KR101941289B1 - Manufacturing method of an array substrate for liquid crystal display - Google Patents
Manufacturing method of an array substrate for liquid crystal display Download PDFInfo
- Publication number
- KR101941289B1 KR101941289B1 KR1020120080757A KR20120080757A KR101941289B1 KR 101941289 B1 KR101941289 B1 KR 101941289B1 KR 1020120080757 A KR1020120080757 A KR 1020120080757A KR 20120080757 A KR20120080757 A KR 20120080757A KR 101941289 B1 KR101941289 B1 KR 101941289B1
- Authority
- KR
- South Korea
- Prior art keywords
- film
- copper
- based metal
- weight
- metal oxide
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 40
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 claims abstract description 89
- 239000002184 metal Substances 0.000 claims abstract description 89
- 229910052802 copper Inorganic materials 0.000 claims abstract description 85
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000005530 etching Methods 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 165
- 238000000034 method Methods 0.000 claims description 35
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 15
- -1 azole compound Chemical class 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- 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
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 claims description 2
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 6
- 230000000052 comparative effect Effects 0.000 description 16
- 239000004094 surface-active agent Substances 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PRSXMVQXAKTVLS-UHFFFAOYSA-N [Cu]=O.[In] Chemical compound [Cu]=O.[In] PRSXMVQXAKTVLS-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—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
-
- 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
- G02F1/133—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
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
Abstract
본 발명은 a)기판 상에 게이트 전극을 형성하는 단계; b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및 e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, 상기 a)단계는 기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하고, 상기 식각액 조성물은, 조성물 총 중량에 대하여 A)과산화수소(H2O2) 1.0 내지 10.0중량%, B)함불소 화합물 0.01 내지 1.0중량%, C)아졸화합물 0.1 내지 5.0 중량%, D)옥살산 또는 이의 염 1.0 내지 5.0중량% 및 E)물 잔량을 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.A) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming a source / drain electrode on the semiconductor layer; And forming a pixel electrode connected to the drain electrode, wherein the step a) includes the step of forming a copper-based metal film or a copper-based metal film and a metal oxide film on the substrate And forming a gate electrode by etching a copper-based metal film or a multi-layered film of a copper-based metal film and a metal oxide film with an etchant composition, wherein the step d) includes forming a copper- Forming a multi-layered film of a metal-based metal film and a metal oxide film, and etching the multi-layered film of the copper-based metal film or the copper-based metal film and the metal oxide film with an etchant composition to form a source / drain electrode, 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 ), B) 0.01 to 1.0% by weight of a fluorine compound, C) 5.0% by weight, D) 1.0 to 5.0% by weight of oxalic acid or a salt thereof, and E) water balance. The present invention also relates to a method for producing an array substrate for a liquid crystal display.
Description
본 발명은 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing an array substrate for a liquid crystal display.
액정표시장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식식각 또는 식각액 조성물을 이용하는 습식식각이 사용된다.The process of forming a metal wiring on a substrate in a liquid crystal display device is usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and a step by an etching process And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.
이러한 액정표시장치에서, 최근 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 왜냐하면 TFT-LCD(thin film transistor-liquid crystal display)에 있어서 RC 신호지연 문제를 해결하는 것이 패널크기 증가와 고해상도 실현에 관건이 되고 있는데, 이는 저항이 RC 신호지연을 유발하는 주요한 인자이기 때문이다. 따라서, TFT-LCD의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는, 저저항의 물질을 개발하는 것이 필수적이다. In such a liquid crystal display device, resistance of metal wiring has recently become a major concern. This is because resolving the RC signal delay problem in a thin film transistor-liquid crystal display (TFT-LCD) is a key factor in increasing the panel size and realizing a high resolution, because the resistor is a major factor causing the RC signal delay. Therefore, it is essential to develop a low-resistance material in order to realize reduction of the RC signal delay, which is indispensably required for enlarging the TFT-LCD.
종래에 주로 사용되었던 크롬(Cr, 비저항: 12.7 ×10-8Ωm), 몰리브덴(Mo, 비저항: 5×10-8Ωm), 알루미늄(Al, 비저항: 2.65 ×10-8Ωm) 및 이들의 합금은 저항이 크기 때문에 대형 TFT LCD에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어렵다. 따라서, 저저항 금속막으로서 구리막 및 구리 몰리브덴막 등의 구리계 금속막과 그에 대한 식각액 조성물이 주목을 받고 있다. 그런데, 현재까지 알려진 구리계 식각액 조성물들은 사용자가 요구하는 성능을 충족시키지 못하고 있기 때문에 성능 향상을 위한 연구개발이 요구되고 있다. Chromium which was mainly used conventionally (Cr, specific resistance: 12.7 × 10 -8 Ωm), molybdenum (Mo, specific resistance: 5 × 10 -8 Ωm), aluminum (Al, specific resistance: 2.65 × 10 -8 Ωm), and alloys thereof Is difficult to be used for gate and data wiring used in a large-sized TFT LCD. Therefore, a copper-based metal film such as a copper film and a copper molybdenum film and an etchant composition therefor are attracting attention as a low resistance metal film. However, since copper etching compositions known to date do not satisfy the performance required by the user, research and development for improving the performance is required.
