KR20060123898A - Etching composition - Google Patents
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- KR20060123898A KR20060123898A KR1020050045545A KR20050045545A KR20060123898A KR 20060123898 A KR20060123898 A KR 20060123898A KR 1020050045545 A KR1020050045545 A KR 1020050045545A KR 20050045545 A KR20050045545 A KR 20050045545A KR 20060123898 A KR20060123898 A KR 20060123898A
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- etching
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- etching composition
- thin film
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- 238000005530 etching Methods 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000010408 film Substances 0.000 claims abstract description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000010410 layer Substances 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010409 thin film Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002356 single layer Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000007836 KH2PO4 Substances 0.000 abstract 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 abstract 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019289 ammonium phosphates Nutrition 0.000 abstract 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 abstract 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 abstract 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 abstract 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 abstract 1
- 235000019797 dipotassium phosphate Nutrition 0.000 abstract 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 abstract 1
- 229910000397 disodium phosphate Inorganic materials 0.000 abstract 1
- 235000019800 disodium phosphate Nutrition 0.000 abstract 1
- 239000002355 dual-layer Substances 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 abstract 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 abstract 1
- 235000019796 monopotassium phosphate Nutrition 0.000 abstract 1
- 235000019799 monosodium phosphate Nutrition 0.000 abstract 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 abstract 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 abstract 1
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 abstract 1
- 235000019798 tripotassium phosphate Nutrition 0.000 abstract 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 abstract 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 abstract 1
- 235000019801 trisodium phosphate Nutrition 0.000 abstract 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract 1
- 230000008569 process Effects 0.000 description 19
- 229910052750 molybdenum Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000001039 wet etching Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052779 Neodymium Inorganic materials 0.000 description 8
- 238000001312 dry etching Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
-
- 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
- C23F1/20—Acidic compositions for etching aluminium 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
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
도 1은 본 발명의 일실시예에 따른 에칭 조성물을 Mo 단일막에 사용하여 형성된 프로파일을 나타낸 사진이다.1 is a photograph showing a profile formed by using an etching composition according to an embodiment of the present invention in a single Mo film.
도 2는 본 발명의 일실시예에 따른 에칭 조성물을 Al-Nd/Mo 이중막에 적용한 결과를 나타낸 사진이다.Figure 2 is a photograph showing the result of applying the etching composition according to an embodiment of the present invention Al-Nd / Mo double layer.
도 3은 본 발명의 일실시예에 따른 에칭 조성물을 Mo/Al-Nd/Mo 삼중막에 적용한 결과를 나타낸 사진이다.Figure 3 is a photograph showing the result of applying the etching composition Mo / Al-Nd / Mo triple layer according to an embodiment of the present invention.
도 4는 본 발명의 일실시예에 따른 에칭 조성물을 Mo 단일막, Al-Nd/Mo 이중막, 및 Mo/Al-Nd/Mo 삼중막에 적용한 결과를 나타낸 사진이다.Figure 4 is a photograph showing the result of applying the etching composition according to an embodiment of the present invention to a Mo single film, Al-Nd / Mo double film, and Mo / Al-Nd / Mo triple film.
도 5는 인산염을 사용하지 않고 제조한 에칭 조성물을 Mo 단일막, Al-Nd/Mo 이중막, 및 Mo/Al-Nd/Mo 삼중막에 적용한 결과를 나타낸 사진이다.5 is a photograph showing the results of applying the etching composition prepared without the phosphate to the Mo single film, Al-Nd / Mo double film, and Mo / Al-Nd / Mo triple film.
도 6은 질산의 함량을 적게 사용하여 제조한 에칭 조성물을 Mo 단일막, Al-Nd/Mo 이중막, 및 Mo/Al-Nd/Mo 삼중막에 적용한 결과를 나타낸 사진이다.Figure 6 is a photograph showing the results of applying the etching composition prepared using a small amount of nitric acid to Mo single film, Al-Nd / Mo double film, and Mo / Al-Nd / Mo triple film.
도 7은 Mo 단일막에 종래 에칭 조성물을 사용한 결과 테이퍼(taper) 불량을 야기된 것을 나타낸 사진이다.7 is a photograph showing that a taper defect is caused as a result of using a conventional etching composition on a Mo single film.
도 8은 Mo/Al-Nd 이중막 및 Mo/Al-Nd/Mo 삼중막에 종래 에칭 조성물을 사용한 결과 상부막인 Mo막의 돌출 현상과 하부막인 Al-Nd 또는 Mo막의 언더컷 현상이 발생된 것을 나타낸 사진이다.8 shows that the protrusion of the Mo film as the upper layer and the undercut phenomenon of the Al-Nd or Mo film as the lower layer were generated as a result of using the conventional etching composition for the Mo / Al-Nd double layer and the Mo / Al-Nd / Mo triple layer. The picture shown.
본 발명은 박막트랜지스터 액정표시장치의 게이트 및 소스/드레인 전극용 금속막의 에칭 조성물에 관한 것으로, 더욱 상세하게는 동일한 조성물을 사용하여 박막트랜지스터 액정표시장치의 TFT(thin film transistor)을 구성하는 게이트(gate) 배선재료인 Al-Nd/Mo 이중막 또는 Mo/Al-Nd/Mo 삼중막을 단일공정으로 하부막인 Al-Nd 또는 Mo의 언더컷(undercut) 현상이 없이 습식 에칭하여 우수한 테이퍼를 수득할 수 있으며, 동시에 소스/드레인(source/drain) 배선재료인 Mo 단일막에서도 우수한 프로파일(profile)을 형성할 수 있는 에칭 조성물에 관한 것이다.The present invention relates to an etching composition of a metal film for a gate and a source / drain electrode of a thin film transistor liquid crystal display device, and more particularly, to form a thin film transistor (TFT) of a thin film transistor liquid crystal display device using the same composition. gate Wet-etched Al-Nd / Mo double layer or Mo / Al-Nd / Mo triple layer can be wet-etched without undercut of Al-Nd or Mo as underlayer in a single process to obtain excellent taper. At the same time, the present invention relates to an etching composition capable of forming an excellent profile even in a single layer of Mo, which is a source / drain wiring material.
