CN110147008A - The method for manufacturing array substrate for liquid crystal display - Google Patents
The method for manufacturing array substrate for liquid crystal display Download PDFInfo
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- CN110147008A CN110147008A CN201910330615.3A CN201910330615A CN110147008A CN 110147008 A CN110147008 A CN 110147008A CN 201910330615 A CN201910330615 A CN 201910330615A CN 110147008 A CN110147008 A CN 110147008A
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- etching
- agent composite
- etching agent
- moti
- copper
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000005530 etching Methods 0.000 claims abstract description 172
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 111
- 239000002131 composite material Substances 0.000 claims abstract description 104
- 239000000463 material Substances 0.000 claims abstract description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 4
- 229910016027 MoTi Inorganic materials 0.000 claims description 42
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 150000003851 azoles Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 6
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 6
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 238000003682 fluorination reaction Methods 0.000 claims 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 235000003270 potassium fluoride Nutrition 0.000 claims 1
- 239000011698 potassium fluoride Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 235000013024 sodium fluoride Nutrition 0.000 claims 1
- 239000011775 sodium fluoride Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 111
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 91
- 229910052802 copper Inorganic materials 0.000 abstract description 80
- 239000010953 base metal Substances 0.000 abstract description 55
- 239000010408 film Substances 0.000 description 102
- 230000000052 comparative effect Effects 0.000 description 30
- 229910001182 Mo alloy Inorganic materials 0.000 description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 17
- 239000011733 molybdenum Substances 0.000 description 17
- 229910052750 molybdenum Inorganic materials 0.000 description 16
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- -1 IDA) class compound Chemical class 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 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 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 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
- 150000004767 nitrides Chemical class 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
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 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
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- G02F1/133351—Manufacturing of individual cells out of a plurality of cells, e.g. by dicing
-
- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Power Engineering (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Computer Hardware Design (AREA)
- Optics & Photonics (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
The present invention relates to a kind of methods for manufacturing array substrate for liquid crystal display, comprising the following steps: gate electrode a) is formed on substrate；B) gate insulation layer is formed on the substrate for including gate electrode；C) semiconductor layer (n is formed on gate insulation layer+A-Si:H and a-Si:H)；D) source/drain electrode is formed on the semiconductor layer；And e) form the pixel electrode connecting with drain electrode, wherein, step a) d) includes the steps that forming each electrode by etching copper base metal film, moreover, the etching agent composite used in etching copper base metal film includes the citric acid as the modifier of the quantity for increasing processed sheet material.
Description
It is on June 4th, 2014 that the application, which is the applying date, application No. is 201410246018.X, entitled " manufacture liquid
The divisional application of the application for a patent for invention of the method for crystal display array substrate ".
Cross reference to related applications
South Korea patent application KR 10-2013-0077822 that is submitted this application claims on July 3rd, 2013, July 3 in 2013
The day South Korea patent application KR 10-2013-0077823 submitted the and South Korea patent application KR 10- submitted on July 3rd, 2013
The equity of 2013-0077824, to be incorporated into the application by being cited in full text.
Technical field
The present invention relates to a kind of methods for manufacturing array substrate for liquid crystal display.
Background technique
A kind of for driving the typical electronic circuit of semiconductor devices and flat-panel monitor is thin film transistor (TFT) (TFT).
In general, the manufacturing process of TFT on substrate the following steps are included: form as the gold for gate electrode line and the material of data line
Belong to film；Photoresist is formed on the selective area of the metal film；And use the photoresist as mask
To etch the metal film.
In general, having by the copper film or tin-copper alloy film containing conductive high and low resistance copper and with copper film or tin-copper alloy film
There is the metal oxide film of high interfacial adhesion to be used as the material for gate electrode line and data line.Recently, in order to improve the property of TFT
Can, it is used for the metal oxide film containing indium oxide, zinc oxide or they and the mixture of gallium oxide.
Meanwhile Korean Patent Application Publication 10-2006-0064881 disclose it is a kind of for copper-molybdenum film etching solution,
The etching solution includes hydrogen peroxide, organic acid, azole compounds, fluorine compounds and the iminodiacetic acid as chelate
(IDA) class compound.When with the etching solution etch copper-molybdenum film, belt profile have it is excellent linear, and after the etching not
There are the residues of molybdenum alloy, there is problems in that: after the etching solution is stored 30 days, copper-molybdenum film sheet material for thus etching
Quantity reduce significantly, so its heat release stability and its storage stability are extremely deteriorated, and it is to such as MoTi/
The etching performance of three layers of copper base metal film of Cu/MoTi film etc. is extremely deteriorated.
