CN103814432B - 增大蚀刻液蚀刻用量的铜/钼合金膜的蚀刻方法 - Google Patents
增大蚀刻液蚀刻用量的铜/钼合金膜的蚀刻方法 Download PDFInfo
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- CN103814432B CN103814432B CN201280040139.8A CN201280040139A CN103814432B CN 103814432 B CN103814432 B CN 103814432B CN 201280040139 A CN201280040139 A CN 201280040139A CN 103814432 B CN103814432 B CN 103814432B
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- etching
- copper
- molybdenum alloy
- alloy film
- etching solution
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- 238000005530 etching Methods 0.000 title claims abstract description 253
- 239000010949 copper Substances 0.000 title claims abstract description 45
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 36
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 45
- 239000002671 adjuvant Substances 0.000 claims description 21
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
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- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 150000003217 pyrazoles Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 229960005137 succinic acid Drugs 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
-
- 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
- H01L21/3063—Electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
- 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
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/45—Ohmic electrodes
- H01L29/456—Ohmic electrodes on silicon
- H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Thin Film Transistor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
本发明涉及一种用于TFT-LCD制造的铜/钼合金膜用蚀刻液的蚀刻用量的增加方法,依据本发明的方法,在使用铜/钼合金膜用蚀刻液进行反复蚀刻时,可使其所发生的蚀刻速度、锥度曲线、蚀刻直线度等低下的蚀刻特性得以恢复,并可增加蚀刻液的蚀刻用量,从而可显著地降低TFT-LCD等的制造费用。