에칭 공정은 궁극적으로 기판 상에 미세회로를 형성하는 과정으로서 현상 공정을 통해 형성된 포토레지스트 패턴과 동일한 금속 패턴을 만든다. The etching process ultimately forms a microcircuit on the substrate to produce the same metal pattern as the photoresist pattern formed through the development process.
에칭 공정은 그 방식에 따라 크게 습식 에칭과 건식 에칭으로 구분하는데, 습식 에칭은 금속 등과 반응하여 부식시키는 산(acid) 계열의 화학 약품을 이용하여 포토레지스트 패턴이 없는 부분을 녹여 내는 것이며, 건식 에칭은 이온(ion)을 가속시켜 노출 부위의 금속을 제거함으로써 패턴을 형성하는 것이다.The etching process is divided into wet etching and dry etching according to the method. The wet etching is an acid-based chemical that reacts with a metal to corrode to melt a portion without a photoresist pattern. The pattern is formed by accelerating silver ions to remove metal at exposed sites.
건식 에칭은 습식 에칭에 비하여 이방성 프로파일을 가지며 에칭 제어력이 우수하다는 장점이 있다. 그러나, 장비가 고가이며 대면적화의 어려움이 있고, 에칭 속도가 느리기 때문에 생산성(throughput)이 저하된다는 문제점이 있다.Dry etching has the advantage of having an anisotropic profile and superior etching control compared to wet etching. However, there is a problem that the equipment is expensive, there is a difficulty in large area, and the throughput is lowered because the etching speed is slow.
반면, 습식 에칭은 건식 에칭에 비하여 대량 및 대형처리가 가능하고 에칭 속도가 빠르므로 생산성이 높으며, 장비가 저렴하다는 장점이 있다. 그러나, 에천트(ethcant) 및 순수 사용량이 많고, 폐액양이 많다는 문제점이 있다.On the other hand, wet etching has the advantages of high productivity and low cost because of the large and large-scale processing and fast etching speed compared to dry etching. However, there is a problem in that the amount of ethcant and pure water is used, and the amount of waste liquid is large.
일반적으로 건식 에칭을 하는 경우 표면의 일부 경화된 포토레지스트(photoresist)를 제거하기 위하여 플라즈마 애싱(plasma ashing) 공정이 추가됨으로써 장비 가격, 공정 시간 손실 등의 생산성 저하 및 제품 경쟁력 약화의 요인으로 작용되기 때문에, 실제 현장에서는 습식 에칭을 주로 사용하고 있는 실정이다.In general, dry etching adds a plasma ashing process to remove partially cured photoresist on the surface, which may cause productivity degradation and product competitiveness, such as equipment cost and process time loss, and weakening product competitiveness. Therefore, in practice, wet etching is mainly used in the field.
또한 습식 에칭에 사용되는 에천트는 보다 정밀한 미세회로가 요구됨에 따라 에칭하고자 하는 금속의 종류에 특정되게 적용되고 있다.In addition, the etchant used for the wet etching has been applied to a specific type of metal to be etched as a more precise microcircuit is required.
일 예로 Al 단일막을 에칭하는 에천트로 대한민국 특허출원 제10-2000-0047933호, 및 미국특허 제4,895,617호가 있으며, 이들은 인산, 질산, 초산, 계면활성제 및 물로 구성되는 에천트를 개시하고 있다. As an example, etchant for etching Al single layer includes Korean Patent Application No. 10-2000-0047933 and US Patent No. 4,895,617, which disclose an etchant consisting of phosphoric acid, nitric acid, acetic acid, surfactant, and water.
또한 대한민국 특허출원 제2000-0047933호는 Al-Nd 막을 식각하기 위하여 인산, 질산, 초산, 물, 및 플루오르 카본계 계면활성제를 포함하는 식각액 조성물에 대하여 개시하고 있으며, 대한민국 특허출원 제2001-0030192호는 알루미늄 및 ITO(indium-tin oxide)를 식각하기 위하여 옥살산 및 조성물의 pH를 3∼4.5로 조절해줄 수 있는 산과 염산, 인산, 질산을 포함하는 식각액 조성물에 대하여 개시하고 있으며, 대한민국 특허출원 제2001-0065327호는 은 또는 은합금을 식각하기 위하여 인산, 질산, 초산, 및 포타슘옥시설페이트를 포함하는 배선용 식각액에 대하여 개시하고 있으며, 대한민국 특허출원 제2002-0010284호는 IZO(indium-zinc oxide)를 식각하기 위하여 염산, 초산, 저해제, 및 물을 포함하는 식각액 조성물에 대하여 개시하고 있다. In addition, Korean Patent Application No. 2000-0047933 discloses an etching liquid composition containing phosphoric acid, nitric acid, acetic acid, water, and a fluorocarbon surfactant for etching an Al-Nd film, and Korean Patent Application No. 2001-0030192 Discloses an etching liquid composition comprising acid, hydrochloric acid, phosphoric acid and nitric acid, which can adjust the pH of oxalic acid and the composition to 3 to 4.5 for etching aluminum and indium-tin oxide (ITO), and Korean Patent Application No. 2001 -0065327 discloses an etching solution for wiring containing phosphoric acid, nitric acid, acetic acid, and potassium oxalate for etching silver or silver alloy, and Korean Patent Application No. 2002-0010284 discloses indium-zinc oxide (IZO). An etching solution composition including hydrochloric acid, acetic acid, an inhibitor, and water for etching is disclosed.
