KR20170111927A - Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same - Google Patents
Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same Download PDFInfo
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- KR20170111927A KR20170111927A KR1020160038231A KR20160038231A KR20170111927A KR 20170111927 A KR20170111927 A KR 20170111927A KR 1020160038231 A KR1020160038231 A KR 1020160038231A KR 20160038231 A KR20160038231 A KR 20160038231A KR 20170111927 A KR20170111927 A KR 20170111927A
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- KR
- South Korea
- Prior art keywords
- molybdenum
- film
- indium
- metal film
- oxide film
- Prior art date
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011733 molybdenum Substances 0.000 title claims abstract description 64
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000000758 substrate Substances 0.000 title claims abstract description 18
- 238000005530 etching Methods 0.000 title claims description 35
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000002443 hydroxylamines Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 10
- -1 azole compound Chemical class 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 21
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910003437 indium oxide Inorganic materials 0.000 claims description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 2
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-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
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- NGULNJDDRUSDPR-UHFFFAOYSA-N (diacetylamino) acetate Chemical compound CC(=O)ON(C(C)=O)C(C)=O NGULNJDDRUSDPR-UHFFFAOYSA-N 0.000 claims 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims 1
- 229910001195 gallium oxide Inorganic materials 0.000 claims 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 91
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 9
- 229910052733 gallium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- CYVJAPJMVQTBPB-UHFFFAOYSA-N C(C)(=O)N(OC(C)=O)C(C)=O.C(C)(=O)N(OC(C)=O)C(C)=O Chemical compound C(C)(=O)N(OC(C)=O)C(C)=O.C(C)(=O)N(OC(C)=O)C(C)=O CYVJAPJMVQTBPB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
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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
- G02F1/1343—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Electrodes Of Semiconductors (AREA)
- Thin Film Transistor (AREA)
Abstract
본 발명은 과산화수소, 불소 화합물, 아졸계 화합물, 히드록실아민 유도체, 및 물을 일정 함량으로 포함하는 몰리브덴(Mo) 함유 금속막의 식각액 조성물 및 이를 이용한 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etchant composition for a metal film containing molybdenum (Mo) containing hydrogen peroxide, a fluorine compound, an azole compound, a hydroxylamine derivative, and water in a predetermined amount, and a method for manufacturing an array substrate for a liquid crystal display device using the same.
Description
본 발명은 몰리브덴(Mo) 함유 금속막의 식각액 조성물 및 이를 이용한 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etchant composition for a metal film containing molybdenum (Mo) and a method for producing an array substrate for a liquid crystal display using the same.
본격적인 정보화 시대로 접어들게 됨에 따라 대량의 정보를 처리 및 표시하는 디스플레이 분야가 급속도로 발전해 왔으며, 이에 부응하여 다양한 평판 디스플레이가 개발되어 각광받고 있다.As the era of information technology becomes full-scale, the display field for processing and displaying a large amount of information has been rapidly developed, and various flat panel displays have been developed in response to this.
이러한 평판 디스플레이 장치의 예로는 액정표시장치(Liquid Crystal Display device: LCD), 플라즈마 디스플레이 장치(Plasma Display Panel device: PDP), 전계방출 디스플레이 장치(Field Emission Display device: FED), 유기발광소자(Organic Light Emitting Diodes: OLED) 등을 들 수 있다. 특히 액정표시장치는 뛰어난 해상도에 따른 선명한 영상을 제공하며, 전기를 적게 소모하고, 디스플레이 화면을 얇게 만들 수 있는 특성 때문에 각광을 받고 있다.Examples of such flat panel display devices include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), an organic light emitting device Emitting Diodes (OLED). Particularly, liquid crystal display devices are attracting attention due to their ability to provide clear images according to excellent resolution, to consume less electricity, and to make display screens thinner.
TFT-LCD 등의 액정표시장치의 화소전극에는 몰리브덴 합금막 및 금속 산화막의 단일막 또는 몰리브덴 합금막과 금속 산화막의 다층막 등이 사용된다. 상기 화소전극은 일반적으로 스퍼터링 등의 방법을 통해 기판상에 적층시키고, 그 위에 포토레지스트를 균일하게 도포한다. 이후 패턴이 새겨진 마스크를 통하여 빛을 조사하고, 현상을 통하여 원하는 패턴의 포토레지스트를 형성시킨다. 이어, 건식 또는 습식 식각으로 포토레지스트 하부에 있는 금속막에 패턴을 전사한 후, 필요 없는 포토레지스트를 박리 공정에 의해 제거하는, 일련의 리소그래피(lithography) 공정을 거쳐 완성된다.As a pixel electrode of a liquid crystal display device such as a TFT-LCD, a single layer of a molybdenum alloy film and a metal oxide film, or a multi-layered film of a molybdenum alloy film and a metal oxide film is used. The pixel electrodes are generally stacked on a substrate by a method such as sputtering, and a photoresist is uniformly applied thereon. Then, light is irradiated through a mask having a pattern formed thereon, and a photoresist of a desired pattern is formed through development. Then, a pattern is transferred to a metal film under the photoresist by dry or wet etching, and then the photoresist is removed by a stripping process, which is completed through a series of lithography processes.
