KR102160286B1 - Manufacturing method of an array substrate for liquid crystal display - Google Patents
Manufacturing method of an array substrate for liquid crystal display Download PDFInfo
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- KR102160286B1 KR102160286B1 KR1020130132820A KR20130132820A KR102160286B1 KR 102160286 B1 KR102160286 B1 KR 102160286B1 KR 1020130132820 A KR1020130132820 A KR 1020130132820A KR 20130132820 A KR20130132820 A KR 20130132820A KR 102160286 B1 KR102160286 B1 KR 102160286B1
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- 239000000758 substrate Substances 0.000 title claims abstract description 33
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 119
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052802 copper Inorganic materials 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 91
- 239000002184 metal Substances 0.000 claims abstract description 91
- 238000005530 etching Methods 0.000 claims abstract description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 azole compound Chemical class 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims description 140
- 238000000034 method Methods 0.000 claims description 28
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003536 tetrazoles Chemical class 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 23
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 8
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 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 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
- G02F1/136277—Active matrix addressed cells formed on a semiconductor substrate, e.g. of silicon
-
- 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
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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
-
- 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
- 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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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Thin Film Transistor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
a)기판 상에 게이트 배선을 형성하는 단계; b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, 상기 a) 또는 d)단계는 기판 또는 반도체 층 상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 식각액 조성물로 식각하여 게이트 배선 또는 소스 및 드레인 전극을 형성하는 단계를 포함하며; 상기 식각액 조성물은 조성물 총 중량에 대하여 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 구리계 금속막 식각액 조성물인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.a) forming a gate wiring on the substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, wherein the step a) or d) comprises forming a copper-based metal film on the substrate or the semiconductor layer, Etching the copper-based metal layer with an etchant composition to form gate wirings or source and drain electrodes; The etchant composition comprises 5 to 25% by weight of hydrogen peroxide, 0.1 to 5% by weight of phosphorous acid, 0.01 to 1.0% by weight of a fluorine compound, 0.1 to 5% by weight of an azole compound, and a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule based on the total weight of the composition. In the method of manufacturing an array substrate for a liquid crystal display, characterized in that it is a copper-based metal film etchant composition containing 0.1 to 5.0% by weight, 0.1 to 5.0% by weight of a sulfate compound, and a residual amount of water so that the total weight of the composition is 100% by weight. About.
Description
본 발명은 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing an array substrate for a liquid crystal display device.
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.In a semiconductor device, the process of forming a metal wire on a substrate typically consists of a metal film formation process by sputtering, a photoresist coating, a photoresist formation process and an etching process in a selective area by exposure and development, It includes a cleaning process before and after individual unit processes. This etching process refers to a process of leaving a metal film in a selective area using a photoresist as a mask, and typically, dry etching using plasma or the like or wet etching using an etching solution composition is used.
통상, 게이트 및 데이터 배선 재료로는 전기 전도도가 좋고 저항이 낮은 구리를 함유하는 구리 단독막 또는 구리 합금막과 이들 막과 계면 접착력이 우수한 금속 산화물막이 사용된다.In general, as the gate and data wiring material, a single copper film or copper alloy film containing copper having good electrical conductivity and low resistance, and a metal oxide film having excellent interfacial adhesion to these films are used.
대한민국 공개특허 제10-2007-0055259호에는 구리 몰리브덴합금막의 식각용액 조성물로 과산화수소, 유기산, 인산염 화합물 등을 포함하는 구리계 금속막 식각액 조성물이 기재되어 있다.Korean Patent Laid-Open Publication No. 10-2007-0055259 discloses a copper-based metal film etchant composition including hydrogen peroxide, an organic acid, and a phosphate compound as an etching solution composition for a copper molybdenum alloy film.
그러나, 상기 식각액 조성물은 구리계 금속막의 후막에 적용시킬 경우 제 1인산염으로 인해 테이퍼 앵글(taper angle)이 높아져 후속 공정 진행시 불량이 발생하는 문제점이 발생한다.However, when the etchant composition is applied to a thick layer of a copper-based metal film, a taper angle increases due to the first phosphate, causing a problem in that a defect occurs during a subsequent process.
한편, 대한민국 공개특허 제10-2010-0090538호에는 구리계 금속막의 식각용 조성물로, 과산화수소(H2O2), 유기산, 및 인산염 화합물 등을 포함하는 조성물이 기재되어 있다. 상기 식각용 조성물로 구리 몰리브덴막을 식각하게 되면 직선성이 우수한 테이프프로파일이 형성되나, 몰리브덴-나이오븀(Mo-Nb)의 몰리브덴계 금속막 및 구리계 금속막을 일괄 식각하는 경우에는 에칭속도가 느려지고, 몰리브덴-나이오븀(Mo-Nb)의 몰리브덴계 금속막은 에칭되지 않거나, 잔사가 발생하는 등 식각 성능이 극히 떨어지는 문제점이 있다.Meanwhile, Korean Patent Publication No. 10-2010-0090538 discloses a composition for etching a copper-based metal film, including hydrogen peroxide (H 2 O 2 ), an organic acid, and a phosphate compound. When the copper molybdenum film is etched with the etching composition, a tape profile having excellent linearity is formed, but when the molybdenum-based metal film and the copper-based metal film of molybdenum-niobium (Mo-Nb) are etched collectively, the etching rate is slowed. The molybdenum-based metal film made of molybdenum-niobium (Mo-Nb) is not etched or there is a problem in that the etching performance is extremely deteriorated, such as a residue.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 구리계 금속막으로 이루어진 액정표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems, and an object of the present invention is to provide a method of manufacturing an array substrate for a liquid crystal display device made of a copper-based metal film.
또한, 본 발명의 구리계 금속막 식각액 조성물을 사용하여 구리계 금속막을 일괄 식각하는 것을 목적으로 한다.In addition, it is an object of the present invention to collectively etch a copper-based metal film by using the copper-based metal film etchant composition.
