TWI608125B - Method of forming wiring of a liquid crystal display and method of manufacturing array substrate for liquid crystal display - Google Patents
Method of forming wiring of a liquid crystal display and method of manufacturing array substrate for liquid crystal display Download PDFInfo
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- TWI608125B TWI608125B TW102139895A TW102139895A TWI608125B TW I608125 B TWI608125 B TW I608125B TW 102139895 A TW102139895 A TW 102139895A TW 102139895 A TW102139895 A TW 102139895A TW I608125 B TWI608125 B TW I608125B
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- 239000000758 substrate Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 23
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000010408 film Substances 0.000 claims description 99
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims description 41
- 150000004706 metal oxides Chemical class 0.000 claims description 41
- 238000005530 etching Methods 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003002 pH adjusting agent Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 7
- 239000002526 disodium citrate Substances 0.000 claims description 6
- 235000019262 disodium citrate Nutrition 0.000 claims description 6
- 229940079896 disodium hydrogen citrate Drugs 0.000 claims description 6
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002524 monosodium citrate Substances 0.000 claims description 3
- 235000018342 monosodium citrate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 29
- 239000004065 semiconductor Substances 0.000 description 12
- 230000003628 erosive effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 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 description 1
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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 potential barriers; including integrated passive circuit elements having potential barriers
- 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 potential barriers; including integrated passive circuit elements having potential barriers 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 potential barriers; including integrated passive circuit elements having potential barriers 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
-
- 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
-
- 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
- C23F1/30—Acidic compositions for etching other metallic material
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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
- G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66742—Thin film unipolar transistors
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- 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
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Mathematical Physics (AREA)
- Organic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Thin Film Transistor (AREA)
- Liquid Crystal (AREA)
Description
本發明涉及蝕刻劑組合物、使用其來形成布線的方法和製造用於液晶顯示器(LCD)的陣列基板的方法,其中,在用於形成薄膜晶體管(TFT)的布線的包括Mo金屬膜/金屬氧化物膜的雙層中,該蝕刻劑組合物可以使對下部金屬氧化物膜的侵蝕最小化、對於上部Mo金屬膜可以形成具有優異線性的錐形輪廓並可以選擇性地僅蝕刻上部Mo金屬膜。 The present invention relates to an etchant composition, a method of forming the same using the same, and a method of manufacturing an array substrate for a liquid crystal display (LCD), wherein a wiring for forming a thin film transistor (TFT) includes a Mo metal film In the double layer of the /metal oxide film, the etchant composition can minimize erosion of the lower metal oxide film, can form an excellent linear tapered profile for the upper Mo metal film, and can selectively etch only the upper portion Mo metal film.
根據基板的種類和所需性能,用於諸如TFT-LCD的半導體裝置的金屬布線材料包括多種金屬或它們的合金,這些金屬或合金的例子可以包括Al、Al-Cu、Ti-W、Ti-N等。具體地,具有低電阻的Al或它的合金主要用於TFT-LCD的源極引線/汲極引線。 The metal wiring material for a semiconductor device such as a TFT-LCD includes a plurality of metals or alloys thereof according to the kind of the substrate and required properties, and examples of such metals or alloys may include Al, Al-Cu, Ti-W, Ti. -N, etc. Specifically, Al having low resistance or an alloy thereof is mainly used for a source lead/dip wire of a TFT-LCD.
然而,近來因為根據過程簡化、成本降低和大基板的製造而應該提高電性能,正在進行取代傳統的Cr單層,或Al或Al合金的單層或多層(例如,Mp/Al-Nd雙層或Mp/Al-Nd/Mo三層)而使用由Mo組成的單層的嘗試。 However, recently, a single layer or a plurality of layers of Al or Al alloy (for example, Mp/Al-Nd double layer) are being replaced in place of a conventional Cr single layer, or Al or Al alloy, because electrical properties should be improved in accordance with process simplification, cost reduction, and fabrication of a large substrate. Or a three-layer Mp/Al-Nd/Mo layer) attempt to use a single layer composed of Mo.