상기 몰리브덴 합금막 및 금속 산화막의 식각을 동일한 식각액으로 실시하는 경우, 제조 공정을 간소화시킬 수 있으나, 일반적으로 몰리브덴 합금막은 내화학성이 우수하여 습식 식각이 용이하지 않다는 문제점이 있다. 또한, 처리매수에 따른 식각 성능 차이가 크므로, 사용 수명이 짧아 공정 비용 상승, 원가 상승의 문제가 있다. When the etching of the molybdenum alloy film and the metal oxide film is performed with the same etching solution, the manufacturing process can be simplified. However, the molybdenum alloy film generally has a problem in that wet etching is not easy because of its excellent chemical resistance. In addition, there is a problem of increase in process cost and increase in cost due to a short service life due to a large difference in etching performance depending on the number of treatments.
본 발명은, 상기 종래 기술의 문제를 해결하기 위하여 안출된 것으로서,SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,
몰리브덴 또는 몰리브덴 합금의 단일막, 또는 상기 단일막 및 금속산화물막을 포함하는 다층막을 식각함에 있어서, 처리매수에 따른 편측식각(side etch) 변화량이 적고, 사용 수명이 우수한 식각액 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide an etchant composition which has a small amount of side etch variation according to the number of treatments and has a long service life in etching a single layer of a molybdenum or molybdenum alloy or a multilayer film comprising the single layer and the metal oxide layer do.
또한, 본 발명은 상기 식각액 조성물을 사용하는 액정표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a method for manufacturing an array substrate for a liquid crystal display device using the etchant composition.
본 발명은,According to the present invention,
조성물 총 중량에 대하여About the total weight of the composition
(A) 과산화수소 5 내지 30 중량%, (B) 불소 화합물 0.1 내지 2 중량%, (C) 아졸계 화합물 0.1 내지 1 중량%, (D) 히드록실아민 유도체 0.1 내지 5 중량%, 및 (E) 잔량의 물을 포함하는 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물을 제공한다.(C) 0.1 to 1% by weight of an azole-based compound, (D) 0.1 to 5% by weight of a hydroxylamine derivative, and (E) Wherein the molybdenum-containing metal film contains water in a residual amount.
또한, 본 발명은In addition,
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 산화물 반도체층을 형성하는 단계;c) forming an oxide semiconductor layer on the gate insulating layer;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the oxide semiconductor layer; And
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 e) 단계는 기판 상에 몰리브덴(Mo) 함유 금속막을 형성하고, 본 발명의 몰리브덴 함유 금속막의 식각액 조성물로 식각하여 화소전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다. Wherein the step (e) comprises forming a molybdenum (Mo) -containing metal film on the substrate, and etching the molybdenum-containing metal film with the etchant composition of the molybdenum-containing metal film of the present invention to form a pixel electrode And a manufacturing method thereof.
본 발명의 몰리브덴 함유 금속막의 식각액 조성물은 과산화수소, 불소 화합물, 아졸계 화합물, 히드록실아민 유도체 및 물을 일정 함량으로 함유함으로써, 몰리브덴 함유 금속막을 식각함에 있어서 처리 매수에 따른 편측 식각(side etch) 변화량이 적고, 사용 수명이 우수한 특성을 제공할 수 있다. The etchant composition of the molybdenum-containing metal film of the present invention contains a certain amount of hydrogen peroxide, a fluorine compound, an azole-based compound, a hydroxylamine derivative, and water so that the amount of side etch change And can provide characteristics excellent in service life.
또한, 본 발명은 상기 식각액 조성물을 사용하여 액정표시장치용 어레이 기판을 제조하는 방법을 제공할 수 있다.Further, the present invention can provide a method of manufacturing an array substrate for a liquid crystal display device using the etchant composition.
본 발명자들은 몰리브덴 함유 금속막을 식각함에 있어서, 처리 매수에 따른 편측식각 변화량이 적은 특성을 가지는 식각액 조성물을 제공하기 위해 예의 노력한 바, 과산화수소, 불소화합물, 아졸계 화합물, 히드록실아민 유도체 및 물을 일정 함량으로 포함하는 식각액 조성물로서 본 발명을 완성하게 되었다. The present inventors have made intensive efforts to provide an etchant composition having a small amount of unilateral etching change according to the number of treatments when etching a metal film containing molybdenum. The present invention has been completed.