Description
技术领域
本发明涉及一种以增大蚀刻液蚀刻用量为特征的、用于TFT-LCD的铜/钼合金膜的蚀刻方法。
背景技术
半导体装置及TFT-LCD等液晶显示装置的微电路是通过在基板上形成的铝、铝合金、铜及铜合金等导电性金属膜或二氧化硅膜、氮化硅薄膜等绝缘膜上,均匀地涂抹光刻胶,然后通过刻有图案的薄膜,进行光照射后成像,使所需的图案光刻胶成像,采用干式蚀刻或湿式蚀刻,在光刻胶下部的金属膜或绝缘膜上显示图案后,剥离去除不需要的光刻胶等一系列的光刻工程而完成的。
用于大型TFT-LCD的栅极及数据金属配线所使用的铜合金,与以往技术中的铝铬配线相比,阻抗低且没有环境问题。铜存在与玻璃基板及绝缘膜的贴附性较低,易扩散为氧化硅膜等问题,所以通常使用钛、钼等作为下部薄膜金属。
另外,随着TFT-LCD的大型化,湿式蚀刻中所使用的蚀刻液的用量越来越大,为了减少制造成本,开发出可减少蚀刻液使用量的技术势在必行。
在以往技术中,在韩国专利公开公报第2003-0082375号、专利公开公报第2004-0051502号、专利公开公报第2006-0064881号及专利公开公报第2006-0099089号等中,公开了过氧化氢基板的铜/钼合金蚀刻液,但其仅对蚀刻液的组成特性进行了说明,尚不能满足前述的目的。
对此,本发明人在研究蚀刻液的蚀刻用量的改善过程中,发现在因反复蚀刻而导致蚀刻特性低下的铜/钼合金用蚀刻液中添加蚀刻添加剂或蚀刻辅助剂时,可维持蚀刻特性,从而完成了本发明。
发明内容
本发明的目的在于,提供一种可解决在蚀刻铜/钼合金膜的过程中,反复使用相同的蚀刻液,使蚀刻特性低下的问题,并可增加蚀刻液的蚀刻用量的方法。
为实现上述发明目的,本发明的铜/钼合金膜的蚀刻方法,包括:在铜/钼合金膜的蚀刻工程中,蚀刻液在达到蚀刻结束点之前或之后,在所述蚀刻液中,添加在由无机酸、无机盐、有机酸及螯合剂构成的群中选择的一个以上的蚀刻添加剂,或是添加由所述蚀刻添加剂、过氧化氢及水构成的蚀刻辅助剂,使蚀刻液的蚀刻用量增加的步骤。
本发明的有益效果是,依据本发明的方法,在使用铜/钼合金膜用蚀刻液进行反复蚀刻时,可使其所发生的蚀刻速度、锥度曲线、蚀刻直线度等低下的蚀刻特性得以恢复,并可增加蚀刻液的蚀刻用量,从而可显著地降低TFT-LCD等的制造费用。
附图说明
图1是在蚀刻液中,溶解5000ppm的铜/钼合金粉末,在铜/钼合金膜蚀刻后,用扫描电子显微镜观察截面的照片;
图2是在本发明实施方式3中,溶解7000ppm的铜/钼合金粉末,在铜/钼合金膜蚀刻后,用扫描电子显微镜观察截面的照片。
具体实施方式
以下就本发明所使用的术语进行定义。
在本发明中所使用的术语“蚀刻液”是指为了减小用于TFT-LCD等的铜/钼合金膜的厚度,或是为了形成图案而使用的液体。
在本发明中所使用的术语“蚀刻添加剂”是指在用于蚀刻液的成分中,具有溶解酸化的金属离子作用的成分。
在本发明中所使用的术语“蚀刻辅助剂”是指除所述蚀刻添加剂以外,含有有助于增加蚀刻用量物质的溶液。
用于TFT-LCD的铜/钼合金膜用蚀刻液由作为主酸化剂用于酸化铜/钼合金膜的过氧化氢、作为蚀刻添加剂将酸化的铜/钼合金膜在溶液中溶解成离子形态,使溶解的铜离子稳定化的有机物及无机物、控制蚀刻速度并形成锥度曲线的蚀刻抑制剂及用于防止由离子化的金属促进分解反应的双氧水稳定剂等构成。
在上述成分中,过氧化氢作为使铜和钼酸化的主要成分,使用低于具有半导体工程用纯度的金属不纯物ppb基准以下的过氧化氢,其含量为整体组成物的5-40重量%。
在上述成分中的蚀刻添加剂,具有溶解酸化的金属离子的性能,使用无机物及有机物。有机物如醋酸、丁酸、柠檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、琥珀酸、葡萄糖酸及其他水溶性有机酸及同时具备氨基和羧酸基的螯合剂,如亚氨基二乙酸、氨三乙酸、乙二胺四乙酸、二乙烯三胺五乙酸、氨基三亚甲基膦酸、1-羟基亚乙基-1,1-二磷酸、乙二胺四甲撑磷酸、二亚乙基三胺五亚甲基磷酸、肌氨酸、丙氨酸、谷氨酸、氨基丁酸及甘氨酸等。无机物如磷酸、硝酸、硫酸及氢氟酸等无机酸及磷酸盐、硝酸盐、硫酸盐及氟化盐等无机盐。
