KR20170035225A - Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same - Google Patents
Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same Download PDFInfo
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- KR20170035225A KR20170035225A KR1020150134059A KR20150134059A KR20170035225A KR 20170035225 A KR20170035225 A KR 20170035225A KR 1020150134059 A KR1020150134059 A KR 1020150134059A KR 20150134059 A KR20150134059 A KR 20150134059A KR 20170035225 A KR20170035225 A KR 20170035225A
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- Prior art keywords
- metal film
- copper
- acid
- etching
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- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 239000000758 substrate Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 28
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 87
- 238000005530 etching Methods 0.000 claims description 62
- 239000010949 copper Substances 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 45
- 229910052802 copper Inorganic materials 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- ZFUNXNSIQZVWSC-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O.C1=C(C=CC2=CC=CC=C12)S(=O)(=O)O ZFUNXNSIQZVWSC-UHFFFAOYSA-N 0.000 claims description 3
- 229950000244 sulfanilic acid Drugs 0.000 claims description 3
- QFVURJSSEKAGEA-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1.NC1=CC=CC(S(O)(=O)=O)=C1 QFVURJSSEKAGEA-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims 1
- -1 sulfuric acid compound Chemical class 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 24
- 239000011521 glass Substances 0.000 description 17
- 239000010936 titanium Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010020710 Hyperphagia Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- SUVCDNHAMXHKQB-UHFFFAOYSA-N OC1=CC=C(C=C1)S(=O)(=O)O.OC1=CC=C(C=C1)S(=O)(=O)O Chemical compound OC1=CC=C(C=C1)S(=O)(=O)O.OC1=CC=C(C=C1)S(=O)(=O)O SUVCDNHAMXHKQB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse 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
- 238000006243 chemical reaction Methods 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
- CIYRLONPFMPRLH-UHFFFAOYSA-N copper tantalum Chemical compound [Cu].[Ta] CIYRLONPFMPRLH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 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
- 235000020830 overeating Nutrition 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 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
- 238000004148 unit process Methods 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
-
- 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
- C23F1/02—Local etching
-
- 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
- G02F1/136286—Wiring, e.g. gate line, drain line
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- 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
-
- 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
- H01L27/1259—Multistep manufacturing methods
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- G02F2001/136295—
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
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- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Thin Film Transistor (AREA)
- Inorganic Chemistry (AREA)
Abstract
Description
본 발명은 금속막의 식각액 조성물 및 이를 이용한 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etching liquid composition for a metal film and a method of manufacturing an array substrate for a liquid crystal display using the same.
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 usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process, And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.
이러한 반도체 장치에서 최근 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 왜냐하면 저항이 RC 신호지연을 유발하는 주요한 인자이므로, 특히 TFT-LCD(thin film transistor-liquid crystal display)의 경우 패널크기 증가와 고해상도 실현이 기술 개발에 관건이 되고 있기 때문이다. 따라서, TFT-LCD의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는, 저-저항의 물질개발이 필수적이다. 따라서, 종래에 주로 사용되었던 크롬(Cr, 비저항: 12.7 ×10- 8Ωm), 몰리브덴(Mo, 비저항: 5×10- 8Ωm), 알루미늄(Al, 비저항: 2.65×10- 8Ωm) 및 이들의 합금은 대형 TFT LCD에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다.In such semiconductor devices, resistance of metal wiring has recently become a major concern. This is because the resistance is a major factor that causes the RC signal delay, especially in the case of TFT-LCD (thin film transistor-liquid crystal display), because the increase in panel size and realization of high resolution are the key to technology development. Therefore, in order to realize the reduction of the RC signal delay which is indispensably required for the enlargement of the TFT-LCD, it is essential to develop a low-resistance material. Thus, the 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 their Is difficult to use for gate and data wiring used in a large-sized TFT LCD.
