KR20200114900A - Etchant composition and manufacturing method of an array substrate for display device using the same - Google Patents
Etchant composition and manufacturing method of an array substrate for display device using the same Download PDFInfo
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- KR20200114900A KR20200114900A KR1020190037436A KR20190037436A KR20200114900A KR 20200114900 A KR20200114900 A KR 20200114900A KR 1020190037436 A KR1020190037436 A KR 1020190037436A KR 20190037436 A KR20190037436 A KR 20190037436A KR 20200114900 A KR20200114900 A KR 20200114900A
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- Prior art keywords
- film
- layer
- acid
- etchant composition
- etching
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 62
- 239000010949 copper Substances 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 24
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZHCLIFKUVIFYBY-UHFFFAOYSA-N 2h-tetrazol-5-ylmethanamine Chemical compound NCC1=NN=NN1 ZHCLIFKUVIFYBY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 235000005985 organic acids Nutrition 0.000 claims abstract description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 10
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- -1 Glycine; Azole compounds Chemical class 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract 5
- 239000010408 film Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000004471 Glycine Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 4
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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Classifications
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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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic 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
- C23F1/16—Acidic compositions
- C23F1/26—Acidic 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
- H01L21/302—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
-
- 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
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
- H01L29/78618—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure
-
- 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
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
- Electrodes Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
본 발명은 식각액 조성물 및 이를 이용하는 표시장치용 어레이 기판의 제조방법에 관한 것이다. 보다 상세하게는 구리막, 티타늄막 및 인듐산화막의 삼중막 식각용 식각액 조성물 및 이를 이용한 표시장치용 어레이 기판의 제조 방법에 관한 것이다. The present invention relates to an etchant composition and a method of manufacturing an array substrate for a display device using the same. More specifically, the present invention relates to an etchant composition for etching a triple layer of a copper layer, a titanium layer, and an indium oxide layer, and a method of manufacturing an array substrate for a display device using the same.
액정 표시 소자(liquid crystal display device, LCD device)는 뛰어난 해상도에 따른 선명한 영상을 제공하며 전기를 적게 소모하고 디스플레이 화면을 얇게 만들 수 있게 하여 준다는 특성 때문에 평판 디스플레이 장치 중 가장 각광을 받고 있다. 오늘날 이러한 액정 등에 사용되는 표시 소자를 구동하는 전자 회로로서 대표적인 것은 박막 트랜지스터(thin film transistor, TFT) 회로로서 전형적인 박막 트랜지스터 액정표시(TFT-LCD) 소자는 디스플레이 화면의 화소(pixel)를 이루고 있다. TFT-LCD 소자에서 스위칭 소자로 작용하는 TFT는 매트릭스 형태로 배열한 TFT용기판과 그 기판을 마주 보는 컬러 필터 기판 사이에 액정 물질을 채워 제조한 것이다. TFT-LCD의 전체 제조 공정은 크게 TFT 기판 제조 공정, 컬러 필터 공정, 셀 공정, 모듈 공정으로 나뉘는데 정확하고 선명한 영상을 나타내는 데 있어서 TFT 기판과 컬러 필터 제조 공정의 중요성은 매우 크다.A liquid crystal display device (LCD device) is receiving the most attention among flat panel display devices because it provides a clear image according to an excellent resolution, consumes less electricity, and allows a display screen to be made thinner. Today, as an electronic circuit for driving display devices used in such liquid crystals, a typical thin film transistor (TFT) circuit is a typical thin film transistor liquid crystal display (TFT-LCD) device that forms a pixel of a display screen. A TFT, which acts as a switching element in a TFT-LCD device, is manufactured by filling a liquid crystal material between a TFT substrate arranged in a matrix form and a color filter substrate facing the substrate. The overall manufacturing process of a TFT-LCD is largely divided into a TFT substrate manufacturing process, a color filter process, a cell process, and a module process. The importance of the TFT substrate and the color filter manufacturing process is very important in displaying an accurate and clear image.
화소표시 전극에 원하는 전기회로의 선로를 구현하려면 회로 패턴대로 박막층을 깎아내는 식각 (etching) 과정이 필요하다.In order to implement a line of a desired electric circuit on the pixel display electrode, an etching process in which the thin film layer is cut out according to the circuit pattern is required.
