KR20180110760A - Etching solution composition, manufacturing method of an array substrate for display device using the same - Google Patents
Etching solution composition, manufacturing method of an array substrate for display device using the same Download PDFInfo
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- KR20180110760A KR20180110760A KR1020170040492A KR20170040492A KR20180110760A KR 20180110760 A KR20180110760 A KR 20180110760A KR 1020170040492 A KR1020170040492 A KR 1020170040492A KR 20170040492 A KR20170040492 A KR 20170040492A KR 20180110760 A KR20180110760 A KR 20180110760A
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- film
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- 238000005530 etching Methods 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- -1 azole compound Chemical class 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 108
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 24
- 239000011733 molybdenum Substances 0.000 claims description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims description 24
- 239000004065 semiconductor Substances 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims 1
- 229940010556 ammonium phosphate Drugs 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 235000019289 ammonium phosphates Nutrition 0.000 claims 1
- 229940116349 dibasic ammonium phosphate Drugs 0.000 claims 1
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 43
- 239000002184 metal Substances 0.000 abstract description 43
- 230000000052 comparative effect Effects 0.000 description 22
- 229910016027 MoTi Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- MPIPASJGOJYODL-SFHVURJKSA-N (R)-isoconazole Chemical compound ClC1=CC(Cl)=CC=C1[C@@H](OCC=1C(=CC=CC=1Cl)Cl)CN1C=NC=C1 MPIPASJGOJYODL-SFHVURJKSA-N 0.000 description 1
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical compound C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- ZFDGMMZLXSFNFU-UHFFFAOYSA-N 2,5-dimethylpyrazol-3-amine Chemical compound CC=1C=C(N)N(C)N=1 ZFDGMMZLXSFNFU-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- ZBRDJMFLJXFIGJ-UHFFFAOYSA-N 3-phenyl-1,2-oxazole Chemical compound O1C=CC(C=2C=CC=CC=2)=N1 ZBRDJMFLJXFIGJ-UHFFFAOYSA-N 0.000 description 1
- JJPWJEGNCRGGGA-UHFFFAOYSA-N 4-[[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]amino]benzoic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)NC1=CC=C(C(=O)O)C=C1 JJPWJEGNCRGGGA-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VIHYIVKEECZGOU-UHFFFAOYSA-N N-acetylimidazole Chemical compound CC(=O)N1C=CN=C1 VIHYIVKEECZGOU-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- PUYZUDWTQPBQFZ-UHFFFAOYSA-N aniline 2H-triazole Chemical compound N1N=NC=C1.NC1=CC=CC=C1 PUYZUDWTQPBQFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229960004849 isoconazole Drugs 0.000 description 1
- 150000003854 isothiazoles Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NYIGEYYREVRXES-UHFFFAOYSA-N pyrazol-1-amine Chemical compound NN1C=CC=N1 NYIGEYYREVRXES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- IFOIAHYDBXLNJX-UHFFFAOYSA-N trioxazole Chemical compound O1OC=NO1 IFOIAHYDBXLNJX-UHFFFAOYSA-N 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
-
- 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
- H01L29/66—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명은 식각액 조성물 및 이를 이용한 디스플레이 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etching liquid composition and a method of manufacturing an array substrate for a display device using the same.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식식각 또는 식각액 조성물을 이용하는 습식식각이 사용된다.The process of forming a metal wiring on a substrate in a semiconductor device is usually composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process, And a cleaning process before and after the individual unit process. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.
이러한 반도체 장치에서 최근 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 왜냐하면 저항이 RC 신호지연을 유발하는 주요한 인자이므로, 특히 TFT-LCD(thin film transistor-liquid crystal display)의 경우 패널크기 증가와 고해상도 실현이 기술 개발에 관건이 되고 있기 때문이다. 따라서, TFT-LCD의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는, 저-저항의 물질개발이 필수적이다. 따라서, 종래에 주로 사용되었던 크롬(Cr, 비저항: 12.7 ×10- 8Ωm), 몰리브데늄(Mo, 비저항: 5×10- 8Ωm), 알루미늄(Al, 비저항: 2.65×10- 8Ωm) 및 이들의 합금은 대형 TFT LCD에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다.In such semiconductor devices, resistance of metal wiring has recently become a major concern. This is because the resistance is a major factor that causes the RC signal delay, especially in the case of TFT-LCD (thin film transistor-liquid crystal display), because the increase in panel size and realization of high resolution are the key to technology development. Therefore, in order to realize the reduction of the RC signal delay which is indispensably required for the enlargement of the TFT-LCD, it is essential to develop a low-resistance material. Thus, the chromium which was mainly used conventionally (Cr, specific resistance: 12.7 × 10 - 8 Ωm) , molybdenum (Mo, specific resistance: 5 × 10 - 8 Ωm) , aluminum (Al, specific resistance: 2.65 × 10 - 8 Ωm) And alloys thereof are difficult to use as gate and data wiring used in a large-sized TFT LCD.