이와 같은 배경 하에서, 새로운 저-저항 금속막으로서 구리막 및 구리 타타늄막 등의 구리계 금속막 및 이의 식각액 조성물에 대한 관심이 높아지고 있고, 이와 관련하여 대한민국 공개특허 제 10-2013-0046065호에서는 인산, 질산, 초산, 불소 함유화합물을 포함하는 다중금속막의 식각액 조성물을 개시하고 있다. 다만, pH가 낮은 식각액 조성에서 함불소 화합물이 존재할 시 발생하는 유리기판의 식각을 제어하기에 한계가 있으며, 두께가 5000Å 이상인 후막에서 Profile 및 유리식각에 대한 문제점이 개선되지 않는 한계점이 있다. Under such background, attention has been paid to a copper-based metal film such as a copper film and a copper-tantalum film as a new low-resistance metal film and an etchant composition thereof, and Korean Patent Publication No. 10-2013-0046065 discloses, , Nitric acid, acetic acid, and a fluorine-containing compound. However, there is a limitation in controlling the etching of the glass substrate that occurs when a fluorinated compound is present in the etching solution composition having a low pH, and there is a limit point in that the problem of profile and glass etching is not improved in a thick film having a thickness of 5000 ANGSTROM or more.
본 발명은 식각액 조성물은 구리막의 두께가 5000Å 이상인 후막에서 식각성능 (Profile) 및 유리식각에 대한 문제점을 개선시킨 면에서 우수한 식각 특성을 갖는 금속막의 식각액 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide an etchant composition for a metal film having excellent etching properties in terms of improving the problems of etch performance and glass etching in a thick film having a copper film thickness of 5000 angstroms or more.
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.
상기 목적을 달성하기 위하여,In order to achieve the above object,
(a) 인산, (b) 질산, (c) 초산, (d) 함불소 화합물, (e) 황산계 화합물, 및 (f) 물을 포함하는 금속막 식각액 조성물로, 상기 (e) 황산계 화합물은 pKa값이 -1 내지 5인 것을 특징으로 하는 금속막 식각액 조성물을 제공한다.(e) a sulfuric acid-based compound (e), wherein the sulfuric acid-based compound (e) is a metal film etchant composition comprising (a) phosphoric acid, (b) nitric acid, (c) acetic acid, Wherein the pKa value is in the range of -1 to 5.
이를 이용한 구리계 금속막의 식각방법 및 액정 표시 장치용 어레이 기판의 제조방법을 제공한다.A method of etching a copper-based metal film using the same, and a method of manufacturing an array substrate for a liquid crystal display device.
또한, 본 발명은 상기 본 발명의 제조방법으로 제조된 액정 표시 장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a liquid crystal display manufactured by the manufacturing method of the present invention.
본 발명의 식각액 조성물은 식각액 조성물은 구리막의 두께가 5000Å 이상인 후막에서 식각성능(Profile) 및 유리식각에 대한 문제점을 개선시킨 면에서 우수한 식각 특성이 있다.The etchant composition of the present invention has excellent etching properties in terms of improving the problems of etch performance and glass etch in a thick film having a copper film thickness of 5000 ANGSTROM or more.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 (a) 인산, (b) 질산, (c) 초산, (d) 함불소 화합물, (e) 황산계 화합물, 및 (f) 물을 포함하는 금속막 식각액 조성물로, 상기 (e) 황산계 화합물은 pKa값이 -1 내지 5인 것을 특징으로 하는 금속막 식각액 조성물에 대한 것이다. 특히 본 발명은 구리계 금속막의 막 두께가 5,000Å 이상의 후막을 식각하기 위한 금속막 식각액 조성물, 식각방법, 액정표시장치용 어레이 기판 및 액정표시장치용 어레이 기판의 제조방법에 관한 것이다. The present invention provides a metal film etchant composition comprising (a) phosphoric acid, (b) nitric acid, (c) acetic acid, (d) fluorine compound, (e) sulfuric acid compound, Wherein the sulfuric acid-based compound has a pKa value of -1 to 5. More particularly, the present invention relates to a metal film etchant composition, an etching method, an array substrate for a liquid crystal display device, and a method of manufacturing an array substrate for a liquid crystal display device for etching a thick film having a copper-based metal film thickness of 5,000 Å or more.
본 발명자는 황산계 화합물로 pKa를 조절함으로써 함불소화합물로 인해 발생하는 금속막 하부 유리기판의 식각율을 감소시킴을 실험적으로 확인하여, 본 발명을 완성하였다. 본 발명의 식각액 조성물은 구리막의 두께가 5000Å 이상인 후막에서 식각특성(Profile) 및 유리식각에 대한 문제점을 개선시킨 면에서 우수한 식각 특성을 갖는다. The present inventors have experimentally confirmed that controlling the pKa with a sulfuric acid-based compound reduces the etching rate of the glass substrate under the metal film caused by the fluorine compound, thereby completing the present invention. The etchant composition of the present invention has excellent etching properties in terms of improving the problems of etch characteristics and glass etching in a thick film having a copper film thickness of 5000 ANGSTROM or more.