또한, 대한민국 특허출원 제2001-0018354호는 소스 및 드레인 전극용 Mo 또는 Mo-W(몰리브덴과 텅스텐의 합금)를 식각하기 위하여 인산, 질산, 초산, 산화조정제, 및 물을 포함하는 식각액 조성물에 대하여 개시하고 있다.In addition, Korean Patent Application No. 2001-0018354 discloses an etching liquid composition containing phosphoric acid, nitric acid, acetic acid, an oxidation regulator, and water to etch Mo or Mo-W (alloy of molybdenum and tungsten) for source and drain electrodes. It is starting.
그러나 상기 종래의 에천트들은 하나의 금속막만을 식각하기 위한 용도로 적용되기 때문에 장비와 공정의 효율성 측면에서 떨어져 동시에 여러 금속막을 식각하기 위한 조성물들이 연구되고 있다.However, since the conventional etchant is used for etching only one metal film, compositions for etching several metal films at the same time apart from the efficiency of equipment and processes have been studied.
일 예로 대한민국 특허출원 제2000-0002886호 및 대한민국 특허출원 제2001-0072758호는 Al/Mo 또는 Al-Nd/Mo, Al-Nd/Mo-W의 이중막을 식각하기 위하여 인산, 질산, 초산, 및 산화조정제를 포함하는 식각액에 대하여 개시하고 있으며, 대한민국 특허출원 제2000-0013867호는 Mo/Al(Al-Nd)/Mo 막을 식각하기 위하여 인산, 질산, 초산, 및 산화조정제를 포함하는 식각액에 대하여 개시하고 있다. As an example, Korean Patent Application No. 2000-0002886 and Korean Patent Application No. 2001-0072758 describe phosphoric acid, nitric acid, acetic acid, and the like for etching Al / Mo or Al-Nd / Mo, Al-Nd / Mo-W bilayers. An etchant containing an oxidizing agent is disclosed, and Korean Patent Application No. 2000-0013867 discloses an etchant containing phosphoric acid, nitric acid, acetic acid, and an oxidizing agent to etch Mo / Al (Al-Nd) / Mo membranes. It is starting.
또한 대한민국 특허출원 제2002-0017093호, 제2003-0080557호, 및 제2004-0010404호는 Al-Nd/Mo, Al-Nd/Mo-W, Mo/Al-Nd/Mo, Mo-W/Al-Nd/Mo-W, Mo 단일막 및 Mo-W 단일막에 모두 적용 가능한 식각액으로 인산, 질산, 초산, 몰리브덴식각억제제(암모늄염, 칼륨염), 및 물을 포함하는 식각액에 대하여 개시하고 있다.In addition, Korean Patent Application Nos. 2002-0017093, 2003-0080557, and 2004-0010404 disclose Al-Nd / Mo, Al-Nd / Mo-W, Mo / Al-Nd / Mo, Mo-W / Al. Disclosed is an etchant including phosphoric acid, nitric acid, acetic acid, molybdenum etchant (ammonium salt, potassium salt), and water as an etchant applicable to all -Nd / Mo-W, Mo monolayer and Mo-W monolayer.
그러나 상기 종래의 에칭 조성물로 박막트랜지스터 액정표시장치를 구성하는 소스/드레인 전극용 금속막인 Mo막을 에칭할 경우에는 프로파일이 도 7과 같이 테이퍼(taper) 불량을 야기시켜 후속 공정에서 적층되는 상부막들의 스텝 커버리지 (step coverage)에 불량을 발생시킬 수 있다는 문제점이 있다.However, when etching the Mo film, which is the metal film for the source / drain electrodes constituting the thin film transistor liquid crystal display device, using the conventional etching composition, a profile may cause a taper defect as shown in FIG. There is a problem that may cause a defect in the step coverage of the.
또한 상기 종래의 에칭 또는 식각액 조성물로 박막트랜지스터 액정표시장치의 TFT를 구성하는 게이트 전극용 금속막인 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막을 에칭하면 도 8과 같이 상부 Mo막의 돌출 현상과 하부 Al-Nd 또는 Mo막의 언더컷 현상이 발생된다는 문제점이 있으며, 이 상부막의 돌출 현상은 추가의 공정을 실시하여 제거해야 하며, 하부막의 언더컷 현상은 경사면에서 상부막의 단선 또는 상하부 금속이 단락되는 문제점이 있다.In addition, when the Al-Nd / Mo double film and the Mo / Al-Nd / Mo triple film, which are the metal film for the gate electrode, which constitute the TFT of the thin film transistor liquid crystal display device with the conventional etching or etching liquid composition, are etched, as shown in FIG. There is a problem that the protrusion of the film and the undercut of the lower Al-Nd or Mo film are generated, and the protrusion of the upper film should be removed by an additional process. There is a problem that is shorted.