또한, 본 발명의 구리계 금속막 식각액 조성물은 잔사가 발생하지 않도록 다층막을 식각하는 것을 목적으로 한다.In addition, the copper-based metal film etchant composition of the present invention aims to etch a multilayer film so that residues do not occur.
상기 목적을 달성하기 위하여,To achieve the above object,
본 발명은 a)기판 상에 게이트 배선을 형성하는 단계; The present invention comprises the steps of: a) forming a gate wiring on a substrate;
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; b) forming a gate insulating layer on the substrate including the gate wiring;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 d) forming source and drain electrodes on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 a) 또는 d)단계는 기판 또는 반도체 층 상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 식각액 조성물로 식각하여 게이트 배선, 또는 소스 및 드레인 전극을 형성하는 단계를 포함하며;The step a) or d) includes forming a copper-based metal film on a substrate or a semiconductor layer, and etching the copper-based metal film with an etchant composition to form gate wirings or source and drain electrodes;
상기 식각액 조성물은 조성물 총 중량에 대하여 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 구리계 금속막 식각액 조성물인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.The etchant composition comprises 5 to 25% by weight of hydrogen peroxide, 0.1 to 5% by weight of phosphorous acid, 0.01 to 1.0% by weight of a fluorine compound, 0.1 to 5% by weight of an azole compound, and a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule based on the total weight of the composition. A method of manufacturing an array substrate for a liquid crystal display, characterized in that it is a copper-based metal film etchant composition containing 0.1 to 5.0% by weight, 0.1 to 5.0% by weight of a sulfate compound, and a residual amount of water so that the total weight of the composition is 100% by weight. to provide.
또한, 본 발명은 조성물 총 중량에 대하여, 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 구리계 금속막 식각액 조성물을 제공한다.In addition, the present invention is based on the total weight of the composition, hydrogen peroxide 5 to 25% by weight, phosphorous acid 0.1 to 5% by weight, fluorine compound 0.01 to 1.0% by weight, azole compound 0.1 to 5% by weight, having a nitrogen atom and a carboxyl group in one molecule It provides a copper-based metal film etchant composition comprising 0.1 to 5.0% by weight of a water-soluble compound, 0.1 to 5.0% by weight of a sulfate compound, and the remaining amount of water so that the total weight of the composition is 100% by weight.
또한, 본 발명은 상기 구리계 금속막 식각액 조성물을 사용하여 식각된 게이트 배선, 소스 전극 및 드레인 전극으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.In addition, the present invention provides an array substrate for a liquid crystal display device including at least one selected from the group consisting of a gate wiring, a source electrode, and a drain electrode etched using the copper-based metal layer etchant composition.
본 발명의 구리계 금속막 식각액 조성물은 식각 속도를 향상시킬 수 있으며, 타 금속막과의 적층막을 잔사가 발생하지 않게 식각할 수 있으며, 구리 농도에 따른 사이드 에치(side etch) 변화량이 일정하게 유지되는 장점이 있다.The copper-based metal film etchant composition of the present invention can improve the etching rate, and can etch the laminated film with other metal films so that no residue is generated, and the amount of side etch change according to the copper concentration is kept constant. It has the advantage of being.
도 1은 실시예 3의 구리계 금속막 식각액 조성물을 사용하여 구리 300ppm 조건에서의 식각 프로파일을 나타낸 SEM 사진이다.
도 2는 실시예 3의 구리계 금속막 식각액 조성물을 사용하여 구리 3000ppm 조건에서의 식각 프로파일을 나타낸 SEM 사진이다.
도 3은 실시예 3의 구리계 금속막 식각액 조성물을 사용하여 구리 5000ppm 조건에서의 식각 프로파일을 나타낸 SEM 사진이다.1 is a SEM photograph showing an etching profile under a condition of 300 ppm copper using the copper-based metal film etchant composition of Example 3. FIG.
FIG. 2 is an SEM photograph showing an etching profile under a condition of 3000 ppm copper using the copper-based metal film etchant composition of Example 3. FIG.
3 is a SEM photograph showing an etching profile under a condition of 5000 ppm copper using the copper-based metal film etchant composition of Example 3. FIG.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 구리계 금속막 식각액 조성물을 이용한 액정표시장치용 어레이 기판의 제조 방법에 관한 것으로 제조 방법은 하기와 같다.The present invention relates to a method of manufacturing an array substrate for a liquid crystal display using a copper-based metal film etchant composition, and the manufacturing method is as follows.
a)기판 상에 게이트 배선을 형성하는 단계; a) forming a gate wiring on the substrate;
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; b) forming a gate insulating layer on the substrate including the gate wiring;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 d) forming source and drain electrodes on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법으로, e) A method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 a) 또는 d)단계는 기판 또는 반도체 층 상에 구리계 금속막을 형성하고 상기 구리계 금속막을 식각액 조성물로 식각하여 게이트 배선, 또는 소스 및 드레인 전극을 형성하는 단계를 포함한다.The step a) or d) includes forming a copper-based metal film on a substrate or a semiconductor layer, and etching the copper-based metal film with an etchant composition to form a gate wiring or source and drain electrodes.
상기 식각액 조성물은 조성물 총 중량에 대하여 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 구리계 금속막 식각액 조성물인 것을 특징으로 한다.The etchant composition comprises 5 to 25% by weight of hydrogen peroxide, 0.1 to 5% by weight of phosphorous acid, 0.01 to 1.0% by weight of a fluorine compound, 0.1 to 5% by weight of an azole compound, and a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule based on the total weight of the composition. It is characterized in that it is a copper-based metal film etchant composition containing 0.1 to 5.0% by weight, 0.1 to 5.0% by weight of a sulfate compound, and the remaining amount of water so that the total weight of the composition is 100% by weight.
상기 액정표시장치용 어레이 기판은 박막트랜지스(TFT) 어레이 기판이다.
The array substrate for a liquid crystal display device is a thin film transistor (TFT) array substrate.