이와 같은 배경 하에서, 새로운 저-저항 금속막으로서 구리막 및 구리 몰리브데늄막 등의 구리계 금속막 및 이의 식각액 조성물에 대한 관심이 높아지고 있고, 이와 관련하여 대한민국 공개특허 제10-2007-0055259호에는 액정표시장치의 구리 및 구리/몰리브데늄 또는 구리/몰리브데늄 합금 전극용 식각 조성물을 개시하고 있다. 다만, 최근 고해상도 요구로 인한 금속 배선이 미세 패턴화되는 추세에서, 하부막인 몰리브데늄막에 손상을 주지 않는 식각액 조성물이 필요하나, 상기 선행문헌의 식각액 조성물은 하부막에 손상을 주어 공정 마진이 떨어지는 단점이 있다.Under such background, attention has been paid to a copper-based metal film such as a copper film and a copper molybdenum film as a new low-resistance metal film and an etchant composition thereof, and Korean Patent Publication No. 10-2007-0055259 Discloses etching compositions for copper and copper / molybdenum or copper / molybdenum alloy electrodes of liquid crystal displays. However, in recent trends of metal patterning due to high-resolution demands for fine patterning, it is necessary to provide an etching composition which does not damage the molybdenum film as a lower film, but the etching composition of the above- There is a downside to this.
따라서, 상부막인 구리막은 식각하면서 하부막인 몰리브데늄막의 식각을 방지할 수 있는 식각액 조성물에 대한 개발이 필요한 상황이다.Therefore, it is necessary to develop an etchant composition capable of preventing the etching of the molybdenum film as the lower film while etching the copper film as the upper film.
본 발명은 식각 속도가 우수하며, 구리계 금속막을 포함하는 다층막 식각시, 구리계 금속막을 선택적으로 식각할 수 있는 식각액 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide an etchant composition which is excellent in etching rate and can selectively etch a copper-based metal film when a multilayer film including a copper-based metal film is etched.
또한, 본 발명은 상기 식각액 조성물을 사용하여 미세패턴이 형성된 디스플레이 장치용 어레이 기판을 제조하는 방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a method for manufacturing an array substrate for a display device in which a fine pattern is formed using the etchant composition.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 과산화수소, 아졸 화합물, 인산염 화합물, 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물, 폴리에틸렌이민, 다가 알코올형 계면활성제 및 물을 포함하는 식각액 조성물로,The present invention relates to an etching solution composition comprising hydrogen peroxide, an azole compound, a phosphate compound, a water-soluble compound containing a nitrogen atom and a carboxyl group in one molecule, a polyethyleneimine, a polyhydric alcohol type surfactant,
상기 폴리에틸렌이민의 분자량은 1,000 내지 10,000인 것을 특징으로 하는 식각액 조성물을 제공한다.And the molecular weight of the polyethyleneimine is 1,000 to 10,000.
또한, 본 발명은 (a) 기판 상에 게이트 배선을 형성하는 단계;The present invention also provides a method of manufacturing a semiconductor device, comprising: (a) forming a gate wiring on a substrate;
(b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(b) forming a gate insulating layer on the substrate including the gate wiring;
(c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;(c) forming a semiconductor layer on the gate insulating layer;
(d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(d) forming source and drain electrodes on the semiconductor layer; And
(e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,(e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 (a) 및 (d)단계는 상기 본 발명의 식각액 조성물로 식각하여 게이트 배선, 소스 전극 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법을 제공한다.The steps (a) and (d) include a step of forming a gate wiring, a source electrode, and a drain electrode by etching with the etchant composition of the present invention.
또한, 본 발명은 상기 제조방법으로 제조된 디스플레이 장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a display device manufactured by the above manufacturing method.
본 발명의 식각액 조성물은 식각 속도가 우수하며, 구리계 금속막을 포함하는 다층막 식각시 구리계 금속만을 선택적으로 식각할 수 있어 미세패턴을 형성할 수 있는 효과를 지니고 있다.The etchant composition of the present invention has an excellent etching rate and is capable of selectively etching only a copper-based metal when etching a multilayer film including a copper-based metal film, thereby forming a fine pattern.
구체적으로, 본 발명의 식각액 조성물은 구리계 금속막/몰리브데늄계 금속막으로 이루어진 이중막 식각시, 구리계 금속막을 식각하면서 몰리브데늄계 금속막의 식각을 방지할 수 있어 몰리브데늄계 금속막에 손상이 발생하는 것을 예방하는 효과를 지니고 있다.Specifically, the etching solution composition of the present invention can prevent the etching of the molybdenum-based metal film while etching the copper-based metal film when the double-layer etching is made of the copper-based metal film / molybdenum-based metal film, It has an effect of preventing damage to the film.
또한, 본 발명의 식각액 조성물은 미세 패턴을 형성할 수 있어 고해상도의 디스플레이 장치용 어레이 기판을 제공할 수 있다.In addition, the etchant composition of the present invention can form a fine pattern and can provide an array substrate for a high-resolution display device.
도 1은 기판의 경사식 식각 공정을 모식적으로 나타낸 도면이다.
도 2는 본 발명에서 사이드에치의 정의를 설명하기 위해 도식화하여 나타낸 이미지이다.BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram schematically showing a step of etching a substrate in an oblique manner; FIG.
Fig. 2 is an image showing the definition of a side value in the present invention.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 과산화수소, 아졸 화합물, 인산염 화합물, 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물, 폴리에틸렌이민, 다가 알코올형 계면활성제 및 물을 포함하는 식각액 조성물로,The present invention relates to an etching solution composition comprising hydrogen peroxide, an azole compound, a phosphate compound, a water-soluble compound containing a nitrogen atom and a carboxyl group in one molecule, a polyethyleneimine, a polyhydric alcohol type surfactant,
상기 폴리에틸렌이민의 분자량은 1,000 내지 10,000인 것을 특징으로 하는 식각액 조성물에 관한 것이다.Wherein the polyethyleneimine has a molecular weight of 1,000 to 10,000.
