KR20050122122A - Etchant composition for pixel layer of fpd - Google Patents
Etchant composition for pixel layer of fpd Download PDFInfo
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- KR20050122122A KR20050122122A KR1020040047290A KR20040047290A KR20050122122A KR 20050122122 A KR20050122122 A KR 20050122122A KR 1020040047290 A KR1020040047290 A KR 1020040047290A KR 20040047290 A KR20040047290 A KR 20040047290A KR 20050122122 A KR20050122122 A KR 20050122122A
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000005530 etching Methods 0.000 claims abstract description 108
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- -1 titanium metals Chemical class 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 89
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 12
- 239000011733 molybdenum Substances 0.000 abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010409 thin film Substances 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000003851 azoles Chemical class 0.000 abstract description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 239000000758 substrate Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- UBSJOWMHLJZVDJ-UHFFFAOYSA-N aluminum neodymium Chemical compound [Al].[Nd] UBSJOWMHLJZVDJ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910000583 Nd alloy Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000001493 electron microscopy Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Weting (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Liquid Crystal (AREA)
Abstract
본 발명은 박막트랜지스터 액정표시장치 등의 평판디스플레이의 제조공정에서 투명도전막인 비정질 산화인듐주석(ITO)막과 산화인듐아연(IZO)막의 패턴에칭을 위해 사용되는 투명도전막의 에칭액 조성물에 관한 것으로서, 진한 황산 1 내지 10 중량%와 투명도전막 이외의 게이트 또는 소스/드레인 막으로 사용되는 알루미늄, 몰리브덴, 동, 티타늄금속 등에 대해 에칭을 시키지 않도록 하는 선택적 식각억제제 역할을 할 수 있도록 Al2(SO4)3, M2MoO4 (M= Na 또는 K 또는 Li 또는 NH4) 또는 아졸계 화합물, 또는 그 혼합물로부터 선택되는 금속식각억제제 0.1 내지 5 중량% 및 나머지가 물로 구성되는 것을 특징으로 하며, 상기 투명도전막용 에칭액 조성물에 에칭속도를 조정하기 위하여 0.1 내지 5중량% 산화제를 추가로 첨가한 것을 특징으로 한다. 또한, 경시변화를 완전히 제어하기 위하여 5 내지 50중량%의 에틸렌 글리콜, 폴리에틸렌 글리콜, 아세트산 등 비점조정제를 추가로 첨가한 것을 특징으로 한다. 본 발명에 따른 투명도전막용 에칭액은 에칭시 잔사 발생현상 및 경시변화 제거특성과 게이트, 소스 및 드레인 금속으로 사용되는 알루미늄, 몰리브덴, 동, 티타늄 등의 단일금속 또는 합금막에 대한 에칭 선택성을 가지게 함으로써 공정수율을 향상시키는 장점이 있다.The present invention relates to an etching liquid composition of a transparent conductive film used for pattern etching of an amorphous indium tin oxide (ITO) film and an indium zinc oxide (IZO) film, which are transparent conductive films, in a manufacturing process of a flat panel display such as a thin film transistor liquid crystal display device. Al 2 (SO 4 ) to act as a selective etch inhibitor to prevent etching of aluminum, molybdenum, copper, titanium metals, etc. used as gate or source / drain films other than 1 to 10% by weight of concentrated sulfuric acid and transparent conductive films 3 , M 2 MoO 4 (M = Na or K or Li or NH 4 ) or 0.1 to 5% by weight of the metal etch inhibitor selected from azole compounds, or mixtures thereof, and the remainder is composed of water, the transparency In order to adjust the etching rate to the etching liquid composition for a whole film, 0.1-5 weight% oxidizing agent was further added, It is characterized by the above-mentioned. In addition, in order to completely control the change over time, 5 to 50% by weight of ethylene glycol, polyethylene glycol, acetic acid such as acetic acid, characterized in that additionally added. The etching solution for the transparent conductive film according to the present invention has a property of removing residues and changes over time when etching and having etching selectivity with respect to a single metal or alloy film such as aluminum, molybdenum, copper, and titanium used as gate, source and drain metals. There is an advantage of improving the process yield.
