KR102245661B1 - Etching solution composition for molybdenum-titanium layer or indium oxide layer and method for etching molybdenum-titanium layer or metal oxide layer using the same - Google Patents
Etching solution composition for molybdenum-titanium layer or indium oxide layer and method for etching molybdenum-titanium layer or metal oxide layer using the same Download PDFInfo
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- KR102245661B1 KR102245661B1 KR1020150016765A KR20150016765A KR102245661B1 KR 102245661 B1 KR102245661 B1 KR 102245661B1 KR 1020150016765 A KR1020150016765 A KR 1020150016765A KR 20150016765 A KR20150016765 A KR 20150016765A KR 102245661 B1 KR102245661 B1 KR 102245661B1
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- molybdenum
- indium oxide
- oxide film
- etchant composition
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- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 79
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 238000005530 etching Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 title 1
- 150000004706 metal oxides Chemical class 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 azole compound Chemical class 0.000 claims abstract description 21
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 142
- 150000001875 compounds Chemical class 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000011161 development Methods 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
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 230000021148 sequestering of metal ion Effects 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- NYUKTFZVAKBIDK-UHFFFAOYSA-N 1h-pyrazole;1,3-thiazole Chemical compound C=1C=NNC=1.C1=CSC=N1 NYUKTFZVAKBIDK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OMSFUHVZHUZHAW-UHFFFAOYSA-N [Ag].[Mo] Chemical compound [Ag].[Mo] OMSFUHVZHUZHAW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
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- 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
- C23F1/26—Acidic compositions for etching refractory metals
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- 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
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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Abstract
본 발명은 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것으로, 보다 자세하게는 과산화수소, 불소 화합물, 아졸 화합물, 술폰산 화합물, 다가 알코올 및 물을 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to a molybdenum-titanium film or indium oxide film etchant composition and a method of manufacturing an array substrate for a liquid crystal display using the same, and more particularly, to a hydrogen peroxide, a fluorine compound, an azole compound, a sulfonic acid compound, a molybdenum containing polyhydric alcohol and water -It relates to a titanium film or indium oxide film etchant composition and a method of manufacturing an array substrate for a liquid crystal display using the same.
Description
본 발명은 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것으로, 보다 자세하게는 과산화수소, 함불소 화합물, 아졸 화합물, 술폰산 화합물, 다가 알코올 및 물을 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to a molybdenum-titanium film or indium oxide film etchant composition and a method of manufacturing an array substrate for a liquid crystal display using the same, and more particularly, to a hydrogen peroxide, a fluorine-containing compound, an azole compound, a sulfonic acid compound, a polyhydric alcohol and water. It relates to a molybdenum-titanium film or indium oxide film etchant composition and a method of manufacturing an array substrate for a liquid crystal display using the same.
액정 표시 소자(liquid crystal display device, LCD device)는 뛰어난 해상도에 따른 선명한 영상을 제공하며 전기를 적게 소모하고, 디스플레이 화면을 얇게 만들 수 있게 하는 특성 때문에 평판 디스플레이 장치 중 가장 각광을 받고 있다. 오늘날 이러한 액정 표시 소자를 구동하는 전자 회로로서 대표적인 것은 박막 트랜지스터(thin film transistor, TFT) 회로로서 전형적인 박막 트랜지스터 액정표시(TFT-LCD) 소자는 디스플레이 화면의 화소(pixel)를 이루고 있다. TFT-LCD 소자에서 스위칭 소자로 작용하는 TFT는 매트릭스 형태로 배열한 TFT용 기판과 그 기판을 마주 보는 컬러 필터 기판 사이에 액정 물질을 채워 제조한 것이다. TFT-LCD의 전체 제조 공정은 크게 TFT 기판 제조 공정, 컬러 필터 공정, 셀 공정, 모듈 공정으로 나뉘는데, 정확하고 선명한 영상을 나타내는데 있어서 TFT 기판과 컬러 필터 제조 공정의 중요성은 매우 크다.A liquid crystal display device (LCD device) is receiving the most attention among flat panel display devices because it provides a clear image according to an excellent resolution, consumes less electricity, and makes a display screen thinner. Today, a typical electronic circuit driving such a liquid crystal display device is a thin film transistor (TFT) circuit, and a typical thin film transistor liquid crystal display (TFT-LCD) device constitutes a pixel of a display screen. A TFT, which acts as a switching element in a TFT-LCD device, is manufactured by filling a liquid crystal material between a TFT substrate arranged in a matrix form and a color filter substrate facing the substrate. The overall manufacturing process of a TFT-LCD is largely divided into a TFT substrate manufacturing process, a color filter process, a cell process, and a module process. The importance of the TFT substrate and color filter manufacturing process is very important in displaying an accurate and clear image.