한편, 기존의 과산화수소를 사용한 구리막 식각액의 경우 구리 또는 구리합금과 몰리브덴 또는 몰리브덴 합금으로 이루어진 다층 금속막의 일괄 습식식각 및 패턴 형성은 가능하다. 그러나 금속층 식각 시 용해되는 금속 이온 특히 구리이온에 의해 과산화수소의 분해속도가 빨라짐에 따른 과열현상으로 식각액의 안정성이 크게 저하되는 문제점이 있다. 또한, 다층 금속막의 경우 용해되는 금속이온 농도가 증가할수록 과산화수소에 의한 구리층의 식각 속도와 불소화합물에 의한 몰리브덴 합금층의 식각 속도 차이 및 전기효과의 영향으로 두 금속층이 접합되어 있는 계면에 대한 변형이 발생하여 식각특성이 양호하지 못하다는 문제점이 있다. On the other hand, in the case of a copper film etchant using conventional hydrogen peroxide, batch wet etching and pattern formation of a multilayer metal film made of copper or a copper alloy and a molybdenum or molybdenum alloy is possible. However, there is a problem that the stability of the etching solution is greatly deteriorated due to an overheating phenomenon as the decomposition rate of the hydrogen peroxide is increased by the metal ions, especially copper ions, dissolved in the metal layer etching. In the case of the multilayer metal film, as the concentration of dissolved metal ions increases, the etching rate of the copper layer due to hydrogen peroxide, the etching rate of the molybdenum alloy layer due to the fluorine compound, And the etching characteristics are not good.
특허를 예로 들면, 대한민국등록특허 10-1002338호에서는 질산, 염산, 과산화수소, 아졸화합물을 포함하는 구리 금속층과 투명 도전층을 일괄식각하는 식각액이 개시되어 있다. 하지만, 상기 특허의 경우, 염산으로 인해 구리 금속층의 손상이 심해 사용하기 어려운 단점이 있다.For example, Korean Patent No. 10-1002338 discloses an etchant for collectively etching a copper metal layer containing nitric acid, hydrochloric acid, hydrogen peroxide, and an azole compound and a transparent conductive layer. However, in the case of the above patent, there is a disadvantage that it is difficult to use due to the damage of the copper metal layer due to hydrochloric acid.
본 발명의 목적은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition capable of etching a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film.
본 발명의 목적은 식각시 직진성이 우수한 테이퍼 프로파일이 형성되고, 금속막의 잔사가 남지 않는, 식각액 조성물을 제공하는 것이다.An object of the present invention is to provide an etching liquid composition in which a taper profile having an excellent straightness during etching is formed and a residue of a metal film is not left.
또한, 본 발명의 목적은 액정표시장치용 어레이 기판의 게이트 전극과 게이트 배선, 소스/드레인 전극과 데이터 배선이 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 포함할 때, 일괄식각이 가능한 식각액 조성물을 제공하는 것이다.It is also an object of the present invention to provide a method of manufacturing a semiconductor device in which when a gate electrode, a gate wiring, a source / drain electrode, and a data wiring of an array substrate for a liquid crystal display device include a copper- And to provide a possible etchant composition.
또한, 본 발명의 목적은 상기 식각액 조성물을 사용하는 배선 형성방법 및 액정표시장치용 어레이 기판의 제조방법을 제공하는 것이다.It is also an object of the present invention to provide a wiring forming method using the etchant composition and a method of manufacturing an array substrate for a liquid crystal display device.
본 발명은 a)기판 상에 게이트 전극을 형성하는 단계; b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및 e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, 상기 a)단계는 기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하고, 상기 식각액 조성물은, 조성물 총 중량에 대하여 A)과산화수소(H2O2) 1.0 내지 10.0중량%, B)함불소 화합물 0.01 내지 1.0중량%, C)아졸화합물 0.1 내지 5.0 중량%, D)옥살산 또는 이의 염 1.0 내지 5.0중량% 및 E)물 잔량을 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.A) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming a source / drain electrode on the semiconductor layer; And forming a pixel electrode connected to the drain electrode, wherein the step a) includes the step of forming a copper-based metal film or a copper-based metal film and a metal oxide film on the substrate And forming a gate electrode by etching a copper-based metal film or a multi-layered film of a copper-based metal film and a metal oxide film with an etchant composition, wherein the step d) includes forming a copper- Forming a multi-layered film of a metal-based metal film and a metal oxide film, and etching the multi-layered film of the copper-based metal film or the copper-based metal film and the metal oxide film with an etchant composition to form a source / drain electrode, 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 ), B) 0.01 to 1.0% by weight of a fluorine compound, C) 5.0% by weight, D) 1.0 to 5.0% by weight of oxalic acid or a salt thereof, and E) water balance. The present invention also provides a method for manufacturing an array substrate for a liquid crystal display.