따라서, 종래 박막트랜지스터 액정표시장치의 TFT를 구성하는 게이트 및 소스/드레인 전극용 금속막을 다중층 구조로 할 경우에는 습식 공정과 건식 공정을 함께 적용함으로써 바람직한 프로파일을 수득하는 것이 일반적이었다. 그러나, 이러한 습식 에칭 및 건식 에칭을 함께 사용하는 것은 공정의 번거로움으로 인한 생산성의 저하 및 비용의 증가 측면에서 불리하다는 문제점이 있다.Therefore, when the gate and source / drain electrode metal films forming the TFT of the conventional thin film transistor liquid crystal display have a multilayer structure, it is common to obtain a desirable profile by applying a wet process and a dry process together. However, the use of such wet etching and dry etching together is disadvantageous in terms of productivity and cost increase due to the cumbersome process.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 동일한 조성물을 사용하여 습식 공정만으로 박막트랜지스터 액정표시장치의 TFT(thin film transistor)을 구성하는 게이트(gate) 배선재료인 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막에서 하부막인 Al-Nd 및 Mo의 언더컷(undercut) 현상이 없이 우수한 테이퍼를 수득할 수 있으며, 동시에 소스/드레인(source/drain) 배선재료인 Mo 단일막에서도 우수한 프로파일(profile)을 형성할 수 있는 에칭 조성물을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention is Al-Nd / Mo double of the gate wiring material constituting the TFT (thin film transistor) of the thin film transistor liquid crystal display only by the wet process using the same composition In the film and Mo / Al-Nd / Mo triple layer, excellent taper can be obtained without undercut phenomenon of Al-Nd and Mo, which is a lower film, and at the same time, Mo single, a source / drain wiring material An object of the present invention is to provide an etching composition capable of forming an excellent profile even in a film.
본 발명의 다른 목적은 동일한 에칭 조성물을 사용하여 박막트랜지스터 액정표시장치의 TFT(thin film transistor)을 구성하는 게이트(gate) 배선재료인 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막과 소스/드레인(source/drain) 배선재료인 Mo 단일막에 적용하여 우수한 에칭 효과를 나타냄으로써 장비의 효율성 증대 및 원가 절감이 가능한 에칭 조성물을 제공하는 것이다.Another object of the present invention is Al-Nd / Mo double layer and Mo / Al-Nd / Mo triple layer, which is a gate wiring material that constitutes a thin film transistor (TFT) of a thin film transistor liquid crystal display using the same etching composition. The present invention provides an etching composition capable of increasing equipment efficiency and reducing costs by showing excellent etching effect by applying to a single layer of Mo, a film and a source / drain wiring material.
본 발명의 또다른 목적은 습식 에칭 후 추가의 건식 에칭을 실시하지 않고도 습식 에칭만으로 게이트(gate) 배선재료인 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막과 소스/드레인(source/drain) 배선재료인 Mo 단일막에 적용하여 우수한 에칭 효과를 나타냄으로써 공정을 단순화할 수 있고, 원가 절감 및 생산성 향상에 효과적인 에칭 조성물을 제공하는 것이다.It is still another object of the present invention to provide a gate wiring material Al-Nd / Mo double layer and Mo / Al-Nd / Mo triple layer and source / drain using only wet etching without performing additional dry etching after wet etching. It is possible to simplify the process by applying to the Mo single film, a source / drain) wiring material, and to provide an etching composition that is effective in cost reduction and productivity improvement.
본 발명의 또다른 목적은 에칭 조성물의 표면장력을 낮추어 에칭 조성물이 잘 퍼지게 함으로써 대형기판에서 에칭 균일성(unifomity)을 향상시킬 수 있는 에칭 조성물을 제공하는 것이다.It is still another object of the present invention to provide an etching composition capable of improving the etching uniformity on a large substrate by lowering the surface tension of the etching composition to spread the etching composition well.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention
a) 인산 40 내지 80 중량%;a) 40 to 80% by weight phosphoric acid;
b) 질산 2 내지 15 중량%;b) 2 to 15 weight percent nitric acid;
c) 초산 3 내지 20 중량%;c) 3 to 20 weight percent acetic acid;
d) 인산염 0.01 내지 5 중량%; d) 0.01-5% by weight of phosphate;
e) 음이온 계면활성제 0.001 내지 1 중량%; 및e) 0.001 to 1 weight percent of anionic surfactant; And
f) 잔량의 물f) remaining water
을 포함하는 박막트랜지스터 액정표시장치의 에칭 조성물을 제공한다. It provides an etching composition of a thin film transistor liquid crystal display device comprising a.
또한 본 발명은 상기 에칭 조성물로 에칭하는 단계를 포함하는 박막트랜지스터 액정표시장치의 제조방법을 제공한다.In another aspect, the present invention provides a method of manufacturing a thin film transistor liquid crystal display device comprising the step of etching with the etching composition.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명의 박막트랜지스터 액정표시장치의 에칭 조성물은 a) 인산 40 내지 80 중량%, b) 질산 2 내지 15 중량%, c) 초산 3 내지 20 중량%, d) 인산염 0.01 내지 5 중량%, e) 음이온 계면활성제 0.001 내지 1 중량%, 및 f) 잔량의 물을 포함하는 하는 것을 특징으로 한다. The etching composition of the thin film transistor liquid crystal display of the present invention is a) 40 to 80% by weight of phosphoric acid, b) 2 to 15% by weight of nitric acid, c) 3 to 20% by weight of acetic acid, d) 0.01 to 5% by weight of phosphate, e) It is characterized in that it comprises 0.001 to 1% by weight of anionic surfactant, and f) the residual amount of water.
본 발명에 사용되는 인산, 질산, 초산, 인산염, 및 물은 반도체 공정용으로 사용가능한 순도의 것을 사용하는 것이 좋으며, 시판되는 것을 사용하거나 공업용 등급을 당업계에 통상적으로 공지된 방법에 따라 정제하여 사용할 수도 있다. Phosphoric acid, nitric acid, acetic acid, phosphate, and water used in the present invention is preferably used in the purity available for the semiconductor process, using commercially available or by purifying industrial grade according to methods commonly known in the art. Can also be used.
본 발명에 사용되는 상기 a)의 인산은 알루미늄 옥사이드를 분해하는 작용을 한다.Phosphoric acid of a) used in the present invention serves to decompose aluminum oxide.
