CN110147008B - Method for manufacturing array substrate for liquid crystal display - Google Patents
Method for manufacturing array substrate for liquid crystal display Download PDFInfo
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- CN110147008B CN110147008B CN201910330615.3A CN201910330615A CN110147008B CN 110147008 B CN110147008 B CN 110147008B CN 201910330615 A CN201910330615 A CN 201910330615A CN 110147008 B CN110147008 B CN 110147008B
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- Prior art keywords
- etchant composition
- copper
- etching
- moti
- forming
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000758 substrate Substances 0.000 title claims abstract description 29
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 116
- 239000010949 copper Substances 0.000 claims abstract description 115
- 238000005530 etching Methods 0.000 claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 93
- 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 48
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 8
- 229910016027 MoTi Inorganic materials 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 15
- -1 azole compound Chemical class 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 7
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 7
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- 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
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims 2
- 235000003270 potassium fluoride Nutrition 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 abstract description 81
- 229910052751 metal Inorganic materials 0.000 abstract description 62
- 239000002184 metal Substances 0.000 abstract description 62
- 239000010408 film Substances 0.000 description 116
- 239000010410 layer Substances 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 34
- 238000011156 evaluation Methods 0.000 description 27
- 229910001182 Mo alloy Inorganic materials 0.000 description 23
- 230000008569 process Effects 0.000 description 23
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 16
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 14
- 229910000881 Cu alloy Inorganic materials 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 9
- 230000008859 change Effects 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
- 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 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 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
- 239000012043 crude product Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- 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 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
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-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
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-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
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 230000007423 decrease Effects 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
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 150000002500 ions Chemical class 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
- 239000012860 organic pigment Substances 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
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- 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)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Power 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 invention relates to a method for manufacturing an array substrate for a liquid crystal display, which comprises the following steps: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer (n) on the gate insulating layer+a-Si: H and a-Si: H); d) forming source/drain electrodes on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein the step a) or d) includes a step of forming each electrode by etching the copper-based metal film, and the etchant composition used in etching the copper-based metal film includes citric acid as an improver for increasing the number of sheets to be processed.
Description
The application is a divisional application of an invention patent application with the application date of 2014, 6, and 4, and the application number of 201410246018.X, and the name of the invention is 'a method for manufacturing an array substrate for a liquid crystal display'.
Cross Reference to Related Applications
The present application claims the rights of korean patent application KR 10-2013-.
Technical Field
The present invention relates to a method of manufacturing an array substrate for a liquid crystal display.
Background
A typical electronic circuit for driving semiconductor devices and flat panel displays is a Thin Film Transistor (TFT). Generally, the manufacturing process of a TFT includes the steps of: forming a metal film as a material for the gate electrode line and the data line on the substrate; forming a photoresist on selective regions of the metal film; and etching the metal film using the photoresist as a mask.
In general, a copper film or a copper alloy film containing copper having high conductivity and low resistance and a metal oxide film having high interfacial adhesion with the copper film or the copper alloy film are used as materials for the gate electrode line and the data line. Recently, in order to improve the performance of TFTs, a metal oxide film containing indium oxide, zinc oxide, or a mixture thereof with gallium oxide has been used.
Meanwhile, korean patent application laid-open No. 10-2006-0064881 discloses an etching solution for a copper-molybdenum film, which includes hydrogen peroxide, an organic acid, an azole compound, a fluorine compound, and an iminodiacetic acid (IDA) based compound as a chelate compound. When a copper-molybdenum film is etched with the etching solution, the band profile has excellent linearity, and there is no residue of molybdenum alloy after etching, but there is a problem in that: after the etching solution was stored for 30 days, the number of sheets of the copper-molybdenum film thus etched was significantly reduced, so that its heat release stability as well as its storage stability were extremely deteriorated, and its etching performance for a three-layer copper-based metal film such as a MoTi/Cu/MoTi film was extremely deteriorated.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent application laid-open No. 10-2006-0064881
Disclosure of Invention
Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing an array substrate for a liquid crystal display, which is made of a copper-based metal film.