또한, 본 발명은 조성물 총 중량에 대하여, 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 구리계 금속막 식각액 조성물에 관한 것이다.In addition, the present invention is based on the total weight of the composition, hydrogen peroxide 5 to 25% by weight, phosphorous acid 0.1 to 5% by weight, fluorine compound 0.01 to 1.0% by weight, azole compound 0.1 to 5% by weight, having a nitrogen atom and a carboxyl group in one molecule It relates to a copper-based metal film etchant composition comprising 0.1 to 5.0% by weight of a water-soluble compound, 0.1 to 5.0% by weight of a sulfate compound, and the remaining amount of water so that the total weight of the composition is 100% by weight.
상기 조성물을 포함함으로써 본 발명의 구리계 금속막 식각액 조성물은 식각 속도를 높일 수 있으며, 구리 및 타 금속막(예컨대, 몰리브덴-나이오븀(Mo-Nb) 합금)으로 이루어진 다층막을 잔사가 발생하지 않도록 식각할 수 있다.By including the composition, the copper-based metal film etchant composition of the present invention can increase the etching rate, and a multilayer film made of copper and other metal films (for example, molybdenum-niobium (Mo-Nb) alloy) is prevented from occurring. Can be etched.
상기 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 구리 또는 구리 합금의 단일막; 및 구리막 또는 구리 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막과 몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 포함한다. 상기 합금막은 질화막 또는 산화막을 포함하는 개념이다.The copper-based metal film includes copper as a component of the film, and includes a single film of copper or a copper alloy; And a multilayer film including at least one film selected from the group consisting of a copper film or a copper alloy film, and at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film. The alloy film is a concept including a nitride film or an oxide film.
상기 다층막의 예로는, 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴 합금막, 구리/티타늄막 등의 2중막 또는 3중막을 들 수 있다. 상기 구리/몰리브덴막은 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 것을 의미하며, 구리 합금/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리 합금층을 포함하는 것을 의미하며, 상기 구리/티타늄막은 티타늄층과 상기 티타늄층 상에 형성된 구리층을 포함하는 것을 의미한다.Examples of the multilayer film include a double or triple film such as a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum alloy film, and a copper/titanium film. The copper/molybdenum film means including a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper/molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, and copper The alloy/molybdenum alloy film means including a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper/titanium film means including a titanium layer and a copper layer formed on the titanium layer.
본 발명의 구리계 금속막 식각액 조성물에서 구리계 금속막은 구리막 및 구리 합금막으로 이루어진 군으로부터 선택되는 1종 이상 및 몰리브덴막 및 몰리브덴 합금막으로 이루어진 군으로부터 선택되는 1종 이상의 막을 포함하는 다층막에 바람직하게 적용될 수 있다.In the copper-based metal film etchant composition of the present invention, the copper-based metal film is applied to a multilayer film including at least one film selected from the group consisting of a copper film and a copper alloy film, and at least one film selected from the group consisting of a molybdenum film and a molybdenum alloy film. It can be preferably applied.
또한, 상기 몰리브덴 합금막은 티타늄(Ti), 나이오븀(Nb) 및 텅스텐(W)으로 이루어진 군으로부터 선택되는 1종 이상의 금속 및 몰리브덴으로 이루어진 몰리브덴의 합금인 것이 바람직하다.
In addition, the molybdenum alloy film is preferably an alloy of molybdenum consisting of at least one metal selected from the group consisting of titanium (Ti), niobium (Nb), and tungsten (W), and molybdenum.
또한, 본 발명의 구리계 금속막 식각액 조성물은 다가 알코올형 계면활성제를 추가로 더 포함하여 사용할 수 있다.In addition, the copper-based metal film etchant composition of the present invention may further include a polyhydric alcohol-type surfactant.
이하, 본 발명의 구리계 금속막 식각액 조성물의 구성을 상세히 설명한다.
Hereinafter, the configuration of the copper-based metal film etchant composition of the present invention will be described in detail.
(A)과산화수소((A) Hydrogen peroxide ( HH 22 OO 22 ))
본 발명의 구리계 금속막 식각액 조성물에 포함되는 과산화수소(H2O2)는 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 구리 몰리브덴막 또는 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 구리 몰리브덴 합금막인 것을 특징으로 하는 구리계 금속막의 식각에 영향을 주는 주산화제이며, 상기 과산화수소(H2O2)는 구리계 금속막 식각액 조성물 총 중량에 대하여, 5 내지 25 중량%, 바람직하게는 15 내지 23 중량%로 포함된다. 상기 과산화수소가 5 중량% 미만으로 포함되면, 구리계 금속막의 식각력이 부족하여 충분한 식각이 이루어지지 않을 수 있으며, 25 중량%를 초과하여 포함될 경우, 구리 이온 증가에 따른 발열 안정성이 크게 감소한다.
Hydrogen peroxide (H 2 O 2 ) contained in the copper-based metal film etchant composition of the present invention is a copper molybdenum film including a molybdenum layer and a copper layer formed on the molybdenum layer, or a molybdenum alloy layer and copper formed on the molybdenum alloy layer. It is a main oxidizing agent that affects the etching of a copper-based metal film, characterized in that it is a copper molybdenum alloy film including a layer, and the hydrogen peroxide (H 2 O 2 ) is 5 to 25 weight based on the total weight of the copper-based metal film etchant composition %, preferably 15 to 23% by weight. When the hydrogen peroxide is contained in an amount of less than 5% by weight, sufficient etching may not be performed due to insufficient etching power of the copper-based metal layer, and when it is included in an amount exceeding 25% by weight, the heat generation stability due to the increase of copper ions is greatly reduced.
(B)아인산((B) Phosphorous acid ( HH 33 POPO 33 ))
본 발명의 구리계 금속막 식각액 조성물에 포함되는 아인산은 pH를 조절하여 식각속도를 증가시켜주는 성분이다. 상기 아인산이 본 발명의 구리계 금속막 식각액 조성물에 포함되지 않으면 식각속도가 매우 낮아 식각 프로파일이 불량하게 될 수 있다. 상기 아인산의 함량은 구리계 금속막 식각액 조성물 총 중량에 대하여 0.1 내지 5.0 중량%로 포함되고, 바람직하게는 0.3 내지 3.0 중량%로 포함된다. 상기 아인산이 0.1 중량% 미만일 경우 식각 프로파일에서 불량이 발생할 수 있으며, 5 중량%를 초과하는 경우에는 구리 또는 구리 합금막의 식각속도가 너무 빨라지거나 몰리브덴 또는 몰리브덴합금막의 식각속도가 너무 느려지는 문제가 발생될 수 있다.