TFT-LCD 장치의 화소 표시 전극 제조에는 투명한 광학적 특성을 가지면서 전기 전도도가 높은 물질로 된 박막이 필요한데, 현재 산화인듐(indium oxide)을 기반으로 한 산화인듐주석(Indium Tin Oxide, ITO)과 산화인듐아연(Indium Zinc Oxide, IZO)이 투명도전막의 재료로 쓰이고 있다. To manufacture the pixel display electrode of a TFT-LCD device, a thin film made of a material having transparent optical properties and high electrical conductivity is required. Currently, indium tin oxide (ITO) and oxidation based on indium oxide are required. Indium Zinc Oxide (IZO) is used as a material for the transparent conductive film.
또한, 화소표시 전극에 원하는 전기회로의 선로를 구현하려면 회로 패턴대로 박막층을 깎아내는 식각(蝕刻, etching) 과정이 필요하다.In addition, in order to implement a line of a desired electric circuit on the pixel display electrode, an etching process in which the thin film layer is cut out according to the circuit pattern is required.
그러나 금속 이중층의 식각에 흔히 쓰이는 기존 식각액으로는 산화물인 ITO의 강한 내화학성 때문에 ITO나 IZO 소재의 투명도전막을 에칭하기 어려웠다. 구체적으로 왕수(aqua regia, HCl+CH3COOH+HNO3)나 염산제2철(Ⅲ)의 염산 용액(FeCl3/HCl), 옥살산수용액이 투명도전막 습식 식각액이 사용되어 왔지만, 왕수계 식각액 또는 염산제2철의 염산 용액을 이용하여 ITO 막을 식각하는 경우 가격은 저렴하나 패턴의 측면에서 더 빨리 식각되서 프로파일(profile)이 불량하며, 식각액을 조성한 후 염산 또는 질산이 휘발하기 때문에 식각액 조성물의 변동이 심하고, 하부 금속에 화학적 어택(Attack)을 발생시킬 수 있다. 대한민국 공개특허 제10-2000-0017470호에는 옥살산(Oxalic Acid)을 이용하여 비정질 ITO(amorphous Indium Tin Oxide)를 식각하였지만, 이러한 경우 ITO 패턴 주위에 잔사가 발생하기 쉬우며, 저온에서 옥살산의 용해도가 낮아 석출물이 발생하여 식각 장비 고장을 발생시키는 문제가 있다.However, it has been difficult to etch transparent conductive films made of ITO or IZO materials due to the strong chemical resistance of ITO, an oxide, with conventional etchants commonly used for etching metal double layers. Specifically, aqua regia (HCl+CH 3 COOH+HNO 3 ), a hydrochloric acid solution of ferric (III) hydrochloride (FeCl 3 /HCl), and an aqueous oxalic acid solution have been used as a transparent conductive film wet etching solution. If the ITO film is etched using a hydrochloric acid solution of ferric hydrochloride, the price is low, but the profile is poor because it is etched more quickly in terms of the pattern, and the etchant composition changes due to the volatilization of hydrochloric acid or nitric acid after forming the etchant. This is severe and can cause a chemical attack on the underlying metal. In Korean Patent Laid-Open No. 10-2000-0017470, amorphous indium tin oxide (ITO) was etched using oxalic acid, but in this case, residues tend to occur around the ITO pattern, and the solubility of oxalic acid at low temperatures It is low, and there is a problem that precipitates are generated, causing failure of the etching equipment.
또한, HI로 이루어진 식각액의 경우, 식각 속도가 크고 측면 식각이 적지만, 가격이 비싸고, 독성과 부식성이 크며, 투명 화소전극 하부에 위치한 데이터 배선에 어택을 발생시킴에 따라 실제 공정에 사용하기에는 한계가 있는 문제점이 있다.In addition, in the case of an etchant made of HI, the etch rate is high and the side etch is low, but it is expensive, has high toxicity and corrosiveness, and it is limited to be used in the actual process as it causes an attack to the data wiring located under the transparent pixel electrode. There is a problem with that.
또한, 대한민국 등록특허 제10-1394133호에는 과산화수소, 불소화합물, 술폰산기를 포함하는 화합물, 부식방지제, 보조산화제, 과수안정제 및 물을 포함하는 몰리브덴 및 ITO막의 식각액 조성물에 관하여 기재되어 있지만, 상기 식각액 조성물은 몰리브덴 및 ITO막의 처리매수를 향상시키지 못한다는 문제가 있다.In addition, Korean Patent Registration No. 10-1394133 describes the etchant composition of molybdenum and ITO films containing hydrogen peroxide, fluorine compounds, compounds containing sulfonic acid groups, corrosion inhibitors, auxiliary oxidizing agents, fruit water stabilizers, and water, but the etchant composition There is a problem that the number of processed silver molybdenum and ITO films cannot be improved.