그러나, 기존의 식각액 조성물들은 주로 베리어(Barrier)막질에 주배선을 증착하여(depositon) 만들어진 이중막들에 대하여 일괄 식각이 가능하지만 좀더 다양한 금속 종류와 좀더 다층적으로 증착된 배선에 대하여 습식식각 공정을 통한 일괄식각이 용이하지 않다. However, conventional etchant compositions mainly allow batch etching for double layers made by depositing main wiring on a barrier layer, but a wet etching process for more diverse metal types and more multilayered wiring. It is not easy to do batch etching through
예를 들면, 대한민국 공개특허 제10-2015-0089887호는 주산화제로 과산화수소를 사용하지 않고, 과황산염을 사용하여 티타늄-구리의 이중막 식각을 하는 식각액 조성물을 개시하고 있다. 그러나, 상기 공개특허의 조성물로 삼중막 이상의 다층적으로 증착된 배선에 대한 습식식각 공정을 진행 할 경우 일괄식각 효과가 떨어지고, 특히 인듐산화막을 포함하는 다중막 식각시에 일부막의 팁(tip) 발생 등 식각특성이 현저히 저하되는 문제점이 있으며, 이를 해결하기 위해 다중막을 식각할 수 있는 개선된 식각액 조성물을 필요로 하는 실정이다. For example, Korean Patent Laid-Open Publication No. 10-2015-0089887 discloses an etchant composition for etching a double layer of titanium-copper using persulfate without using hydrogen peroxide as the main oxidizing agent. However, when the wet etching process is performed on the wirings deposited in multiple layers of more than a triple layer with the composition of the disclosed patent, the batch etching effect is inferior, and in particular, a tip of some layers is generated when etching a multilayer including an indium oxide layer. There is a problem in that the etching characteristics are significantly deteriorated, and there is a need for an improved etchant composition capable of etching a multilayer in order to solve this problem.
본 발명은 구리막, 티타늄막 및 인듐산화막의 삼중막을 우수한 효율 및 식각 특성을 유지한 채 일괄식각 할 수 있는 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an etching solution composition capable of batch etching while maintaining excellent efficiency and etching characteristics of a triple layer of a copper layer, a titanium layer, and an indium oxide layer.
본 발명은 상기 구리막, 티타늄막 및 인듐산화막의 삼중막 식각용 식각액 조성물을 이용한 표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a method of manufacturing an array substrate for a display device using an etchant composition for etching a triple layer of the copper layer, the titanium layer, and the indium oxide layer.
본 발명은, 상기 목적을 달성하기 위하여, 과황산염; 불소화합물; 무기산; 유기산; 글라이신; 아미노테트라졸 및 아미노메틸테트라졸을 포함하는 아졸계 화합물; 및 물을 포함하는, 구리막, 티타늄막 및 산화주석인듐(ITO)막의 삼중막 식각용 식각액 조성물을 제공한다.The present invention, in order to achieve the above object, persulfate; Fluorine compounds; Inorganic acids; Organic acids; Glycine; Azole compounds including aminotetrazole and aminomethyltetrazole; And it provides an etchant composition for etching a triple layer of a copper film, a titanium film, and an indium tin oxide (ITO) film containing water.
또한, 본 발명은 a) 기판 상에 게이트 배선을 형성하는 단계; b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계; d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서, 상기 d) 단계는 산화물 반도체층 상에 구리막, 티타늄막 및 산화주석인듐(ITO)막의 삼중막을 형성하고, 상기 삼중막을 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하며, 상기 식각액 조성물은 상술한 본 발명의 삼중막 식각용 식각액 조성물인 것을 특징으로 하는 표시장치용 어레이 기판의 제조방법을 제공한다. In addition, the present invention comprises the steps of: a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming an oxide semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the oxide semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, wherein step d) comprises a copper film, a titanium film, and indium tin oxide (ITO) on an oxide semiconductor layer. Forming a triple layer of a film, and etching the triple layer with an etchant composition to form source and drain electrodes, wherein the etchant composition is an etchant composition for etching a triple layer of the present invention. It provides a method of manufacturing a substrate.
본 발명의 실시예들에 따르면, 구리막, 티타늄막 및 인듐산화막의 삼중막으로 이루어진 배선들을 본 발명의 식각액만으로 일괄 습식 식각할 수 있어, 식각 공정의 간소화 및 생산성 향상 효과를 제공할 수 있다.According to embodiments of the present invention, wirings made of a triple layer of a copper layer, a titanium layer, and an indium oxide layer may be wet etched only with the etching solution of the present invention, thereby simplifying an etching process and improving productivity.