고해상도를 구현하기 위하여 미세 패턴을 형성할 수 있는 식각액 조성물이 요구되고 있다. 종래에는 구리계 금속막/몰리브데늄계 금속막의 이중막을 일괄 식각하는 식각액 조성물이 사용되었으나, 상기 이중막을 일괄 식각하면 미세 패턴을 형성하는데 어려움이 있다. 따라서, 최근에는 식각액 조성물로 상부의 구리계 금속막을 식각하고, 상부막 식각 후 진공 공정으로 하부의 몰리브데늄계 금속막을 식각하여 미세 패턴을 형성하는 방법이 사용되고 있다.There is a demand for an etchant composition capable of forming a fine pattern in order to realize high resolution. Conventionally, an etchant composition for collectively etching a double-layered film of a copper-based metal film / molybdenum-based metal film is used, but it is difficult to form a fine pattern by collectively etching the double-layer film. Accordingly, recently, a method has been used in which a copper-based metal film on an upper portion is etched with an etching liquid composition, and a lower molybdenum-based metal film is etched by a vacuum process after etching the upper portion to form a fine pattern.
상기의 방법으로 미세 패턴을 형성하기 위해서는 식각액 조성물이 하부막은 식각하지 않고 상부막만을 식각해야 한다.In order to form a fine pattern by the above-described method, only the upper film should be etched without etching the lower film of the etching solution composition.
따라서, 본 발명에서는 상기 분자량은 1,000 내지 10,000의 폴리에틸렌이민을 포함함으로써 하부막에 손상을 가하지 않고, 상부막만을 식각할 수 있는 식각액 조성물을 제공하고자 하였다.Accordingly, the present invention provides an etchant composition capable of etching only the upper film without damaging the lower film by including polyethyleneimine having a molecular weight of 1,000 to 10,000.
본 발명의 식각액 조성물은 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막과 몰리브데늄막 및 몰리브데늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 식각하는 식각액 조성물이며, 바람직하게는 구리막 또는 구리 합금막/몰리브데늄막 또는 몰리브데늄 합금막으로 이루어진 다층막을 식각하는 식각액 조성물이며, 보다 구체적으로 상기 다층막 중 구리막 또는 구리합금막은 식각하면서 몰리브데늄막 또는 몰리브데늄 합금막은 실질적으로 식각하지 않는 식각액 조성물이다.The etchant composition of the present invention is an etchant composition for etching a multilayer film comprising at least one film selected from a copper film and a copper alloy film and at least one film selected from the group consisting of a molybdenum film and a molybdenum alloy film, Layered film made of a copper film or a copper alloy film / molybdenum alloy film or a molybdenum alloy film. More specifically, the copper film or copper alloy film of the multilayer film is a molybdenum film or a molybdenum film The alloy film is an etchant composition that is not substantially etched.
상기 구리 합금막에서, 상기 합금은 예컨대 티타늄(Ti), 셀레늄(Se) 및 텔레늄(Te)으로 이루어진 군에서 선택되는 1종 이상의 금속과 구리의 합금으로 이루어진 합금막을 의미한다.In the copper alloy film, the alloy means an alloy film composed of at least one metal selected from the group consisting of titanium (Ti), selenium (Se), and tellurium (Te) and an alloy of copper.
상기 몰리브데늄 합금막에서, 상기 합금은 예컨대 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In) 등으로 이루어진 군에서 선택되는 1종 이상의 금속과 몰리브데늄의 합금으로 이루어진 합금막을 의미한다.In the molybdenum alloy film, the alloy is selected from the group consisting of, for example, Ti, Ta, Cr, Ni, Ne, Quot; means an alloy film composed of an alloy of at least one metal and molybdenum.
이하, 본 발명의 식각액 조성물의 각 성분을 설명하기로 한다.Hereinafter, each component of the etchant composition of the present invention will be described.
(A)과산화수소((A) hydrogen peroxide HH 22 OO 22 ))
본 발명의 식각액 조성물에 포함되는 과산화수소(H2O2)는 구리계 금속막 및 몰리브데늄계 금속막의 식각 속도에 영향을 주는 주산화제이다.The hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is a main oxidizing agent which affects the etching rate of the copper-based metal film and the molybdenum-based metal film.
상기 과산화수소는 본 발명의 식각액 조성물 총 중량에 대하여 15 내지 25 중량%로 포함되며, 바람직하게는 18 내지 23 중량%로 포함된다.The hydrogen peroxide is contained in an amount of 15 to 25% by weight, and preferably 18 to 23% by weight based on the total weight of the etchant composition of the present invention.
상기 과산화수소가 15 중량% 내지 25 중량%로 포함되면 구리계 금속막 및 몰리브데늄계 금속막의 충분한 식각이 이루어질 수 있으며, 식각액 조성물의 안정성을 확보할 수 있다.When the hydrogen peroxide is contained in an amount of 15 to 25 wt%, sufficient etching of the copper-based metal film and the molybdenum-based metal film can be performed, and the stability of the etchant composition can be secured.
(B)(B) 아졸Azole 화합물 compound
본 발명의 식각액 조성물에 포함되는 아졸 화합물은 구리계 금속막의 식각 속도를 조절하는 역할을 한다.The azole compound included in the etchant composition of the present invention serves to control the etching rate of the copper-based metal film.
