KR101702129B1 - Manufacturing method of an array substrate for liquid crystal display - Google Patents
Manufacturing method of an array substrate for liquid crystal display Download PDFInfo
- Publication number
- KR101702129B1 KR101702129B1 KR1020100047623A KR20100047623A KR101702129B1 KR 101702129 B1 KR101702129 B1 KR 101702129B1 KR 1020100047623 A KR1020100047623 A KR 1020100047623A KR 20100047623 A KR20100047623 A KR 20100047623A KR 101702129 B1 KR101702129 B1 KR 101702129B1
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- South Korea
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- film
- metal film
- molybdenum
- copper
- indium
- Prior art date
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- 239000000758 substrate Substances 0.000 title claims abstract description 39
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 120
- 239000002184 metal Substances 0.000 claims abstract description 120
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- 239000010949 copper Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 37
- 229910052738 indium Inorganic materials 0.000 claims abstract description 36
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011733 molybdenum Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004065 semiconductor Substances 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 267
- 238000005530 etching Methods 0.000 claims description 79
- 239000000203 mixture Substances 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 150000001805 chlorine compounds Chemical class 0.000 claims description 11
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 11
- -1 cyclic amine compound Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
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- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- ULIDRMKBVYYVIQ-UHFFFAOYSA-N 1-phenyltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC=C1 ULIDRMKBVYYVIQ-UHFFFAOYSA-N 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
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- 239000000956 alloy Substances 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 36
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 36
- 229910003437 indium oxide Inorganic materials 0.000 description 16
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
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- 230000000052 comparative effect Effects 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
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- 239000011247 coating layer Substances 0.000 description 6
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- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- OWFALUNDSZEADU-PBHICJAKSA-N n-[(2r,4s)-2-butyl-4-[(2-fluorophenyl)carbamoylamino]-5-methyl-3-oxohexyl]-n-hydroxyformamide Chemical compound CCCC[C@H](CN(O)C=O)C(=O)[C@H](C(C)C)NC(=O)NC1=CC=CC=C1F OWFALUNDSZEADU-PBHICJAKSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
-
- 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
- G02F1/133345—Insulating layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Thin Film Transistor (AREA)
- Weting (AREA)
Abstract
본 발명은, (a)기판 상에 게이트 전극을 형성하는 단계; (b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; (c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; (d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 (e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 TFT 어레이 기판의 제조방법에 있어서; 상기 (a), (d) 및 (e)단계 중 하나 이상의 단계가 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하고, 상기 금속막을 식각액 조성물로 식각하여 각각의 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.(A) forming a gate electrode on a substrate; (b) forming a gate insulating layer on the substrate including the gate electrode; (c) forming a semiconductor layer on the gate insulating layer; (d) forming source and drain electrodes on the semiconductor layer; And (e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of: Wherein at least one of the steps (a), (d), and (e) forms a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film, And forming a plurality of electrodes on the substrate.
Description
본 발명은 액정표시장치용 어레이 기판의 제조방법; 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각액 조성물; 및 상기 식각액 조성물을 사용하는 금속막의 식각방법에 관한 것이다.The present invention relates to a method of manufacturing an array substrate for a liquid crystal display device; An etchant composition of a metal film comprising at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film; And a method of etching a metal film using the etchant composition.
평판디스플레이의 화상 구현을 위해서는 TFT(Thin Film Transistor) 어레이에 투명 화소전극, 게이트전극, 소스전극 및 드레인 전극이 사용된다. 통상, 화소전극으로는 인듐을 주성분으로 하는 투명전도막 및 몰리브텐-티타늄 합금막이 사용되고 있다. 또한, 게이트 전극, 소스전극 및 드레인 전극으로는 Cr, Cu, Mo, Ti, Al 등을 주성분으로 단일막 또는 다중막이 사용되고 있으나, TFT-LCD의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서, 저저항 금속막으로서 구리막, 구리 몰리브덴막, 구리-질화물/몰리브덴-티타늄 합금막 등의 구리계 금속막이 많이 사용되고 있다.A transparent pixel electrode, a gate electrode, a source electrode, and a drain electrode are used in a TFT (Thin Film Transistor) array for image implementation of a flat panel display. Usually, a transparent conductive film and a molybdenum-titanium alloy film containing indium as a main component are used as the pixel electrode. As a gate electrode, a source electrode, and a drain electrode, a single film or a multilayer film mainly composed of Cr, Cu, Mo, Ti, and Al is used, but the RC signal delay required for the enlargement of the TFT- A copper-based metal film such as a copper film, a copper molybdenum film, and a copper-nitride / molybdenum-titanium alloy film is often used as a low resistance metal film.
최근에는 생산공정을 단순화하여 생산량을 증가시키기 위하여 TFT-LCD에 사용되는 상기와 같은 다양한 금속막질을 일괄식각할 수 있는 식각액에 대한 관심이 증대되고 있다. 특히, 구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막 및 인듐계 산화막을 통합적으로 일괄식각할 수 있는 식각액 조성물은 TFT-LCD의 생산성 향상에 크게 기여할 것으로 기대되고 있다.In recent years, there has been an increasing interest in etchants that can batch etch various metal films used in TFT-LCDs in order to simplify the production process and increase the throughput. Particularly, it is expected that the etchant composition capable of integrally collectively etching the copper-nitride / molybdenum-titanium alloy film, the molybdenum-titanium alloy film, and the indium oxide film contributes to the improvement of the productivity of the TFT-LCD.
그러나, 현재 사용되고 있는 식각액 조성물은 구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막 및 인듐계 산화막을 일괄식각할 수는 있으나, 구리-질화물/몰리브덴-티타늄의 식각 프로파일이 불량한 문제를 야기하므로 기대에 못 미치고 있다. However, currently used etchant compositions can etch a copper-nitride / molybdenum-titanium alloy film, a molybdenum-titanium alloy film and an indium-based oxide film at a time, but the etchant profile of copper-nitride / molybdenum- So it is not expected.
그러므로, 구리-질화물/몰리브덴-티타늄 합금막에 대하여 적절한 부식속도와 양호한 식각 프로파일을 제공하면서도, 몰리브덴-티타늄 합금막 및 인듐계 산화막도 효과적으로 식각할 수 있는 식각액 조성물의 개발이 요구되고 있다.
