TWI673344B - Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same - Google Patents
Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same Download PDFInfo
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- TWI673344B TWI673344B TW104141109A TW104141109A TWI673344B TW I673344 B TWI673344 B TW I673344B TW 104141109 A TW104141109 A TW 104141109A TW 104141109 A TW104141109 A TW 104141109A TW I673344 B TWI673344 B TW I673344B
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- Prior art keywords
- oxide layer
- indium oxide
- layer
- indium
- etching
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 128
- 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 128
- 238000005530 etching Methods 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000000758 substrate Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 12
- 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 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 150000003851 azoles Chemical class 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 180
- 239000010949 copper Substances 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- -1 azole compound Chemical class 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 19
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 239000011698 potassium fluoride Substances 0.000 claims 1
- 235000003270 potassium fluoride Nutrition 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 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
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-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
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 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
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- SRLLRIILXLQLHZ-UHFFFAOYSA-N sodium;hydrofluoride Chemical compound F.[Na] SRLLRIILXLQLHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
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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
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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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
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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
- G02F1/136—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
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- 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
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- 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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- Organic Chemistry (AREA)
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- Power Engineering (AREA)
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- Thin Film Transistor (AREA)
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Abstract
本發明涉及氧化銦層蝕刻液組合物和利用其製造液晶顯示裝置的陣列基板的方法，更具體地說，涉及不包括硫酸鹽或乙酸鹽、而是包括硝酸、唑類化合物、含氟化合物和水的氧化銦層蝕刻液組合物，以及利用其製造液晶顯示裝置的陣列基板的方法。 The present invention relates to an indium oxide layer etchant composition and a method for manufacturing an array substrate of a liquid crystal display device using the same, and more particularly, it does not include sulfate or acetate, but includes nitric acid, azole compounds, fluorine-containing compounds, and Water indium oxide layer etching solution composition and method for manufacturing array substrate of liquid crystal display device using the same.
Description
本發明涉及氧化銦層蝕刻液組合物和利用其製造液晶顯示裝置的陣列基板的方法，更具體地說，涉及不包括硫酸鹽或乙酸鹽、而是包括硝酸、唑類化合物、含氟化合物和水的氧化銦層蝕刻液組合物，以及利用其製造液晶顯示裝置的陣列基板的方法。 The present invention relates to an indium oxide layer etchant composition and a method for manufacturing an array substrate of a liquid crystal display device using the same, and more particularly, it does not include sulfate or acetate, but includes nitric acid, azole compounds, fluorine compounds, and Water indium oxide layer etching solution composition and method for manufacturing array substrate of liquid crystal display device using the same.
液晶顯示裝置(LCD)在平板顯示裝置之中是最受喜愛的，因為它們提供了解析度優秀的清晰圖像、耗能較少、並且能夠使顯示幕變薄。現今驅動這種液晶顯示裝置的典型電子電路是薄膜電晶體(TFT)電路，並且典型的薄膜電晶體液晶顯示裝置(TFT-LCD)形成顯示幕的像素。在TFT-LCD中起到開關裝置功能的TFT通過用液晶材料填充以矩陣形式排列的TFT的基板和面對所述TFT基板的彩色 濾光片基板之間的空間來製造。完整的TFT-LCD製造過程大體上分成TFT基板製造過程、彩色濾光片過程、單元過程和組件過程，並且所述TFT基板製造過程和所述彩色濾光片製造過程在呈現準確又清晰的圖像方面非常重要。 Liquid crystal display devices (LCDs) are the most popular among flat panel display devices because they provide clear images with excellent resolution, consume less energy, and can make the display screen thinner. A typical electronic circuit driving such a liquid crystal display device today is a thin film transistor (TFT) circuit, and a typical thin film transistor liquid crystal display device (TFT-LCD) forms pixels of a display screen. A TFT that functions as a switching device in a TFT-LCD is formed by filling a substrate of TFTs arranged in a matrix form with a liquid crystal material and a color that faces the TFT substrate. The space between the filter substrates is manufactured. The complete TFT-LCD manufacturing process is roughly divided into a TFT substrate manufacturing process, a color filter process, a unit process, and an assembly process, and the TFT substrate manufacturing process and the color filter manufacturing process present accurate and clear diagrams. The image aspect is very important.
當製造TFT-LCD的像素顯示電極時，需要由具有高電導率同時具有透明光學性質的材料製成的薄膜，並且基於氧化銦的氧化銦錫(ITO)和氧化銦鋅(IZO)當前用作透明導電膜的材料。 When manufacturing a pixel display electrode for a TFT-LCD, a thin film made of a material having high electrical conductivity and transparent optical properties is required, and indium tin oxide (ITO) and indium zinc oxide (IZO) based on indium oxide are currently used as Material of transparent conductive film.