It is another object of the present invention to provide an etchant composition for a copper-based metal film, which provides an excellent etching profile and improves storage stability, and which can be suitably used for a three-layer metal film including a molybdenum-based metal film and a copper-based metal film.
In order to achieve the above objects, an aspect of the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method comprising the steps of: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer (n) on the gate insulating layer+a-Si: H and a-Si: H); d) forming source/drain electrodes on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein the step a) or d) includes a step of forming each electrode by etching a copper-based metal film, and an etchant composition used in etching the copper-based metal film includes citric acid as an improver for increasing the number of processed sheets.
Another aspect of the present invention provides an etchant composition for a copper-based metal film, which includes citric acid as an improver for increasing the number of processed sheets.
Detailed Description
The present invention relates to an etchant composition for a copper-based metal film, which includes citric acid as an improver for increasing the number of sheets to be processed.
In the present invention, a copper-based metal film (which is a copper-containing film) includes: a single layer film of copper or copper alloy; and a multilayer film including at least one selected from a copper film and a copper alloy film and at least one selected from a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film.
Here, the alloy film may include a nitride film or an oxide film.
Examples of the multilayer film may include a two-layer film and a three-layer film such as a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum alloy film, a copper/titanium film, and the like. Here, the copper/molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer; the copper/molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer; the copper alloy/molybdenum alloy film includes a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer; and the copper/titanium film includes a titanium layer and a copper layer formed on the titanium layer.
Further, the molybdenum alloy layer is a layer made of an alloy of molybdenum and at least one metal selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In).
Further, the etchant composition of the present invention can be preferably applied to a multilayer film including a copper or copper alloy film and a molybdenum or molybdenum alloy film.
Specifically, the copper-based metal film may be a three-layer film including a molybdenum alloy layer, a copper layer formed on the molybdenum alloy layer, and a molybdenum alloy layer formed on the copper layer. Preferably, the copper-based metal film may be a three-layer film including a molybdenum-based metal film and a copper-based metal film. Specific examples of the three-layer film may include a molybdenum/copper/molybdenum film, a molybdenum alloy/copper/molybdenum alloy film, a molybdenum/copper alloy/molybdenum film, a molybdenum alloy/copper alloy/molybdenum alloy film, and the like.
1. Etchant composition
The citric acid contained in the etchant composition of the present invention is an improver for increasing the number of sheets to be processed, and is used for increasing the number of sheets to be processed of a copper-based metal film. As a conventional improver for increasing the number of processed sheets, an iminodiacetic acid (IDA) -based compound is an essential component for increasing the number of processed sheets of a copper-based metal film during an etching process; however, because it has self-decomposing properties, the number of sheets it is processed decreases over time. Further, there are many examples of the organic acid used for etching the copper-based metal film, but not all of the organic acid contributes to increase in the number of processed sheets, and only citric acid plays a role in increasing the number of processed sheets of the copper-based metal film during the etching process. The citric acid is contained in an amount of 1.0 to 10.0 wt%, preferably 3.0 to 7.0 wt%, based on the total weight of the etchant composition. When the amount of citric acid is less than 1.0 wt%, the etching rate of the copper-based metal film is reduced, and thus an etching residue may be present. When the amount thereof is more than 10.0 wt%, the copper-based metal film may be excessively etched.
The etchant composition further includes one or more selected from the group consisting of a fluorine-containing compound, an azole compound, and a polyol-type surfactant. The etchant composition may also include a balance of water.
Hydrogen peroxide (H) included in etchant composition2O2) Is a main component for etching a copper-based metal film, and plays a role in increasing the activity of a fluorine-containing compound.
Hydrogen peroxide (H) contained based on the total weight of the etchant composition2O2) The amount of (B) is 15.0 to 25.0 wt%, preferably 18.0 to 23.0 wt%. When the amount of hydrogen peroxide is less than 15.0 wt%, the copper-based metal film is not etched, or the etching rate of the copper-based metal film is decreased. When the amount thereof is more than 25.0 wt%, the etching rate of the copper-based metal film is completely increased, and thus it is difficult to control the process.