본 발명은, 조성물 총 중량에 대하여The present invention relates to a composition comprising
(A) 과산화수소 5 내지 30 중량%, (B) 불소 화합물 0.1 내지 2 중량%, (C) 아졸계 화합물 0.1 내지 1 중량%, (D) 히드록실아민 유도체 0.1 내지 5 중량%, 및 (E) 잔량의 물을 포함하는 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물에 관한 것이다.(C) 0.1 to 1% by weight of an azole-based compound, (D) 0.1 to 5% by weight of a hydroxylamine derivative, and (E) Wherein the molybdenum-containing metal film comprises water of a residual amount.
상기 몰리브덴 함유 금속막은 막의 구성 성분 중에 몰리브덴이 포함되는 것으로서, 단일막 및 이중막 이상의 다층막을 포함하는 개념이다. 상기 몰리브덴(Mo) 함유 금속막은 몰리브덴(Mo) 또는 몰리브덴 합금(Mo alloy)의 단일막, 또는 상기 단일막과 금속 산화물막으로 이루어진 다층막 등을 들 수 있으나, 이에 한정하는 것은 아니다.The molybdenum-containing metal film includes molybdenum as a constituent component of the film, and includes a multilayer film of a single film and a double film or more. The molybdenum (Mo) -containing metal film may be a single film of molybdenum (Mo) or a molybdenum alloy (Mo alloy), or a multilayer film of the single film and the metal oxide film.
이하, 본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물을 구성하는 각 성분을 설명한다.Hereinafter, each component constituting the etchant composition of the molybdenum (Mo) -containing metal film of the present invention will be described.
(A) 과산화수소(A) hydrogen peroxide
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물에 포함되는 과산화수소(H2O2)는 주산화제로 사용되는 성분으로서, 몰리브덴 함유 금속막의 식각 속도에 영향을 준다.Hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the molybdenum (Mo) -containing metal film of the present invention is a component used as a main oxidizing agent and affects the etching rate of the molybdenum-containing metal film.
상기 과산화수소(H2O2)는 몰리브덴(Mo) 함유 금속막의 식각액 조성물 총 중량에 대하여 5 내지 30 중량%로 포함되며, 바람직하게는 10 내지 25 중량%로 포함되는 것이 좋다. 상기 과산화수소가 5 중량% 미만으로 포함되면 몰리브덴 함유 금속막의 식각 속도 저하를 야기할 수 있으며, 이로 인해 충분한 식각이 이루어지지 않을 수 있다. 반면, 30 중량%를 초과하여 포함되는 경우에는 과산화수소(H2O2)의 농도가 지나치게 높아짐에 따라 몰리브덴막, 몰리브덴 합금막 또는 금속 산화물막 등에 과식각 현상이 발생할 수 있으며, 식각액의 안정성이 저하될 우려가 있다. 여기에서 과식각 현상은 식각 속도(etch rate)가 너무 높아 식각 시 금속막 또는 금속 산화물막이 유실되는 현상을 의미하는 것으로 이해할 수 있다.The hydrogen peroxide (H 2 O 2 ) is contained in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, based on the total weight of the etchant composition of the metal film containing molybdenum (Mo). If the hydrogen peroxide is contained in an amount of less than 5% by weight, the etching rate of the metal film containing molybdenum may be lowered, and thus sufficient etching may not be performed. On the other hand, when the concentration exceeds 30% by weight, overcorrection may occur in a molybdenum film, a molybdenum alloy film or a metal oxide film due to an excessively high concentration of hydrogen peroxide (H 2 O 2 ) There is a concern. Here, it can be understood that the over-etching phenomenon means that the metal film or the metal oxide film is lost during the etching because the etch rate is too high.
(B) 불소 화합물(B) Fluorine compound
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물에 포함되는 불소 화합물은 물 등에 해리되어 플루오라이드 이온(F-)을 제공할 수 있는 화합물을 의미한다. 상기 불소 화합물은 몰리브덴 함유 금속막의 식각 속도에 영향을 주는 해리제로서, 몰리브덴 함유 금속막의 식각 속도를 조절하는 역할을 한다.The fluorine compound contained in the etchant composition of the metal film containing molybdenum (Mo) of the present invention means a compound capable of dissociating into water or the like and capable of providing fluoride ion (F - ). The fluorine compound is a dissociating agent that affects the etching rate of the molybdenum-containing metal film, and serves to control the etching rate of the metal film containing molybdenum.
상기 불소 화합물은 당업계에서 사용되는 것이면 특별히 한정하지 않으나, 구체적인 예로서 불화수소(HF), 불화나트륨(NaF), 불화암모늄(NH4F), 플루오르화붕산염(NH4BF4), 플루오르화수소암모늄(NH4FHF), 플루오르화칼륨(KF), 플루오르화수소칼륨(KHF2), 불화알루미늄(AlF3) 및 테트라플루오로붕산(HBF4)으로부터 선택되는 1종 이상을 사용할 수 있다. 보다 바람직하게는 플루오르화수소암모늄 (NH4FHF)을 사용할 수 있다.The fluorine compound is not particularly limited as long as it is used in the art, and specific examples thereof include hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH 4 F), fluoroborate (NH 4 BF 4 ) Ammonium hydrogen fluoride (NH 4 FHF), At least one selected from potassium fluoride (KF), potassium fluoride (KHF 2 ), aluminum fluoride (AlF 3 ) and tetrafluoroboric acid (HBF 4 ) can be used. More preferably, ammonium hydrogen fluoride (NH 4 FHF) can be used.