在上述成分中的蚀刻抑制剂是用于调节蚀刻速度、在蚀刻时使铜/钼合金膜的蚀刻轮廓维持适当的锥度角进行蚀刻的物质,如吡唑、咪唑、1,2,4-三氮唑、四唑、氨基四唑、吲哚、嘌呤、吡啶、嘧啶、吡咯、吡咯烷酮及吡咯林等环形胺类化合物。
上述双氧水稳定剂可为磷酸盐、乙二醇类、环形胺类等。
大型TFT-LCD制造设备的蚀刻喷涂腔的下面,具有可装有一定量蚀刻液的蚀刻液槽。在蚀刻液槽内装入一定量的蚀刻液后,使用相同的蚀刻液进行反复蚀刻。但是,相同的蚀刻液进行反复使用时,会发生蚀刻特性降低的问题,从而导致蚀刻液的可蚀刻次数减少。蚀刻液的可蚀刻次数,在相同的蚀刻液进行反复蚀刻时,其蚀刻速度、锥度曲线及蚀刻直线度等蚀刻特性不发生变化时,则为蚀刻用量。
大型TFT-LCD制造设备的蚀刻液使用量较多,为了减少蚀刻液的使用量,增加蚀刻用量是非常重要的。对此,本发明提供了一种可增加可蚀刻次数,即增加蚀刻液的蚀刻用量的方法。
利用相同的蚀刻液进行反复蚀刻时,蚀刻液内的金属离子的浓度会有所增加。在利用作为酸化剂的过氧化氢的铜/钼合金膜用蚀刻液中,必须抑制金属离子发生酸化还原反应并促进过氧化氢分解的反应,因此需要有物质来控制金属离子和过氧化氢的反应。
金属离子的非活性化是因金属离子形成蚀刻液内的物质和螯合剂,而防止金属离子在自由状态下,与过氧化氢相遇并进行酸化还原反应。不能形成螯合剂的金属离子与过氧化氢反应,分解过氧化氢,由此产生的反应热会进一步促进反应,引起蚀刻液的***。因此,金属离子螯合化在铜/钼合金膜用蚀刻液中是非常重要的过程。金属离子的螯合化可为蚀刻添加剂的无机物、有机酸、螯合剂等,优选为与螯合剂结合的非活性化。
金属的蚀刻速度、锥度曲线及蚀刻直线度等蚀刻特性取决于在铜/钼合金膜用蚀刻液成分中的蚀刻添加剂和蚀刻抑制剂的比。蚀刻添加剂多于蚀刻抑制剂时,蚀刻速度快,CD(criticaldimension)变大;蚀刻添加剂少于蚀刻抑制剂时,蚀刻速度慢,锥度变大。当形成一定值以上的锥度时,会显现出不均一的金属直线度,会发生残渣,导致斑点等不合格问题,致使产品无法使用。因此,在使用蚀刻液的过程中,使蚀刻添加剂和蚀刻抑制剂具有并维持均一的比,这与铜/钼合金膜用蚀刻液的可使用次数,即蚀刻液的蚀刻用量紧密相关。
利用相同的蚀刻液进行反复蚀刻时,蚀刻液内部的蚀刻添加剂可使蚀刻并离子化的金属离子和螯合剂形成,从而使进行蚀刻的附加蚀刻添加剂的量持续减少。也就是说,在蚀刻液内的蚀刻添加剂中,参与到新蚀刻中的自由的蚀刻添加剂有所减少,但是用于可形成螯合剂的蚀刻添加剂则有所增加。相反,蚀刻抑制剂仅用于为形成均一的锥度角而控制蚀刻速度的工程中,因此即使蚀刻反复进行,其组成也几乎不会减少。
因此,利用相同的蚀刻液进行反复蚀刻,使蚀刻液内的金属离子增加时,与参与蚀刻的蚀刻添加剂相比,控制蚀刻速度的蚀刻抑制剂的比更多,蚀刻锥度角会增加,从而使蚀刻速度的增加及蚀刻直线度发生问题(如图1)。由此可见,蚀刻添加剂和蚀刻抑制剂的比的变化,会减少蚀刻液使用次数,即使用用量,使蚀刻无法继续进行。
为了解决上述问题,本发明添加因蚀刻反复而减少的蚀刻添加剂,使在蚀刻液内的蚀刻添加剂和蚀刻抑制剂的比,维持在可发挥蚀刻特性的状态下。本发明为了维持一定的金属酸化力,除了上述的蚀刻添加剂外,还在蚀刻液中添加含有过氧化氢及水的蚀刻辅助剂,从而增加蚀刻用量。
本发明包括:在铜/钼合金膜的蚀刻工程中,蚀刻液在达到蚀刻结束点之前或之后,在所述蚀刻液中,添加在由无机酸、无机盐、有机酸及螯合剂构成的群中选择的一个以上的蚀刻添加剂,或是添加由所述蚀刻添加剂、过氧化氢及水构成的蚀刻辅助剂,使蚀刻液的蚀刻用量增加的步骤。
在本发明中,“蚀刻结束点”是指蚀刻完成的点,对此本技术领域的技术人员可通过肉眼识别。
本发明的方法可适用于铜/钼合金膜用蚀刻液,所述蚀刻液的成分及其例如前述说明。
