KR102282957B1 - Etchant composition and manufacturing method of an array for liquid crystal display - Google Patents
Etchant composition and manufacturing method of an array for liquid crystal display Download PDFInfo
- Publication number
- KR102282957B1 KR102282957B1 KR1020150038248A KR20150038248A KR102282957B1 KR 102282957 B1 KR102282957 B1 KR 102282957B1 KR 1020150038248 A KR1020150038248 A KR 1020150038248A KR 20150038248 A KR20150038248 A KR 20150038248A KR 102282957 B1 KR102282957 B1 KR 102282957B1
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- South Korea
- Prior art keywords
- film
- copper
- based metal
- etchant composition
- metal film
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000010408 film Substances 0.000 claims description 150
- 239000010949 copper Substances 0.000 claims description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 83
- 229910052802 copper Inorganic materials 0.000 claims description 81
- 229910052751 metal Inorganic materials 0.000 claims description 75
- 239000002184 metal Substances 0.000 claims description 75
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229910044991 metal oxide Inorganic materials 0.000 claims description 26
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- 239000000460 chlorine Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 14
- -1 azole compound Chemical class 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 11
- 239000013522 chelant Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 235000013399 edible fruits Nutrition 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-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
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-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
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-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
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 claims description 2
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 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
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- 108010077895 Sarcosine Proteins 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002738 chelating agent Substances 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
- 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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043230 sarcosine Drugs 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000002420 orchard Substances 0.000 claims 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims 1
- 238000005530 etching Methods 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 20
- 229910003437 indium oxide Inorganic materials 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
본 발명은 식각액 조성물 및 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etchant composition and a method for manufacturing an array substrate for a liquid crystal display.
Description
본 발명은 식각액 조성물 및 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.
The present invention relates to an etchant composition and a method for manufacturing an array substrate for a liquid crystal display.
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, etc., a photoresist forming process in a selective area by photoresist application, exposure and development, and an etching process. , and cleaning processes before and after individual unit processes. Such an etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically dry etching using plasma or wet etching using an etchant 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 기술개발에 관건이 되고 있기 때문이다. 따라서, TFT-LCD의 대형화에 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는, 저저항의 물질개발이 필수적이다. 따라서, 종래에 주로 사용되었던 크롬(Cr, 비저항: 12.7 ×10-8Ωm), 몰리브덴(Mo, 비저항: 5×10-8Ωm), 알루미늄(Al, 비저항: 2.65×10-8Ωm) 및 이들의 합금은 대형 TFT LCD 에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다.In such a semiconductor device, the resistance of metal wiring has recently emerged as a major concern. This is because resistance is a major factor that causes RC signal delay, and in particular, in the case of TFT-LCD (thin film transistor-liquid crystal display), an increase in panel size and realization of high resolution are key to technology development. Therefore, in order to realize the reduction of the RC signal delay, which is essential for the enlargement of the TFT-LCD, it is essential to develop a low-resistance material. Therefore, chromium (Cr, resistivity: 12.7×10 -8 Ωm), molybdenum (Mo, resistivity: 5×10 -8 Ωm), aluminum (Al, resistivity: 2.65×10 -8 Ωm), which have been mainly used in the prior art, and these It is difficult to use the alloy for gate and data wiring used in large TFT LCDs.
이와 같은 배경하에서, 새로운 저저항 금속막으로서 구리막 및 구리 몰리브덴막 등의 구리계 금속막 및 이의 식각액 조성물에 대한 관심이 높다. 하지만, 구리계 금속막에 대한 식각액 조성물의 경우 현재 여러 종류가 사용되고 있으나, 사용자가 요구하는 성능을 충족시키지 못하고 있는 실정이다. 일례로 한국공개특허 제2010-0090538호에서는 일정 함량의 과산화수소, 유기산, 인산염 화합물, 수용성 시클릭 아민 화합물, 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물, 함불소 화합물, 다가알콜형 계면활성제 및 물을 포함하는 구리계 금속막의 식각액 조성물을 개시하고 있으나, 후막 금속층(Cu) 식각 시 사이드 에칭 조절 및 처리매수에 따른 식각속도 유지면에서 한계를 가지고 있다.Under this background, interest in a copper-based metal film such as a copper film and a copper molybdenum film and an etchant composition thereof as a new low-resistance metal film is high. However, in the case of an etchant composition for a copper-based metal film, various types are currently used, but the performance required by the user is not satisfied. For example, in Korea Patent Publication No. 2010-0090538, a certain amount of hydrogen peroxide, an organic acid, a phosphate compound, a water-soluble cyclic amine compound, a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, a fluorine-containing compound, a polyalcohol type surfactant, and water Disclosed is an etchant composition for a copper-based metal film comprising a, but has limitations in terms of side etching control and maintaining an etch rate according to the number of treatments when etching a thick metal layer (Cu).
또한, 종래의 식각액 조성물은 구리(Cu)에 대한 처리 수용능력(Capacity)이 매우 부족하여 공정적용 어려움이 있다.
In addition, the conventional etchant composition has a very insufficient processing capacity for copper (Cu), so there is a difficulty in process application.