同時,用於驅動平板顯示器的TFT的半導體層主要由非晶矽或多晶矽形成。就膜形成過程而言,非晶矽是簡單的,並且生產成本低,但它的電可靠性沒有確保;而多晶矽由於高加工溫度而非常難以應用到大面積的形成,且不可能確保取决於晶化過程的均勻性。 Meanwhile, the semiconductor layer of the TFT for driving the flat panel display is mainly formed of amorphous germanium or polycrystalline germanium. In terms of the film formation process, amorphous germanium is simple and low in production cost, but its electrical reliability is not ensured; and polycrystalline germanium is very difficult to apply to large-area formation due to high processing temperature, and it is impossible to ensure that it depends on Uniformity of the crystallization process.
然而,在半導體層由氧化物組成的情況下,甚至當它在低溫下形成時,也可以獲得高遷移率,而且電阻的改變大,與氧含量成比例,從而非常易於得到所需的性質。因此,將它應用於TFT受到極大的關注。 However, in the case where the semiconductor layer is composed of an oxide, even when it is formed at a low temperature, high mobility can be obtained, and the change in electrical resistance is large, proportional to the oxygen content, so that the desired properties are very easy to obtain. Therefore, its application to TFT has received great attention.
例如,嘗試使用一種製造下述TFT的方法以形成TFT陣列的布線,該TFT使用包括Mo金屬膜/金屬氧化物膜的雙層。為此,需要能夠選擇性地僅蝕刻Mo金屬膜而不侵蝕下部金屬氧化物的技術。 For example, an attempt has been made to form a wiring of a TFT array using a double layer including a Mo metal film/metal oxide film using a method of manufacturing a TFT described below. For this reason, a technique capable of selectively etching only the Mo metal film without eroding the lower metal oxide is required.
就此而言,韓國專利申請公布10-2010-0082094公開了蝕刻劑組合物,該蝕刻劑組合物用於Cu膜、Cu合金膜、Ti膜、Ti合金膜、Mo金屬膜、Mo合金膜或包括它們的層疊的多層膜。該蝕刻劑組合物包含選自過硫酸鈉、過硫酸鉀及它們的混合物的過氧化物,氧化劑,含氟化合物,添加劑和去離子水。此外,韓國專利申請公布10-2007-0005275公開了濕蝕刻劑組合物,該濕蝕刻劑組合物適用於包括Mo、Al、Mo合金或Al合金的單層或多層,該蝕刻劑組合物包含磷酸、硝酸、無機磷酸鹽類化合物或無機硝酸鹽類化合物以及餘量的水(H2O)。 In this regard, the Korean Patent Application Publication No. 10-2010-0082094 discloses an etchant composition for a Cu film, a Cu alloy film, a Ti film, a Ti alloy film, a Mo metal film, a Mo alloy film or the like. Their laminated multilayer film. The etchant composition comprises a peroxide selected from the group consisting of sodium persulfate, potassium persulfate, and mixtures thereof, an oxidizing agent, a fluorine-containing compound, an additive, and deionized water. In addition, Korean Patent Application Publication No. 10-2007-0005275 discloses a wet etchant composition suitable for a single layer or a plurality of layers including Mo, Al, Mo alloy or Al alloy, the etchant composition comprising phosphoric acid , nitric acid, inorganic phosphate compounds or inorganic nitrate compounds and the balance of water (H 2 O).
然而,因為在製造使用包括Mo金屬膜/金屬氧化物膜的雙層的TFT的方法中,在蝕刻Mo金屬膜時,存在對下部金屬氧化物的侵蝕的擔憂,所以這些蝕刻劑組合物是有問題的。 However, since in the method of manufacturing a TFT using a double layer including a Mo metal film/metal oxide film, there is a fear of erosion of the lower metal oxide when etching the Mo metal film, so these etchant compositions are questionable.
[引文列表] [citation list]
[專利文件] [Patent Document]
韓國專利申請公布10-2010-0082094 Korean Patent Application Publication 10-2010-0082094
韓國專利申請公布10-2007-0005275 Korean Patent Application Publication 10-2007-0005275
因此,本發明牢記在相關技術中所遇到的上述問題,而且本發明的目的是提供蝕刻劑組合物、使用所述蝕刻劑組合物形成布線的方法以及製造用於液晶顯示器的陣列基板的方法,其中,在 用於形成TFT陣列的布線的包括Mo金屬膜/金屬氧化物膜的雙層中,所述蝕刻劑組合物可以使對下部金屬氧化物膜的侵蝕最小化、對於上部Mo金屬膜可以形成具有優異線性的錐形輪廓並可以選擇性地僅蝕刻上部Mo金屬膜。 Accordingly, the present invention bears in mind the above problems encountered in the related art, and an object of the present invention is to provide an etchant composition, a method of forming a wiring using the etchant composition, and an array substrate for manufacturing a liquid crystal display. Method, in which In the double layer including the Mo metal film/metal oxide film for forming the wiring of the TFT array, the etchant composition can minimize erosion of the lower metal oxide film, and can be formed for the upper Mo metal film An excellent linear tapered profile and optionally only the upper Mo metal film is etched.