[existing technical literature]
[patent document]
(patent document 1) Korean Patent Application Publication 10-2006-0064881
Summary of the invention
Therefore, to solve the above-mentioned problems, the present invention has been made, it is an object of the present invention to provide a kind of manufacture liquid crystal
The method of display array substrate, the array substrate are made of copper base metal film.
It is a further object of the present invention to provide a kind of etching agent composite for copper base metal film, the etchant combinations
Object provides excellent etching outline and improves storage stability, and the etching agent composite can be suitable for including molybdenum base
The three-layered metal film of metal film and copper base metal film.
In order to achieve the above object, one aspect of the present invention provides a kind of side for manufacturing array substrate for liquid crystal display
Method the described method comprises the following steps: gate electrode a) is formed on substrate；B) grid are formed on the substrate for including the gate electrode
Insulating layer；C) semiconductor layer (n is formed on the gate insulation layer+A-Si:H and a-Si:H)；D) shape on the semiconductor layer
At source/drain electrode；And e) form the pixel electrode that connect with the drain electrode, wherein the step a) d) includes
By etching copper base metal film come the step of forming each electrode, moreover, being etched used in the copper base metal film etching
Agent composition includes the citric acid as the modifier of the quantity for increasing processed sheet material.
Another aspect of the present invention provides a kind of etching agent composite for copper base metal film, the etching agent composite
Citric acid including the modifier as the quantity for increasing processed sheet material.
Specific embodiment
The present invention relates to a kind of etching agent composite for copper base metal film, the etching agent composite includes as use
In the citric acid of the modifier for the quantity for increasing processed sheet material.
In the present invention, copper base metal film (it is a kind of film of cupric) includes: the monofilm of copper or copper alloy；And packet
Include selected from least one of copper film and tin-copper alloy film and in molybdenum film, molybdenum alloy film, titanium film and titanium alloy film at least
A kind of multilayer film.
Here, alloy film may include nitride film or oxidation film.
The example of multilayer film may include duplicature and trilamellar membrane, and such as copper/molybdenum film, copper/molybdenum alloy film, copper alloy/molybdenum close
Golden film, copper/titanium film etc..Here, copper/molybdenum film includes molybdenum layer and the layers of copper that is formed on the molybdenum layer；Copper/molybdenum alloy film includes that molybdenum closes
Layer gold and the layers of copper being formed on the Mo alloy；Copper alloy/molybdenum alloy film includes Mo alloy and is formed in the Mo alloy
On copper alloy layer；And copper/titanium film includes titanium layer and the layers of copper that is formed on the titanium layer.
In addition, Mo alloy is by molybdenum and selected from by titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) and indium (In)
Layer made of the alloy of at least one of group of composition metal.
In addition, etching agent composite of the invention can be preferably applied in including copper or tin-copper alloy film and molybdenum or molybdenum alloy
The multilayer film of film.
Specifically, copper base metal film can be including Mo alloy, the layers of copper being formed on the Mo alloy and be formed in
The trilamellar membrane of Mo alloy in the layers of copper.Preferably, copper base metal film can be including molybdenum base metal film and copper base metal film
Trilamellar membrane.The specific example of trilamellar membrane may include molybdenum/copper/molybdenum film, molybdenum alloy/copper/molybdenum alloy film, molybdenum/copper alloy/molybdenum film,
Molybdenum alloy/copper alloy/molybdenum alloy film etc..
1, etching agent composite
The citric acid for including in etching agent composite of the invention is a kind of for increasing changing for the quantity of processed sheet material
Into agent, and the quantity of the processed sheet material for increasing copper base metal film.As the normal of the quantity for increasing processed sheet material
Modifier is advised, iminodiacetic acid (IDA) class compound is during etch process for increasing being processed for copper base metal film
The essential component of the quantity of sheet material；But because it has selfdecomposition property, it is processed quantity the pushing away with the time of sheet material
It moves and reduces.Further, there are many examples for etching the organic acid of copper base metal film, but not every organic acid is all
Help to increase the quantity of processed sheet material, and only citric acid plays during etch process and increases being processed for copper base metal film
The effect of the quantity of sheet material.Total weight based on etching agent composite, the amount of contained citric acid are 1.0~10.0wt%,
It is preferred that 3.0~7.0wt%.When the amount of citric acid is less than 1.0wt%, the etch-rate of copper base metal film is reduced, it is thus possible to
There are etch residues.When its amount is greater than 10.0wt%, copper base metal film may be etched excessively.
