CN105820819B - The method of indium oxide layer etchant and the array substrate using its manufacture liquid crystal display device - Google Patents
The method of indium oxide layer etchant and the array substrate using its manufacture liquid crystal display device Download PDFInfo
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- CN105820819B CN105820819B CN201510951854.2A CN201510951854A CN105820819B CN 105820819 B CN105820819 B CN 105820819B CN 201510951854 A CN201510951854 A CN 201510951854A CN 105820819 B CN105820819 B CN 105820819B
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- Prior art keywords
- indium oxide
- oxide layer
- layer
- etchant
- indium
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 125
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 183
- 238000005530 etching Methods 0.000 claims description 54
- 239000010949 copper Substances 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 239000010953 base metal Substances 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 22
- 230000003628 erosive effect Effects 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- -1 tetrazole compound Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 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 1
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
-
- 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
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
-
- 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
-
- 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
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Mathematical Physics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
- Weting (AREA)
Abstract
The present invention relates to indium oxide layer etchant and utilize the method for its array substrate for manufacturing liquid crystal display device, more specifically, it is related to not including sulfate or acetate but the indium oxide layer etchant including nitric acid, azole compounds, fluorochemical and water, and utilizes the method for its array substrate for manufacturing liquid crystal display device.
Description
Technical field
The present invention relates to indium oxide layer etchant and utilize the side of its array substrate for manufacturing liquid crystal display device
Method, more specifically to do not include sulfate or acetate but including nitric acid, azole compounds, fluorochemical and water
Indium oxide layer etchant, and using its manufacture liquid crystal display device array substrate method.
Background technique
Liquid crystal display device (LCD) be among panel display apparatus it is most preferred because they provide resolution ratio
Outstanding clear image, less energy intensive and display screen can be made thinning.The typical electrical of this liquid crystal display device is driven now
Sub-circuit is thin film transistor (TFT) (TFT) circuit, and typical thin-film transistor LCD device (TFT-LCD) forms display
The pixel of screen.The TFT of switching device function is played in TFT-LCD by being arranged in matrix with liquid crystal material filling
The substrate of TFT and space between the colored filter substrate of the TFT substrate manufacture.Complete TFT-LCD manufacture
Process is substantially divided into TFT substrate manufacturing process, colored filter process, unit process and component process, and the TFT base
Board manufacturing process and the colored filter manufacturing process are accurate in presentation and clearly extremely important in terms of image.
When manufacturing the pixel display electrode of TFT-LCD, need by with high conductivity while there is transparent optical property
Material made of film, and the tin indium oxide (ITO) based on indium oxide and indium zinc oxide (IZO) are currently used as electrically conducting transparent
The material of film.
In addition, needing to trim film layer according to circuit pattern to obtain objective circuit line in pixel display electrode
Etching process.
However, with the existing etching solution commonly used in etching metal bi, it is difficult due to the strong chemical resistance of ITO oxide
To etch the transparent conductive film made of ITO or IZO material.Specifically, chloroazotic acid (HCl+CH3COOH+HNO3), iron chloride
(III) hydrochloric acid solution (FeCl3/ HCl) or oxalic acid aqueous solution already function as the wet etch solution of transparent conductive film, however, when benefit
When etching ITO layer with the hydrochloric acid solution of etching solution or iron chloride based on chloroazotic acid, it is at low cost but due in pattern side surface
Faster, profile is inferior for etching, and because hydrochloric acid or nitric acid volatilize after etching solution is formed, the wave in the etchant
It is dynamic serious, and chemical erosion can be occurred to the metal of lower part.Korean patent application publication No.10-2000-0017470 benefit
With oxalic acid etching method for amorphous tin indium oxide (ITO), however, in this case, residue is easy to appear around ITO pattern, and
Because oxalic acid has low solubility at low temperature, sediment is caused to generate, so there is the problem of etching machines failure.
In addition, the etching solution etch-rate height made of HI and side surface etching are few, but it is expensive, there is high toxicity and corruption
Corrosion, and cause the erosion to the data line for being located at transparent pixel electrode bottom, therefore, in the actual process using with limit
System.