상기 아졸 화합물은 당 업계에서 사용되는 것이라면 그 종류를 특별히 제한하는 것은 아니나, 바람직하게는 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 디아졸(thiazole)계 및 이소디아졸(isothiazole)계 화합물로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The azole compound is not particularly limited as long as it is used in the art, but it is preferably a pyrazole compound, an imidazole compound, a triazole compound, a tetrazole compound, At least one compound selected from the group consisting of oxazole, isoxazole, thiazole and isothiazole compounds may be used.
상기 피라졸계 화합물은 구체적으로 예를 들어, 다이메틸피라졸, 1-아미노피라졸, 및 5-아미노, 1,3-다이메틸 피라졸 등을 들 수 있다.Specific examples of the pyrazole-based compound include dimethylpyrazole, 1-aminopyrazole, and 5-amino, 1,3-dimethylpyrazole, and the like.
상기 이미다졸계 화합물은 구체적으로 예를 들어, N-아세틸이미다졸, 1-알리이미다졸 및 2-아미노벤젠이미다졸 등을 들 수 있다.Specific examples of the imidazole-based compound include N-acetylimidazole, 1-allyimidazole, and 2-aminobenzeneimidazole.
상기 트리아졸계 화합물은 구체적으로 예를 들어, 5-아미노트리아졸, 및 2-아미노벤젠트리아졸 등을 들 수 있다.Specific examples of the triazole-based compound include 5-aminotriazole, 2-aminobenzene triazole, and the like.
상기 테트라졸계 화합물은 구체적으로 예를 들어, 5-아미노테트라졸, 5-메틸테트라졸 및 5-아미노-1-메틸테트라졸 등을 들 수 있다.Specific examples of the tetrazole compound include 5-aminotetrazole, 5-methyltetrazole, and 5-amino-1-methyltetrazole.
상기 옥사졸계 화합물은 구체적으로 예를 들어, 트리옥사졸 및 벤조옥사졸 등을 들 수 있다.Specific examples of the oxazole-based compound include trioxazole and benzoxazole.
상기 이소옥사졸계 화합물은 구체적으로 예를 들어, 페닐이속사졸 및 이속사졸 메톡시 페닐 등을 들 수 있다.Specific examples of the isoxazole compound include phenyl isoxazole and isoxazole methoxyphenyl.
상기 디아졸계 화합물은 구체적으로 예를 들어, 옥사디아졸 및 1,2,4-옥사디아졸 등을 들 수 있다.Specific examples of the diazole-based compound include oxadiazole and 1,2,4-oxadiazole.
상기 이소디아졸계 화합물은 구체적으로 예를 들어, 이소코나졸 및 1,3-아이소디아졸 등을 들 수 있다.Specific examples of the isodazole-based compound include isoconazole and 1,3-isothiazole.
상기 아졸계 화합물 중 테트라졸계 화합물을 사용하는 것이 바람직하고, 상기 테트라졸계 화합물 중에서도 5-아미노테트라졸(5-aminotetrazole)을 사용하는 것이 가장 바람직하다.Among these azole-based compounds, tetrazole-based compounds are preferably used, and among the tetrazole-based compounds, 5-aminotetrazole is most preferably used.
상기 아졸 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.1 내지 1 중량%로 포함되며, 바람직하게는 0.2 내지 0.8 중량%로 포함된다.The azole compound is contained in an amount of 0.1 to 1% by weight, preferably 0.2 to 0.8% by weight based on the total weight of the etchant composition of the present invention.
상기 아졸 화합물이 0.1 내지 1 중량%로 포함되면 몰리브데늄계 막의 손상을 방지할 수 있다.If the azole compound is contained in an amount of 0.1 to 1% by weight, damage to the molybdenum-based film can be prevented.
또한, 1 중량%를 초과하여 포함되면 몰리브데늄계 금속막의 식각 속도가 감소하여 공정시간에 손실이 발생할 수 있다.If it is contained in an amount exceeding 1% by weight, the etching rate of the molybdenum-based metal film may decrease, resulting in a loss in the processing time.
(C)인산염 화합물(C) Phosphate compound
본 발명의 식각액 조성물에 포함되는 인산염 화합물은 구리계 금속막, 바람직하게는 구리계 금속막을 포함하는 이중막의 식각 속도를 조절하는 역할을 한다.The phosphate compound contained in the etchant composition of the present invention serves to control the etching rate of the double-layer film including the copper-based metal film, preferably the copper-based metal film.
만일, 본 발명의 식각액 조성물이 인산염 화합물을 포함하지 않으면 식각 속도가 매우 낮아 식각 프로파일이 불량하게 될 수 있다.If the etchant composition of the present invention does not contain a phosphate compound, the etch rate may be very low and the etch profile may become poor.
상기 인산염 화합물은 인산의 수소가 알칼리 금속 또는 알칼리 토금속으로 하나 또는 두 개 치환된 염에서 선택되는 것이면 특별히 한정되지 않으며, 제1인산암모늄(ammonium phosphate monobasic), 제2 인산암모늄(ammonium phosphate dibasic), 제1인산나트륨(sodium phosphate monobasic), 제2 인산나트륨(sodium phosphate dibasic), 제1인산칼륨(potassium phosphate monobasic) 및 제2 인산칼륨(potassium phosphate dibasic)이루어진 군으로부터 선택되는 1종 이상이 사용될 수 있다. 바람직하게는 제1 인산나트륨(sodium phosphate monobasic)을 사용할 수 있다.The phosphate compound is not particularly limited as long as the phosphoric acid salt is selected from a salt in which hydrogen of the phosphoric acid is substituted with an alkali metal or an alkaline earth metal in one or two substitution, and ammonium phosphate monobasic, ammonium phosphate dibasic, At least one selected from the group consisting of sodium phosphate monobasic, sodium phosphate dibasic, potassium phosphate monobasic and potassium phosphate dibasic can be used have. Preferably, sodium phosphate monobasic can be used.