Etching agent composite further includes being selected to be made of fluorochemical, azole compounds and EPE polyol EPE
One of group or a variety of.Etching agent composite can also include the water of surplus.
Hydrogen peroxide (the H for including in etching agent composite2O2) it is main component for etching copper base metal film, it plays
Increase the active effect of fluorochemical.
Total weight based on etching agent composite, the hydrogen peroxide (H for including2O2) amount be 15.0~25.0wt%, preferably
18.0~23.0wt%.When the amount of hydrogen peroxide is less than 15.0wt%, copper base metal film is not etched or copper base metal film
Etch-rate decline.When its amount is greater than 25.0wt%, the etch-rate of copper base metal film increases completely, and therefore, it is difficult to control this
Technique.
The fluorochemical for including in etching agent composite of the invention is dissociated in water to generate the chemical combination of fluorine ion
Object.Fluorochemical is the main component for etching copper base metal film, plays removal and is necessarily led to by molybdenum film or molybdenum alloy film
Remaining dregs effect.
Total weight based on etching agent composite, the amount for the fluorochemical for including are 0.01~1.0wt%, preferably 0.05
~0.20wt%.When the amount of fluorochemical is less than 0.01wt%, the etch-rate decline of molybdenum film or molybdenum alloy film, therefore can
There can be etch residue.When its amount is greater than 1.0wt%, there are problems that the etch-rate of glass substrate increases.
As long as fluorochemical can be dissociated into fluorine ion or polynary fluorine ion, it can be used in related fields
Without limiting.However, it is preferred that fluorochemical is selected from by ammonium fluoride (NH4F), sodium fluoride (NaF), potassium fluoride
(KF), ammonium acid fluoride (NH4FHF), at least one in the group of sodium bifluoride (NaFHF) and potassium hydrogen fluoride (KFHF) composition
Kind.
The azole compounds for including in etching agent composite of the invention play control copper base metal film etch-rate and
Reduce the effect of the CD loss of pattern, therefore the nargin (margin) during increasing.
Total weight based on etching agent composite, the amount for the azole compounds for including are 0.1~5.0wt%, preferably 0.3~
1.0wt%.When the amount of azole compounds is less than 0.1wt%, the etch-rate of copper base metal film is quicklyd increase, therefore CD loses
May excessively it increase.When its amount is greater than 5.0wt%, the etch-rate excessive descent of copper base metal film, it is thus possible to there is erosion
Carve residue.Preferably, azole compounds are selected from by 5- aminotriazole(ATA), 3- amino-1,2,4-triazole, 4- amino -4H-1 2,
4- triazole, Aminotetrazole, benzotriazole, tolyl-triazole, pyrazoles, pyrroles, imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- third
At least one of base imidazoles, 2- aminooimidazole, 4-methylimidazole, 4- ethyl imidazol(e) and group of 4- propyl imidazole composition.
The water for including in etching agent composite of the invention is not specially limited, it is preferable that can be deionized water.
It is highly preferred that water can be the deionized water that resistivity (going the degree of deionization in water) is 18M Ω cm or more.Include surplus
Water so that the total weight of etching agent composite is 100wt%.
Meanwhile the EPE polyol EPE in etching agent composite of the invention including is risen by reducing surface tension
To the effect for improving etch uniformity.In addition, passing through the copper ion for including in the etchant after surrounding etching to inhibit
The activity of copper ion, EPE polyol EPE play the role of inhibiting the decomposition reaction of hydrogen peroxide.Similarly, when copper from
When the activity of son reduces, advance with can making process stabilizing during using etchant.Total weight based on etching agent composite,
The amount for the EPE polyol EPE for including is 0.001~5.0wt%, preferably 0.1 to 3.0wt%.When polyol type surface
When the amount of activating agent is less than 0.001wt%, have the following problems: etch uniformity is deteriorated, and the decomposition of hydrogen peroxide accelerates,
Therefore exothermic phenomenon occurs when handling copper with amount more than predetermined amount.When its amount is greater than 5.0wt%, exists and generate a large amount of gas
The problem of bubble.
EPE polyol EPE can be selected from the group being made of glycerol, triethylene glycol and polyethylene glycol.Preferably, more
First alcohol type surfactant can be triethylene glycol.