The fluorine-containing compound contained in the etchant composition of the present invention is a compound that dissociates in water to generate fluorine ions. The fluorine-containing compound is a main component for etching the copper-based metal film, and plays a role of removing residual dross inevitably generated from the molybdenum film or the molybdenum alloy film.
The fluorine-containing compound is included in an amount of 0.01 to 1.0 wt%, preferably 0.05 to 0.20 wt%, based on the total weight of the etchant composition. When the amount of the fluorine-containing compound is less than 0.01 wt%, the etching rate of the molybdenum film or the molybdenum alloy film is decreased, and thus an etching residue may be present. When the amount thereof is more than 1.0 wt%, there is a problem in that the etching rate of the glass substrate increases.
The fluorine-containing compound may be used in the related art without limitation as long as it can be dissociated into fluoride ions or multi-fluoride ions. Preferably, however, the fluorine-containing compound is selected from the group consisting of ammonium fluoride (NH)4F) Sodium fluoride (NaF), potassium fluoride (KF), ammonium hydrogen fluoride (NH)4F & HF), sodium bifluoride (NaF & HF) and potassium bifluoride (KF & HF).
The azole compound contained in the etchant composition of the present invention functions to control the etching rate of the copper-based metal film and reduce the CD loss of the pattern, thereby increasing the margin in the process (margin).
The azole compound is included in an amount of 0.1 to 5.0 wt%, preferably 0.3 to 1.0 wt%, based on the total weight of the etchant composition. When the amount of the azole compound is less than 0.1 wt%, the etching rate of the copper-based metal film is rapidly increased, and thus the CD loss may be excessively increased. When the amount thereof is more than 5.0 wt%, the etching rate of the copper-based metal film is excessively decreased, and thus etching residues may be present. Preferably, the azole compound is at least one selected from the group consisting of 5-aminotriazole, 3-amino-1, 2, 4-triazole, 4-amino-4H-1, 2, 4-triazole, aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole.
The water contained in the etchant composition of the present invention is not particularly limited, but preferably, may be deionized water. More preferably, the water may be deionized water having a resistivity (degree of ion removal in water) of 18M Ω · cm or more. The balance of water is included such that the total weight of the etchant composition is 100 wt%.
Meanwhile, the polyol-type surfactant included in the etchant composition of the present invention serves to improve etching uniformity by reducing surface tension. Further, the polyol-type surfactant functions to suppress the decomposition reaction of hydrogen peroxide by surrounding copper ions contained in the etchant after etching the copper film to suppress the activity of the copper ions. Also, when the activity of copper ions is reduced, the process can be stably advanced during the use of the etchant. The polyol-type surfactant is included in an amount of 0.001 to 5.0 wt%, preferably 0.1 to 3.0 wt%, based on the total weight of the etchant composition. When the amount of the polyol-type surfactant is less than 0.001 wt%, the following problems are present: etching uniformity becomes poor and decomposition of hydrogen peroxide is accelerated, so that an exothermic phenomenon occurs when copper is treated in an amount of a predetermined amount or more. When the amount thereof is more than 5.0 wt%, there is a problem that a large amount of bubbles are generated.
The polyol-type surfactant may be selected from the group consisting of glycerin, triethylene glycol and polyethylene glycol. Preferably, the polyol-type surfactant may be triethylene glycol.
The components used in the present invention can be prepared by known methods. Preferably, the etchant composition of the present invention has a purity sufficient for use in semiconductor processing.
2. Method for manufacturing array substrate for liquid crystal display
The method for manufacturing the array substrate for the liquid crystal display according to the present invention comprises the steps of: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer (n) on the gate insulating layer+a-Si: H and a-Si: H); d) forming source/drain electrodes on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein the step a) or d) includes the steps of: a copper-based metal film is formed on a substrate, and then etched using an etchant composition to form a gate electrode line or source and drain electrodes. The array substrate for a liquid crystal display may be a TFT array substrate.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. However, these examples and comparative examples are presented to illustrate the present invention, and the scope of the present invention is not limited thereto.
