KR20140078924A - 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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- KR20140078924A KR20140078924A KR1020120148232A KR20120148232A KR20140078924A KR 20140078924 A KR20140078924 A KR 20140078924A KR 1020120148232 A KR1020120148232 A KR 1020120148232A KR 20120148232 A KR20120148232 A KR 20120148232A KR 20140078924 A KR20140078924 A KR 20140078924A
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- 238000005530 etching Methods 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052802 copper Inorganic materials 0.000 claims abstract description 63
- -1 sulfonic acid compound Chemical class 0.000 claims abstract description 39
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 13
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 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
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 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
- 238000010030 laminating Methods 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
- 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic 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
- 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
- 150000003839 salts Chemical class 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 117
- 230000000052 comparative effect Effects 0.000 description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- 239000010410 layer Substances 0.000 description 4
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 239000010936 titanium 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
- 230000002950 deficient Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000635 electron micrograph Methods 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
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 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
- 206010020710 Hyperphagia Diseases 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
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003446 ligand 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
- 235000020830 overeating Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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 adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
Abstract
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 etchant composition capable of simultaneously etching a double film of a copper film and an indium tin oxide film, a copper film and a metal film, and an etching method using the same.
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 size 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 has been developed and used in which a copper metal wiring used as a conventional low resistance wiring is applied to a gate and a source / drain electrode (S / D) have. In such an array substrate process, there is an advantage that the movement speed of electrons can be controlled according to the thickness of the copper metal film and the barrier film (barrier layer, Ti, Mo, Mo alloy, etc.). Further, when a transparent electrode such as an indium tin oxide (ITO) layer is formed as a barrier film under the copper metal film in a gate electrode, wiring, or the like, it is possible to improve the response speed in a display panel such as an LCD There are advantages.
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 a double film of a copper film and an indium tin oxide film (Cu / ITO) is formed as an electrode or a wiring of a display panel, it is difficult to form an electrode or a wiring by simultaneously etching the copper film and the indium tin oxide film all at once, The copper film and the indium tin oxide film must be separately etched by a separate process (second etching), and therefore, it is troublesome to perform a 5-mask process. As an etchant composition for etching the copper film or the indium tin oxide film, an oxidizing agent solution mainly containing hydrogen peroxide, inorganic acid, organic acid, etc. is mainly used. However, such a conventional etching composition has no particular problem at the time of single-layer etching of a copper film or an indium tin oxide film. However, since the etching rate of an indium tin oxide film is generally faster than that of a copper film, The tantalum of the indium tin oxide film as the barrier film, the etching profile failure, and the taper angle are defective. Further, the conventional etching solution composition is insufficient in stability, and may precipitate, such as residues and residual layers, over time.
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.An object of the present invention is to provide an etchant composition capable of simultaneously etching a metal film, in particular, 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.
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 etchant composition having an excellent etch profile such as a taper angle even when the copper film and the indium tin oxide film are double-etched, and an etching method using the same.
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.
It is still another object of the present invention to provide an etchant composition capable of treating a large number of substrates in a short period of time with high etching speed, stabilizing unstable hydrogen peroxide with organic acid, and improving stability, and an etching method using the same.
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, 0.1 to 5% by weight of a sulfonic acid compound; 0.1 to 2% by weight of a carbonyl-based organic acid compound; 0.1 to 0.4% by weight of a fluorine compound; 0.01 to 3% by weight of an azole-based compound; And the remainder of the 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.
The present invention also provides a method of manufacturing a semiconductor device, comprising: forming a photoresist pattern having a predetermined shape on a substrate having a metal film formed thereon; And etching the metal film from the substrate by using the photoresist pattern as a mask and bringing the etchant composition into contact with the etchant.
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.
The etchant composition according to the present invention can simultaneously etch away the upper copper film and the lower transparent electrode film (ITO) or the lower metal film separately (second etching), and can simultaneously etch the same, Not only the etching rate is fast but also 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 micrograph of a copper film and an indium tin oxide bilayer film etched using the compositions of Examples 1 to 5 of the present invention.