In addition, Korean patent application publication No.10-2010-0053175 discloses the etch combination of transparent conductive film,
It includes halogen contained compound, auxiliary oxidizing agent, etching control agent, residue inhibitor, corrosion inhibitor and water, and sulfate
Etching control agent and residue inhibitor are used separately as with acetate.However, when including sulfate and acetate in etch combination
When, lateral etch rate is low, causes side etching amount small, and the problem of subsurface damage occur.
[existing technical literature]
[patent document]
(patent document 1) Korean patent application publication No.10-2000-0017470
(patent document 2) Korean patent application publication No.10-2010-0053175
Summary of the invention
The purpose of the present invention is by with do not include selected from as composed by sulfate and acetate group one of or it is more
The indium oxide layer etchant of kind effectively etches indium oxide layer at high speed, thus maximum etch process efficiency.
It is also object of the invention to improve thin film transistor (TFT)-liquid by minimizing the erosion to the lower layer of indium oxide layer
The driveability of crystal device (TFT-LCD).
Therefore, the purpose of the present invention is to provide can be improved etching process efficiency and Thin Film Transistors-LCD display device
(TFT-LCD) the indium oxide layer etchant of driveability utilizes its engraving method, and manufacture liquid crystal display device
Array substrate method.
In view of above-mentioned, one aspect of the present invention provides indium oxide layer etchant, does not include selected from by sulphur
It is one or more in group composed by hydrochlorate and acetate, but the total weight relative to the indium oxide layer etchant
The azole compounds of nitric acid, 0.1 to 10 weight % including 3 to 30 weight % and the fluorochemical of 0.01 to 5 weight %, with
And the water of surplus, so that the total weight of the indium oxide layer etchant becomes 100 weight %.
Another aspect of the present invention provide etching indium oxide layer method, the method includes (1) on substrate shape
At indium oxide layer；(2) photoreactive material is selectively left in the indium oxide layer；(3) indium oxide of the invention is utilized
Layer etchant etches the indium oxide layer.
An additional aspect of the present invention provides the method for the array substrate of manufacture liquid crystal display device, the method includes
(1) grid lead is formed on substrate；(2) gate insulating layer is formed on the substrate for including the grid lead；(3) described
Oxide semiconductor layer is formed on gate insulating layer；(4) source and drain electrode are formed on the oxide semiconductor layer；(5) shape
At the pixel electrode with the drain electrode connection, wherein step (1) includes that copper/indium oxide layer or copper alloy/oxygen are formed on substrate
Change indium layer and is led by forming grid using the etchant etching copper/indium oxide layer or copper alloy/indium oxide layer
Line, step (5) form pixel electrode including forming indium oxide layer and etching the indium oxide layer using etchant, and
And the etchant is indium oxide layer etchant of the invention.
Another aspect of the invention provides the array substrate of liquid crystal display device comprising selected from by utilizing the present invention
Indium oxide layer etchant etching grid lead and pixel electrode composed by group one of or it is a variety of.
Specific embodiment
Hereinafter, the present invention will be described in further detail.
The present invention relates to indium oxide layer etchants, do not include selected from the group as composed by sulfate and acetate
One of or it is a variety of, but the total weight relative to the indium oxide layer etchant includes the nitre of 3 to 30 weight %
The water of acid, the fluorochemical of the azole compounds of 0.1 to 10 weight % and 0.01 to 5 weight % and surplus, so that described
The total weight of indium oxide layer etchant becomes 100 weight %.
Because not including selected from one of group or a variety of, of the invention indium oxide layers as composed by sulfate and acetate
Etchant can etch indium oxide layer with higher rate, it is thus possible to improve etching process efficiency.
Indium oxide layer in the present invention includes selected from by tin indium oxide (ITO) layer, indium zinc oxide (IZO) layer and indium gallium
One of group or a variety of composed by zinc (IGZO) layer.
It is formed in addition, can be with the indium oxide layer that indium oxide layer etchant of the invention etches with indium oxide layer
Single layer；Or the multilayer formed with the single layer and copper base metal layer, and the copper base metal layer can be layers of copper or copper closes
Layer gold.The concept of the alloy-layer also includes nitride layer or oxide skin(coating).