另外，為了在像素顯示電極中得到目標電路線，需要按照電路圖案修剪薄膜層的蝕刻過程。 In addition, in order to obtain the target circuit line in the pixel display electrode, the etching process of the thin film layer needs to be trimmed according to the circuit pattern.
然而，用通常用於蝕刻金屬雙層的現有蝕刻液，由於ITO氧化物的強耐化學性，難以蝕刻由ITO或IZO材料製成的透明導電膜。具體地說，王水(HCl+CH3COOH+HNO3)、氯化鐵(Ⅲ)的鹽酸溶液(FeCl3/HCl)、或草酸水溶液已經用作透明導電膜的濕蝕刻液，然而，當利用基於王水的蝕刻液或氯化鐵的鹽酸溶液蝕刻ITO層時，成本低但是由於在圖案側表面的蝕刻更快，輪廓低劣，並且因為鹽酸或硝酸在蝕刻液形成後揮發，所述蝕刻液組合物中的波動嚴重，而且可以對下部的金屬發生化學侵蝕。韓國專利申請公佈No.10-2000-0017470利用草酸蝕刻非晶氧化銦錫(ITO)，然而，在這種情況下，在ITO圖案周圍容易出現殘渣，並且因為草酸在低溫下具有低溶解度，引起沉澱物產生，故而出現蝕刻設備故障的問題。 However, it is difficult to etch a transparent conductive film made of an ITO or IZO material with an existing etching solution generally used for etching a metal double layer due to the strong chemical resistance of ITO oxide. Specifically, aqua regia (HCl + CH 3 COOH + HNO 3 ), a hydrochloric acid solution of iron (III) chloride (FeCl 3 / HCl), or an aqueous oxalic acid solution has been used as a wet etching solution for transparent conductive films. However, when When etching an ITO layer using an aqua regia-based etching solution or a ferric chloride-based hydrochloric acid solution, the cost is low, but because the etching on the pattern side surface is faster, the profile is poor, and because hydrochloric acid or nitric acid is volatilized after the etchant is formed, the etching Fluctuations in the liquid composition are severe and can chemically attack the underlying metal. Korean Patent Application Publication No. 10-2000-0017470 uses oxalic acid to etch amorphous indium tin oxide (ITO), however, in this case, residues are likely to occur around the ITO pattern, and because oxalic acid has low solubility at low temperatures, it causes Precipitation is generated, which causes the problem of failure of the etching equipment.
另外，由HI製成的蝕刻液蝕刻速率高和側表面蝕刻 少，但是昂貴，具有高毒性和腐蝕性，並且引起對位於透明像素電極底部的資料線的侵蝕，因此，在實際過程中使用具有限制。 In addition, the etchant made of HI has a high etching rate and side surface etching It is less, but expensive, has high toxicity and corrosiveness, and causes erosion of the data line located at the bottom of the transparent pixel electrode. Therefore, it has a limitation in practical use.
此外，韓國專利申請公佈No.10-2010-0053175公開了透明導電膜的蝕刻組合物，其包括含鹵素化合物、輔助氧化劑、蝕刻控制劑、殘渣抑制劑、腐蝕抑制劑和水，並且硫酸鹽和乙酸鹽分別用作蝕刻控制劑和殘渣抑制劑。然而，當蝕刻組合物中包括硫酸鹽和乙酸鹽時，橫向蝕刻速率低，導致側面蝕刻量小，並出現下層損傷的問題。 In addition, Korean Patent Application Publication No. 10-2010-0053175 discloses an etching composition of a transparent conductive film, which includes a halogen-containing compound, an auxiliary oxidant, an etching control agent, a residue inhibitor, a corrosion inhibitor, and water, and a sulfate and Acetate is used as an etching control agent and a residue inhibitor, respectively. However, when sulfate and acetate are included in the etching composition, the lateral etching rate is low, resulting in a small amount of side etching and the problem of damage to the lower layer.
【現有技術文獻】 [Existing technical literature]
【專利文獻】 [Patent Literature]
(專利文獻1)韓國專利申請公佈No.10-2000-0017470 (Patent Document 1) Korean Patent Application Publication No. 10-2000-0017470
(專利文獻2)韓國專利申請公佈No.10-2010-0053175 (Patent Document 2) Korean Patent Application Publication No. 10-2010-0053175
本發明的目的是通過以不包括選自由硫酸鹽和乙酸鹽所組成的組中的一種或多種的氧化銦層蝕刻液組合物高速地有效蝕刻氧化銦層，從而最大化蝕刻過程效率。 An object of the present invention is to maximize the etching process efficiency by efficiently etching an indium oxide layer at a high speed with an indium oxide layer etchant composition not including one or more selected from the group consisting of sulfates and acetates.