본 발명은 식각액 조성물에 다가 알코올을 포함함으로써, 몰리브덴-티타늄막 또는 인듐산화막의 사이드 에치(side etch)를 향상시키는 것을 목적으로 한다.An object of the present invention is to improve side etch of a molybdenum-titanium film or an indium oxide film by including a polyhydric alcohol in an etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하여 몰리브덴-티타늄막 또는 인듐산화막을 식각하여 상기 식각된 몰리브덴-티타늄막 또는 인듐산화막을 액정표시 장치용 어레이 기판의 화소전극으로 사용함으로써, 액정표시소자의 구동 특성을 향상시키는 것을 목적으로 한다.In addition, in the present invention, the molybdenum-titanium film or indium oxide film is etched using the etchant composition, and the etched molybdenum-titanium film or indium oxide film is used as a pixel electrode of an array substrate for a liquid crystal display device, thereby driving a liquid crystal display device. It aims to improve the properties.
상기 목적을 달성하기 위하여,To achieve the above object,
본 발명은 식각액 조성물 총 중량에 대하여, 과산화수소 15 내지 25 중량%, 함불소 화합물 0.1 내지 2 중량%, 아졸 화합물 0.1 내지 1 중량%, 술폰산 화합물 0.3 내지 1 중량%, 다가 알코올 0.01 내지 2 중량% 및 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물을 제공한다.The present invention is based on the total weight of the etchant composition, hydrogen peroxide 15 to 25% by weight, fluorine-containing compound 0.1 to 2% by weight, azole compound 0.1 to 1% by weight, sulfonic acid compound 0.3 to 1% by weight, polyhydric alcohol 0.01 to 2% by weight and It provides a molybdenum-titanium film or indium oxide film etchant composition containing the remaining amount of water so that the total weight of the etchant composition is 100% by weight.
또한, 본 발명은 (1)기판 상에 몰리브덴-티타늄막 또는 인듐산화막을 형성하는 단계;In addition, the present invention includes the steps of (1) forming a molybdenum-titanium film or an indium oxide film on a substrate;
(2)상기 몰리브덴-티타늄막 또는 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및(2) selectively leaving a photoreactive material on the molybdenum-titanium film or indium oxide film; And
(3)본 발명의 식각액 조성물을 사용하여 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각하는 단계를 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각방법을 제공한다.(3) A molybdenum-titanium layer or indium oxide layer etching method comprising the step of etching the molybdenum-titanium layer or indium oxide layer using the etchant composition of the present invention is provided.
또한, 본 발명은 (1)기판 상에 게이트 배선을 형성하는 단계;In addition, the present invention includes the steps of (1) forming a gate wiring on a substrate;
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(2) forming a gate insulating layer on a substrate including the gate wiring;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;(3) forming an oxide semiconductor layer on the gate insulating layer;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(4) forming source and drain electrodes on the oxide semiconductor layer; And
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,(5) 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 (5)단계는 몰리브덴-티타늄막 또는 인듐산화막을 형성하고, 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며,The step (5) includes forming a molybdenum-titanium film or an indium oxide film, and etching the molybdenum-titanium film or indium oxide film with an etchant composition to form a pixel electrode,
상기 식각액 조성물은 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법을 제공한다.The etchant composition is a molybdenum-titanium film or indium oxide film etchant composition of the present invention. It provides a method of manufacturing an array substrate for a liquid crystal display device.
또한, 본 발명은 본 발명의 제조방법으로 제조된 액정 표시 장치용 어레이 기판을 제공한다.Further, the present invention provides an array substrate for a liquid crystal display device manufactured by the manufacturing method of the present invention.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물은 다가 알코올을 포함함으로써, 몰리브덴-티타늄막 또는 인듐산화막의 사이드 에치(side etch)를 향상시킬 수 있다.The molybdenum-titanium film or indium oxide film etchant composition of the present invention includes a polyhydric alcohol to improve side etch of the molybdenum-titanium film or indium oxide film.
또한, 본 발명의 식각액 조성물은 몰리브덴-티타늄막 또는 인듐산화막을 식각하여 액정 표시 장치의 화소전극을 형성할 수 있으며, 상기 화소전극을 포함하는 액정표시소자는 구동 특성이 향상된 효과를 지니고 있다.In addition, the etchant composition of the present invention may form a pixel electrode of a liquid crystal display device by etching a molybdenum-titanium film or an indium oxide film, and a liquid crystal display device including the pixel electrode has an effect of improving driving characteristics.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 식각액 조성물 총 중량에 대하여, 과산화수소 15 내지 25 중량%, 함불소 화합물 0.1 내지 2 중량%, 아졸 화합물 0.1 내지 1 중량%, 술폰산 화합물 0.3 내지 1 중량%, 다가 알코올 0.01 내지 2 중량% 및 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 관한 것이다.
The present invention is based on the total weight of the etchant composition, hydrogen peroxide 15 to 25% by weight, fluorine-containing compound 0.1 to 2% by weight, azole compound 0.1 to 1% by weight, sulfonic acid compound 0.3 to 1% by weight, polyhydric alcohol 0.01 to 2% by weight and It relates to a molybdenum-titanium film or indium oxide film etchant composition containing the remaining amount of water so that the total weight of the etchant composition is 100% by weight.
