KR102048022B1 - Composition for etching metal layer and method for etching using the same - Google Patents
Composition for etching metal layer and method for etching using the same Download PDFInfo
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- KR102048022B1 KR102048022B1 KR1020120148232A KR20120148232A KR102048022B1 KR 102048022 B1 KR102048022 B1 KR 102048022B1 KR 1020120148232 A KR1020120148232 A KR 1020120148232A KR 20120148232 A KR20120148232 A KR 20120148232A KR 102048022 B1 KR102048022 B1 KR 102048022B1
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- 238000005530 etching Methods 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 66
- -1 sulfonic acid compound Chemical class 0.000 claims abstract description 46
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017855 NH 4 F 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 101100396546 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-6 gene Proteins 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 120
- 230000000052 comparative effect Effects 0.000 description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 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 description 1
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
- H01L29/456—Ohmic electrodes on silicon
- H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
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Abstract
구리막 및 인듐틴산화막의 이중막 또는 구리막 및 금속막의 이중막을 동시에 식각할 수 있는 식각액 조성물 및 이를 이용한 식각 방법이 개시된다. 상기 식각액 조성물은, 5 내지 20 중량%의 과산화수소, 0.1 내지 5 중량%의 술폰산 화합물, 0.1 내지 2 중량%의 카보닐계 유기산 화합물, 0.1 내지 0.4 중량%의 불소 화합물, 0.01 내지 3 중량%의 아졸계 화합물, 및 나머지 물을 포함한다.An etching liquid composition capable of simultaneously etching a double film of a copper film and an indium tin oxide film or a double film of a copper film and a metal film, and an etching method using the same are disclosed. The etchant composition is 5 to 20% by weight of hydrogen peroxide, 0.1 to 5% by weight of sulfonic acid compound, 0.1 to 2% by weight of carbonyl-based organic acid compound, 0.1 to 0.4% by weight of fluorine compound, 0.01 to 3% by weight of azole Compound, and the remaining water.
Description
본 발명은 금속막 식각액 조성물에 관한 것으로서, 더욱 상세하게는, 구리막 및 인듐틴산화막의 이중막, 구리막 및 금속막의 이중막을 동시에 식각할 수 있는 식각액 조성물 및 이를 이용한 식각 방법에 관한 것이다.
The present invention relates to a metal film etchant composition, and more particularly, to an etching solution composition and an etching method using the same, which can simultaneously etch a double film of a copper film and an indium tin oxide film, a copper film and a metal film.
최근, 액정표시장치(LCD) 등, 디스플레이 패널의 고품질, 고화질 및 대면적화에 따라, 화소 전극이 형성되는 픽셀(pixel)의 개수가 증가하고 있으므로, 디스플레이 패널의 응답 속도를 향상시킬 필요가 있다. 이를 위하여, 종래의 저(低)저항 배선으로 사용되는 구리 금속 배선을, 게이트(Gate) 및 소오스/드레인(S/D, Source/Drain) 전극에 적용하는 어레이(Array) 기판 공정이 개발되어 사용되고 있다. 이와 같은 어레이 기판 공정에 있어서는, 구리 금속막 및 하부 배리어막(barrier layer, Ti, Mo, Mo alloy 등)의 두께에 따라 전자의 이동속도를 조절할 수 있는 장점이 있다. 또한, 게이트 전극 또는 배선 등에 있어서, 구리 금속막 하부의 배리어막으로서, 인듐틴산화막(ITO, indium tin oxide layer) 등의 투명전극을 형성하면, LCD 등 디스플레이 패널에서의 응답속도를 향상시킬 수 있는 장점이 있다.
In recent years, as the number of pixels in which pixel electrodes are formed increases with the high quality, high image quality, and large area of a display panel, such as a liquid crystal display (LCD), it is necessary to improve the response speed of the display panel. To this end, an array substrate process for applying a copper metal wiring, which is used as a conventional low resistance wiring, to a gate and a source / drain electrode, has been developed and used. have. In such an array substrate process, there is an advantage that the movement speed of the electrons can be adjusted according to the thickness of the copper metal layer and the lower barrier layer (Ti, Mo, Mo alloy, etc.). In addition, when a transparent electrode such as an indium tin oxide layer (ITO) is formed as a barrier film under a copper metal film in a gate electrode or a wiring, the response speed in a display panel such as an LCD can be improved. There is an advantage.