Phosphorous acid contained in the copper-based metal film etchant composition of the present invention is a component that increases the etching rate by adjusting the pH. If the phosphorous acid is not included in the copper-based metal film etchant composition of the present invention, the etching rate may be very low, and the etching profile may be poor. The content of phosphorous acid is contained in an amount of 0.1 to 5.0% by weight, preferably 0.3 to 3.0% by weight, based on the total weight of the copper-based metal film etchant composition. If the phosphorous acid is less than 0.1% by weight, defects may occur in the etching profile, and if it exceeds 5% by weight, the etching rate of the copper or copper alloy layer becomes too fast, or the etching rate of the molybdenum or molybdenum alloy layer is too slow. Can be.
(C)불소화합물(C) fluorine compounds
상기 불소화합물은 물에 해리되어 불소 이온을 낼 수 있는 화합물을 말한다. 상기 불소화합물은 몰리브덴 합금막의 식각 속도에 영향을 주는 보조산화제이며, 몰리브덴 합금막의 식각 속도를 조절한다.The fluorine compound refers to a compound capable of dissociating in water to produce fluorine ions. The fluorine compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum alloy layer, and controls the etching rate of the molybdenum alloy layer.
상기 불소화합물은 당업계에서 사용되는 것이라면 특별히 한정하지 않지만 HF, NaF, NH4F, NH4BF4, NH4FHF, NH4F2 , KF, KHF2, AlF3 및 HBF4로 이루어진 군으로부터 선택되는 1종 이상인 것이 바람직하고, NH4F2가 보다 바람직하다.The fluorine compound is not particularly limited as long as it is used in the art, but from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, NH 4 F 2 , KF, KHF 2 , AlF 3 and HBF 4 It is preferably at least one selected, and more preferably NH 4 F 2 .
또한, 상기 불소화합물은 구리계 금속막 식각액 조성물 총 중량에 대하여, 0.01 내지 1.0 중량%, 바람직하게는 0.1 내지 1.0 중량%로 포함된다. 상기 불소화합물의 함량이 0.01 중량% 미만이면 몰리브덴 합금막의 식각 속도가 느려지고, 1.0 중량%를 초과하면 몰리브덴 합금막의 식각 성능은 향상되지만, 식각 속도가 전체적으로 빨라지기 때문에 언더컷 현상이나 하부층(n+ a-Si:H, a-Si:G)의 식각으로 인한 손실이 크게 나타난다.
In addition, the fluorine compound is contained in an amount of 0.01 to 1.0% by weight, preferably 0.1 to 1.0% by weight, based on the total weight of the copper-based metal film etchant composition. If the content of the fluorine compound is less than 0.01% by weight, the etching rate of the molybdenum alloy layer is slow, and when it exceeds 1.0% by weight, the etching performance of the molybdenum alloy layer is improved, but the etching rate is increased as a whole, so undercut or lower layer (n+a-Si :H, a-Si:G) loss due to etching appears large.
(D)(D) 아졸화합물Azole compounds
본 발명의 구리계 금속막 식각액 조성물에 포함되는 아졸화합물은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주고, Etch Profile 변동을 감소시켜주어 공정상의 마진을 높이는 역할을 한다.The azole compound contained in the copper-based metal film etchant composition of the present invention controls the etching rate of the copper-based metal film, reduces the CD loss of the pattern, and reduces the etch profile variation, thereby increasing the margin of the process. do.
상기 아졸화합물로는 예컨대, 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 디아졸(thiazole)계 및 이소디아졸(isothiazole)계 등이 있으며, 이들은 단독 또는 2종 이상이 함께 사용될 수 있다. 상기 아졸화합물 중에서 트리아졸(triazole)계 또는 테트라졸(tetrazole)계 화합물이 바람직하며, 그 중에서도 3-아미노트리아졸, 4-아미노트리아졸, 5-메틸테트라졸 및 5-아미노테트라졸로 이루어진 군으로부터 선택되는 1종 이상이 가장 바람직하다. 본 발명에서는 3-아미노트리아졸, 4-아미노트리아졸, 5-메틸테트라졸 및 5-아미노테트라졸을 혼용하여 사용할 경우, 식각속도 조절 및 처리매수에 따른 Etch Profile 변동 감소 능력이 화합물마다 다른 특성이 나타나므로 공정 조건에 맞는 배합비를 산출하여 적용하는 것이 바람직하다.The azole compounds include, for example, pyrrole, pyrazole, imidazole, triazole, tetrazole, pentazole, oxazole There are (oxazole)-based, isoxazole-based, diazole-based, and iso-diazole-based, and these may be used alone or in combination of two or more. Among the azole compounds, triazole-based or tetrazole-based compounds are preferred, and among them, from the group consisting of 3-aminotriazole, 4-aminotriazole, 5-methyltetrazole and 5-aminotetrazole At least one selected is most preferred. In the present invention, when using a mixture of 3-aminotriazole, 4-aminotriazole, 5-methyltetrazole, and 5-aminotetrazole, the ability to control the etch rate and reduce the variation of the etch profile according to the number of processed sheets is different for each compound. Since appears, it is desirable to calculate and apply a blending ratio that meets the process conditions.
상기 아졸화합물은 조성물 총 중량에 대하여, 0.1 내지 5.0 중량%로 포함되고, 바람직하게는 0.5 내지 1.5 중량%로 포함된다. 상기 0.1 중량% 미만으로 포함되면 식각 속도가 빠르게 되어 시디로스가 너무 크게 발생될 수 있으며, 상기 5.0 중량%를 초과하여 포함되면 구리계 금속막의 식각 속도가 너무 느려지게 되어 공정 시간이 증가하며, 또한 상대적으로 금속 산화물막의 식각 속도가 빨라지게 되므로 언더컷이 발생될 수 있다.