본 발명은 바람직하게 구리계 금속막의 식각을 위한 것이며, 상기 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 단일막 및 이중막 등의 다층막을 포함하며 상부막의 두께가 5000Å 이상인 후막이다. 예컨대, 구리 또는 구리 합금의 단일막, 티타늄 또는 티타늄 합금막, 다층막으로서 구리 티타늄막, 구리 티타늄 합금막 등이 포함된다. 상기 구리 티타늄막은 티타늄층과 상기 티타늄층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리 티타늄 합금막은 티타늄 합금층과 상기 티타늄 합금층 상에 형성된 구리층을 포함하는 것을 의미한다. 또한, 상기 티타늄 합금층은 예컨대, 몰리브데늄(Mo), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni) 및 네오디늄(Nd) 등으로 이루어진 군에서 선택되는 하나 이상과 티타늄의 합금을 의미한다. The present invention is preferably for etching a copper-based metal film, and 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 titanium or titanium alloy film, a multilayer film of copper, a titanium film of copper, a titanium film of copper alloy, or the like. The copper titanium film means a titanium layer and a copper layer formed on the titanium layer, and the copper titanium alloy film includes a titanium alloy layer and a copper layer formed on the titanium alloy layer. The titanium alloy layer may include at least one selected from the group consisting of molybdenum (Mo), tantalum (Ta), chromium (Cr), nickel (Ni) and neodymium it means.
본 발명의 식각액 조성물은 게이트 전극과 게이트 배선 및 소스/드레인 전극과 데이터 배선의 일괄 식각이 가능한 구리계 금속막의 식각액 조성물로, (a) 인산, (b) 질산, (c) 초산, (d) 함불소 화합물, (e) 황산계 화합물, 및 (f) 물을 포함한다.(B) nitric acid, (c) acetic acid, (d) phosphoric acid, and (c) nitric acid. The etching solution composition of the present invention is an etching solution composition of a copper-based metal film capable of collectively etching gate electrodes, gate wirings, source / (E) a sulfuric acid-based compound, and (f) water.
본 발명의 식각액 조성물에 포함되는 (d) 황산계 화합물은 pKa를 조절하여 유리 식각 속도 조절을 가능하게 한다.The sulfuric acid compound (d) contained in the etchant composition of the present invention enables control of the glass etch rate by controlling the pKa.
이하, 본 발명을 구성 별로 상세히 설명한다. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(a) 인산(a) phosphoric acid
본 발명의 식각액에 포함되는 인산(H3PO4)은 주 산화제로 사용되는 성분으로서, 금속막을 산화시켜 습식 식각하는 역할을 수행한다. Phosphoric acid (H 3 PO 4 ) contained in the etching solution of the present invention is a component used as a main oxidizing agent and performs a role of oxidizing the metal film to wet-etch the metal film.
그 함량은 식각액 조성물 총중량에 대하여 10 내지 50 중량%이며, 바람직하게는 10 내지 30 중량%로 포함된다. 인산의 함량이 상술한 범위 미만인 경우에는 구리의 식각 속도 저하와 잔사 발생에 따른 불량을 야기시킬 수 있으며, 범위를 초과하는 경우에는 티타늄막의 식각 속도는 저하되고, 구리막의 식각 속도는 너무 빨라져 티타늄막의 잔사 발생 및 구리막의 과식각 현상 발생으로 후속공정에 문제가 되는 불리한 점이 있다.The content thereof is 10 to 50% by weight, preferably 10 to 30% by weight, based on the total weight of the etchant composition. If the content of phosphoric acid is less than the above range, the etching rate of copper may be lowered and defects may be caused by the residue. If the content exceeds the range, the etching rate of the titanium film is lowered and the etching rate of the copper film becomes too fast. There is a disadvantage in that it is a problem in the subsequent process due to the occurrence of residues and over-etching of the copper film.