另外，本發明的目的是通過最小化對氧化銦層的下層的侵蝕，提高薄膜電晶體-液晶顯示裝置(TFT-LCD)的驅動性能。 In addition, the object of the present invention is to improve the driving performance of a thin film transistor-liquid crystal display device (TFT-LCD) by minimizing the erosion of the lower layer of the indium oxide layer.
因此，本發明的目的是提供能夠提高蝕刻過程效率和薄膜電晶體-液晶顯示裝置(TFT-LCD)的驅動性能的氧化銦層蝕刻液組合物，利用其的蝕刻方法，和製造液晶顯示 裝置的陣列基板的方法。 Therefore, an object of the present invention is to provide an indium oxide layer etchant composition capable of improving the efficiency of the etching process and the driving performance of a thin film transistor-liquid crystal display device (TFT-LCD), an etching method using the same, and a liquid crystal display. Method of device array substrate.
鑒於上述，本發明的一個方面提供了氧化銦層蝕刻液組合物，其不包括選自由硫酸鹽和乙酸鹽所組成的組中一種或多種，但是相對於所述氧化銦層蝕刻液組合物的總重量包括3至30重量%的硝酸、0.1至10重量%的唑類化合物和0.01至5重量%的含氟化合物，以及餘量的水，使得所述氧化銦層蝕刻液組合物的總重量成為100重量%。 In view of the above, an aspect of the present invention provides an indium oxide layer etchant composition, which does not include one or more selected from the group consisting of sulfate and acetate, but is relative to the indium oxide layer etchant composition. The total weight includes 3 to 30% by weight of nitric acid, 0.1 to 10% by weight of azole compounds and 0.01 to 5% by weight of fluorinated compounds, and the balance of water, so that the total weight of the indium oxide layer etching solution composition It becomes 100% by weight.
本發明的另一個方面提供了蝕刻氧化銦層的方法，所述方法包括(1)在基板上形成氧化銦層；(2)在所述氧化銦層上選擇性留下光反應性材料；和(3)利用本發明的氧化銦層蝕刻液組合物蝕刻所述氧化銦層。 Another aspect of the present invention provides a method of etching an indium oxide layer, the method comprising (1) forming an indium oxide layer on a substrate; (2) selectively leaving a photoreactive material on the indium oxide layer; and (3) The indium oxide layer is etched using the indium oxide layer etchant composition of the present invention.
本發明的又一個方面提供製造液晶顯示裝置的陣列基板的方法，所述方法包括(1)在基板上形成柵極導線；(2)在包括所述柵極導線的基板上形成柵極絕緣層；(3)在所述柵極絕緣層上形成氧化物半導體層；(4)在所述氧化物半導體層上形成源和漏極；和(5)形成與所述漏極連接的像素電極，其中步驟(1)包括在基板上形成銅/氧化銦層或銅合金/氧化銦層、和通過利用蝕刻液組合物蝕刻所述銅/氧化銦層或銅合金/氧化銦層形成柵極導線，步驟(5)包括形成氧化銦層、和利用蝕刻液組合物蝕刻所述氧化銦層形成像素電極，並且所述蝕刻液組合物是本發明的氧化銦層蝕刻液組合物。 Another aspect of the present invention provides a method of manufacturing an array substrate for a liquid crystal display device, the method including (1) forming a gate wire on a substrate; and (2) forming a gate insulating layer on a substrate including the gate wire. (3) forming an oxide semiconductor layer on the gate insulating layer; (4) forming a source and a drain on the oxide semiconductor layer; and (5) forming a pixel electrode connected to the drain, Step (1) includes forming a copper / indium oxide layer or a copper alloy / indium oxide layer on a substrate, and forming a gate wire by etching the copper / indium oxide layer or copper alloy / indium oxide layer using an etchant composition, Step (5) includes forming an indium oxide layer, and etching the indium oxide layer with an etchant composition to form a pixel electrode, and the etchant composition is the indium oxide layer etchant composition of the present invention.