(preparation of etchant composition and evaluation of its Properties 1)
Examples 1-1 to 1-4 and comparative examples 1-1 to 1-4: preparation of etchant composition
As given in Table 1 below, 180kg of the etchant compositions of examples 1-1 to 1-4 and comparative examples 1-1 to 1-4 were prepared.
[ Table 1]
(unit: wt%)
Additionally, fluorine-containing compounds: ammonium hydrogen fluoride (NH)4F·HF)
The crude product is a red azole compound: 3-amino-1, 2, 4-triazoles
Additionally, IDA: iminodiacetic acid
In addition, NTA: nitrilotriacetic acid
Test example: performance evaluation of etchant compositions
< Cu/MoTi etching >
MoTi was deposited on a glass substrate (100mm × 100mm), a copper film was deposited on MoTi, and then a photoresist having a predetermined pattern was formed on the glass substrate through a photolithography process. Thereafter, the etching process of Cu/MoTi was performed using each of the etchant compositions of examples 1-1 to 1-4 and comparative examples 1-1 to 1-4.
The etching process is performed using an injection type etching apparatus (model name: etcher (TFT)) (etcher (TFT)), manufactured by SEMES corporation. In the etching process, the temperature of the etchant composition is set to about 30 ℃ and the etching time is set to 100 to 300 seconds. The profile of the copper-based metal film etched during the etching process was examined using SEM (model name: S-4700, manufactured by hitachi corporation), and the results thereof are shown in table 2 below.
< evaluation of the number of sheets to be processed >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 1-1 to 1-4 and comparative examples 1-1 to 1-4. Copper powder was then added to each etchant composition from 10g to 80g (in 5g increments), and the temperature change of each etchant composition was then observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction does not occur even after the predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
The evaluation results thereof are shown in table 2 below.
< evaluation of the number of sheets processed after 30 days of storage >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 1-1 to 1-4 and comparative examples 1-1 to 1-4. Subsequently, each of the provided etchant compositions was stored at room temperature for 30 days, copper powder was added thereto from 10g to 80g (in increments of 5 g), and then the temperature change of each etchant composition was observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction did not occur even after the predetermined time had elapsed was defined as the number of processed sheets of the etchant composition stored for 30 days. The evaluation results are shown in table 2 below.
[ Table 2]
| Directory | Etching profile | Etch linearity | Number of sheets to be processed | Number of sheets processed after 30 days of storage |
| Layer(s) | Cu/MoTi | Cu/MoTi | Cu/MoTi | Cu/MoTi |
| Examples 1 to 1 | O | O | Cu 4000ppm | Cu 4000ppm |
| Examples 1 to 2 | O | O | Cu 4000ppm | Cu 4000ppm |
| Examples 1 to 3 | O | O | Cu 3000ppm | Cu 3000ppm |
| Examples 1 to 4 | O | O | Cu 6000ppm | Cu 6000ppm |
| Comparative example 1-1 | O | O | Cu 200ppm | Cu 200ppm |
| Comparative examples 1 to 2 | O | O | Cu 2000pm | Cu 500ppm |
| ComparisonExamples 1 to 3 | O | O | Cu 4000ppm | Cu 2500ppm |
| Comparative examples 1 to 4 | 0 | 0 | Cu 5000ppm | Cu 1000ppm |
< evaluation criteria of etching Profile >
O: the cone angle is more than 35 DEG to less than 60 DEG
And (delta): the cone angle is more than 30 degrees and less than 35 degrees or 60 degrees and 65 degrees
X: the cone angle is less than 30 degrees or more than 65 degrees
Non-etching: is not etched
< evaluation criteria for etch Linearity >
O: form a pattern in a straight line
And (delta): curve pattern with rate less than 20%
X: curved pattern at a ratio greater than 20%
Non-etching: is not etched
Referring to table 2 above, it can be confirmed that all of the etchant compositions of examples 1-1 to 1-4 exhibited good etching properties. Further, it can be confirmed that the etchant compositions of examples 1-1 to 1-4 increase the number of processed sheets of the copper-based metal film when etching the copper-based metal film; moreover, their self-decomposition over time did not occur after they were stored for 30 days.