본 발명은 상기 종래기술의 문제점을 해결하고자 한 것으로, 액정표시장치용 어레이 기판 제조 시에 구리계 금속막을 일괄 식각할 수 있으면서도 후막(Cu) 금속층 식각 시 사이드 에칭 조절 및 처리매수에 따른 식각속도를 유지할 수 있는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is intended to solve the problems of the prior art, and it is possible to batch etch a copper-based metal film when manufacturing an array substrate for a liquid crystal display device, and to control the side etching when etching a thick (Cu) metal layer and to control the etching rate according to the number of treatments. An object of the present invention is to provide an etchant composition that can be maintained.
또한, 구리(Cu)에 대한 처리능력(Capacity)이 증가되고, 발열 안정성이 개선되는 식각액 조성물을 제공하는 것을 목적으로 한다.
In addition, an object of the present invention is to provide an etchant composition having increased processing capacity for copper (Cu) and improved thermal stability.
본 발명은 조성물 총 중량백분율에 대하여 과산화수소(H2O2) 5 ~ 25 중량%, 함불소 화합물 0.1~3.0중량%, 아졸화합물 0.1 ~ 3.0중량%, 염소(Cl)염 0.5 ~ 3.0 중량%, 킬레이트제 1.0 ~ 3.0 중량%, 과수안정제 1.0 ~ 3.0중량 및 잔량의 물을 포함하는 구리계 금속막 및 금속산화물막 식각액 조성물을 제공한다.The present invention is hydrogen peroxide (H 2 O 2 ) 5 to 25% by weight, 0.1 to 3.0% by weight of a fluorine-containing compound, 0.1 to 3.0% by weight of an azole compound, 0.5 to 3.0% by weight of a chlorine (Cl) salt, It provides a copper-based metal film and metal oxide film etchant composition comprising 1.0 to 3.0% by weight of a chelating agent, 1.0 to 3.0% by weight of an fruit water stabilizer, and the remaining amount of water.
본 발명의 다른 태양은 a) 기판 상에 게이트 배선을 형성하는 단계, 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 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, 상기 a)단계는 기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 본 발명의 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 본 발명의 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법을 제공한다. Another aspect of the present invention includes the steps of a) forming a gate wiring on a substrate, b) forming a gate insulating layer on a 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, in the method of manufacturing an array substrate for a liquid crystal display, the step a) Forms a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film on a substrate, and etching the multilayer film of the copper-based metal film or a copper-based metal film and a metal oxide film with the etchant composition of the present invention to form a gate electrode Including a step, wherein step d) forms a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film on the semiconductor layer, and the copper-based metal film or a multilayer film of the copper-based metal film and the metal oxide film of the present invention Provided is a method of manufacturing an array substrate for a liquid crystal display, comprising the step of forming source/drain electrodes by etching with an etchant composition.
또한, 본 발명은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 배선, 소스 전극 및 드레인 전극 중에서 하나 이상을 포함하는 액정표시장치용 어레이 기판을 제공한다.
In addition, the present invention provides an array substrate for a liquid crystal display including at least one of a gate wiring, a source electrode, and a drain electrode etched using the etchant composition of the present invention.
본 발명은 액정표시장치용 어레이 기판 제조시, 구리계 금속막을 일괄 식각할 수 있으며, 후막 금속층(Cu) 식각 시 사이드 에칭 조절 및 처리매수에 따른 식각속도를 유지할 수 있다.According to the present invention, when manufacturing an array substrate for a liquid crystal display, a copper-based metal film can be etched at once, and when etching a thick metal layer (Cu), the etching rate can be maintained according to the side etching control and the number of treatments.
또한, 구리(Cu)에 대한 처리능력(Capacity)이 증가되고, 발열 안정성이 개선될 수 있다. 나아가, 식각액을 사용하는 동안 안정적으로 공정을 진행 할 수 있다.
In addition, capacity for copper (Cu) may be increased, and thermal stability may be improved. Furthermore, the process can be performed stably while using the etchant.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
종래의 식각액 조성물은 구리(Cu)에 대한 처리 수용능력(Capacity)이 매우 부족하여 공정적용 어려움이 있다.The conventional etchant composition has a very low processing capacity for copper (Cu), so there is a difficulty in process application.
이를 해결하기 위하여 본 발명자들은 식각액 조성물에 염소(Cl)염을 포함함으로써, 상기의 문제점을 해결할 수 있다는 것을 발견하고 본 발명을 완성하였다. In order to solve this problem, the present inventors have found that the above problems can be solved by including a chlorine (Cl) salt in the etchant composition and completed the present invention.
즉, 본 발명은 조성물 총 중량백분율에 대하여 과산화수소(H2O2) 5 ~ 25 중량%, 함불소 화합물 0.01 ~ 3.0 중량%, 아졸화합물 0.1 ~ 3.0중량%, 염소염 0.5 ~ 3.0 중량%, 킬레이트 화합물 1.0 ~ 3.0 중량%, 과수안정제 1.0 ~ 3.0중량 및 잔량의 물을 포함하는 구리계 금속막 및 금속산화물막 식각액 조성물을 제공한다.
That is, the present invention is hydrogen peroxide (H 2 O 2 ) 5-25 wt%, fluorine-containing compound 0.01-3.0 wt%, azole compound 0.1-3.0 wt%, chlorine salt 0.5-3.0 wt%, chelate with respect to the total weight percentage of the composition It provides a copper-based metal film and metal oxide film etchant composition comprising 1.0 to 3.0 weight % of the compound, 1.0 to 3.0 weight percent of the fruit water stabilizer, and the remaining amount of water.
이하, 본 발명의 구성을 설명한다.