그러나, 디스플레이 패널의 전극 또는 배선으로서, 구리막 및 인듐틴산화막(Cu/ITO)의 이중막을 형성할 경우, 구리막 및 인듐틴산화막을 일괄적으로 동시에 식각하여 전극 또는 배선을 형성하기 곤란하므로, 구리막 및 인듐틴산화막을 각각 별도의 공정으로 식각하여야 하며(2차 식각), 이를 위하여, 5-마스크(Mask) 공정을 수행하여야 하는 번거로움이 있었다. 또한, 상기 구리막 또는 인듐틴산화막을 식각하기 위한 식각액 조성물로서, 과산화수소, 무기산, 유기산 등을 주성분으로 하는 산화제 용액이 주로 사용되고 있다. 그러나, 이러한 종래의 식각액 조성물은, 구리막 또는 인듐틴산화막의 단일막 식각 시에는 특별한 문제가 없지만, 일반적으로, 구리막과 비교하여 인듐틴산화막의 식각 속도가 빠르므로, 구리막 및 인듐틴산화막의 이중막 식각 시에는, 배리어 막인 인듐틴산화막의 테일(Tail), 식각 프로파일 불량, 테이퍼 각(taper Angle) 불량 등을 유발하는 단점이 있다. 또한, 종래의 식각액 조성물은, 안정성이 부족하여, 사용 시간의 경과에 따라, 잔사(residue), 잔막(residual layer) 등의 석출물을 발생시키기도 한다.
However, when forming a double layer of a copper film and an indium tin oxide film (Cu / ITO) as electrodes or wirings of a display panel, since the copper film and the indium tin oxide film are simultaneously etched simultaneously, it is difficult to form electrodes or wires. The copper film and the indium tin oxide film should be etched in separate processes (secondary etching), and for this purpose, a 5-mask process has to be performed. In addition, as an etching liquid composition for etching the copper film or the indium tin oxide film, an oxidant solution mainly containing hydrogen peroxide, an inorganic acid, an organic acid, or the like is mainly used. However, such a conventional etching liquid composition has no particular problem when etching a single film of a copper film or an indium tin oxide film, but in general, since the etching rate of the indium tin oxide film is faster than that of the copper film, the copper film and the indium tin oxide film In etching a double layer, there is a disadvantage in that a tail, an etching profile defect, a taper angle defect, and the like of the indium tin oxide film, which is a barrier film, are caused. In addition, the conventional etching liquid composition is insufficient in stability, and may generate precipitates such as a residue, a residual layer, etc. over time of use.
본 발명의 목적은, 금속막, 특히, 구리막 및 인듐틴산화막의 이중막 또는 구리막 및 금속막의 이중막을 동시에 식각할 수 있는 식각액 조성물 및 이를 이용한 식각 방법을 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to provide an etching liquid composition capable of simultaneously etching a double layer of a metal film, particularly, a copper film and an indium tin oxide film, or a double film of a copper film and a metal film, and an etching method using the same.
본 발명의 다른 목적은, 구리막 및 인듐틴산화막의 이중막 식각 시에도, 테이퍼 각 등 식각 프로파일이 우수한 식각액 조성물 및 이를 이용한 식각 방법을 제공하는 것이다.Another object of the present invention is to provide an etching liquid composition having an excellent etching profile such as a taper angle and an etching method using the same even when etching a double layer of a copper film and an indium tin oxide film.
본 발명의 또 다른 목적은, 식각 속도가 빨라, 단시간에 많은 기판을 처리할 수 있고, 불안정한 과산화수소를 유기산으로 안정시켜, 안정성이 향상된 식각액 조성물 및 이를 이용한 식각 방법을 제공하는 것이다.
Still another object of the present invention is to provide an etching solution composition and an etching method using the same, wherein the etching rate is fast, and many substrates can be processed in a short time, and unstable hydrogen peroxide is stabilized with an organic acid, thereby improving stability.
상기 목적을 달성하기 위하여, 본 발명은, 5 내지 20 중량%의 과산화수소; 0.1 내지 5 중량%의 술폰산 화합물; 0.1 내지 2 중량%의 카보닐계 유기산 화합물; 0.1 내지 0.4 중량%의 불소 화합물; 0.01 내지 3 중량%의 아졸계 화합물; 및 나머지 물을 포함하는 식각액 조성물을 제공한다. In order to achieve the above object, the present invention, 5 to 20% by weight of hydrogen peroxide; 0.1-5% by weight of sulfonic acid compound; 0.1 to 2 wt% carbonyl organic acid compound; 0.1 to 0.4% by weight of fluorine compound; 0.01-3% by weight of an azole compound; And it provides an etchant composition comprising the remaining water.
또한, 본 발명은, 금속막이 형성된 기판에 소정 형상의 포토레지스트 패턴을 형성하는 단계; 및 상기 포토레지스트 패턴을 마스크로 사용하고, 상기 식각액 조성물을 접촉시켜, 기판으로부터 금속막을 식각하여 제거하는 단계를 포함하는 식각 방법을 제공한다.
In addition, the present invention, forming a photoresist pattern of a predetermined shape on a substrate on which a metal film is formed; And etching the metal film from the substrate by using the photoresist pattern as a mask and contacting the etchant composition to provide an etching method.
본 발명에 따른 식각액 조성물은, 상부 구리막과 하부 투명전극막(ITO) 또는 하부 금속막을 각각 별도로 식각하는(2차 식각) 대신, 동시에 일괄 식각할 수 있으며, 테이퍼 각 등 식각 프로파일이 우수하고, 식각 속도가 빠를 뿐만 아니라, 안정성이 우수한 장점이 있다.
