum base metal layer/copper base metal layer.
In addition, multilayer includes for example：The bilayer of titanium-based metal layer/copper base metal layer, copper metal layer are lower layer and titanium-based
Metal layer is upper layer；The bilayer of copper base metal layer/titanium-based metal layer, titanium coating is lower layer and copper base metal layer is upper layer；
And the multilayer more than three layers, copper base metal layer and titanium-based metal layer are stacked on one another, such as titanium-based metal layer/copper base metal layer/
Titanium-based metal layer or copper base metal layer/titanium-based metal layer/copper base metal layer.
The multiple material for considering to constitute upper layer or lower layer or with the adhesiveness of layer etc., it may be determined that the interlayer of multilayer combines
Structure.
Copper, molybdenum or titanium alloy layer refer to using other different metals using copper, molybdenum or titanium as main component and according to film character
The metal layer that is produced of alloy.For example, Mo alloy refers to using molybdenum as main component and containing selected from titanium (Ti), tantalum
(Ta), the layer that one or more alloys in chromium (Cr), nickel (Ni), neodymium (Nd) and indium (In) are produced.
Specifically, etchant of the invention is preferred for etch copper base metal layer, copper base metal layer/Mo layer
Or copper base metal layer/titanium-based metal layer.However, the application of the composition is not limited to bilayer.
Further, the present invention relates to a kind of methods of manufacture array substrate for liquid crystal display, including：
A) the step of forming grid on substrate；
B) the step of forming gate insulator on the substrate comprising grid；
C) the step of forming semiconductor layer on gate insulator；
D) the step of forming source/drain on the semiconductor layer；With
E) the step of forming the pixel electrode being connect with source/drain；
Wherein, step a), d) or e) include forming metal layer and with etchant according to the present invention erosion
Metal layer is carved come the step of forming electrode.
According to comprising with superior etch profile electrode, the array substrate for liquid crystal display produced by the above method has
Excellent drive characteristic.
Array substrate for liquid crystal display can be thin film transistor (TFT) (TFT) array substrate.
Below, the present invention will be described in more detail by present embodiment.However, the following examples are for detailed
Carefully explain that the present invention, the scope of the present invention are not limited to the following examples.Within the scope of the invention, people in the art
Member can be appropriately modified the following examples.
Embodiment 1-8 and comparative example 1-3：The preparation of etchant
Etchant is prepared by mixing these ingredients with the regulation content described in following table 1.
【Table 1】
(unit：Weight %)
Experimental example 1：The evaluation of etchant
(1) etching of Cu/Mo-Ti bilayers
It is etched Cu/Mo-Ti bilayers using the etchant of embodiment 1 to 8 and comparative example 1 to 3.It is being lost
When quarter, the etchant for being about 30 DEG C with temperature etches 100 seconds.With the naked eye measure EPD (End Point Detection
(end-point detection), metal etch timing) obtain the etch-rate according to the time.As a result it is shown in following table 2.
Experimental example 2：The evaluation of pending number of sheets
Reference test (with reference to etching) is carried out by using the etchant of embodiment 1 to 8 and comparative example 1 to 3, and
And the copper powder of 4000ppm is added to the etching solution of reference test and is made it completely dissolved.Hereafter, it is etched again to be referred to
Experiment, and the suppression ratio of etch-rate is evaluated, and also result is shown in following table 2.
<Evaluation criterion>
○：Excellent (suppression ratio of etch-rate is less than 10%)
△：Well (suppression ratio of etch-rate is 10% to 20%)
×：Bad (suppression ratio of etch-rate is more than 20%)
【Table 2】
Claims (5)
1. a kind of etchant, based on the total weight of the composition, including：The peroxidating of 1 weight % to 10 weight %
Hydrogen, the compound to the nitrogen atom of 10 weight % of fluorine compounds, 1 weight % of 0.1 weight % to 5 weight %, 0.01 weight
The phosphonic acids of % to 10 weight %, the water of 0.1 weight % to the glycol and surplus of 10 weight % are measured,
Wherein, the compound of the nitrogen atom is glycine, and
Wherein, the glycol is triethylene glycol.
2. etchant according to claim 1, wherein phosphonic acids is selected from by following chemical formula 1 and chemical formula 2
It is one or more in the group of composition：
[chemical formula 1]
[chemical formula 2]
Wherein, in the chemical formula 1 and the chemical formula 2,
N is 1 to 4 integer；And
R is organic group, can be identical or different from each other, and is alkyl, alkenyl, alkynyl, the virtue of C1~C20 linear chain or branched chains
Base or aralkyl；
Wherein, the alkyl, alkenyl, alkynyl, aryl or aralkyl can include select free hydroxyl, carbonyl, carboxyl, epoxy group,
One kind in the group that ether, amino, nitro, cyano, thio group, silicyl, sulfo group, phosphate radical, halogenation base ,-O- and-N- are formed
Or it is a variety of.
3. etchant according to claim 1, wherein the etchant is for etching copper base metal
Layer, molybdenum base metal layer, titanium-based metal layer or the multilayer being made of them.
4. etchant according to claim 3, wherein the multilayer is copper base metal layer/molybdenum base metal layer, copper
Base metal layer/titanium-based metal layer or copper base metal layer/molybdenum-titanium-based metal layer.
5. a kind of method of manufacture array substrate for liquid crystal display, including：
A) the step of forming grid on substrate；
B) the step of forming gate insulator on the substrate comprising grid；
C) the step of forming semiconductor layer on gate insulator；
D) the step of forming source/drain on the semiconductor layer；With
E) the step of forming the pixel electrode being connect with source/drain；
Wherein, the step a), d) or e) include forming metal layer and with erosion according to any one of claim 1 to 4
It carves liquid composition and etches the metal layer come the step of forming electrode.
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| KR1020140079816A KR102209423B1 (en) | 2014-06-27 | 2014-06-27 | Etching solution composition for metal layer and manufacturing method of an array substrate for liquid crystal display using the same |
| KR10-2014-0079816 | 2014-06-27 |
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| KR102415960B1 (en) * | 2016-02-05 | 2022-07-01 | 동우 화인켐 주식회사 | Etching solution composition for a silicon nitride layer and method for manufacturing a semiconductor device and a TFT array substrate using the same |
| KR101972207B1 (en) * | 2016-12-09 | 2019-04-26 | 경북대학교 산학협력단 | Smart screw |
| CN106637209A (en) * | 2016-12-29 | 2017-05-10 | 深圳市华星光电技术有限公司 | Etching solution composition and metal film etching method using same |
| KR102379072B1 (en) * | 2017-03-28 | 2022-03-28 | 동우 화인켐 주식회사 | Etchant composition |
| KR102379074B1 (en) * | 2017-03-28 | 2022-03-25 | 동우 화인켐 주식회사 | Etchant composition |
| KR102433304B1 (en) * | 2017-08-11 | 2022-08-16 | 동우 화인켐 주식회사 | Etchant composition for etching metal layer and method of forming conductive pattern using the same |
| US11629315B2 (en) | 2018-04-27 | 2023-04-18 | Mitsubishi Gas Chemical Company, Inc. | Aqueous composition and cleaning method using same |
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