KR20110054718A - Manufacturing method of an array substrate for liquid crystal display - Google Patents
Manufacturing method of an array substrate for liquid crystal display Download PDFInfo
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- KR20110054718A KR20110054718A KR1020090111470A KR20090111470A KR20110054718A KR 20110054718 A KR20110054718 A KR 20110054718A KR 1020090111470 A KR1020090111470 A KR 1020090111470A KR 20090111470 A KR20090111470 A KR 20090111470A KR 20110054718 A KR20110054718 A KR 20110054718A
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- Prior art keywords
- copper
- film
- metal film
- based metal
- etching
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- 239000000758 substrate Substances 0.000 title claims abstract description 29
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 27
- -1 cyclohexylamine compound Chemical class 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Natural products NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 238000002955 isolation Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—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
-
- 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
- H01L29/456—Ohmic electrodes on silicon
- H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Nonlinear Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Thin Film Transistor (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 액정표시장치용 어레이 기판의 제조방법, 구리계 금속막의 식각액 조성물, 및 상기 식각액 조성물을 사용하는 구리계 금속막의 식각방법에 관한 것이다. The present invention relates to a method of manufacturing an array substrate for a liquid crystal display device, an etching liquid composition of a copper metal film, and an etching method of a copper metal film using the etching liquid composition.
반도체 장치에서 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 the metal wiring on the substrate in the semiconductor device is generally composed of a metal film forming process by sputtering or the like, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. And washing processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically, a dry etching using a plasma or the like and a wet etching using an etching liquid composition are used.
이러한 반도체 장치에서, 최근 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 저항은 RC 신호지연을 유발하는 주요한 인자이므로, 특히 TFT LCD(thin film transistor liquid crystal display)의 경우 패널크기 증가와 고해상도 실현 에 관건이 되고 있기 때문이다. 따라서, TFT LCD 의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는, 저저항의 물질개발이 필수적이며 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 대형 TFT LCD 에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다. In such semiconductor devices, the resistance of metallization has recently emerged as a major concern. Resistance is a major factor that causes RC signal delay, especially for TFT LCD (thin film transistor liquid crystal display), which is a key factor in increasing panel size and realizing high resolution. Therefore, in order to realize the reduction of RC signal delay, which is essential for the large-sized TFT LCD, low-resistance material development is essential, and chromium (Cr, specific resistance: 12.7 × 10 -8 Ωm), molybdenum ( Mo, resistivity: 5 x 10 -8 mm, aluminum (Al, resistivity: 2.65 x 10 -8 mm), and alloys thereof are difficult to use for gate and data wiring used in large-sized TFT LCDs.
따라서, 저저항 금속막으로서 구리막 및 구리 몰리브덴막 등의 구리계 금속막과 그에 대한 식각액 조성물이 주목을 받고 있다. Accordingly, attention has been paid to copper-based metal films such as copper films and copper molybdenum films and etching liquid compositions thereof.
한편, 이러한 구리계 금속막에 대한 식각액으로서 현재까지 알려진 식각액 조성물들은 사용자가 요구하는 성능을 충족시키지 못하고 있어서 이의 개선을 위한 연구개발이 요구되고 있다. On the other hand, the etchant compositions known to date as an etchant for such a copper-based metal film does not meet the performance required by the user, and research and development for improvement thereof is required.
즉, 구리계 금속막에 대한 식각액으로서 여러 종류의 식각액 조성물들이 사용되고 있으나, 이러한 식각액 조성물들은 주로 과산화수소 또는 과황산염 등의 과산화물을 주산화제로 사용하고 있어서, 과산화물의 자체 분해반응에 의한 저장안정성 저하라는 문제를 야기하고 있다. 또한, 과산화수소를 주산화제로 사용하는 경우에는 식각시 식각액 내의 구리이온 농도가 높아짐에 따라 과산화수소의 연쇄분해 반응이 일어나므로 그로 인한 과열의 위험이 문제가 되고 있다.That is, although various types of etchant compositions are used as etching solutions for copper-based metal films, these etchant compositions mainly use peroxides such as hydrogen peroxide or persulfate as main oxidizing agents, and thus, storage stability due to self-decomposition of peroxides is reduced. It is causing a problem. In addition, when hydrogen peroxide is used as the main oxidizing agent, a chain decomposition reaction of hydrogen peroxide occurs as the copper ion concentration in the etching solution increases during etching, thereby causing a risk of overheating.