Description
본 발명은 평판디스플레이용 액정표시장치 등에서 투명전극의 미세패턴을 형성하는데 사용되는 비정질 산화인듐주석막 (이하 ‘ITO막’이라 함.) 또는 산화인듐아연막 (이하 ‘IZO막’이라 함.)인 투명도전막을 에칭시키는 평판디스플레이용 투명도전막의 에칭액 조성물에 관한 것이다.In the present invention, an amorphous indium tin oxide film (hereinafter referred to as an "ITO film") or an indium zinc oxide film (hereinafter referred to as an "IZO film") used in forming a fine pattern of a transparent electrode in a liquid crystal display device for a flat panel display. The etching liquid composition of the transparent conductive film for flat panel displays which etches a phosphorus transparent conductive film is related.
투명도전막은 박막트랜지스터 액정표시장치, 플라즈마 디스플레이 패널표시장치, 일렉트로 루미네센스 표시장치 등의 평판디스플레이용 표시장치에 폭넓게 사용되고 있는 박막으로서, 상기 평판디스플레이용 표시장치에 투명도전막을 형성하기 위해서는 원하는 미세패턴을 형성시키는 에칭 공정이 필요하며, 이때 사용되는 투명도전막으로서는 IZO막 또는 ITO막이 주로 사용되고 있다.The transparent conductive film is a thin film widely used in flat panel display devices such as a thin film transistor liquid crystal display device, a plasma display panel display device, an electroluminescence display device, and the like, in order to form a transparent conductive film on the flat panel display device. An etching process for forming a pattern is required, and an IZO film or an ITO film is mainly used as the transparent conductive film used at this time.
상기 ITO막 또는 IZO막의 사용은 보호막 등의 위에 ITO막 또는 IZO막을 형성시킨 다음 포토레지스터를 마스크로서 도포 한 후 ITO막 또는 IZO막을 에칭하게 되는 것으로 기존의 ITO막 또는 IZO막용 에칭액으로는 염산·질산 혼합수용액(왕수계), 염산·초산 혼합수용액, 염화제이철 수용액, 요소산 수용액, 인산수용액, 옥살산(수산)수용액 등이 사용되고 있지만, 이러한 종래의 ITO막 또는 IZO막용 에칭액 들은 아래와 같은 문제점을 내재하고 있다.The use of the ITO film or the IZO film is to form an ITO film or an IZO film on a protective film, and then to apply a photoresist as a mask and then to etch the ITO film or the IZO film. Mixed aqueous solution (Aqua regia), mixed hydrochloric acid and acetic acid solution, ferric chloride aqueous solution, urea aqueous solution, phosphoric acid aqueous solution, oxalic acid (aqueous acid) aqueous solution, etc. are used, but these conventional ITO or IZO film etching solutions have the following problems. have.
첫째, 염산·질산 혼합수용액과 염산·초산 혼합수용액은 에칭속도는 크고 안정되어 있지만, 에칭액이 경시변화가 나타나는 점과 염산에 의한 장치 부식현상과 박막트랜지스터 제조공정에서 게이트 전극으로 사용하고 있는 알루미늄 또는 알루미늄·네오디늄 합금을 에칭시키는 단점이 있다.First, the mixed solution of hydrochloric acid and nitric acid and mixed solution of hydrochloric acid and acetic acid are large and stable in etching speed, but the etching solution shows the change over time, the corrosion of the device by hydrochloric acid, and the aluminum used as gate electrode in the thin film transistor manufacturing process. There is a disadvantage that the aluminum neodymium alloy is etched.
둘째, 염화제이철 수용액은 에칭속도는 크고 안정되어 있지만, 상대적으로 측면 에칭량이 크고 철의 오염을 유발시키는 단점이 있다.Second, the ferric chloride solution has a large etching rate and is stable, but has a relatively large amount of side etching and causes iron contamination.
셋째, 요소산수용액은 상대적 측면 에칭량이 작고 양호한 에칭특성을 가지지만, 에칭액의 경시변화가 큰 단점이 있다.Third, although the urea acid aqueous solution has a small relative side etching amount and good etching characteristics, the urea acid aqueous solution has a large disadvantage over time.
넷째, 인산수용액은 게이트 전극으로 사용되고 있는 알루미늄 또는 알루미늄·네오디늄 합금을 에칭시키는 단점이 있다.Fourth, the aqueous solution of phosphate has the disadvantage of etching the aluminum or aluminum neodymium alloy used as the gate electrode.