본 발명의 식각액 조성물은 몰리브덴-티타늄막, 인듐산화막 또는 상기 몰리브덴-티타늄막과 인듐산화막의 다층막을 식각할 수 있는 식각액 조성물이다.The etchant composition of the present invention is an etchant composition capable of etching a molybdenum-titanium film, an indium oxide film, or a multilayer film of the molybdenum-titanium film and an indium oxide film.
상기 인듐산화막은 인듐주석산화막(ITO), 인듐아연산화막(IZO) 및 인듐갈륨아연산화막(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이다.
The indium oxide film includes at least one selected from the group consisting of an indium tin oxide film (ITO), an indium zinc oxide film (IZO), and an indium gallium zinc oxide film (IGZO).
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 과산화수소(H2O2)는 몰리브덴-티타늄막 또는 인듐산화막의 식각속도에 영향을 주는 주산화제이다. Hydrogen peroxide (H 2 O 2 ) contained in the molybdenum-titanium film or indium oxide film etchant composition of the present invention is a main oxidizing agent that affects the etch rate of the molybdenum-titanium film or indium oxide film.
상기 과산화수소는 식각액 조성물 총 중량에 대하여 15 내지 25 중량%로 포함되며, 바람직하게는 18 내지 23 중량%로 포함된다. 상기 과산화수소가 15 중량% 미만으로 포함되면, 몰리브덴-티타늄막 또는 인듐산화막의 식각 속도가 느려 충분한 식각이 이루어지지 않을 수 있으며, 25 중량%를 초과하여 포함되면, 과산화수소의 농도가 지나치게 높아져 식각액의 안정성이 감소될 수 있다.
The hydrogen peroxide is included in an amount of 15 to 25% by weight, preferably 18 to 23% by weight, based on the total weight of the etchant composition. When the hydrogen peroxide is contained in an amount of less than 15% by weight, the etching rate of the molybdenum-titanium layer or the indium oxide layer is slow, so that sufficient etching may not be performed.If it is contained in an amount exceeding 25% by weight, the concentration of hydrogen peroxide is excessively high and the stability of the etchant Can be reduced.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 함불소 화합물은 물에 해리되어 불소 이온 또는 다원자 불소 이온을 낼 수 있는 화합물을 뜻한다. 상기 함불소 화합물은 몰리브덴-티타늄막 또는 인듐산화막의 식각 속도에 영향을 주는 해리제이며, 보다 구체적으로는 몰리브덴-티타늄막의 식각 속도를 조절하는 역할을 한다.The fluorine-containing compound contained in the molybdenum-titanium film or indium oxide film etchant composition of the present invention refers to a compound capable of generating fluorine ions or polyatomic fluorine ions by dissociation in water. The fluorine-containing compound is a dissociating agent that affects the etching rate of the molybdenum-titanium layer or the indium oxide layer, and more specifically, serves to control the etching rate of the molybdenum-titanium layer.
상기 함불소 화합물은 당 업계에서 사용되는 것이라면, 그 종류를 특별히 한정하지는 않으나, 바람직하게는 HF, NaF, NH4F, NH4BF4, NH4FHF, KF, KHF2, AlF3 및 HBF4로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 화소 전극 하부의 산화물 반도체층(SiO2)에 손상을 발생시키지 않을 수 있는 HF기가 없는 NH4F를 포함하는 것이 가장 바람직하다.If the fluorinated compound is used in the art, its kind is not particularly limited, but preferably HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, KF, KHF 2 , AlF 3 and HBF 4 Most preferably, it includes at least one selected from the group consisting of, and contains NH 4 F without HF groups that may not cause damage to the oxide semiconductor layer (SiO 2) under the pixel electrode.
또한, 상기 함불소 화합물은 식각액 조성물 총 중량에 대하여 0.1 내지 2 중량%로 포함되며, 바람직하게는 0.5 내지 1.5 중량%로 포함된다. 상기 함불소 화합물이 0.1 중량% 미만으로 포함되면, 몰리브덴-티타늄막 또는 인듐산화막의 식각 속도가 느려지며, 2 중량%를 초과하여 포함되면, 몰리브덴-티타늄막 또는 인듐산화막의 식각 성능은 향상되나, 하부막인 Si계열의 산화물 반도체층에 손상이 가해질 수 있다.
In addition, the fluorinated compound is contained in an amount of 0.1 to 2% by weight, preferably 0.5 to 1.5% by weight, based on the total weight of the etchant composition. When the fluorine-containing compound is contained in an amount of less than 0.1% by weight, the etching rate of the molybdenum-titanium layer or the indium oxide layer is slow, and when it is included in an amount exceeding 2% by weight, the etching performance of the molybdenum-titanium layer or the indium oxide layer is improved. Damage may be applied to the underlying Si-based oxide semiconductor layer.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 아졸 화합물은 화소 전극으로 사용되는 몰리브덴-티타늄막 또는 인듐산화막과 접촉하게 되는 구리 배선(data 배선)의 식각 속도를 조절하는 역할을 한다.The azole compound included in the molybdenum-titanium film or indium oxide film etchant composition of the present invention controls the etching rate of the copper wire (data wire) that comes into contact with the molybdenum-titanium film or indium oxide film used as a pixel electrode.