Instead of separately etching the upper copper layer and the lower transparent electrode layer (ITO) or the lower metal layer (secondary etching), the etchant composition according to the present invention may simultaneously etch simultaneously, and has an excellent etching profile such as a taper angle. In addition to the fast etching speed, the stability is excellent.
도 1은 본 발명의 실시예 1 내지 5의 조성물을 사용하여 식각한 구리막 및 인듐틴산화막 이중막의 전자 주사 현미경 사진.
도 2는 본 발명의 비교예 1 내지 5의 조성물을 사용하여 식각한 구리막 및 인듐틴산화막 이중막의 전자 주사 현미경 사진.1 is an electron scanning micrograph of a copper film and an indium tin oxide double film etched using the compositions of Examples 1 to 5 of the present invention.
2 is an electron scanning micrograph of a copper film and an indium tin oxide double film etched using the compositions of Comparative Examples 1 to 5 of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 식각액 조성물은, 구리막을 포함하는 이중막을 동시에 식각하기 위한 것으로서, 5 내지 20 중량%의 과산화수소(H2O2), 0.1 내지 5 중량%의 술폰산 화합물, 0.1 내지 2 중량%의 카보닐계 유기산 화합물, 0.1 내지 0.4 중량%의 불소 화합물(Fluoride), 0.01 내지 3 중량%의 아졸계 화합물 및 나머지 물을 포함한다.
The etchant composition according to the present invention is for simultaneously etching a double film including a copper film, 5 to 20% by weight of hydrogen peroxide (H 2 O 2 ), 0.1 to 5% by weight of sulfonic acid compound , 0.1 to 2% by weight of carbo It includes a nile organic acid compound, 0.1 to 0.4% by weight of fluoride (Fluoride), 0.01 to 3% by weight of the azole compound and the remaining water.
본 발명의 식각액 조성물에 사용되는 과산화수소(H2O2)는, 하기 반응식 1과 같은 과정을 통해, 구리막을 산화시켜 식각하기 위한 산화제이다. Hydrogen peroxide (H 2 O 2 ) used in the etchant composition of the present invention is an oxidant for oxidizing and etching the copper film through the same process as in Scheme 1 below.
[반응식 1]Scheme 1
Cu + H2O2 → CuO + H2OCu + H 2 O 2 → CuO + H 2 O
상기 과산화수소(H2O2)의 함량은, 전체 식각액 조성물에 대하여, 5 내지 20 중량%, 바람직하게는 5 내지 15 중량%, 더욱 바람직하게는 5 내지 10 중량%이다. 상기 과산화수소(H2O2)의 함량이 너무 작으면, 구리막이 불충분하게 식각될 우려가 있고, 너무 많으면, 구리막의 식각 속도가 과도하게 빨라져, 구리막/인듐틴산화막의 이중막 식각에서 구리막이 과식각될 우려가 있다.
The content of the hydrogen peroxide (H 2 O 2 ) is 5 to 20% by weight, preferably 5 to 15% by weight, more preferably 5 to 10% by weight based on the total etching liquid composition. If the content of hydrogen peroxide (H 2 O 2 ) is too small, there is a fear that the copper film is insufficiently etched, if too much, the etching speed of the copper film is excessively fast, the copper film in the double film etching of the copper film / indium tin oxide film There is a risk of over-etching.
상기 술폰산 화합물(sulfonic acid)은 구리막 및 인듐틴산화막(투명전극막)의 보조 산화제이다. 상기 술폰산 화합물로는, 수용액 중에서 설포네이트 이온(sulfonate ion, SO3 -)을 생성하는 화합물로서, 벤젠술폰산(benzenesulfonic acid, C6H5SO3H), 톨루엔술폰산(toluenesulfonic acid. 예를 들면, p-CH3C6H4SO3H), 메탄술폰산(methanesulfonic acid, CH3SO3H) 등의 탄소수 1 내지 10의 고리형 또는 사슬형 탄화수소계 술폰산 화합물, 아미노술폰산(aminosulfonic acid, NH2SO3H) 등의 무기 술폰산 화합물, 이들의 염(예를 들면, 암모늄염), 이들의 혼합물 등을 사용할 수 있고, 바람직하게는 메탄술폰산(CH3SO3H)을 사용할 수 있다. 상기 술폰산 화합물의 함량은, 전체 조성물에 대하여, 0.1 내지 5 중량%, 바람직하게는 0.2 내지 3 중량%, 더욱 바람직하게는 0.5 내지 2 중량%이다. 상기 술폰산 화합물의 함량이 상기 범위 미만이면, 구리막의 식각이 불충분할 우려가 있고, 상기 범위를 초과하면, 구리막의 식각 속도가 너무 빨라져, 공정 조절이 곤란하게 될 우려가 있다.