상기 인산염 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.1 내지 1.5 중량%로 포함되며, 바람직하게는 0.1 내지 1 중량%로 포함된다.The phosphate compound is contained in an amount of 0.1 to 1.5% by weight, preferably 0.1 to 1% by weight based on the total weight of the etchant composition of the present invention.
상기 인산염 화합물이 0.1 내지 1.5 중량%로 포함되면 우수한 식각 속도를 나타내어 잔사 발생을 억제할 수 있으며, 씨디로스 발생을 억제할 수 있다.When the phosphate compound is contained in an amount of 0.1 to 1.5% by weight, an excellent etching rate can be exhibited and the residue can be suppressed and the occurrence of seed loss can be suppressed.
(D)한 분자 내에 (D) within one molecule 질소원자Nitrogen atom 및 카르복실기를 포함하는 수용성 화합물 And a water-soluble compound containing a carboxyl group
일반적으로 과산화수소를 포함하는 식각액 조성물은 보관 시 과산화수소가 자체 분해하여 보관기간이 길지 못하고, 보관 용기가 폭발할 수 있는 위험성이 있다.Generally, the etching solution composition containing hydrogen peroxide has a problem that the storage period of the hydrogen peroxide is self-decomposed during storage, so that the storage container may explode.
본 발명의 식각액 조성물은 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물을 포함함으로써 상기의 문제점을 방지할 수 있다. The etching solution composition of the present invention can prevent the above problems by including a water-soluble compound containing a nitrogen atom and a carboxyl group in one molecule.
즉, 과산화수소의 분해 속도를 약 10배 가까이 감소시켜 보관기간 및 안정성을 확보시킬 수 있다. That is, the decomposition rate of hydrogen peroxide is reduced to about 10 times, and the storage period and stability can be ensured.
또한, 구리계 금속막의 경우, 식각액 조성물 내에 구리 이온이 다량 잔존하면 구리 이온이 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 발생할 수 있으나, 상기 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물을 포함함으로써 상기 현상을 예방할 수 있다.In the case of a copper-based metal film, if a large amount of copper ions remain in the etchant composition, a copper ion may form a passivation film and may be further oxidized after being oxidized to black. However, The above phenomenon can be prevented by including a water-soluble compound.
상기 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물은 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 바람직하게는 이미노디아세트산을 사용할 수 있다.The water-soluble compound containing a nitrogen atom and a carboxyl group in the above-mentioned molecule may be selected from the group consisting of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid, acid, and sarcosine, and iminodiacetic acid can be preferably used.
상기 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.5 내지 5 중량%, 바람직하게는 1 내지 3 중량%로 포함된다.The water-soluble compound containing a nitrogen atom and a carboxyl group in the molecule is included in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight based on the total weight of the etching solution composition of the present invention.
상기 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물이 0.5 내지 5 중량%로 포함되면 약 500매 이상의 다수의 기판 식각시 패시베이션 막이 형성되는 것을 방지할 수 있다.When 0.5 to 5% by weight of the water-soluble compound containing a nitrogen atom and a carboxyl group is contained in the molecule, it is possible to prevent the passivation film from being formed when etching a plurality of substrates of about 500 sheets or more.
만약 상기 한 분자 내에 질소원자 및 카르복실기를 포함하는 수용성 화합물이 5 중량%를 초과하여 포함되면 식각액 조성물의 점도가 증가하여 5세대 이상의 대형 기판의 상부 및 하부의 식각 특성이 다르게 나타날 수 있다.If the water-soluble compound containing nitrogen atoms and carboxyl groups in the molecule is contained in an amount exceeding 5% by weight, the viscosity of the etching solution composition may increase, and the etching characteristics of upper and lower portions of the large-sized substrate of the fifth generation or more may be different.
(E)폴리에틸렌이민(E) Polyethyleneimine
본 발명의 식각액 조성물은 분자량 1,000 내지 10,000의 폴리에틸렌이민(Polyethyleneimine)을 포함한다.The etchant composition of the present invention comprises polyethyleneimine having a molecular weight of 1,000 to 10,000.
상기 폴리에틸렌이민은 몰리브데늄계 금속막의 식각을 방지하는 역할을 한다. 보다 구체적으로 폴리에틸렌이민의 질소 원자(N)가 몰리브데늄계 금속막에 흡착되어 몰리브데늄계 금속막을 보호하는 역할, 즉 부식방지제의 역할을 함으로써 몰리브데늄계 금속막의 식각을 방지할 수 있다.The polyethylene imine serves to prevent etching of the molybdenum-based metal film. More specifically, the nitrogen atoms (N) of polyethyleneimine are adsorbed on the molybdenum-based metal film to protect the molybdenum-based metal film, that is, to serve as a corrosion inhibitor, thereby preventing the molybdenum-based metal film from being etched .