本發明的再一個方面提供了液晶顯示裝置的陣列基板，其包括選自由利用本發明的氧化銦層蝕刻液組合物蝕 刻的柵極導線和像素電極所組成的組中的一種或多種。 According to another aspect of the present invention, there is provided an array substrate for a liquid crystal display device. The array substrate is selected from the group consisting of substrates etched by using the indium oxide layer etchant composition of the present invention. One or more of the group consisting of a carved gate wire and a pixel electrode.
在下文中，將更詳細地描述本發明。 Hereinafter, the present invention will be described in more detail.
本發明涉及氧化銦層蝕刻液組合物，其不包括選自由硫酸鹽和乙酸鹽所組成的組中的一種或多種，但是相對於所述氧化銦層蝕刻液組合物的總重量包括3至30重量%的硝酸、0.1至10重量%的唑類化合物和0.01至5重量%的含氟化合物，以及餘量的水，使得所述氧化銦層蝕刻液組合物的總重量成為100重量%。 The present invention relates to an indium oxide layer etchant composition, which does not include one or more selected from the group consisting of sulfate and acetate, but includes 3 to 30 relative to the total weight of the indium oxide layer etchant composition. The weight percent of nitric acid, 0.1 to 10 weight percent of azole compounds, and 0.01 to 5 weight percent of fluorinated compounds, and the balance of water make the total weight of the indium oxide layer etchant composition 100%.
因不包括選自由硫酸鹽和乙酸鹽所組成的組中的一種或多種，本發明的氧化銦層蝕刻液組合物能夠以更高的速率蝕刻氧化銦層，因此，可以提高蝕刻過程效率。 Since one or more members selected from the group consisting of sulfate and acetate are not included, the indium oxide layer etchant composition of the present invention can etch the indium oxide layer at a higher rate, and therefore, the efficiency of the etching process can be improved.
本發明中的氧化銦層包括選自由氧化銦錫(ITO)層、氧化銦鋅(IZO)層和氧化銦鎵鋅(IGZO)層所組成的組中的一種或多種。 The indium oxide layer in the present invention includes one or more selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, and an indium gallium zinc oxide (IGZO) layer.
另外，用本發明的氧化銦層蝕刻液組合物蝕刻的氧化銦層可以是以氧化銦層形成的單層；或以所述單層和銅基金屬層形成的多層，並且所述銅基金屬層可以是銅層或銅合金層。所述合金層的概念也包括氮化物層或氧化物層。 In addition, the indium oxide layer etched with the indium oxide layer etchant composition of the present invention may be a single layer formed by an indium oxide layer; or a plurality of layers formed by the single layer and a copper-based metal layer, and the copper-based metal layer It can be a copper layer or a copper alloy layer. The concept of the alloy layer also includes a nitride layer or an oxide layer.
本發明的氧化銦層蝕刻液組合物中包括的硝酸(HNO3)是氧化銦層的主要氧化劑，並且執行蝕刻所述氧 化銦層的作用。另外，硝酸對於氧化銦層具有高蝕刻速率並且能夠在蝕刻過程中確保所需的側面蝕刻大。 The nitric acid (HNO 3 ) included in the indium oxide layer etching solution composition of the present invention is a main oxidant of the indium oxide layer, and performs a role of etching the indium oxide layer. In addition, nitric acid has a high etch rate for the indium oxide layer and can ensure a large side etch required during the etching process.
相對於所述氧化銦層蝕刻液組合物的總重量，硝酸占3至30重量%，並優選占5至25重量%。當硝酸占小於3重量%時，可以降低氧化銦層的蝕刻速率，而當大於30重量%時，有可能出現對所述氧化銦層的底部和相鄰金屬的化學侵蝕的問題，並且由於蝕刻速率過高而難以進行程序控制。 Relative to the total weight of the indium oxide layer etching solution composition, nitric acid accounts for 3 to 30% by weight, and preferably accounts for 5 to 25% by weight. When the nitric acid accounts for less than 3% by weight, the etching rate of the indium oxide layer can be reduced, and when it exceeds 30% by weight, the problem of chemical attack on the bottom of the indium oxide layer and adjacent metals may occur, and due to the etching The rate is too high for program control.
本發明的氧化銦層蝕刻液組合物中包括的唑類化合物執行最小化對接觸氧化銦層的銅導線的侵蝕的作用，所述氧化銦層用作液晶顯示裝置的陣列基板的像素電極。換句話說，所述唑類化合物執行最小化對銅基金屬層的侵蝕的作用，所述銅基金屬層是所述氧化銦層的下層。 The azole-based compound included in the indium oxide layer etching solution composition of the present invention performs the effect of minimizing the erosion of the copper wires contacting the indium oxide layer, which is used as a pixel electrode of an array substrate of a liquid crystal display device. In other words, the azole-based compound performs an effect of minimizing the erosion of the copper-based metal layer, which is an underlying layer of the indium oxide layer.
