KR101674679B1 - 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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- KR101674679B1 KR101674679B1 KR1020090088315A KR20090088315A KR101674679B1 KR 101674679 B1 KR101674679 B1 KR 101674679B1 KR 1020090088315 A KR1020090088315 A KR 1020090088315A KR 20090088315 A KR20090088315 A KR 20090088315A KR 101674679 B1 KR101674679 B1 KR 101674679B1
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- Prior art keywords
- copper
- metal film
- based metal
- forming
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- 239000000758 substrate Substances 0.000 title claims abstract description 33
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 65
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 63
- 238000005530 etching Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 27
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 14
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 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 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 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
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 3
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011651 chromium Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- XMEDDALPOKNUEP-UHFFFAOYSA-N [Mo].[In] Chemical compound [Mo].[In] XMEDDALPOKNUEP-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
- 239000002981 blocking agent Substances 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
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 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
- 238000012360 testing method Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000005406 washing 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
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- 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
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
Abstract
본 발명은 a)기판 상에 게이트 배선을 형성하는 단계; b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스 및 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 금속막을 형성하고 상기 구리계 금속막을 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하며, 상기 식각액 조성물은, 조성물 총 중량에 대하여, A)과산화수소(H2O2) 0.1 내지 25 중량%, B)과황산염 1 내지 20 중량%, C)함불소화합물 0.01 내지 5.0 중량% 및 D)잔량의 물을 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention provides a method of manufacturing a semiconductor device, comprising: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; And forming a pixel electrode connected to the drain electrode, wherein the step a) includes the steps of: forming a copper-based metal film on the substrate and forming the copper-based metal film on the etchant composition Wherein 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 to form source and drain electrodes, Wherein the etchant composition comprises 0.1 to 25% by weight of A) hydrogen peroxide (H 2 O 2 ), 1 to 20% by weight of a sulfate and 0.01 to 5.0% by weight of a fluorine compound, and D) Of water in the liquid crystal display device.
구리막, 액정표시장치, 게이트, 소스, 드레인, 과산화수소, 식각액 Copper film, liquid crystal display, gate, source, drain, hydrogen peroxide, etchant
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 for manufacturing an array substrate for a liquid crystal display, an etching liquid composition for a copper-based metal film, and a method for etching a copper-based 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 a metal wiring on a substrate in a semiconductor device is generally 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 an etching process , A cleaning process before and after the individual unit process, and the like. 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 반도체 장치에서, 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 되 는데, 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 semiconductor device, resistance of metal wiring has recently become a major concern. This is because resolving the RC signal delay problem in TFT-LCD (thin film transistor-liquid crystal display) is a key factor in increasing the panel size and realizing high resolution, because the resistance is the main 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.
본 발명은 구리계 금속막의 식각시 산화제로 사용되는 과산화수소의 함량을 최소화하여, 식각액 내로 용출된 구리이온의 농도가 높아짐에 따라 발생하는, 과산화수소의 연쇄분해 반응을 최소화함으로써 과열로 인한 위험을 예방하면서도 다량의 과산화수소를 사용할 때와 동등 이상의 식각특성을 유지하는 구리계 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention minimizes the amount of hydrogen peroxide used as an oxidizing agent when etching a copper-based metal film, minimizes the chain decomposition reaction of hydrogen peroxide, which occurs as the concentration of copper ions eluted into the etchant increases, An object of the present invention is to provide an etchant composition for a copper-based metal film that maintains an etching property equal to or greater than that when a large amount of hydrogen peroxide is used.
또한, 본 발명은 식각시 직선성이 우수한 테이퍼프로파일이 형성되고, 금속막의 잔사가 남지 않는 구리계 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an etching solution composition for a copper-based metal film in which a tapered profile having excellent linearity at the time of etching is formed and a residue of a metal film is not left.
또한, 본 발명은 게이트 전극과 게이트 배선 및 소스/드레인 전극과 데이터 배선의 일괄 식각이 가능한 구리계 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a copper-based metal film etchant composition capable of collectively etching gate electrodes, gate wirings, source / drain electrodes, and data wirings.