상기 폴리에틸렌이민의 분자량은 2,500 내지 10,000인 것이 보다 바람직하며, 분자량이 1,000 미만이면 몰리브데늄계 막의 식각, 즉 손상을 방지하는 효과가 매우 미미하며, 10,000을 초과하면 식각액 조성물의 점도가 상승하여 구리계 금속막을 식각할 수 없다. The molecular weight of the polyethyleneimine is more preferably from 2,500 to 10,000. If the molecular weight is less than 1,000, the effect of preventing the etching of the molybdenum-based film is very small. When the molecular weight exceeds 10,000, the viscosity of the etching solution composition is increased, The metal film can not be etched.
본 발명에서 폴리에틸렌이민의 분자량은 평균 분자량을 의미한다.The molecular weight of the polyethyleneimine in the present invention means the average molecular weight.
상기 폴리에틸렌이민은 본 발명의 식각액 조성물 총 중량에 대하여 0.1 내지 2 중량%, 바람직하게는 0.5 내지 1 중량%로 포함된다.The polyethyleneimine is contained in an amount of 0.1 to 2% by weight, preferably 0.5 to 1% by weight based on the total weight of the etchant composition of the present invention.
상기 폴리에틸렌이민이 0.1 내지 2 중량%로 포함되면 몰리브데늄계 금속막의 식각을 효과적으로 방지할 수 있으며, 점도의 상승을 방지하여 우수한 속도로 구리계 금속막을 식각할 수 있다.If the amount of the polyethyleneimine is in the range of 0.1 to 2% by weight, etching of the molybdenum-based metal film can be effectively prevented, and the copper-based metal film can be etched at a high speed by preventing an increase in viscosity.
(F)다가 알코올형 계면활성제(F) a polyhydric alcohol type surfactant
본 발명의 식각액 조성물에 포함되는 다가 알코올형 계면활성제는 표면 장력을 저하시켜 식각 균일성을 증가시키는 역할을 한다. 또한, 구리계 금속막을 식각한 후 식각액 조성물에 해리된 구리 이온(Cu2 +)을 둘러쌈으로써 구리 이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제시키는 역할을 하며, 상기 구리 이온의 활동도 억제로 인하여 식각액 조성물을 사용하는 동안 식각 공정을 안정적으로 진행할 수 있다.The polyhydric alcohol surfactant contained in the etchant composition of the present invention has a role of lowering the surface tension and increasing the etching uniformity. In addition, it acts to suppress the decomposition reaction of hydrogen peroxide by suppressing the activity of copper ions by surrounding the copper ions (Cu 2 + ) dissociated to the etchant composition after etching the copper-based metal film, The etching process can be performed stably during the use of the etching composition.
상기 다가 알코올형 계면 활성제는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol) 및 폴리에틸렌 글리콜(polyethylene glycol)로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 바람직하게는 트리에틸렌글리콜을 사용할 수 있다.The polyhydric alcohol surfactant may be at least one selected from the group consisting of glycerol, triethylene glycol and polyethylene glycol, and preferably triethylene glycol may be used. .
상기 다가 알코올형 계면 활성제는 본 발명의 식각액 조성물 총 중량에 대하여 1 내지 5 중량%, 바람직하게는 1.5 내지 3 중량%로 포함된다.The polyhydric alcohol type surfactant is contained in an amount of 1 to 5% by weight, preferably 1.5 to 3% by weight based on the total weight of the etchant composition of the present invention.
상기 다가 알코올형 계면 활성제가 1 내지 5 중량%로 포함되면, 과산화수소의 분해를 방지할 수 있어 안정성을 확보할 수 있으며, 식각시 거품이 발생하지 않아 효율적으로 식각할 수 있다.When the polyhydric alcohol type surfactant is contained in an amount of 1 to 5% by weight, the decomposition of hydrogen peroxide can be prevented, stability can be ensured, and bubbles are not generated during etching.
(G)물(G) Water
본 발명의 식각액 조성물에 포함되는 물은 특별히 한정하지 않으나, 탈이온수를 이용하는 것이 바람직하며, 상기 탈이온수는 반도체 공정용으로 비저항값이 18 ㏁/㎝ 이상인 것을 사용하는 것이 바람직하다.The water contained in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water. It is preferable that the deionized water has a resistivity value of 18 M? / Cm or more for semiconductor processing.
또한, 본 발명은 In addition,
(a) 기판 상에 게이트 배선을 형성하는 단계;(a) forming a gate wiring on a substrate;
(b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;(b) forming a gate insulating layer on the substrate including the gate wiring;
(c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;(c) forming a semiconductor layer on the gate insulating layer;
(d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및(d) forming source and drain electrodes on the semiconductor layer; And
(e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,(e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 (a) 및 (d)단계는 상기 본 발명의 식각액 조성물로 식각하여 게이트 배선, 소스 전극 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법에 관한 것이다.The steps (a) and (d) include a step of forming a gate wiring, a source electrode, and a drain electrode by etching the etchant composition of the present invention.
상기 화소 전극은 바람직하게는 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막과 몰리브데늄막 및 몰리브데늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막을 포함하는 다층막일 수 있으며, 상기 다층막을 본 발명의 식각액 조성물로 식각하여 화소 전극을 제조할 수 있다.The pixel electrode may preferably be a multilayer film including at least one film selected from a copper film and a copper alloy film, at least one film selected from the group consisting of a molybdenum film and a molybdenum alloy film, The pixel electrode can be manufactured by etching with the etchant composition of the present invention.
상기 구리 합금막 및 몰리브데늄 합금막에 대한 내용은 상술한 내용이 동일하게 적용될 수 있다.The content of the copper alloy film and the molybdenum alloy film may be the same as described above.