所述唑類化合物優選包括選自由***類化合物、四唑類化合物、咪唑類化合物、吲哚類化合物、嘌呤類化合物、吡唑類化合物、吡啶類化合物、嘧啶類化合物、吡咯類化合物、吡咯烷類化合物和吡咯啉類化合物所組成的組中的一種或多種。 The azole compound preferably includes a triazole compound, a tetrazole compound, an imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, or a pyrrole One or more of the group consisting of an alkane compound and a pyrroline compound.
另外，更具體地說，所述唑類化合物優選包括選自由氨基四唑、苯並***、甲苯基***、2-甲基咪唑、2-乙基咪唑、2-丙基咪唑、2-氨基咪唑、4-甲基咪唑、4-乙基咪唑和4-丙基咪唑所組成的組中的一種或多種。 In addition, more specifically, the azole compound preferably includes a member selected from the group consisting of aminotetrazole, benzotriazole, tolyltriazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2- One or more of the group consisting of aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole.
相對於所述氧化銦層蝕刻液組合物的總重量，所述唑類化合物占0.1至10重量%，並優選占0.5至5重量%。當所述唑類化合物占小於0.1重量%時，可能會對作為氧化銦層下 層的銅層侵蝕，而當大於10重量%時，可以防止對所述銅層的侵蝕，然而，氧化銦層的蝕刻速率可能降低。 The azole compound accounts for 0.1 to 10% by weight, and preferably accounts for 0.5 to 5% by weight, relative to the total weight of the indium oxide layer etchant composition. When the azole compound accounts for less than 0.1% by weight, The copper layer of the layer is eroded, and when it is more than 10% by weight, the copper layer can be prevented from being eroded, however, the etching rate of the indium oxide layer may be reduced.
本發明的氧化銦層蝕刻液組合物中包括的含氟化合物當蝕刻氧化銦層時執行去除殘渣的作用。 The fluorine-containing compound included in the indium oxide layer etching solution composition of the present invention performs a role of removing residues when etching the indium oxide layer.
所述含氟化合物沒有特別的限制，只要它能夠在溶液中解離成氟離子或多原子氟離子即可，但是優選包括選自由氟化銨(NH4F)、氟化鈉(NaF)、氟化鉀(KF)、氟氫化銨(NH4F．HF)、氟氫化鈉(NaF．HF)和氟氫化鉀(KF．HF)所組成的組中的一種或多種。 The fluorine-containing compound is not particularly limited as long as it can dissociate into a fluoride ion or a polyatomic fluoride ion in the solution, but preferably includes a member selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), fluorine One or more of the group consisting of potassium sulfide (KF), ammonium hydride (NH 4 F.HF), sodium fluorohydride (NaF.HF), and potassium hydride (KF.HF).
另外，相對於所述氧化銦層蝕刻液組合物的總重量，所述含氟化合物占0.01至5重量%，並優選占0.01至3重量%。當所述含氟化合物占小於0.01重量%時，當蝕刻氧化銦層時可能出現殘渣，而當大於5重量%時，有玻璃基板或矽層的蝕刻速率增加的問題。 In addition, the fluorine-containing compound accounts for 0.01 to 5% by weight, and preferably 0.01 to 3% by weight, relative to the total weight of the indium oxide layer etching solution composition. When the fluorine-containing compound accounts for less than 0.01% by weight, a residue may occur when the indium oxide layer is etched, and when it is more than 5% by weight, there is a problem that an etching rate of a glass substrate or a silicon layer increases.
本發明的氧化銦層蝕刻液組合物中包括的水占餘量，使得所述組合物的總重量成為100重量%。水沒有特別的限制，然而，優選使用去離子水。另外，優選使用比電阻值為18MΩ．cm或更高的去離子水，比電阻值是顯示水中離子去除程度的值。 The balance of water included in the indium oxide layer etching solution composition of the present invention is such that the total weight of the composition becomes 100% by weight. Water is not particularly limited, however, deionized water is preferably used. In addition, it is preferable to use a specific resistance value of 18 MΩ. cm or more of deionized water, the specific resistance value is a value showing the degree of ion removal in water.
另外，本發明的氧化銦層蝕刻液組合物還可以包括選自由金屬離子螯合劑和腐蝕抑制劑所組成的組中的一種或多種。另外，所述添加劑不限於此，為了促進本發明的效果，可以選擇和添加本領域已知的各種其它添加劑。 In addition, the indium oxide layer etchant composition of the present invention may further include one or more selected from the group consisting of a metal ion chelator and a corrosion inhibitor. In addition, the additives are not limited thereto, and in order to promote the effect of the present invention, various other additives known in the art may be selected and added.