Hereinafter, the configuration of the present invention will be described.
본 발명에서 구리계 금속막은 막의 구성성분 중에 구리가 포함되는 것으로서, 단일막 및 이중막 등의 다층막을 포함하는 개념이다. 상기 구리계 금속막은 구리 또는 구리 합금막일 수 있다In the present invention, the copper-based metal film includes copper as a component of the film, and is a concept including a single film and a multilayer film such as a double film. The copper-based metal film may be a copper or copper alloy film.
구체적으로, 상기 구리계 금속막은 구리 또는 구리 합금의 단일막; 또는 몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막과 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막을 포함하는 다층막인 것일 수 있으며, 상기 합금막이라 함은 질화막 또는 산화막을 포함할 수 있다. Specifically, the copper-based metal film may include a single film of copper or a copper alloy; Or it may be a multilayer film including at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film and a titanium alloy film, and at least one film selected from a copper film and a copper alloy film, the alloy film is It may include a nitride film or an oxide film.
예컨대, 상기 다층막은 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴 합금막, 구리/티타늄막 등의 2중막, 또는 3중막을 들 수 있다. 상기 구리/몰리브덴막은 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 것을 의미하고, 구리 합금/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리 합금층을 포함하는 것을 의미하며, 상기 구리/티타늄막은 티타늄층과 상기 티타늄층 상에 형성된 구리층을 포함하는 것을 의미한다.For example, the multilayer film may include a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum alloy film, a double film such as a copper/titanium film, or a triple film. The copper / molybdenum film means comprising a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film means comprising a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer, copper The alloy/molybdenum alloy film means including a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper/titanium film includes a titanium layer and a copper layer formed on the titanium layer.
또한, 상기 몰리브덴 합금층은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In)으로 이루어진 군에서 선택되는 1종 이상의 금속과 몰리브덴의 합금으로 이루어진 층을 의미한다.In addition, the molybdenum alloy layer is, for example, one or more metals selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In). It means a layer made of an alloy of and molybdenum.
본 발명에서 후막(Cu) 금속층의 두께는 5000Å이상인 것일 수 있다. 상기 후막의 경우 종래 공지된 식각액으로는 부식속도가 느려 공정 시간이 증가하게 되며, 이에 따라 후막 금속층의 두께가 5000Å이상인 경우에는 적용이 불가하나, 본 발명의 식각액 조성물은 후막 금속층의 두께가 5000Å이상이어도 적용이 가능한 것이 특징이다.In the present invention, the thickness of the thick (Cu) metal layer may be 5000 Å or more. In the case of the thick film, the conventionally known etchant has a slow corrosion rate and increases the process time. Accordingly, it is not applicable when the thickness of the thick metal layer is 5000 Å or more, but the etchant composition of the present invention has a thick metal layer having a thickness of 5000 Å or more. The feature is that it can also be applied to the ear.
. 본 발명에서 금속 산화물막은 통상 AxByCzO(A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0)의 조합으로 이루어진 삼성분계 또는 사성분계 산화물을 함유하여 구성된 막으로서, 산화물 반도체층이라고 불리거나 또는 산화물 반도체층을 구성하는 막일 수 있다. 본 발명의 바람직한 실시예에 따르면, 상기 금속산화물막은 인듐산화막일 수 있다.
. In the present invention, the metal oxide film is a ternary or quaternary oxide composed of a combination of AxByCzO (A, B, C = Zn, Cd, Ga, In, Sn, Hf, Zr, Ta; x, y, z≥0). As a film constituted by containing it, it may be called an oxide semiconductor layer or a film constituting an oxide semiconductor layer. According to a preferred embodiment of the present invention, the metal oxide film may be an indium oxide film.
상기 과산화수소(H2O2)는 조성물 총 중량백분율에 대하여, 5.0 내지 25.0중량%로 포함되고, 바람직하게는 10.0 내지 20.0중량%로 포함된다. 상술한 범위 미만으로 포함되면, 구리계 금속막이 식각되지 않거나 식각 속도가 아주 느려진다. 상술한 범위를 초과하여 포함되면, 식각 속도가 전체적으로 빨라지기 때문에 공정 컨트롤이 어렵다.
The hydrogen peroxide (H 2 O 2 ) is included in 5.0 to 25.0 wt%, preferably 10.0 to 20.0 wt%, based on the total weight percentage of the composition. When included below the above range, the copper-based metal layer is not etched or the etching rate is very slow. When it exceeds the above-mentioned range, it is difficult to control the process because the etch rate increases as a whole.
본 발명의 식각액 조성물에 포함되는 함불소 화합물은 물에 해리되어 플루오르 이온을 낼 수 있는 화합물을 의미한다. 상기 함불소 화합물은 산화인듐계 금속막을 식각하는 주성분이며, 구리계 금속막과 산화인듐계 금속막을 동시에 식각하는 용액에서 필연적으로 발생하는 잔사를 제거해 주는 역할을 한다. The fluorine-containing compound included in the etchant composition of the present invention means a compound capable of dissociating in water to produce fluorine ions. The fluorine-containing compound is a main component for etching the indium oxide-based metal film, and serves to remove residues inevitably generated in a solution for simultaneously etching the copper-based metal film and the indium oxide-based metal film.