Each component used in the present invention can be prepared by known method.Preferably, etchant group of the invention
Closing object has the purity for being sufficient to semiconductor technology.
2, the method for array substrate for liquid crystal display is manufactured
The method of manufacture array substrate for liquid crystal display according to the present invention on substrate the following steps are included: a) form
Gate electrode；B) gate insulation layer is formed on the substrate for including the gate electrode；C) semiconductor layer is formed on the gate insulation layer
(n+A-Si:H and a-Si:H)；D) source/drain electrode is formed on the semiconductor layer；And it e) is formed and the drain electrode
The pixel electrode of connection, wherein step a) or d) comprising steps of on substrate formed copper base metal film, then use etchant
Composition etches copper base metal film to form gate electrode line or source electrode and drain electrode.Array substrate for liquid crystal display can be with
It is tft array substrate.
Hereinafter, the present invention is described in more detail referring to the following examples and comparative example.However, these realities
It applies example and comparative example is suggested to illustrate the present invention, and the scope of the invention is not limited to this.
(preparation of etching agent composite and its Performance Evaluation 1)
Embodiment 1-1 to 1-4 and comparative example 1-1 to 1-4: the preparation of etching agent composite
Going out as given in following table 1, the etching of the embodiment 1-1 to 1-4 and comparative example 1-1 to 1-4 of 180kg are prepared
Agent composition.
[table 1]
(unit: wt%)
※ fluorochemical: ammonium acid fluoride (NH4F·HF)
※ azole compounds: 3- amino -1,2,4- triazole
※ IDA: iminodiacetic acid
※ NTA: nitrilotriacetic acid
Test case: the Performance Evaluation of etching agent composite
<Cu/MoTi etching>
MoTi is deposited on glass substrate (100mm × 100mm), by copper layer deposition on MoTi, then passes through photoetching
Technique forms the photoresist with predetermined pattern on the glass substrate.Hereafter, using embodiment 1-1 to 1-4 and compare
Each etching agent composite of example 1-1 to 1-4 carries out the etch process of Cu/MoTi.
It uses injection-type Etaching device (model name: ETCHER (TFT) (etching machine (TFT)) is manufactured by SEMES company)
To be etched technique.In the etch process, the temperature of etching agent composite is arranged to about 30 DEG C, and etching period is arranged to
100~300 seconds.It is etched during etch process using SEM (model name: S-4700 is manufactured by Hitachi, Ltd) to check
Copper base metal film profile, and show its result in following table 2.
<assessment for being processed the quantity of sheet material>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 1-1 to 1-4 and comparative example 1-1 to 1-4
Part sample.Then, copper powder is added in each etching agent composite (using 5g as increment) from 10g to 80g, then in pre- timing
The temperature change of the interior each etching agent composite of observation.When not occurring even if exothermic reaction after the predetermined time passes by
The maximum concentration of measured etching agent composite is defined as the quantity of the processed sheet material of etching agent composite.
Its assessment result is shown in following table 2.
<storage 30 days after, be processed sheet material quantity assessment>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 1-1 to 1-4 and comparative example 1-1 to 1-4
Part sample.Then, each provided etching agent composite is stored 30 days at room temperature, (using 5g as increment) from 10g to 80g
Copper powder is added to wherein, then observes the temperature change of each etching agent composite in the given time.Even if in pre- timing
Between pass by after exothermic reaction when also not occurring the maximum concentration of measured etching agent composite be defined as storage 30 days
The quantity of the processed sheet material of etching agent composite afterwards.Assessment result is shown in following table 2.