In contrast, it can be confirmed that, in the etching of the copper-based metal film, the etchant composition of comparative example 1-1, although containing glycolic acid as an organic acid, exhibited good basic etching performance; but does not contribute to increase in the number of processed sheets of the copper-based metal film.
In contrast, it can be confirmed that, in the etching of the copper-based metal film, the etchant compositions of comparative examples 1-2, although containing glycolic acid as an organic acid, exhibited good basic etching performance; but after it was stored for 30 days, the number of processed sheets of the copper-based metal film was significantly reduced due to self-decomposition of glycolic acid with the passage of time.
Further, it can be confirmed that although the etchant compositions of comparative examples 1 to 3 and 1 to 4 containing IDA as an improver for increasing the number of processed sheets exhibited good basic etching performance and increased the number of processed sheets in the process of etching the copper-based metal film; but after they were stored for 30 days, the number of processed sheets of the copper-based metal film was significantly reduced due to self-decomposition of IDA with the passage of time.
(preparation of etchant composition and evaluation of its Properties 2)
Examples 2-1 to 2-4 and comparative examples 2-1 to 2-3: preparation of etchant composition
As given in Table 3 below, 180kg of the etchant compositions of examples 2-1 to 2-4 and comparative examples 2-1 to 2-3 were prepared.
[ Table 3]
(unit: wt%)
Additionally, fluorine-containing compounds: ammonium hydrogen fluoride (NH)4F·HF)
The crude product is a red azole compound: 3-amino-1, 2, 4-triazoles
In addition, TEG: triethylene glycol
Additionally, IDA: iminodiacetic acid
Test example: performance evaluation of etchant compositions
< Cu/MoTi etching >
MoTi was deposited on a glass substrate (100mm × 100mm), a copper film was deposited on MoTi, and then a photoresist having a predetermined pattern was formed on the glass substrate through a photolithography process. Thereafter, the etching process of Cu/MoTi was performed using each of the etchant compositions of examples 2-1 to 2-4 and comparative examples 2-1 to 2-3.
The etching process is performed using an injection type etching apparatus (model name: etcher (TFT)) (etcher (TFT)), manufactured by SEMES corporation. In the etching process, the temperature of the etchant composition is set to about 30 ℃ and the etching time is set to 100 to 300 seconds. The profile of the copper-based metal film etched during the etching process was examined using SEM (model name: S-4700, manufactured by hitachi corporation), and the results thereof are shown in table 4 below.
< evaluation of the number of sheets to be processed >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 2-1 to 2-4 and comparative examples 2-1 to 2-3. Copper powder was then added to each etchant composition from 10g to 80g (in 5g increments), and the temperature change of each etchant composition was then observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction does not occur even after the predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
The evaluation results thereof are shown in table 4 below.
< evaluation of the number of processed sheets after 30 days of storage >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 2-1 to 2-4 and comparative examples 2-1 to 2-3. Subsequently, each of the provided etchant compositions was stored at room temperature for 30 days, copper powder was added thereto from 10g to 80g (in increments of 5 g), and then the temperature change of each etchant composition was observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction did not occur even after the predetermined time had elapsed was defined as the number of processed sheets of the etchant composition stored for 30 days.
The evaluation results thereof are shown in table 4 below.
< evaluation of storage stability >
Each of the etchant compositions of examples 2-1 to 2-4 and comparative examples 2-1 to 2-3 was prepared in an amount of 10L. Subsequently, each of the prepared etchant compositions was stored at room temperature for 30 days, 50g of copper powder was added thereto, and then the temperature change of each etchant composition was observed.
The evaluation results thereof are shown in table 4 below.