Nitric acid (the HNO for including in indium oxide layer etchant of the invention3) be indium oxide layer primary oxidizers,
And execute the effect for etching the indium oxide layer.In addition, nitric acid has high etch rates for indium oxide layer and can be
Ensure that required side etching is big in etching process.
Relative to the total weight of the indium oxide layer etchant, nitric acid accounts for 3 to 30 weight %, and preferably account for 5 to
25 weight %.When nitric acid is accounted for less than 3 weight %, the etch-rate of indium oxide layer can be reduced, and when being greater than 30 weight %,
It is possible that there is the problem of chemical erosion to the bottom of the indium oxide layer and adjacent metal, and since etch-rate is excessively high
And it is difficult to carry out process control.
The azole compounds for including in indium oxide layer etchant of the invention, which execute, to be minimized to contact indium oxide
The effect of the erosion of the copper conductor of layer, the indium oxide layer are used as the pixel electrode of the array substrate of liquid crystal display device.Change sentence
It talks about, the azole compounds execute the effect for minimizing the erosion to copper base metal layer, and the copper base metal layer is the oxygen
Change the lower layer of indium layer.
The azole compounds are preferably included selected from by triazole class compounds, tetrazole compound, glyoxaline compound, Yin
Diindyl class compound, purine compound, pyrazole compound, pyridine compounds and their, pyrimidines, azoles,
One of group or a variety of composed by pyrrolidines and pyrrolines.
In addition, more specifically, the azole compounds are preferably included selected from by Aminotetrazole, benzotriazole, tolyl
Triazole, 2-methylimidazole, 2- ethyl imidazol(e), 2- propyl imidazole, 2- aminooimidazole, 4-methylimidazole, 4- ethyl imidazol(e) and 4- third
One of group or a variety of composed by base imidazoles.
Relative to the total weight of the indium oxide layer etchant, the azole compounds account for 0.1 to 10 weight %,
And preferably account for 0.5 to 5 weight %.It, may be to as under indium oxide layer when the azole compounds are accounted for less than 0.1 weight %
The layers of copper of layer corrodes, and when being greater than 10 weight %, the erosion to the layers of copper can be prevented, however, the etching of indium oxide layer
Rate may be decreased.
The fluorochemical for including in indium oxide layer etchant of the invention is executed when etching indium oxide layer and is gone
Except the effect of residue.
The fluorochemical is not particularly limited, as long as it can be dissociated into fluorine ion or polyatom fluorine in the solution
Ion, it is preferred that including selected from by ammonium fluoride (NH4F), sodium fluoride (NaF), potassium fluoride (KF), ammonium acid fluoride (NH4F·
HF), one of sodium bifluoride (NaFHF) and the composed group of potassium bifluoride (KFHF) or a variety of.
In addition, the total weight relative to the indium oxide layer etchant, the fluorochemical account for 0.01 to 5 weight
% is measured, and preferably accounts for 0.01 to 3 weight %.When the fluorochemical is accounted for less than 0.01 weight %, when etching indium oxide layer
When be likely to occur residue, and when being greater than 5 weight %, there is the problem of etch-rate of glass substrate or silicon layer increase.
The water for including in indium oxide layer etchant of the invention accounts for surplus so that the total weight of the composition at
For 100 weight %.Water is not particularly limited, it is however preferred to use deionized water.Additionally, it is preferred that the use of specific resistance value being 18M
Ω cm or higher deionized water, specific resistance value are to show the value of water intermediate ion removal degree.
In addition, indium oxide layer etchant of the invention can also include selected from by metal ion chelation agent and corrosion
One of group or a variety of composed by inhibitor.In addition, the additive is without being limited thereto, in order to promote effect of the invention,
It can choose and add various other additives known in the art.
The component of indium oxide layer etchant of the invention can use the preparation of method as commonly known in the art, and
It is preferable to use the purity for semiconductor technology.
Moreover, it relates to the method for etching indium oxide layer, the method includes (1), and indium oxide is formed on substrate
Layer；(2) photoreactive material is selectively left in the indium oxide layer；(3) indium oxide layer etching solution of the invention is utilized
Composition etches the indium oxide layer.
In engraving method of the invention, the photoreactive material is preferably common photo anti-corrosion agent material, and
It can use common exposure and imaging process selectively to be left.