本發明的氧化銦層蝕刻液組合物的組分可以利用本領 域普遍知道的方法製備，並優選使用用於半導體工藝的純度。 The composition of the indium oxide layer etching solution composition of the present invention can utilize the ability The method is generally known in the art and is preferably used for purity in semiconductor processes.
另外，本發明涉及蝕刻氧化銦層的方法，所述方法包括(1)在基板上形成氧化銦層；(2)在所述氧化銦層上選擇性留下光反應性材料；和(3)利用本發明的氧化銦層蝕刻液組合物蝕刻所述氧化銦層。 In addition, the present invention relates to a method of etching an indium oxide layer, the method including (1) forming an indium oxide layer on a substrate; (2) selectively leaving a photoreactive material on the indium oxide layer; and (3) The indium oxide layer is etched using the indium oxide layer etching solution composition of the present invention.
在本發明的蝕刻方法中，所述光反應性材料優選是常用的光致抗蝕劑材料，並且可以利用常用的曝光和顯影過程被選擇性留下。 In the etching method of the present invention, the photo-reactive material is preferably a commonly used photoresist material, and can be selectively left using a common exposure and development process.
此外，本發明涉及製造液晶顯示裝置的陣列基板的方法，包括(1)在基板上形成柵極導線；(2)在包括所述柵極導線的基板上形成柵極絕緣層；(3)在所述柵極絕緣層上形成氧化物半導體層；(4)在所述氧化物半導體層上形成源和漏極；和(5)形成與所述漏極連接的像素電極，其中步驟(1)包括在基板上形成銅/氧化銦層或銅合金/氧化銦層、和通過利用蝕刻液組合物蝕刻所述銅/氧化銦層或銅合金/氧化銦層形成柵極導線，步驟(5)包括形成氧化銦層、和利用蝕刻液組合物蝕刻所述氧化銦層形成圖元電極，並且所述蝕刻液組合物是本發明的氧化銦層蝕刻液組合物。 In addition, the present invention relates to a method of manufacturing an array substrate for a liquid crystal display device, including (1) forming a gate wire on a substrate; (2) forming a gate insulating layer on a substrate including the gate wire; (3) Forming an oxide semiconductor layer on the gate insulating layer; (4) forming a source and a drain on the oxide semiconductor layer; and (5) forming a pixel electrode connected to the drain, wherein step (1) Step (5) includes forming a copper / indium oxide layer or a copper alloy / indium oxide layer on a substrate, and forming a gate wire by etching the copper / indium oxide layer or copper alloy / indium oxide layer using an etchant composition. An indium oxide layer is formed, and the indium oxide layer is etched with an etchant composition to form a picture element electrode, and the etchant composition is the indium oxide layer etchant composition of the present invention.
包括硫酸鹽或乙酸鹽的現有氧化銦層蝕刻液組合物具有緩慢的橫向蝕刻速率，因此當蝕刻步驟(5)的像素電極時，側面蝕刻量小。然而，本發明的氧化銦層蝕刻液組合物不包括硫酸鹽和乙酸鹽，由此可以解決這種問題，並可 以防止對氧化銦層下層的銅基金屬層的侵蝕。 The existing indium oxide layer etchant composition including sulfate or acetate has a slow lateral etching rate, so when the pixel electrode of step (5) is etched, the amount of side etching is small. However, the indium oxide layer etchant composition of the present invention does not include sulfates and acetates, so that this problem can be solved, and In order to prevent the copper-based metal layer under the indium oxide layer from being eroded.
在步驟(1)的基板上形成的氧化銦層是銅/氧化銦層或銅合金/氧化銦層的多層，而在步驟(5)中形成的氧化銦層是氧化銦層的單層。 The indium oxide layer formed on the substrate in step (1) is a multilayer of a copper / indium oxide layer or a copper alloy / indium oxide layer, and the indium oxide layer formed in step (5) is a single layer of an indium oxide layer.
所述氧化銦層包括選自由氧化銦錫(ITO)層、氧化銦鋅(IZO)層和氧化銦鎵鋅(IGZO)層所組成的組中的一種或多種。 The indium oxide layer includes one or more selected from the group consisting of an indium tin oxide (ITO) layer, an indium zinc oxide (IZO) layer, and an indium gallium zinc oxide (IGZO) layer.