다섯째, 옥살산(수산)수용액은 에칭특성이 안정되어 있고 에칭액의 경시변화도 일어나지 않아 양호하지만 에칭시 잔사가 발생하기 쉬운 단점을 가지고 있다.Fifth, the oxalic acid (aqueous acid) aqueous solution is stable because the etching characteristics are stable and does not change with time of the etching solution is good, but it has a disadvantage that residues occur easily during etching.
한편 본 발명자들은 상기의 문제점을 극복하기 위하여 평판디스플레이용 액정표시장치의 투명도전막인 ITO막을 에칭시키는 에칭액 조성물에 대하여 10-2001-18351호와 10-2003-0029922호를 출원한 바 있으며, 상기 발명에 따른 에칭액은 주성분인 MHSO4(M=K 또는 Na 또는 NH4)의 농도를 조절하거나 첨가제로 KMnO4, H2O2, H2SO4, MHSO5(M=K 또는 Na 또는 NH4)등을 첨가함으로서 에칭시 잔사 발생현상과 알루미늄·네오디늄 함금과 몰리브덴 또는 몰리브덴·텅스텐 합금 등의 ITO 막 이외의 다른 박막을 에칭시키는 현상을 제거하는 효과를 제공한다.On the other hand, the present inventors have applied for 10-2001-18351 and 10-2003-0029922 with respect to the etching liquid composition for etching the ITO film of the transparent conductive film of the liquid crystal display device for flat panel display in order to overcome the above problems. The etching solution according to the present invention controls the concentration of the main component MHSO 4 (M = K or Na or NH 4 ) or as an additive KMnO 4 , H 2 O 2 , H 2 SO 4 , MHSO 5 (M = K or Na or NH 4 ) The addition of the film and the like provides the effect of eliminating residues during etching and etching of thin films other than ITO films such as aluminum, neodymium alloys and molybdenum or molybdenum tungsten alloys.
그러나 상기 에칭액 조성물들은 알루미늄 또는 알루미늄·네오디늄 합금 등 ITO막 또는 IZO막 이외의 다른 박막의 측면 에칭현상, 경시변화현상, 에칭시 잔사 발생현상을 완벽하게 방지하는 데에는 한계가 있다는 단점이 있다.However, the etchant compositions have a disadvantage in that there is a limit in completely preventing side etching, change over time, and residues during etching of other thin films other than ITO film or IZO film such as aluminum or aluminum neodymium alloy.
따라서 본 발명의 목적은 기존의 ITO막 또는 IZO막용 에칭액인 염산·질산혼합수용액(왕수계), 염산·초산혼합수용액, 염화제이철 수용액, 요소산수용액, 인산수용액, 옥살산(수산)수용액 사용시 발생되는 측면 에칭현상, 경시변화현상, 에칭시 잔사 발생현상, 등의 단점을 극복할 수 있는 평판디스플레이용 표시장치의 에칭액 조성물을 제공하는 것이며, 특히 투명도전막 이외의 게이트, 소스 및 드레인 금속막으로 사용되는 알루미늄 또는 알루미늄·네오디늄 합금, 몰리브덴, 동, 티타늄 등의 단일금속 또는 합금막을 에칭시키는 현상을 제거하는 에칭 선택성을 가지게 함으로써 ITO막 또는 IZO막 에칭공정에서의 에칭 불량률을 감소시켜 공정수율을 향상시킬 수 있는 평판디스플레이용 표시장치의 투명도전막용 에칭액 조성물을 제공하는 것이다. Therefore, an object of the present invention is to produce a conventional solution for the ITO film or IZO film that is generated when using a mixture of hydrochloric acid and nitric acid solution (aqua regia), mixed hydrochloric acid and acetic acid solution, ferric chloride solution, urea solution, phosphoric acid solution, oxalic acid solution (oxalic acid) The present invention provides an etching liquid composition of a display device for a flat panel display that can overcome the disadvantages of side etching, change with time, residue generation during etching, and the like. Etch selectivity eliminates the phenomenon of etching single metals or alloy films such as aluminum or aluminum-neodynium alloys, molybdenum, copper, titanium, etc., thereby reducing the etching defect rate in the ITO film or IZO film etching process to improve process yield. The etching liquid composition for transparent conductive films of the display apparatus for flat panel displays which can be provided is provided.