따라서, 본 발명은 저장안정성이 우수하여 장기간 우수한 식각특성이 유지되고, 과산화수소의 사용에 의해 발생하는 과열로 인한 위험이 없는 구리계 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다. Accordingly, an object of the present invention is to provide an etching liquid composition of a copper-based metal film which has excellent storage stability, maintains excellent etching characteristics for a long time, and is free from danger of overheating caused by the use of hydrogen peroxide.
또한, 본 발명은 식각시 직선성이 우수한 테이퍼프로파일이 형성되고 잔사가 남지 않으며, 게이트 전극 및 게이트 배선, 데이터 전극 및 데이터 배선의 일괄 식각이 가능한 구리계 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching liquid composition of a copper-based metal film capable of forming a tapered profile excellent in linearity during etching and leaving no residue, and capable of collectively etching gate electrodes, gate wirings, data electrodes, and data wirings. .
또한, 본 발명은 상기 식각액 조성물을 사용하는 구리계 금속막의 식각방법 및 액정표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etching method of a copper-based metal film and a method of manufacturing an array substrate for a liquid crystal display device using the etching liquid composition.
본 발명은, 조성물 총중량에 대하여The present invention is based on the total weight of the composition
A) 과황산염 화합물 0.5 내지 20 중량%;A) 0.5-20 wt% persulfate compound;
B) 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물 0.01 내지 5.0 중량%; 및B) 0.01-5.0 wt% of a cyclohexylamine compound unsubstituted or substituted with one or more C 1 -C 4 straight or branched chain alkyl groups; And
C) 잔량의 물을 포함하며, 과산화수소를 포함하지 않는 구리계 금속막의 식각액 조성물을 제공한다.C) provides an etching liquid composition of a copper-based metal film containing a residual amount of water, and does not contain hydrogen peroxide.
또한, 본 발명은In addition,
Ⅰ) 기판 상에 구리계 금속막을 형성하는 단계;I) forming a copper-based metal film on the substrate;
Ⅱ) 상기 구리계 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및II) selectively leaving a photoreactive material on the copper-based metal film; And
Ⅲ) 본 발명의 식각액 조성물을 사용하여 상기 구리계 금속막을 식각하는 단계를 포함하는 구리계 금속막의 식각방법을 제공한다.III) An etching method of a copper-based metal film comprising etching the copper-based metal film using the etching solution composition of the present invention.
또한, 본 발명은,In addition, the present invention,
a) 기판 상에 게이트 배선을 형성하는 단계;a) forming a gate wiring on the substrate;
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; And
e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조 방법에 있어서,(e) forming a pixel electrode connected to the drain electrode;
상기 a) 단계에서는 기판 상에 구리계 금속막을 형성한 후, 본 발명의 식각액 조성물로 식각하여 게이트 배선을 형성하고, 상기 d) 단계에서는 구리계 금속막을 형성한 후, 본 발명의 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조 방법을 제공한다.In the step a), after forming the copper-based metal film on the substrate, the gate wiring is formed by etching with the etchant composition of the present invention, and in the step d) after forming the copper-based metal film, the etchant with the etchant composition of the present invention The present invention provides a method of manufacturing an array substrate for a liquid crystal display device, wherein source and drain electrodes are formed.
또한, 본 발명은 상기 식각액 조성물을 사용하여 식각된 게이트 배선 및 소스 및 드레인 전극 중 하나 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a liquid crystal display device including at least one of a gate wiring and a source and a drain electrode etched using the etchant composition.
본 발명의 식각액 조성물은 저장안정성이 우수하여 장기간 우수한 식각특성 이 유지되며, 과산화수소의 사용에 의해 발생하는 과열로 인한 위험이 없는 효과를 제공한다. The etchant composition of the present invention is excellent storage stability is maintained excellent etching characteristics for a long time, and provides an effect without the risk of overheating caused by the use of hydrogen peroxide.
또한, 본 발명의 식각액 조성물로 구리계 금속막을 식각하게 되면 직선성이 우수한 테이퍼프로파일이 형성되고 구리계 금속막의 잔사가 남지 않으므로 전기적인 쇼트나 배선의 불량, 휘도의 감소 등의 문제로부터 자유로울 수 있다.In addition, when the copper-based metal film is etched by the etching solution composition of the present invention, a taper profile having excellent linearity is formed and the residue of the copper-based metal film does not remain, which can be free from problems such as electrical shorts, poor wiring, and reduced luminance. .