또한, 상기 디스플레이 장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.In addition, the array substrate for a display device may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 본 발명의 제조방법으로 제조된 디스플레이 장치용 어레이 기판에 관한 것이다.The present invention also relates to an array substrate for a display device manufactured by the manufacturing method of the present invention.
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않으며, 다양하게 수정 및 변경될 수 있다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.
<< 식각액Etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 20 및 1 to 20 and 비교예Comparative Example 1 내지 7. 1-7.
하기 표 1에 나타낸 조성 및 함량으로 실시예 1 내지 20 및 비교예 1 내지 7의 식각액 조성물을 제조하였으며, 조성물 총 중량이 100 중량%가 되도록 잔량의 탈이온수를 포함하였다.The etchant compositions of Examples 1 to 20 and Comparative Examples 1 to 7 were prepared by the compositions and contents shown in Table 1 below, and the remaining amount of deionized water was included so that the total weight of the composition was 100% by weight.
ATZ : 5-Aminotetrazole,ATZ: 5-Aminotetrazole,
IDA: Iminodiacetic acid,IDA: Iminodiacetic acid,
NHP: sodium phosphate monobasic,NHP: sodium phosphate monobasic,
TEG : triethyleneglycol,TEG: triethyleneglycol,
PEI : Polyethyleneimine,PEI: Polyethyleneimine,
ABF : ammonium bifluoride,ABF: ammonium bifluoride,
GA : glycolic acidGA: glycolic acid
실험예Experimental Example 1. One. 식각액Etchant 조성물의 특성 평가 Evaluation of composition characteristics
상기 실시예 1 내지 20 및 비교예 1 내지 7에서 제조한 식각액 조성물을 이용하여 Cu 및 Mo-Ti막의 식각속도(etching rate, E/R)을 측정하였다.The etch rate (E / R) of the Cu and Mo-Ti films was measured using the etchant compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 7.
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 식각액 조성물의 온도는 약 33℃ 내외로 하였다. 식각 시간은 식각 온도에 따라서 다를 수 있으나, LCD Etching 공정에서 통상 50 내지 80초 정도로 진행하였다. 상기 식각 공정에서 식각된 구리계 금속막의 식각 속도를 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 측정하였다. 식각공정에 사용된 구리계 금속막의 경우 Cu/Mo-Ti 5000/100Å 박막 기판을 사용하였다.(ETCHER (TFT), manufactured by SEMES Co., Ltd.) was used as the etchant, and the temperature of the etchant composition was set to about 33 캜 in the etching process. The etching time may vary depending on the etching temperature, but the etching time is usually about 50 to 80 seconds in the LCD etching process. The etching rate of the copper-based metal film etched in the etching process was measured using a cross-sectional SEM (product of Hitachi, Model S-4700). Cu / Mo-Ti 5000/100 Å thin film substrates were used for the copper-based metal films used in the etching process.
Cu의 E/R은 80 내지 120Å/sec가 바람직하며, 하부막인 Mo-Ti의 손상을 최소화하기 위하여 Mo-Ti의 E/R은 5Å/sec 이하인 것이 바람직하다.The E / R of Cu is preferably 80 to 120 Å / sec, and the E / R of the Mo-Ti is preferably 5 Å / sec or less in order to minimize the damage of the Mo-Ti underlying film.
본 식각 속도 측정 평가에서 Cu의 E/R는 80 내지 120Å/sec이고, Mo-Ti의 E/R은 5Å/sec이하인 조건이 충족되는 경우에 식각액 조성물을 식각 공정에 계속 사용할 수 있는 것으로 정하고 실험을 실시하였으며, 결과를 하기 표 2에 나타내었다.It is determined that the etching solution composition can be continuously used in the etching process when the condition that E / R of Cu is 80-120 Å / sec and E / R of Mo-Ti is 5 Å / sec or less is satisfied in the etching rate measurement evaluation, And the results are shown in Table 2 below.
실험예Experimental Example 2. 2. 식각액Etchant 조성물의 사이드 The side of the composition 에치Etch 측정 Measure
분사식 식각 방식의 실험장비(모델명: ETCHER, K.C.Tech사) 내에 상기 실시예 1 내지 20 및 비교예 1 내지 7의 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 60 내지 200초로 실시하였다. The etchant compositions of Examples 1 to 20 and Comparative Examples 1 to 7 were placed in an experimental apparatus (model name: ETCHER, KCTech) of a spray-type etch system, and after the temperature was set at 40 DEG C, When the temperature reached 0.1 占 폚, the above-mentioned sample was etched. The total etching time was 60 to 200 seconds.
식각은 도 1에 예시된 바와 같은 방식으로 기판 상, 하부에 5도의 경사차이를 주어 실시하였으며, 기판의 사이즈는 680X880mm이며, 기판은 Cu/Mo-Ti 5000/100Å를 사용하였다. Etching was performed on the substrate in the manner as illustrated in FIG. 1, with an inclination difference of 5 degrees on the substrate. The size of the substrate was 680 × 880 mm, and the substrate was Cu / Mo-Ti 5000/100 Å.