상기 함불소 화합물은 조성물 총 중량백분율에 대하여 0.01 내지 3.0중량%로 포함되고, 바람직하게는 0.1 내지 1.0 중량%로 포함된다. 상술한 범위 미만으로 포함되면, 식각 잔사가 발생될 수 있다. 상술한 범위를 초과하여 포함되면, 유리 기판 식각율이 커지는 문제가 있다. The fluorine-containing compound is included in an amount of 0.01 to 3.0 wt%, preferably 0.1 to 1.0 wt%, based on the total weight percentage of the composition. When included below the above-described range, etching residue may be generated. When included in excess of the above-mentioned range, there is a problem in that the etching rate of the glass substrate increases.
상기 함불소 화합물은 이 분야에서 사용되는 물질로서 용액 내에서 플루오르 이온 혹은 다원자 플루오르 이온으로 해리될 수 있는 것이라면 특별히 한정되지 않는다. 하지만 상기 함불소 화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF), 불산(Hydrofluoric acid: HF), 테트라플루오르붕산암모늄(Tetrafluoroboric acid: NH4BF4), 불화알루미늄(Aluminium fluoride: AlF3), 붕불화수소산(HBF4) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종이상을 포함하는 것이 바람직하다.The fluorine-containing compound is not particularly limited as long as it can be dissociated into a fluorine ion or a polyatomic fluorine ion in a solution as a material used in this field. However, the fluorine-containing compound is ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F HF), medium fluoride Sodium bifluoride (NaF·HF), Hydrofluoric acid (HF), Tetrafluoroboric acid (NH 4 BF 4 ), Aluminum fluoride (AlF 3 ), Hydrofluoric acid (HBF 4 ) And it is preferable to include at least one selected from the group consisting of potassium bifluoride (KF·HF).
본 발명의 식각액 조성물에 포함되는 아졸화합물은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주어 공정상의 마진을 높이는 역할을 한다.
The azole compound included in the etchant composition of the present invention controls the etching rate of the copper-based metal layer and reduces the CD loss of the pattern, thereby increasing the process margin.
상기 아졸화합물은 조성물 총 중량백분율에 대하여, 0.1 내지 3.0중량%으로 포함되고, 바람직하게는 0.5 내지 1.5중량%로 포함된다. 상술한 범위 미만으로 포함되면, 식각 속도가 빠르게 되어 시디로스가 너무 크게 발생될 수 있다. 상술한 범위를 초과하여 포함되면, 구리계 금속막의 식각 속도가 너무 느려지게 되어 상대적으로 산화인듐계 금속막의 식각 속도가 빨라지게 되므로 언더컷이 발생될 수 있다. The azole compound is included in an amount of 0.1 to 3.0% by weight, preferably 0.5 to 1.5% by weight, based on the total weight percentage of the composition. When the content is less than the above-mentioned range, the etching rate may be increased, so that the CD loss may be excessively generated. When the content exceeds the above-mentioned range, the etching rate of the copper-based metal layer becomes too slow, and the etching rate of the indium oxide-based metal layer becomes relatively high, so that an undercut may occur.
상기 아졸화합물은 아미노테트라졸(aminotetrazole), 벤조트리아졸 (benzotriazole), 톨릴트리아졸(tolyltriazole), 피라졸(pyrazole), 피롤(pyrrole), 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸 및 4-프로필이미다졸로 이루어진 군에서 선택되는 1종 이상을 포함할 수 있다.
The azole compound is aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethyl At least one selected from the group consisting of midazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole may be included.
본 발명의 식각액 조성물에 포함되는 염소(Cl)염 중에서 선택되는 1종 이상의 화합물은 식각용액의 pH를 조절하여 구리 식각속도 및 산화인듐 합금 식각속도를 조절하는 역할을 한다. 상기 염소(Cl)염의 함량은 조성물 총 중량백분율에 대하여, 0.5 내지 3.0 중량%을 포함할수 있고, 1.0 ~ 2.0 중량% 범위인 조성물이 특히 바람직하다. 상기 염소(Cl)염 중에서 선택되는 1종 이상의 화합물의 함량이 0.5 중량% 미만인 경우 식각 속도가 저하되고, 3.0 중량%를 초과하면 식각속도가 너무 빨라짐으로 인한 과다침식 불량 발생 및 PR에 어택(Attack)을 주는 문제가 발생한다. At least one compound selected from chlorine (Cl) salts included in the etchant composition of the present invention serves to control the etching rate of copper and indium oxide alloy by adjusting the pH of the etchant. The content of the chlorine (Cl) salt may include 0.5 to 3.0 wt% based on the total weight percentage of the composition, and a composition in the range of 1.0 to 2.0 wt% is particularly preferred. When the content of one or more compounds selected from the chlorine (Cl) salt is less than 0.5 wt%, the etching rate is lowered, and when it exceeds 3.0 wt%, excessive erosion defects occur due to the etching rate being too fast and PR is attacked (Attack) ), the problem arises.
본 발명의 바람직한 일실시예에 따르면, 상기 염소(Cl)염은 염화나트륨(NaCl), 염화암모늄(ACl) 및 염화칼슘(KCl)중 선택되는 1종이상을 포함할 수 있다.
According to a preferred embodiment of the present invention, the chlorine (Cl) salt may include at least one selected from sodium chloride (NaCl), ammonium chloride (ACl), and calcium chloride (KCl).