본 발명은 조성물 총 중량에 대하여, A)과산화수소(H2O2) 1.0 내지 10.0중량%; B)함불소 화합물 0.01 내지 1.0중량%; C)아졸화합물 0.1 내지 5.0 중량%; D)옥살산 또는 이의 염 1.0 내지 5.0중량%; 및 E)물 잔량을 포함하는 것을 특징으로 하는, 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막용 식각액 조성물을 제공한다.The present invention relates to a composition comprising: A) from 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 ); B) 0.01 to 1.0% by weight of a fluorine compound; C) from 0.1 to 5.0% by weight of an azole compound; D) from 1.0 to 5.0% by weight of oxalic acid or a salt thereof; And E) a residual amount of water. The present invention provides an etchant composition for a multilayer film of a copper-based metal film or a copper-based metal film and a metal oxide film.
본 발명은 Ⅰ)기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하는 단계; Ⅱ)상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막 상에 선택적으로 광반응 물질을 남기는 단계; 및 Ⅲ)본 발명의 식각액 조성물을 사용하여 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각하는 단계를 포함하는 배선 형성방법을 제공한다.The present invention provides a method of manufacturing a semiconductor device, comprising: (I) forming a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film on a substrate; II) selectively leaving a photoreactive material on the copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film; And (III) etching the multilayer film of the copper-based metal film or the copper-based metal film and the metal oxide film using the etchant composition of the present invention.
본 발명은 상기 식각액 조성물을 사용하여 식각된 게이트 배선, 게이트 전극, 데이터 배선 및 소스/드레인 전극 중 하나 이상을 포함하는 액정표시장치용 어레이 기판에 관한 것이다.The present invention relates to an array substrate for a liquid crystal display comprising at least one of gate wirings, gate electrodes, data lines and source / drain electrodes etched using the etchant composition.
본 발명의 식각액 조성물은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각할 때, 식각 균일성 및 직진성이 우수한 테이퍼 프로파일을 구현할 수 있다.The etchant composition of the present invention can realize a taper profile having excellent etching uniformity and straightness when etching a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film.
본 발명의 식각액 조성물은 식각할 때, 잔사를 발생시키지 않으므로 전기적인 쇼트나 배선의 불량, 휘도의 감소 등의 문제로부터 자유롭다.Since the etchant composition of the present invention does not generate residues when etching, it is free from problems such as electrical shorts, poor wiring, and reduced luminance.
또한, 본 발명의 식각액 조성물은 액정표시장치용 어레이 기판을 제조시, 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 포함하는, 게이트 전극과 게이트 배선, 소스/드레인 전극과 데이터 배선을 일괄식각할 수 있어, 식각공정을 단순화시키며 공정수율을 극대화시킨다.In addition, the etchant composition of the present invention can be used as a gate electrode, a gate wiring, a source / drain electrode, and a data wiring including a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film at the time of manufacturing an array substrate for a liquid crystal display It enables batch etching, simplifying etching process and maximizing process yield.
따라서, 본 발명의 식각액 조성물은 대화면, 고휘도의 회로가 구현되는 액정표시장치용 어레이 기판의 제조시에 매우 유용하게 사용될 수 있다.Therefore, the etchant composition of the present invention can be very usefully used in manufacturing an array substrate for a liquid crystal display device in which a circuit of a large screen and a high luminance is realized.
도 1은 실시예4의 식각액 조성물을 이용하여 식각한 Cu/ITO 이중막의 식각 프로파일을 나타낸 사진이다.
도 2는 실시예4의 식각액 조성물을 이용하여 식각한 Cu/ITO 이중막의 직진성을 나타낸 사진이다.1 is a photograph showing an etched profile of a Cu / ITO double-layer film etched using the etchant composition of Example 4. FIG.
2 is a photograph showing the straightness of a Cu / ITO double layer etched using the etchant composition of Example 4. Fig.
이하, 본 발명을 상세히 설명하면 다음과 같다.
Hereinafter, the present invention will be described in detail.
본 발명은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 과열현상 없이 일괄식각할 수 있도록, 안정성을 크게 향상시킨 식각액 조성물, 식각방법, 액정표시장치용 어레이 기판 및 액정표시장치용 어레이 기판의 제조방법에 관한 것이다. 여기서, 상기 식각액 조성물은 과산화수소 외에, 함불소 화합물, 아졸화합물, 옥살산 또는 이의 염 및 물을 포함하는 것을 가장 큰 특징으로 한다.The present invention relates to an etchant composition, an etching method, an array substrate for a liquid crystal display device, and an array for a liquid crystal display device, which can greatly improve stability in batch etching a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film without overheating. And a method of manufacturing a substrate. Here, the etchant composition is characterized mainly by a fluorine compound, an azole compound, oxalic acid or a salt thereof, and water in addition to hydrogen peroxide.
본 발명에서 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 단일막 및 이중막 등의 다층막을 포함하는 개념이다. 상기 구리계 금속막은 구리 또는 구리 합금막일 수 있다.In the present invention, the copper-based metal film includes copper as a constituent component of the film, and includes a multilayer film such as a single film and a double film. The copper-based metal film may be copper or a copper alloy film.