2 is an electron micrograph of a copper film and an indium tin oxide bilayer 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 used for simultaneously etching a double film including a copper film, which comprises 5 to 20 wt% of hydrogen peroxide (H 2 O 2 ), 0.1 to 5 wt% of a sulfonic acid compound , 0.1 to 2 wt% Based organic acid compound, 0.1 to 0.4 wt% of a fluorine compound, 0.01 to 3 wt% of an azole-based compound, and the balance 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 etching solution composition of the present invention is an oxidizing agent for oxidizing and etching the copper film through the process as shown in the following reaction formula (1).
[반응식 1][Reaction 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 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 solution composition. If the content of the hydrogen peroxide (H 2 O 2 ) is too small, the copper film may be insufficiently etched. If the content is too large, the etching rate of the copper film becomes excessively high, There is a risk of overeating.
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 is a co-oxidant of a copper film and an indium tin oxide film (transparent electrode film). With the sulfonic acid compound is an aqueous solution sulfonate ion (sulfonate ion, SO 3 -) a compound that generates, for sulfonic acid (benzenesulfonic acid, C 6 H 5 SO 3 H), toluenesulfonic acid (toluenesulfonic acid eg. p-CH 3 C 6 H 4 SO 3 H), methanesulfonic acid (methanesulfonic acid, CH 3 SO 3 H) C 1 -C 10 cyclic or chain-like hydrocarbon-based sulfonic acid compounds of the, such as, an amino acid (aminosulfonic acid, NH 2 SO 3 H), salts thereof (for example, ammonium salts), and mixtures thereof, and methanesulfonic acid (CH 3 SO 3 H) can be preferably 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. If the content of the sulfonic acid compound is less than the above range, the etching of the copper film may be insufficient. If the content is in excess of the above range, the etching rate of the copper film becomes too high and the process control may become 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 serves as a chelating agent which alleviates the reduction of the oxidizing power of the hydrogen peroxide by the copper ion by the ligand bonding with the primary copper ion generated by the etching of the copper film. 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 Compound, and lactic acid may be preferably used. The content of the carbonyl-based 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. If the content of the carbonyl organic acid compound is less than the above range, there is a possibility that the stabilization of the copper ion may be insufficient. If the content is in excess of the above range, the addition of the carbonyl organic acid compound does not contribute to the stabilization of the copper ion. 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 speed of the indium tin oxide (ITO) transparent electrode, which is a barrier film of the copper film, and functions to form a taper angle in the double film or the multiple film. 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 , a mixture thereof, or the like, and more preferably NaF (sodium fluoride) can be used. 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 whole 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 become poor. If the content exceeds the above range, the copper film or the glass film under the transparent positive film is etched by fluorine ions , There is a possibility that the barrier film is over-deflected.
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 not only etches the copper film but also controls the etch rate of the copper film and indium tin oxide (ITO), as well as the cut dimension loss of the copper metal wiring, CD loss), thereby making it possible to use metal wiring as a gate and a data wiring. As the azole compound, a 5-membered heterocyclic compound containing a nitrogen atom and at least one or more non-carbon atoms in the ring may be used. For example, benzotriazole, aminotetrazole, CH 3 N 5 ), imidazole, pyrazole, and mixtures thereof. Aminotetrazole can be preferably 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, the copper film may be excessively etched. If the content exceeds the above range, it is economically undesirable without any special benefit.
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 this specification), preferably deionized water (DI), distilled water and the like. The etchant composition according to the present invention may further contain conventional additives such as a pH adjuster and a corrosion inhibitor as necessary to the extent that the objects and effects of the invention are achieved. The etchant composition according to the present invention can be produced by any known method. For example, a sulfonic acid compound , a carbonyl organic acid compound, a fluoride compound, an azole compound or the like is added at a necessary concentration to an aqueous medium such as deionized water or distilled water, and then an aqueous hydrogen peroxide (H 2 O 2 ) To the medium at a desired concentration to prepare the composition of the present invention.