Therefore, there is a need for the development of etchant compositions that can effectively etch molybdenum-titanium alloy films and indium-based oxide films while providing appropriate corrosion rates and good etch profiles for copper-nitride / molybdenum-titanium alloy films.
본 발명은, 액정표시장치용 어레이 기판의 전극으로 병행하여 사용되고 있는, 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막, 즉 단일막 또는 다층막을 효과적으로 일괄식각 할 수 있는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention relates to a metal film including a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film, that is, a single film or a multilayer film, which is used concurrently as an electrode of an array substrate for a liquid crystal display It is an object of the present invention to provide an etchant composition capable of batch etching.
또한, 본 발명은 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막의 각각의 막질에 대한 식각특성이 우수하여 박막트랜지스터-액정표시소자(TFT-LCD)의 구동 특성을 향상 시키며, 기판의 크기가 커도 식각 균일성이 유지되는 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention has an excellent etching property for each film quality of a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film to improve driving characteristics of a thin film transistor-liquid crystal display device (TFT-LCD) And an etchant uniformity is maintained even when the etching rate is large.
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, 조성물 총 중량에 대하여, The present invention relates to a composition,
A)과산화수소(H2O2) 5 내지 30중량%, A) 5 to 30% by weight of hydrogen peroxide (H 2 O 2 )
B)함불소화합물 0.01 내지 5중량%, B) 0.01 to 5% by weight of a fluorine compound,
C)수용성 시클릭아민 화합물 0.05 내지 8중량%, C) 0.05 to 8% by weight of a water-soluble cyclic amine compound,
D)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.05 내지 8중량%, D) 0.05 to 8% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule,
E)함염소 화합물 0.01 내지 8중량%, 및 E) 0.01 to 8% by weight of a chlorine compound, and
F)잔량의 물을 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각액 조성물을 제공한다.F) at least one film selected from the group consisting of a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film including a residual amount of water.
또한, 본 발명은,Further, according to the present invention,
a)기판 상에 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하는 단계;a) forming a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film on a substrate;
b)상기 a)단계에서 형성된 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및b) selectively leaving a photoreactive material on the metal film formed in the step a); And
c)본 발명의 식각액 조성물을 사용하여 상기 b)단계에서 처리된 금속막을 식각하는 단계를 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각방법을 제공한다.c) etching the metal film comprising at least one film selected from the group consisting of a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film including a step of etching the metal film treated in the step b) ≪ / RTI >
또한, 본 발명은In addition,
(a)기판 상에 게이트 전극을 형성하는 단계; (b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; (c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; (d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 (e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 TFT 어레이 기판의 제조방법에 있어서, (a) forming a gate electrode on a substrate; (b) forming a gate insulating layer on the substrate including the gate electrode; (c) forming a semiconductor layer on the gate insulating layer; (d) forming source and drain electrodes on the semiconductor layer; And (e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
상기 (a), (d) 및 (e)단계 중 하나 이상의 단계가 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하고, 상기 금속막을 본 발명의 식각액 조성물로 식각하여 각각의 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.Wherein at least one of the steps (a), (d), and (e) forms a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film, And etching each of the electrodes with an etchant composition to form an array of electrodes for the liquid crystal display device.
또한, 본 발명은, 본 발명의 식각액 조성물을 사용하여 식각된 게이트 전극, 소스 및 드레인 전극, 및 화소전극 중 하나 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a liquid crystal display comprising at least one of a gate electrode, a source and a drain electrode, and a pixel electrode etched using the etchant composition of the present invention.
본 발명의 식각액 조성물은 액정표시장치용 어레이 기판에 사용되고 있는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각 공정시, 이들을 효과적으로 일괄식각할 수 있기 때문에 식각공정의 효율성 및 생산성을 크게 향상시킨다. , The etching composition of the present invention can effectively etch a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film used for an array substrate for a liquid crystal display device Which greatly improves the efficiency and productivity of the etching process. ,
또한, 본 발명의 식각액 조성물은 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막의 각각의 막질에 대한 식각특성이 우수하여, 박막트랜지스터-액정표시소자(TFT-LCD)의 구동 특성을 향상 시키며, 기판의 크기가 커도 식각 균일성을 유지하므로 박막트랜지스터-액정표시소자(TFT-LCD)의 품질향상 및 생산성 향상에 크게 기여한다.
In addition, the etching composition of the present invention has excellent etching properties for each of the copper-based metal film, the molybdenum-based metal film and the indium-based oxide film to improve the driving characteristics of the thin film transistor-liquid crystal display device (TFT-LCD) , The etching uniformity is maintained even if the size of the substrate is large, which contributes greatly to the improvement of quality and productivity of the thin film transistor-liquid crystal display device (TFT-LCD).
도1은 본 발명의 실시예1의 식각액 조성물로 식각한 구리-질화물/몰리브덴-티타늄 합금막의 표면에 대한 SEM 사진이다.
도2는 본 발명의 실시예1의 식각액 조성물로 식각한 몰리브덴-티타늄 합금막의 표면에 대한 SEM 사진이다.
도3은 본 발명의 실시예1의 식각액 조성물로 식각한 인듐주석산화막(ITO)의 표면에 대한 SEM 사진이다.
도4는 본 발명의 비교예1의 식각액 조성물로 식각한 구리-질화물/몰리브덴-티타늄 합금막의 표면에 대한 SEM 사진이다.
도5는 본 발명의 비교예1의 식각액 조성물로 식각한 몰리브덴-티타늄 합금막의 표면에 대한 SEM 사진이다.
도6은 본 발명의 비교예1의 식각액 조성물로 식각한 인듐주석산화막(ITO)의 표면에 대한 SEM 사진이다.
도7은 본 발명의 비교예2의 식각액 조성물로 식각한 구리-질화물/몰리브덴-티타늄 합금막의 식각 프로파일을 촬영한 SEM 사진이다.
도8은 본 발명의 비교예3의 식각액 조성물로 식각한 인듐주석산화막(ITO)의 표면에 대한 SEM 사진이다. 1 is a SEM photograph of the surface of a copper-nitride / molybdenum-titanium alloy film etched with the etchant composition of Example 1 of the present invention.
2 is a SEM photograph of the surface of a molybdenum-titanium alloy film etched with the etchant composition of Example 1 of the present invention.
3 is a SEM photograph of the surface of an indium tin oxide film (ITO) etched with the etchant composition of Example 1 of the present invention.