또한, 본 발명에 따른 식각액 조성물만으로 게이트 전극 및 게이트 배선, 데이터 전극 및 데이터 배선을 일괄 식각하는 것이 가능하므로, 공정이 매우 단순화되어 공정수율을 극대화 할 수 있다.In addition, since it is possible to collectively etch the gate electrode, the gate wiring, the data electrode and the data wiring using only the etchant composition according to the present invention, the process may be very simplified and the process yield may be maximized.
더욱이, 본 발명에 따른 식각액 조성물을 사용할 경우, 저항이 낮은 구리 또는 구리 합금 배선을 이용하여 대화면, 고휘도의 회로를 구현함과 더불어 환경친화적인 반도체 장치를 제작할 수 있다.In addition, when using the etchant composition according to the present invention, it is possible to implement a large screen, high-brightness circuit using a low-resistance copper or copper alloy wiring and to manufacture an environmentally friendly semiconductor device.
본 발명은, A) 과황산염 화합물, B) 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물 및 C) 물을 포함하며, 과산화수소를 포함하지 않는 구리계 금속막의 식각액 조성물에 관한 것이다. The present invention comprises A) a persulfate compound, B) a cyclohexylamine compound unsubstituted or substituted with one or more C1 to C4 linear or branched alkyl groups, and C) a copper-based metal that does not contain hydrogen peroxide. The etchant composition of the membrane.
본 발명에서 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 단일막 및 이중막 등의 다층막을 포함하는 개념이다. 예컨대, 구리 또는 구리 합금(구리의 산화막, 질화막 포함)의 단일막, 다층막으로서 구리 또는 구리 합금막 과 몰리브덴 또는 몰리브덴 합금막으로 이루어진 다층막 등이 포함된다. 상기 몰리브덴 합금막은 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In) 등으로 이루어진 군에서 선택되는 하나 이상과 몰리브덴의 합금을 의미한다.In the present invention, the copper-based metal film includes copper as a constituent of the film, and is a concept including a multilayer film such as a single film and a double film. For example, a single film of copper or a copper alloy (including a copper oxide film and a nitride film), a multilayer film made of a copper or copper alloy film and a molybdenum or molybdenum alloy film as the multilayer film, and the like are included. The molybdenum alloy film means an alloy of molybdenum and at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodynium (Nd), indium (In), and the like. do.
상기에서 과황산염은 구리계 금속막을 식각하는 주성분이다. 과황산염의 구체적인 예로는 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8), 과황산암모늄((NH4)2S2O8) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.Persulfate is the main component for etching the copper-based metal film. Specific examples of the persulfate include potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), and the like. One kind alone or two or more kinds may be used together.
상기 과황산염의 함량은 조성물 총중량에 대하여 0.5 내지 20중량%인 것이 바람직하다. 과황산염의 함량이 0.5중량% 미만이면 구리계 금속의 식각이 되지 안되거나 식각속도가 아주 느리고, 20중량%를 초과할 경우에는 식각속도가 전체적으로 빨라지기 때문에 공정을 컨트롤하는 것이 어려워진다.The content of the persulfate is preferably 0.5 to 20% by weight based on the total weight of the composition. If the content of the persulfate is less than 0.5% by weight, the copper-based metal may not be etched or the etching rate is very slow. If the content of the persulfate exceeds 20% by weight, the process may be difficult to control because the etching rate may be faster.
상기 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물은 과황산염의 분해 속도를 늦추는 역할을 한다. 상기 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물의 구체적인 예로는 하기 화학식1로 표시되는 화합물을 들 수 있다.The cyclohexylamine compound substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups serves to slow down the decomposition rate of persulfate. Specific examples of the cyclohexylamine compound substituted or unsubstituted with at least one C1 to C4 linear or branched alkyl group include compounds represented by the following general formula (1).
[화학식1][Formula 1]
상기 식에서 R1 및 R2는 각각 독립적으로, 수소 또는 C1~C4의 직쇄 또는 분지쇄의 알킬기이다.In the above formula, R1 and R2 are each independently hydrogen or a C1-C4 linear or branched alkyl group.
상기에서 C1~C4의 직쇄 또는 분지쇄의 알킬기로는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기, tert-부틸기 등을 들 수 있다.As said C1-C4 linear or branched alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl group, tert- butyl group, etc. are mentioned.