為了實現上述目的,本發明提供了蝕刻劑組合物,包含:(A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑;以及(C)餘量的水,其中,在包括Mo金屬膜/金屬氧化物膜的雙層中,上部Mo金屬膜被所述蝕刻劑組合物蝕刻。 In order to achieve the above object, the present invention provides an etchant composition comprising: (A) 5.0 to 25.0% by weight of hydrogen peroxide (H2O2); (B) 1.0 to 5.0% by weight of a pH adjuster; and (C) An amount of water in which an upper Mo metal film is etched by the etchant composition in a double layer including a Mo metal film/metal oxide film.
此外,本發明提供形成液晶顯示器的布線的方法,所述方法包括:(I)在基板上形成金屬氧化物膜;(II)在所述金屬氧化物膜上形成Mo金屬膜;(III)選擇性地將光敏材料留在所述Mo金屬膜上;以及(IV)使用蝕刻劑組合物蝕刻所述Mo金屬膜,其中,基於所述組合物的總重量,所述蝕刻劑組合物包含:(A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑和(C)餘量的水。 Further, the present invention provides a method of forming a wiring of a liquid crystal display, the method comprising: (I) forming a metal oxide film on a substrate; (II) forming a Mo metal film on the metal oxide film; (III) Selectively leaving a photosensitive material on the Mo metal film; and (IV) etching the Mo metal film using an etchant composition, wherein the etchant composition comprises: based on the total weight of the composition: (A) 5.0 to 25.0 wt% of hydrogen peroxide (H 2 O 2 ); (B) 1.0 to 5.0 wt% of a pH adjuster and (C) a balance of water.
此外,本發明提供製造用於液晶顯示器的陣列基板的方法,所述方法包括:(a)在基板上形成閘極;(b)在具有所述閘極的基板上形成閘絕緣層;(c)在所述閘絕緣層上形成作為金屬氧化物膜的金屬氧化物半導體層(有源層);以及(d)在所述金屬氧化物半導體層上形成Mo金屬膜(源極/汲極),其中,(d)包括在所述金屬氧化物半導體層上形成所述Mo金屬膜和使用蝕刻劑組合物來蝕刻所述Mo金屬膜,基於所述組合物的總重量,所述蝕刻劑組合物包含:(A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑和(C)餘量的水。 Further, the present invention provides a method of manufacturing an array substrate for a liquid crystal display, the method comprising: (a) forming a gate on a substrate; (b) forming a gate insulating layer on the substrate having the gate; Forming a metal oxide semiconductor layer (active layer) as a metal oxide film on the gate insulating layer; and (d) forming a Mo metal film (source/drain) on the metal oxide semiconductor layer Wherein (d) includes forming the Mo metal film on the metal oxide semiconductor layer and etching the Mo metal film using an etchant composition, the etchant combination based on the total weight of the composition The material comprises: (A) 5.0 to 25.0 wt% of hydrogen peroxide (H 2 O 2 ); (B) 1.0 to 5.0 wt% of a pH adjuster and (C) a balance of water.
從下面結合附圖的詳細描述中,本發明上述及其它的目的、特徵和優勢將被更清楚地理解,其中:圖1示出使用實施例1的蝕刻劑組合物所蝕刻的Mo金屬膜和 金屬氧化物膜的掃描電子顯微鏡(SEM)圖像;圖2示出使用實施例3的蝕刻劑組合物所蝕刻的Mo金屬膜和金屬氧化物膜的SEM圖像;圖3示出使用實施例4的蝕刻劑組合物所蝕刻的Mo金屬膜和金屬氧化物膜的SEM圖像;以及圖4示出使用比較例2的蝕刻劑組合物所蝕刻的Mo金屬膜和金屬氧化物膜的SEM圖像。 The above and other objects, features, and advantages of the present invention will be more clearly understood from Scanning electron microscope (SEM) image of metal oxide film; FIG. 2 shows SEM image of Mo metal film and metal oxide film etched using the etchant composition of Example 3; FIG. 3 shows an example of use SEM image of the Mo metal film and the metal oxide film etched by the etchant composition of 4; and FIG. 4 shows an SEM image of the Mo metal film and the metal oxide film etched using the etchant composition of Comparative Example 2. image.