The azole compound is contained in an amount of 0.1 to 5.0% by weight, and preferably 0.5 to 1.5% by weight, based on the total weight of the composition. If it is contained in an amount of less than 0.1% by weight, the etching rate may be accelerated, resulting in excessively large cydiros. If it is contained in an amount exceeding 5.0% by weight, the etching rate of the copper-based metal film is too slow to increase the process time. Since the etching speed of the metal oxide layer is relatively increased, undercut may occur.
(E)한 분자 내에 (E) within one molecule 질소원자Nitrogen atom 및 카르복실기를 가지는 수용성 화합물 And a water-soluble compound having a carboxyl group
본 발명의 구리계 금속막 식각액 조성물에 포함되는 한 분자 내에 질소원자 및 카르복실기를 가지는 수용성 화합물은 식각액 조성물의 보관 시 발생할 수 있는 과산화수소수의 자체 분해 반응을 막아주고, 많은 수의 기판을 식각할 시에 식각 특성이 변하는 것을 방지한다. The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the copper-based metal film etchant composition of the present invention prevents the self-decomposition reaction of hydrogen peroxide that may occur when the etchant composition is stored, and when a large number of substrates are etched. It prevents the etch characteristics from changing.
일반적으로 과산화수소수를 사용하는 식각액 조성물의 경우 보관시 과산화수소수가 자체 분해하여 그 보관기간이 길지 못하고, 용기가 폭발할 수 있는 위험요소까지 갖추고 있다. 그러나 상기 한 분자 내에 질소원자 및 카르복실기를 가지는 수용성 화합물이 포함될 경우 과산화수소수의 분해 속도가 10배 가까이 감소하여 보관기간 및 안정성을 확보할 수 있다. 특히 구리층의 경우 식각액 조성물 내에 구리 이온이 다량 잔존할 경우에 보호막(passivation)을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 많이 발생할 수 있으나, 상기 화합물을 첨가하였을 경우 이런 현상을 막을 수 있다. In general, in the case of an etchant composition using hydrogen peroxide water, the hydrogen peroxide water self-decomposes during storage, so that the storage period is not long, and the container has a risk factor that may explode. However, when a water-soluble compound having a nitrogen atom and a carboxyl group is included in the molecule, the decomposition rate of the hydrogen peroxide solution is reduced by about 10 times, so that the storage period and stability can be secured. In particular, in the case of the copper layer, when a large amount of copper ions remain in the etchant composition, a passivation may be formed and then oxidized to black, and then there may be many cases where it is no longer etched.However, this phenomenon can be prevented when the compound is added. have.
상기 한 분자 내에 질소원자 및 카르복실기를 가지는 수용성 화합물은 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 그 중에서도 이미노디아세트산(iminodiacetic acid)이 가장 바람직하다.The water-soluble compounds having a nitrogen atom and a carboxyl group in one molecule are alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ethylenediaminetetraacetic acid. acid), nitrilotriacetic acid, and sarcosine may be used, and among them, iminodiacetic acid is most preferred.
또한, 상기 한 분자 내에 질소원자 및 카르복실기를 가지는 수용성 화합물의 함량은 구리계 금속막 식각액 조성물 총 중량에 대하여 0.1 내지 5.0 중량%로 포함되고, 바람직하게는 1.0 내지 3.0 중량% 범위로 포함된다. 상기 한 분자 내에 질소원자 및 카르복실기를 가지는 수용성 화합물의 함량이 0.1 중량% 미만일 경우 다량의 기판(약 500매)의 식각 후 보호막이 형성되어 충분한 공정 마진을 얻기가 어려워지며, 5 중량%를 초과할 경우 몰리브덴 막 또는 몰리브덴 합금막의 식각속도가 느려져 구리 몰리브덴막 또는 구리 몰리브덴합금막의 경우 몰리브덴 또는 몰리브덴합금막의 잔사 문제가 발생할 수 있다.
In addition, the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is contained in an amount of 0.1 to 5.0% by weight, preferably 1.0 to 3.0% by weight, based on the total weight of the copper-based metal film etchant composition. When the content of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule is less than 0.1% by weight, a protective film is formed after etching a large amount of substrate (about 500 sheets), making it difficult to obtain a sufficient process margin, and the content exceeds 5% by weight. In this case, the etching rate of the molybdenum film or the molybdenum alloy film is slow, and thus, in the case of the copper molybdenum film or the copper molybdenum alloy film, a residual problem of the molybdenum or molybdenum alloy film may occur.
(F)황산염 화합물(F) sulfate compound
본 발명의 구리계 금속막 식각액 조성물에 포함되는 황산염 화합물은 상부 구리막의 테이퍼각을 조절해주고, 구리를 포함하는 막의 식각속도를 조절하여 원하는 사이드 에칭(side etching)을 조절할 수 있게 하는 성분이다. 상기 황산염 화합물이 본 발명의 구리계 금속막 식각액 조성물에 포함되지 않으면 낮은 식각속도로 공정에서 양산 성능을 저하시키는 문제를 발생할 수 있다. The sulfate compound included in the copper-based metal film etchant composition of the present invention is a component that adjusts the taper angle of the upper copper film and adjusts the etching rate of the film containing copper to control desired side etching. If the sulfate compound is not included in the copper-based metal film etchant composition of the present invention, a problem of deteriorating mass production performance in a process at a low etching rate may occur.