[table 2]
| Catalogue | Etching outline | Etching is linear | It is processed the quantity of sheet material | After storage 30 days, it is processed the quantity of sheet material |
| Layer | Cu/MoTi | Cu/MoTi | Cu/MoTi | Cu/MoTi |
| Embodiment 1-1 | O | O | Cu 4000ppm | Cu 4000ppm |
| Embodiment 1-2 | O | O | Cu 4000ppm | Cu 4000ppm |
| Embodiment 1-3 | O | O | Cu 3000ppm | Cu 3000ppm |
| Embodiment 1-4 | O | O | Cu 6000ppm | Cu 6000ppm |
| Comparative example 1-1 | O | O | Cu 200ppm | Cu 200ppm |
| Comparative example 1-2 | O | O | Cu 2000pm | Cu 500ppm |
| Comparative example 1-3 | O | O | Cu 4000ppm | Cu 2500ppm |
| Comparative example 1-4 | 0 | 0 | Cu 5000ppm | Cu 1000ppm |
<evaluation criteria of etching outline>
Zero: cone angle is 35 ° less than 60 °
△: cone angle is 30 ° less than 35 ° or 60 ° to 65 °
X: cone angle is 30 ° or less or greater than 65 °
It does not etch: not being etched
<etching linear evaluation criteria>
Zero: pattern is formed with straight line
△: being that 20% curve below forms pattern with ratio
X: the curve with ratio greater than 20% forms pattern
It does not etch: not being etched
Referring to table 2 above, it can be determined that, all etching agent composites of embodiment 1-1 to 1-4 are all shown
Good etching performance.Furthermore it is possible to it is well established that when etching copper base metal film, the etchant group of embodiment 1-1 to 1-4
Close the quantity that object increases the processed sheet material of copper base metal film；Moreover, after they are stored for 30 days, over time
Selfdecomposition there is no.
In contrast, it can be determined that, in the etching of copper base metal film, although containing glycolic as organic acid
The etching agent composite of comparative example 1-1 show good basic etching performance；But it is helpless to increase copper base metal film
Processed sheet material quantity.
In contrast, it can be determined that, in the etching of copper base metal film, although containing glycolic as organic acid
The etching agent composite of comparative example 1-2 show good basic etching performance；But after it is stored for 30 days, by
It is remarkably decreased in the quantity of the selfdecomposition of glycolic over time, the processed sheet material of copper base metal film.
Although furthermore it is possible to it is well established that contain IDA during etching copper base metal film and be used as increasing quilt
The etching agent composite of the comparative example 1-3 and 1-4 of the modifier of the quantity of working sheet show good basic etching
Performance and the quantity for increasing processed sheet material；But after they are stored for 30 days, due to IDA dividing certainly over time
The quantity of solution, the processed sheet material of copper base metal film significantly reduces.
(preparation of etching agent composite and its Performance Evaluation 2)
Embodiment 2-1 to 2-4 and comparative example 2-1 to 2-3: the preparation of etching agent composite
Going out as given in following table 3, the etching of the embodiment 2-1 to 2-4 and comparative example 2-1 to 2-3 of 180kg are prepared
Agent composition.
[table 3]
(unit: wt%)
※ fluorochemical: ammonium acid fluoride (NH4F·HF)
※ azole compounds: 3- amino -1,2,4- triazole
※ TEG: triethylene glycol
※ IDA: iminodiacetic acid
Test case: the Performance Evaluation of etching agent composite
<Cu/MoTi etching>
MoTi is deposited on glass substrate (100mm × 100mm), by copper layer deposition on MoTi, then passes through photoetching
Technique forms the photoresist with predetermined pattern on the glass substrate.Hereafter, using embodiment 2-1 to 2-4 and compare
Each etching agent composite of example 2-1 to 2-3 carries out the etch process of Cu/MoTi.
It uses injection-type Etaching device (model name: ETCHER (TFT) (etching machine (TFT)) is manufactured by SEMES company)
To be etched technique.In the etch process, the temperature of etching agent composite is arranged to about 30 DEG C, and etching period is arranged to
100~300 seconds.It is etched during etch process using SEM (model name: S-4700 is manufactured by Hitachi, Ltd) to check
Copper base metal film profile, and show its result in following table 4.
<the quantity assessment for being processed sheet material>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 2-1 to 2-4 and comparative example 2-1 to 2-3
Part sample.Then, copper powder is added in each etching agent composite (using 5g as increment) from 10g to 80g, then in pre- timing
The temperature change of the interior each etching agent composite of observation.When not occurring even if exothermic reaction after the predetermined time passes by
The maximum concentration of measured etching agent composite is defined as the quantity of the processed sheet material of etching agent composite.
Its assessment result is shown in following table 4.
<storage 30 days after, be processed sheet material quantity assessment>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 2-1 to 2-4 and comparative example 2-1 to 2-3
Part sample.Then, each provided etching agent composite is stored 30 days at room temperature, (using 5g as increment) from 10g to 80g
Copper powder is added to wherein, then observes the temperature change of each etching agent composite in the given time.Even if in pre- timing
Between pass by after exothermic reaction when also not occurring the maximum concentration of measured etching agent composite be defined as storage 30 days
The quantity of the processed sheet material of etching agent composite afterwards.