본 발명에서 금속산화물막은 통상 AxByCzO(A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0)의 조합으로 이루어진 삼성분계 또는 사성분계 산화물을 함유하여 구성된 막으로서, 산화물 반도체층이라고 불리거나 또는 산화물 반도체층을 구성하는 막일 수 있다.In the present invention, the metal oxide film is generally composed of a ternary or tetragonal oxide composed of a combination of AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr and Ta; x, Or may be a film which is called an oxide semiconductor layer or constitutes an oxide semiconductor layer.
본 발명에서, 구리계 금속막과 금속산화물막의 다층막으로는 구리 산화인듐막(ITO), 구리 산화인듐 합금막, 구리 갈륨산화아연막(IGZO) 등을 들 수 있다. 상기 구리 산화인듐막은 산화인듐계 금속막과 상기 산화인듐계 금속막 상에 형성된 구리계 금속막을 포함하는 다층막을 의미한다. 상기 구리 산화인듐계 합금막은 산화인듐계 합금막과 상기 산화인듐 합금막 상에 형성된 구리계 금속막을 포함하는 다층막을 의미한다. 상기 구리계 금속막과 금속산화물막의 적층 순서는 바뀔 수 있다.
In the present invention, examples of the multi-layered film of the copper-based metal film and the metal oxide film include an indium-tin oxide (ITO) film, an indium-copper alloy oxide film and a copper gallium oxide zinc film (IGZO). The indium copper oxide film means a multi-layered film including an indium oxide-based metal film and a copper-based metal film formed on the indium oxide-based metal film. The indium-based copper alloy alloy film refers to a multi-layered film including an indium oxide-based alloy film and a copper-based metal film formed on the indium oxide alloy film. The order of lamination of the copper-based metal film and the metal oxide film may be changed.
1. One. 식각액Etchant 조성물 Composition
본 발명의 식각액 조성물은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막용 식각액 조성물로서, A)과산화수소(H2O2), B)함불소 화합물, C)아졸화합물, D)옥살산 또는 이의 염 및 E)물을 포함한다.The etchant composition of the present invention is an etchant composition for a multilayer film of a copper-based metal film or a copper-based metal film and a metal oxide film, which comprises A) hydrogen peroxide (H 2 O 2 ), B) fluorine compound, C) azole compound, D) Salts thereof and E) water.
본 발명의 식각액 조성물에 포함되는 A)과산화수소(H2O2)는 구리계 금속막을 식각하는 주성분이고, 상기 B)함불소 화합물의 활성도를 높여주는 역할도 한다.The A) hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is the main component for etching the copper-based metal film and also enhances the activity of the fluorine compound (B).
상기 A)과산화수소(H2O2)는 조성물 총 중량에 대하여, 1.0 내지 10.0중량%로 포함되고, 바람직하게는 3.0 내지 8.0중량%로 포함된다. 상술한 범위 미만으로 포함되면, 구리계 금속막이 식각되지 않거나 식각 속도가 아주 느려진다. 상술한 범위를 초과하여 포함되면, 식각 속도가 전체적으로 빨라지기 때문에 공정 컨트롤이 어렵다.
The A) hydrogen peroxide (H 2 O 2 ) is contained in an amount of 1.0 to 10.0% by weight, preferably 3.0 to 8.0% by weight, based on the total weight of the composition. If it is contained below the above-mentioned range, the copper-based metal film is not etched or the etching rate is very slow. If it exceeds the above-mentioned range, it is difficult to control the process because the etching rate is accelerated as a whole.
본 발명의 식각액 조성물에 포함되는 B)함불소 화합물은 물에 해리되어 플루오르 이온을 낼 수 있는 화합물을 의미한다. 상기 B)함불소 화합물은 금속산화물막을 식각하는 주성분이며, 구리계 금속막과 금속산화물막을 동시에 식각하는 용액에서 필연적으로 발생하는 잔사를 제거해 주는 역할을 한다. The fluorine-containing compound (B) contained in the etchant composition of the present invention means a compound capable of releasing fluorine ions by being dissolved in water. The B) fluorine compound is a main component that etches the metal oxide film and removes residues that are inevitably generated in a solution for simultaneously etching the copper-based metal film and the metal oxide film.
상기 B)함불소 화합물은 조성물 총 중량에 대하여 0.01 내지 1.0중량%로 포함되고, 바람직하게는 0.05 내지 0.2중량%로 포함된다. 상술한 범위 미만으로 포함되면, 식각 잔사가 발생될 수 있다. 상술한 범위를 초과하여 포함되면, 유리 기판 식각율이 커지는 문제가 있다. The fluorine-containing compound (B) is contained in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.2% by weight based on the total weight of the composition. If included below the above-mentioned range, etch residues can be generated. If it exceeds the above range, there is a problem that the etching rate of the glass substrate becomes large.
상기 B)함불소 화합물은 이 분야에서 사용되는 물질로서 용액 내에서 플루오르 이온 혹은 다원자 플루오르 이온으로 해리될 수 있는 것이라면 특별히 한정되지 않는다. 하지만, 상기 B)함불소 화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·F) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것이 바람직하다.