In addition, the present invention relates to the method for the array substrate of manufacture liquid crystal display device, including (1) forms grid on substrate
Polar conductor；(2) gate insulating layer is formed on the substrate for including the grid lead；(3) it is formed on the gate insulating layer
Oxide semiconductor layer；(4) source and drain electrode are formed on the oxide semiconductor layer；(5) it is formed and is connected with the drain electrode
Pixel electrode, wherein step (1) includes forming copper/indium oxide layer or copper alloy/indium oxide layer on substrate and passing through utilization
Etchant etches the copper/indium oxide layer or copper alloy/indium oxide layer forms grid lead, and step (5) includes being formed
Indium oxide layer and utilization etchant etch the indium oxide layer and form pixel electrode, and the etchant
It is indium oxide layer etchant of the invention.
Existing indium oxide layer etchant including sulfate or acetate has slow lateral etch rate, because
, when the pixel electrode of etching step (5), side etching amount is small for this.However, indium oxide layer etchant of the invention is not
Including sulfate and acetate, it is possible thereby to solve the problems, such as this, and the copper base metal layer to indium oxide layer lower layer can be prevented
Erosion.
The indium oxide layer formed on the substrate of step (1) is copper/indium oxide layer or copper alloy/indium oxide layer multilayer,
And the indium oxide layer formed in step (5) is the single layer of indium oxide layer.
The indium oxide layer includes selected from by tin indium oxide (ITO) layer, indium zinc oxide (IZO) layer and indium gallium zinc
(IGZO) one of group or a variety of composed by layer.
By being etched with indium oxide layer etchant of the invention, the grid can be formed in step (1) and led
Line, and the pixel electrode can be formed in step (5).
The array substrate of liquid crystal display device can be thin film transistor (TFT) (TFT) array substrate.
Moreover, it relates to the array substrate of liquid crystal display device comprising selected from by utilizing indium oxide of the invention
One of group composed by the grid lead and pixel electrode of layer etchant etching is a variety of.
Hereinafter, by reference implementation example, the present invention will be described in more detail.However, following embodiment is only for illustrative
Purpose, the scope of the present invention are not limited to following embodiment.Following embodiment can be within the scope of the invention by art technology
Personnel are appropriately modified or change.
<preparation indium oxide layer etchant>
Embodiment 1 to 3 and comparative example 1 to 10
The indium oxide layer etchant of embodiment 1 to 3 and comparative example 1 to 10 is prepared with the composition shown in the following table 1,
And the water including surplus makes total weight become 100 weight %.
[table 1]
(weight %)
| Nitric acid | BTA | ABF | Potassium sulfate | Ammonium acetate | Potassium chloride | Ammonium nitrate | Sulfuric acid | |
| Embodiment 1 | 8 | 1.0 | 0.1 | - | - | - | - | - |
| Embodiment 2 | 15 | 1.5 | 0.1 | - | - | - | - | - |
| Embodiment 3 | 10 | 0.7 | 1.0 | - | - | - | - | - |
| Comparative example 1 | 2 | 1.0 | 0.1 | - | - | - | - | - |
| Comparative example 2 | 35 | 1.0 | 0.1 | - | - | - | - | - |
| Comparative example 3 | 7 | 0.05 | 0.1 | - | - | - | - | - |
| Comparative example 4 | 7 | 12 | 0.05 | - | - | - | - | - |
| Comparative example 5 | 9 | 0.5 | 7 | - | - | - | - | - |
| Comparative example 6 | 8 | 0.6 | 0.1 | 6 | - | - | - | - |
| Comparative example 7 | 8 | 0.6 | 0.1 | - | 4 | - | - | - |
| Comparative example 8 | 9 | 0.5 | - | - | - | 5 | - | - |
| Comparative example 9 | - | 0.5 | 0.1 | - | - | - | 7 | - |
| Comparative example 10 | - | 0.7 | 0.1 | - | - | - | - | 8 |
BTA: benzotriazole
ABF: ammonium acid fluoride
Properties evaluations of the test example 1. to indium oxide layer etchant
After copper layer forms source/drain on glass substrate (100mm x 100mm), by the layers of copper
Upper stacking silicon forms hole, to expose metal layer-copper of the source/drain.Later, deposited oxide indium layer, and benefit on it
It forms the photoresist with predetermined pattern on the substrate with photoetching process, then utilizes embodiment 1 to 3 and comparative example
1 to 10 various indium oxide layer etchants carry out the etching process of the indium oxide layer.