The sulfonic acid compound is an auxiliary oxidant of the copper film and the indium tin oxide film (transparent electrode film). The sulfonic acid compound is a compound that generates sulfonate ions (SO 3 − ) in an aqueous solution, and includes benzenesulfonic acid (C 6 H 5 SO 3 H) and toluenesulfonic acid. p-CH 3 C 6 H 4 SO 3 H), cyclic or chain hydrocarbon sulfonic acid compound having 1 to 10 carbon atoms, such as methanesulfonic acid (CH 3 SO 3 H), aminosulfonic acid (amino 2) Inorganic sulfonic acid compounds such as SO 3 H), salts thereof (for example, ammonium salts), mixtures thereof, and the like, and preferably methanesulfonic acid (CH 3 SO 3 H) can be used. The content of the sulfonic acid compound is 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.5 to 2% by weight based on the total composition. When the content of the sulfonic acid compound is less than the above range, the etching of the copper film may be insufficient. When the sulfonic acid compound is above the above range, the etching rate of the copper film may be too high, and process control may be difficult.
상기 카보닐계 유기산 화합물은, 구리막의 식각에 의하여 발생한 일차 구리 이온과 리간드 결합하여, 구리 이온에 의하여, 과산화수소의 산화력이 시간의 경과에 따라 감소하는 것을 완화시켜 주는, 킬레이팅제의 역할을 한다. 상기 카보닐계 유기산 화합물로는, 말론산(malonic acid), 석신산(succinic acid), 개미산(formic acid), 젓산(lactic acid, C3H6O3), 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물을 사용할 수 있으며, 바람직하게는 젓산(lactic acid)을 사용할 수 있다. 상기 카보닐계 유기산 화합물의 함량은, 전체 조성물에 대하여, 0.1 내지 2 중량%, 바람직하게는 0.1 내지 1 중량%, 더욱 바람직하게는 0.1 내지 0.5 중량%이다. 상기 카보닐계 유기산 화합물의 함량이 상기 범위 미만이면, 구리 이온의 안정화가 불충분하게 될 우려가 있고, 상기 범위를 초과하면, 구리 이온의 안정화에 추가적인 도움이 되지 않고, 오히려 식각액 조성물의 식각 능력이 저하될 우려가 있다.
The carbonyl-based organic acid compound is ligand-bonded with primary copper ions generated by etching of the copper film, and serves as a chelating agent to mitigate the decrease in the oxidation power of hydrogen peroxide by the copper ions over time. The carbonyl organic acid compound may be selected from the group consisting of malonic acid, succinic acid, formic acid, lactic acid, C 3 H 6 O 3 , and mixtures thereof. Compounds can be used, preferably lactic acid. The content of the carbonyl organic acid compound is 0.1 to 2% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5% by weight based on the total composition. When the content of the carbonyl organic acid compound is less than the above range, there is a concern that the stabilization of the copper ions may be insufficient. When the content of the carbonyl-based organic acid compound exceeds the above range, it does not help additionally stabilize the copper ions, but rather the etching ability of the etchant composition decreases. There is a concern.
상기 불소 화합물(Fluoride)은, 구리막의 배리어막인 인듐틴산화막(ITO) 투명전극의 식각 속도를 조절하고, 이중막 또는 다중막에서 테이퍼 각을 형성시키는 역할을 한다. 상기 불소 화합물로는, 수용액 중에서 플루오라이드 이온(fluoride ion, F-)을 생성하는 다양한 화합물을 사용할 수 있으며, 바람직하게는 KF, NaF, NH4F(ammonium fluoride), NH4HF2(ammonium bifluoride), H2SiF6, HBF4, H2TiF6, H2ZrF6, 이들의 혼합물 등을 사용할 수 있고, 더욱 바람직하게는 NaF(불화 나트륨)를 사용할 수 있다. 상기 불소 화합물의 함량은, 전체 조성물에 대하여, 0.1 내지 0.4 중량%, 바람직하게는 0.1 내지 0.2 중량%이다. 상기 불소 화합물의 함량이 상기 범위 미만이면, 배리어막의 식각 속도가 저하되어, 테이퍼 각이 불량해질 우려가 있고, 상기 범위를 초과하면, 불소 이온에 의해 구리막 또는 투명적극막 하부의 유리막이 식각되거나, 배리어막이 과식각될 우려가 있다.
The fluoride compound controls the etching rate of the indium tin oxide (ITO) transparent electrode, which is a barrier film of the copper film, and serves to form a taper angle in the double film or multiple films. With the fluorine compound, the aqueous solution in the fluoride ion (fluoride ion, F -) can be used a variety of compounds that produce a preferably KF, NaF, NH 4 F ( ammonium fluoride), NH 4 HF 2 (ammonium bifluoride ), H 2 SiF 6 , HBF 4 , H 2 TiF 6 , H 2 ZrF 6 , mixtures thereof, and the like, and more preferably NaF (sodium fluoride). The content of the fluorine compound is 0.1 to 0.4% by weight, preferably 0.1 to 0.2% by weight based on the total composition. If the content of the fluorine compound is less than the above range, the etching rate of the barrier film may be lowered and the taper angle may be poor. If the content of the above fluorine compound exceeds the above range, the copper film or the glass film below the transparent positive electrode film is etched by the fluorine ion. The barrier film may be overetched.