(b) 질산 (b) nitric acid
본 발명의 식각액에 포함되는 질산(HNO3)은 보조 산화제로 사용되는 성분으로서, 금속막을 산화시켜 습식 식각하는 역할을 수행한다. The nitric acid (HNO 3 ) contained in the etchant of the present invention is a component used as a co-oxidant and performs a wet etching process by oxidizing the metal film.
그 함량은 식각액 조성물 총 중량에 대하여 3 내지 8 중량%이다. 질산의 함량이 3 중량% 미만인 경우에는 금속막의 식각 속도 저하가 발생하며 이로써 기판내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 8 중량%를 초과하는 경우에는 금속막의 식각 속도가 가속화 되어 과식각이 발생할 수 있다.The content thereof is 3 to 8% by weight based on the total weight of the etchant composition. When the content of nitric acid is less than 3% by weight, the etching rate of the metal film is lowered, which results in unevenness in the uniformity of the substrate, resulting in unevenness. When the content of nitric acid is more than 8% by weight, Overeating angle can occur.
(c) 초산 (c) Acetic acid
본 발명의 식각액에 포함되는 초산(CH3COOH)은 보조 산화제로 사용되는 성분으로서, 반응 속도 등을 조절하기 위해 완충제로도 작용하여 질산의 분해속도를 조절하며, 일반적으로 분해 속도를 감소시키는 역할을 한다. Acetic acid (CH 3 COOH) contained in the etchant of the present invention is a component used as a co-oxidant. It controls the decomposition rate of nitric acid by acting as a buffer to control the reaction rate and the like, .
그 함량은 식각액 조성물 총중량에 대하여 10 내지 60 중량%이다. 초산의 함량이 10 중량% 미만인 경우에는 기판 내의 식각 속도 불균일로 얼룩이 발생하는 문제점이 있고, 60 중량%를 초과하는 경우에는 거품발생이 야기되며 이러한 거품이 기판내에 존재하게 되면 완전한 식각이 이루어지지 않아 후속공정에 문제를 야기할 수 있다.The content thereof is 10 to 60% by weight based on the total weight of the etchant composition. If the content of acetic acid is less than 10% by weight, unevenness in etching rate in the substrate may cause unevenness. When the content of acetic acid exceeds 60% by weight, foaming may occur. If such a bubble is present in the substrate, Which can cause problems in subsequent processes.
(d) (d) 함불소Fluorine 화합물 compound
본 발명의 식각액 조성물에 포함되는 함불소화합물은 물에 해리되어 플루오르 이온을 낼 수 있는 화합물을 의미한다. 상기 불소화합물은 티타늄, 티타늄 합금막에서 필연적으로 발생하는 잔사를 제거해 주는 역할을 한다. The fluorinated compound contained in the etchant composition of the present invention means a compound capable of releasing fluoride ions by being dissolved in water. The fluorine compound serves to remove residues necessarily generated in titanium and titanium alloy films.
상기 함불소화합물은 이 분야에서 사용되는 물질로서 용액 내에서 플루오르 이온 혹은 다원자 플루오르 이온으로 해리될 수 있는 것이라면 특별히 한정되지 않는다. 하지만, 상기 불소화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것이 바람직하다.The fluorinated compound is not particularly limited as long as it can be dissociated into a fluoride ion or a polyatomic fluoride ion in a solution used in this field. However, the fluorine compound is not limited to ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF) Sodium bifluoride (NaF 占 HF) and potassium bifluoride (KF 占 HF).
상기 함불소화합물은 조성물 총 중량에 대하여 0.01 내지 2.0 중량%로 포함되고, 바람직하게는 0.05 내지 1.0 중량%로 포함된다. 상술한 범위 미만으로 포함되면, 티타늄, 티타늄 합금막의 식각 속도가 느려져 식각 잔사가 발생될 수 있다. 상술한 범위를 초과하여 포함되면, 유리 기판 식각율이 커지는 문제가 있다.The fluorinated compound is contained in an amount of 0.01 to 2.0% by weight, preferably 0.05 to 1.0% by weight based on the total weight of the composition. If it is contained below the above-mentioned range, the etch rate of the titanium or titanium alloy film may become slow, and etch residues may be generated. If it exceeds the above range, there is a problem that the etching rate of the glass substrate becomes large.