The B) fluorine compound is not particularly limited as long as it can be dissociated into a fluorine ion or a polyatomic fluorine ion in a solution used in this field. However, the B) fluorine compound may be at least one selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF ), Sodium bifluoride (NaF 占.), Potassium bifluoride (KF 占 HF), and the like.
본 발명의 식각액 조성물에 포함되는 C)아졸화합물은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주어 공정상의 마진을 높이는 역할을 한다. The C) azole compound contained in the etchant composition of the present invention controls the etch rate of the copper-based metal film and reduces the CD loss of the pattern, thereby enhancing the process margin.
상기 C)아졸화합물은 조성물 총 중량에 대하여, 0.1 내지 5.0중량%으로 포함되고, 바람직하게는 0.5 내지 1.5중량%로 포함된다. 상술한 범위 미만으로 포함되면, 식각 속도가 빠르게 되어 시디로스가 너무 크게 발생될 수 있다. 상술한 범위를 초과하여 포함되면, 구리계 금속막의 식각 속도가 너무 느려지게 되어 상대적으로 금속산화물막의 식각 속도가 빨라지게 되므로 언더컷이 발생될 수 있다. The C) azole compound is contained in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 1.5% by weight based on the total weight of the composition. If it is included below the above-mentioned range, the etching rate becomes high and the seed loss can be caused to be too large. If the amount exceeds the above-mentioned range, the etching rate of the copper-based metal film becomes too slow, so that the etching rate of the metal oxide film is relatively increased, and undercut can occur.
상기 C)아졸화합물은 아미노테트라졸(aminotetrazole), 벤조트리아졸 (benzotriazole), 톨릴트리아졸(tolyltriazole), 피라졸(pyrazole), 피롤(pyrrole), 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸 및 4-프로필이미다졸로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다.
The C) azole compound may be selected from the group consisting of aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2- Is at least one member selected from the group consisting of ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole desirable.
본 발명의 식각액 조성물에 포함되는 D)옥살산 또는 이의 염은 pH를 조절할 뿐 아니라 산화인듐막에 대한 보조산화제 역할을 한다. 또한, 식각 시에 식각액 상에 용해되어 있는 구리와의 배위결합을 통해 안정화시킴으로써 약액 안정성을 향상시키고 처리매수 상승 효과를 가져온다.The D) oxalic acid or its salt contained in the etchant composition of the present invention not only controls the pH but also serves as a co-oxidant for the indium oxide film. In addition, it is stabilized through coordination with copper dissolved in the etching solution at the time of etching, thereby improving chemical stability and increasing the number of treatments.
상기 D)옥살산 또는 이의 염은 조성물 총 중량에 대하여, 1 내지 5.0중량%로 포함되고, 바람직하게는 2.0 내지 4.0중량%로 포함된다. 상술한 범위 미만으로 포함되면, pH 조절효과가 크지 않음에 따라 식각 속도가 낮은 문제점이 있고, 또한 착화제로써의 용량 자체가 적으므로 착화제의 성능이 발휘되지 않는다. 상술한 범위를 초과하여 포함되면, 너무 빠른 식각속도로 인해 공정컨트롤이 어려우며, 장비 운용시 용해도차에 의해 콜로이드 형태의 부유물질이 발생할 수 있다. The D) oxalic acid or a salt thereof is contained in an amount of 1 to 5.0% by weight, and preferably 2.0 to 4.0% by weight based on the total weight of the composition. If the amount is less than the above-mentioned range, there is a problem in that the etching rate is low as the pH adjusting effect is not large, and the capacity as a complexing agent itself is small, so that the performance of the complexing agent is not exerted. If it is included in the above range, it is difficult to control the process due to a too high etching rate, and colloid-type suspended solids may be generated due to the solubility difference during operation of the apparatus.
상기 옥살산의 염은 상기 옥살산의 염은 수산암모늄(ammonium oxalate), 수산나트륨(sodium oxalate), 수산칼슘(calcium oxalate) 및 수산칼륨(potassium oxalate)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것이 바람직하다.
The salt of oxalic acid may be one or more selected from the group consisting of ammonium oxalate, sodium oxalate, calcium oxalate and potassium oxalate. desirable.
본 발명의 식각액 조성물에 포함되는 E)물은 특별히 한정되는 것은 아니나, 탈이온수가 바람직하다. 더욱 바람직하게는 물의 비저항 값(즉, 물속에 이온이 제거된 정도)이 18㏁·㎝이상인 탈이온수를 사용하는 것이 좋다. 상기 E)물은 본 발명의 식각액 조성물의 총 중량이 100중량%가 되도록 잔량 포함된다.
The E) water contained in the etchant composition of the present invention is not particularly limited, but deionized water is preferred. More preferably, it is preferable to use deionized water having a resistivity value of water (i.e., the degree of removal of ions in water) of 18 M OMEGA .cm or more. The E) water is contained in such an amount that the total weight of the etchant composition of the present invention is 100% by weight.