[ Table 4]
< evaluation criteria of etching Profile >
O: the cone angle is more than 35 DEG to less than 60 DEG
And (delta): the cone angle is more than 30 degrees and less than 35 degrees or 60 degrees and 65 degrees
X: the cone angle is less than 30 degrees or more than 65 degrees
Non-etching: is not etched
< evaluation criteria for etch Linearity >
O: form a pattern in a straight line
And (delta): curve pattern with rate less than 20%
X: curved pattern at a ratio greater than 20%
Non-etching: is not etched
Referring to table 4 above, it can be confirmed that all of the etchant compositions of examples 2-1 to 2-4 exhibited good etching properties. Further, it can be confirmed that, when the etchant compositions of examples 2-1 to 2-4 were compared with each other, the number of processed sheets increased as the amount of the polyol-type surfactant increased. Specifically, it can be confirmed that the etchant compositions of examples 2-1 to 2-4 containing the polyol-type surfactant increased the number of processed sheets of the copper-based metal film when etching the copper-based metal film; moreover, their self-decomposition over time did not occur after they were stored for 30 days.
In contrast, it can be confirmed that although the etchant composition of comparative example 1-1 containing glycolic acid instead of citric acid exhibited good basic etching performance in the process of etching the copper-based metal film; but does not contribute to increase in the number of processed sheets of the copper-based metal film.
Further, it can be confirmed that, although the etchant composition of comparative example 2-1 containing IDA as an improver for increasing the number of processed sheets exhibited good basic etching performance, after it was stored for 30 days, the number of processed sheets of the copper-based metal film was significantly reduced due to self-decomposition of IDA with the passage of time.
Further, it can be confirmed that the etchant composition of comparative examples 2 to 3 is not effective for increasing the number of processed sheets because the etchant composition of comparative examples 2 to 3 does not contain the polyol-type surfactant, compared with the etchant composition of example 2 to 1. Therefore, it can be confirmed that the polyol-type surfactant effectively increases the number of processed sheets of the copper (Cu) -based metal film.
Further, it can be confirmed that, in the case of the etchant compositions of examples 2-1 to 2-4, even when they were stored for 30 days and then 5000ppm of copper (Cu) was added thereto, their temperatures were maintained at the initial temperatures of 28 to 31 ℃ and thus their exothermic stabilities were very excellent.
In contrast, it can be confirmed that, since the etchant composition of comparative example 2-1, which was stored for 30 days, had a copper etching ability of less than 700ppm, copper could not be melted when copper was added in an amount of 5000 ppm.
In the case of the etchant composition of comparative example 2-2, IDA was present in the etchant composition, but decomposed therein. Therefore, the etchant composition does not contain an additional component for capturing copper ions, and thus the reaction of the added copper ions with hydrogen peroxide causes an exotherm.
It can be confirmed that although the etchant compositions of comparative examples 2 to 3 contained citric acid, it did not contain a polyol-type surfactant, and thus storage stability thereof was deteriorated.
(preparation of etchant composition and evaluation of its Properties 3)
Examples 3-1 to 3-5 and comparative examples 3-1 to 3-3: preparation of etchant composition
As given in Table 5 below, 180kg of the etchant compositions of examples 3-1 to 3-5 and comparative examples 3-1 to 3-3 were prepared.
[ Table 5]
(unit: wt%)
Additionally, fluorine-containing compounds: ammonium hydrogen fluoride (NH)4F·HF)
The crude product is a red azole compound: 3-amino-1, 2, 4-triazoles
The organic pigment is polyol type surfactant: triethylene glycol
Additionally, IDA: iminodiacetic acid
In addition, phosphate: sodium dihydrogen phosphate
Test example: evaluation of etchant composition Performance
< MoTi/Cu/MoTi etching >
MoTi was deposited on a glass substrate (100mm × 100mm), a copper film was deposited on MoTi, and then a photoresist having a predetermined pattern was formed on the glass substrate through a photolithography process. Thereafter, an etching process of a three-layer film (MoTi/Cu/MoTi) was performed using each of the etchant compositions of examples 3-1 to 3-5 and comparative examples 3-1 to 3-3.