Using spraying etch pattern testing equipment (model name: ETCHER (TFT), SEMES Co.Ltd.), and etched
The temperature for using about 35 DEG C in journey for the etchant, however, the proper temperature can depend on it when necessary
His process condition and other factors and change.Etching period is different depending on etch temperature, however, in LCD etching process
Etching usually carries out about 50 to 100 seconds.The indium oxide layer section etched in etching process using section SEM (Hitachi,
Ltd. product, model name S-4700) it checks, and observe side etching, residue appearance, glass etching rate and lower metal
(Cu) it corrodes.As the result is shown in the following Table 2.
[table 2]
According to the result of table 2, identify indium oxide layer etchant of the present invention in embodiment 1 to 3 show it is outstanding
Side etching, without residue occur and outstanding glass etching rate, and without erosion lower layer layers of copper.
Meanwhile there is the indium oxide layer etchant of comparative example 1 and 2 peroxide except the scope of the invention to contain
Amount, side etching is few, has pattern loss, and lose in the indium oxide layer that peroxide content is less than comparative example 1 of the invention
It carves in liquid composition, residue occurs.
In the indium oxide layer etchant of the lesser comparative example 3 of azole compounds content, have to the layers of copper of lower layer
It corrodes, and in the indium oxide layer etchant of the excessive comparative example 4 of azole compounds content, side etching is not outstanding simultaneously
And there is residue.
The indium oxide layer etchant of the excessive comparative example 5 of fluorochemical content does not have glass etching rate
The result of benefit.
In addition, in the indium oxide layer etchant and comparative example 7 including acetate that include the comparative example 6 of sulfate
Indium oxide layer etchant in, side etching result and glass etching result be not outstanding, and identify there is residue.
Do not include the indium oxide layer etchant of the comparative example 8 of fluorochemical, and does not include peroxide
The indium oxide layer etchant of comparative example 9 and 10, without outstanding side etching, and there is residue in all of which.
Therefore, indium oxide layer etchant of the invention is not by including being selected to be made of sulfate and acetate
One of group or a variety of, the effect of side etching and glass etching rate can be increased.
In addition, indium oxide layer etchant of the invention does not cause residue to occur during etching, and when manufacture
The layers of copper of indium oxide layer lower layer is not corroded when the array substrate of liquid crystal display device, therefore can be prevented as layers of copper
The disconnection defect of source/drain, and can effectively etch indium oxide layer.
Indium oxide layer etchant of the invention passes through not include selected from as composed by sulfate and acetate
One of group is a variety of and improve etch-rate, can effectively etch indium oxide layer, and therefore can be improved etching process effect
Rate.
In addition, indium oxide layer etchant of the invention can minimize the copper-based gold to the indium oxide layer lower layer
Therefore the erosion for belonging to layer is capable of the driveability of enhanced film Transistors-LCD display device (TFT-LCD), and even if work as
Still have the advantages that keep etch uniformity when substrate size is big.
Claims (11)
1. indium oxide layer etchant does not include being selected from one of group or more as composed by sulfate and acetate
Kind, and the total weight relative to the indium oxide layer etchant includes:
The nitric acid of 3 to 30 weight %；
The benzotriazole of 0.1 to 10 weight %；
The ammonium acid fluoride of 0.01 to 5 weight %；With
The water of surplus, so that the total weight of the indium oxide layer etchant becomes 100 weight %.
2. indium oxide layer etchant according to claim 1, wherein the indium oxide layer is with indium oxide layer shape
At single layer；Or the multilayer formed with the single layer and copper base metal layer.
3. indium oxide layer etchant according to claim 1, wherein the indium oxide layer includes selecting free oxidation
One of group or a variety of composed by indium tin layer, IZO layer and indium gallium zinc layers.