(e) 황산계 화합물(e) a sulfuric acid-based compound
본 발명의 식각액 조성물에 포함되는 황산계 화합물은 화합물의 작용기에 따라 pKa 값을 조절할 수 있으며 높은 pKa값을 가진 황산계 화합물의 경우 식각액 내의 불소이온 활동도를 저하시켜 금속막 하부의 유리 식각에 따른 문제점을 개선해 주는 역할을 한다. 이러한 역할을 위해, 본 발명의 황산계 화합물은 pKa -1 내지 5를 갖는 것 일 수 있다. The sulfuric acid-based compound contained in the etching solution composition of the present invention can control the pKa value according to the functional group of the compound. In the case of the sulfuric acid compound having a high pKa value, the fluorine ion activity in the etching solution is lowered, It plays a role in improving the problem. For this role, the sulfuric acid-based compound of the present invention may have a pKa-1 to 5.
구체적으로, pKa -1내지 5를 갖는, 본 발명의 황산계 화합물은 다음의 구조식을 갖는 화합물일 수 있다. Specifically, the sulfuric acid compound of the present invention having pKa -1 to 5 may be a compound having the following structural formula.
<화학식 1>≪ Formula 1 >
2-나프탈렌 술폰산(2-Naphthalene sulfonic acid)2-Naphthalene sulfonic acid (2-naphthalene sulfonic acid)
<화학식 2>(2)
술팜산(Sulfamic acid)Sulfamic acid
<화학식 3>(3)
설파닐산(Sulfanilic acid)Sulfanilic acid
<화학식 4>≪ Formula 4 >
3-아미노벤젠술폰산(3-Aminobenzene sulfonic acid)3-Aminobenzene sulfonic acid (3-aminobenzene sulfonic acid)
<화학식 5>≪ Formula 5 >
4-하이드록시 벤젠술폰산(4-Hydroxy benzenesulfonic acid)4-Hydroxy benzenesulfonic acid (4-hydroxybenzenesulfonic acid)
황산계 화합물의 pKa가 -1 미만일 경우에는 유리식각율 저하의 효과가 없고, 5를 초과할 경우에는 식각액의 산도(acidity)를 저하시켜 금속막의 식각속도에 부정적 영향을 미칠 수 있다.If the pKa of the sulfuric acid compound is less than -1, there is no effect of lowering the glass etch rate. If the pKa is more than 5, the acidity of the etchant may be lowered and the etching rate of the metal film may be adversely affected.
상기 황산계 화합물은 조성물 총 중량에 대하여, 0.01 내지 10.0중량%으로 포함되고, 바람직하게는 0.1 내지 5.0중량%로 포함된다. 상술한 범위 미만으로 포함되면, 유리 식각율의 저하 효과가 없고. 상술한 범위를 초과하여 포함되어도 추가 개선 효과는 없다. The sulfuric acid compound is contained in an amount of 0.01 to 10.0% by weight, preferably 0.1 to 5.0% by weight, based on the total weight of the composition. If it is contained below the above-mentioned range, there is no effect of lowering the glass etching rate. There is no additional improvement effect even if it is included in the range exceeding the above-mentioned range.
(f) 물(f) Water
본 발명의 구리 티타늄 합금막 식각액 조성물에 포함되는 물은 조성물 총 중량이 100 중량%가 되도록 잔량 포함된다. 이때 물의 양이 총 중량의 30중량% 이상이 될 경우 식각액의 산화력이 현저히 저하되어 식각불량을 야기 할 수 있다. 상기 물은 특별히 한정하지 않으나, 탈이온수를 이용하는 것이 바람직하다. 그리고, 상기 물은 물속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·㎝ 이상인 탈이온수를 이용하는 것이 좋다.The water contained in the copper titanium alloy film etchant composition of the present invention contains the balance so that the total weight of the composition is 100% by weight. If the amount of water is 30 wt% or more of the total weight, the oxidizing power of the etching solution is significantly lowered, which may cause etching failure. The water is not particularly limited, but it is preferable to use deionized water. The water is preferably deionized water having a specific resistance value of 18 M OMEGA. Or more to show the degree of removal of ions in the water.