상기 황산염 화합물은 황산에서 수소가 암모늄, 알칼리 금속 혹은 알칼리 토금속으로 하나 또는 두 개 치환된 염에서 선택되는 것이면 특별히 한정하지 않으나, 제 1황산암모늄(ammonium sulfate monobasic), 제 1황산나트륨(sodium sulfate monobasic), 제 1황산칼륨(potassium sulfate monobasic), 황산암모늄(ammonium sulfate), 황산나트륨(sodium sulfate) 및 황산칼륨(potassium sulfate)으로 이루어진 군으로부터 선택되는 1종 이상이 바람직하며, 황산나트륨 또는 황산칼륨이 가장 바람직하다.The sulfate compound is not particularly limited as long as hydrogen in sulfuric acid is selected from one or two substituted salts of ammonium, alkali metal or alkaline earth metal, but first ammonium sulfate monobasic, sodium sulfate monobasic , At least one selected from the group consisting of potassium sulfate monobasic, ammonium sulfate, sodium sulfate, and potassium sulfate is preferred, and sodium sulfate or potassium sulfate is most preferred. Do.
상기 황산염 화합물은 구리계 금속막 식각액 조성물 총 중량에 대하여 0.1 내지 5.0 중량%로 포함되고, 바람직하게는 0.5 내지 3.0 중량%로 포함된다. 상기 황산염 화합물의 함량이 0.1 중량% 미만일 경우 낮은 식각속도로 공정에서 양산 성능을 저하시키며, 5.0 중량%를 초과하는 경우에는 부분적 과침식 현상으로 인해 식각 프로파일이 불량하게 될수 있는 문제가 발생할 수 있다.
The sulfate compound is contained in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, based on the total weight of the copper-based metal film etchant composition. When the content of the sulfate compound is less than 0.1% by weight, mass production performance is degraded in the process at a low etching rate, and when it exceeds 5.0% by weight, the etching profile may be poor due to partial overerosion.
(G)물(G) water
본 발명의 구리계 금속막 식각액 조성물에 포함되는 물은 구리계 금속막 식각액 조성물 총 중량이 100 중량%가 되도록 잔량 포함한다. 상기 물은 특별히 한정하지 않으나, 탈이온수를 이용하는 것이 바람직하다. 또한, 물 속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·cm 이상인 탈이온수를 이용하는 것이 보다 바람직하다.
The water contained in the copper-based metal film etchant composition of the present invention contains the remaining amount so that the total weight of the copper-based metal film etchant composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is more preferable to use deionized water having a specific resistance value of 18㏁·cm or more, which shows the degree to which ions have been removed from the water.
(H)다가 알코올형 계면활성제(H) polyhydric alcohol type surfactant
본 발명의 구리계 금속막 식각액 조성물에 추가로 포함시킬 수 있는 다가 알코올형 계면활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 또한, 상기 다가 알코올형 계면활성제는 구리막을 식각한 후 식각액에 녹아져 나오는 구리 이온을 둘러 쌈으로서 구리 이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제하게 한다. 상기와 같이 구리 이온의 활동도를 낮추게 되면 식각액을 사용하는 동안 안정적으로 공정을 진행 할 수 있게 된다. The polyhydric alcohol-type surfactant that can be additionally included in the copper-based metal film etchant composition of the present invention serves to increase the uniformity of etching by lowering the surface tension. In addition, the polyhydric alcohol-type surfactant suppresses the activity of the copper ions by enclosing the copper ions dissolved in the etching solution after etching the copper film, thereby suppressing the decomposition reaction of hydrogen peroxide. If the activity of copper ions is lowered as described above, the process can be stably performed while the etchant is used.
상기 다가 알코올형 계면활성제는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol) 및 폴리에틸렌 글리콜(polyethylene glycol)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 그 중에서도 트리에틸렌글리콜(triethylene glycol)이 바람직하다.The polyhydric alcohol-type surfactant may be one or more selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol, among which triethylene glycol is used. desirable.
상기 다가 알코올형 계면활성제는 구리계 금속막 식각액 조성물 총 중량에 대하여 0.001 내지 5.0 중량%로 포함되고, 바람직하게는 0.1 내지 3.0 중량% 범위로 포함된다. 상기 함량이 0.001 중량% 미만일 경우 식각 균일성이 저하되고 과산화수소의 분해가 가속화 되는 문제점이 생길 수 있으며, 5.0 중량%를 초과할 경우 거품이 많이 발생되는 단점이 있다.
The polyhydric alcohol-type surfactant is included in an amount of 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the total weight of the copper-based metal film etchant composition. If the content is less than 0.001% by weight, etching uniformity may be lowered and decomposition of hydrogen peroxide may be accelerated, and if it exceeds 5.0% by weight, there is a disadvantage that a lot of bubbles are generated.
본 발명의 구리계 금속막 식각액 조성물은 상기 성분 이외에 첨가제를 추가로 포함할 수 있으며, 상기 첨가제로는 금속 이온 봉쇄제 및 부식 방지제 등이 있다.The copper-based metal film etchant composition of the present invention may further contain additives in addition to the above components, and examples of the additives include metal ion sequestering agents and corrosion inhibitors.
본 발명에서 사용되는 구리계 금속막 식각액 조성물의 구성 성분은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 구리계 금속막 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다.The constituent components of the copper-based metal film etchant composition used in the present invention can be prepared by a conventionally known method, and the copper-based metal film etchant composition of the present invention preferably has a purity for semiconductor processing.
또한, 본 발명은 상기 구리계 금속막 식각액 조성물을 사용하여 식각된 게이트 배선, 소스 전극 및 드레인 전극으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.
In addition, the present invention provides an array substrate for a liquid crystal display device including at least one selected from the group consisting of a gate wiring, a source electrode, and a drain electrode etched using the copper-based metal layer etchant composition.
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예 및 비교예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.
Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples and comparative examples are intended to illustrate the present invention, and the present invention is not limited by the following and may be variously modified and changed.
<구리계 <Copper system 금속막Metal film 식각액Etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 4 및 1 to 4 and 비교예Comparative example 1 내지 4. 1 to 4.
하기 표 1에 나타낸 조성에 따라 실시예 1 내지 4 및 비교예 1 내지 4의 구리계 금속막 식각액 조성물을 180kg 제조하였다.According to the composition shown in Table 1 below, 180 kg of the copper-based metal film etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared.