상기 불소 화합물은 본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물 총 중량에 대하여 0.1 내지 2 중량%로 포함되며, 바람직하게는 0.5 내지 1.5 중량%로 포함되는 것이 좋다. 상기 불소 화합물의 함량이 0.1 중량% 미만일 경우, 몰리브덴 함유 금속막의 식각 속도가 저하되며, 2 중량%를 초과하면 몰리브덴 함유 금속막에 대한 식각 성능은 향상되나, Si 계열 하부막에 대한 손상(damage)이 크게 나타나 바람직하지 않다.The fluorine 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 of the metal film containing molybdenum (Mo) of the present invention. If the content of the fluorine compound is less than 0.1 wt%, the etching rate of the molybdenum-containing metal film is lowered. If the content of the fluorine compound is more than 2 wt%, the etching performance of the metal film containing molybdenum is improved, Which is undesirable.
(C) (C) 아졸계Azole series 화합물 compound
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물에 포함되는 아졸계 화합물은 몰리브덴 함유 금속막 및 금속 산화물막과 접촉하게 되는 구리 등의 데이터 배선의 식각 속도를 조절하는 역할을 한다.The azole compound included in the etchant composition of the molybdenum (Mo) -containing metal film of the present invention serves to control the etch rate of the data wiring such as copper to be in contact with the molybdenum-containing metal film and the metal oxide film.
상기 아졸계 화합물은 당업계에서 사용되는 것이면 특별히 한정하지 않으나, 구체적인 예로서 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 티아졸(thiazole)계 및 이소티아졸(isothiazole)계 화합물 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. 이 중 트리아졸(triazole)계 화합물이 바람직하며, 트리아졸계 화합물의 구체적인 예로서 벤조트리아졸(benzotriazole)이 보다 바람직할 수 있다.The azole compound is not particularly limited as long as it is used in the art, and specific examples thereof include pyrrole, pyrazole, imidazole, triazole, tetrazole, ), A pentazole-based compound, an oxazole-based compound, an isoxazole-based compound, a thiazole-based compound, and an isothiazole-based compound. Or two or more of them may be used together. Among them, a triazole-based compound is preferable, and benzotriazole is more preferable as a specific example of the triazole-based compound.
상기 아졸계 화합물은 본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물 총 중량에 대하여 0.1 내지 1 중량%로 포함되며, 바람직하게는 0.2 내지 0.8 중량%로 포함되는 것이 좋다. 아졸계 화합물이 0.1 중량% 미만으로 포함될 경우 구리 등의 배선에 대한 식각 속도가 증가하여 어택(attack) 방지 효과가 떨어진다. 반면, 1 중량%를 초과하여 포함되는 경우 몰리브덴(Mo) 함유 금속막, 금속 산화물막에 대한 식각 속도가 감소하여 공정 시간이 길어지는 등의 손실이 있을 수 있다.The azole-based compound is contained 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 of the molybdenum (Mo) -containing metal film of the present invention. When the azole-based compound is contained in an amount less than 0.1% by weight, the etching speed against the wiring such as copper increases to deteriorate the attack preventing effect. On the other hand, if it is contained in an amount exceeding 1% by weight, the etching rate for the metal film containing molybdenum (Mo) and the metal oxide film may be decreased and the process time may be lengthened.
(D) 히드록실아민 유도체(D) Hydroxylamine derivatives
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물에 포함되는 히드록실아민 유도체는 금속의 킬레이트제로 작용하여, 처리매수 진행 시 편측식각(side etch) 변화율을 감소시키는 역할을 한다. The hydroxylamine derivative contained in the etchant composition of the molybdenum (Mo) -containing metal film of the present invention serves as a chelating agent for the metal, and serves to reduce the rate of side etch change during the treatment.
상기 히드록실아민 유도체는 당업계에서 사용되는 것이면 특별히 한정하지 않으나, 구체적인 예로서 히드록실아민(Hydroxylamine), 히드록실아민-O-설폰산(hydroxylamine-o-sulfonic acid), 히드록실아민 설페이트(hydroxylamine sulfate), N,N-다이에틸히드록실아민(N,N-Diethylhydroxylamine), N-메틸히드록실아민(N-Methylhydroxylamine), N,N-다이벤질히드록실아민(N,N-Dibenzylhydroxylamine), N,N,O-트리아세틸히드록실아민(N,N,O-Triacetylhydroxylamine) 등을 들 수 있다. 이들은 1종 단독으로 또는 2종 이상을 함께 사용할 수 있다. 이 중에서, N,N-다이에틸히드록실아민(N,N-Diethylhydroxylamine)이 보다 바람직할 수 있다. The hydroxylamine derivative is not particularly limited as long as it is used in the art, and specific examples thereof include hydroxylamine, hydroxylamine-o-sulfonic acid, hydroxylamine sulfate, N, N-diethylhydroxylamine, N-methylhydroxylamine, N, N-dibenzylhydroxylamine, N , N, O-triacetylhydroxylamine (N, N, O-triacetylhydroxylamine) and the like. These may be used alone or in combination of two or more. Of these, N, N-Diethylhydroxylamine may be more preferable.