본 발명의 식각액 조성물에 사용되는 아졸계 화합물은, 구리막의 식각을 억제하여, 구리막과 인듐틴산화막(ITO)의 식각 속도를 조절할 뿐 만 아니라, 구리 금속 배선의 컷 디멘션 손실(cut dimension loss, CD loss)을 줄임으로써, 금속 배선을 게이트 및 데이터 배선으로 사용할 수 있도록 하는 역할을 한다. 상기 아졸계 화합물로는, 질소 원자 및 적어도 하나 이상의 비탄소 원자를 고리 속에 포함하는 5원 헤테로고리 화합물을 사용할 수 있고, 예를 들면, 벤조트리아졸(benzotriazole), 아미노테트라졸(aminotetrazole, CH3N5), 이미다졸(imidazole), 피라졸(pyrazole), 이들의 혼합물 등을 사용할 수 있고, 바람직하게는 아미노테트라졸을 사용할 수 있다. 상기 아졸계 화합물의 함량은, 전체 조성물에 대하여, 0.01 내지 3 중량%, 바람직하게는 0.05 내지 1 중량%, 더욱 바람직하게는 0.1 내지 0.2 중량%이다. 상기 아졸계 화합물의 함량이 상기 범위 미만이면, 구리막이 과도하게 식각될 우려가 있고, 상기 범위를 초과하면, 특별한 이익이 없이, 경제적으로 바람직하지 못하다.
The azole compound used in the etchant composition of the present invention suppresses the etching of the copper film, thereby controlling the etching rate of the copper film and the indium tin oxide film (ITO), as well as the cut dimension loss of the copper metal wiring. By reducing CD loss, metal wiring can be used as gate and data wiring. As the azole compound, a 5-membered heterocyclic compound containing a nitrogen atom and at least one non-carbon atom in the ring can be used. For example, benzotriazole, aminotetrazole, CH 3 N 5 ), imidazole, pyrazole, mixtures thereof, and the like, preferably aminotetrazole can be used. The content of the azole compound is 0.01 to 3% by weight, preferably 0.05 to 1% by weight, more preferably 0.1 to 0.2% by weight based on the total composition. If the content of the azole compound is less than the above range, there is a fear that the copper film is excessively etched, if it exceeds the above range, there is no particular benefit, it is economically undesirable.
본 발명의 식각액 조성물에 있어서, 나머지 성분은 물(본 명세서에 있어서, "물"과 동일한 기능을 하는 수성 매질을 포함한다), 바람직하게는 탈이온수(deionized water, DI), 증류수 등이다. 본 발명에 따른 식각액 조성물은, 발명의 목적 및 효과를 달성하는 한도 내에서, 필요에 따라, pH 조절제, 부식 방지제 등의 통상의 첨가제를 더욱 포함할 수 있다. 본 발명에 따른 식각액 조성물은, 공지된 임의의 방법으로 제조될 수 있다. 예를 들면, 술폰산 화합물, 카보닐계 유기산 화합물, 불소 화합물(Fluoride), 아졸계 화합물 등을 탈이온수, 증류수 등의 수성 매질에 필요한 농도로 첨가한 다음, 과산화수소(H2O2) 수용액을 상기 수성 매질에 원하는 농도로 첨가하여, 본 발명의 조성물을 제조할 수 있다.
In the etchant composition of the present invention, the remaining components are water (including an aqueous medium having the same function as "water" in the present specification), preferably deionized water (DI), distilled water and the like. The etchant composition according to the present invention may further include conventional additives, such as a pH adjuster and a corrosion inhibitor, as necessary, within the limits of achieving the object and effect of the invention. The etchant composition according to the present invention may be prepared by any known method. For example, a sulfonic acid compound , a carbonyl organic acid compound, a fluorine compound, an azole compound, and the like are added at a concentration required for an aqueous medium such as deionized water and distilled water, and then an aqueous solution of hydrogen peroxide (H 2 O 2 ) is added to the aqueous solution. The composition of the present invention can be prepared by adding to the medium at a desired concentration.