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 etchant composition according to the present invention comprises a metal film, preferably a double film of a copper film / indium tin oxide film formed by laminating a copper film and an indium tin oxide film, (ii) a copper film and a copper film formed by laminating a metal film / It is useful for collective etching of double layer of metal film and so on. 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 made of an indium tin oxide film and a copper When the thin film transistor electrode wiring is formed by superimposing, the double film can be effectively etched by 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, particularly a copper / metal alloy film such as a copper / molybdenum-titanium (MoTi) alloy film is used as a source or drain electrode Is used. The copper film may be a single component copper film made of pure copper or may be an alloy containing copper and other metals such as molybdenum (Mo) and titanium (Ti). In the case of an alloy, The proportion of copper is not particularly limited, but is at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight. In addition, the indium tin oxide film includes indium oxide and tin oxide (in this case, the content of indium oxide with respect to the tin oxide component is usually 20 mol% or more, preferably 50 mol% ), And may be doped with Al, Ni, Cu, Ta, Hf, Ti or the like, if necessary. As a method for etching the metal film (preferably, the copper film and the indium tin oxide film / metal film double film) using the etchant composition of the present invention, a conventional method for contacting a metal film-etchant composition can be used. For example, a photoresist pattern of a predetermined shape may be formed on a double-layered substrate, the photoresist pattern may be used as a mask, and the etchant composition of the present invention may be brought into contact with the double-layered film.
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.
The etchant composition according to the present invention can be used to form a conventional gate wiring by using a 5-mask to perform a secondary etching of a double film of a copper film / indium tin oxide film using a 4-mask The double film of the copper film / indium tin oxide film can be collectively etched, so that the process can be simplified and the production yield can be improved. Further, when the etchant composition according to the present invention is used, since the source / drain (S / D) wiring can be simultaneously etched, the gate and the source / drain electrodes can be etched in a batch. Further, according to the present invention, a rapid etching process and excellent taper etching and profile can be obtained in the formation of a wiring of a copper metal film which requires a dual etching process or a multilayer process.
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 by way of specific examples and comparative examples. The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention.
[실시예 1~5, 비교예 1~5] 식각액 조성물의 제조 및 평가 [Examples 1 to 5, Comparative Examples 1 to 5] Preparation and evaluation of an etchant 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.(H 2 O 2 ), methanesulfonic acid (MSA, CH 3 SO 3 H), lactic acid (C 3 H 3 ), and the like were added to the etching solution composition in order to evaluate the etching performance of the etching solution composition. (Examples 1 to 5, Comparative Examples 1 to 5) containing sodium fluoride (H 2 O 3 ), sodium fluoride (NaF), aminotetrazole (ATZ, CH 3 N 5 ) and deionized water Respectively.
(H2O2)Hydrogen peroxide
(H 2 O 2 )
(CH3SO3H)Methanesulfonic acid
(CH 3 SO 3 H)
(C3H6O3)Lactic acid
(C 3 H 6 O 3 )
(NaF)Sodium fluoride
(NaF)
(CH3N5)Aminotetrazole
(CH 3 N 5)
구리막/인듐틴산화막 및 구리막/금속막의 식각 시험Etching 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, upper film) / indium tin oxide film (ITO, lower film) and (ii) a copper film (Cu, upper film) / molybdenum- titanium alloy film ) Was etched with the etchant compositions of Examples 1 to 5 and Comparative Examples 1 to 5, and over-etching was performed at 100% over time from EPD (End Point Detection) of the lower film. 1 (Examples 1 to 5) and 2 (Comparative Examples 1 to 5), and the etching characteristics (etching speed, CD skew (Critical dimension skew represents the distance between the end of the photoresist film and the end of the copper film and the distance must be in the appropriate range for less tapering and tapered etching to be performed evenly) and a taper angle And 40 to 45 degrees are appropriate values), and the results are shown in Tables 2 and 3, respectively. In the following Tables 2 and 3, when the etching speed is 30 to 50 seconds (sec), it is very good (?), When 50 to 60 seconds is excellent (?), When it exceeds 60 seconds, (?) When the thickness is from 0.8 to 1.0 占 퐉, excellent (?) When the thickness is from 0.3 to 0.8 占 퐉, defective (X) when the thickness is less than 0.3 占 퐉, (°) for 70 °, and defective (X) for 70 ° to 90 °