또한, 본 발명의 식각액 조성물을 이용하면 인듐산화막, 특히, 산화아연인듐막 뿐만 아니라 산화주석인듐(ITO)막의 팁(tip) 발생을 억제하여 식각 균일성을 향상시킬 수 있어 후속공정에서 발생될 수 있는 배선의 단락이나 단선 등의 문제를 예방할 수 있다.In addition, when the etchant composition of the present invention is used, it is possible to improve the etching uniformity by suppressing the generation of the tip of the indium tin oxide (ITO) film as well as the indium zinc oxide film, which can be generated in a subsequent process. Problems such as short circuit or disconnection of existing wiring can be prevented.
도 1은 본 발명의 실시예의 조성물 및 비교예 조성물을 사용하여, 티타늄/구리/산화아연인듐(IZO)의 삼중막 식각실험을 수행한 결과에 대한 도면이다.
도 2는 본 발명의 실시예의 조성물 및 비교예 조성물을 사용하여, 티타늄/구리/산화주석인듐(ITO)의 삼중막 식각실험을 수행한 결과에 대한 도면이다.1 is a view showing the result of performing a triple-layer etching experiment of titanium/copper/indium zinc oxide (IZO) using the composition of the Example of the present invention and the composition of Comparative Example.
FIG. 2 is a diagram illustrating a result of performing a triple film etching experiment of titanium/copper/indium tin oxide (ITO) using the composition of the Example of the present invention and the composition of Comparative Example.
본 발명은 구리막, 티타늄막 및 인듐산화막으로 이루어진 삼중막을 일괄 식각하기 위해 활용될 수 있는 식각액 조성물 및 이를 이용한 표시장치용 어레이 기판의 제조방법을 제공한다.The present invention provides an etchant composition that can be used for batch etching a triple layer made of a copper layer, a titanium layer, and an indium oxide layer, and a method of manufacturing an array substrate for a display device using the same.
본 발명에서, 상기 인듐산화막은 산화주석인듐(ITO)막, 산화아연인듐(IZO)막, 산화주석아연인듐(ITZO)막 및 산화갈륨아연인듐(IGZO)으로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있으며, 바람직하게는 산화주석인듐(ITO)막 또는 산화아연인듐(IZO)막일 수 있다. In the present invention, the indium oxide film includes at least one selected from the group consisting of indium tin oxide (ITO) film, indium zinc oxide (IZO) film, indium tin oxide (ITZO) film, and indium gallium zinc oxide (IGZO). And, preferably, an indium tin oxide (ITO) film or an indium zinc oxide (IZO) film.
본 발명에 따른 식각액 조성물을 이용하여 상기 삼중막을 식각하면, 식각 공정의 간소화 및 생산성을 향상시킬 수 있으며. 특히, 산화주석인듐막의 팁 발생을 억제할 수 있어 향상된 식각 균일성을 제공하여 배선의 단락이나 단선 등의 문제를 예방할 수 있다.When the triple layer is etched using the etchant composition according to the present invention, the etching process can be simplified and productivity can be improved. In particular, it is possible to suppress the occurrence of the tip of the indium tin oxide film, thereby providing improved etching uniformity, thereby preventing problems such as short circuit or disconnection of wiring.
이하, 본 발명에 대해 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
<식각액 조성물><Etching liquid composition>
본 발명에 따른 식각액 조성물은 과황산염, 불소화합물, 무기산, 유기산, 글라이신, 아미노테트라졸 및 아미노메틸테트라졸을 포함하는 아졸계 화합물, 및 물을 포함할 수 있다.The etchant composition according to the present invention may include persulfate, fluorine compounds, inorganic acids, organic acids, azole compounds including glycine, aminotetrazole, and aminomethyltetrazole, and water.
(A) 과황산염(A) persulfate
과황산염은 구리막에 대한 주산화제로 포함될 수 있다. 과황산염에 의해 구리막, 티타늄막 및 인듐산화막으로 이루어진 삼중막 중 구리막에 대한 식각이 개시될 수 있다.Persulfate may be included as a main oxidizing agent for the copper film. Etching of the copper layer among the triple layers composed of the copper layer, the titanium layer, and the indium oxide layer may be initiated by the persulfate.