通過用本發明的氧化銦層蝕刻液組合物蝕刻，可以在步驟(1)中形成所述柵極導線，並可以在步驟(5)形成所述像素電極。 By etching with the indium oxide layer etchant composition of the present invention, the gate wiring can be formed in step (1), and the pixel electrode can be formed in step (5).
液晶顯示裝置的陣列基板可以是薄膜電晶體(TFT)陣列基板。 The array substrate of the liquid crystal display device may be a thin film transistor (TFT) array substrate.
另外，本發明涉及液晶顯示裝置的陣列基板，其包括選自由利用本發明的氧化銦層蝕刻液組合物蝕刻的柵極導線和像素電極所組成的組中的一種或多種。 In addition, the present invention relates to an array substrate of a liquid crystal display device, which includes one or more selected from the group consisting of a gate wire and a pixel electrode etched with the indium oxide layer etchant composition of the present invention.
在下文中，將參考實施例更詳細地描述本發明。然而，以下實施例只為了說明性的目的，本發明的範圍不限於以下實施例。以下實施例可以在本發明的範圍內由本領域技術人員適當地修改或改變。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited to the following examples. The following embodiments may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
<製備氧化銦層蝕刻液組合物><Preparation of Indium Oxide Layer Etching Liquid Composition>
實施例1至3和比較例1至10Examples 1 to 3 and Comparative Examples 1 to 10
用下表1中顯示的組成製備實施例1至3和比較例1至10的氧化銦層蝕刻液組合物，並包括餘量的水使得總重量成為100重量%。 The indium oxide layer etchant compositions of Examples 1 to 3 and Comparative Examples 1 to 10 were prepared with the compositions shown in Table 1 below, and the balance of water was included so that the total weight became 100% by weight.
BTA：苯並*** BTA: benzotriazole
ABF：氟氫化銨 ABF: ammonium hydride
試驗例1. 對氧化銦層蝕刻液組合物的性質評價Test Example 1. Evaluation of properties of indium oxide layer etching solution composition
通過在玻璃基板(100mm x 100mm)上沉積銅層形成源極/漏極後，通過在所述銅層上層疊矽形成孔，以便曝光所述源極/漏極的金屬層-銅。之後，在其上沉積氧化銦層，並利用光刻過程在所述基板上形成具有規定圖案的光 致抗蝕劑，然後利用實施例1至3和比較例1至10的各種氧化銦層蝕刻液組合物進行所述氧化銦層的蝕刻過程。 After the source / drain is formed by depositing a copper layer on a glass substrate (100 mm x 100 mm), a hole is formed by stacking silicon on the copper layer to expose the metal layer-copper of the source / drain. After that, an indium oxide layer is deposited thereon, and light having a prescribed pattern is formed on the substrate by a photolithography process. A resist is then used to perform the etching process of the indium oxide layer using the various indium oxide layer etching solution compositions of Examples 1 to 3 and Comparative Examples 1 to 10.
使用噴霧蝕刻型試驗設備(型號名稱：ETCHER(TFT)，SEMES Co.Ltd.)，並在蝕刻過程中對於所述蝕刻液組合物使用大約35℃的溫度，然而，必要時該適當溫度可以取決於其他過程條件和其他因素而改變。蝕刻時間取決於蝕刻溫度而不同，然而，在LCD蝕刻過程中蝕刻通常進行大約50至100秒。蝕刻過程中蝕刻的氧化銦層剖面利用截面SEM(Hitachi，Ltd.的產品，型號名稱S-4700)檢查，並觀察側面蝕刻、殘渣出現、玻璃蝕刻速率和下部金屬(Cu)侵蝕。結果顯示在下面表2中。 A spray etching type test equipment (model name: ETCHER (TFT), SEMES Co. Ltd.) was used, and a temperature of about 35 ° C was used for the etchant composition during the etching process, however, the appropriate temperature may be determined if necessary Due to other process conditions and other factors. The etching time differs depending on the etching temperature, however, the etching usually takes about 50 to 100 seconds during the LCD etching process. The cross section of the indium oxide layer etched during the etching process was examined using a cross-sectional SEM (product of Hitachi, Ltd., model name S-4700), and side etching, residue occurrence, glass etching rate, and lower metal (Cu) erosion were observed. The results are shown in Table 2 below.
根據表2的結果，鑒定了實施例1至3中本發明氧化銦層蝕刻液組合物表現出優秀的側面蝕刻，沒有殘渣出現，和優秀的玻璃蝕刻速率，並且沒有侵蝕下層的銅層。 Based on the results in Table 2, it was identified that the indium oxide layer etchant composition of the present invention in Examples 1 to 3 exhibited excellent side etching, no residue appeared, and excellent glass etch rate, and did not corrode the underlying copper layer.