Its assessment result is shown in following table 4.
<assessment of storage stability>
Each etching agent composite of embodiment 2-1 to 2-4 and comparative example 2-1 to 2-3 are prepared for the amount of 10L.Then,
Each prepared etching agent composite is stored 30 days at room temperature, the copper powder of 50g is added to wherein, then observation is each
The temperature change of etching agent composite.
Its assessment result is shown in following table 4.
[table 4]
<evaluation criteria of etching outline>
Zero: cone angle is 35 ° less than 60 °
△: cone angle is 30 ° less than 35 ° or 60 ° to 65 °
X: cone angle is 30 ° or less or greater than 65 °
It does not etch: not being etched
<etching linear evaluation criteria>
Zero: pattern is formed with straight line
△: being that 20% curve below forms pattern with ratio
X: the curve with ratio greater than 20% forms pattern
It does not etch: not being etched
Referring to table 4 above, it can be determined that, all etching agent composites of embodiment 2-1 to 2-4 are all shown
Good etching performance.Furthermore it is possible to be processed it is well established that be compared to each other the etching agent composite of embodiment 2-1 to 2-4
The quantity of sheet material increases with the increase of the amount of EPE polyol EPE.Specifically, it can be determined that, in etch copper
When Base Metal film, the etching agent composite of the embodiment 2-1 to 2-4 containing EPE polyol EPE increases copper base metal
The quantity of the processed sheet material of film；Moreover, after they are stored for 30 days, selfdecomposition over time there is no.
In contrast, it can be determined that, although during etching copper base metal film, containing glycolic rather than lemon
The etching agent composite of the comparative example 1-1 of lemon acid shows good basic etching performance；But it is helpless to increase copper-based gold
Belong to the quantity of the processed sheet material of film.
Although furthermore it is possible to it is well established that contain ratio of the IDA as the modifier of the quantity for increasing processed sheet material
Etching agent composite compared with example 2-1 shows good basic etching performance, but after it is stored for 30 days, due to
The quantity of the selfdecomposition of IDA over time, the processed sheet material of copper base metal film substantially reduces.
Furthermore it is possible to it is well established that the etching agent composite of etching agent composite and embodiment 2-1 to comparative example 2-3
It is compared, because the etching agent composite of comparative example 2-3 does not contain EPE polyol EPE, it is for increasing quilt
The quantity of working sheet is invalid.Therefore, it can be determined that, EPE polyol EPE effectively increases copper (Cu)
The quantity of the processed sheet material of Base Metal film.
Furthermore it is possible to it is well established that in the case where the etching agent composite of embodiment 2-1 to 2-4, even if working as their quilts
Storage 30 days, when being then added to the copper of 5000ppm (Cu) wherein, their temperature is maintained at 28~31 DEG C of initial temperature,
Therefore their heat release stability is very excellent.
In contrast, it can be determined that, because storage 30 days comparative example 2-1 etching agent composite copper etch energy
Power is less than 700ppm, so copper cannot be melted when adding copper with the amount of 5000ppm.
In the case where the etching agent composite of comparative example 2-2, IDA is present in the etching agent composite, but wherein
It decomposes.Therefore, the etching agent composite is without containing the additional component for capturing copper ion, therefore the copper ion and peroxide added
Change hydrogen reaction and causes heat release.
It can be determined that it does not contain polyol type although the etching agent composite of comparative example 2-3 contains citric acid
Surfactant, therefore its storage stability is deteriorated.
(preparation of etching agent composite and its Performance Evaluation 3)
Embodiment 3-1 to 3-5 and comparative example 3-1 to 3-3: the preparation of etching agent composite
Going out as given in following table 5, the etching of the embodiment 3-1 to 3-5 and comparative example 3-1 to 3-3 of 180kg are prepared
Agent composition.
[table 5]
(unit: wt%)
※ fluorochemical: ammonium acid fluoride (NH4F·HF)
※ azole compounds: 3- amino -1,2,4- triazole
※ EPE polyol EPE: triethylene glycol
※ IDA: iminodiacetic acid
※ phosphate: sodium dihydrogen phosphate
Test case: the performance of etching agent composite is assessed
<MoTi/Cu/MoTi etching>
MoTi is deposited on glass substrate (100mm × 100mm), by copper layer deposition on MoTi, then passes through photoetching
Technique forms the photoresist with predetermined pattern on the glass substrate.Hereafter, using embodiment 3-1 to 3-5 and compare
Each etching agent composite of example 3-1 to 3-3 carries out the etch process of trilamellar membrane (MoTi/Cu/MoTi).