상기 인산은 에칭 조성물에 40 내지 80 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 50 내지 75 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 질산과 알루미늄과 반응하여 형성된 알루미늄 옥사이드가 적절히 분해되어 에칭 속도가 빨라져 생산성이 향상되는 효과가 있다.The phosphoric acid is preferably included in the etching composition 40 to 80% by weight, more preferably 50 to 75% by weight. When the content is in the above range, the aluminum oxide formed by reacting with nitric acid and aluminum is appropriately decomposed to increase the etching rate, thereby improving productivity.
본 발명에 사용되는 상기 b)의 질산은 알루미늄과 반응하여 알루미늄 옥사이드를 형성시킨다.The nitric acid of b) used in the present invention reacts with aluminum to form aluminum oxide.
상기 질산은 에칭 조성물에 2 내지 15 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 3 내지 10 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 상부막인 Mo막 및 하부막인 Al-Nd 및 Mo막으로 구성된 게이트 금속막과 다른 층들 사이의 선택비를 효과적으로 조절할 수 있다는 효과가 있으며, 특히 상기 질산이 2 중량% 미만일 경우에는 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막에서 상부막과 하부 Mo막이 돌출되는 현상이 발생된다는 문제점이 있다.The nitric acid is preferably included in the etching composition 2 to 15% by weight, more preferably 3 to 10% by weight. When the content is within the above range, there is an effect that the selectivity between the gate metal film composed of the Mo film as the upper film and the Al-Nd and Mo film as the lower film and the other layers can be effectively controlled. If less than%, there is a problem that the upper layer and the lower Mo layer protrudes from the Al-Nd / Mo double layer and Mo / Al-Nd / Mo triple layer occurs.
본 발명에 사용되는 상기 c)의 초산은 반응 속도를 조절하는 완충제 작용을 한다.Acetic acid c) used in the present invention acts as a buffer to control the reaction rate.
상기 초산은 에칭 조성물에 3 내지 20 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 8 내지 15 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 반응 속도를 적절히 조절하여 에칭 속도를 향상시키고, 이에 따라 생산성을 향상시킬 수 있는 효과가 있다.The acetic acid is preferably contained in 3 to 20% by weight, more preferably 8 to 15% by weight in the etching composition. When the content is in the above range, the reaction rate is appropriately adjusted to improve the etching rate, thereby improving the productivity.
본 발명에 사용되는 상기 d)의 인산염은 Mo 단일막에 우수한 프로파일을 형성시키는 작용을 한다. 특히, 상기 인산염은 에칭 조성물에 사용됨으로써 동일한 에칭 조성물을 사용하여 소스/드레인 Mo 단일막에서 우수한 에칭 효과를 나타내는 작용을 할 뿐만 아니라, Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막에서도 우수한 에칭 효과를 나타내는 작용을 한다.The phosphate of d) used in the present invention functions to form an excellent profile in the Mo single layer. In particular, the phosphate is used in the etching composition, not only serves to exhibit an excellent etching effect in the source / drain Mo single film using the same etching composition, but also triple the Al-Nd / Mo bi-layer and Mo / Al-Nd / Mo The film also functions to exhibit an excellent etching effect.
상기 인산염은 NaH2PO4, Na2HPO4, Na3PO4, NH4H2PO4, (NH4)3PO4, KH2PO4, K2HPO4, K3PO4, Ca(H2PO4)2, Ca2HPO4, 또는 Ca3PO4 등을 사용할 수 있으며, 바람직하게는 K3PO4 또는 (NH4)3PO4를 사용하는 것이다.The phosphate salt may be NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 , NH 4 H 2 PO 4 , (NH 4 ) 3 PO 4 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , Ca ( H 2 PO 4 ) 2 , Ca 2 HPO 4 , or Ca 3 PO 4 may be used, and K 3 PO 4 or (NH 4 ) 3 PO 4 may be preferably used.
상기 인산염은 에칭 조성물에 0.01 내지 5 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 0.1 내지 3 중량%로 포함되는 것이다. 그 함량이 상기 범위일 경우에는 Al-Nd/Mo 이중막 또는 Mo/Al-Nd/Mo 삼중막에서 하부막인 Al-Nd 또는 Mo의 언더컷 현상을 발생시키지 않을 뿐만 아니라, 동시에 Mo 단일막에서도 우수한 프로파일을 형성시킬 수 있는 효과가 있다.The phosphate salt is preferably included in the etching composition in an amount of 0.01 to 5% by weight, more preferably 0.1 to 3% by weight. If the content is in the above range, the Al-Nd / Mo double film or Mo / Al-Nd / Mo triple film does not cause undercut phenomenon of Al-Nd or Mo, which is a lower film, but is also excellent in Mo single film. There is an effect that can form a profile.
본 발명에 사용되는 상기 e)의 음이온 계면활성제는 산(acid)에 사용가능하여 에칭 조성물이 Al-Nd막에 대한 접촉각을 낮춤으로써 에칭 조성물의 젖음성을 개선시켜 에칭 조성물의 점도를 저하시키고 에칭 균일성을 증가시키는 작용을 한다.The anionic surfactant of e) used in the present invention can be used in an acid to improve the wettability of the etching composition by lowering the contact angle of the etching composition to the Al-Nd film, thereby lowering the viscosity of the etching composition and etching uniformity. It works to increase sex.
상기 음이온 계면활성제는 암모늄 플루오로알킬설폰이미드(ammonium fluoroalkylsulfonimide) 또는 암모늄 퍼플루오로옥탄-1-설포네이트(C8F17SO3NH4)를 사용하는 것이 바람직하다.As the anionic surfactant, ammonium fluoroalkylsulfonimide or ammonium perfluorooctane-1-sulfonate (C 8 F 17 SO 3 NH 4 ) is preferably used.