The etching process is performed using an injection type etching apparatus (model name: etcher (TFT)) (etcher (TFT)), manufactured by SEMES corporation. In the etching process, the temperature of the etchant composition is set to about 30 ℃ and the etching time is set to 100 to 300 seconds. The profile of the copper-based metal film etched during the etching process was examined using SEM (model name: S-4700, manufactured by hitachi corporation), and the results thereof are shown in table 6 below.
< evaluation of the number of sheets to be processed >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 3-1 to 3-5 and comparative examples 3-1 to 3-3. Copper powder was then added to each etchant composition from 10g to 80g (in 5g increments), and the temperature change of each etchant composition was then observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction does not occur even after the predetermined time has elapsed is defined as the number of processed sheets of the etchant composition.
The evaluation results thereof are shown in table 6 below.
< evaluation of the number of sheets processed after 30 days of storage >
Fifteen aliquots of 10 liters were prepared from each of the etchant compositions of examples 3-1 to 3-5 and comparative examples 3-1 to 3-3. Subsequently, each of the provided etchant compositions was stored at room temperature for 30 days, copper powder was added thereto from 10g to 80g (in increments of 5 g), and then the temperature change of each etchant composition was observed over a predetermined time. The maximum concentration of the etchant composition measured when the exothermic reaction did not occur even after the predetermined time had elapsed was defined as the number of processed sheets of the etchant composition stored for 30 days.
The evaluation results thereof are shown in table 6 below.
[ Table 6]
< evaluation criteria of etching Profile >
Cu/MoTi layer
O: the cone angle is more than 35 DEG to less than 60 DEG
And (delta): the cone angle is 30 ° or more to less than 35 ° or 60 ° to 65 ° X: the cone angle is less than 30 degrees or more than 65 degrees
Non-etching: is not etched
MoTi/Cu/MoTi layer
O: the cone angle is more than 30 degrees and less than 45 degrees
And (delta): the cone angle is 20 ° or more to less than 30 ° or 45 ° to 65 ° X: the cone angle is less than 20 deg. or more than 65 deg
Non-etching: is not etched
< evaluation criteria for etch Linearity >
O: form a pattern in a straight line
And (delta): curve pattern with rate less than 20%
X: curved pattern at a ratio greater than 20%
Non-etching: is not etched
< evaluation criteria of Upper MoTi tip >
O: MoTi tip of more than 0.00 (mu m) to less than 0.03 (mu m)
And (delta): MoTi tip of more than 0.03 (mu m) to less than 0.10 (mu m)
X: MoTi tip of 0.10 μm or more
Non-etching: is not etched
Referring to table 6 above, it can be confirmed that all of the etchant compositions of examples 3-1 to 3-5 exhibited good etching properties. Further, it can be confirmed that, comparing the etchant compositions of examples 3-1 to 3-5 with each other, the number of processed sheets increased as the amount of citric acid increased. Further, it can be confirmed that comparing the etchant compositions of examples 3 to 4 with the etchant compositions of examples 3 to 5, the number of processed sheets increased when the polyol-type surfactant was added. Specifically, it can be confirmed that the etchant compositions of examples 3-1 to 3-5 containing the polyol-type surfactant increased the number of worked pieces of the copper-based metal film when etching the copper-based metal film; moreover, their self-decomposition over time did not occur after they were stored for 30 days. Further, it can be confirmed from examples 3-1 to 3-5 that citric acid is an essential component required for controlling the MoTi tip and maintaining the etching profile below 45 ° in the etching of the three-layer film (MoTi/Cu/MoTi).
In contrast, it can be confirmed that the etchant composition of comparative example 3-1 containing Glycolic Acid (GA) as an organic acid exhibited good basic etching performance in the etching of the copper-based metal film; but does not contribute to increase in the number of sheets to be processed of the copper-based metal film; moreover, in the etching of the three-layer film (MoTi/Cu/MoTi), the etching profile and etching linearity were not good.