본 발명에서 사용되는 인산, 질산, 초산, 함불소화합물, 황 화합물 및 물 등은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다. The phosphoric acid, nitric acid, nitric acid, fluorine compound, sulfur compound and water used in the present invention can be prepared by a conventionally known method, and the etchant composition of the present invention preferably has purity for semiconductor processing.
또한, 본 발명은 In addition,
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 In addition,
a)기판 상에 게이트 전극을 형성하는 단계;a) forming a gate electrode on a substrate;
b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate electrode;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및d) forming a source / drain electrode on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
상기 a)단계는 기판 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하여 게이트 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.
또한, 상기 액정 표시 장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.In addition, the array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 제조방법으로 제조된 액정 표시 장치용 어레이 기판에 관한 것이다.The present invention also relates to an array substrate for a liquid crystal display manufactured by the above manufacturing method.
상기 액정 표시 장치용 어레이 기판은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 배선 및/또는 소스 및 드레인 전극을 포함할 수 있다.The array substrate for a liquid crystal display may include gate wirings and / or source and drain electrodes etched using the etchant composition of the present invention.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<본 발명 조성물의 우수한 식각특성 확인><Confirmation of excellent etching properties of the composition of the present invention>
실시예1Example 1 내지 To 실시예2Example 2 , , 비교예1Comparative Example 1 내지 To 비교예9Comparative Example 9 : : 식각액Etchant 조성물의 제조 Preparation of composition
하기 표 1에 나타낸 조성에 따라(단위 : 중량%) 실시예 및 비교예의 식각액 조성물 각각 180㎏을 제조하였다.(Unit: wt%) According to the composition shown in the following Table 1, 180 kg of each of the etchant compositions of Examples and Comparative Examples were prepared.
실험예Experimental Example 1. One. 식각액Etchant 조성물의 특성평가 Evaluation of composition characteristics
유리기판(100mmⅩ100mm)상에 티타늄합금막을 증착시키고 상기막 상에 구리막을 증착시킨 뒤 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 한 후, 실시예 1 내지 2 및 비교예 1 내지 9의 조성물을 각각 사용하여 구리계 금속막에 대하여 식각공정을 실시하였다. 분사식 식각 방식의 실험장비(모델명 : ETCHER(TFT), SEMES사)를 이용하였고, 식각공정시 식각액 조성물의 온도는 약 40℃ 내외로 하였으나, 적정온도는 다른 공정조건과 기타 요인에 의해 필요에 따라 변경될 수 있다. 식각시간은 식각 온도에 따라서 다를 수 있으나, 통상 50~180초 정도로 진행하였다. 상기 식각공정에서 식각된 구리계 금속막의 프로파일을 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였고, 결과를 표 2에 기재하였다.A titanium alloy film was deposited on a glass substrate (100 mm x 100 mm), a copper film was deposited on the film, and a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. Then, And the compositions of Comparative Examples 1 to 9 were used, respectively, to etch the copper-based metal film. (ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set to about 40 ° C during the etching process. However, the optimum temperature was determined according to other process conditions and other factors can be changed. The etching time may vary depending on the etching temperature, but is usually about 50 to 180 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (product of Hitachi, Model S-4700), and the results are shown in Table 2.
<식각 평가 기준><Etching Evaluation Standard>
Cu Etch Rate : O (200Å/sec ~ 300Å/sec) , △(200Å/sec 미만, 300Å/sec 초과), X (Unetch)Cu Etch Rate: O (200 Å / sec to 300 Å / sec), Δ (less than 200 Å / sec, more than 300 Å / sec), X (Unetch)
Ti Etch Rate : O (10Å/sec 이상) , △(10Å/sec 미만), X (Unetch)Ti Etch Rate: O (10 Å / sec or more), Δ (less than 10 Å / sec), X (Unetch)
Cu Etch 균일도 : O (우수), △(보통), X(불량)Cu Etch Uniformity: O (Excellent), Δ (Normal), X (Bad)
유리식각속도 : O (10Å/sec 이하) , X (10Å/sec 초과)Glass Angular Velocity: O (10 Å / sec or less), X (10 Å / sec or more)
구리막이 Unetch 될 경우 하부 Ti와 유리식각속도 및 균일도는 측정불가함.If the copper film is unetch, the lower Ti and glass angular velocity and uniformity can not be measured.