본 발명의 식각액 조성물은 계면활성제를 더 포함할 수 있다. 상기 계면활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 상기 계면활성제는 본 발명의 식각액 조성물에 견딜 수 있고, 상용성이 있는 것이라면 특별히 한정되지 않으나, 음이온성 계면활성제, 양이온성 계면활성제, 양쪽 이온성 계면활성제, 비이온성 계면활성제 및 다가알코올형 계면활성제로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. The etchant composition of the present invention may further comprise a surfactant. The surfactant serves to lower the surface tension and increase the uniformity of the etching. The surfactant is not particularly limited as long as it can withstand the etching composition of the present invention and is compatible with the surfactant. However, the surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and a polyhydric alcohol surfactant , Or a combination thereof.
또한, 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 금속 이온 봉쇄제, 및 부식 방지제 등을 들 수 있다.
In addition to the above-described components, conventional additives may be further added. Examples of the additive include a metal ion blocking agent and a corrosion inhibitor.
본 발명에서 사용되는 A)과산화수소(H2O2), B)함불소 화합물, C)아졸화합물, D)옥살산 또는 이의 염은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다.
A) hydrogen peroxide (H 2 O 2 ) used in the present invention, B) fluorine compound, C) azole compound, D) oxalic acid or a salt thereof can be produced by a conventionally known method, Preferably has a purity for semiconductor processing.
본 발명의 식각액 조성물은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각할 때, 식각 균일성 및 직진성이 우수한 테이퍼 프로파일을 구현할 수 있다. 본 발명의 식각액 조성물은 식각할 때, 잔사를 발생시키지 않으므로 전기적인 쇼트나 배선의 불량, 휘도의 감소 등의 문제로부터 자유롭다. 또한, 본 발명의 식각액 조성물은 액정표시장치용 어레이 기판을 제조시, 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 포함하는, 게이트 전극과 게이트 배선, 소스/드레인 전극과 데이터 배선을 일괄식각할 수 있어, 식각공정을 단순화시키며 공정수율을 극대화시킨다. 따라서, 본 발명의 식각액 조성물은 대화면, 고휘도의 회로가 구현되는 액정표시장치용 어레이 기판의 제조시에 매우 유용하게 사용될 수 있다.
The etchant composition of the present invention can realize a taper profile having excellent etching uniformity and straightness when etching a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film. Since the etchant composition of the present invention does not generate residues when etching, it is free from problems such as electrical shorts, poor wiring, and reduced luminance. In addition, the etchant composition of the present invention can be used as a gate electrode, a gate wiring, a source / drain electrode, and a data wiring including a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film at the time of manufacturing an array substrate for a liquid crystal display It enables batch etching, simplifying etching process and maximizing process yield. Therefore, the etchant composition of the present invention can be very usefully used in manufacturing an array substrate for a liquid crystal display device in which a circuit of a large screen and a high luminance is realized.
2. 배선 형성방법2. Wiring method
본 발명의 배선 형성방법은The wiring forming method of the present invention
Ⅰ)기판 상에 구리계 금속막, 금속산화물막, 금속막 또는 이들의 다층막을 형성하는 단계;(I) forming a copper-based metal film, a metal oxide film, a metal film or a multilayer film thereof on a substrate;
Ⅱ)상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막 상에 선택적으로 광반응 물질을 남기는 단계; 및II) selectively leaving a photoreactive material on the copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film; And
Ⅲ)본 발명의 식각액 조성물을 사용하여 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각하는 단계를 포함한다.III) etching the copper-based metal film or the multilayer film of the copper-based metal film and the metal oxide film using the etching liquid composition of the present invention.
본 발명의 배선 형성방법에서, 상기 광반응 물질은 통상적인 포토레지스트 물질인 것이 바람직하며, 통상적인 노광 및 현상 공정에 의해 선택적으로 남겨질 수 있다.
In the wiring forming method of the present invention, the photoreactive material is preferably a conventional photoresist material, and can be selectively left by a conventional exposure and development process.
3. 액정표시장치용 어레이 기판의 제조방법3. Manufacturing Method of Array Substrate for Liquid Crystal Display
본 발명의 액정표시장치용 어레이 기판의 제조방법은, In the method for manufacturing an array substrate for a liquid crystal display of the present invention,
a)기판 상에 게이트 전극을 형성하는 단계;a) forming a gate electrode on a substrate;
b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate electrode;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및d) forming a source / drain electrode on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
상기 a)단계는 기판 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고,The step a) includes forming a copper-based metal film on the substrate and etching the copper-based metal film with the etchant composition of the present invention to form a gate electrode,
상기 d)단계는 반도체층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하고,The step d) includes forming a copper-based metal film on the semiconductor layer and etching the copper-based metal film with the etchant composition of the present invention to form source / drain electrodes,
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. 그리고, 상기 액정표시장치용 어레이 기판은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 전극, 게이트 배선, 소스/드레인 전극 및 데이터 배선 중 하나 이상을 포함한다.
The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate. The array substrate for a liquid crystal display includes at least one of a gate electrode, a gate wiring, a source / drain electrode, and a data wiring which are etched using the etching solution composition of the present invention.