상기 과황산염은 상기 식각액 조성물 총 중량에 대하여 약 0.5 중량% 내지 약 20 중량%의 함량으로 포함될 수 있다. 과황산염의 함량이 상기 함량범위로 포함되는 경우, 식각률이 감소하여 충분한 식각이 이루어지지 않는 것을 방지할 수 고, 식각속도가 지나치게 빨라지지 않도록 유지하여 과식각(overetching)이 발생되지 않는 이점이 있다.The persulfate may be included in an amount of about 0.5% to about 20% by weight based on the total weight of the etchant composition. When the content of persulfate is included in the above content range, there is an advantage in that the etching rate is reduced to prevent insufficient etching, and the etching rate is maintained so as not to be too fast, so that overetching does not occur. .
바람직하게는, 상기 삼중막에 대한 식각률을 확보하면서도 과식각을 억제하는 측면에서 과황산염의 함량은 약 5.0 중량% 내지 20.0 중량%일 수 있다. Preferably, the content of persulfate may be about 5.0 wt% to 20.0 wt% in terms of preventing overetching while securing an etch rate for the triple layer.
상기 과황산염은 예를 들어, 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8), 또는 과황산암모늄((NH4)2S2O8)을 포함할 수 있으며, 또는 이들 중 두 종 이상의 혼합물을 포함할 수 있다.The persulfate may include, for example, potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), or ammonium persulfate ((NH 4 ) 2 S 2 O 8 ). And, or a mixture of two or more of them may be included.
(B) 불소화합물(B) fluorine compounds
불소화합물은 티타늄막을 식각하며, 상기 식각에 의해 발생할 수 있는 잔사를 제거하기 위한 성분으로 포함될 수 있다.The fluorine compound may be included as a component for etching the titanium layer and removing residues that may be generated by the etching.
상기 불소 화합합물은 상기 식각액 조성물 총 중량에 대하여 약 0.01 중량% 내지 약 2.0 중량%의 함량으로 포함될 수 있으며, 바람직하게는 0.1 중량% 내지 1.0 중량%로 포함될 수 있다. 불소화합물의 함량이 상기 함량범위로 포함되는 경우, 티타늄막에 대한 식각률을 확보할 수 있고 잔사 발생을 방지할 수 있다. The fluorine compound may be included in an amount of about 0.01% to about 2.0% by weight, preferably 0.1% to 1.0% by weight, based on the total weight of the etchant composition. When the content of the fluorine compound is included in the above content range, the etching rate for the titanium film can be secured and the generation of residues can be prevented.
상기 불소화합물은, 예를 들어, 불화암모늄(ammonium fluoride), 불화나트륨(sodium fluoride), 불화칼륨 (potassium fluoride), 중불화암모늄(ammonium bifluoride), 중불화나트륨(sodium bifluoride), 또는 중불화칼륨(potassium bifluoride)을 포함할 수 있다. 또한 상기 불소 화합물은 이들 중 두 종 이상의 혼합물을 포함할 수 있다.The fluorine compound is, for example, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, or potassium bifluoride. (potassium bifluoride) may be included. In addition, the fluorine compound may include a mixture of two or more of them.
(C) 무기산(C) inorganic acid
무기산은 본 발명의 식각액 조성물에 보조 산화제로 포함될 수 있다.The inorganic acid may be included as a secondary oxidizing agent in the etchant composition of the present invention.
일 실시예에 있어서, 상기 무기산의 상기 식각액 조성물 내의 함량에 따라 식각 속도가 제어될 수 있다.In one embodiment, the etching rate may be controlled according to the content of the inorganic acid in the etchant composition.
예를 들면, 식각 공정에 의해 구리막이 식각되면, 기판 내 구리이온이 용출되어 식각액 조성물 내에 구리이온이 존재하게 되는데, 상기 무기산은 식각액 조성물 내의 구리이온과 반응하여 식각액 내 구리이온의 증가를 막을 수 있으므로, 식각률이 감소하는 것을 방지할 수 있다. For example, when a copper film is etched by an etching process, copper ions in the substrate are eluted and copper ions are present in the etchant composition, and the inorganic acid reacts with copper ions in the etchant composition to prevent the increase of copper ions in the etchant. Therefore, it is possible to prevent the etch rate from decreasing.