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 solution compositions of Examples 1 to 5 have excellent etching properties and CD skew, and have a taper angle of 40 to 45 없이, In the etching solution compositions of Comparative Examples 1 to 5, the etching characteristics were poor 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 포함하는 식각액 조성물.5 to 20% by weight of hydrogen peroxide;
0.1 to 5% by weight of a sulfonic acid compound;
0.1 to 2% by weight of a carbonyl-based organic acid compound;
0.1 to 0.4% by weight of a fluorine compound;
0.01 to 3% by weight of an azole-based compound; And
Lt; RTI ID = 0.0 > water. ≪ / RTI >
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 포함하는 것인 식각 방법.Forming a photoresist pattern of a predetermined shape on a substrate having a metal film formed thereon; And
Etching the metal film from the substrate by using the photoresist pattern as a mask, and contacting the etchant composition,
The etchant composition comprises 5 to 20 wt% of hydrogen peroxide, 0.1 to 5 wt% of a sulfonic acid compound, 0.1 to 2 wt% of a carbonyl organic acid compound, 0.1 to 0.4 wt% of a fluorine compound, 0.01 to 3 wt% of an azole compound , And the remainder of the water.
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| PCT/KR2013/011158 WO2014098392A1 (en) | 2012-12-18 | 2013-12-04 | Metal-film etching-solution composition and etching method using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180237923A1 (en) * | 2015-08-26 | 2018-08-23 | Adeka Corporation | Etching liquid composition and etching method |
| WO2019124962A1 (en) * | 2017-12-22 | 2019-06-27 | 주식회사 포스코 | Etching composition for removing patterned surface defects of zinc-electroplated cold rolled steel sheet, and pickling composition comprising etching composition |
| CN110284139A (en) * | 2018-03-19 | 2019-09-27 | 三星显示有限公司 | Etchant composition and method of fabricating metal pattern and array substrate using the same |
| US10920143B2 (en) | 2015-08-26 | 2021-02-16 | Adeka Corporation | Etching liquid composition and etching method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102603630B1 (en) * | 2016-04-25 | 2023-11-17 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for a display divice |
| KR20180012372A (en) * | 2016-07-26 | 2018-02-06 | 삼성디스플레이 주식회사 | Etching solution composition and method of manufacturing metal pattern |
| JP7027323B2 (en) * | 2016-10-21 | 2022-03-01 | 株式会社Adeka | 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 |
| 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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| KR101594465B1 (en) * | 2009-01-08 | 2016-02-16 | 솔브레인 주식회사 | Etchant for thin film transistor-liquid crystal displays |
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| KR20090030225A (en) * | 2007-09-19 | 2009-03-24 | 나가세케무텍쿠스가부시키가이샤 | Etching composition |
| KR100883960B1 (en) * | 2007-10-01 | 2009-02-17 | (주)이그잭스 | Echant for layers of copper or copper alloy |
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| US20180237923A1 (en) * | 2015-08-26 | 2018-08-23 | Adeka Corporation | Etching liquid composition and etching method |
| US10920143B2 (en) | 2015-08-26 | 2021-02-16 | Adeka Corporation | Etching liquid composition and etching method |
| WO2019124962A1 (en) * | 2017-12-22 | 2019-06-27 | 주식회사 포스코 | Etching composition for removing patterned surface defects of zinc-electroplated cold rolled steel sheet, and pickling composition comprising etching composition |
| KR20190076109A (en) * | 2017-12-22 | 2019-07-02 | 주식회사 포스코 | Etching composition and pickling composition comprising the etching composition |
| CN110284139A (en) * | 2018-03-19 | 2019-09-27 | 三星显示有限公司 | Etchant composition and method of fabricating metal pattern and array substrate using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104838040B (en) | 2018-01-23 |
| KR102048022B1 (en) | 2019-12-02 |
| WO2014098392A1 (en) | 2014-06-26 |
| CN104838040A (en) | 2015-08-12 |
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