또한, 본 발명은 상기 식각액 조성물을 사용하는 구리계 금속막의 식각방법 및 액정표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다. It is still another object of the present invention to provide a method of etching a copper-based metal film using the etchant composition and a method of manufacturing an array substrate for a liquid crystal display device.
본 발명은 조성물 총중량에 대하여, A)과산화수소(H2O2) 0.1 내지 25 중량%, B)과황산염 1 내지 20 중량%, C)함불소화합물 0.01 내지 5.0 중량% 및 D)잔량의 물을 포함하는 구리계 금속막의 식각액 조성물을 제공한다.The present invention relates to a composition comprising: A) from 0.1 to 25% by weight of hydrogen peroxide (H 2 O 2 ); B) from 1 to 20% by weight of sulfuric acid; C) from 0.01 to 5.0% by weight of a fluorine compound; and D) Based metal film.
또한, 본 발명은 Ⅰ)기판 상에 구리계 금속막을 형성하는 단계; Ⅱ)상기 구리계 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및 Ⅲ)본 발명의 식각액 조성물을 사용하여 상기 구리계 금속막을 식각하는 단계를 포함하는 구리계 금속막의 식각방법을 제공한다.The present invention also provides a method of manufacturing a semiconductor device, comprising: (I) forming a copper-based metal film on a substrate; II) selectively leaving a photoreactive material on the copper-based metal film; And (III) etching the copper-based metal film using the etchant composition of the present invention.
또한, 본 발명은 a)기판 상에 게이트 배선을 형성하는 단계; b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스 및 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 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.The present invention also provides a method of manufacturing a semiconductor device, comprising the steps of: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; And forming a pixel electrode connected to the drain electrode, wherein the step a) includes forming a copper-based metal film on the substrate and forming the copper-based metal film on the substrate according to the present invention And forming a gate wiring by etching with the etchant composition of the present invention. In the step d), a copper-based metal film is formed on the semiconductor layer and the copper-based metal film is etched by the etchant composition of the present invention to form source and drain electrodes The method comprising the steps of: forming an array substrate on a substrate;
또한, 본 발명은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 배선 및 소스/드레인 전극 중 하나 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a liquid crystal display comprising at least one of gate wirings and source / drain electrodes etched using the etchant composition of the present invention.
본 발명의 식각액 조성물은 과산화수소의 함량을 최소화하여, 식각액 내로 용출된 구리이온의 농도가 높아짐에 따라 발생하는, 과산화수소의 연쇄분해 반응을 최소화함으로써 과열로 인한 위험을 예방하면서도 다량의 과산화수소를 사용할 때와 동등 이상의 식각특성을 유지하므로, 효율적으로 식각공정의 수행을 가능하게 한다.The etchant composition of the present invention minimizes the amount of hydrogen peroxide, minimizes the chain decomposition reaction of hydrogen peroxide as the concentration of copper ions eluted into the etching solution is minimized, and prevents the risk of overheating, while using a large amount of hydrogen peroxide The etching process can be performed efficiently because the same etching characteristics are maintained.
또한, 본 발명의 식각액 조성물은 구리계 금속막을 식각할 때, 직선성이 우수한 테이퍼프로파일을 구현하며, 잔사를 발생시키지 않으므로 전기적인 쇼트나 배선의 불량, 휘도의 감소 등의 문제로부터 자유롭다.In addition, the etching composition of the present invention realizes a taper profile having excellent linearity when etching a copper-based metal film, and does not generate residues, so that it is free from problems such as electrical shorts, poor wiring, and reduced luminance.
또한, 본 발명의 식각액 조성물은 액정표시장치용 어레이 기판을 제조시, 게이트 전극과 게이트 배선 및 소스/드레인과 데이터 배선을 일괄 식각할 수 있어, 식각공정을 단순화시키며 공정수율을 극대화시킨다.In addition, the etchant composition of the present invention can collectively etch gate electrodes, gate wirings, source / drain and data wirings at the time of manufacturing an array substrate for a liquid crystal display, thereby simplifying the etching process and maximizing the process yield.