4 is a SEM photograph of the surface of a copper-nitride / molybdenum-titanium alloy film etched with the etchant composition of Comparative Example 1 of the present invention.
5 is a SEM photograph of the surface of a molybdenum-titanium alloy film etched with the etchant composition of Comparative Example 1 of the present invention.
6 is a SEM photograph of the surface of an indium tin oxide film (ITO) etched with the etchant composition of Comparative Example 1 of the present invention.
7 is an SEM photograph of an etched profile of a copper-nitride / molybdenum-titanium alloy film etched with the etchant composition of Comparative Example 2 of the present invention.
8 is an SEM photograph of the surface of an indium tin oxide film (ITO) etched with the etchant composition of Comparative Example 3 of the present invention.
본 발명은 조성물 총 중량에 대하여, A)과산화수소(H2O2) 5 내지 30중량%, B)함불소화합물 0.01 내지 5중량%, C)수용성 시클릭아민 화합물 0.05 내지 8중량%, D)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.05 내지 8 중량%, E)함염소 화합물 0.01 내지 8 중량% 및 F)잔량의 물을 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각액 조성물에 관한 것이다.(D) 5 to 30% by weight of hydrogen peroxide (H 2 O 2 ), (B) 0.01 to 5% by weight of a fluorine compound, (C) 0.05 to 8% by weight of a water-soluble cyclic amine compound, 0.05 to 8% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, E) 0.01 to 8% by weight of a chlorine compound, and F) a water of a remaining amount, a molybdenum-based metal film and an indium-based oxide film To an etchant composition of a metal film comprising at least one selected film.
본 발명의 식각액 조성물은, 박막트랜지스터-액정표시소자(TFT-LCD)에 사용되는 구리계 금속막, 몰리브덴계 금속막, 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막, 즉 단일막 또는 다층막을 효율적으로 일괄식각할 수 있는 특징을 갖는다. 예컨대, 본 발명의 식각액 조성물은 구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막 인듐계 산화막 등을 효율적으로 일괄식각할 수 있다.The etchant composition of the present invention is a metal film containing at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film used for a thin film transistor-liquid crystal display device (TFT-LCD) So that the multilayered film can be efficiently etched in batch. For example, the etchant composition of the present invention can effectively etch a copper-nitride / molybdenum-titanium alloy film, a molybdenum-titanium alloy film indium oxide film, and the like efficiently.
특히, 종래에 인듐계 산화막 식각액으로 사용되고 있는 옥살산 계열의 식각액에 비해, 인듐계 산화막의 식각 속도가 빠르며 인듐계 산화막의 잔사도 발생시키지 않으므로, 인듐계 산화막의 식각액으로서도 병행 사용이 가능하므로 공정 단순화를 극대화 시킬 수 있다. 또한, 옥살산 계열의 인듐계 산화막 식각액의 문제점인 0℃ 이하에서의 옥살산의 결정화에 대한 염려가 없으며, 염산 계열의 식각액에서 나타나는 하부 금속막에 대한 영향도 없으므로, TFT-LCD의 제조공정에서 효과적으로 생산성을 높이는데 기여할 수 있다.
In particular, since the etching rate of the indium oxide film is fast and the residue of the indium oxide film is not generated as compared with the oxalic acid type etching solution which has been conventionally used as the etching solution of the indium oxide film, it is possible to use the indium oxide film as an etchant in parallel. Can be maximized. In addition, there is no concern about the crystallization of oxalic acid at a temperature of 0 ° C or lower, which is a problem of the oxalic acid based indium oxide film etchant, and there is no influence on the underlying metal film in the hydrochloric acid based etchant. Can contribute to heightening.
본 발명의 식각액 조성물에서 구리계 금속막은 구리를 주성분으로 하는 금속막으로서, 순수 구리막 및, 구리 산화막, 구리 질화막 등을 포함하는 구리합금막을 포함한다. In the etchant composition of the present invention, the copper-based metal film is a metal film containing copper as a main component, and includes a pure copper film and a copper alloy film including a copper oxide film, a copper nitride film and the like.
몰리브덴계 금속막은 몰리브데늄을 주성분으로 하는 금속막으로서, 순수 몰리브데늄막 및 몰리브데늄 합금막을 포함하며, 상기 몰리브데늄 합금막은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In) 등으로 이루어진 군으로부터 선택되는 1종 이상의 금속과 몰리브데늄의 합금막을 의미한다. The molybdenum-based metal film is a metal film containing molybdenum as a main component and includes a pure molybdenum alloy film and a molybdenum alloy film. The molybdenum alloy film is made of, for example, titanium (Ti), tantalum (Ta) ), Nickel (Ni), neodymium (Nd), indium (In), and the like, and an alloy film of molybdenum and at least one metal.
인듐계 산화막 인듐을 주성분으로 하는 금속막으로서, 인듐아연산화막(IZO), 인듐주석산화막(ITO), 비정질 인듐주석산화막(a-ITO) 등을 포함한다.Indium zinc oxide (IZO), indium tin oxide (ITO), amorphous indium tin oxide (a-ITO), indium tin oxide And the like.
본 발명에서 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막은 그러한 금속막을 포함하는 단일막 또는 다층막을 포함한다. 상기 단일막의 대표적인 예로는 인듐계 산화막, 몰리브덴-티타늄 합금막 등을 들 수 있으며, 다층막의 대표적인 예로는 구리-질화물/몰리브덴-티타늄 합금막의 2중막 등을 들 수 있다.
In the present invention, a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film includes a single film or a multilayer film including such a metal film. Representative examples of the single film include indium oxide film and molybdenum-titanium alloy film. Representative examples of the multi-layer film include a double-layer film of a copper-nitride / molybdenum-titanium alloy film.
본 발명에서 사용되는 H2O2, 함불소 화합물, 수용성 시클릭아민 화합물, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 및 함염소 화합물은 통상적으로 공지된 방법에 따라 제조가능하며, 특히 반도체 공정용 순도를 가지는 것이 바람직하다.H 2 O 2, the fluorinated compound, a water-soluble cyclic amine compounds, water-soluble compounds, and also the chlorine compounds having a nitrogen atom and a carboxyl group in one molecule can be prepared according to a known method and, in particular semiconductor process used in the present invention It is preferable to have purity for use.