본 발명은 TFT-LCD를 포함한 평판디스플레이용 표시장치의 투명도전막인 ITO 또는 IZO막의 패턴에칭시 적용되는 투명도전막 에칭액에 관한 것으로서, 본 발명에 따른 ITO막 또는 IZO막용 에칭액은 황산을 주성분으로 하고, 상기의 투명도전막 이외의 게이트, 소스 및 드레인 금속막으로 사용되는 알루미늄, 몰리브덴, 동, 티타늄 등의 단일금속 또는 합금막을 에칭시키는 현상을 제거하여 줄 수 있는 식각억제의 특성을 부여하는 목적으로 Al2(SO4)3, M2MoO4(M=Na 또는 K 또는 Li 또는 NH4), 아졸계화합물 등의 유·무기 화합물을 첨가제로 사용하는 것을 특징으로 하고 있다.The present invention relates to a transparent conductive film etching solution applied to pattern etching of an ITO or IZO film, which is a transparent conductive film of a flat panel display including a TFT-LCD, wherein the etching solution for an ITO film or an IZO film has sulfuric acid as a main component, Al 2 for the purpose of imparting etch inhibiting properties that can eliminate the phenomenon of etching a single metal or alloy film such as aluminum, molybdenum, copper, titanium, etc. used as gate, source, and drain metal films other than the above transparent conductive film. Organic and inorganic compounds such as (SO 4 ) 3 , M 2 MoO 4 (M = Na or K or Li or NH 4 ) and azole compounds are used as additives.
본 발명에 따른 평판디스플레이용 표시장치의 투명도전막용 에칭액 조성물은 진한 황산 1 내지 10 중량%와 Al2(SO4)3, M2MoO4 (M= Na 또는 K 또는 Li 또는 NH4) 또는 아졸계 화합물, 또는 그 혼합물로부터 선택되는 금속식각억제제 0.1 내지 5 중량% 및 나머지가 물로 구성되는 것을 특징으로 한다.The transparent conductive film etching liquid composition of the display device for a flat panel display according to the present invention comprises 1 to 10% by weight of concentrated sulfuric acid and Al 2 (SO 4 ) 3 , M 2 MoO 4 (M = Na or K or Li or NH 4 ) or 0.1 to 5% by weight of the metal etch inhibitor selected from the sol-based compound, or mixtures thereof, and the remainder is composed of water.
진한 황산은 에칭의 조건에 따라 1 내지 10 중량%의 범위 내에서 조절이 가능하지만 2 내지 4 중량%가 에칭의 생산성 및 에칭특성의 면에서 더욱 바람직하다.Concentrated sulfuric acid can be adjusted in the range of 1 to 10% by weight depending on the conditions of the etching, but 2 to 4% by weight is more preferable in terms of the productivity and etching characteristics of the etching.
상기 아졸계 화합물은 트리아졸, 아미노테트라졸, 벤조트리아졸, 이미다졸, 테트라졸, 티아졸 또는 피라졸, 또는 이들의 혼합물을 포함하며, 특히 아미노테트라졸, 벤조트리아졸 또는 이미다졸, 또는 이들의 혼합물이 바람직하다.The azole compound includes triazole, aminotetrazole, benzotriazole, imidazole, tetrazole, thiazole or pyrazole, or mixtures thereof, in particular aminotetrazole, benzotriazole or imidazole, or these A mixture of is preferred.
한편, 금속식각억제제는 0.1 내지 5 중량% 의 범위이면 적절한 성능을 발휘하나, 0.5 내지 3 중량%의 범위일 때 에칭선택성이 높아진다.On the other hand, the metal etching inhibitor exhibits proper performance if it is in the range of 0.1 to 5% by weight, but the etching selectivity is increased when it is in the range of 0.5 to 3% by weight.