상기 무기산은 상기 식각액 조성물 총 중량에 대하여 약 0.1 중량% 내지 약 10 중량%의 함량으로 포함될 수 있고, 바람직하게는 약 2 중량% 내지 5중량%로 포함될 있다. 무기산의 함량이 상기 함량범위로 포함되면, 식각률이 감소하여 충분한 식각 속도에 도달하지 못하는 것을 방지할 수 있다. 또한, 금속막 식각시 사용되는 감광막에 균열(crack)이 생기거나 상기 감광막이 벗겨져 감광막의 하부에 위치한 산화주석인듐막과 같은 인듐산화막이나 구리막, 티타늄막의 금속막이 과도하게 식각되는 것을 방지할 수 있다. The inorganic acid may be included in an amount of about 0.1% to about 10% by weight based on the total weight of the etchant composition, and preferably, about 2% to 5% by weight. When the content of the inorganic acid is included in the above content range, the etch rate decreases to prevent failure to reach a sufficient etch rate. In addition, it is possible to prevent excessive etching of an indium oxide film such as an indium tin oxide film, a copper film, or a titanium film, such as an indium tin oxide film located under the photosensitive film when a crack occurs in the photosensitive film used when etching the metal film or the photosensitive film is peeled off. have.
본 발명의 식각액 조성물에서, 상기 무기산은 예를 들어, 질산, 황산, 인산, 또는 과염소산을 포함할 수 있으며, 또는 이들 중 두 종 이상의 혼합물을 포함할 수 있다.In the etchant composition of the present invention, the inorganic acid may include, for example, nitric acid, sulfuric acid, phosphoric acid, or perchloric acid, or a mixture of two or more of them.
(D) 유기산(D) organic acid
유기산은 금속막의 식각 속도를 조절하기 위한 것으로 포함될 수 있다. The organic acid may be included to control the etching rate of the metal layer.
상기 유기산은 상기 식각액 내의 함량이 증가함에 따라 모든 금속막의 식각 속도를 높일 수 있다. 상기 유기산 같은 경우는 식각액 조성물 총 중량에 대하여 약 0.1 중량% 내지 약 20.0중량%의 함량으로 포함될 수 있다. 유기산의 함량이 상기 범위로 포함되는 경우, 식각 속도가 저하되거나 지나치게 빨라지는 것을 조절할 수 있으며, 이에 의해 형성된 배선의 테이퍼 각(Taper Angle)이 의도했던 것보다 높아지는 문제를 방지할 수 있다.The organic acid may increase the etching rate of all metal films as the content of the organic acid increases. The organic acid may be included in an amount of about 0.1% to about 20.0% by weight based on the total weight of the etchant composition. When the content of the organic acid is included in the above range, it is possible to control that the etching rate is lowered or excessively increased, thereby preventing a problem in which the taper angle of the formed wiring becomes higher than intended.
바람직한 일 실시예에 있어서, 상기 유기산의 함량은 1.0 중량% 내지 15.0 중량%의 범위로 조절될 수 있다. In a preferred embodiment, the content of the organic acid may be adjusted in the range of 1.0% to 15.0% by weight.
예를 들면, 상기 유기산은 주석산(Tartaric Acid), 아세트산(acetic acid), 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜(glycolic acid), 말론산(malonic acid), 펜탄산(pentanoic acid) 및/또는 옥살산(oxalic acid)등 으로 이루어진 군으로부터 선택되는 1종이상을 포함할 수 있으며, 이에 제한되지 않는다.For example, the organic acid is tartaric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycol (glycolic acid) , Malonic acid, pentanoic acid, and/or oxalic acid may include at least one selected from the group consisting of, but is not limited thereto.
(E) 글라이신(E) glycine
글라이신은 금속막에 대한 부식방지제 및 처음 의도했던 Side Etch량을 유지시켜 주는 역할을 한다. 또한, 글라이신은 성분자체의 경시변화도 없고, 약액에 용출되는 금속이온들을 잘 킬레이팅 시켜 약액을 안정화 시키는 역할도 할 수 있다. Glycine is a corrosion inhibitor for the metal film and plays a role in maintaining the initially intended side etch amount. In addition, glycine does not change over time of the component itself, and can play a role of stabilizing the chemical solution by chelating the metal ions eluted in the chemical solution well.
상기 글라이신은 식각액 조성물 총 중량에 대하여 약 0.1중량% 내지 약 5.0중량%의 함량으로 포함될 수 있다. 글라이신의 함량이 상기 범위로 포함되는 경우, 금속막에서 용출되는 금속이온에 대한 킬레이팅 효과를 제공할 수 있고, 약액 안정성이 향상될 수 있으며, 금속막에 대한 식각 속도가 저하되어 공정 시간이 길어지는 문제를 방지할 수 있다.The glycine may be included in an amount of about 0.1% to about 5.0% by weight based on the total weight of the etchant composition. When the content of glycine is included in the above range, a chelating effect for metal ions eluted from the metal film can be provided, stability of the chemical solution can be improved, and the etching rate for the metal film is reduced, resulting in a long process time. Losing problems can be avoided.