본 발명의 식각액 조성물에서 A)H2O2는 구리계 금속막 및 질화물, 몰리브덴계 금속막을 포함하는 금속막을 식각하는 주 산화제로 된다. In the etching solution composition of the present invention, A) H 2 O 2 is a main oxidizing agent for etching a metal film including a copper-based metal film, a nitride film, and a molybdenum-based metal film.
상기 H2O2는 조성물의 총 중량에 대하여 5 내지 30중량%로 포함되는 것이 바람직하며, 10 내지 25중량%가 더욱 바람직하다. 5중량% 미만으로 포함될 경우, 식각력이 부족하여 충분한 식각이 이루어지지 않을 수 있으며, 30중량%를 초과할 경우, 식각속도가 전체적으로 빨라지기 때문에 공정 컨트롤이 어렵다.The amount of the H 2 O 2 is preferably 5 to 30% by weight, more preferably 10 to 25% by weight based on the total weight of the composition. If it is contained in an amount of less than 5% by weight, sufficient etching may not be performed due to insufficient etching force, and if it exceeds 30% by weight, process control is difficult because the etching speed is entirely accelerated.
본 발명의 식각액 조성물에서 B)함불소 화합물은 해리되어 F 이온을 낼 수 있는 화합물을 의미하며, 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각 속도에 영향을 주는 성분으로서 식각 속도를 빠르게 함과 동시에 식각 잔사를 제거하는 역할을 한다. 함불소 화합물의 구체적인 예로는, HF, NaF, NH4F, NH4BF4, NH4FHF, KF, KHF2, AlF3, 및 HBF4 등을 들 수 있으며, 이들은 1종 또는 2종 이상을 함께 사용될 수 있다. 이들 중에서 NH4FHF가 바람직하게 사용된다.The B) fluorine compound in the etching solution composition of the present invention refers to a compound capable of releasing F ions and capable of dissociating F ions. The etching solution of the metal film containing at least one film selected from a copper-based metal film, a molybdenum- As a component that affects the speed, it accelerates the etching rate and removes the etching residue. Specific examples of fluorine compounds include HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, KF, KHF 2 , AlF 3 and HBF 4 , Can be used together. Of these, NH 4 FHF is preferably used.
상기 함불소 화합물은 조성물의 총 중량에 대하여 0.01 내지 5중량%로 포함되는 것이 바람직하며, 0.1 내지 2중량%가 더욱 바람직하다. 0.01중량% 미만으로 포함되면 식각 속도가 느려지게 되고 식각 잔사가 남을 수 있으며, 5중량%를 초과하여 포함되는 경우, Etch 성능의 향상 효과는 없으면서 하부 패시베이션(Passivation)층 및 하부막 금속배선의 손상이 크게 발생할 수 있다.The content of the fluorinated compound is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight based on the total weight of the composition. If it is contained in an amount of less than 0.01% by weight, the etching rate may be slowed down and etch residues may remain. If it is contained in an amount exceeding 5% by weight, damage to the passivation layer and the underlying metal wiring .
본 발명의 식각액 조성물에서 C)수용성 시클릭아민 화합물은 구리계 금속막의 에칭 속도를 조절해 준다. 구체적인 예로는, 벤조트리아졸, 아미노테트라졸(aminotetrazole)계 화합물, 이미다졸(imidazole), 인돌(indole), 푸린(purine), 피라졸(pyrazole), 피리딘(pyridine), 피리미딘(pyrimidine), 피롤(pyrrole), 피롤리딘(pyrrolidine), 피롤린(pyrroline) 등을 들 수 있으며, 이들은 1종 또는 2종 이상이 함께 사용될 수 있다. 특히, 아미노테트라졸계 화합물이 바람직하게 사용될 수 있으며, 아미노테트라졸계 화합물의 구체적인 예로는, 아미노테트라졸, 5-아미노-1-페닐테트라졸, 5-아미노-1-(1-나프틸)테트라졸, 1-메틸-5-아미노테트라졸, 1,5-디아미노테트라졸 등을 들 수 있다. 이들 중에서도, 아미노테트라졸이 더욱 바람직하다.The C) water-soluble cyclic amine compound in the etchant composition of the present invention controls the etching rate of the copper-based metal film. Specific examples thereof include benzotriazole, aminotetrazole-based compounds, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, Pyrrole, pyrrolidine, pyrroline and the like. These may be used singly or in combination of two or more. Particularly, an aminotetrazole-based compound can be preferably used, and specific examples of the aminotetrazole-based compound include aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1- (1-naphthyl) , 1-methyl-5-aminotetrazole, and 1,5-diaminotetrazole. Of these, aminotetrazole is more preferable.
상기 수용성 시클릭아민 화합물은 조성물의 총 중량에 대하여 0.05 내지 8중량% 포함되는 것이 바람직하며, 0.1 내지 5중량%가 더욱 바람직하다. 0.05중량% 미만으로 포함되는 경우, 구리계 금속막의 에칭 속도가 빨라져서 제어가 어렵고, 8중량%를 초과하여 포함되는 경우에는 다층막에 대한 에칭 속도가 느려져서 CD bias를 제어하기는 용이하지만 몰리브덴-티타늄 합금막에 대한 식각 속도가 저하되어 몰리브덴-티타늄 합금 잔사가 발생할 수 있다.The amount of the water-soluble cyclic amine compound is preferably 0.05 to 8 wt%, more preferably 0.1 to 5 wt%, based on the total weight of the composition. If it is contained in an amount of less than 0.05% by weight, the etching rate of the copper-based metal film is increased, which is difficult to control. If the content exceeds 8% by weight, the etching rate for the multilayer film is slowed to control the CD bias. The etch rate for the film may be lowered and molybdenum-titanium alloy residues may occur.