상기 아졸 화합물은 예를 들어, 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)계로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 바람직하게는 트리아졸(triazole)계이며, 구체적으로 벤조트리아졸(benzotriazole)계를 포함하는 것이 가장 바람직하다.The azole compounds are, for example, pyrrole, pyrazole, imidazole, triazole, tetrazole, pentazole, oxa It contains one or more selected from the group consisting of sol (oxazole), isoxazole (isoxazole), diazole (thiazole) and isodiazole (isothiazole), preferably triazole (triazole) It is most preferred to include, specifically, a benzotriazole system.
상기 아졸 화합물은 식각액 조성물 총 중량에 대하여 0.1 내지 1 중량%로 포함되며, 바람직하게는 0.2 내지 0.8 중량%로 포함된다. 상기 아졸 화합물이 0.1 중량% 미만으로 포함되면, 구리 배선의 손상을 방지하는 효과가 감소하며, 1 중량%를 초과하여 포함되면, 몰리브덴-티타늄막 또는 인듐산화막의 식각 속도가 감소하게 되어 공정시간이 길어져 공정 효율이 감소하게 되는 문제점이 발생한다.
The azole compound is included in an amount of 0.1 to 1% by weight, preferably 0.2 to 0.8% by weight, based on the total weight of the etchant composition. When the azole compound is contained in an amount of less than 0.1% by weight, the effect of preventing damage to the copper wiring decreases, and when it is included in an amount exceeding 1% by weight, the etching rate of the molybdenum-titanium layer or the indium oxide layer decreases, thereby reducing the process time. As it becomes longer, there is a problem that the process efficiency decreases.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 술폰산 화합물은 식각액 조성물의 pH를 0.5 내지 4.5로 맞추어 주어 과산화수소의 활동도를 증가시켜줌으로써, 몰리브덴-티타늄막 또는 인듐산화막의 식각 조절 및 사이드 에치를 향상시키는 역할을 한다. The sulfonic acid compound contained in the molybdenum-titanium film or indium oxide film etchant composition of the present invention increases the activity of hydrogen peroxide by adjusting the pH of the etchant composition to 0.5 to 4.5, thereby controlling the etch control and side of the molybdenum-titanium film or indium oxide film. It serves to improve the etch.
상기 술폰산 화합물은 술폰산기(-SO3H)가 있는 화합물을 총칭하는 것이며, 지방족 술폰산, 방향족 술폰산, 클로로 술폰산 및 술파민산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 바람직하게는 메탄술폰산이 사용될 수 있다.The sulfonic acid compound is a generic term for a compound having a sulfonic acid group (-SO 3 H), and includes at least one selected from the group consisting of aliphatic sulfonic acid, aromatic sulfonic acid, chloro sulfonic acid, and sulfamic acid, and preferably methanesulfonic acid is Can be used.
상기 술폰산 화합물은 식각액 조성물 총 중량에 대하여 0.3 내지 1 중량%로 포함되며, 바람직하게는 0.5 내지 0.8 중량%로 포함된다. 상기 술폰산 화합물이 0.3 중량% 미만으로 포함되면, 공정에 적합한 pH를 조절하는 능력이 부족해져 pH 0.5 내지 4.5를 유지하기 어려워져 식각 속도가 저하되며, 처리매수에 따른 사이드 에치의 변화량이 크게 발생하며, 1 중량%를 초과하여 포함되면, 식각 속도가 지나치게 빨라져 패턴이 유실되는 부분적 과침식 현상이 발생할 수 있다.
The sulfonic acid compound is included in an amount of 0.3 to 1% by weight, preferably 0.5 to 0.8% by weight, based on the total weight of the etchant composition. When the sulfonic acid compound is contained in an amount of less than 0.3% by weight, the ability to adjust the pH suitable for the process is insufficient, making it difficult to maintain pH 0.5 to 4.5, resulting in a decrease in the etch rate, and a large amount of side etch change according to the number of processed sheets occurs, If it is included in an amount exceeding 1% by weight, the etching rate may be excessively increased, resulting in a partial overerosion phenomenon in which the pattern is lost.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 다가 알코올은 식각액 조성물의 pH를 0.5 내지 4.5로 조절하여 과산화수소 및 술폰산 화합물의 활동도를 증가시켜줌으로써, 몰리브덴-티타늄막 또는 인듐산화막의 식각을 조절하는 역할을 한다.The polyhydric alcohol contained in the molybdenum-titanium film or indium oxide film etchant composition of the present invention increases the activity of hydrogen peroxide and sulfonic acid compounds by adjusting the pH of the etchant composition to 0.5 to 4.5, thereby etching the molybdenum-titanium film or indium oxide film. It plays a role in regulating.