在本发明的方法中,所使用的“蚀刻添加剂”是指可形成金属离子和螯合的物质,可选自无机酸、无机盐、有机酸及螯合剂构成的群。无机酸、无机盐、有机酸及螯合剂的具体示例如前述。
在本发明的方法中,所使用的“蚀刻辅助剂”是指由蚀刻添加剂、过氧化氢及水构成的水溶液。蚀刻辅助剂因包含过氧化氢,可维持一定的金属酸化力,与蚀刻添加剂相比,更便于添加。过氧化氢的含量与蚀刻前的蚀刻液内的过氧化氢的含量相同,或是与蚀刻液内的过氧化氢的含量相比,可在±20%以内的范围内增减。
在本发明的一实施方式中,蚀刻辅助剂由5-40重量%的过氧化氢、1-10重量%的一个以上的蚀刻添加剂及余量的水,优选为脱离子水构成。
在蚀刻辅助剂内的蚀刻添加剂的含量,优选为多于蚀刻前的蚀刻液内的蚀刻添加剂的含量。蚀刻辅助剂是在蚀刻液中附加添加的组成物,因此当蚀刻添加剂的含量大于蚀刻液时,即使蚀刻辅助剂的添加量较少时,也可以实现更大的蚀刻用量的增加。
铜/钼合金膜用蚀刻液由过氧化氢、各种种类的蚀刻添加剂、蚀刻抑制剂及双氧水稳定剂等构成,相反,在本发明的方法中,所使用的蚀刻添加剂或蚀刻辅助剂其构成更为单纯化,尤其是不使用单价高但制造竞争力相对较低的蚀刻抑制剂,因此可提高TFT-LCD制造的竞争力。另外,在本发明所使用的蚀刻添加剂或蚀刻辅助剂中附加添加同等量的蚀刻液时,蚀刻用量可有效的增大。
在制造大型TFT-LCD时,可维持蚀刻特性的蚀刻用量可测定在蚀刻液中离子化的金属离子的浓度,决定蚀刻液的蚀刻反复次数。因此,在蚀刻液的蚀刻浓度到达所定蚀刻用量(极限使用用量)时,添加一定量的本发明蚀刻添加剂或蚀刻辅助剂,然后可再增加可蚀刻金属离子的浓度,然后再达到所定蚀刻用量时,可反复的添加蚀刻添加剂或蚀刻辅助剂。这个过程可持续到蚀刻液内的蚀刻抑制剂可发挥蚀刻特性的过程为止,反复进行。其次数与蚀刻装备的蚀刻液槽及蚀刻用量有关,可依据反复评价来决定。
在本发明的方法中,蚀刻添加剂或蚀刻辅助剂可按照一定的量分开或是连续添加,也就是说,到蚀刻液内的蚀刻抑制剂可发挥特性时为止,可按照一定的量,分开或是连续添加,以此来增加蚀刻液的蚀刻用量。
接下来,为了更详细的说明本发明所采用的实施方式,仅为本发明的示例,本发明的内容并不局限于此。
实施例实施例1-3:蚀刻辅助剂的制造
蚀刻辅助剂(实施例1-3)及铜/钼合金膜用蚀刻液(参考例)依据表1制造而成,下表表1的成分含量是重量%的值。
表1
实施例1-4及对比例1-2:蚀刻评价
为了评价本发明方法的效用性,通过下列方式,在蚀刻时在蚀刻液中添加实施例实施例1-3的溶液后,将其与对比例进行蚀刻特性对比。具体来说,铜/钼合金在沉积的钼合金后,沉积的铜,对上述试片进行光刻工程,使用有图案的玻璃。蚀刻在可以喷涂的装备(Mini-etcherME-001)上进行,蚀刻液可使用表1的参考例。在进行蚀刻时,通过肉眼观察蚀刻结束点,利用扫描电子显微镜(日立集团,S-4800)观察蚀刻特性之CD(criticaldimension)损失、锥度角及蚀刻直线度。
在蚀刻液中添加铜/钼合金的同时,进行蚀刻评价,在可致使CD(criticaldimension)损失、锥度角及蚀刻直线度等蚀刻特性失去的金属浓度5000ppm以上时,添加实施例实施例1-3的溶液,附加添加铜/钼合金,进行蚀刻评价,确认蚀刻特性。为了对比,在对比例1中不添加任何溶液,在对比例2中添加蚀刻液(参考例1),其测定结果如表2所示。
表2
在蚀刻液失去蚀刻特性的金属含量为5000ppm时,添加10%的实施例1-3及参考例的溶液及蚀刻液,在添加铜/钼合金的同时,进行蚀刻评价的结果显示,如上表所述,与不做任何添加的对比例1及添加蚀刻液的对比例2相比,添加实施例1-3的实施例1-3中,可维持蚀刻特性的铜/钼合金含量有所增加。另外,如实施例4所示,实施例3的溶液分成两次添加时,蚀刻用量可进一步增加。
由上述结果可见,使用铜/钼合金膜用蚀刻液时,在蚀刻工程中,在蚀刻液中添加本发明的蚀刻辅助剂,可维持蚀刻特性,增加蚀刻液的蚀刻用量。
Claims (5)