본 발명의 식각액 조성물에 포함되는 킬레이트 화합물은 식각액 조성물의 보관 시 발생할 수 있는 과산화수소수의 자체 분해 반응을 막아주고 많은 수의 기판을 식각할 시에 식각 특성이 변하는 것을 방지한다. 일반적으로 과산화수소수를 사용하는 식각액 조성물의 경우 보관시 과산화수소수가 자체 분해하여 그 보관기간이 길지가 못하고 용기가 폭발할 수 있는 위험요소까지 갖추고 있다. 그러나 상기 킬레이트 화합물이 포함될 경우 과산화수소수의 분해 속도가 10배 가까이 줄어들어 보관기간 및 안정성 확보에 유리하다. 특히 구리층의 경우 식각액 조성물 내에 구리 이온이 다량 잔존할 경우에 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 많이 발생할 수 있으나 이 화합물을 첨가하였을 경우 이런 현상을 막을 수 있다. 상기 킬레이트 화합물의 함량이 조성물 총 중량백분율에 대하여 1.0 내지 3.0 중량%로 포함되고, 1.5 내지 2.5 중량% 범위인 조성물이 특히 바람직하다. 상기 킬레이트 화합물의 함량이 상술한 범위 미만일 경우, 다량의 기판의 식각 후에는 패시베이션 막이 형성되어 충분한 공정 마진을 얻기가 어려워진다. 또한, 상기 킬레이트 화합물의 함량이 상술한 범위를 초과할 경우, 금속산화물막의 식각속도가 느려지는 문제가 있다.The chelate compound included in the etchant composition of the present invention prevents the self-decomposition reaction of hydrogen peroxide that may occur during storage of the etchant composition and prevents the etching characteristics from changing when a large number of substrates are etched. In general, in the case of an etchant composition using hydrogen peroxide solution, the hydrogen peroxide solution self-decomposes during storage, so the storage period is not long and the container has a risk of explosion. However, when the chelate compound is included, the decomposition rate of hydrogen peroxide is reduced by nearly 10 times, which is advantageous in securing storage period and stability. In particular, in the case of a copper layer, when a large amount of copper ions remain in the etchant composition, a passivation film is formed and is oxidized to black, and there are many cases where it is not etched anymore, but this phenomenon can be prevented when this compound is added. . A composition in which the content of the chelate compound is included in an amount of 1.0 to 3.0% by weight, and in a range of 1.5 to 2.5% by weight based on the total weight of the composition is particularly preferred. When the content of the chelate compound is less than the above range, a passivation layer is formed after etching a large amount of the substrate, making it difficult to obtain a sufficient process margin. In addition, when the content of the chelate compound exceeds the above-described range, there is a problem in that the etching rate of the metal oxide film is slow.
본 발명의 바람직한 일실시예에 따르면, 상기 킬레이트 화합물은 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물일 수 있고, 바람직하게는 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine) 으로 이루어진 군 중에서 선택되는 1 종 이상을 포함할 수 있다. 그리고 이중에서 이미노디아세트산(iminodiacetic acid)이 가장 바람직하다.According to a preferred embodiment of the present invention, the chelate compound may be a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, preferably alanine, aminobutyric acid, glutamic acid, It may include at least one selected from the group consisting of glycine, iminodiacetic acid, nitrilotriacetic acid, and sarcosine. And among them, iminodiacetic acid is most preferred.
상기 과수안정제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 또한, 상기 과수안정제는 구리막을 식각한 후 식각액에 녹아져 나오는 구리 이온을 둘러 쌈으로서 구리이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제하게 된다. 이렇게 구리 이온의 활동도를 낮추게 되면 식각액을 사용하는 동안 안정적으로 공정을 진행 할 수 있게 된다. 상기 과수안정제의 함량은 조성물 총 중량백분율에 대하여 1.0 내지 3.0 중량%로 포함되고, 1.5 내지 2.0 중량% 범위인 조성물이 특히 바람직하다. 상기 과수안정제의 함량이 상술한 범위 미만인 경우, 식각 균일성이 저하되고 과산화수소의 분해가 가속화 되는 문제점이 생길 수 있다. 상기 과수안정제의 함량이 상술함 범위 이상이면 거품이 많이 발생되는 단점이 있다.The fruit water stabilizer serves to increase the uniformity of the etching by reducing the surface tension. In addition, the perwater stabilizer suppresses the activity of copper ions by surrounding copper ions dissolved in the etchant after etching the copper film, thereby suppressing the decomposition reaction of hydrogen peroxide. If the activity of copper ions is lowered in this way, the process can be performed stably while using the etchant. The content of the fruit water stabilizer is included in 1.0 to 3.0% by weight based on the total weight percentage of the composition, and the composition is particularly preferably in the range of 1.5 to 2.0% by weight. If the content of the perwater stabilizer is less than the above range, there may be problems in that the etching uniformity is lowered and the decomposition of hydrogen peroxide is accelerated. If the content of the fruit water stabilizer is more than the above-mentioned range, there is a disadvantage in that a lot of bubbles are generated.
상기 과수안정제는 다가알코올형 계면활성제일 수 있고, 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol), 폴리에틸렌 글리콜(polyethylene glycol), 프로판디올(propandiol), 부탄디올(butanediol)으로 이루어진 군 중에서 선택되는 1 종 이상을 포함할 수 있다. 그리고 이중에서 트리에틸렌글리콜(triethylene glycol)이 바람직하다.
The fruit water stabilizer may be a polyhydric alcohol-type surfactant, It may include at least one selected from the group consisting of glycerol, triethylene glycol, polyethylene glycol, propandiol, and butanediol. And among them, triethylene glycol is preferable.