본 발명의 식각액 조성물에 포함되는 D)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 식각액 조성물의 보관 시 발생할 수 있는 과산화수소수의 자체 분해 반응을 막아주고 많은 수의 기판을 식각할 시에 식각 특성이 변하는 것을 방지한다. 일반적으로 과산화수소수를 사용하는 식각액 조성물의 경우 보관시 과산화수소수가 자체 분해하여 그 보관기간이 길지가 못하고 용기가 폭발할 수 있는 위험요소까지 갖추고 있다. 그러나 상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물이 포함될 경우 과산화수소수의 분해 속도가 10배 가까이 줄어들어 보관기간 및 안정성 확보에 유리하다. 특히 구리층의 경우 식각액 조성물 내에 구리 이온이 다량 잔존할 경우에 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 많이 발생할 수 있으나 이 화합물을 첨가하였을 경우 이런 현상을 막을 수 있다.The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the etching liquid composition of the present invention prevents the self-decomposition reaction of the hydrogen peroxide water which may occur in the storage of the etching solution composition, and when etching a large number of substrates, . In general, the etching solution composition using hydrogen peroxide water has a risk that the storage of the hydrogen peroxide is self-decomposed during storage and the container can explode because the storage period is not long. However, when a water-soluble compound having a nitrogen atom and a carboxyl group is included in the molecule, the decomposition rate of the hydrogen peroxide solution is reduced to about 10 times, which is advantageous for securing the storage period and stability. Particularly, in the case of a copper layer, when a large amount of copper ions remain in the etchant composition, a passivation film is formed, which is then oxidized to black and then etched. However, such a phenomenon can be prevented by adding this compound .
상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물로는 알라닌(alanine), 아미노부티르산(aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것이 사용될 수 있다. Examples of the water-soluble compound having a nitrogen atom and a carboxyl group in the molecule include alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid, acid and sarcosine may be used alone or in combination of two or more.
본 발명의 식각액 조성물에서 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 조성물 총 중량에 대하여 0.05내지 8 중량%로 포함되는 것이 바람직하며, 0.1 내지 5중량%가 더욱 바람직하다. 0.05중량% 미만으로 포함되는 경우, 과산화수소의 자체 분해의 억제효과가 미미하며, pH의 조절 능력도 부족해져서 pH를, 구리계 금속막이 식각되기 쉬운 환경인, 0.5 내지 4.5정도로 유지하기도 어려워진다. 또한, 8중량%를 초과할 경우, 구리계 금속막의 식각속도가 빨라지고 몰리브덴 또는 몰리브덴합금의 식각속도가 느려짐에 따라 구리계 금속막의 씨디로스(CD Loss)가 커지게 되고 몰리브덴 또는 몰리브덴합금의 잔사가 발생할 가능성이 커지게 된다.In the etchant composition of the present invention, the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is preferably contained in an amount of 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the composition. If it is contained in an amount of less than 0.05% by weight, the effect of inhibiting the self-decomposition of hydrogen peroxide is insignificant and the pH control ability becomes insufficient, so that it becomes difficult to maintain the pH at 0.5 to 4.5 which is an environment in which the copper- If it exceeds 8% by weight, the etching rate of the copper-based metal film becomes faster and the etching rate of the molybdenum or molybdenum alloy becomes slower, so that the CD loss of the copper-based metal film becomes larger and the residue of the molybdenum or molybdenum alloy becomes larger The probability of occurrence is increased.
본 발명의 식각액 조성물에서 E)함염소 화합물은 해리되어 염소 이온을 낼 수 있는 화합물을 의미하며, 구리계 금속막을 식각하는 보조 산화제 역할을 한다. 함염소 화합물로는 HCl, NaCl, KCl, NH4Cl 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. The E) chlorine compound in the etching solution composition of the present invention refers to a compound capable of dissociating to give chloride ion, and serves as a co-oxidant for etching the copper-based metal film. Examples of the chlorine compound include HCl, NaCl, KCl and NH 4 Cl, and these may be used singly or in combination of two or more.
상기 함염소 화합물은 조성물 총 중량에 대하여 0.01 내지 8 중량%가 바람직하며, 0.01 내지 5중량%가 더욱 바람직하다. 0.01중량% 미만으로 포함되는 경우에는 구리계 금속막의 식각속도가 저하되어 식각 프로파일이 불량하게 되며, 8중량%를 초과하게 되면 과식각이 발생하여 배선이 소실 될 수 있다. The amount of the chlorine compound is preferably 0.01 to 8% by weight, more preferably 0.01 to 5% by weight based on the total weight of the composition. If it is less than 0.01% by weight, the etching rate of the copper-based metal film is lowered and the etching profile becomes poor. If it exceeds 8% by weight, an excessive angle may occur and the wiring may be lost.
본 발명의 식각액 조성물에서 물은 특별히 한정되는 것은 아니나, 탈이온수를 사용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 물의 비저항 값이 18㏁/㎝ 이상인 탈이온수를 사용하는 것이 더욱 바람직하다.In the etchant composition of the present invention, water is not particularly limited, but it is preferable to use deionized water. It is more preferable to use deionized water having a resistivity value of water of 18 M? / Cm or more to show the degree of removal of ions in water .
본 발명의 식각액 조성물은 또한, 식각 성능을 향상시키기 위하여 이 분야에 공지되어 있는 임의의 첨가제를 더 포함할 수 있다. 이러한 첨가제는 조성물의 총 중량에 대해 0.0001 내지 0.01중량%로 포함될 수 있다.The etchant compositions of the present invention may further comprise any additive known in the art for improving etch performance. Such an additive may be included in an amount of 0.0001 to 0.01% by weight based on the total weight of the composition.
상기 첨가제로는 계면 활성제, 금속이온 봉쇄제, 및 부식 방지제 등을 사용할 수 있다. 계면 활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 이러한 계면활성제로는 식각액에 견딜 수 있고 상용성이 있는 형태의 것이 바람직하며, 예컨대, 임의의 음이온성, 양이온성, 양쪽 이온성 또는 비이온성 계면 활성제 등을 들 수 있다. 또한, 계면활성제로서 불소계 계면활성제를 사용할 수도 있다.
As the additive, a surfactant, a sequestering agent, and a corrosion inhibitor may be used. Surfactants decrease the surface tension and increase the uniformity of etching. Such surfactants are preferably those which are resistant to an etching solution and have compatibility with each other, and examples thereof include any anionic, cationic, amphoteric or nonionic surfactants and the like. Further, a fluorine-based surfactant may be used as a surfactant.
또한, 본 발명은,Further, according to the present invention,
a)기판 상에 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하는 단계;a) forming a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film on a substrate;
b)상기 a)단계에서 형성된 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및b) selectively leaving a photoreactive material on the metal film formed in the step a); And
c)본 발명의 식각액 조성물을 사용하여 상기 b)단계에서 처리된 금속막을 식각하는 단계를 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각방법에 관한 것이다.
c) etching the metal film comprising at least one film selected from the group consisting of a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film including a step of etching the metal film treated in the step b) ≪ / RTI >
상기 (a)단계는, (a1)기판을 제조하는 단계 및 (a2)상기 기판 상에 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하는 단계를 포함할 수 있다. 물론 기판 상에 통상적인 세정공정을 수행하고, 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 증착할 수도 있다. Wherein the step (a) comprises the steps of: (a1) fabricating a substrate; and (a2) forming a metal film on the substrate, the metal film including at least one film selected from a copper-based metal film, a molybdenum- . ≪ / RTI > Of course, a conventional cleaning process may be performed on the substrate, and a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film may be deposited.