1.一种铜/钼合金膜的蚀刻方法,其特征在于,包括:在铜/钼合金膜的蚀刻工程中,蚀刻液的浓度达到所定蚀刻用量时,所述所定蚀刻用量为极限使用用量,在所述蚀刻液中,分开或连续地添加由过氧化氢、亚氨基二乙酸及水构成的蚀刻辅助剂,使蚀刻液的蚀刻用量增加的步骤。
2.根据权利要求1所述的铜/钼合金膜蚀刻方法,其特征在于,所述蚀刻辅助剂还包含硫酸。
3.根据权利要求1所述的铜/钼合金膜蚀刻方法,其特征在于,所述蚀刻辅助剂还包含乙醇酸。
4.根据权利要求1所述的铜/钼合金膜蚀刻方法,其特征在于,所述蚀刻辅助剂由5-40重量%的过氧化氢、1-10重量%的亚氨基二乙酸及余量的水构成。
5.根据权利要求1所述的铜/钼合金膜蚀刻方法,其特征在于,添加对于蚀刻液的总重量,含量为5-50重量%的所述蚀刻辅助剂。
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PCT/KR2012/006329 WO2013025003A2 (ko) | 2011-08-18 | 2012-08-09 | 식각액의 식각 용량이 증대된 구리/몰리브데늄 합금막의 식각 방법 |
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CN110230059A (zh) * | 2019-07-01 | 2019-09-13 | 深圳市华星光电技术有限公司 | 显示面板的金属图案制作方法 |
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CN104280916A (zh) * | 2013-07-03 | 2015-01-14 | 东友精细化工有限公司 | 制造液晶显示器用阵列基板的方法 |
KR102261638B1 (ko) | 2013-11-15 | 2021-06-08 | 삼성디스플레이 주식회사 | 세정제 조성물 및 이를 이용한 금속배선 제조방법 |
KR102218669B1 (ko) * | 2014-06-27 | 2021-02-22 | 동우 화인켐 주식회사 | 금속막의 식각액 조성물 및 이를 이용한 액정 표시 장치용 어레이 기판의 제조방법 |
WO2016037426A1 (zh) * | 2014-09-09 | 2016-03-17 | 中国电器科学研究院有限公司 | 一种从底层电镀铜/镍材料中回收稀贵/惰性金属的方法及试剂 |
CN104498951B (zh) * | 2014-12-11 | 2017-05-17 | 深圳新宙邦科技股份有限公司 | 一种双氧水系铜钼合金膜用蚀刻液 |
WO2017086758A1 (ko) * | 2015-11-19 | 2017-05-26 | 오씨아이 주식회사 | 구리 식각용 조성물 및 과산화수소계 금속 식각용 조성물 |
KR101669772B1 (ko) * | 2015-11-19 | 2016-10-27 | 오씨아이 주식회사 | 구리 식각용 조성물 |
CN106498398A (zh) * | 2016-12-01 | 2017-03-15 | 深圳市华星光电技术有限公司 | 用于铜/钼膜层的金属蚀刻液及其蚀刻方法 |
CN110105956A (zh) * | 2019-04-17 | 2019-08-09 | 杭州格林达电子材料股份有限公司 | 一种适用于光刻工艺铜制程的无氟酸性刻蚀液及配制方法 |
CN113774382B (zh) * | 2021-08-30 | 2024-01-16 | 漳州思美科新材料有限公司 | 一种CuNi-Al-Mo蚀刻液 |
CN115353886B (zh) * | 2022-08-31 | 2023-08-25 | 湖北兴福电子材料股份有限公司 | 一种磷酸基蚀刻液及其配制方法 |
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