在下文中,本發明將被詳細描述。 Hereinafter, the present invention will be described in detail.
本發明提出蝕刻劑組合物,所述蝕刻劑組合物包含:A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑;以及(C)餘量的水,其中,在包括Mo金屬膜/金屬氧化物膜的雙層中,上部Mo金屬膜被所述蝕刻劑組合物蝕刻。 The present invention provides an etchant composition comprising: A) 5.0 to 25.0% by weight of hydrogen peroxide (H 2 O 2 ); (B) 1.0 to 5.0% by weight of a pH adjuster; and (C) The balance of water, wherein, in the double layer including the Mo metal film/metal oxide film, the upper Mo metal film is etched by the etchant composition.
如本文中所使用的,術語“金屬氧化物膜”是指含有AxByCzO(A、B、C=Zn、Cd、Ga、In、Sn、Hf、Zr、Ta;x、y、z0,其中x、y和z中的兩個或更多個不是零)的三元氧化物或四元氧化物的膜,且可以指氧化物半導體層或用於氧化物半導體層的膜。 As used herein, the term "metal oxide film" means containing AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z) A film of a ternary oxide or a quaternary oxide of 0, wherein two or more of x, y, and z are not zero, and may refer to an oxide semiconductor layer or a film for an oxide semiconductor layer.
在根據本發明的蝕刻劑組合物中,(A)過氧化氫(H2O2)用作蝕刻上部Mo金屬膜的主氧化劑。另外,基於組合物的總重量,以5.0~25.0wt%的量,且優選以8.0~16.0wt%的量使用(A)過氧化氫(H2O2)。如果它的量小於上述下限,所得的組合物的蝕刻性能變差,從而不能進行充分蝕刻。與此相反,如果它的量超過25.0wt%,總蝕刻速率可能增加,使得難以控制該過程。 In the etchant composition according to the present invention, (A) hydrogen peroxide (H 2 O 2 ) is used as a primary oxidant for etching the upper Mo metal film. Further, (A) hydrogen peroxide (H 2 O 2 ) is used in an amount of 5.0 to 25.0% by weight, and preferably 8.0 to 16.0% by weight, based on the total weight of the composition. If the amount thereof is less than the above lower limit, the etching property of the resulting composition is deteriorated, so that sufficient etching cannot be performed. In contrast, if its amount exceeds 25.0% by weight, the total etching rate may increase, making it difficult to control the process.
在根據本發明的蝕刻劑組合物中,(B)pH調節劑是指在過氧化氫和水中解離以提高蝕刻劑的pH的化合物。(B)pH調節劑起增加上部Mo金屬膜的蝕刻速率、除去主要由蝕刻劑溶液產生的殘渣並使對下部金屬氧化物膜的侵蝕最小化的作用。 In the etchant composition according to the present invention, (B) a pH adjuster refers to a compound which dissociates in hydrogen peroxide and water to increase the pH of the etchant. (B) The pH adjuster functions to increase the etching rate of the upper Mo metal film, remove the residue mainly caused by the etchant solution, and minimize the erosion of the lower metal oxide film.
基於組合物的總重量,以1.0~5.0wt%的量使用(B)pH調節劑。如果它的量小於上述下限,上部Mo金屬膜的蝕刻速率可能下降,從而部分不刻蝕或可能產生殘渣,且對下部金屬氧化物膜的侵蝕可能變嚴重。與此相反,如果它的量超過5.0wt%,上部Mo金屬膜可能被過度蝕刻,從而該金屬膜可能從基板上剝離(lift-off)。 The (B) pH adjuster is used in an amount of 1.0 to 5.0% by weight based on the total weight of the composition. If its amount is less than the above lower limit, the etching rate of the upper Mo metal film may be lowered, so that part of it may not be etched or residue may be generated, and the erosion of the lower metal oxide film may become severe. In contrast, if its amount exceeds 5.0% by weight, the upper Mo metal film may be excessively etched, so that the metal film may be lift-off from the substrate.