상기 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물의 함량은 조성물 총 중량에 대하여 0.01 내지 5.0 중량%인 것이 바람직하며, 0.01 중량% 미만인 경우 과산화수소수의 분해 속도 억제력이 낮아지고, 5.0 중량%를 초과하는 경우 식각 속도가 느려지게 되는 단점이 있다.The content of the cyclohexylamine compound substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups is preferably 0.01 to 5.0% by weight based on the total weight of the composition, and when less than 0.01% by weight, decomposition of hydrogen peroxide The speed inhibiting power is lowered, the etching rate is lowered when it exceeds 5.0% by weight.
상기 물은 특별히 한정되는 것은 아니나, 탈이온수가 바람직하다. 더욱 바람직하게는 물의 비저항 값(즉, 물속에 이온이 제거된 정도)이 18㏁/㎝이상인 탈이온수를 사용하는 것이 좋다. Although the said water is not specifically limited, Deionized water is preferable. More preferably, deionized water having a specific resistance value of the water (that is, the degree to which ions are removed in the water) is 18 kW / cm or more is used.
본 발명에 따른 식각액 조성물에 대해서는 전술한 성분 이외에 글리콜에테르류 화합물을 포함할 수 있다. 글리콜에테르류 화합물은 시클로헥실아민의 과황산염 안정화 효과를 보조하는 역할을 하며, 동시에 표면장력을 저하시켜 식각의 균일성 을 증가시키는 역할을 한다. The etching solution composition according to the present invention may include a glycol ether compound in addition to the aforementioned components. Glycol ether compounds serve to assist the persulfate stabilizing effect of cyclohexylamine, and at the same time serves to increase the uniformity of etching by lowering the surface tension.
글리콜에테르류의 구체적인 예로는 에틸렌글리콜(EG), 프로필렌글리콜(PG), 디에틸렌글리콜(DEG), 트리에틸렌글리콜(TEG), 폴리에틸렌글리콜(PEG), 폴리프로필렌글리콜(PPG) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상이 함께 사용될 수 있다.Specific examples of the glycol ethers include ethylene glycol (EG), propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG), polypropylene glycol (PPG), and the like. These may be used alone or in combination of two or more thereof.
상기 글리콜에테르류 화합물의 함량은 조성물 총 중량에 대하여 0.01 내지 4중량%인 것이 바람직하며, 0.01중량% 미만인 경우 식각 균일성이 저하되고, 4중량% 이상이면 거품이 많이 발생되는 단점이 있다.The content of the glycol ether compound is preferably 0.01 to 4% by weight based on the total weight of the composition, when less than 0.01% by weight, the etching uniformity is lowered, if more than 4% by weight has a disadvantage of generating a lot of bubbles.
본 발명에 따른 식각액 조성물에는 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 금속 이온 봉쇄제, 및 부식 방지제 등을 사용할 수 있다. In addition to the above components, a conventional additive may be further added to the etching liquid composition according to the present invention, and as the additive, a metal ion blocking agent, a corrosion inhibitor, or the like may be used.
본 발명에서 사용되는 과황산염 및 하나 이상의 C1~C4의 직쇄 또는 분지쇄의 알킬기로 치환 또는 비치환된 시클로헥실아민 화합물은 통상적으로 공지된 방법에 의해서 제조 가능하고, 반도체 공정용의 순도를 가지는 것이 바람직하다.The persulfate and the cyclohexylamine compound substituted or unsubstituted with one or more C1 to C4 linear or branched alkyl groups used in the present invention may be prepared by a known method, and have a purity for a semiconductor process. desirable.
본 발명에 따른 구리계 금속막의 식각액 조성물은 구리계 금속으로 이루어진 액정표시장치의 게이트 전극 및 게이트 배선, 데이터 전극 및 데이터 배선을 일괄 식각할 수 있다.The etching liquid composition of the copper-based metal film according to the present invention may collectively etch the gate electrode, the gate wiring, the data electrode, and the data wiring of the liquid crystal display device made of the copper-based metal.
또한, 본 발명은,In addition, the present invention,
Ⅰ) 기판 상에 구리계 금속막을 형성하는 단계;I) forming a copper-based metal film on the substrate;
Ⅱ) 상기 구리계 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및II) selectively leaving a photoreactive material on the copper-based metal film; And
Ⅲ) 본 발명의 식각액 조성물을 사용하여 상기 구리계 금속막을 식각하는 단계를 포함하는 구리계 금속막의 식각방법에 관한 것이다.III) Etching method of the copper-based metal film comprising the step of etching the copper-based metal film using the etching liquid composition of the present invention.