상기 (a1)단계에서 기판은 유리기판 또는 석영기판일 수 있으며, 유리기판이 바람직하다. In the step (a1), the substrate may be a glass substrate or a quartz substrate, and preferably a glass substrate.
상기 (a2)단계에서 기판 상에 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하는 방법으로는 이 분야에서 공지된 다양한 방법을 사용할 수 있으며, 구체적인 예로는 스퍼터링법에 의해 금속막을 기판 상에 증착하는 방법을 들 수 있다. 막의 두께는 대략 200~500Å이 되도록 증착시킬 수 있다.The method for forming a metal film including at least one film selected from the group consisting of a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film on the substrate in the step (a2) A specific example is a method of depositing a metal film on a substrate by a sputtering method. The thickness of the film may be approximately 200 to 500 ANGSTROM.
상기 (a)단계는 상기 기판과 상기 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막 사이에 액정표시장치용 구조물을 형성하는 단계를 더 포함할 수도 있다.The step (a) may further include forming a structure for a liquid crystal display device between the substrate and a metal film including at least one film selected from the copper-based metal film, the molybdenum-based metal film, and the indium-based oxide film have.
상기에서 액정표시장치용 구조물은 화학기상증착 등의 방법에 의한 유기 절연막, 스퍼터링 등의 방법에 의한 도전성 물질, 및 비정질 또는 다결정성의 실리콘막과 같은 반도체막 등을 의미하며, 포토공정, 식각공정 등으로 제조한 구조물일 수도 있다.The structure for a liquid crystal display in the above description means a semiconductor film such as an amorphous or polycrystalline silicon film, a conductive material by an organic insulating film, a sputtering method or the like by chemical vapor deposition or the like. .
상기 (b)단계는, (b1) a)단계에서 형성된 금속막상에 광반응물질을 도포하여 광반응물질 코팅층을 형성하는 단계; (b2)포토마스크를 통해 상기 광반응물질 코팅층을 선택적으로 노광하는 단계; 및 (b3)상기 광반응물질 코팅층의 전체영역 중 일정 영역이 a)단계에서 형성된 금속막 상에 남도록, 현상액을 이용하여 상기 광반응물질 코팅층을 현상하는 단계를 포함할 수 있다.In the step (b), a photoreactive material coating layer is formed by applying a photoreactive material on the metal film formed in the step (b1). (b2) selectively exposing the photoreactive material coating layer through a photomask; And (b3) developing the photoreactive material coating layer using a developing solution so that a certain region of the entire region of the photoreactive material coating layer remains on the metal film formed in the step a).
상기 (b1)단계에서는, 스핀코터(spin coater)를 이용하여 a)단계에서 형성된 금속막에 광반응물질을 도포할 수 있으며, 그 두께는 1㎛ 내외인 것이 바람직하다. 여기서, 스핀코터 이외에도 슬릿코터를 이용할 수도 있으며, 또한 스핀코터와 슬릿코터를 혼용하여 사용할 수도 있다. 상기 도포공정은 에싱(ashing), 열처리 등 통상적으로 진행되는 과정를 더 포함할 수 있다.In the step (b1), a photoreactive material may be applied to the metal film formed in the step (a) using a spin coater, and the thickness thereof is preferably about 1 μm or less. Here, a slit coater may be used in addition to the spin coater, or a spin coater and a slit coater may be used in combination. The coating process may further include a conventional process such as ashing or heat treatment.
상기 (b1)단계에서는 광반응물질로 포토레지스트를 사용할 수 있다. 포토레지스트는 특정 파장대의 빛을 받으면(노광:photo exposure) 반응하는 일종의 감광성 고분자 화합물(photosensitive polymer)로서, 이때 반응이라 함은 포토레지스트의 일정 부분이 노광 되었을 때 노광된 부분의 폴리머(polymer) 사슬이 끊어지거나 혹은 더 강하게 결합하는 것을 의미한다. 따라서, 노광된 부분의 폴리머(polymer) 결합사슬이 끊어지는 양극형(positive) 포토레지스트와 그 반대의 음극형(negative) 포토레지스트 중에서 선택하여 사용할 수 있다.In the step (b1), a photoresist may be used as the photoreactive material. A photoresist is a kind of photosensitive polymer that reacts when exposed to light of a specific wavelength (exposure), in which case a reaction occurs when a certain portion of the photoresist is exposed, Or more strongly coupled. Therefore, a positive photoresist in which a polymer bonding chain of an exposed part breaks can be selected from a negative photoresist opposite to the positive photoresist.
상기 (b2)단계에서는 포토마스크(photo mask)를 사용하여 광반응물질 코팅층에 선택적으로 자외선 영역의 빛을 조사한다.In the step (b2), a photo-reactive material coating layer is selectively irradiated with ultraviolet light using a photo mask.
상기 (b3)단계에서는 노광공정(b2)을 통해 상대적으로 결합이 약해져 있는 부분의 광반응물질 코팅층을 현상액을 사용하여 녹여낸다. 따라서 기판에 형성된 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막 상에 선택적으로 광반응 물질을 남길 수 있게 된다.In the step (b3), a portion of the photoreactive material coating layer relatively weakly bonded through the exposure step (b2) is melted using a developing solution. Accordingly, it is possible to selectively leave a photoreactive material on a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film formed on a substrate.
상기(c)단계에서의 식각공정은 이 분야에서 공지된 방법에 따라 수행될 수 있으며, 침지시키는 방법, 분사(spray)하는 방법 등을 예로 들 수 있다. 식각 공정시 식각용액의 온도는 30~50℃일 수 있으며, 적정 온도는 다른 공정과 기타 요인을 고려하여 필요에 따라 변경할 수 있다.
The etching process in the step (c) can be carried out according to a method known in the art, for example, a method of dipping, a method of spraying, and the like. During the etching process, the temperature of the etching solution may be in the range of 30 to 50 ° C., and the optimum temperature may be changed as necessary in consideration of other processes and other factors.