본 발명에 따른 평판디스플레이용 표시장치의 투명도전막용 에칭액 조성물은 종래의 ITO 또는 IZO 에칭액의 단점을 완전히 제거하기 위하여 선택적으로 투명도전막 이외의 금속막에 대한 에칭현상이 없는 범위 내에서 에칭속도와 패턴에칭의 제특성을 조정하기 위하여 제 2의 첨가제로 H2O2, HNO3, HClO4. MClO4 (M=NH4 또는 Na 또는 K), KMnO4 등의 산화제를 함께 사용할 수 있다. 상기 산화제는 황산과 금속식각억제제 및 물로 이루어진 투명도전막용 에칭액 조성물에 0.1 내지 5중량%의 범위로 추가할 수 있으며, 특히 투명도전막용 에칭액 조성물에 1 내지 3중량%의 범위에서 첨가할 때 에칭속도와 패턴에칭의 제특성의 조정이 적절히 이루어지며, 에칭되는 속도를 더욱 빠르게 할 수 있다.In order to completely eliminate the disadvantages of the conventional ITO or IZO etching solution, the etching liquid composition of the transparent conductive film etching liquid composition of the flat panel display device according to the present invention has an etching rate and a pattern within a range where there is no etching phenomenon for a metal film other than the transparent conductive film. Secondary additives such as H 2 O 2 , HNO 3 , HClO 4 . Oxidizing agents such as MClO 4 (M = NH 4 or Na or K), KMnO 4 and the like can be used together. The oxidizing agent may be added in the range of 0.1 to 5% by weight to the etching solution composition for transparent conductive film consisting of sulfuric acid, metal etching inhibitor and water, especially when added in the range of 1 to 3% by weight to the etching solution composition for transparent conductive film And the proper characteristics of the pattern etching can be adjusted properly, and the etching speed can be made faster.
그리고, 본 발명에서는 종래의 ITO 또는 IZO 에칭액의 단점인 경시변화를 완전히 제거하기 위하여 제 3의 첨가제로서는 에틸렌 글리콜, 폴리에칠렌 글리콜, 아세트산, 또는 이들의 혼합물로부터 선택되는 것을 에칭액의 비점조정제 역할을 구현할 목적으로 추가로 함께 사용할 수 있다.In the present invention, the third additive is selected from ethylene glycol, polyethylene glycol, acetic acid, or a mixture thereof in order to completely eliminate the time-dependent change of the conventional ITO or IZO etching solution. Can be used together as an additional.
상기의 비점조정제는 황산과 금속식각억제제 및 물로 이루어진 투명도전막용 에칭액 조성물에 5 내지 50중량%의 범위로 추가할 수 있으며, 특히 투명도전막용 에칭액 조성물에 20 내지 30중량%의 범위에서 첨가할 때 경시변화 특성의 조정이 적절히 이루어질 수 있다.The non-pointing agent may be added in the range of 5 to 50% by weight to the etching solution composition for the transparent conductive film consisting of sulfuric acid, metal etching inhibitor and water, especially when added in the range of 20 to 30% by weight to the etching solution composition for transparent conductive film Adjustment of the change characteristic over time can be appropriately made.
본 발명의 투명도전막 에칭액의 에칭 메카니즘은 아래와 같다.The etching mechanism of the transparent conductive film etching liquid of this invention is as follows.
ITO는 In2O3와 SnO2, IZO는 In2O3와 ZnO의 혼합물로 이루어져있으므로, 각 산화물과 투명도전막 에칭액의 주요성분인 H2SO4와의 반응으로 이루어지며, 각각의 반응식을 표시해보면 아래와 같이 나타낼 수 있다.Since ITO is composed of In 2 O 3 and SnO 2 , and IZO is a mixture of In 2 O 3 and ZnO, each reaction is performed with H 2 SO 4 , which is the main component of the transparent conductive film etching solution. It can be represented as
In2O3 + 3H2SO4 --> In2(SO4)3 + 3H2OIn 2 O 3 + 3H 2 SO 4- > In 2 (SO 4 ) 3 + 3H 2 O
SnO2 + 2H2SO4 --> Sn(SO4)2 + 2H2OSnO 2 + 2H 2 SO 4- > Sn (SO 4 ) 2 + 2H 2 O
ZnO + H2SO4 --> ZnSO4 + H2OZnO + H 2 SO 4- > ZnSO 4 + H 2 O
본 발명은 하기의 실시예로 더 잘 이해할 수 있으며, 하기의 실시 예는 본 발명의 예시 목적을 위한 것으로 첨부된 특허청구범위에 의하여 한정되는 보호 범위를 제한하고자 하는 것은 아니다.The invention is better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
[실시예 1]Example 1
진한 황산 3중량%와 Al2(SO4)3 2중량% 그리고 물 95 중량%의 조성으로 투명도전막용 에칭액을 제조하였다.An etching solution for a transparent conductive film was prepared in a composition of 3 wt% concentrated sulfuric acid, 2 wt% Al 2 (SO 4 ) 3, and 95 wt% water.