또한, 상기와 같은 효과를 제공하므로 본 발명의 식각액 조성물은 대화면, 고휘도의 회로가 구현되는 액정표시장치용 어레이 기판의 제조시에 매우 유용하게 사용될 수 있다.In addition, since the above-mentioned effects are provided, 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.
본 발명은, A)과산화수소(H2O2) 0.1 내지 25 중량%, B)과황산염 1 내지 20 중량%, C)함불소화합물 0.01 내지 5.0 중량% 및 D)잔량의 물을 포함하는 구리계 금속막의 식각액 조성물에 관한 것이다. The present invention relates to a process for the production of copper-based alloys comprising A) 0.1 to 25% by weight of hydrogen peroxide (H 2 O 2 ), B) 1 to 20% by weight of sulfates, C) 0.01 to 5.0% To an etchant composition of a metal film.
본 발명에서 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 단일막 및 이중막 등의 다층막을 포함하는 개념이다. 예컨대, 구리 또는 구리 합금의 단일막, 다층막으로서 구리 몰리브덴막, 구리 몰리브덴 합금막, 구리 티타 늄막 등이 포함된다. 상기 구리 몰리브덴막은 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리 몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리 티타늄막은 티타늄층과 상기 티타늄층 상에 형성된 구리층을 포함하는 것을 의미한다.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. For example, a single film of copper or a copper alloy, a multi-layer film of copper, a copper molybdenum film, a copper molybdenum alloy film, a copper titanium film, or the like. The copper molybdenum film means that the copper molybdenum film includes a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, The term " film " refers to a titanium layer and a copper layer formed on the titanium layer.
또한, 상기 몰리브덴 합금층은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In) 등으로 이루어진 군에서 선택되는 하나 이상과 몰리브덴의 합금을 의미한다.The molybdenum alloy layer may include at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium Molybdenum alloy.
본 발명의 식각액 조성물에 포함되는 A)과산화수소(H2O2)는 구리계 금속막을 식각하는 주성분으로서, 조성물 총중량에 대하여 0.1 내지 25 중량%로 포함될 수 있으며, 바람직하게는 0.5 내지 5 중량%로 포함된다. 상기 A)과산화수소의 함량이 0.1 중량% 미만이면, 구리계 금속의 식각이 되지 안거나 식각속도가 아주 느려지며, 25 중량%를 초과하면 식각속도가 전체적으로 빨라지기 때문에 공정 컨트롤이 어렵다.A) hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is a main component for etching the copper-based metal film and may be contained in an amount of 0.1 to 25 wt%, preferably 0.5 to 5 wt% . If the A) content of hydrogen peroxide is less than 0.1% by weight, the copper-based metal is not etched or the etching rate is very slow. If the content is more than 25% by weight, the etching speed is generally accelerated.
본 발명의 식각액 조성물에 포함되는 B)과황산염은 과산화수소와 더불어 구리막 또는 구리합금막을 식각하는 주성분이다. The B) and sulfate contained in the etchant composition of the present invention is the main component that etches the copper film or the copper alloy film together with the hydrogen peroxide.
상기 B)과황산염은 조성물 총 중량에 대하여 1 내지 20 중량%로 포함되는 것 이 바람직하며, 더욱 바람직하게는 5 내지 15 중량%로 포함된다. 상기 B)과황산염의 함량이 1 중량% 미만이면 식각 속도가 너무 느려져 언에치(unetch)가 발생될 수 있고, 20 중량%를 초과하면 식각속도가 너무 빠르기 때문에 공정제어가 어렵다.The amount of B) and the sulfate is preferably 1 to 20% by weight, more preferably 5 to 15% by weight based on the total weight of the composition. If the content of B) and sulfate is less than 1% by weight, the etching rate may be too slow to cause unetch. If the content of B) exceeds 20% by weight, the etching rate is too fast.