상기 다가 알코올은 글리세롤, 에틸렌글리콜, 트리에틸렌 글리콜 및 폴리에틸렌 글리콜로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 바람직하게는 글리세롤을 포함한다.The polyhydric alcohol includes at least one selected from the group consisting of glycerol, ethylene glycol, triethylene glycol, and polyethylene glycol, and preferably includes glycerol.
상기 다가 알코올은 식각액 조성물 총 중량에 대하여 0.01 내지 2 중량%로 포함되고, 바람직하게는 0.5 내지 1 중량%로 포함된다. 상기 다가 알코올이 0.01 중량% 미만으로 포함되면 식각 속도가 저하되고, 2 중량%를 초과하여 포함되면 식각 속도가 지나치게 빨라져 패턴이 유실되는 현상이 발생한다.
The polyhydric alcohol is included in an amount of 0.01 to 2% by weight, preferably 0.5 to 1% by weight, based on the total weight of the etchant composition. When the polyhydric alcohol is contained in an amount of less than 0.01% by weight, the etching rate is lowered, and when the polyhydric alcohol is contained in an amount exceeding 2% by weight, the etching rate is excessively increased, resulting in a pattern loss.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물에 포함되는 물은 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함된다. 상기 물은 특별히 한정되지 않으나, 탈이온수를 이용하는 것이 바람직하다. 그리고, 상기 물은 물속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·㎝ 이상인 탈이온수를 이용하는 것이 바람직하다.
Water contained in the molybdenum-titanium film or indium oxide film etchant composition of the present invention is included in the balance so that the total weight of the composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is 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.
또한, 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물은 추가로 금속 이온 봉쇄제 및 부식 방지제로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. 또한, 상기 첨가제는 이에만 한정되는 것이 아니라, 본 발명의 효과를 더욱 양호하게 하기 위하여, 당 업계에 공지되어 있는 여러 다른 첨가제들을 선택하여 첨가할 수도 있다.In addition, the molybdenum-titanium film or indium oxide film etchant composition of the present invention may further include at least one selected from the group consisting of a metal ion sequestering agent and a corrosion inhibitor. In addition, the additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물의 성분들은 통상적으로 공지된 방법에 의하여 제조 가능하며, 반도체 공정용의 순도로 사용하는 것이 바람직하다.
The components of the molybdenum-titanium film or indium oxide film etchant composition of the present invention can be prepared by a conventionally known method, and are preferably used with purity for semiconductor processing.
또한, 본 발명은 In addition, the present invention
(1)기판 상에 몰리브덴-티타늄막 또는 인듐산화막을 형성하는 단계;(1) forming a molybdenum-titanium film or an indium oxide film on a substrate;
(2)상기 몰리브덴-티타늄막 또는 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및(2) selectively leaving a photoreactive material on the molybdenum-titanium film or indium oxide film; And
(3)상기 본 발명의 식각액 조성물을 사용하여 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각하는 단계를 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각방법에 관한 것이다.(3) A method for etching a molybdenum-titanium layer or an indium oxide layer comprising the step of etching the molybdenum-titanium layer or indium oxide layer using the etchant 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 a conventional exposure and development process.
또한, 상기 몰리브덴-티타늄막 또는 인듐산화막은 단일막이거나, 상기 몰리브덴-티타늄막과 인듐산화막의 다층막일 수 있다.In addition, the molybdenum-titanium layer or the indium oxide layer may be a single layer or a multilayered layer of the molybdenum-titanium layer and the indium oxide layer.
상기 인듐산화막은 인듐주석산화막(ITO), 인듐아연산화막(IZO) 및 인듐갈륨아연산화막(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이다.
The indium oxide film includes at least one selected from the group consisting of an indium tin oxide film (ITO), an indium zinc oxide film (IZO), and an indium gallium zinc oxide film (IGZO).
또한, 본 발명은In addition, the present invention
(1)기판 상에 게이트 배선을 형성하는 단계;(1) forming a gate wiring on a substrate;
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(2) forming a gate insulating layer on a substrate including the gate wiring;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;(3) forming an oxide semiconductor layer on the gate insulating layer;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(4) forming source and drain electrodes on the oxide semiconductor layer; And
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,(5) 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 (5)단계는 몰리브덴-티타늄막 또는 인듐산화막을 형성하고, 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며,The step (5) includes forming a molybdenum-titanium film or an indium oxide film, and etching the molybdenum-titanium film or indium oxide film with an etchant composition to form a pixel electrode,
상기 식각액 조성물은 상기 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법에 관한 것이다.
The etchant composition is a molybdenum-titanium film or indium oxide film etchant composition of the present invention relates to a method of manufacturing an array substrate for a liquid crystal display device.
상기 몰리브덴-티타늄막 또는 인듐산화막은 단일막이거나, 상기 몰리브덴-티타늄막과 인듐산화막의 다층막일 수 있다.The molybdenum-titanium layer or the indium oxide layer may be a single layer or a multilayered layer of the molybdenum-titanium layer and the indium oxide layer.