상기 음이온 계면활성제는 에칭 조성물에 0.001 내지 1 중량%로 포함되는 것이 바람직하며, 그 함량이 상기 범위내일 경우에는 Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막의 언더컷 현상 및 Mo 단일막의 프로파일 형성에 영향을 주지 않으면서 에칭 조성물의 표면장력을 낮추어 에칭 조성물이 잘 퍼지게 함으로써 대형기판에서 에칭 균일성(unifomity)을 증가시킬 수 있는 효과가 있다.The anionic surfactant is preferably included in the etching composition in an amount of 0.001 to 1% by weight, and if the content is within the above range, the undercut phenomenon of Al-Nd / Mo double layer and Mo / Al-Nd / Mo triple layer and Mo single By lowering the surface tension of the etching composition without affecting the profile formation of the film, it is possible to increase the etching uniformity in the large substrate by spreading the etching composition well.
본 발명에 사용되는 상기 f)의 물은 에칭 조성물에 잔량으로 포함되어 질산과 알루미늄이 반응하여 생성된 알루미늄 옥사이드를 분해하고, 에칭 조성물을 희 석하는 작용을 한다.The water of f) used in the present invention is included in the etching composition as a residual amount to decompose aluminum oxide generated by the reaction of nitric acid and aluminum, and to dilute the etching composition.
상기 물은 잔량의 이온교환수지를 통하여 여과한 순수를 사용하는 것이 바람직하며, 특히 비저항이 18 메가오옴(㏁) 이상인 초순수를 사용하는 것이 더욱 바람직하다.It is preferable to use pure water filtered through the residual amount of ion-exchange resin, and more preferably, ultrapure water having a specific resistance of 18 megohms or more.
또한 본 발명은 상기와 같은 성분으로 이루어지는 에칭 조성물로 에칭하는 단계를 포함하는 박막트랜지스터 액정표시장치의 제조방법을 제공한다. 상기와 같은 에칭 전후의 박막트랜지스터 액정표시장치의 제조방법에 적용되는 통상적인 공정들이 적용될 수 있음은 물론이다.In another aspect, the present invention provides a method of manufacturing a thin film transistor liquid crystal display device comprising the step of etching with an etching composition consisting of the above components. As a matter of course, conventional processes applied to the method of manufacturing the thin film transistor liquid crystal display device before and after the etching may be applied.
본 발명의 박막트랜지스터 액정표시장치의 제조방법은 상기와 같은 성분을 포함하는 본 발명의 에칭 조성물을 사용하여 습식 에칭 후 추가의 건식 에칭을 실시하지 않고도 동일한 조성물을 사용하여 습식 공정만으로 박막트랜지스터 액정표시장치의 TFT(thin film transistor)을 구성하는 게이트(gate) 배선재료인 Al-Nd/Mo 이중막 및 Mo/Al-Nd/Mo 삼중막을 하부막인 Al-Nd 또는 Mo의 언더컷(undercut) 현상이 없이 우수한 테이퍼를 수득함으로써 후속공정 시 경사면에서 단선되는 불량을 방지할 수 있으며, 동시에 소스/드레인(source/drain) 배선재료인 Mo 단일막에서도 역테이퍼 현상을 막아 상/하층이 단락되는 불량을 방지할 수 있으며, 도 1에 나타낸 바와 같이 각도가 50∼70 °인 우수한 프로파일(profile)을 형성할 수 있는 장점이 있다. 또한, 동일한 에칭 조성물을 사용하여 게이트(gate) 배선재료인 Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막, 소스/드레인(source/drain) 배선재료인 Mo 단일막에 적용함으로써 공정의 단순화, 장비의 효율성 증대 및 원가 절감이 가능할 뿐만 아니라, 에칭 조성물의 표면장력을 낮추어 에칭 조성물이 잘 퍼지게 함으로써 대형기판에서 에칭 균일성(unifomity)을 증가시킬 수 있는 효과가 있다.In the method of manufacturing the thin film transistor liquid crystal display device of the present invention, the thin film transistor liquid crystal display using only the wet process using the same composition without performing additional dry etching after wet etching using the etching composition of the present invention comprising the above components. Undercut of Al-Nd / Mo double layer and Mo / Al-Nd / Mo triple layer, which are the gate wiring materials constituting the thin film transistor (TFT) of the device, A good taper can be obtained to prevent short circuits on the inclined surface during the subsequent process, and at the same time, a reverse taper phenomenon can be prevented even in a single layer of source / drain wiring material, thereby preventing short circuits in the upper and lower layers. As shown in FIG. 1, there is an advantage of forming an excellent profile having an angle of 50 to 70 °. In addition, by using the same etching composition, it is applied to an Al-Nd / Mo double layer, a gate wiring material, a Mo / Al-Nd / Mo triple layer, and a Mo single layer, a source / drain wiring material. In addition to simplifying the process, increasing the efficiency of the equipment and reducing the cost, it is possible to increase the etching uniformity in the large substrate by lowering the surface tension of the etching composition to spread the etching composition well.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
실시예 1Example 1
인산 63 중량%, 질산 4 중량%, 초산 17 중량%, 인산염으로 K3PO4 1 중량%, 음이온 계면활성제로 암모늄 플루오로알킬설폰이미드 0.005 중량%, 및 잔량의 물을 균일하게 혼합하여 에칭 조성물을 제조하였다.Etch by mixing 63% by weight of phosphoric acid, 4% by weight of nitric acid, 17% by weight of acetic acid, 1% by weight of K 3 PO 4 with phosphate, 0.005% by weight of ammonium fluoroalkylsulfonimide with anionic surfactant, and the balance of water The composition was prepared.
상기 에칭 조성물을 Mo 단일막에 적용한 결과 도 1에 나타낸 바와 같이 프로파일의 각도가 50∼70 °로 우수하게 나타남을 확인할 수 있었다.As a result of applying the etching composition to the Mo single film, as shown in FIG. 1, it was confirmed that the angle of the profile was excellent at 50 to 70 °.