표 2에서 알수 있듯이 실시예1 내지 실시예2의 식각액 조성물은 구리막의 두께가 5000Å 이상인 후막에서 Profile 및 유리식각에 대한 문제점을 개선시킨 면에서 우수한 식각 특성을 나타내었다. As can be seen from Table 2, the etchant compositions of Examples 1 and 2 exhibited excellent etching properties in terms of improving the profile and glass etching problems in a thick film having a copper film thickness of 5000 angstroms or more.
반면 비교예1 내지 비교예9 의 경우 Etch Profile 에서 식각 균일도가 불량하고 얼룩이 발생하였으며 유리식각에 의한 문제점 또한 발생 하였다. On the other hand, in the case of Comparative Examples 1 to 9, the etch profile was poor in etch uniformity, stains were formed, and glass etching problems also occurred.
< 황산계 화합물의 pKa에 따른, 식각액 조성물의 식각특성 확인><Confirmation of Etching Characteristics of Etchant Composition According to pKa of Sulfuric Acid Compound>
실시예3Example 3 내지 To 실시예4Example 4 , , 비교예10Comparative Example 10 내지 To 비교예14Comparative Example 14 : : 식각액Etchant 조성물의 제조 Preparation of composition
하기 표 3에 나타낸 조성에 따라(단위 : 중량%) 실시예 및 비교예 의 식각액 조성물 각각 180㎏을 제조하였으며, 각 조성물의 pKa를 나타내었다.According to the composition shown in Table 3 below (unit: wt%), 180 kg of each of the etchant compositions of Examples and Comparative Examples was prepared, and the pKa of each composition was shown.
실험예Experimental Example 2. 2. 식각액Etchant 조성물의 특성평가 Evaluation of composition characteristics
상기 실험예 1과 동일한 방법으로, 실시예와 비교예의 식각 조성물의 특성을 평가하여 표 4에 나타내었다. The properties of the etching compositions of Examples and Comparative Examples were evaluated in the same manner as in Experimental Example 1,
표 4에서 알수 있듯이 pKa범위가 -1~5인 황산계 화합물을 사용한 실시예3 내지 실시예4의 식각액 조성물은, 구리막의 두께가 5000Å 이상인 후막에서 Profile 및 유리식각에 대한 문제점을 개선시킨 면에서 우수한 식각 특성을 나타내었다. As can be seen from Table 4, the etchant compositions of Examples 3 to 4 using the sulfuric acid compound having the pKa range of -1 to 5 improved the profile and the glass etching problem in the thick film having the copper film thickness of 5000 Å or more And showed excellent etching characteristics.
반면 pKa -1~5 범위를 벗어나는 황산계 화합물을 사용한, 비교예11 내지 비교예14 의 경우 Etch Profile 에서 구리 에칭속도가 충분하지 않거나, 유리식각에 의한 문제점이 발생 하였다. On the other hand, in Comparative Examples 11 to 14 using sulfuric acid compounds out of the range of pKa -1 to 5, the copper etching rate was insufficient in the Etch Profile, or a problem caused by the glass etching occurred.
상기 실험결과를 통해, 본 발명의 식각액 조성물은 pKa범위가 -1~5인 황산계 화합물을 사용함에 따라, 우수한 식각 특성을 가짐을 확인할 수 있었다. From the above experimental results, it was confirmed that the etching solution composition of the present invention had excellent etching characteristics by using the sulfuric acid compound having the pKa range of -1 to 5.
Claims (10)
(e) a sulfuric acid-based compound (e), wherein the sulfuric acid-based compound (e) is a metal film etchant composition comprising (a) phosphoric acid, (b) nitric acid, (c) acetic acid, Wherein the pKa value is in the range of -1 to 5.
(e) 황산계 화합물은 하기 화합물 중 하나 이상인 금속막 식각액 조성물:
<화학식 1>
2-나프탈렌 술폰산(2-Naphthalene sulfonic acid)
<화학식 2>
술팜산(Sulfamic acid)
<화학식 3>
설파닐산(Sulfanilic acid)
<화학식 4>
3-아미노벤젠술폰산(3-Aminobenzene sulfonic acid)
<화학식 5>
4-하이드록시 벤젠술폰산(4-Hydroxy benzenesulfonic acid).