(B)pH調節劑用於激活過氧化氫的蝕刻行為,它的例子可包括檸檬酸二氫鈉/檸檬酸氫二鈉、檸檬酸氫二鈉/檸檬酸三鈉,或醋酸銨。此外,這種調節劑是通常在蝕刻劑溶液中使用的添加劑,並可包括另一種添加劑而沒有特別限制,另一種添加劑的例子可以包括表面活性劑、螯合劑等。添加表面活性劑以降低蝕刻溶液的粘度從而改善蝕刻均勻性,且可以使用任何陰離子表面活性劑、陽離子表面活性劑、兩性表面活性劑或非離子表面活性劑,優選氟化表面活性劑,只要它耐蝕刻溶液並與其相容。 (B) Etching behavior of the pH adjuster for activating hydrogen peroxide, and examples thereof may include sodium dihydrogen citrate / disodium hydrogen citrate, disodium hydrogen citrate / trisodium citrate, or ammonium acetate. Further, such a regulator is an additive which is usually used in an etchant solution, and may include another additive without particular limitation, and examples of the other additive may include a surfactant, a chelating agent and the like. A surfactant is added to lower the viscosity of the etching solution to improve etching uniformity, and any anionic surfactant, cationic surfactant, amphoteric surfactant or nonionic surfactant, preferably a fluorinated surfactant, may be used as long as it is Resistant to and compatible with the etching solution.
在根據本發明的蝕刻劑組合物中,(C)水不受特別限制,但優選包括去離子水(DIW)。特別有用的是電阻率(即,從水中去除離子的程度)至少為18MΩ cm的去離子水。另外,以餘量來使用(C)水從而使根據本發明的蝕刻劑組合物的總重量是100wt%。 In the etchant composition according to the present invention, (C) water is not particularly limited, but preferably includes deionized water (DIW). Particularly useful is deionized water having a resistivity (i.e., the extent of ion removal from water) of at least 18 M[Omega] cm. Further, (C) water is used in the balance so that the total weight of the etchant composition according to the present invention is 100% by weight.
除上述組分外,還可以使用通常的添加劑,而且可以包括例如螯合劑、抗腐蝕劑等。 In addition to the above components, usual additives may be used, and may include, for example, a chelating agent, an anticorrosive agent, and the like.
在本發明中,由通常已知的方法來製備(A)過氧化氫(H2O2)、(B)pH調節劑和(C)水,而且根據本發明的蝕刻劑組合物優選具有適用於半導體過程的純度。 In the present invention, (A) hydrogen peroxide (H 2 O 2 ), (B) pH adjuster and (C) water are prepared by a generally known method, and the etchant composition according to the present invention preferably has an application. The purity of the semiconductor process.
此外,本發明提出形成液晶顯示器的布線的方法,所述方法包括:(I)在基板上形成金屬氧化物膜;(II)在所述金屬氧化物膜上形成Mo金屬膜;(III)選擇性地將光敏材料留在所述Mo金屬膜上;以及(IV)使用蝕刻劑組合物蝕刻所述Mo金屬膜,其 中,基於組合物的總重量,所述蝕刻劑組合物包含:(A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑和(C)餘量的水。 Further, the present invention proposes a method of forming a wiring of a liquid crystal display, the method comprising: (I) forming a metal oxide film on a substrate; (II) forming a Mo metal film on the metal oxide film; (III) Selectively leaving a photosensitive material on the Mo metal film; and (IV) etching the Mo metal film using an etchant composition, wherein the etchant composition comprises: (A) based on the total weight of the composition ) 5.0 to 25.0 wt% of hydrogen peroxide (H 2 O 2 ); (B) 1.0 to 5.0 wt% of a pH adjuster and (C) a balance of water.
在根據本發明的形成布線的方法中,光敏材料優選是通常的光阻材料,並且可以使用通常的曝光和顯影而選擇性地留下。 In the method of forming a wiring according to the present invention, the photosensitive material is preferably a usual photoresist material, and can be selectively left using usual exposure and development.