실시예 2 및 비교예 1∼2Example 2 and Comparative Examples 1-2
상기 실시예 1에서 하기 표 1에 나타낸 조성비로 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 에칭 조성물을 제조하였다. 이때, 하기 표 1의 단위는 중량%이다.Except for using the composition ratio shown in Table 1 in Example 1 was carried out in the same manner as in Example 1 to prepare an etching composition. At this time, the unit of Table 1 is weight%.
상기 실시예 1 또는 2 및 비교예 1 또는 2에서 제조한 에칭 조성물의 성능은 하기와 같이 통상적인 방법에 따라 실시하고, 그 결과를 하기 표 2 및 도 2 내지 6에 나타내었다.The performance of the etching composition prepared in Examples 1 or 2 and Comparative Examples 1 or 2 was carried out according to a conventional method as follows, the results are shown in Table 2 and Figures 2 to 6 below.
먼저, 유리 기판상에 Mo/Al-Nd 이중막, Mo/Al-Nd/Mo 삼중막, 및 Mo 단일막을 각각 스퍼터링을 통하여 형성시킨 후, 포토레지스트를 코팅하고 현상을 통하여 패턴을 형성시킨 시편에 상기 실시예 1 또는 2 및 비교예 1 또는 2에서 제조한 에칭 조성물을 스프레이하여 에칭 처리하였다. 그 다음, 에칭 후 단면을 주사전자현미경(SEM, S-4100, 히다찌사)으로 관찰하여 에칭 조성물 성능을 하기의 평가기준에 따라 평가하였다. First, a Mo / Al-Nd double layer, a Mo / Al-Nd / Mo triple layer, and a Mo single layer are formed on the glass substrate by sputtering, and then, the photoresist is coated and the pattern is formed through development. The etching composition prepared in Examples 1 or 2 and Comparative Examples 1 or 2 was sprayed to perform an etching treatment. Then, the cross-section after etching was observed with a scanning electron microscope (SEM, S-4100, Hitachi, Inc.) to evaluate the etching composition performance according to the following evaluation criteria.
상기 표 2를 통하여, 본 발명에 따라 제조한 실시예 1 또는 2의 에칭 조성물이 비교예 1 또는 2와 비교하여 Al-Nd/Mo 이중막(도 2, 도 4)과 Mo/Al-Nd/Mo 삼중막(도 3, 도 4) 및 Mo 단일막(도 1, 도 4)에서 모두 우수한 에칭 효과를 나타냄을 확인할 수 있었다.Through Table 2, the etching composition of Example 1 or 2 prepared according to the present invention is compared to Comparative Example 1 or 2 Al-Nd / Mo double layer (Fig. 2, 4) and Mo / Al-Nd / It was confirmed that the Mo triple film (FIGS. 3 and 4) and the Mo single film (FIGS. 1 and 4) showed excellent etching effects.
반면 인산염을 사용하지 않은 비교예 1 및 질산을 4 중량% 미만으로 사용한 비교예 2의 경우에는 도 5 및 도 6에 나타낸 바와 같이 Al-Nd/Mo 이중막에서 언더컷 현상이 발생하였으며, Mo/Al-Nd/Mo 삼중막에서 상부 및 하부 Mo의 돌출현상이 발생하였다. 뿐만 아니라, Mo 단일막에서도 프로파일의 형성이 불량함을 확인할 수 있었다.On the other hand, in Comparative Example 1 without phosphate and Comparative Example 2 using less than 4% by weight of nitric acid, an undercut phenomenon occurred in the Al-Nd / Mo double layer, as shown in FIGS. 5 and 6, and Mo / Al. An overhang of upper and lower Mo occurred in the -Nd / Mo triple layer. In addition, it was confirmed that the formation of the profile is poor even in the Mo single film.
상기 실시예 2의 에칭 조성물은 도 4에 나타낸 바와 같이 Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막에서 상부막인 Mo 막의 돌출현상과 하부막인 Al-Nd 또는 Mo막의 언더컷 현상이 발생된 비교예 1(도 5)와 비교하여 하부막인 Al-Nd의 언더컷 현상이 없이 우수한 테이퍼를 얻을 수 있음을 확인할 수 있었으며, 또한 Mo 단일막에서도 테이퍼 불량을 야기시켜 후속 공정에서 적층되는 상부막들의 스텝 커버리지에 문제를 발생시킨 비교예 1(도 5)와 비교하여 도 4에 나타낸 바와 같이 우수한 테이퍼를 얻을 수 있음을 확인할 수 있었다.As shown in FIG. 4, the etching composition of Example 2 has the protrusion of the Mo film as the upper layer and the undercut of the Al-Nd or Mo layer as the lower layer in the Al-Nd / Mo double layer and the Mo / Al-Nd / Mo triple layer. Compared with Comparative Example 1 (FIG. 5) in which the phenomenon occurred, it was confirmed that an excellent taper could be obtained without the undercut phenomenon of Al-Nd, which is a lower layer. As shown in FIG. 4, it was confirmed that excellent taper was obtained as compared with Comparative Example 1 (FIG. 5) which caused a problem in the step coverage of the upper films.
상기와 같은 결과를 통하여, 본 발명에 따른 에칭 조성물은 종래 에칭 조성물에 의한 에칭보다 우수한 스텝 커버리지를 형성하였음을 알 수 있었다.Through the above results, it can be seen that the etching composition according to the present invention formed better step coverage than the etching by the conventional etching composition.