본 발명에 따른 식각액 조성물은, 금속막, 바람직하게는 (i) 구리막 및 인듐틴산화막이 적층되어 형성된 구리막/인듐틴산화막의 이중막, (ii) 구리막 및 금속막이 적층되어 형성된 구리막/금속막의 이중막 등의 일괄 식각에 유용하게 사용된다. 예를 들면, 액정표시장치(LCD) 패널 등의 제조에 있어서, 구리막/인듐틴산화막의 이중막으로 이루어진 화소 전극 또는 박막 트랜지스터(TFT) 전극을 형성하거나, 인듐틴산화막으로 이루어진 화소 전극과 구리막으로 이루어진 박막 트랜지스터 전극 배선을 중첩하여 형성하는 경우, 본 발명의 조성물을 이용하여 이중막을 효과적으로 식각할 수 있다. 대표적으로, 구리막/인듐틴산화막 이중막은 게이트 전극으로 사용되고, 또한, 구리/금속막, 특히, 구리/금속 합금막, 예를 들면, 구리/몰리브덴-티타늄(MoTi) 합금막은 소오스 또는 드레인 전극으로 사용된다. 여기서, 상기 구리막은, 순수한 구리(Cu)로 이루어진 단일 성분 구리막일 수도 있고, 구리(Cu)와 몰리브덴(Mo), 티타늄(Ti) 등의 다른 금속을 포함하는 합금일 수도 있으며, 합금의 경우, 구리의 비율은, 특별히 한정하는 것은 아니지만, 10 중량% 이상, 바람직하게는 30 중량% 이상, 더욱 바람직하게는 50 중량% 이상이다. 또한, 상기 인듐틴산화막은 인듐 산화물(Indium oxide)과 주석 산화물(Tin Oxide)을 포함하는 것으로서(이 경우, 주석 산화물 성분에 대한 인듐 산화물의 함량은 통상 20 몰% 이상, 바람직하게는 50 몰% 이상이다), 필요에 따라, Al, Ni, Cu, Ta, Hf, Ti 등이 도핑되어 있을 수도 있다. 본 발명의 식각액 조성물을 이용하여, 금속막(바람직하게는, 구리막 및 인듐틴산화막/금속막의 이중막)을 식각하는 방법으로는, 통상의 금속막 - 식각액 조성물 접촉 방법이 사용될 수 있다. 예를 들면, 이중막이 형성된 기판에 소정 형상의 포토레지스트 패턴을 형성하고, 상기 포토레지스트 패턴을 마스크로 사용하고, 본 발명의 식각액 조성물을 접촉시켜, 기판으로부터 이중막을 동시에 식각하여 제거할 수 있다.
The etching liquid composition according to the present invention is a metal film, preferably (i) a double film of a copper film / indium tin oxide film formed by laminating a copper film and an indium tin oxide film, and (ii) a copper film formed by laminating a copper film and a metal film. It is useful for batch etching of double film of metal film. For example, in manufacturing a liquid crystal display (LCD) panel or the like, a pixel electrode or a thin film transistor (TFT) electrode made of a double film of a copper film / indium tin oxide film is formed, or a pixel electrode and copper made of an indium tin oxide film are formed. In the case where the thin film transistor electrode wiring made of a film is superimposed, the double film can be effectively etched using the composition of the present invention. Typically, a copper film / indium tin oxide double film is used as a gate electrode, and a copper / metal film, in particular, a copper / metal alloy film, for example, a copper / molybdenum-titanium (MoTi) alloy film, is used as a source or drain electrode. Used. Here, the copper film may be a single component copper film made of pure copper (Cu), an alloy containing copper (Cu) and other metals such as molybdenum (Mo), titanium (Ti), or, in the case of an alloy, Although the ratio of copper is not specifically limited, It is 10 weight% or more, Preferably it is 30 weight% or more, More preferably, it is 50 weight% or more. Further, the indium tin oxide film includes indium oxide and tin oxide (in this case, the content of indium oxide relative to the tin oxide component is usually 20 mol% or more, preferably 50 mol% As mentioned above, Al, Ni, Cu, Ta, Hf, Ti, etc. may be doped as needed. As the method for etching a metal film (preferably a double film of a copper film and an indium tin oxide film / metal film) using the etching liquid composition of the present invention, a conventional metal film-etching liquid composition contacting method can be used. For example, a photoresist pattern having a predetermined shape may be formed on a substrate on which a double layer is formed, and the photoresist pattern may be used as a mask, and the etching solution composition of the present invention may be contacted to simultaneously remove and remove the double layer from the substrate.
본 발명에 따른 식각액 조성물을 사용하면, 종래의 게이트 배선 형성을 위하여, 5-마스크(mask)를 이용하여 구리막/인듐틴산화막의 이중막을 2차 식각하던 것을, 4-마스크(mask)를 이용하여 구리막/인듐틴산화막의 이중막을 일괄 식각할 수 있으므로, 공정을 단순화하고, 생산 수율을 향상 시킬 수 있다. 또한, 본 발명에 따른 식각액 조성물을 사용하면, 소오스/드레인(S/D, Source/Drain) 배선도 동시에 식각할 수 있으므로, 실질적으로 게이트 및 소오스/드레인 전극을 일괄 식각할 수 있다. 또한, 본 발명에 의하면, 이중막 또는 다중막의 일괄 식각을 필요로 하는 구리 금속막의 배선 형성에 있어, 빠른 식각 공정과 우수한 테이퍼 식각 및 프로파일을 얻을 수 있다.
Using the etchant composition according to the present invention, in order to form a conventional gate wiring, the second etching of the double layer of the copper film / indium tin oxide film using a 5 mask (mask), using a 4 mask (mask) In this case, the double layer of the copper film / indium tin oxide film can be etched in a batch, thereby simplifying the process and improving the production yield. In addition, when the etchant composition according to the present invention is used, source / drain (S / D) wiring may be simultaneously etched, and thus, the gate and source / drain electrodes may be substantially etched collectively. Further, according to the present invention, in the formation of the wiring of the copper metal film which requires the batch etching of the double film or the multilayer film, a fast etching process and excellent tapered etching and profile can be obtained.
이하, 구체적인 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples. The following examples are intended to illustrate the present invention in more detail, and the present invention is not limited by the following examples.