제조된 에칭액을 사용하여 포토레지스터로 패턴을 형성한 IZO막 기판 (두께 : 2000Å)을 40℃에서 3분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.The IZO film substrate (thickness: 2000 kPa) which formed the pattern by the photoresist using the prepared etching liquid was sprayed at 40 degreeC for 3 minutes, and it etched, washed with ultrapure water for about 1 minute, and dried using nitrogen.
이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that.
[실시예 2]Example 2
진한 황산 3중량%와 아미노테트라졸 1중량% 물 96중량%의 조성으로 투명도전막용 에칭액을 제조하였다.An etching solution for a transparent conductive film was prepared in a composition of 3 wt% concentrated sulfuric acid and 96 wt% aminotetrazole 1 wt% water.
제조된 에칭액을 사용하여 포토레지스트로 패턴을 형성한 비정질 ITO막 기판 (두께 : 2000Å)을 40℃에서 3분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using the prepared etching solution, an amorphous ITO film substrate (thickness: 2000 kPa) formed with a photoresist was sprayed at 40 ° C. for 3 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .
이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, 비정질 ITO막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching phenomenon on the aluminum neodymium film and the molybdenum film. The amorphous ITO film was well etched. It could be confirmed.
[실시예 3]Example 3
진한 황산 3중량%, 질산 1중량%, Al2(SO4)3 2중량%, 물 94중량%의 조성으로 투명도전막용 에칭액을 제조하였다.An etching solution for a transparent conductive film was prepared in a composition of 3 wt% concentrated sulfuric acid, 1 wt% nitric acid, 2 wt% Al 2 (SO 4 ) 3 , and 94 wt% water.
제조된 에칭액을 사용하여 포토레지스트로 패턴을 형성한 비정질 ITO막 기판 (두께 : 2000Å)을 40℃에서 2분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.Using the prepared etching solution, an amorphous ITO film substrate (thickness: 2000 kPa) formed with a photoresist was sprayed at 40 ° C. for 2 minutes for etching, washed with ultrapure water for about 1 minute, and dried using nitrogen. .
이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, 비정질 ITO막은 양호하게 에칭이 된 것을 확인할 수 있었다. 또한 에칭시간을 1분으로 줄여도 동일한 효과를 가지는 것임을 알 수 있어 첨가된 산화제에 의한 우수한 효과를 가지는 것임을 알 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching phenomenon on the aluminum neodymium film and the molybdenum film. The amorphous ITO film was well etched. It could be confirmed. In addition, even if the etching time is reduced to 1 minute it can be seen that it has the same effect, it was found that it has an excellent effect by the added oxidizing agent.
[실시예 4]Example 4
진한 황산 3중량%, 질산 1중량%, 아미노테트라졸 1중량%, 물 95 중량%의 조성으로 투명도전막용 에칭액을 제조하였다.An etching solution for a transparent conductive film was prepared in a composition of 3 wt% concentrated sulfuric acid, 1 wt% nitric acid, 1 wt% aminotetrazole, and 95 wt% water.
제조된 에칭액을 사용하여 포토레지스트로 패턴을 형성한 IZO막 기판 (두께 : 2000Å)을 40℃에서 2분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.The IZO film substrate (thickness: 2000 kPa) which formed the pattern with the photoresist using the prepared etching liquid was sprayed at 40 degreeC for 2 minutes, and it etched, washed with ultrapure water for about 1 minute, and dried using nitrogen.
이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다. 또한 에칭시간을 1분으로 줄여도 동일한 효과를 가지는 것임을 알 수 있어 첨가된 산화제에 의한 우수한 효과를 가지는 것임을 알 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that. In addition, even if the etching time is reduced to 1 minute it can be seen that it has the same effect, it was found that it has an excellent effect by the added oxidizing agent.