바람직한 일 실시예에 있어서, 글라이신은 식각액 조성물 총 중량에 대하여 0.1 중량% 내지 3.0 중량%이 함량으로 포함될 수 있다.In a preferred embodiment, glycine may be included in an amount of 0.1% to 3.0% by weight based on the total weight of the etchant composition.
(F) 아졸계 화합물(F) azole compound
아졸계 화합물은 본 발명의 식각액 조성물에 부식 방지제로 포함될 수 있다. 상기 아졸계 화합물은 아미노테트라졸(aminotetrazole) 및 아미노메틸테트라졸(Amino MethylTetrazole)을 필수 성분으로 포함한다.The azole-based compound may be included as a corrosion inhibitor in the etchant composition of the present invention. The azole-based compound includes aminotetrazole and aminomethyltetrazole as essential components.
예시적인 실시예들에 있어서, 아졸계 화합물은 상기 식각액 조성물 총 중량에 대하여 약 0.1 중량% 내지 약 5.0 중량%의 함량으로 포함될 수 있고, 바람직하게는, 0.3 중량% 내지 3.0 중량%의 함량으로 포함될 수 있다.In exemplary embodiments, the azole-based compound may be included in an amount of about 0.1% to about 5.0% by weight, and preferably, in an amount of 0.3% to 3.0% by weight based on the total weight of the etchant composition. I can.
아졸계 화합물의 함량이 상기 함량범위로 포함되면, 식각률을 균일하게 유지시킬 수 있어, 금속막이 과식각되거나 원하는 정도의 식각을 달성하지 못하는 문제가 발생되지 않도록 할 수 있다. When the content of the azole-based compound is included in the above content range, the etch rate can be uniformly maintained, so that a problem in which the metal film is not overetched or a desired level of etching is not achieved may occur.
(G) 물(G) water
본 발명의 식각액 조성물에 포함되는 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water contained in the etchant composition of the present invention may be deionized water for semiconductor processing, and preferably 18㏁/cm or more of the deionized water may be used.
상기 물의 함량은 조성물 총 중량이 100 중량%가 되도록 하는 잔량으로 포함될 수 있다. 구체적으로, 본 발명의 “잔량”은 본 발명의 필수 성분 및 그 외 추가 성분들을 더 포함한 총 조성물의 중량이 100중량%가 되도록 하는 잔량을 의미하며, 상기 “잔량”의 의미로 인해 본 발명의 조성물이 추가 성분이 포함되지 않는 것으로 한정되지 않는다.The content of water may be included in a residual amount such that the total weight of the composition is 100% by weight. Specifically, the "remaining amount" of the present invention means the remaining amount such that the total weight of the composition further including the essential ingredients and other additional ingredients of the present invention is 100% by weight, and due to the meaning of the "remaining amount" The composition is not limited to not containing additional ingredients.
<표시장치용 어레이 기판의 제조방법><Method of manufacturing array substrate for display device>
또한, 본 발명은 a) 기판 상에 게이트 배선을 형성하는 단계; b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계; d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서, In addition, the present invention is a) forming a gate wiring on a substrate; b) forming a gate insulating layer on the substrate including the gate wiring; c) forming an oxide semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the oxide semiconductor layer; And e) forming a pixel electrode connected to the drain electrode, the method comprising:
상기 d) 단계는 산화물 반도체층 상에 구리막, 티타늄막 및 인듐산화막의 삼중막을 형성하고, 상기 삼중막을 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하며, 상기 식각액 조성물은 상술한 본 발명의 식각액 조성물인 것을 특징으로 하는 표시 장치용 어레이 기판의 제조방법을 제공한다.The step d) includes forming a triple layer of a copper layer, a titanium layer, and an indium oxide layer on the oxide semiconductor layer, and etching the triple layer with an etchant composition to form source and drain electrodes, wherein the etchant composition is described above. It provides a method of manufacturing an array substrate for a display device, which is the etchant composition of the present invention.