이하에서, 본 발명을 실시예 등을 통하여 상세히 설명한다. 그러나, 하기의 실시예 등은 본 발명을 더욱 상세하게 설명하기 위해 제공되는 것이며, 이들에 의해 본 발명의 범위가 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail through examples and the like. However, the following examples are provided to further illustrate the present invention, and the scope of the present invention is not limited thereto.
실시예1Example 1 내지 To 실시예7Example 7 , , 비교예1Comparative Example 1 내지 To 비교예4Comparative Example 4 : : 식각액Etchant 조성물의 제조 Preparation of composition
하기 표 1에 나타낸 조성에 따라 실시예1 내지 실시예7, 비교예1 내지 비교예4의 식각액 조성물 180㎏을 제조하였다.180 kg of the etching solution compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared according to the compositions shown in Table 1 below.
(중량%)H 2 O 2
(weight%)
(중량%)Fluorine compound
(weight%)
(중량%)Deionized water
(weight%)
ATZ: 아미노테트라졸
ATZ: Aminotetrazole
시험예Test Example : : 식각액Etchant 조성물의 특성평가 Evaluation of composition characteristics
<Cu/IT0 및 Cu/IGZOx의 식각><Etching of Cu / IT0 and Cu / IGZOx>
유리기판(100㎜Ⅹ100㎜) 상에 ITO 또는 Cu/IGZOx를 증착시키고 상기 ITO 또는 Cu/IGZOx상에 구리막을 증착시킨 뒤 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 하였다. 그 후, 실시예1 내지 실시예7, 비교예1 내지 비교예4의 식각액 조성물을 각각 사용하여 Cu/ITO 이중막에 대하여 식각 공정을 실시하였다.ITO or Cu / IGZOx was deposited on a glass substrate (100 mm × 100 mm), and a copper film was deposited on the ITO or Cu / IGZOx. Then, a photoresist having a predetermined pattern was formed on the substrate through a photolithography process Respectively. Thereafter, etching processes were performed on the Cu / ITO bilayers using the etching composition compositions of Examples 1 to 7 and Comparative Examples 1 to 4, respectively.
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 식각액 조성물의 온도는 약 30℃ 내외로 하였다. 식각 시간은 100초 정도로 진행하였다. 상기 식각 공정에서 식각된 구리계 금속막의 프로파일을 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였고, 결과를 하기 표2에 기재하였다.
(ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 30 캜 in the etching process. The etching time was about 100 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, model name S-4700), and the results are shown in Table 2 below.
(주) ○: 좋음, △: 보통, Х: 나쁨
(Note): Good: Fair: Fair: X: Bad
표 2를 참조하면, 실시예1 내지 실시예7의 식각액 조성물은 모두 양호한 식각 특성을 나타내었다. Referring to Table 2, the etching composition compositions of Examples 1 to 7 all exhibited good etching properties.
따라서, 본 발명의 식각액 조성물은 구리계 금속막, 금속산화물막의 식각에 매우 적합하고, 이들의 일괄식각에도 매우 접합한 것을 알 수 있다.Therefore, it can be seen that the etching solution composition of the present invention is very suitable for etching the copper-based metal film and the metal oxide film, and is also bonded to the batch etching thereof.
반면, 비교예1의 식각액의 경우 금속이온 용해의 착화제로서 옥살산이 없어 Cu가 식각되지 않는 현상이 나타남을 알 수 있다. 비교예2에서 알 수 있듯이 불화물이 없을 경우 구리막은 식각 가능하나 구리막 하부 ITO막은 식각 효과가 없었다. 한편, 본 발명에서 제시한 옥산살의 함량이 0.5중량%인 비교예3, 7.0중량%인 비교예4의 경우 식각 특성이 좋지 않았다.On the other hand, in the case of the etchant of Comparative Example 1, there is no oxalic acid as a complexing agent for dissolving metal ions, and Cu is not etched. As can be seen from Comparative Example 2, the copper film could be etched without fluoride, but the ITO film below the copper film had no etching effect. On the other hand, in the case of Comparative Example 3 in which the content of oxalic acid was 0.5% by weight and Comparative Example 4 in which 7.0% by weight was present in the present invention, the etching properties were not good.
한편, 도 1은 실시예4의 식각액 조성물을 이용하여 식각한 Cu/ITO 이중막의 식각 프로파일을 나타낸 사진이다. 도 2는 실시예4의 식각액 조성물을 이용하여 식각한 Cu/ITO 이중막의 직진성을 나타낸 사진이다. Meanwhile, FIG. 1 is a photograph showing the etching profile of a Cu / ITO double film etched using the etching solution composition of Example 4. FIG. 2 is a photograph showing the straightness of a Cu / ITO double layer etched using the etchant composition of Example 4. Fig.
도 1 및 도 2을 참조하면, 실시예 4에 따른 식각액 조성물로 식각한 Cu/ITO 이중막은 양호한 테이퍼 프로파일과 우수한 직진성을 나타내었다.Referring to FIGS. 1 and 2, the Cu / ITO double layer etched with the etchant composition according to Example 4 exhibited a good taper profile and excellent straightness.