4. indium oxide layer etchant according to claim 2, wherein the copper base metal layer is that layers of copper or copper close
Layer gold.
5. indium oxide layer etchant according to claim 1, further include selected from by metal ion chelation agent and
One of group or a variety of composed by corrosion inhibitor.
6. the method for etching indium oxide layer, comprising:
(1) indium oxide layer is formed on substrate；
(2) photoreactive material is selectively left in the indium oxide layer；With
(3) indium oxide layer is etched using indium oxide layer etchant according to any one of claims 1 to 5.
7. the method for etching indium oxide layer according to claim 6, wherein the photoreactive material is photoresist
Material, and selectively left by exposure and imaging process.
8. the method for manufacturing the array substrate of liquid crystal display device, which comprises
(1) grid lead is formed on substrate；
(2) gate insulating layer is formed on the substrate for including the grid lead；
(3) oxide semiconductor layer is formed on the gate insulating layer；
(4) source and drain electrode are formed on the oxide semiconductor layer；With
(5) pixel electrode with the drain electrode connection is formed,
Wherein step (1) includes formation copper/indium oxide layer or copper alloy/indium oxide layer on substrate, and by utilizing etching solution
Composition etches the copper/indium oxide layer or copper alloy/indium oxide layer forms grid lead；
Step (5) includes forming indium oxide layer, and etch the indium oxide layer using etchant and form pixel electrode；And
And
The etchant is indium oxide layer etchant according to any one of claims 1 to 5.
9. the method for the array substrate of manufacture liquid crystal display device according to claim 8, wherein the indium oxide layer packet
It includes and is selected from one of group or a variety of as composed by indium tin oxide layer, IZO layer and indium gallium zinc layers.
10. the method for the array substrate of manufacture liquid crystal display device according to claim 8, wherein the liquid crystal display fills
The array substrate set is thin film transistor (TFT) (TFT) array substrate.
11. the array substrate of liquid crystal display device comprising selected from by utilizing oxygen according to any one of claims 1 to 5
Change one of group composed by the grid lead and pixel electrode of indium layer etchant etching or a variety of.
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| KR20000017470A (en) | 1998-08-18 | 2000-03-25 | 이기원 | ITO etchant composition |
| KR101264421B1 (en) * | 2005-12-09 | 2013-05-14 | 동우 화인켐 주식회사 | Etchant for metal layer |
| KR101284390B1 (en) * | 2007-06-13 | 2013-07-09 | 동우 화인켐 주식회사 | Method for fabricating array substrate for a liquidcrystal display device |
| KR101647838B1 (en) * | 2008-10-23 | 2016-08-12 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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| KR20120070101A (en) * | 2010-12-21 | 2012-06-29 | 동우 화인켐 주식회사 | Etching solution composition for alloy layer comprising mo and ti, or induim oxide layer |
| KR101774484B1 (en) * | 2011-02-15 | 2017-09-05 | 삼성디스플레이 주식회사 | Non-halogenated etchant for etching an indium oxide layer and method of manufacturing a display substrate using the non-halogenated etchant |
| CN102983101B (en) * | 2011-08-04 | 2015-06-17 | 东友精细化工有限公司 | Manufacturing method of array substrate for liquid crystal display |
| KR20130018531A (en) * | 2011-08-04 | 2013-02-25 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
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| KR20130084717A (en) * | 2012-01-18 | 2013-07-26 | 솔브레인 주식회사 | Etchant composition and method of manufacturing a display substrate using the etchant composition |
| KR101394133B1 (en) * | 2012-08-22 | 2014-05-15 | 주식회사 이엔에프테크놀로지 | Etchant composition for molybdenum alloy layer and indium oxide layer |
| KR101972170B1 (en) * | 2012-11-19 | 2019-04-25 | 동우 화인켐 주식회사 | Method of Manufacturing an Array Substrate for Liquid Crystal Display Device |
| KR102028578B1 (en) * | 2012-12-24 | 2019-10-04 | 동우 화인켐 주식회사 | Method of preparing array of thin film transistor |
| KR101905195B1 (en) * | 2012-12-24 | 2018-10-05 | 동우 화인켐 주식회사 | Etchant composition for Ag thin layer and method for fabricating metal pattern using the same |
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