본 발명의 식각방법에서, 상기 광반응 물질은 통상적인 포토레지스트 물질인 것이 바람직하며, 통상적인 노광 및 현상 공정에 의해 선택적으로 남겨질 수 있다.In the etching method of the present invention, the photoreactive material is preferably a conventional photoresist material, and may be selectively left by conventional exposure and development processes.
또한, 본 발명은, In addition, the present invention,
a) 기판 상에 게이트 배선을 형성하는 단계;a) forming a gate wiring on the substrate;
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; And
e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조 방법에 있어서, (e) forming a pixel electrode connected to the drain electrode;
상기 a) 단계에서는 기판 상에 구리계 금속막을 형성한 후, 본 발명의 식각액 조성물로 식각하여 게이트 배선을 형성하고, 상기 d) 단계에서는 구리계 금속막을 형성한 후, 본 발명의 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조 방법에 관한 것이다.In the step a), after forming the copper-based metal film on the substrate, the gate wiring is formed by etching with the etchant composition of the present invention, and in the step d) after forming the copper-based metal film, the etchant with the etchant composition of the present invention The present invention relates to a method for manufacturing an array substrate for a liquid crystal display device, wherein the source and drain electrodes are formed.
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. The array substrate for a liquid crystal display device may be a thin film transistor (TFT) array substrate.
이하에서 본 발명을 실시예를 통하여 더욱 구체적으로 설명한다. 그러나, 하기의 실시예에 의하여 본 발명의 범위가 제한되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by the following examples.
실시예 1 및 비교예1: 식각액 조성물의 제조 및 식각특성 평가Example 1 and Comparative Example 1: Preparation of etching liquid composition and evaluation of etching characteristics
하기 표 1에 나타낸 조성에 따라 실시예 1 및 비교예 1의 식각액 조성물을 제조하였다. 그리고, 그 식각액 조성물을 이용하여 구리 단일막의 식각공정을 수행하였다.To the etchant composition of Example 1 and Comparative Example 1 according to the composition shown in Table 1. The etching process of the copper single layer was performed using the etching solution composition.
<식각특성평가><Etch Characteristic Evaluation>
분사식 식각 방식의 실험장비(제조사: SEMES사, 모델명: ETCHER(TFT)) 내에 실시예1 내지 비교예1의 식각액 조성물을 넣고 온도를 25℃로 세팅하여 가온하였다. 그 후, 온도가 30±0.1℃에 도달한 후, 식각 공정을 수행하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍(熱風) 건조장치를 이용하여 건조하고, 포토레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 제조사: HITACHI사, 모델명: S-4700)을 이용하여 잔사 여부 및 식각 특성을 평가하여, 그 결과를 하기 표 1에 나타내었다. The etching liquid composition of Example 1 to Comparative Example 1 was placed in an experimental equipment of a spray etching method (manufacturer: SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C. and heated. Then, after the temperature reached 30 ± 0.1 ℃, the etching process was performed. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper. After washing and drying, using an electron scanning microscope (SEM; manufacturer: HITACHI, model name: S-4700) to evaluate the residue and etching characteristics, the results are shown in Table 1 below.
<안정성 평가><Stability Evaluation>
상기 식각특성평가를 수행한 실시예1 내지 비교예1의 식각액을 보관하면서 상기 처음 식각을 수행한 날로부터 각각 3일, 7일, 15일이 지난 후에 기판을 1매씩 식각하여 저장 안정성을 평가하였다. 즉, 제조된 식각액 조성물을 장기 보관하여 식각특성 평가를 반복 시행함으로써, 장기 보관에 따른 식각성능의 변화를 평가하였다. After storing the etching solution of Examples 1 to Comparative Example 1 where the etching characteristic evaluation was performed, the substrates were etched one by one after 3, 7 and 15 days from the first etching, respectively, to evaluate storage stability. . That is, the long-term storage of the prepared etchant composition was repeated to evaluate the etching characteristics, thereby evaluating the change in etching performance according to long-term storage.
상기 표1의 평가결과에 나타난 바와 같이, 시클로헥실아민 화합물이 포함되지 않은 식각액(비교예1)과 비교하여 시클로헥실아민 화합물이 포함된 본 발명의 식각액(실시예1)은 저장 안정성이 우수하게 확보됨을 확인할 수 있다.As shown in the evaluation results of Table 1, the etching solution (Example 1) of the present invention containing a cyclohexylamine compound compared to the etching solution (Comparative Example 1) does not contain a cyclohexylamine compound has excellent storage stability It can be confirmed that it is secured.
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