同時，比較例1和2的氧化銦層蝕刻液組合物具有本發明範圍之外的過氧化物含量，其側面蝕刻少，有圖案丟失，並且在過氧化物含量小於本發明的比較例1的氧化銦層蝕刻液組合物中，出現殘渣。 Meanwhile, the indium oxide layer etchant compositions of Comparative Examples 1 and 2 had a peroxide content outside the scope of the present invention, had less side etching, pattern loss, and had a peroxide content less than that of Comparative Example 1 of the present invention. Residues appeared in the indium oxide layer etching solution composition.
在唑類化合物含量較小的比較例3的氧化銦層蝕刻液組合物中，對下層的銅層有侵蝕，而在唑類化合物含量過多的比較例4的氧化銦層蝕刻液組合物中，側面蝕刻不優秀並且出現殘渣。 In the indium oxide layer etchant composition of Comparative Example 3 with a small azole compound content, the underlying copper layer is corroded, and in the indium oxide layer etchant composition of Comparative Example 4 with an excessive azole compound content, Side etching is not excellent and residues appear.
含氟化合物含量過多的比較例5的氧化銦層蝕刻液組合物對玻璃蝕刻速率沒有有利的結果。 The indium oxide layer etchant composition of Comparative Example 5 with too much fluorine-containing compound content did not have a favorable result on the glass etching rate.
另外，在包括硫酸鹽的比較例6的氧化銦層蝕刻液組合物和包括乙酸鹽的比較例7的氧化銦層蝕刻液組合物中，側面蝕刻結果和玻璃蝕刻結果不優秀，並鑒定出現殘渣。 In addition, in the indium oxide layer etchant composition of Comparative Example 6 including sulfate and the indium oxide layer etchant composition of Comparative Example 7 including acetate, the results of side etching and glass etching were not excellent, and residues were identified to be present. .
不包括含氟化合物的比較例8的氧化銦層蝕刻液組合物，以及不包括過氧化物的比較例9和10的氧化銦層蝕刻液組合物，不具有優秀的側面蝕刻，並且它們全部出現殘渣。 The indium oxide layer etchant composition of Comparative Example 8 excluding a fluorine-containing compound, and the indium oxide layer etchant composition of Comparative Examples 9 and 10 excluding a peroxide, did not have excellent side etching, and they all appeared Residue.
因此，本發明的氧化銦層蝕刻液組合物通過不包括選 自由硫酸鹽和乙酸鹽所組成的組中的一種或多種，能夠增加側面蝕刻和玻璃蝕刻速率的效果。 Therefore, the indium oxide layer etchant composition of the present invention is One or more of the group consisting of free sulfate and acetate can increase the effect of side etching and glass etching rate.
另外，本發明的氧化銦層蝕刻液組合物在蝕刻期間不引起殘渣出現，並且當製造液晶顯示裝置的陣列基板時對氧化銦層下層的銅層沒有侵蝕，因此可以防止身為銅層的源/漏極的斷開缺陷，並可以有效蝕刻氧化銦層。 In addition, the indium oxide layer etchant composition of the present invention does not cause residues to appear during etching, and does not erode the copper layer under the indium oxide layer when the array substrate of the liquid crystal display device is manufactured, so it can prevent the source as a copper layer / Drain defect, and can effectively etch the indium oxide layer.
本發明的氧化銦層蝕刻液組合物通過以不包括選自由硫酸鹽和乙酸鹽所組成的組中的一種或多種而改善蝕刻速率，能夠有效蝕刻氧化銦層，並因此能夠提高蝕刻過程效率。 The indium oxide layer etchant composition of the present invention can effectively etch the indium oxide layer by improving the etching rate by not including one or more selected from the group consisting of sulfate and acetate, and thus can improve the efficiency of the etching process.
另外，本發明的氧化銦層蝕刻液組合物能夠最小化對所述氧化銦層下層的銅基金屬層的侵蝕，因此，能夠增強薄膜電晶體-液晶顯示裝置(TFT-LCD)的驅動性能，並且即使當基板尺寸大的時候仍然具有保持蝕刻均勻性的優點。 In addition, the indium oxide layer etchant composition of the present invention can minimize the erosion of the copper-based metal layer underlying the indium oxide layer, and thus can enhance the driving performance of a thin film transistor-liquid crystal display device (TFT-LCD). And even when the substrate size is large, it still has the advantage of maintaining etching uniformity.
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