상기 B)과황산염으로는 이 분야에서 공지되어 있는 물질을 사용할 수 있다. 구체적인 예로는 과황산암모늄(Ammonium Persulfate), 과황산나트륨(Sodium Persulfate), 과황산칼륨(Potassim Persulfate) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.The above-mentioned B) and sulfate may be materials known in the art. Specific examples thereof include ammonium persulfate, sodium persulfate, and potassium persulfate, which may be used singly or in combination of two or more.
본 발명의 식각액 조성물에 포함되는 C)함불소화합물은 물에 해리되어 플루오르 이온을 낼 수 있는 화합물을 의미한다. 상기 C)함불소화합물은 구리막과 몰리브덴막을 동시에 식각하는 용액에서 필연적으로 발생하는 잔사를 제거하여 주는 역할을 한다. 상기 C)함불소화합물의 함량은 조성물 총중량에 대하여 0.01 내지 5.0 중량%가 바람직하며, 더욱 바람직하게는 0.05 내지 2.0 중량%로 포함된다. 상기 C)함불소화합물의 함량이 0.01 중량% 미만인 경우, 식각 잔사가 발생될 수 있으며, 5.0 중량%를 초과하는 경우에는 유리 기판 식각율이 크게 발생 되는 문제가 있다.The C) fluorine compound contained in the etchant composition of the present invention means a compound capable of releasing fluorine ions by being dissolved in water. The C) fluorine compound serves to remove residues that are inevitably generated in a solution which simultaneously etches the copper film and the molybdenum film. The content of the C) fluorine compound is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 2.0% by weight based on the total weight of the composition. If the content of the C) fluorine compound is less than 0.01% by weight, etching residues may be generated. If the content is more than 5.0% by weight, a glass substrate etching rate may be significantly increased.
상기 C)함불소화합물은 이 분야에서 사용되는 물질로서 용액 내에서 플루오르 이온 혹은 다원자 플루오르 이온으로 해리될 수 있는 것이라면 특별히 한정되지 않으나, 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4FHF), 중불화나트륨(sodium bifluoride: NaFHF), 중불화칼륨(potassium bifluoride: KFHF) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.The C) 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 the field, but ammonium fluoride (NH 4 F), sodium fluoride fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 FHF), sodium bifluoride (NaFHF) and potassium bifluoride (KFHF) , Which may be used alone or in combination of two or more.
본 발명의 식각액 조성물에 포함되는 D)물은 특별히 한정되는 것은 아니나, 탈이온수가 바람직하다. 더욱 바람직하게는 물의 비저항 값(즉, 물속에 이온이 제거된 정도)이 18㏁/㎝이상인 탈이온수를 사용하는 것이 좋다. The D) 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? / Cm or more.
본 발명의 식각액 조성물은 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 금속 이온 봉쇄제, 및 부식 방지제 등을 들 수 있다. 또한, 본 발명의 효과를 더욱 양호하게 하기 위하여, 당 업계에 공지되어 있는 여러 다른 첨가제들을 선택하여 첨가할 수도 있다.In the etchant composition of the present invention, conventional additives may be further added in addition to the above-mentioned components. Examples of the additive include a metal ion blocking agent and a corrosion inhibitor. In order to further improve the effects of the present invention, various other additives known in the art may be selected and added.
본 발명의 식각액 조성물에 사용되는 A)과산화수소(H2O2), B)과황산염, C)함불소화합물 및 D)물은 반도체 공정용의 순도를 가지는 것이 바람직하다.It is preferred that A) hydrogen peroxide (H 2 O 2 ), B) and sulphate, C) fluorine compound and D) water used in the etchant composition of the present invention have purity for semiconductor processing.
본 발명의 식각액 조성물은 구리계 금속으로 이루어진 액정표시장치의 게이트 전극과 게이트 배선 및 소스/드레인 전극과 데이터 배선을 일괄 식각할 수 있 다.The etchant composition of the present invention can collectively etch gate electrodes, gate wirings, source / drain electrodes, and data wirings of a liquid crystal display made of a copper-based metal.