It uses injection-type Etaching device (model name: ETCHER (TFT) (etching machine (TFT)) is manufactured by SEMES company)
To be etched technique.In the etch process, the temperature of etching agent composite is arranged to about 30 DEG C, and etching period is arranged to
100~300 seconds.It is etched during etch process using SEM (model name: S-4700 is manufactured by Hitachi, Ltd) to check
The profile of copper base metal film, and its result is shown in following table 6.
<assessment for being processed the quantity of sheet material>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 3-1 to 3-5 and comparative example 3-1 to 3-3
Part sample.Then, copper powder is added in each etching agent composite (using 5g as increment) from 10g to 80g, then in pre- timing
The temperature change of the interior each etching agent composite of observation.When not occurring even if exothermic reaction after the predetermined time passes by
The maximum concentration of measured etching agent composite is defined as the quantity of the processed sheet material of etching agent composite.
Its assessment result is shown in following table 6.
<storage 30 days after, be processed sheet material quantity assessment>
15 etc. of 10 liters are prepared for by each etching agent composite of embodiment 3-1 to 3-5 and comparative example 3-1 to 3-3
Part sample.Then, each provided etching agent composite is stored 30 days at room temperature, (using 5g as increment) from 10g to 80g
Copper powder is added to wherein, then observes the temperature change of each etching agent composite in the given time.Even if in pre- timing
Between pass by after exothermic reaction when also not occurring the maximum concentration of measured etching agent composite be defined as storage 30 days
The quantity of the processed sheet material of etching agent composite afterwards.
Its assessment result is shown in following table 6.
[table 6]
<evaluation criteria of etching outline>
Cu/MoTi layers
Zero: cone angle is 35 ° less than 60 °
△: cone angle is 30 ° of less than 35 ° or 60 ° to 65 ° X: cone angle is 30 ° or less or greater than 65 °
It does not etch: not being etched
MoTi/Cu/MoTi layers
Zero: cone angle is 30 ° less than 45 °
△: cone angle is 20 ° of less than 30 ° or 45 ° to 65 ° X: cone angle is 20 ° or less or greater than 65 °
It does not etch: not being etched
<etching linear evaluation criteria>
Zero: pattern is formed with straight line
△: being that 20% curve below forms pattern with ratio
X: the curve with ratio greater than 20% forms pattern
It does not etch: not being etched
<evaluation criteria at the top tip MoTi>
The tip zero: MoTi be 0.00 (μm) more than~less than 0.03 (μm)
The tip △: MoTi be 0.03 (μm) more than~less than 0.10 (μm)
The tip X:MoTi is 0.10 (μm) or more
It does not etch: not being etched
Referring to table 6 above, it can be determined that, all etching agent composites of embodiment 3-1 to 3-5 are all shown
Good etching performance.Furthermore it is possible to be processed it is well established that be compared to each other the etching agent composite of embodiment 3-1 to 3-5
The quantity of sheet material increases with the increase of the amount of citric acid.Furthermore it is possible to it is well established that the etchant of comparing embodiment 3-4
The etching agent composite of composition and embodiment 3-5, when adding EPE polyol EPE, the quantity for being processed sheet material increases
Add.Specifically, it can be determined that, when etching copper base metal film, the embodiment 3-1 containing EPE polyol EPE is extremely
The etching agent composite of 3-5 increases the number of the processing piece of copper base metal film；Moreover, after they are stored for 30 days,
Selfdecomposition over time there is no.In addition, by embodiment 3-1 to 3-5 it can be determined that, in trilamellar membrane (MoTi/
Cu/MoTi in etching), citric acid is for controlling the tip MoTi and keep must be at needed for 45 ° of etching outlines below
Point.
In contrast, it can be determined that, although containing the glycolic as organic acid in the etching of copper base metal film
(GA) etching agent composite of comparative example 3-1 shows good basic etching performance；But it is helpless to increase copper-based gold
Belong to the quantity of the processed sheet material of film；Moreover, in the etching of trilamellar membrane (MoTi/Cu/MoTi), etching outline and etching line
Property is bad.