상기 인듐산화막은 인듐주석산화막(ITO), 인듐아연산화막(IZO) 및 인듐갈륨아연산화막(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이다.The indium oxide film includes at least one selected from the group consisting of an indium tin oxide film (ITO), an indium zinc oxide film (IZO), and an indium gallium zinc oxide film (IGZO).
본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물로 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각하여, 상기 (5)단계의 화소 전극을 형성할 수 있다.The pixel electrode of step (5) may be formed by etching the molybdenum-titanium film or indium oxide film with the molybdenum-titanium film or indium oxide film etchant composition of the present invention.
또한, 상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.
In addition, the liquid crystal display array substrate may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 제조방법으로 제조된 액정 표시 장치용 어레이 기판에 관한 것이다.In addition, the present invention relates to an array substrate for a liquid crystal display device manufactured by the above manufacturing method.
상기 액정 표시 장치용 어레이 기판은 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물을 사용하여 식각된 화소 전극을 포함한다.
The array substrate for a liquid crystal display device includes a pixel electrode etched using the molybdenum-titanium film or indium oxide film 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 through examples. However, the following examples are for explaining the present invention more specifically, 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.
<몰리브덴-<Molybdenum- 티타늄막Titanium film 또는 or 인듐산화막Indium oxide film 식각액Etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 6 및 1 to 6 and 비교예Comparative example 1 내지 4. 1 to 4.
하기 표 1에 나타낸 조성에 따라 실시예 1 내지 6 및 비교예 1 내지 4의 식각액 조성물을 제조하였으며, 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하였다.The etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared according to the composition shown in Table 1 below, and the remaining amount of water was included so that the total weight of the etchant composition was 100% by weight.
AF : Ammonium fluorideAF: Ammonium fluoride
BTZ : BenzotriazoleBTZ: Benzotriazole
MSA : Methane sulfonic acidMSA: Methane sulfonic acid
ABF : Ammonium bifluoride
ABF: Ammonium bifluoride
실험예Experimental example 1. One. 식각액Etchant 조성물의 처리매수에 따른 사이드 Side according to the number of processed sheets of the composition 에치Etch 평가 evaluation
유리 기판(100mmⅩ100mm)상에 Mo-Ti(300Å)막을 증착시킨 뒤, 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 한 후, 실시예 1 내지 6 및 비교예 1 내지 4의 식각액 조성물을 각각 사용하여 Mo-Ti 막에 대하여 식각공정을 실시하였다. After depositing a Mo-Ti (300Å) film on a glass substrate (100mm×100mm), a photoresist having a predetermined pattern was formed on the substrate through a photolithography process, and Examples 1 to 6 and Comparative Examples An etching process was performed on the Mo-Ti film using each of the etchant compositions of 1 to 4, respectively.
분사식 식각 방식의 실험장비(모델명 : ETCHER(TFT), SEMES사)를 이용하였고, 식각공정시 식각액 조성물의 온도는 약 35℃ 내외로 하였으나, 적정온도는 다른 공정조건과 기타 요인에 의해 필요에 따라 변경될 수 있다. 식각시간은 식각 온도에 따라서 다를 수 있으나, 몰리브덴-티타늄막 또는 인듐산화물막은 LCD 에칭 공정에서 통상 80 내지 100초 정도로 진행하였다. Spray-etching type experimental equipment (model name: ETCHER(TFT), SEMES) was used, and during the etching process, the temperature of the etchant composition was around 35°C, but the appropriate temperature was determined by other process conditions and other factors. can be changed. The etching time may vary depending on the etching temperature, but the molybdenum-titanium film or the indium oxide film was generally performed for about 80 to 100 seconds in the LCD etching process.
또한, 포토레지스트/SiO2로 구성된 막질을 100초 동안 식각하여 식각된 단면을 관찰하여 SiO2 damage를 관찰하였다.In addition, a film composed of photoresist/SiO 2 was etched for 100 seconds to observe the etched cross section to observe SiO 2 damage.
상기 식각공정에서 식각된 Mo-Ti막의 사이드 에치(side etch)의 단면은 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였으며, Mo-Ti막의 사이드 에치 만족 수준은 0.3μm 이상이나, 1μm 이상이면 패턴의 유실이 관찰되었다.The cross-section of the side etch of the Mo-Ti film etched in the etching process was inspected using SEM (Hitachi Corporation, model name S-4700), and the side etch satisfaction level of the Mo-Ti film was 0.3 μm or more, If it was 1 μm or more, loss of the pattern was observed.
사이드 에치의 결과를 하기 표 2에 나타내었다.
The results of the side etch are shown in Table 2 below.
상기 표 2의 결과에서, 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물인 실시예 1 내지 6은 몰리브덴-티타늄(Mo-Ti)막의 사이드 에치가 모두 0.3μm 이상인 결과를 보였다.In the results of Table 2, Examples 1 to 6, which are the molybdenum-titanium film or indium oxide film etchant composition of the present invention, showed the result that the side etch of the molybdenum-titanium (Mo-Ti) film was all 0.3 μm or more.