此外,本發明提出製造用於液晶顯示器的陣列基板的方法,所述方法包括:(a)在基板上形成閘極;(b)在具有所述閘極的基板上形成閘絕緣層;(c)在所述閘絕緣層上形成作為金屬氧化物膜的金屬氧化物半導體層(有源層);以及(d)在所述金屬氧化物半導體層上形成Mo金屬膜(源極/汲極),其中,(d)包括在所述金屬氧化物半導體層上形成所述Mo金屬膜和使用蝕刻劑組合物來蝕刻所述Mo金屬膜,基於組合物的總重量,所述蝕刻劑組合物包含:(A)5.0~25.0wt%的過氧化氫(H2O2);(B)1.0~5.0wt%的pH調節劑和(C)餘量的水。 Further, the present invention proposes a method of manufacturing an array substrate for a liquid crystal display, the method comprising: (a) forming a gate on a substrate; (b) forming a gate insulating layer on a substrate having the gate; Forming a metal oxide semiconductor layer (active layer) as a metal oxide film on the gate insulating layer; and (d) forming a Mo metal film (source/drain) on the metal oxide semiconductor layer Wherein (d) includes forming the Mo metal film on the metal oxide semiconductor layer and etching the Mo metal film using an etchant composition, the etchant composition comprising, based on the total weight of the composition (A) 5.0 to 25.0 wt% of hydrogen peroxide (H 2 O 2 ); (B) 1.0 to 5.0 wt% of a pH adjuster and (C) a balance of water.
根據本發明的製造用於液晶顯示器的陣列基板的方法使能夠形成包括Mo金屬膜/金屬氧化物膜的雙層。 The method of manufacturing an array substrate for a liquid crystal display according to the present invention enables formation of a double layer including a Mo metal film/metal oxide film.
上述用於液晶顯示器的陣列基板可以是TFT陣列基板。該用於液晶顯示器的陣列基板包括使用根據本發明的蝕刻劑組合物來蝕刻的Mo金屬膜。 The above array substrate for a liquid crystal display may be a TFT array substrate. The array substrate for a liquid crystal display includes a Mo metal film etched using the etchant composition according to the present invention.
可以使用包括例如浸沒、濺灑(spill)等的本領域通常已知的工藝來進行使用蝕刻劑組合物蝕刻Mo金屬膜。可以在20~50℃的溫度下,優選在30~45℃的溫度下進行蝕刻過程;而且如果需要,可以根據其它加工條件和加工因素來確定合適的加工溫度。 The etching of the Mo metal film using the etchant composition can be performed using a process generally known in the art including, for example, immersion, sputtering, and the like. The etching process can be carried out at a temperature of 20 to 50 ° C, preferably at a temperature of 30 to 45 ° C; and if necessary, a suitable processing temperature can be determined according to other processing conditions and processing factors.
根據溫度和薄膜的厚度,使用蝕刻劑組合物來蝕刻Mo金屬膜所需的時間可能變化,但是通常被設置為幾秒鐘至幾十分鐘之間的範圍。 The time required to etch the Mo metal film using the etchant composition may vary depending on the temperature and the thickness of the film, but is usually set to a range between several seconds to several tens of minutes.
此外,本發明提出用於液晶顯示器的陣列基板,該陣列基板包括使用根據本發明的蝕刻劑組合物所蝕刻的源極和汲極。 Furthermore, the present invention proposes an array substrate for a liquid crystal display comprising a source and a drain etched using the etchant composition according to the present invention.
下面是通過下面的實施例和比較例的本發明的更詳細的描述。 The following is a more detailed description of the invention by the following examples and comparative examples.
<實施例> <Example>
蝕刻劑組合物的製備 Preparation of etchant composition
使用下面表1中所示的組成來製備實施例1~4及比較例1和2的蝕刻劑組合物。 The etchant compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were prepared using the compositions shown in Table 1 below.