본 발명의 식각액 조성물에 포함되는 물은 특별히 한정되는 것은 아니나, 탈이온수가 바람직하다. 더욱 바람직하게는 물의 비저항 값, 즉, 물속에 이온이 제거된 정도가 18Ω·cm이상인 탈이온수를 사용하는 것이 좋다. 상기 물은 본 발명의 식각액 조성물의 총 중량이 100중량%가 되도록 잔량 포함된다.
The water included in the etchant composition of the present invention is not particularly limited, but deionized water is preferable. More preferably, it is preferable to use deionized water having a specific resistance value of water, that is, a degree of ion removal in water of 18Ω·cm or more. The remaining amount of water is included so that the total weight of the etchant composition of the present invention is 100% by weight.
본 발명의 식각액 조성물은 계면활성제를 더 포함할 수 있다. 상기 계면활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 상기 계면활성제는 본 발명의 식각액 조성물에 견딜 수 있고, 상용성이 있는 것이라면 특별히 한정되지 않는다. 그러나, 음이온성 계면활성제, 양이온성 계면활성제, 양쪽 이온성 계면활성제, 비이온성 계면활성제 및 다가알코올형 계면활성제로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. The etchant composition of the present invention may further include a surfactant. The surfactant serves to increase the uniformity of the etching by reducing the surface tension. The surfactant is not particularly limited as long as it can withstand the etchant composition of the present invention and has compatibility. However, one or two or more selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants and polyalcohol surfactants are preferable.
또한, 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 금속 이온 봉쇄제, 및 부식 방지제 등을 들 수 있다.
In addition, conventional additives may be further added in addition to the above-mentioned components, and examples of the additives include a metal ion sequestrant and a corrosion inhibitor.
본 발명에서 사용되는 과산화수소(H2O2), 함불소 화합물, 아졸화합물, 킬레이트 화합물, 염소(Cl)염 및 과수안정제등은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다.
Hydrogen peroxide (H 2 O 2 ), fluorine-containing compounds, azole compounds, chelate compounds, chlorine (Cl) salts and peroxide stabilizers used in the present invention can be prepared by conventionally known methods, and the etchant composition of the present invention It is desirable that the silver has a purity for semiconductor processing.
본 발명의 식각액 조성물은 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 식각할 때, 식각 균일성 및 직진성이 우수한 테이퍼 프로파일을 구현할 수 있다. 본 발명의 식각액 조성물은 식각할 때, 잔사를 발생시키지 않으므로 전기적인 쇼트나 배선의 불량, 휘도의 감소 등의 문제로부터 자유롭다. 또한, 본 발명의 식각액 조성물은 액정표시장치용 어레이 기판을 제조시, 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 포함하는, 게이트 전극과 게이트 배선, 소스/드레인 전극과 데이터 배선을 일괄식각할 수 있어, 식각공정을 단순화시키며 공정수율을 극대화시킨다. 따라서, 본 발명의 식각액 조성물은 대화면, 고휘도의 회로가 구현되는 액정표시장치용 어레이 기판의 제조시에 매우 유용하게 사용될 수 있다.
When etching a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film, the etchant composition of the present invention can implement a tapered profile excellent in etching uniformity and straightness. The etchant composition of the present invention does not generate a residue during etching, so it is free from problems such as an electrical short, a wiring defect, and a decrease in luminance. In addition, the etchant composition of the present invention comprises a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film when manufacturing an array substrate for a liquid crystal display device, a gate electrode and a gate wiring, a source / drain electrode and a data wiring Batch etching is possible, simplifying the etching process and maximizing the process yield. Therefore, the etchant composition of the present invention can be very usefully used in the manufacture of an array substrate for a liquid crystal display in which a circuit having a large screen and high luminance is implemented.
본 발명의 식각액 조성물은 구리계 금속으로 이루어진 액정표시장치의 게이트 전극과 게이트 배선 및 소스/드레인 전극과 데이터 배선 층을 일괄 식각할 수 있다. The etchant composition of the present invention can batch etch the gate electrode, the gate wiring, the source/drain electrode, and the data wiring layer of the liquid crystal display made of copper-based metal.
본 발명의 액정표시장치용 어레이 기판의 제조방법은, a)기판 상에 게이트 전극을 형성하는 단계; b)상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c)상기 게이트 절연층 상에 반도체층을 형성하는 단계; d)상기 반도체층 상에 소스/드레인 전극을 형성하는 단계; 및 e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서, 상기 a)단계는 기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 본 발명의 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고, 상기 d)단계는 반도체층 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 본 발명의 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함한다.A method of manufacturing an array substrate for a liquid crystal display according to the present invention comprises the steps of: a) forming a gate electrode on the substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming source/drain electrodes on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein step a) comprises forming a copper-based metal film or a copper-based metal film and a metal oxide film on the substrate. and forming a multilayer film and etching the copper-based metal film or the multilayer film of the copper-based metal film and the metal oxide film with the etchant composition of the present invention to form a gate electrode, wherein step d) is a copper-based metal film on the semiconductor layer and forming a multilayer film of a film or a copper-based metal film and a metal oxide film, and etching the copper-based metal film or a multilayer film of the copper-based metal film and a metal oxide film with the etchant composition of the present invention to form source/drain electrodes.