상기 히드록실아민 유도체는 본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물 총 중량에 대하여 0.1 내지 5 중량%로 포함되며, 0.3 내지 3 중량%로 포함되는 것이 보다 바람직할 수 있다. 상기한 기준으로, 함량이 0.1 중량% 미만인 경우 처리매수 진행 시 편측식각(side etch) 변화량이 증가하고, 5 중량%를 초과하면 식각 속도가 지나치게 느려져 식각 시간(etch time)이 길어져 생산량 감소를 발생시킨다. The hydroxylamine derivative may be contained in an amount of 0.1 to 5% by weight, and more preferably 0.3 to 3% by weight based on the total weight of the etchant composition of the molybdenum (Mo) -containing metal film of the present invention. On the basis of the above-mentioned criteria, when the content is less than 0.1% by weight, the amount of side etch change increases when the number of treatments is proceeded. If the content exceeds 5% by weight, the etch rate is excessively slowed, .
(E) 물(E) Water
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물에 포함되는 물은 특별히 한정하지 않으나, 반도체 공정용으로서 탈이온수를 이용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 비저항값이 18 ㏁/㎝ 이상인 탈이온수를 이용하는 것이 보다 바람직하다.The water contained in the etchant composition of the molybdenum (Mo) -containing metal film of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing, and it is preferable that the resistivity value showing the degree of removal of ions in water is 18 MΩ / Or more of deionized water.
상기 물은 본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함될 수 있다. The water may be contained in a balance such that the total weight of the etchant composition of the molybdenum (Mo) -containing metal film of the present invention is 100% by weight.
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물은 상기에 언급한 성분들 외에 식각 조절제, 계면활성제, 금속 이온 봉쇄제, 부식 방지제, pH 조절제 및 이에 국한되지 않는 다른 첨가제로부터 선택되는 1종 이상을 추가로 포함할 수 있다. 상기 첨가제는, 본 발명의 범위 내에서 본 발명의 효과를 더욱 양호하게 하기 위하여, 당해 분야에서 통상적으로 사용하는 첨가제들로부터 선택하여 사용할 수 있다. The etchant composition of the molybdenum (Mo) -containing metal film of the present invention may contain, in addition to the above-mentioned components, at least one selected from an etchant, a surfactant, a sequestering agent, a corrosion inhibitor, a pH adjusting agent, May be further included. The above additives can be selected from additives commonly used in the art in order to further improve the effects of the present invention within the scope of the present invention.
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하며, 각 구성 성분들은 통상적으로 공지된 방법에 의해서 제조가 가능하다.It is preferable that the etchant composition of the metal film containing molybdenum (Mo) of the present invention has a purity for semiconductor processing, and each component can be manufactured by a conventionally known method.
본 발명의 몰리브덴(Mo) 함유 금속막의 식각액 조성물이 적용되는 몰리브덴(Mo) 함유 금속막은, 막의 구성 성분 중에 몰리브덴(Mo)이 포함되는 것으로서, 몰리브덴(Mo) 또는 몰리브덴 합금의 단일막, 또는 상기 단일막과 금속 산화물막으로 구성된 다층막 등을 들 수 있으나, 이에 한정하는 것은 아니다.The molybdenum (Mo) -containing metal film to which the etchant composition of the molybdenum (Mo) -containing metal film of the present invention is applied is a single film of molybdenum (Mo) or molybdenum alloy, A multi-layered film composed of a film and a metal oxide film, but the present invention is not limited thereto.