ABF: Ammonium BifluorideABF: Ammonium Bifluoride
5-ATZ: 5-aminotetrazole5-ATZ: 5-aminotetrazole
IDA : Iminodiacetic acid
IDA: Iminodiacetic acid
실험예Experimental example 1. One. 실시예Example 1 내지 4 및 1 to 4 and 비교예Comparative example 1 내지 4의 구리계 1 to 4 copper-based 금속막Metal film 식각액Etchant 조성물의 Composition of 식각Etching 공정 fair
상기 실시예 1 내지 4 및 비교예 1 내지 4의 구리계 금속막 식각액 조성물을 각각 사용하여 식각 공정을 실시하였다. 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 구리계 금속막 식각액 조성물의 온도는 약 33℃ 내외로 하였다. 식각 시간은 식각 온도에 따라서 다를 수 있으나, LCD Etching 공정에서 통상 30 내지 80초 정도로 진행하였다. 상기 식각 공정에서 식각된 구리계 금속막의 프로파일을 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 단면을 관찰하였고, 결과를 하기 표 2에 기재하였다. 식각 공정에 사용된 구리계 금속막은 Cu/Mo-Nb 3000/300Å 박막 기판을 사용하였다.An etching process was performed using the copper-based metal film etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 4, respectively. Experimental equipment (model name: ETCHER (TFT), SEMES) of the spray etching method was used, and during the etching process, the temperature of the copper-based metal film etchant composition was about 33°C. The etching time may vary depending on the etching temperature, but it was generally performed in about 30 to 80 seconds in the LCD etching process. The profile of the copper-based metal film etched in the etching process was observed in cross section using SEM (Hitachi, model name S-4700), and the results are shown in Table 2 below. The copper-based metal film used in the etching process was a Cu/Mo-Nb 3000/300Å thin film substrate.
(Cu 300~5000ppm)Change in number of processed sheets (㎛)
(Cu 300~5000ppm)
(○: 좋음, △: 보통, Х: 나쁨, Unetch : 식각불가)(○: Good, △: Normal, Х: Bad, Unetch: Etching impossible)
실시예 1 내지 4의 구리계 금속막 식각액 조성물은 모두 식각 프로파일 및 직진성이 우수하였으며, 몰리브덴(Mo), 나이오븀(Nb) 잔사 또한 발생하지 않았다. 또한 처리매수 변화량(Side Etch 변화량)도 ±0.1 ㎛인 조건에 모두 충족하여 양호한 식각 특성을 나타내는 것을 확인하였다. 상기 실시예 1 내지 4 중에서도 실시예 3의 구리계 금속막 식각액 조성물이 가장 우수한 식각 특성을 나타내었다.All of the copper-based metal film etchant compositions of Examples 1 to 4 had excellent etching profiles and straightness, and no molybdenum (Mo) and niobium (Nb) residues were generated. In addition, it was confirmed that the number of processed sheets (side etch change amount) satisfies all of the conditions of ±0.1 µm to exhibit good etching characteristics. Among Examples 1 to 4, the copper-based metal film etchant composition of Example 3 exhibited the most excellent etching properties.
반면, 아인산이 포함되지 않은 비교예 1의 경우 식각속도가 매우 느려 Unetch 현상이 나타났다. 아인산이 0.1 중량% 미만으로 포함된 비교예 3의 경우 처리매수 변화량은 0.1㎛ 조건을 충족시켰으나, 식각속도가 매우 느려 식각 프로파일 및 직진성이 보통 수준이었으며, 아인산이 5 중량%를 초과한 비교예 4의 경우 과도한 식각속도로 인해 Pattern out 현상이 발생하였다. 또한, 황산칼륨이 포함되지 않은 비교예 2는 처리매수 변화량이 0.1 ㎛로 조건을 충족시켰으나, 식각 profile 및 식각 직진성이 모두 보통으로 나타나 우수한 식각 특성을 보이지 못하였다.
On the other hand, in the case of Comparative Example 1 in which phosphorous acid was not included, the etch rate was very slow, resulting in an unetch phenomenon. In the case of Comparative Example 3 containing less than 0.1% by weight of phosphorous acid, the amount of change in the number of processed sheets satisfies the condition of 0.1 μm, but the etching rate was very slow, so the etching profile and straightness were normal, and the phosphorous acid exceeded 5% by weight. In the case of, pattern out occurred due to excessive etching speed. In addition, Comparative Example 2 in which potassium sulfate was not included satisfies the condition of 0.1 μm in the number of processed sheets, but both the etching profile and the etching straightness were normal, indicating excellent etching characteristics.
실험예Experimental example 2. 2. 실시예Example 3 및 3 and 비교예Comparative example 1 내지 2의 구리계 1 to 2 copper-based 금속막Metal film 식각액Etchant 조성물의 구리 농도에 따른 According to the copper concentration of the composition 식각특성Etching characteristics 평가 evaluation
실시예 3 및 비교예 1 내지 2의 구리계 금속막 식각액 조성물을 사용하여 구리 농도에 따른 식각특성을 평가하였다. 식각공정에 사용된 구리계 금속막은 Cu/Mo-Nb 3000/300Å 박막 기판을 사용하였다.The etching characteristics according to the copper concentration were evaluated using the copper-based metal film etchant compositions of Example 3 and Comparative Examples 1 to 2. The copper-based metal film used in the etching process was a Cu/Mo-Nb 3000/300Å thin film substrate.
구리 농도에 따른 Side Etch(㎛) 변화량을 측정하였다. Side Etch는 식각 후에 측정된 포토레지스트 끝단과 하부 금속 끝단 사이의 거리를 말한다. Side etch 량이 변화 하면, TFT 구동시 신호 전달 속도가 변화하게 되어 얼룩이 발생 될 수 있기 때문에, Side Etch 변화량은 최소화 되는 것이 바람직하다. 본 평가에서는 Side Etch 변화량이 ±0.1 ㎛ 인 조건이 충족되는 경우에 식각액 조성물을 식각 공정에 계속 사용할 수 있는 것으로 정하고 실험을 실시하였다.Side etch (㎛) change according to the copper concentration was measured. Side Etch refers to the distance between the end of the photoresist and the end of the lower metal measured after etching. If the amount of side etch is changed, the signal transmission speed during TFT driving may change, resulting in spots, so it is desirable to minimize the amount of side etch change. In this evaluation, when the condition of the side etch change amount of ±0.1 µm is satisfied, the etchant composition was determined to be continuously used in the etching process, and an experiment was conducted.