[실시예 1~5, 비교예 1~5] 식각액 조성물의 제조 및 평가 [Examples 1-5, Comparative Examples 1-5] Preparation and Evaluation of Etching Liquid Composition
식각액 조성물의 식각 성능을 평가하기 위하여, 하기 표 1에 나타낸 함량(단위: 중량%)의 과산화수소(H2O2), 메탄술폰산(MSA, CH3SO3H), 젓산(lactic acid, C3H6O3), 불화 나트륨(NaF), 아미노테트라졸(ATZ, CH3N5) 및 나머지 물(deionized water)을 포함하는 식각액 조성물(실시예 1~5, 비교예 1~5)을 제조하였다.In order to evaluate the etching performance of the etchant composition, hydrogen peroxide (H 2 O 2 ), methanesulfonic acid (MSA, CH 3 SO 3 H), lactic acid (C 3) Preparation of an etchant composition (Examples 1 to 5, Comparative Examples 1 to 5) comprising H 6 O 3 ), sodium fluoride (NaF), aminotetrazole (ATZ, CH 3 N 5 ), and deionized water It was.
(H2O2)Hydrogen peroxide
(H 2 O 2 )
(CH3SO3H)Methanesulfonic acid
(CH 3 SO 3 H)
(C3H6O3)Chopsan
(C 3 H 6 O 3 )
(NaF)Sodium fluoride
(NaF)
(CH3N5)Aminotetrazole
(CH 3 N 5 )
구리막/인듐틴산화막 및 구리막/금속막의 식각 시험Etch test of copper film / indium tin oxide film and copper film / metal film
(i) 구리막(Cu, 상부막)/인듐틴산화막(ITO, 하부막)으로 이루어진 이중막 및 (ii) 구리막(Cu, 상부막)/몰리브덴-티타늄 합금막(Mo/Ti, 하부막)으로 이루어진 이중막을 실시예 1~5 및 비교예 1~5의 식각액 조성물로 식각하되, 하부막의 EPD(End Point Detection)로부터 시간 기준으로 100 % 과식각(over etching)하였다. 식각된 이중막의 측단면 사진을 전자주사현미경으로 촬영하여, 도 1(실시예 1 내지 5) 및 도 2(비교예 1 내지 5)에 나타내었으며, 이로부터 식각 특성(식각 속도, CD skew (Critical dimension skew, 포토레지스트막 말단과 구리막 말단 사이의 거리를 나타내며, 단차가 적고, 테이퍼 식각이 고르게 수행되려면, 이 거리가 적절한 범위에 있어야 한다), 및 테이퍼 각(Taper Angle, 식각된 금속막의 측면에서 본 경사, 40~45° 정도가 적절한 값이다))을 평가하여, 그 결과를 하기 표 2 및 3에 각각 나타내었다. 하기 표 2 및 3에서, 식각 속도가 30 ~ 50 초(sec)이면 매우 우수(◎), 50 ~ 60 초이면 우수(○), 60 초를 초과하면 불량(X)으로 나타내었고, CD skew가 0.8 ~ 1.0 ㎛이면 매우 우수(◎), 0.3 ~ 0.8 ㎛이면 우수(○), 0.3 ㎛ 미만이면 불량(X)으로 나타내었고, 테이퍼 각이 40 ~ 45°이면 매우 우수(◎), 45 ~ 70°이면 우수(○), 70 ~ 90°이면 불량(X)으로 나타내었다 (i) a double film consisting of a copper film (Cu, top film) / indium tin oxide film (ITO, bottom film) and (ii) a copper film (Cu, top film) / molybdenum-titanium alloy film (Mo / Ti, bottom film) ) Was etched with the etchant compositions of Examples 1-5 and Comparative Examples 1-5, but was 100% overetched on a time basis from EPD (End Point Detection) of the lower layer. Side cross-sectional images of the etched bilayers were taken with an electron scanning microscope, and are shown in FIGS. 1 (Examples 1 to 5) and 2 (Comparative Examples 1 to 5), from which the etching characteristics (etch rate, CD skew (Critical) dimension skew, which represents the distance between the photoresist film end and the copper film end, the steps are small, and in order for the taper etching to be performed evenly, this distance must be in an appropriate range), and the taper angle (the side of the etched metal film) Inclination, about 40-45 ° is an appropriate value)), and the results are shown in Tables 2 and 3, respectively. In Tables 2 and 3, when the etching rate is 30 to 50 seconds (sec), very good (◎), 50 to 60 seconds is excellent (○), when exceeding 60 seconds is represented as poor (X), CD skew is Very good (◎) for 0.8 to 1.0 μm, good (○) for 0.3 to 0.8 μm, and poor (X) for less than 0.3 μm, and very good (◎) for taper angles of 40 to 45 °. If it is °, it is excellent (○), and if it is 70 to 90 °, it is indicated as bad (X).