The method according to claim 1,
(e) the sulfuric acid-based compound is at least one of the following compounds:
≪ Formula 1 >
2-Naphthalene sulfonic acid (2-naphthalene sulfonic acid)
(2)
Sulfamic acid
(3)
Sulfanilic acid
≪ Formula 4 >
3-Aminobenzene sulfonic acid (3-aminobenzene sulfonic acid)
≪ Formula 5 >
4-Hydroxybenzenesulfonic acid.
(d) 함불소 화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF) 및 중불화칼륨(potassium bifluoride: KF·HF) 중 하나 이상인 금속막 식각액 조성물.
The method according to claim 1,
(d) The fluorinated compound may be selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F.HF) Wherein the composition is at least one of sodium bifluoride (NaF.HF) and potassium bifluoride (KF.HF).
(a) 인산 10 내지 50 중량%,
(b) 질산 3 내지 8 중량%,
(c) 초산 10 내지 60 중량%,
(d) 함불소 화합물 0.01 내지 2.0중량%,
(e) 황산계 화합물 0.01 내지 10.0중량%, 및
(f) 물 잔량을 포함하는 금속막 식각액 조성물.
The method of claim 1, wherein, based on the total weight of the etchant composition,
(a) 10 to 50% by weight of phosphoric acid,
(b) 3 to 8% by weight of nitric acid,
(c) 10 to 60% by weight of acetic acid,
(d) 0.01 to 2.0% by weight of a fluorine compound,
(e) 0.01 to 10.0% by weight of a sulfuric acid-based compound, and
(f) a residual amount of water.
The method of claim 1, wherein the metal film is a single film of copper or a copper alloy; Or a copper-based metal film that is a multilayer film including at least one film selected from the group consisting of a copper-titanium film and a copper-titanium alloy film.
The metal film etch composition according to claim 1, wherein the metal film is a copper-based metal film having a thickness of 5000 ANGSTROM or more.
Ⅱ)상기 구리계 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및
Ⅲ) 청구항 1 내지 6 중 어느 한 항의 금속막 식각액 조성물을 사용하여 상기 구리계 금속막을 식각하는 단계를 포함하는 구리계 금속막의 식각방법.
I) forming a copper-based metal film on a substrate;
II) selectively leaving a photoreactive material on the copper-based metal film; And
III) A method for etching a copper-based metal film, comprising etching the copper-based metal film using the metal film etching liquid composition according to any one of claims 1 to 6.
b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 a)단계는 기판 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 청구항 1 내지 6 중 어느 한 항의 금속막 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하며,
상기 d)단계는 반도체층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 상기 금속막 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.
a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
Wherein the step a) comprises forming a copper-based metal film on the substrate and etching the copper-based metal film with the metal film etchant composition according to any one of claims 1 to 6 to form a gate wiring,
Wherein the step d) comprises forming a copper-based metal film on the semiconductor layer and etching the copper-based metal film with the metal film etchant composition to form source and drain electrodes. Gt;
The method of manufacturing an array substrate for a liquid crystal display according to claim 8, wherein the array substrate for a liquid crystal display is a thin film transistor (TFT) array substrate.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150134059A KR102368376B1 (en) | 2015-09-22 | 2015-09-22 | Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same |
| TW105128030A TWI632254B (en) | 2015-09-22 | 2016-08-31 | Etchant composition for metal layer, method for etching copper-based metal layer using the same, method for preparing array substrate for liquid crystal display device, array substrate for liquid crystal display device prepared therefrom |
| CN201610839181.6A CN106555187B (en) | 2015-09-22 | 2016-09-21 | Etchant composition, method for etching copper-based metal layer, method for manufacturing array substrate and array substrate manufactured by same |
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| CN110093606A (en) * | 2019-06-14 | 2019-08-06 | 大连亚太电子有限公司 | A kind of etching solution and preparation method thereof for pcb board |
| CN110195229B (en) * | 2019-06-21 | 2021-05-14 | 湖北兴福电子材料有限公司 | Etching solution for tungsten and titanium nitride metal film and use method thereof |
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| Publication number | Publication date |
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| TWI632254B (en) | 2018-08-11 |
| TW201712155A (en) | 2017-04-01 |
| CN106555187A (en) | 2017-04-05 |
| KR102368376B1 (en) | 2022-02-28 |
| CN106555187B (en) | 2019-12-17 |
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