본 발명에 다른 에칭 조성물은 습식 에칭 후 추가의 건식 에칭을 실시하지 않고도 동일한 조성물을 사용하여 습식 공정만으로 박막트랜지스터 액정표시장치의 TFT(thin film transistor)을 구성하는 게이트(gate) 배선재료인 Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막을 하부막인 Al-Nd 또는 Mo의 언더컷(undercut) 현상이 없이 우수한 테이퍼를 수득할 수 있으며, 동시에 소스/드레인(source/drain) 배선재료인 Mo 단일막에서도 우수한 프로파일(profile)을 형성할 수 있는 장점이 있다. 또한, 동일한 에칭 조성물을 사용하여 게이트(gate) 배선재료인 Al-Nd/Mo 이중막과 Mo/Al-Nd/Mo 삼중막 및 소스/드레인(source/drain) 배선재료인 Mo 단일막에 적용함으로써 공정의 단순화, 장비의 효율성 증대 및 원가 절감이 가능할 뿐만 아니라, 에칭 조성물의 표면장력을 낮추어 에칭 조성물이 잘 퍼지게 함으로써 대형기판에서 에칭 균일성(unifomity)을 증가시킬 수 있는 효과가 있다.The etching composition according to the present invention is Al-, a gate wiring material for forming a thin film transistor (TFT) of a thin film transistor liquid crystal display device using only the wet process using the same composition without performing additional dry etching after wet etching. Excellent taper can be obtained without undercut of Nd / Mo double layer and Mo / Al-Nd / Mo triple layer without undercut of Al-Nd or Mo as a lower layer, and at the same time source / drain wiring material Even in a single Mo film, there is an advantage of forming an excellent profile. In addition, by using the same etching composition, it is applied to the Al-Nd / Mo double film as the gate wiring material, the Mo / Al-Nd / Mo triple film and the Mo single film as the source / drain wiring material. In addition to simplifying the process, increasing the efficiency of the equipment and reducing the cost, it is possible to increase the etching uniformity in the large substrate by lowering the surface tension of the etching composition to spread the etching composition well.
Claims (6)
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| KR1020050045545A KR101216651B1 (en) | 2005-05-30 | 2005-05-30 | etching composition |
| JP2006138377A JP2006339635A (en) | 2005-05-30 | 2006-05-18 | Etching composition |
| TW095118583A TW200706701A (en) | 2005-05-30 | 2006-05-25 | Etching composition |
| CN2006100846947A CN1873054B (en) | 2005-05-30 | 2006-05-29 | Etching composition |
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| KR101323458B1 (en) * | 2007-06-15 | 2013-10-29 | 동우 화인켐 주식회사 | Etchant composition for silver |
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| JP4864434B2 (en) * | 2005-11-29 | 2012-02-01 | エルジー ディスプレイ カンパニー リミテッド | Etching composition for thin film transistor liquid crystal display device |
| KR101299131B1 (en) * | 2006-05-10 | 2013-08-22 | 주식회사 동진쎄미켐 | Etching composition for tft lcd |
| KR101393599B1 (en) * | 2007-09-18 | 2014-05-12 | 주식회사 동진쎄미켐 | Etchant composition for patterning circuits in thin film transistor-liquid crystal devices |
| KR20090059961A (en) * | 2007-12-07 | 2009-06-11 | 주식회사 동진쎄미켐 | Etchant composition for patterning circuits in thin film transistor-liquid crystal devices |
| JP2010163661A (en) * | 2009-01-16 | 2010-07-29 | Sanyo Handotai Seizo Kk | Etching solution composition |
| JP2009218601A (en) * | 2009-03-19 | 2009-09-24 | Lg Display Co Ltd | Etching composition for thin-film transistor liquid crystal display |
| KR101805187B1 (en) * | 2009-10-30 | 2017-12-06 | 동우 화인켐 주식회사 | An etching solution composition |
| WO2014171054A1 (en) | 2013-04-19 | 2014-10-23 | パナソニック株式会社 | Etching liquid for aluminum-oxide films and thin-film-semiconductor-device manufacturing method using said etching liquid |
| FR3008093B1 (en) * | 2013-07-04 | 2015-12-11 | Rhodia Operations | PROCESS FOR FLUORINATION OF HALIDE COMPOUNDS OF SULFONYL |
| KR20160108944A (en) * | 2015-03-09 | 2016-09-21 | 동우 화인켐 주식회사 | Etching solution composition for silver-containing layer and manufacturing method of an array substrate for display device using the same |
| CN106618617B (en) * | 2015-10-30 | 2021-12-21 | 通用电气公司 | X-ray detector and method for manufacturing same |
| JP2017139295A (en) | 2016-02-02 | 2017-08-10 | 東芝メモリ株式会社 | Substrate processing device, substrate processing method, and substrate processing liquid |
| CN110129797A (en) * | 2019-04-08 | 2019-08-16 | 江苏中德电子材料科技有限公司 | A kind of compatibility etching solution of molybdenum aluminium molybdenum |
| CN113529084A (en) * | 2021-06-09 | 2021-10-22 | 昆山晶科微电子材料有限公司 | Etching solution for TFT-array substrate |
| CN114507859A (en) * | 2021-12-06 | 2022-05-17 | 福建中安高新材料研究院有限公司 | Etching solution, preparation method thereof and metal film material treatment method |
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| JP3985620B2 (en) | 2001-07-23 | 2007-10-03 | ソニー株式会社 | Etching method |
| KR100944300B1 (en) * | 2001-10-22 | 2010-02-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching method for aluminum-molybdenum laminate film |
| TWI245071B (en) * | 2002-04-24 | 2005-12-11 | Mitsubishi Chem Corp | Etchant and method of etching |
| JP4478383B2 (en) * | 2002-11-26 | 2010-06-09 | 関東化学株式会社 | Etching solution composition for metal thin film mainly composed of silver |
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| CN1873054A (en) | 2006-12-06 |
| JP2006339635A (en) | 2006-12-14 |
| TW200706701A (en) | 2007-02-16 |
| CN1873054B (en) | 2010-04-14 |
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