상기 몰리브덴 함유 금속막은 특별히 한정하지 않으나 구체적인 예로서, 몰리브덴(Mo)막, 몰리브덴을 주성분으로 하며 네오디늄(Nd), 탄탈륨(Ta), 인듐(In), 구리(Cu), 팔라듐(Pd), 니오븀(Nb), 니켈(Ni), 크롬(Cr), 마그네슘(Mg), 텅스텐(W), 프로트악티늄(Pa) 및 티타늄(Ti) 등으로부터 선택되는 1종 이상의 금속을 포함하는 몰리브덴 합금막 등의 단일막; 상기 단일막과 금속 산화물막으로 구성된 다층막; 등을 들 수 있다. 상기 금속 산화물막은 통상 AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0)의 조합으로 이루어진 삼성분계 또는 사성분계 산화물을 함유하여 구성된 막으로서, 화소 전극으로 사용될 수 있다. 상기 금속 산화물막의 구체예로서 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 또는 산화갈륨아연인듐(IGZO) 등을 들 수 있으나 이에 한정하는 것은 아니다. The molybdenum-containing metal film is not particularly limited, but specific examples thereof include a molybdenum (Mo) film, molybdenum as a main component, neodymium, tantalum, indium, copper, palladium, A molybdenum alloy film containing at least one metal selected from niobium (Nb), nickel (Ni), chrome (Cr), magnesium (Mg), tungsten (W), protactinium (Pa), titanium ≪ / RTI > A multilayer film composed of the single film and the metal oxide film; And the like. The metal oxide film contains a ternary or tetragonal oxide composed of a combination of AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr and Ta; x, And can be used as a pixel electrode. Specific examples of the metal oxide film include but are not limited to indium tin oxide (ITO), zinc oxide indium (IZO), zinc tin oxide indium (ITZO), gallium gallium indium zinc oxide (IGZO)
상기 다층막의 보다 구체적인 예로서, 인듐산화막/몰리브덴(Mo) 또는 인듐산화막/몰리브덴 합금(Molybdenum alloy) 등의 이중막, 인듐산화막/몰리브덴(Mo)/인듐산화막 또는 인듐산화막/몰리브덴 합금/인듐산화막 등의 삼중막 등을 들 수 있으나 이에 한정하는 것은 아니다.As a more specific example of the multi-layered film, a double layer film such as indium oxide / molybdenum (Mo) or an indium oxide / molybdenum alloy, indium oxide / molybdenum (Mo) / indium oxide film, indium oxide film / molybdenum alloy / indium oxide film And the like, but the present invention is not limited thereto.
또한, 본 발명은In addition,
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 산화물 반도체층을 형성하는 단계;c) forming an oxide semiconductor layer on the gate insulating layer;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the oxide semiconductor layer; And
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 액정 표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 e) 단계는 기판 상에 몰리브덴(Mo) 함유 금속막을 형성하고, 본 발명의 몰리브덴 함유 금속막의 식각액 조성물로 식각하여 화소전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.Wherein the step (e) comprises forming a molybdenum (Mo) -containing metal film on the substrate, and etching the molybdenum-containing metal film with the etchant composition of the molybdenum-containing metal film of the present invention to form a pixel electrode And a manufacturing method thereof.
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.The array substrate for a liquid crystal display may be a thin film transistor (TFT) array substrate.
상기 몰리브덴 함유 금속막은, 몰리브덴(Mo) 또는 몰리브덴 합금의 단일막, 또는 상기 단일막과 금속 산화물막으로 구성된 다층막일 수 있으며, 상기 몰리브덴 합금은 몰리브덴(Mo)을 주성분으로 하며, 네오디늄(Nd), 탄탈륨(Ta), 인듐(In), 구리(Cu), 팔라듐(Pd), 니오븀(Nb), 니켈(Ni), 크롬(Cr), 마그네슘(Mg), 텅스텐(W), 프로트악티늄(Pa) 및 티타늄(Ti) 등으로부터 선택되는 1종 이상의 금속을 포함하는 합금 형태 등일 수 있다.The molybdenum-containing metal film may be a single film of molybdenum (Mo) or molybdenum alloy, or a multilayer film composed of the single film and the metal oxide film. The molybdenum alloy includes molybdenum (Mo) as a main component and neodymium (Nd) , Tantalum (Ta), indium (In), tantalum (1) selected from the group consisting of Cu, Pd, Nb, Ni, Cr, Mg, W, An alloy type containing more than two kinds of metals, and the like.
상기 금속 산화물막의 구체예로서, 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 또는 산화갈륨아연인듐(IGZO) 등을 들 수 있으나 이에 한정하는 것은 아니다.Specific examples of the metal oxide film include, but are not limited to, indium tin oxide (ITO), zinc oxide indium (IZO), zinc tin oxide indium (ITZO), gallium gallium indium zinc oxide (IGZO)
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않으며, 다양하게 수정 및 변경될 수 있다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.
<< 실시예Example 및 And 비교예Comparative Example > > 식각액Etchant 조성물의 제조 Preparation of composition
하기 표 1에 나타낸 조성 및 함량에, 잔량의 물을 포함하는 실시예 1~10 및 비교예 1~3의 식각액 조성물 6kg을 각각 제조하였다.6 kg of the etching solution compositions of Examples 1 to 10 and Comparative Examples 1 to 3 containing water in the residual amounts were respectively prepared in the compositions and contents shown in Table 1 below.