[실시예 5]Example 5
진한 황산 3중량%, 질산 1중량%, 아미노테트라졸 1중량%, 에틸렌글리콜 30중량%, 물 65중량%의 조성으로 투명도전막용 에칭액을 제조하였다.An etching solution for a transparent conductive film was prepared in a composition of 3 wt% concentrated sulfuric acid, 1 wt% nitric acid, 1 wt% aminotetrazole, 30 wt% ethylene glycol, and 65 wt% water.
제조된 에칭액을 사용하여 포토레지스트로 패턴을 형성한 IZO막 기판 (두께 : 2000Å)을 40℃에서 2분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의해 수세를 행한 후 질소를 사용하여 건조시켰다.The IZO film substrate (thickness: 2000 kPa) which formed the pattern with the photoresist using the prepared etching liquid was sprayed at 40 degreeC for 2 minutes, and it etched, washed with ultrapure water for about 1 minute, and dried using nitrogen.
이와 같이 에칭을 완료한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았고 알루미늄·네오디늄막과 몰리브덴막에 대한 에칭현상도 없었으며, IZO막은 양호하게 에칭이 된 것을 확인할 수 있었다. 또한 에칭시간을 1분으로 줄여도 동일한 효과를 가지는 것임을 알 수 있어 첨가된 산화제에 의한 우수한 효과를 가지는 것임을 알 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and there was no etching on the aluminum neodymium film and the molybdenum film. The IZO film was well etched. I could confirm that. In addition, even if the etching time is reduced to 1 minute it can be seen that it has the same effect, it was found that it has an excellent effect by the added oxidizing agent.
또한, 장시간 사용시에도 에칭액의 증발속도가 감소되어 경시변화 특성이 70% 정도 개선되는 것을 알 수 있었다.In addition, the evaporation rate of the etchant is reduced even when used for a long time it can be seen that the change with time characteristics is improved by about 70%.
본 발명의 투명도전막용 에칭액은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 투명도전막인 비정질 ITO막 또는 IZO막의 패턴에칭을 위하여 적용할 경우 종래의 ITO 또는 IZO막용 에칭액과는 달리 에칭시 잔사발생 현상이나 알루미늄 또는 알루미늄·네오디늄 합금과 몰리브덴 또는 몰리브덴·스텐 합금과 동, 티타늄 금속과 같은 투명도전막 이외의 다른 박막을 에칭시키는 문제점이 발생하지 않기 때문에 제조원가 절감과 동시에 공정수율을 향상시키는 효과를 가지는 장점이 있다.The etching solution for the transparent conductive film of the present invention, when applied for pattern etching of an amorphous ITO film or an IZO film, which is a transparent conductive film of a flat panel display device including a thin film transistor liquid crystal display device, the residue during etching unlike the conventional etching solution for ITO or IZO film There is no problem of etching or thin film other than transparent conductive film such as aluminum, aluminum, neodymium alloy, molybdenum, molybdenum, sten alloy, copper, and titanium metal, so it is possible to reduce manufacturing cost and improve process yield. It has its advantages.
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| WO2013077580A1 (en) * | 2011-11-24 | 2013-05-30 | 주식회사 이엔에프테크놀로지 | Etchant composition for copper/molybdenum alloy film |
| CN112342548A (en) * | 2020-11-12 | 2021-02-09 | 江苏和达电子科技有限公司 | Copper-containing laminated etching solution, etching method and application thereof |
| CN116024574A (en) * | 2022-12-28 | 2023-04-28 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013077580A1 (en) * | 2011-11-24 | 2013-05-30 | 주식회사 이엔에프테크놀로지 | Etchant composition for copper/molybdenum alloy film |
| KR101333551B1 (en) * | 2011-11-24 | 2013-11-28 | 주식회사 이엔에프테크놀로지 | Etching composition for copper and molibdenum alloy |
| CN103890232A (en) * | 2011-11-24 | 2014-06-25 | 易安爱富科技有限公司 | Etchant composition for copper/molybdenum alloy film |
| CN112342548A (en) * | 2020-11-12 | 2021-02-09 | 江苏和达电子科技有限公司 | Copper-containing laminated etching solution, etching method and application thereof |
| CN112342548B (en) * | 2020-11-12 | 2022-03-15 | 江苏和达电子科技有限公司 | Copper-containing laminated etching solution, etching method and application thereof |
| CN116024574A (en) * | 2022-12-28 | 2023-04-28 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
| CN116024574B (en) * | 2022-12-28 | 2023-12-05 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
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