본 발명에 있어서, 상기 인듐산화막은 산화주석인듐(ITO)막, 산화아연인듐(IZO)막, 산화주석아연인듐(ITZO)막 및 산화갈륨아연인듐(IGZO)으로 이루어진 군에서 선택되는 하나 이상을 포함할 수 있으며, 바람직하게는 산화주석인듐(ITO)막 또는 산화아연인듐(IZO)막이다.In the present invention, the indium oxide film comprises at least one selected from the group consisting of indium tin oxide (ITO) film, indium zinc oxide (IZO) film, indium tin oxide (ITZO) film, and indium gallium zinc oxide (IGZO). It may include, and is preferably an indium tin oxide (ITO) film or an indium zinc oxide (IZO) film.
상술한 본 발명의 식각액 조성물에 대한 사항은, 상기 표시 장치용 어레이 기판의 제조방법에 동일하게 적용된다. 또한, 본 발명의 표시 장치용 어레이 기판의 제조방법은 상기 식각액 조성물을 사용하는 점 이외에는, 당업자에게 알려진 표시 장치용 어레이 기판의 제조방법의 각 단계에 관한 내용을 포함할 수 있다. The above-described matters regarding the etchant composition of the present invention are equally applied to the method of manufacturing the array substrate for a display device. In addition, the method of manufacturing an array substrate for a display device according to the present invention may include information on each step of a method of manufacturing an array substrate for a display device known to those skilled in the art, other than using the etchant composition.
이하, 본 발명의 이해를 돕기 위하여 구체적인 실시예들 및 비교예들을 포함하는 실험예를 제시하나, 이는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, experimental examples including specific examples and comparative examples are presented to aid in understanding of the present invention, but this is only illustrative of the present invention and does not limit the scope of the appended claims, and the scope and technology of the present invention It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope of the spirit, and it is natural that such modifications and modifications fall within the appended claims.
실시예 및 비교예: 식각액 조성물 제조Examples and Comparative Examples: Preparation of etchant composition
하기 표 1에 기재된 성분 및 함량(중량%)으로 실시예들 및 비교예들에 따른 식각액 조성물을 제조하였다.The etchant compositions according to Examples and Comparative Examples were prepared using the components and contents (% by weight) shown in Table 1 below.
ABF: Ammonium bifluoride
AcOH: Acetic acidAPS: Ammonium persulfate
ABF: Ammonium bifluoride
AcOH: Acetic acid
실험예: 삼중막 식각 평가Experimental Example: Trilayer Etch Evaluation
각 약액을 30℃로 유지한 후, 각 조성별로 3중막에 대한 일괄 식각 가능 여부를 알아보기 위한 실험 조건이다. Etcher는 0.5세대 Glass Size를 처리할 수 있는 장비를 사용하며, 약액 분사는 Spray Type이고 Spray압력은 0.1MPa이다. Etcher zone에서의 배기압력은 20Pa를 유지한다. 각 조성별 약액을 30℃로 유지한 후, Ti/Cu/IZO 삼중막 기판과 Ti/Cu/ITO 삼중막 기판을 준비하고 이때 상부 IZO와 ITO의 두께는 동일하게 500Å 이다. 총 식각시간은 Cu식각시간 기준으로 2배를 곱해 오버식각(Over Etch)을 진행하며, Etcher와 Spray, 배기 조건은 각각 동등하다.After maintaining each chemical solution at 30°C, this is an experimental condition to determine whether batch etching of the triple layer for each composition is possible. Etcher uses equipment that can process 0.5G Glass Size, and spraying of chemical liquid is spray type and spray pressure is 0.1MPa. The exhaust pressure in the etcher zone is maintained at 20Pa. After maintaining the chemical solution for each composition at 30°C, a Ti/Cu/IZO triple layer substrate and a Ti/Cu/ITO triple layer substrate are prepared. At this time, the thickness of the upper IZO and ITO is equal to 500Å. The total etch time is multiplied by 2 times based on the Cu etch time to perform over etch, and the etch, spray, and exhaust conditions are the same.