Claims (10)
b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 a)단계는 기판 상에 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고,
상기 d)단계는 반도체층 상에 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막과 금속산화물막의 다층막을 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하고,
상기 식각액 조성물은, 조성물 총 중량에 대하여 A)과산화수소(H2O2) 1.0 내지 10.0중량%, B)함불소 화합물 0.01 내지 1.0중량%, C)아졸화합물 0.1 내지 5.0 중량%, D)옥살산 또는 이의 염 1.0 내지 5.0중량% 및 E)물 잔량을 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
The step a) includes forming a multi-layered film of a copper-based metal film and a metal oxide film on a substrate, and etching the multi-layered film of the copper-based metal film and the metal oxide film with an etchant composition to form a gate electrode,
In the step d), a multi-layered film of a copper-based metal film and a metal oxide film is formed on the semiconductor layer and a multi-layered film of the copper-based metal film and the metal oxide film is etched with an etchant composition to form source / drain electrodes,
Wherein the etchant composition comprises: A) from 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 ), from 0.01 to 1.0% by weight of a fluorine compound, C) from 0.1 to 5.0% by weight of an azole compound, D) 1.0 to 5.0% by weight of a salt thereof, and E) water.
상기 액정표시장치용 어레이 기판이 박막트랜지스터(TFT) 어레이 기판인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법. The method according to claim 1,
Wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate.
Ⅱ)상기 구리계 금속막과 금속산화물막의 다층막 상에 선택적으로 광반응 물질을 남기는 단계; 및
Ⅲ) 식각액 조성물을 사용하여 상기 구리계 금속막과 금속산화물막의 다층막을 식각하는 단계를 포함하는 배선 형성방법에 있어서,
상기 식각액 조성물은 조성물 총 중량에 대하여 A)과산화수소(H2O2) 1.0 내지 10.0중량%, B)함불소 화합물 0.01 내지 1.0중량%, C)아졸화합물 0.1 내지 5.0 중량%, D)옥살산 또는 이의 염 1.0 내지 5.0중량% 및 E)물 잔량을 포함하는 것을 특징으로 하는 배선 형성방법.(I) forming a multilayer film of a copper-based metal film and a metal oxide film on a substrate;
II) selectively leaving a photoreactive material on the multi-layered film of the copper-based metal film and the metal oxide film; And
III) etching the multi-layered film of the copper-based metal film and the metal oxide film using the etching liquid composition,
Wherein the etchant composition comprises: A) from 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 ), from 0.01 to 1.0% by weight of a fluorine compound, C) from 0.1 to 5.0% by weight of an azole compound, D) 1.0 to 5.0% by weight of a salt and E) water.
A)과산화수소(H2O2) 1.0 내지 10.0중량%;
B)함불소 화합물 0.01 내지 1.0중량%;
C)아졸화합물 0.1 내지 5.0 중량%;
D)옥살산 또는 이의 염 1.0 내지 5.0중량%; 및
E)물 잔량을 포함하는 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.With respect to the total weight of the composition,
A) 1.0 to 10.0% by weight of hydrogen peroxide (H 2 O 2 );
B) 0.01 to 1.0% by weight of a fluorine compound;
C) from 0.1 to 5.0% by weight of an azole compound;
D) from 1.0 to 5.0% by weight of oxalic acid or a salt thereof; And
E) water balance.
Layer structure of a copper-based metal film and a metal oxide film.
상기 B)함불소 화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.The method of claim 4,
The B) fluorine compound may be at least one selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF) Characterized in that it is at least one selected from the group consisting of sodium bifluoride (NaF.HF) and potassium bifluoride (KF.HF)
Layer structure of a copper-based metal film and a metal oxide film.
상기 C)아졸화합물은 아미노테트라졸(aminotetrazole), 벤조트리아졸 (benzotriazole), 톨릴트리아졸(tolyltriazole), 피라졸(pyrazole), 피롤(pyrrole), 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸 및 4-프로필이미다졸로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.The method of claim 4,
The C) azole compound may be selected from the group consisting of aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2- Ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole Features,
Layer structure of a copper-based metal film and a metal oxide film.
상기 옥살산의 염은 수산암모늄(ammonium oxalate), 수산나트륨(sodium oxalate), 수산칼슘(calcium oxalate) 및 수산칼륨(potassium oxalate)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.The method of claim 4,
Wherein the salt of oxalic acid is at least one selected from the group consisting of ammonium oxalate, sodium oxalate, calcium oxalate and potassium oxalate.
Layer structure of a copper-based metal film and a metal oxide film.
상기 구리계 금속막은 구리 또는 구리 합금막인 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.The method of claim 4,
Wherein the copper-based metal film is a copper or copper alloy film.
Layer structure of a copper-based metal film and a metal oxide film.
상기 금속산화물막은 AxByCzO(A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0)의 조합으로 이루어진 삼성분계 또는 사성분계 산화물을 함유하여 구성된 막인 것을 특징으로 하는,
구리계 금속막과 금속산화물막의 다층막용 식각액 조성물.The method of claim 4,
Wherein the metal oxide film comprises a ternary or tetragonal oxide composed of a combination of AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, Wherein the film-
Layer structure of a copper-based metal film and a metal oxide film.
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