테트라졸Amino
Tetrazole
히드록실아민N, N-diethyl
Hydroxylamine
주)week)
ABF: 플루오르화수소암모늄ABF: Ammonium hydrogen fluoride
<< 실험예Experimental Example > > 식각액Etchant 조성물의 성능 테스트 Performance testing of the composition
상기 실시예 1~10 및 비교예 1~3의 식각액 조성물의 성능 테스트에는 유리(SiO2)기판 상에 몰리브덴계 금속막 및 금속 산화물막 Mo-Ti/a-ITO 100/400 Å이 증착된 박막 기판을 시편으로 사용하였다. 상기 실시예 1~10 및 비교예 1~3의 식각액 조성물을 사용하여 하기와 같이 성능 테스트를 진행하였다.In the performance tests of the etching solution compositions of Examples 1 to 10 and Comparative Examples 1 to 3, a molybdenum-based metal film and a thin film of metal oxide film Mo-Ti / a-ITO 100/400 Å deposited on a glass (SiO 2 ) The substrate was used as a specimen. Using the etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 3, performance tests were carried out as follows.
실험예Experimental Example 1. 처리 매수에 따른 1. Depending on the number of processed products 편측식각Unilateral etching (side etch) 테스트(side etch) test
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1~10 및 비교예 1~3의 식각액 조성물을 각각 넣고, 식각액 조성물의 온도를 약 35℃ 내외로 설정하여 가온하였다. 총 식각 시간은 식각 온도에 따라 다를 수 있으나, 몰리브덴계 금속막 및 금속 산화물막은 LCD Etching 공정에서 통상 80 내지 100초 정도로 진행하였다.The etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were placed in an experimental apparatus (model name: ETCHER (TFT), SEMES) of a spray-type etch system, and the temperature of the etchant composition was set at about 35 캜, Respectively. The total etching time may vary depending on the etching temperature, but the molybdenum-based metal film and the metal oxide film are generally processed in an LCD etching process for about 80 to 100 seconds.
처리매수에 따른 편측식각 테스트의 경우, 막질에 포함된 Mo-Ti 및 ITO 파우더를 투입하여 진행하였다. 1,000 ppm의 경우 Mo-Ti powder 500 ppm 및 ITO powder 500 ppm, 2,000 ppm의 경우 Mo-Ti powder 1,000 ppm 및 ITO powder 1,000 ppm을 투입하여 실험을 진행하였다.In the unilateral etching test according to the number of treatments, Mo-Ti and ITO powder contained in the film were charged. 500 ppm of Mo-Ti powder, 500 ppm of ITO powder, 1,000 ppm of Mo-Ti powder and 1,000 ppm of ITO powder were added for 1,000 ppm and 2,000 ppm, respectively.
상기 식각 공정에서 식각된 몰리브덴계 금속막 및 금속 산화물막의 처리 매수별 편측식각(side etch) 단면은 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였고, 결과를 하기 표 2에 기재하였다.The etched side surfaces of the etched molybdenum-based metal film and the metal oxide film were examined using SEM (product name: S-4700, manufactured by Hitachi, Ltd.), and the results are shown in Table 2 below .
(Mo-Ti 0 +ITO 0)0 ppm
(Mo-Ti0 + ITO0)
(Mo-Ti 500 +ITO 500)1000ppm
(Mo-Ti 500 + ITO 500)
(Mo-Ti 1000 +ITO 1000)2000 ppm
(Mo-Ti 1000 + ITO 1000)
상기 표 2를 통해 알 수 있듯이, 실시예 1~10의 식각액 조성물은 처리매수 진행 시 편측식각 변화량이 0.04㎛ 이하로 우수한 식각 특성을 나타내었다. As can be seen from Table 2, the etchant compositions of Examples 1 to 10 exhibited excellent etching characteristics with a unilateral etching change of 0.04 탆 or less in the course of the treatment.
반면, 히드록실아민 유도체의 함량이 본 발명의 범위 미만인 비교예 1과 히드록실아민 유도체를 포함하지 않는 비교예 3의 경우, 처리매수 0~2,000 ppm 진행 시 편측식각 변화량이 각각 0.14㎛, 0.27㎛ 수준으로 불량한 것을 확인하였다. 히드록실아민 유도체의 함량이 본 발명의 범위를 초과하는 비교예 2의 경우에는, 초기 편측식각이 감소하였고, 양산 기준인 0.3㎛ 수준을 만족하기 위해서는 식각 공정 시간이 증가하므로 생산량 감소의 문제가 발생한다.On the other hand, in Comparative Example 1 in which the content of the hydroxylamine derivative was less than the range of the present invention and Comparative Example 3 in which the hydroxylamine derivative was not contained, when the number of treatments was 0 to 2,000 ppm, the unilateral etching variations were 0.14 탆 and 0.27 탆 Level. In the case of Comparative Example 2 in which the content of the hydroxylamine derivative exceeded the range of the present invention, the initial unilateral etching was reduced, and in order to satisfy the mass production standard of 0.3 탆, the etching process time was increased, do.