또한, 본 발명은In addition,
(a)기판 상에 게이트 전극을 형성하는 단계; (b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; (c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; (d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 (e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 TFT 어레이 기판의 제조방법에 있어서, (a) forming a gate electrode on a substrate; (b) forming a gate insulating layer on the substrate including the gate electrode; (c) forming a semiconductor layer on the gate insulating layer; (d) forming source and drain electrodes on the semiconductor layer; And (e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
상기 (a), (d) 및 (e)단계 중 하나 이상의 단계가 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하고, 상기 금속막을 본 발명의 식각액 조성물로 식각하여 각각의 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.Wherein at least one of the steps (a), (d), and (e) forms a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film, And etching each of the electrodes with an etchant composition to form the respective electrodes.
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.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예 1-20: 식각액 조성물의 제조 및 식각특성의 평가Example 1-20: Preparation of etchant composition and evaluation of etching properties
시
예room
city
Yes
이미노디아세틱엑시드/함염소 화합물/탈이온수(단위: 중량%)H 2 O 2 / NH 4 FHF / Aminotetrazole /
Imino acetic acid / chlorine compound / deionized water (unit:% by weight)
몰리브덴-티타늄 합금막Copper-nitride /
Molybdenum-titanium alloy film
Indium oxide film
(1) 식각액 조성물의 제조(1) Preparation of etchant composition
반도체 공정용 등급인 H2O2, NH4FHF, 아미노테트라졸, 이미노디아세트산 및 함염소 화합물을 상기 표 1에 기재된 조성비로 혼합하고, 상기 표 1에 기재된 조성비로 탈이온수를 첨가하여 실시예1-20의 식각액 조성물을 각각 6 kg씩 제조하였다.H 2 O 2 , NH 4 FHF, aminotetrazole, iminodiacetic acid and chlorine compound, which are grades for semiconductor processing, were mixed at the composition ratios shown in Table 1, and deionized water was added at the composition ratios shown in Table 1, 6 kg of each of the etchant compositions of 1-20 were prepared.
(2) 식각특성 평가(2) Evaluation of etching characteristics
상기에서 제조된 실시예1 내지 20의 식각액 조성물을 사용하여 스퍼터링법으로 유리 기판 상에 증착한 구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막, 및 인듐계 산화막으로서 비정질 인듐주석산화막을 각각 식각하였다.A copper-nitride / molybdenum-titanium alloy film, a molybdenum-titanium alloy film, and an amorphous indium tin oxide film as an indium oxide film deposited on a glass substrate by the sputtering method using the etching composition compositions of Examples 1 to 20 prepared above, Respectively.
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 제조된 식각액을 넣고 온도를 30℃로 설정하여 가온한 후, 온도가 30±0.1℃에 도달하였을 때 식각 공정을 수행하였다. 기판을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 모델명: S-4700, HITACHI사 제조)을 이용하여 식각 특성을 평가하여 상기 표1에 나타내었다.The etching solution prepared in the injection type etching equipment (model name: ETCHER (TFT), SEMES) was put and heated at a temperature of 30 ° C, and the etching process was performed when the temperature reached 30 ± 0.1 ° C. Substrate was injected and injection was started. When etching was completed, the substrate was taken out, washed with deionized water, dried using a hot air dryer, and photoresist was removed using a photoresist stripper. After washing and drying, etching characteristics were evaluated using an electron microscope (SEM; model name: S-4700, manufactured by Hitachi), and the results are shown in Table 1 above.
상기 표1 및, 실시예1의 식각액 조성물로 식각한 시험편의 전자주사현미경 사진인 도1-3에서 확인 되는 바와 같이, 본 발명의 실시예 의 식각액 조성물은 구리-질화물/몰리브덴-티타늄 합금막(도1), 몰리브덴-티타늄 합금막(도2), 및 인듐계 산화막(도3)에 대하여 양호한 식각 특성과 잔사 특성을 나타냈다.As can be seen from FIGS. 1-3, which are electron micrographs of the test pieces etched with the etchant compositions of Table 1 and Example 1, the etchant compositions of the examples of the present invention are copper-nitride / molybdenum-titanium alloy films (Fig. 1), the molybdenum-titanium alloy film (Fig. 2), and the indium oxide film (Fig. 3).
즉, 도1의 사진에서 확인할 수 있는 바와 같이, 본 발명의 실시예 1의 식각액 조성물은 구리-질화물/몰리브덴-티타늄 합금막에 대하여 우수한 식각 특성을 나타냈으며, 구리-질화물/몰리브덴-티타늄 합금막의 잔사도 남기지 않았다. 1, the etchant composition of Example 1 of the present invention exhibited excellent etching characteristics with respect to the copper-nitride / molybdenum-titanium alloy film, and the copper-nitride / molybdenum-titanium alloy film I did not leave any residue.
또한, 도2의 사진에서 확인할 수 있는 바와 같이, 본 발명의 실시예1의 식각액 조성물은 몰리브덴-티타늄 합금막에 대하여 우수한 식각 특성을 나타내었으며, 몰리브덴-티타늄 합금막의 잔사도 남기지 않았다.Further, as can be seen from the photograph of FIG. 2, the etching composition of Example 1 of the present invention exhibited excellent etching properties with respect to the molybdenum-titanium alloy film, and remnants of the molybdenum-titanium alloy film remained.
또한, 도3의 사진에서 확인할 수 있는 바와 같이, 본 발명의 실시예1의 식각액 조성물은 인듐주석산화막(ITO)에 대하여 우수한 식각 특성을 나타냈으며, 인듐주석산화막(ITO)의 잔사도 남기지 않았다.
As can be seen from the photograph of FIG. 3, the etching composition of Example 1 of the present invention exhibited excellent etching properties for indium tin oxide (ITO) and remained indium tin oxide (ITO) remnants.