◎:優異(CD扭斜(Skew):1μm,錐角:40°~60°) ◎: Excellent (CD skew (Skew): 1μm, cone angle: 40°~60°)
○:良好(CD扭斜:1.5μm,錐角:30°~60°) ○: Good (CD skew: 1.5μm, cone angle: 30°~60°)
△:一般(CD扭斜:2μm,錐角:20°~60°) △: General (CD skew: 2μm, cone angle: 20°~60°)
x:差(金屬膜損失且產生殘渣) x: poor (metal film loss and residue generation)
測試例:蝕刻劑組合物的性能評估 Test example: Performance evaluation of etchant composition
使用實施例1~4及比較例1和2中的每個組合物來蝕刻上部Mo金屬膜和下部金屬氧化物膜。為此,使用了噴霧式蝕刻機(從SEMES獲得的蝕刻機(ETCHER)(TFT)),並在蝕刻時將蝕刻劑組合物的溫度設置為約40℃。然而,如果需要,根據其它加工條件和加工因素,合適的溫度可以變化。根據蝕刻溫度,蝕刻時間可以變化,但通常設置為約100秒。使用SEM(從HITACHI獲得 的S-4700)來觀察蝕刻過程中所蝕刻的Mo金屬膜和金屬氧化物膜的圖像。 Each of the compositions of Examples 1 to 4 and Comparative Examples 1 and 2 was used to etch the upper Mo metal film and the lower metal oxide film. For this purpose, a spray etch machine (etching machine (TFT) obtained from SEMES) was used, and the temperature of the etchant composition was set to about 40 ° C at the time of etching. However, if desired, the appropriate temperature can vary depending on other processing conditions and processing factors. The etching time may vary depending on the etching temperature, but is usually set to about 100 seconds. Use SEM (obtained from HITACHI S-4700) to observe the image of the Mo metal film and the metal oxide film etched during the etching process.
從表1和圖1~3中明顯可見,實施例1~4中的所有蝕刻劑表現出與過氧化氫的量的增長成比例的良好的蝕刻性能且不產生殘渣。具體地,含有大量過氧化氫的實施例4的蝕刻劑顯示出對Mo金屬膜的高蝕刻速率。 As is apparent from Table 1 and Figs. 1 to 3, all of the etchants in Examples 1 to 4 exhibited good etching performance in proportion to the increase in the amount of hydrogen peroxide and did not generate residue. Specifically, the etchant of Example 4 containing a large amount of hydrogen peroxide exhibited a high etching rate to the Mo metal film.
而且,如圖2中所見,當pH調節劑的量增加時,實施例3的蝕刻劑就Mo金屬膜的蝕刻速率而言增加。 Moreover, as seen in FIG. 2, when the amount of the pH adjuster is increased, the etchant of Example 3 is increased in terms of the etching rate of the Mo metal film.
比較例1的蝕刻劑含有過氧化氫的量遠低於上述範圍,因此Mo金屬膜部分未被蝕刻且產生殘渣。如圖4中所見,比較例2的蝕刻劑表現出對上部Mo金屬膜的優異蝕刻性能,但因沒有使用pH調節劑而顯示出對下部金屬氧化物膜的侵蝕。 The amount of hydrogen peroxide contained in the etchant of Comparative Example 1 was much lower than the above range, and thus the Mo metal film portion was not etched and residue was generated. As seen in Fig. 4, the etchant of Comparative Example 2 exhibited excellent etching performance for the upper Mo metal film, but showed erosion of the lower metal oxide film because no pH adjusting agent was used.
如以上所描述的,本發明提供製造用於液晶顯示器的陣列基板的方法。根據本發明,在用於形成TFT陣列的布線的包括Mo金屬膜/金屬氧化物膜的雙層中,蝕刻劑組合物能夠使對下部金屬氧化物膜的侵蝕最小化、對於上部Mo金屬膜能夠形成具有優異線性的錐形輪廓並且能夠選擇性地僅蝕刻上部Mo金屬膜。 As described above, the present invention provides a method of fabricating an array substrate for a liquid crystal display. According to the present invention, in the double layer including the Mo metal film/metal oxide film for forming the wiring of the TFT array, the etchant composition can minimize the erosion of the lower metal oxide film, for the upper Mo metal film It is possible to form a tapered profile having excellent linearity and to selectively etch only the upper Mo metal film.
雖然本發明的優選實施方式為了說明目的已被公開,但是本領域技術人員將理解可進行各種修改、增添和替換而不背離如在所附的申請專利範圍中所公開的本發明的範圍和精神。 While the preferred embodiment of the present invention has been disclosed for the purposes of illustration, it will be understood by those skilled in the art .
Claims (4)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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KR1020120130686A KR20140065616A (en) | 2012-11-19 | 2012-11-19 | Manufacturing method of an array substrate for liquid crystal display |
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CN111755461B (en) * | 2019-03-29 | 2024-07-26 | 东友精细化工有限公司 | Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same |
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