Although furthermore it is possible to it is well established that contain the glycolic as organic acid during etching copper base metal film
The etching agent composite of comparative example 3-2 show good basic etching performance；But after it is stored for 30 days, by
It is substantially reduced in the quantity of its selfdecomposition over time, the processed sheet material of copper base metal film.
Although furthermore it is possible to it is well established that contain ratio of the IDA as the modifier of the quantity for increasing processed sheet material
Etching agent composite compared with example 3-3 shows good basic etching performance；But after they are stored for 30 days, due to
Its selfdecomposition over time, the quantity of the processed sheet material of copper base metal film substantially reduce；Moreover, in trilamellar membrane (MoTi/
Cu/MoTi in etching), etching outline and etching are linear bad.
As described above, the advantages of etching agent composite of copper base metal film according to the present invention, is: this etchant group
The citric acid that object contains the modifier as the quantity for increasing processed sheet material is closed, therefore is processed sheet material by etching
The significant increase of quantity, also, particularly, even if it still shows logical after the long-time that it is stored for 30 days or more
Overetch is processed the excellent effect on the quantitative aspects of sheet material, to improve storage stability significantly.In addition, this etching
The advantages of agent composition is: its heat release stability significantly improves, and its three layers of copper to MoTi/Cu/MoTi film etc.
The etching performance of Base Metal film is very excellent.
Although the preferred embodiment of the present invention has been disclosed for illustration purposes, it will be appreciated by those skilled in the art that
, various modifications, addition and replacement be it is possible, without departing from such as model of present invention disclosed in the following claims
It encloses and spiritual.
Claims (4)
1. a kind of method for manufacturing array substrate for liquid crystal display, the described method comprises the following steps:
A) gate electrode is formed on substrate；
B) gate insulation layer is formed on the substrate for including the gate electrode；
C) semiconductor layer (n is formed on the gate insulation layer+A-Si:H and a-Si:H)；
D) source/drain electrode is formed on the semiconductor layer；And
E) pixel electrode connecting with the drain electrode is formed,
Wherein, the step a) or d) include forming the step of each electrode by etching the trilamellar membrane including MoTi/Cu/MoTi
Suddenly, moreover, the etching agent composite used in the etching trilamellar membrane including MoTi/Cu/MoTi includes as increasing
Add the citric acid of the modifier of the quantity of processed sheet material,
Wherein, the total weight based on the etching agent composite, the etching agent composite include:
The citric acid of 1.0~10.0wt%；
The hydrogen peroxide of 15.0~25.0wt%；
The fluorochemical of 0.01~1.0wt%；
The azole compounds of 0.1~5.0wt%；
The EPE polyol EPE of 0.001~5.0wt%；With
The water of surplus,
Wherein, the azole compounds are 3- amino-1,2,4-triazoles, and the EPE polyol EPE is three second two
Alcohol.
2. according to the method described in claim 1, wherein, the fluorochemical is selected from by ammonium fluoride, sodium fluoride, fluorination
At least one of potassium, ammonium acid fluoride, sodium bifluoride and group of potassium hydrogen fluoride composition.
3. a kind of etching agent composite for the trilamellar membrane including MoTi/Cu/MoTi, based on the total of the etching agent composite
Weight, the etching agent composite include:
The citric acid of 1.0~10.0wt%；
The hydrogen peroxide of 15.0~25.0wt%；
The fluorochemical of 0.01~1.0wt%；
The azole compounds of 0.1~5.0wt%；
The EPE polyol EPE of 0.001~5.0wt%；With
The water of surplus,
Wherein, the azole compounds are 3- amino-1,2,4-triazoles, and the EPE polyol EPE is three second two
Alcohol.
4. etching agent composite according to claim 3, wherein the fluorochemical is selected from by ammonium fluoride, fluorination
At least one of sodium, potassium fluoride, ammonium acid fluoride, sodium bifluoride and group of potassium hydrogen fluoride composition.
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| KR20130077822A KR20150004970A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
| KR1020130077824A KR20150004972A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
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| KR102384564B1 (en) * | 2016-03-25 | 2022-04-08 | 동우 화인켐 주식회사 | Composition for Etching Indium Oxide Layer and Molybdenum Layer |
| KR101978019B1 (en) * | 2016-03-28 | 2019-05-13 | 동우 화인켐 주식회사 | Composition for Etching Copper-Containing Metal Layer |
| KR102367814B1 (en) * | 2016-03-30 | 2022-02-25 | 동우 화인켐 주식회사 | Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same |
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| CN104280916A (en) | 2015-01-14 |
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