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. 그리고, 상기 액정표시장치용 어레이 기판은 본 발명의 식각액 조성물을 사용하여 식각된 게이트 전극, 게이트 배선, 소스/드레인 전극 및 데이터 배선 중 하나 이상을 포함한다.
The array substrate for the liquid crystal display may be a thin film transistor (TFT) array substrate. In addition, the array substrate for a liquid crystal display includes at least one of a gate electrode, a gate wire, a source/drain electrode, and a data wire etched using the etchant composition of the present invention.
이하 본 발명을 실시예에 기초하여 더욱 상세하게 설명하지만, 하기에 개시되는 본 발명의 실시 형태는 어디까지 예시로써, 본 발명의 범위는 이들의 실시 형태에 한정되지 않는다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.
Hereinafter, the present invention will be described in more detail based on Examples, but the embodiments of the present invention disclosed below are merely illustrative, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it embraces all modifications within the meaning and scope equivalent to those recorded in the claims. In addition, in the following examples and comparative examples, "%" and "part" indicating the content are by weight unless otherwise specified.
실시예Example 1 내지 1 to 실시예Example 5 및 5 and 비교예comparative example 1 내지 1 to 비교예comparative example 5: 5: 식각액etchant 조성물의 제조 Preparation of the composition
하기 표 1에 나타낸 조성에 따라 실시예1 내지 실시예 5 및 비교예 1 내지 비교예 5의 식각액 조성물 180㎏을 제조하였다. According to the composition shown in Table 1 below, 180 kg of the etchant compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were prepared.
(주) 5-ATZ: 5-aminotetrazole, IDA: iminodiacetic acid, Co., Ltd. 5-ATZ: 5-aminotetrazole, IDA: iminodiacetic acid,
TEG: triethyleneglycol
TEG: triethyleneglycol
실험예Experimental example : : 식각액etchant 조성물의 특성평가 Characterization of the composition
<Cu/a-ITO의 식각><Etch of Cu/a-ITO>
유리기판(100㎜Ⅹ100㎜) 상에 a-ITO를 증착시키고 상기 a-ITO상에 구리막을 증착시킨 뒤 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 하였다. 그 후, 실시예1 내지 실시예5, 비교예1 내지 비교예 5의 식각액 조성물을 각각 사용하여 Cu/a-ITO에 대하여 식각 공정을 실시하였다.After depositing a-ITO on a glass substrate (100 mm×100 mm) and depositing a copper film on the a-ITO, a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. Then, an etching process was performed on Cu/a-ITO using the etching solution compositions of Examples 1 to 5 and Comparative Examples 1 to 5, respectively.
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 식각액 조성물의 온도는 약 30℃ 내외로 하였다. 식각 시간은 80초 정도로 진행하였다. 상기 식각 공정에서 식각된 구리계 금속막의 프로파일을 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였다.Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the etchant composition during the etching process was about 30°C. The etching time was about 80 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (manufactured by Hitachi, model name S-4700).
식각 프로파일 및 식각 직진성은 하기의 기준에 따라 육안으로 평가하여 표2에 나타내었다.The etch profile and etch straightness were visually evaluated according to the following criteria, and are shown in Table 2.
<식각 프로파일 평가 기준><Etch Profile Evaluation Criteria>
○: 우수, △: 양호, X: 식각 안 됨.○: Excellent, △: Good, X: Not etched.
<식각 직진성 평가 기준><Estimation standard for etch straightness>
○: 패턴이 직선으로 형성됨, △: 패턴에 곡선으로 형성됨, X : 식각 안 됨○: Pattern is formed in a straight line, △: Pattern is formed in a curve, X: Not etched
<a-ITO Tail><a-ITO Tail>
○: 0.20㎛미만, △: 0.20이상~0.50㎛미만, X : 0.50㎛ 이상 ~ unetch○: less than 0.20㎛, △: more than 0.20 ~ less than 0.50㎛, X: more than 0.50㎛ ~ unetch
또한 구리의 농도를 300에서 5000ppm까지 증가시켰을 경우 식각 특성 및 발열(최대 90도 이상)이 없는 조건이 충족되는 경우에 구리계 금속막 식각액 조성물을 식각 공정에 계속 사용할수 있는 것으로 정하고, 실험을 실시하였다.In addition, when the copper concentration is increased from 300 to 5000 ppm, the copper-based metal film etchant composition can be continued to be used in the etching process if the etching characteristics and the condition that there is no heat (up to 90 degrees or more) are satisfied, and the experiment was conducted. did.
(℃, Cu 5000ppm)maximum heating temperature
(℃, Cu 5000ppm)
직진도etching
straightness
직진도etching
straightness
실험예에서 발열은 실시예의 조성물에 탈이온수가 포함되어 있으므로 90도 이상의 경우 탈이온수가 증발하기 때문에 최대 90도로 하여 실험을 실시하였다. In the experimental example, since deionized water is included in the composition of Examples, the experiment was conducted at a maximum of 90 degrees because the deionized water evaporates when the temperature is higher than 90 degrees.