또한, 본 발명은,Further, according to the present invention,
Ⅰ)기판 상에 구리계 금속막을 형성하는 단계;I) forming a copper-based metal film on a 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 the copper-based metal film using the etching solution 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, Further, according to 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; 및 d) forming source and drain electrodes 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 배선을 형성하는 단계를 포함하며, 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 wiring,
상기 d)단계는 반도체층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.And d) 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 and drain electrodes. And a manufacturing method thereof.
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. The array substrate for a liquid crystal display 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 more specifically with reference to examples. However, the scope of the present invention is not limited by the following examples.
실시예1 및 비교예1: 구리계 금속막의 식각액 조성물의 제조 Example 1 and Comparative Example 1: Preparation of an etchant composition of a copper-based metal film
하기 표 1에 나타낸 조성에 따라 실시예1 및 비교예1의 식각액 조성물 6 kg을 제조하였다. 6 kg of the etchant compositions of Example 1 and Comparative Example 1 were prepared according to the compositions shown in Table 1 below.
(단위:중량%)(Unit: wt%)
시험예: 식각액 조성물의 특성평가Test Example: Characteristic Evaluation of Etchant Composition
실시예1 및 비교예1의 식각액 조성물을 사용하여 스퍼터링법으로 유리 기판 상에 증착한 구리막을 식각하였다. 분사식 식각 방식의 실험장비 (모델명: ETCHER(TFT), SEMES사) 내에 제조된 식각액을 넣고 온도를 30℃로 설정하여 가온한 후, 온도가 30±0.1℃에 도달하였을 때 식각 공정을 수행하였다. 총 식각 시간은 엔드포인트 검출(End Point Detection, EPD)을 기준으로 하여 오버 에치(Over Etch) 40%를 주어 실시하였다. 기판을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경 (SEM; 모델명: S-4700, HITACHI사 제조)을 이용하여 식각 특성을 평가하여 하기 표 2에 나타내었다. The copper film deposited on the glass substrate was etched by the sputtering method using the etchant compositions of Example 1 and Comparative Example 1. The etching solution prepared in the injection type etching equipment (model name: ETCHER (TFT), SEMES) was put and heated to 30 ° C, and the etching process was performed when the temperature reached 30 ± 0.1 ° C. The total etch time was 40% over etch based on end point detection (EPD). Substrate was injected and injection was started. When etching was completed, the substrate was taken out, washed with deionized water, dried using a hot air dryer, and photoresist was removed using a photoresist stripper. After washing and drying, the etching characteristics were evaluated using an electron microscope (SEM; model: S-4700, manufactured by Hitachi), and the results are shown in Table 2 below.
또한, 과산화수소수의 연쇄분해반응에 의한 과열정도를 측정하기 위하여, 상기 실시예1 및 비교예2에 해당하는 식각액에 3000ppm에 해당하는 Cu 분말을 용출 시킨 후, 일정 시간 방치하여 온도를 측정하였다. 상기 실험결과를 하기 표 2에 기재하였다.Further, in order to measure the degree of superheat by the chain decomposition reaction of hydrogen peroxide, 3000 ppm of Cu powder was eluted in the etchant corresponding to Example 1 and Comparative Example 2, and the temperature was measured by leaving it for a predetermined time. The experimental results are shown in Table 2 below.
상기 표 2에서 볼 수 있는 바와 같이, 실시예1 및 비교예1의 식각액은 모두 양호한 식각특성을 나타내었다. 그러나, 비교예1 식각액의 경우는 Cu 3000ppm 용출 후 온도가 99.2℃까지 상승하여 안정성이 현저히 저하되는 특성을 보인 반면, 실시예1의 식각액의 경우는 39.7℃까지만 상승하여 비교예1의 식각액과 비교하여 크게 향상된 안정성을 나타냈다.As can be seen from Table 2 above, the etching solutions of Example 1 and Comparative Example 1 all exhibited good etching properties. However, in the case of the etching solution of Comparative Example 1, the temperature rose to 99.2 ° C after elution of 3000 ppm of Cu, and the stability remarkably decreased. On the other hand, in the case of the etching solution of Example 1, the etching solution was only increased to 39.7 ° C and compared with the etching solution of Comparative Example 1 And showed significantly improved stability.
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