기판을 위치시키고 분사를 시작하여 60 내지 200초의 식각 시간이 다 되면 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 모델명: S-4700, HITACHI사 제조)을 이용하여 도 2에 도시된 사이드 에치를 측정하였다. 실험은 기판 상부 및 하부의 사이드 에치를 각각 측정하고, 상부 및 하부의 사이드 에치 차이(△상부-하부)를 구하였다. 상기 상부 및 하부의 사이드 에치 차이는 1 미만이 바람직하며, 1 이상이면 상부 및 하부의 사이드 에치 차이가 지나치게 크게 발생하여 식각 불량을 발생시킨다.After the substrate was placed and spraying was started, when the etching time was reached for 60 to 200 seconds, the substrate was washed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist stripper. After washing and drying, side etches shown in FIG. 2 were measured using an electron microscope (SEM; model: S-4700, manufactured by Hitachi). In the experiment, the values were measured on the upper and lower sides of the substrate, and the upper and lower side etch differences (? Upper-lower) were obtained. The difference between the upper and lower side etches is preferably less than 1, and if it is more than 1, the upper and lower side etch differences are too large to cause etching failure.
상기 상부 및 하부의 사이드 에치 차이 결과를 하기 표 2에 나타내었다.The upper and lower side etch difference results are shown in Table 2 below.
상기 표 2의 결과에서, 분자량 1,000 내지 10,000의 폴리에틸렌이민을 포함한 본 발명의 식각액 조성물인 실시예 1 내지 20은 MoTi막을 식각하지 않고 Cu막을 식각한 결과를 보였다. 즉, 본 발명의 식각액 조성물은 Cu/MoTi 이중막 식각시, MoTi막의 식각을 방지하면서 Cu를 식각하는 것을 실험을 통하여 확인할 수 있었다. In the results of Table 2, Examples 1 to 20, which are the etching solution compositions of the present invention containing polyethyleneimine having a molecular weight of 1,000 to 10,000, showed the results of etching the Cu film without etching the MoTi film. That is, the etching solution composition of the present invention can confirm the etching of Cu while preventing the etching of the MoTi film during the etching of the Cu / MoTi double layer.
일반적으로 함불소 화합물을 포함하면 MoTi막이 식각된다. 그러나, 상기 실시예 17 내지 20은 함불소 화합물을 포함하더라도 MoTi막이 식각되지 않는 결과를 보였다. 즉, 본 발명의 식각액 조성물은 식각액 조성물에 함불소 화합물이 포함되더라도, 분자량 1,000 내지 10,000의 폴리에틸렌이민을 포함하면, MoTi막은 식각하지 않으면서 Cu막만을 식각하는 것을 알 수 있다.In general, MoFi films are etched if they contain fluorinated compounds. However, in Examples 17 to 20, MoTi films were not etched even when fluorine compounds were included. That is, even if the etchant composition of the present invention contains a fluorine compound in the etchant composition, it can be seen that only the Cu film is etched without etching the MoTi film if it contains polyethyleneimine having a molecular weight of 1,000 to 10,000.
분자량 1,000 내지 10,000의 폴리에틸렌이민을 포함하지 않는 비교예 1 및 2의 식각액 조성물은 MoTi막을 식각하였으며, 또한, 분자량 1,000 미만의 폴리에틸렌이민을 포함한 비교예 3 및 4의 식각액 조성물은 MoTi막을 식각하였다.The etchant compositions of Comparative Examples 1 and 2, which did not contain polyethyleneimine having a molecular weight of 1,000 to 10,000, etched the MoTi film and also etched the MoTi film of the etchant compositions of Comparative Examples 3 and 4 containing polyethyleneimine having a molecular weight of less than 1,000.
분자량 10,000을 초과하는 폴리에틸렌이민을 포함한 비교예 5 및 6의 식각액 조성물은 MoTi막을 식각하지는 않았지만 조성물의 점도가 높아 상부 및 하부의 식각 차이 발생을 보였으며, 폴리에틸렌이민 대신 유기산을 포함한 비교예 7의 식각액 조성물은 MoTi막을 식각하는 결과를 보였다.The etchant compositions of Comparative Examples 5 and 6 containing polyethyleneimine having a molecular weight of more than 10,000 did not etch the MoTi film, but showed a difference in etch between the upper and lower portions due to the high viscosity of the composition. In contrast to the polyethyleneimine, The composition showed the result of etching the MoTi film.
따라서, 본 발명의 식각액 조성물은 구리계 금속막을 선택적으로 식각할 수 있는 효과를 지니고 있으며, 그로 인하여 미세패턴을 형성할 수 있어 고해상도의 디스플레이 장치를 제공할 수 있다.Therefore, the etchant composition of the present invention has the effect of selectively etching the copper-based metal film, thereby forming a fine pattern, thereby providing a high-resolution display device.
Claims (10)
상기 폴리에틸렌이민의 분자량은 1,000 내지 10,000인 것을 특징으로 하는 식각액 조성물.An etching solution composition comprising hydrogen peroxide, an azole compound, a phosphate compound, a water-soluble compound containing a nitrogen atom and a carboxyl group in one molecule, a polyethyleneimine, a polyhydric alcohol type surfactant and water,
Wherein the polyethyleneimine has a molecular weight of 1,000 to 10,000.
(b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
(c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;
(d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
(e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,
상기 (a) 및 (d)단계는 상기 청구항 1 내지 7 중 어느 한 항의 식각액 조성물로 식각하여 게이트 배선, 소스 전극 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법.(a) forming a gate wiring on a substrate;
(b) forming a gate insulating layer on the substrate including the gate wiring;
(c) forming a semiconductor layer on the gate insulating layer;
(d) forming source and drain electrodes on the semiconductor layer; And
(e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
Wherein the steps (a) and (d) comprise a step of forming a gate wiring, a source electrode, and a drain electrode by etching with the etching liquid composition of any one of claims 1 to 7. Way.
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