상기 표 2 및 3, 도 1 및 2에 나타낸 바와 같이, 실시예 1 ~ 5의 식각액 조성물은 큰 유의차 없이, 식각 특성 및 CD skew가 우수하고, 테이퍼 각이 40 내지 45ㅀ로 조절되는 반면, 비교예 1 ~ 5의 식각액 조성물은 일부 성분의 함량이 너무 적거나 많음에 따라, 식각 특성이 불량하였다. As shown in Tables 2 and 3 and FIGS. 1 and 2, the etching liquid compositions of Examples 1 to 5 have excellent etching characteristics and CD skew without significant difference, while the taper angle is adjusted to 40 to 45 mm 3, The etchant compositions of Comparative Examples 1 to 5 were poor in etching characteristics as the content of some components was too small or too large.
Claims (9)
0.1 내지 5 중량%의 술폰산 화합물;
0.1 내지 2 중량%의 카보닐계 유기산 화합물;
0.1 내지 0.4 중량%의 불소 화합물;
0.01 내지 3 중량%의 아졸계 화합물; 및
나머지 물을 포함하며,
상기 술폰산 화합물은 벤젠술폰산, 톨루엔술폰산, 메탄술폰산, 아미노술폰산, 이들의 염 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물인 식각액 조성물.5-20 wt% hydrogen peroxide;
0.1-5% by weight of sulfonic acid compound;
0.1 to 2 wt% carbonyl organic acid compound;
0.1 to 0.4% by weight of fluorine compound;
0.01-3% by weight of an azole compound; And
Contains the rest of the water,
The sulfonic acid compound is an etching solution composition is a compound selected from the group consisting of benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, aminosulfonic acid, salts thereof and mixtures thereof.
상기 포토레지스트 패턴을 마스크로 사용하고, 식각액 조성물을 접촉시켜, 기판으로부터 금속막을 식각하여 제거하는 단계를 포함하며,
상기 식각액 조성물은 5 내지 20 중량%의 과산화수소, 0.1 내지 5 중량%의 술폰산 화합물, 0.1 내지 2 중량%의 카보닐계 유기산 화합물, 0.1 내지 0.4 중량%의 불소 화합물, 0.01 내지 3 중량%의 아졸계 화합물 및 나머지 물을 포함하며, 상기 술폰산 화합물은 벤젠술폰산, 톨루엔술폰산, 메탄술폰산, 아미노술폰산, 이들의 염 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물인 것인 식각 방법.Forming a photoresist pattern having a predetermined shape on the substrate on which the metal film is formed; And
Using the photoresist pattern as a mask and contacting an etchant composition to etch and remove the metal film from the substrate,
The etchant composition comprises 5 to 20 wt% hydrogen peroxide, 0.1 to 5 wt% sulfonic acid compound, 0.1 to 2 wt% carbonyl organic acid compound, 0.1 to 0.4 wt% fluorine compound, 0.01 to 3 wt% azole compound And remaining water, wherein the sulfonic acid compound is a compound selected from the group consisting of benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, aminosulfonic acid, salts thereof, and mixtures thereof.
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| KR1020120148232A KR102048022B1 (en) | 2012-12-18 | 2012-12-18 | Composition for etching metal layer and method for etching using the same |
| PCT/KR2013/011158 WO2014098392A1 (en) | 2012-12-18 | 2013-12-04 | Metal-film etching-solution composition and etching method using same |
| CN201380064446.4A CN104838040B (en) | 2012-12-18 | 2013-12-04 | Metal film etchant and the engraving method that make use of said composition |
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| US10920143B2 (en) | 2015-08-26 | 2021-02-16 | Adeka Corporation | Etching liquid composition and etching method |
| KR102603630B1 (en) * | 2016-04-25 | 2023-11-17 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for a display divice |
| CN107653451B (en) * | 2016-07-26 | 2020-09-15 | 三星显示有限公司 | Etching solution composition and method for manufacturing metal pattern using the same |
| KR102340997B1 (en) * | 2016-10-21 | 2021-12-21 | 가부시키가이샤 아데카 | Etching liquid composition and etching method |
| KR20190027019A (en) * | 2017-09-04 | 2019-03-14 | 삼성디스플레이 주식회사 | Etchant and fabrication method of metal pattern and thin film transistor substrate using the same |
| KR102020414B1 (en) * | 2017-12-22 | 2019-09-10 | 주식회사 포스코 | Etching composition and pickling composition comprising the etching composition |
| KR102487940B1 (en) * | 2018-03-19 | 2023-01-16 | 삼성디스플레이 주식회사 | Etchant composition, and method for manufacturing metal pattern and array substrate using the same |
| EP3674442A1 (en) | 2018-12-24 | 2020-07-01 | IMEC vzw | Etching using an electrolyzed chloride solution |
| CN111945163A (en) * | 2020-08-03 | 2020-11-17 | 镇江润晶高纯化工科技股份有限公司 | Copper etching liquid composition |
| CN114164003A (en) * | 2021-12-06 | 2022-03-11 | Tcl华星光电技术有限公司 | Etchant composition for display panel and etching method of display panel |
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| KR20110120422A (en) * | 2010-04-29 | 2011-11-04 | 동우 화인켐 주식회사 | An etching solution composition for metal layer comprising copper and titanium |
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