Further, it can be confirmed that the etchant composition of comparative example 3-2 containing glycolic acid as an organic acid exhibited good basic etching performance in the process of etching the copper-based metal film; but after it was stored for 30 days, the number of processed sheets of the copper-based metal film was significantly reduced due to self-decomposition thereof with the passage of time.
Further, it can be confirmed that although the etchant compositions of comparative examples 3 to 3 containing IDA as an improver for increasing the number of processed sheets exhibited good basic etching performance; but after they were stored for 30 days, the number of processed sheets of the copper-based metal film was significantly reduced due to self-decomposition thereof with the passage of time; moreover, in the etching of the three-layer film (MoTi/Cu/MoTi), the etching profile and etching linearity were not good.
As described above, the etchant composition for copper-based metal films according to the present invention is advantageous in that: this etchant composition contains citric acid as an improver for increasing the number of processed sheets, and therefore the number of processed sheets by etching is significantly increased, and in particular, even after it is stored for a long time of 30 days or more, it still exhibits an excellent effect in the number of processed sheets by etching, thereby significantly improving the storage stability. Furthermore, such an etchant composition has the advantages of: the exothermic stability is remarkably improved, and the etching performance of the film to a three-layer copper-based metal film such as a MoTi/Cu/MoTi film is excellent.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (4)
1. A method of manufacturing an array substrate for a liquid crystal display, the method comprising:
a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer (n) on the gate insulating layer+a-Si: H and a-Si: H);
d) forming source/drain electrodes on the semiconductor layer; and
e) forming a pixel electrode connected to the drain electrode,
wherein the step a) or d) includes a step of forming each electrode by etching a three-layer film including MoTi/Cu/MoTi, and an etchant composition used in etching the three-layer film including MoTi/Cu/MoTi includes citric acid as an improver for increasing the number of processed sheets,
wherein the etchant composition comprises, based on the total weight of the etchant composition:
1.0-10.0 wt% citric acid;
15.0 to 25.0 wt% of hydrogen peroxide;
0.01 to 1.0 wt% of a fluorine-containing compound;
0.1-5.0 wt% of azole compound;
0.001 to 5.0 wt% of a polyol-type surfactant; and
the balance of water is added into the mixture,
wherein the azole compound is 3-amino-1, 2, 4-triazole, and the polyol-type surfactant is triethylene glycol,
the etchant composition did not undergo an exothermic reaction up to 7,000ppm when copper powder was added thereto after 30 days of storage at room temperature.
2. The method according to claim 1, wherein the fluorine-containing compound is at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride.
3. An etchant composition for a three layer film comprising MoTi/Cu/MoTi, the etchant composition comprising, based on the total weight of the etchant composition:
1.0-10.0 wt% citric acid;
15.0 to 25.0 wt% of hydrogen peroxide;
0.01 to 1.0 wt% of a fluorine-containing compound;
0.1-5.0 wt% of azole compound;
0.001 to 5.0 wt% of a polyol-type surfactant; and
the balance of water is added into the mixture,
wherein the azole compound is 3-amino-1, 2, 4-triazole, and the polyol-type surfactant is triethylene glycol,
the etchant composition did not undergo an exothermic reaction up to 7,000ppm when copper powder was added thereto after 30 days of storage at room temperature.
4. The etchant composition according to claim 3, wherein the fluorine-containing compound is at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, and potassium bifluoride.
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| KR10-2013-0077824 | 2013-07-03 | ||
| 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 |
| KR10-2013-0077822 | 2013-07-03 | ||
| KR10-2013-0077823 | 2013-07-03 | ||
| KR20130077823A KR20150004971A (en) | 2013-07-03 | 2013-07-03 | Manufacturing method of an array substrate for liquid crystal display |
| CN201410246018.XA CN104280916A (en) | 2013-07-03 | 2014-06-04 | Method for manufacturing array substrate of liquid crystal display |
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| TW201503331A (en) | 2015-01-16 |
| CN104280916A (en) | 2015-01-14 |
| CN110147008A (en) | 2019-08-20 |
| TWI632670B (en) | 2018-08-11 |
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