표 2에 기재된 내용은 각각의 실시예 및 비교예 조성별로 티타늄/구리/산화아연인듐(IZO)의 3중막과, 티타늄/구리/산화주석인듐(ITO)의 3중막 식각 후 SEM측정으로 얻어낸 결과값이다. 실시예 1 내지 3은, 약 100초의 식각 시간동안 티타늄/구리/산화아연인듐(IZO)의 3중막에서 상부 인듐산화막(IZO)의 팁(tip)이 관찰되지 않았고, 티타늄/구리/산화주석인듐(ITO)의 3중막에서 후속 공정에서 특별히 문제를 일으키지 않는 정도인 0.1㎛ 미만의 아주 미세한 ITO Tip이 관찰되었다. 이로부터 본 발명에 따른 식각액 조성물은 구리막, 티타늄막 및 산화주석인듐(ITO)막의 삼중막에 대한 일괄 식각이 가능함을 알 수 있다.Table 2 shows the results obtained by SEM measurement after etching the triple film of titanium/copper/indium zinc oxide (IZO) and the triple film of titanium/copper/indium tin oxide (ITO) for each composition of Example and Comparative Example. Value. In Examples 1 to 3, the tip of the upper indium oxide film (IZO) was not observed in the triple film of titanium/copper/indium zinc oxide (IZO) for an etching time of about 100 seconds, and titanium/copper/indium tin oxide A very fine ITO tip of less than 0.1 μm was observed in the triple film of (ITO), which does not cause any problems in the subsequent process. From this, it can be seen that the etchant composition according to the present invention can collectively etch a triple layer of a copper layer, a titanium layer, and an indium tin oxide (ITO) layer.
반면, 비교예 1 내지 4의 경우, 티타늄/구리/산화아연인듐(IZO)의 3중막에 대한 일괄식각은 가능하나, 티타늄/구리/산화주석인듐(ITO)의 3중막 식각시에는 산화주석인듐(ITO)의 잔사량이 상대적으로 큰 것을 확인할 수 있었다. 통상 0.1㎛ 보다 큰 경우 후속공정에서 스텝커버리지(Step coverage)를 야기하며, 배선의 단선이나 단락의 원인이 되므로 비교예 1 내지 4는 구리막, 티타늄막 및 산화주석인듐(ITO)막의 삼중막 식각에 사용할 수 없는 수준임을 알 수 있다.On the other hand, in the case of Comparative Examples 1 to 4, batch etching of the triple layer of titanium/copper/indium zinc oxide (IZO) is possible, but indium tin oxide when etching the triple layer of titanium/copper/indium tin oxide (ITO) It was confirmed that the residual amount of (ITO) was relatively large. In general, if it is larger than 0.1 μm, step coverage is caused in the subsequent process, and since it may cause disconnection or short circuit of the wiring, Comparative Examples 1 to 4 are trilayer etching of a copper film, a titanium film, and an indium tin oxide (ITO) film. It can be seen that the level cannot be used.
Claims (10)
식각액 조성물 총 중량에 대하여,
과황산염 0.5 중량% 내지 20 중량%;
불소화합물 0.01 중량% 내지 2 중량%;
무기산 0.1 중량% 내지 10중량%;
유기산 0.1 중량% 내지 20 중량%;
글라이신 0.1 중량% 내지 5.0중량%;
아미노테트라졸 및 아미노메틸테트라졸을 포함하는 아졸계 화합물 0.1 중량% 내지 5 중량%; 및
잔량의 물을 포함하는, 구리막, 티타늄막 및 인듐산화막의 삼중막 식각용 식각액 조성물. The method according to claim 1,
Based on the total weight of the etchant composition,
0.5% to 20% by weight persulfate;
0.01% to 2% by weight of a fluorine compound;
0.1% to 10% by weight of inorganic acid;
0.1% to 20% by weight of organic acid;
0.1% to 5.0% glycine;
0.1% to 5% by weight of an azole-based compound including aminotetrazole and aminomethyltetrazole; And
An etchant composition for etching a triple layer of a copper film, a titanium film, and an indium oxide film containing the remaining amount of water.
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 산화물 반도체층을 형성하는 단계;
d) 상기 산화물 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,
상기 d) 단계는 산화물 반도체층 상에 구리막, 티타늄막 및 인듐산화막의 삼중막을 형성하고, 상기 삼중막을 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하며,
상기 식각액 조성물은 청구항 1 내지 청구항 9 중 어느 한 항의 식각액 조성물인 것을 특징으로 하는, 표시 장치용 어레이 기판의 제조방법.a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming an oxide semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the oxide semiconductor layer; And
e) A method of manufacturing an array substrate for a display device comprising the step of forming a pixel electrode connected to the drain electrode,
Step d) includes forming a triple layer of a copper layer, a titanium layer, and an indium oxide layer on the oxide semiconductor layer, and etching the triple layer with an etchant composition to form source and drain electrodes,
The method of manufacturing an array substrate for a display device, wherein the etchant composition is the etchant composition according to any one of claims 1 to 9.
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