Claims (9)
(A) 과산화수소 5 내지 30 중량%, (B) 불소 화합물 0.1 내지 2 중량%, (C) 아졸계 화합물 0.1 내지 1 중량%, (D) 히드록실아민 유도체 0.1 내지 5 중량%, 및 (E) 잔량의 물을 포함하는 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.With respect to the total weight of the composition,
(C) 0.1 to 1% by weight of an azole-based compound, (D) 0.1 to 5% by weight of a hydroxylamine derivative, and (E) Wherein the molybdenum-containing metal film contains water in a residual amount.
몰리브덴 함유 금속막의 식각액 조성물은 몰리브덴 또는 몰리브덴 합금으로 이루어진 단일막, 또는 상기 단일막과 금속 산화물막으로 구성되는 다층막을 식각할 수 있는 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method according to claim 1,
Wherein the etchant composition of the metal film containing molybdenum is capable of etching a single film made of molybdenum or a molybdenum alloy or a multilayer film composed of the single film and the metal oxide film.
상기 금속 산화물막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로부터 선택되는 1종 이상인 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method of claim 2,
Wherein the metal oxide film is at least one selected from indium tin oxide (ITO), zinc indium oxide (IZO), zinc tin oxide indium (ITZO), and gallium oxide zinc indium (IGZO).
상기 단일막과 금속 산화물막으로 구성되는 다층막은 인듐산화막/몰리브덴, 인듐산화막/몰리브덴 합금, 인듐산화막/몰리브덴/인듐산화막 또는 인듐산화막/몰리브덴 합금/인듐산화막인 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method of claim 2,
Wherein the multilayer film composed of the single film and the metal oxide film is an indium oxide film / molybdenum film, an indium oxide film / molybdenum alloy film, an indium oxide film / molybdenum / indium oxide film, or an indium oxide film / molybdenum alloy / indium oxide film. .
상기 몰리브덴 합금은 몰리브덴(Mo) 및, 네오디늄(Nd), 탄탈륨(Ta), 인듐(In), 구리(Cu), 팔라듐(Pd), 니오븀(Nb), 니켈(Ni), 크롬(Cr), 마그네슘(Mg), 텅스텐(W), 프로트악티늄(Pa) 및 티타늄(Ti)으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method of claim 2,
The molybdenum alloy includes at least one of molybdenum (Mo), neodymium (Nd), tantalum (Ta), indium (In), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni) , Magnesium (Mg), tungsten (W), protactinium (Pa), and titanium (Ti).
상기 불소 화합물은 불화수소(HF), 불화나트륨(NaF), 불화암모늄(NH4F), 플루오르화붕산염(NH4BF4), 플루오르화수소암모늄(NH4FHF), 플루오르화칼륨(KF), 플루오르화수소칼륨(KHF2), 불화알루미늄(AlF3) 및 테트라플루오로붕산(HBF4)으로부터 선택되는 1종 이상인 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method according to claim 1,
The fluorine compound is selected from the group consisting of hydrogen fluoride (HF), sodium fluoride (NaF), ammonium fluoride (NH 4 F), fluoroborate (NH 4 BF 4 ) Ammonium hydrogen fluoride (NH 4 FHF), Wherein at least one selected from the group consisting of potassium fluoride (KF), potassium fluoride (KHF 2 ), aluminum fluoride (AlF 3 ) and tetrafluoroboric acid (HBF 4 ) is used.
상기 아졸계 화합물은 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 티아졸(thiazole)계 및 이소티아졸(isothiazole)계 화합물로부터 선택되는 1종 이상인 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물.The method according to claim 1,
The azole compound may be at least one selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, tetrazole, pentazole, oxazole, ), An isoxazole-based, a thiazole-based, and an isothiazole-based compound. The etching solution composition of the metal film containing molybdenum according to claim 1,
상기 히드록실아민 유도체는 히드록실아민, 히드록실아민-O-설폰산, 히드록실아민 설페이트, N,N-다이에틸히드록실아민, N-메틸히드록실아민, N,N-다이벤질히드록실아민 및 N,N,O-트리아세틸히드록실아민으로부터 선택되는 1종 이상인 것을 특징으로 하는 몰리브덴 함유 금속막의 식각액 조성물. The method according to claim 1,
Wherein the hydroxylamine derivative is selected from the group consisting of hydroxylamine, hydroxylamine-O-sulfonic acid, hydroxylamine sulfate, N, N-diethylhydroxylamine, N-methylhydroxylamine, N, N- dibenzylhydroxylamine And at least one selected from N, N, O-triacetylhydroxylamine.
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 e) 단계는 기판 상에 몰리브덴 함유 금속막을 형성하고, 청구항 1의 몰리브덴 함유 금속막의 식각액 조성물로 식각하여 화소전극을 형성하는 단계를 포함하는 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 an oxide semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the oxide semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
Wherein the step (e) comprises forming a molybdenum-containing metal film on the substrate, and etching the molybdenum-containing metal film of the molybdenum-containing metal film of claim 1 to form a pixel electrode.
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