상기 실험의 결과를 하기 표 3에 기재하였다.The results of the experiment are shown in Table 3 below.
본 발명의 구리계 금속막 식각액 조성물인 실시예 3은 구리의 농도가 높아져도 Side Etch 충족 조건인 ±0.1 ㎛을 만족시키는 우수한 식각 특성을 나타내었다.Example 3, which is a copper-based metal film etchant composition of the present invention, exhibited excellent etching properties that satisfies the side etch satisfaction condition of ±0.1 µm even when the concentration of copper was increased.
반면에, 아인산이 포함되지 않은 비교예 1은 식각이 불가능하였고, 황산칼륨이 포함되지 않은 비교예 2는 식각은 되었지만, 구리의 농도가 높아질수록 Side Etch 충족 조건인 ±0.1 ㎛ 범위를 벗어난 것을 확인할 수 있었다.On the other hand, Comparative Example 1 without phosphorous acid was not etched, and Comparative Example 2 without potassium sulfate was etched, but as the concentration of copper increased, it was confirmed that it was outside the range of ±0.1 µm, which is the condition to satisfy Side Etch. Could
따라서, 본 발명의 구리계 금속막 식각액 조성물은 식각 Profile 및 식각 직진성이 우수하며, 구리 농도에 따라 Side Etch 변화량이 일정 수준으로 유지되는 우수한 특성을 지니고 있다고 할 수 있다.
Accordingly, it can be said that the copper-based metal film etchant composition of the present invention has excellent etch profile and etch straightness, and has excellent characteristics in which the amount of side etch change according to the copper concentration is maintained at a certain level.
Claims (13)
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 a) 또는 d)단계는 기판 또는 반도체 층 상에 구리계 금속막을 형성하고, 상기 구리계 금속막을 식각액 조성물로 식각하여 게이트 배선, 또는 소스 및 드레인 전극을 형성하는 단계를 포함하며;
상기 식각액 조성물은 조성물 총 중량에 대하여 과산화수소 5 내지 25 중량%, 아인산 0.1 내지 5 중량%, 불소 화합물 0.01 내지 1.0 중량%, 아졸 화합물 0.1 내지 5 중량%, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.1 내지 5.0 중량%, 황산염 화합물 0.1 내지 5.0 중량% 및 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하며,
상기 불소 화합물은 HF, NaF, NH4F, NH4BF4, NH4FHF, NH4F2, KF, KHF2 및 AlF3으로 이루어진 군으로부터 선택되는 1종 이상이고,
상기 황산염 화합물은 제1황산암모늄, 제1황산나트륨, 제1황산칼륨, 황산암모늄, 황산나트륨 및 황산칼륨으로 이루어진 군으로부터 선택되는 1종 이상인, 구리계 금속막 식각액 조성물인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; And
e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
The step a) or d) includes forming a copper-based metal film on a substrate or a semiconductor layer, and etching the copper-based metal film with an etchant composition to form gate wirings or source and drain electrodes;
The etchant composition comprises 5 to 25% by weight of hydrogen peroxide, 0.1 to 5% by weight of phosphorous acid, 0.01 to 1.0% by weight of a fluorine compound, 0.1 to 5% by weight of an azole compound, and a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule based on the total weight of the composition. 0.1 to 5.0% by weight, 0.1 to 5.0% by weight of the sulfate compound, and the remaining amount of water so that the total weight of the composition is 100% by weight,
The fluorine compound is at least one selected from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, NH 4 F 2 , KF, KHF 2 and AlF 3 ,
The sulfate compound is at least one selected from the group consisting of first ammonium sulfate, first sodium sulfate, first potassium sulfate, ammonium sulfate, sodium sulfate, and potassium sulfate, and is a copper-based metal film etchant composition. Method of manufacturing an array substrate.
상기 불소 화합물은 HF, NaF, NH4F, NH4BF4, NH4FHF, NH4F2, KF, KHF2 및 AlF3으로 이루어진 군으로부터 선택되는 1종 이상이고,
상기 황산염 화합물은 제1황산암모늄, 제1황산나트륨, 제1황산칼륨, 황산암모늄, 황산나트륨 및 황산칼륨으로 이루어진 군으로부터 선택되는 1종 이상인, 구리계 금속막 식각액 조성물.Based on the total weight of the composition, hydrogen peroxide 5 to 25% by weight, phosphorous acid 0.1 to 5% by weight, fluorine compound 0.01 to 1.0% by weight, azole compound 0.1 to 5% by weight, water-soluble compound having a nitrogen atom and a carboxyl group in one molecule 0.1 to 5.0 It contains the remaining amount of water so that the weight%, 0.1 to 5.0% by weight of the sulfate compound and the total weight of the composition is 100% by weight,
The fluorine compound is at least one selected from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, NH 4 F 2 , KF, KHF 2 and AlF 3 ,
The sulfate compound is at least one selected from the group consisting of first ammonium sulfate, first sodium sulfate, first potassium sulfate, ammonium sulfate, sodium sulfate, and potassium sulfate, a copper-based metal film etchant composition.
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| KR102012426B1 (en) * | 2015-08-17 | 2019-08-20 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for display device |
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| KR102603630B1 (en) * | 2016-04-25 | 2023-11-17 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for a display divice |
| KR102400343B1 (en) * | 2016-07-19 | 2022-05-23 | 동우 화인켐 주식회사 | Metal film etchant composition and manufacturing method of an array substrate for display device |
| KR102677476B1 (en) * | 2016-07-26 | 2024-06-24 | 삼성디스플레이 주식회사 | Etching solution composition and method of manufacturing metal pattern |
| CN108018556A (en) * | 2016-10-31 | 2018-05-11 | 易案爱富科技有限公司 | Etch combination |
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