비교예 1-3: 식각액 조성물의 제조 및 식각특성의 평가Comparative Example 1-3: Preparation of etching composition and evaluation of etching properties
몰리브덴-티타늄 합금막Copper-nitride /
Molybdenum-titanium alloy film
Indium oxide film
(15/1/84)H 2 O 2 / NH 4 COOH / deionized water
(15/1/84)
탈이온수
(15/0.2/0.5/84.3)H 2 O 2 / NH 4 FHF / Aminotetrazole /
Deionized water
(15 / 0.2 / 0.5 / 84.3)
(프로파일불량)Etchable
(Bad profile)
인산염/탈이온수
(15/0.2/0.5/1/83.3)H 2 O 2 / NH 4 FHF / Aminotetrazole /
Phosphate / deionized water
(15 / 0.2 / 0.5 / 1 / 83.3)
구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막 또는 인듐계 산화막의 식각에 사용되는 기존의 식각액 조성으로서 표2에 기재된 조성에 따라 비교예1 내지 3의 식각액 조성물을 제조하고, 상기 실시예1 내지 20의 식각액 조성물과 동일한 방법으로 식각 특성을 테스트 하였다. The etchant compositions of Comparative Examples 1 to 3 were prepared according to the compositions shown in Table 2 as the conventional etchant compositions used for etching copper-nitride / molybdenum-titanium alloy films, molybdenum-titanium alloy films or indium oxide films, The etching properties were tested in the same manner as the etching solution compositions of Examples 1 to 20.
상기 표2 및 도4-8에서 확인되는 바와 같이, As can be seen in Table 2 and Figures 4-8,
상기 비교예1의 식각액 조성물로 식각한 경우, 구리-질화물/몰리브덴-티타늄 합금막(도4), 몰리브덴-티타늄 합금막(도5), 및 인듐계 산화막(도6)의 통합적인 식각이 불가능 하였다.When the etching composition of Comparative Example 1 was etched, it was impossible to etch the copper-nitride / molybdenum-titanium alloy film (FIG. 4), the molybdenum-titanium alloy film (FIG. 5), and the indium oxide film Respectively.
또한, 비교예2의 식각 조성물로 식각하는 경우, 구리-질화물/몰리브덴-티타늄 합금막, 몰리브덴-티타늄 합금막, 또는 인듐계 산화막의 통합적인 식각은 가능하였으나, 구리-질화물/몰리브덴-티타늄의 식각 프로파일이 불량하였다(도7). In the case of etching with the etching composition of Comparative Example 2, integrated etching of the copper-nitride / molybdenum-titanium alloy film, the molybdenum-titanium alloy film, or the indium oxide film was possible, but the etching of the copper- The profile was poor (Fig. 7).
또한, 비교예3의 식각액 조성물로 식각하는 경우, 인듐계 산화막의 식각이 불가능(도8)하여 통합적인 식각이 불가능 하였다.Further, when the etching solution composition of Comparative Example 3 was etched, it was impossible to etch the indium oxide film (FIG. 8), and thus the integrated etching was impossible.
Claims (13)
상기 (a), (d) 및 (e)단계 중 하나 이상의 단계가 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막을 형성하고, 상기 금속막을 식각액 조성물로 식각하여 각각의 전극을 형성하는 단계를 포함하며,
상기 식각액 조성물은, 조성물 총 중량에 대하여, A)과산화수소(H2O2) 5 내지 30중량%, B)함불소화합물 0.01 내지 5중량%, C)수용성 시클릭아민 화합물 0.05 내지 8 중량%, D)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.05 내지 8 중량%, E)함염소 화합물 0.01 내지 8 중량% 및 F)잔량의 물을 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.(a) forming a gate electrode on a substrate; (b) forming a gate insulating layer on the substrate including the gate electrode; (c) forming a semiconductor layer on the gate insulating layer; (d) forming source and drain electrodes on the semiconductor layer; And (e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
Wherein at least one of the steps (a), (d), and (e) forms a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film, To form respective electrodes,
Wherein the etchant composition comprises A) from 5 to 30% by weight of hydrogen peroxide (H 2 O 2 ), from 0.01 to 5% by weight of a fluorine compound, B) from 0.05 to 8% by weight of a water-soluble cyclic amine compound, D) 0.05 to 8% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, E) 0.01 to 8% by weight of a chlorine compound, and F) a remaining amount of water. Way.
A)과산화수소(H2O2) 5 내지 30중량%,
B)함불소화합물 0.01 내지 5중량%,
C)수용성 시클릭아민 화합물 0.05 내지 8 중량%,
D)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.05 내지 8 중량%,
E)함염소 화합물 0.01 내지 8 중량%, 및
F)잔량의 물을 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각액 조성물. With respect to the total weight of the composition,
A) 5 to 30% by weight of hydrogen peroxide (H 2 O 2 )
B) 0.01 to 5% by weight of a fluorine compound,
C) 0.05 to 8% by weight of a water-soluble cyclic amine compound,
D) 0.05 to 8% by weight of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule,
E) 0.01 to 8% by weight of a chlorine compound, and
F) at least one film selected from the group consisting of a copper-based metal film, a molybdenum-based metal film, and an indium-based oxide film containing a residual amount of water.
상기 구리계 금속막은 순수 구리막 및 구리합금막을 포함하며,
상기 몰리브덴계 금속막은 순수 몰리브데늄막 및 몰리브데늄 합금막을 포함하며, 상기 몰리브데늄 합금막은 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In)으로 이루어진 군으로부터 선택되는 1종 이상의 금속과 몰리브데늄의 합금막이며,
상기 인듐계 산화막은 인듐아연산화막(IZO), 인듐주석산화막(ITO) 및 비정질 인듐주석산화막(a-ITO)으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각액 조성물.
The method according to any one of claims 3 to 10,
Wherein the copper-based metal film comprises a pure copper film and a copper alloy film,
Wherein the molybdenum alloy film includes at least one of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) , And indium (In), and an alloy film of molybdenum and at least one metal selected from the group consisting of indium (In)
Wherein the indium-based oxide film is selected from the group consisting of indium zinc oxide (IZO), indium tin oxide (ITO), and amorphous indium tin oxide (a-ITO). An oxide film, and an oxide film.
b)상기 a)단계에서 형성된 금속막 상에 선택적으로 광반응 물질을 남기는 단계; 및
c)청구항3의 식각액 조성물을 사용하여 상기 b)단계에서 처리된 금속막을 식각하는 단계를 포함하는 구리계 금속막, 몰리브덴계 금속막 및 인듐계 산화막 중에서 선택되는 1종 이상의 막을 포함하는 금속막의 식각방법.a) forming a metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film on a substrate;
b) selectively leaving a photoreactive material on the metal film formed in the step a); And
c) etching the metal film including at least one film selected from a copper-based metal film, a molybdenum-based metal film and an indium-based oxide film, which comprises etching the metal film treated in the step b) using the etching liquid composition of claim 3; Way.
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