반면, 다가 알코올을 포함하지 않은 비교예 1의 식각액 조성물은 사이드 에치가 0.3μm 미만으로 나타났으며, 종래의 술폰산 화합물 및 다가 알코올을 모두 포함하지 않은 비교예 2의 식각액 조성물은 사이드 에치가 가장 작게 나타났다. On the other hand, the etchant composition of Comparative Example 1 that did not contain a polyhydric alcohol was found to have a side etch of less than 0.3 μm. appear.
또한, 다가 알코올이 식각액 조성물 총 중량에 대하여 0.01 중량% 미만으로 포함된 비교예 3의 식각액 조성물은 사이드 에치 증가 효과가 미비하게 나타났으며, 다가 알코올이 식각액 조성물 총 중량에 대하여 2 중량%를 초과하여 포함된 비교예 4의 식각액 조성물은 사이드 에치가 지나치게 증가하여 패턴 유실 현상이 발생하였다.In addition, the etchant composition of Comparative Example 3, in which the polyhydric alcohol was contained in an amount of less than 0.01% by weight based on the total weight of the etchant composition, showed insignificant side etch increase effect, and the polyhydric alcohol exceeded 2 wt% based on the total weight of the etchant composition. In the included etchant composition of Comparative Example 4, the side etch was excessively increased, resulting in a pattern loss phenomenon.
따라서, 다가 알코올을 포함하며, 상기 다가 알코올을 식각액 조성물 총 중량에 대하여 0.01 내지 2 중량%로 포함하는 본 발명의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물은 상기 몰리브덴-티타늄막 또는 인듐산화막의 사이드 에치를 향상시킬 수 있는 효과를 지니고 있다는 것을 실험을 통하여 확인할 수 있었다.Accordingly, the molybdenum-titanium film or indium oxide film etchant composition of the present invention comprising a polyhydric alcohol and containing 0.01 to 2% by weight of the polyhydric alcohol on the side of the molybdenum-titanium film or indium oxide film It was confirmed through an experiment that it has the effect of improving the teeth.
Claims (13)
상기 술폰산 화합물은, 메탄술폰산(Methane sulfonic acid)이고,
상기 식각액 조성물에 의해 식각된 몰리브덴-티타늄막 또는 인듐산화막의 사이드 에치(side etch)가 0.3㎛ 이상 및 1.0㎛ 미만인, 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물.Based on the total weight of the etchant composition, hydrogen peroxide 15 to 25% by weight, fluorine-containing compound 0.1 to 2% by weight, azole compound 0.1 to 1% by weight, sulfonic acid compound 0.3 to 1% by weight, polyhydric alcohol 0.01 to 2% by weight, and the total amount of etchant composition It contains the remaining amount of water so that the weight is 100% by weight,
The sulfonic acid compound is methane sulfonic acid,
A side etch of the molybdenum-titanium film or indium oxide film etched by the etchant composition is 0.3㎛ or more and less than 1.0㎛, molybdenum-titanium film or indium oxide film etchant composition.
(2)상기 몰리브덴-티타늄막 또는 인듐산화막 상에 선택적으로 광반응 물질을 남기는 단계; 및
(3)청구항 1 내지 청구항 6 중 어느 한 항의 식각액 조성물을 사용하여 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각하는 단계를 포함하는 몰리브덴-티타늄막 또는 인듐산화막 식각방법.(1) forming a molybdenum-titanium film or an indium oxide film on a substrate;
(2) selectively leaving a photoreactive material on the molybdenum-titanium film or indium oxide film; And
(3) A molybdenum-titanium film or indium oxide film etching method comprising the step of etching the molybdenum-titanium film or indium oxide film using the etchant composition of any one of claims 1 to 6.
(2)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
(3)상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;
(4)상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
(5)상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 (5)단계는 몰리브덴-티타늄막 또는 인듐산화막을 형성하고, 상기 몰리브덴-티타늄막 또는 인듐산화막을 식각액 조성물로 식각하여 화소 전극을 형성하는 단계를 포함하며,
상기 식각액 조성물은 청구항 1 내지 청구항 6 중 어느 한 항의 몰리브덴-티타늄막 또는 인듐산화막 식각액 조성물인 것을 특징으로 하는 액정 표시 장치용 어레이 기판의 제조방법.(1) forming a gate wiring on a substrate;
(2) forming a gate insulating layer on a substrate including the gate wiring;
(3) forming an oxide semiconductor layer on the gate insulating layer;
(4) forming source and drain electrodes on the oxide semiconductor layer; And
(5) 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 (5) includes forming a molybdenum-titanium film or an indium oxide film, and etching the molybdenum-titanium film or indium oxide film with an etchant composition to form a pixel electrode,
The method of manufacturing an array substrate for a liquid crystal display, wherein the etchant composition is the molybdenum-titanium film or indium oxide film etchant composition of any one of claims 1 to 6.
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