표 2를 참조하면, 실시예1 내지 실시예5의 식각액 조성물은 모두 양호한 식각 특성을 나타내었다. 또한, Cu 5,000ppm하에서도 최대 발열온도가 36.2도로 90도보다 현저히 낮았다. 반면에, 염소(Cl)염이 범위 미만으로 포함된 비교예 1의 경우, 산화인듐계 금속막의 식각 속도가 느려져 식각 특성이 좋지 않음을 알 수 있었다. 그리고 염소(Cl)염이 상술 범위 초과로 포함된 비교예 2의 경우 구리 금속막의 식각 속도가 산화인듐계 금속막의 식각속도에 비해 너무 빨라져 산화인듐계 금속막의 Tail이 길어져 특성이 좋지 않음을 알 수 있다. 또한 킬레이트 화합물이 상술범위 미만으로 포함된 비교예 3경우 식각 Profile 및 직진성 및 ITO Tail 측면에서 우수한 특성을 나타내었지만 최대발열 온도가 100이상의 현상이 발생하여 식각액으로 특성이 좋지 않음을 알 수 있었다. 그리고, 킬레이트 화합물이 상술 범위 초과로 포함된 비교예4의 경우 ITO Etch Rate이 너무 늦어져 unetch 현상이 발생하였다. 과수안정제가 상술범위 미만으로 포함된 비교예5의 경우 나머지 특성은 만족하지만 최대발열 온도가 100이상의 현상이 발생함을 알 수 있다.Referring to Table 2, the etchant compositions of Examples 1 to 5 all exhibited good etching properties. In addition, the maximum exothermic temperature was significantly lower than 90 degrees at 36.2 degrees even under 5,000 ppm of Cu. On the other hand, in the case of Comparative Example 1 in which the chlorine (Cl) salt was included in less than the range, it was found that the etching rate of the indium oxide-based metal layer was slowed, and thus the etching characteristics were not good. And in the case of Comparative Example 2 in which the chlorine (Cl) salt was included in excess of the above range, the etching rate of the copper metal film was too fast compared to the etching rate of the indium oxide-based metal film. there is. In addition, in the case of Comparative Example 3 in which the chelate compound was included below the above-mentioned range, it exhibited excellent properties in terms of etching profile, straightness, and ITO tail, but the maximum exothermic temperature was 100 or more, and it was found that the characteristics of the etchant were not good. And, in the case of Comparative Example 4 in which the chelate compound was included in excess of the above-mentioned range, the ITO Etch Rate was too slow, and an unetch phenomenon occurred. In the case of Comparative Example 5, in which the fruit water stabilizer was included below the above range, it can be seen that the remaining characteristics were satisfied, but the maximum exothermic temperature was 100 or more.
따라서, 본 발명의 식각액 조성물은 구리계 금속막, 산화인듐계 금속막의 식각에 매우 적합하고, 이들의 일괄식각에도 매우 적합한 것을 알 수 있다.Therefore, it can be seen that the etchant composition of the present invention is very suitable for etching a copper-based metal film and an indium oxide-based metal film, and is also very suitable for batch etching thereof.
Claims (10)
상기 염소(Cl)염은 염화나트륨(NaCl)이며,
상기 구리계 금속막은 두께가 5000Å이상인 후막인 것인,
구리계 금속막 및 금속산화물막의 식각액 조성물. 5 to 25% by weight of hydrogen peroxide (H2O2), 0.01 to 3.0% by weight of a fluorine-containing compound, 0.1 to 3.0% by weight of an azole compound, 0.5 to 3.0% by weight of a chlorine (Cl) salt, 1.0 to 3.0% by weight of a chelating agent based on the total weight percentage of the composition %, an etchant composition of a copper-based metal film and a metal oxide film containing 1.0 to 3.0% by weight of an orchard stabilizer and the remaining amount of water,
The chlorine (Cl) salt is sodium chloride (NaCl),
The copper-based metal film is a thick film having a thickness of 5000 Å or more,
An etchant composition for a copper-based metal film and a metal oxide film.
상기 구리계 금속막은 구리 또는 구리 합금의 단일막; 또는
몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막과 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막을 포함하는 다층막인 것을 특징으로 하는 구리계 금속막 및 금속산화물막의 식각액 조성물.The method according to claim 1,
The copper-based metal film may include a single film of copper or a copper alloy; or
Copper-based metal film and metal oxide, characterized in that it is a multilayer film comprising at least one film selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film, and at least one film selected from a copper film and a copper alloy film The etchant composition of the membrane.
상기 함불소화합물은 불화암모늄(ammonium fluoride: NH4F), 불화나트륨(sodium fluoride: NaF), 불화칼륨(potassium fluoride: KF), 중불화암모늄(ammonium bifluoride: NH4F·HF), 중불화나트륨(sodium bifluoride: NaF·HF), 불산(Hydrofluoric acid: HF), 테트라플루오르붕산암모늄(Tetrafluoroboric acid: NH4BF4), 불화알루미늄(Aluminium fluoride: AlF3), 붕불화수소산(HBF4) 및 중불화칼륨(potassium bifluoride: KF·HF)으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 구리계 금속막 및 금속산화물막의 식각액 조성물.The method according to claim 1,
The fluorinated compound is ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F HF), heavy fluoride sodium (sodium bifluoride: NaF HF), hydrofluoric acid (HF), ammonium tetrafluoroboric acid (NH 4 BF 4 ), aluminum fluoride (AlF 3 ), hydroboric acid (HBF 4 ), and An etchant composition for a copper-based metal film and a metal oxide film, comprising at least one selected from the group consisting of potassium bifluoride (KF·HF).
상기 아졸화합물은 아미노테트라졸(aminotetrazole), 벤조트리아졸 (benzotriazole), 톨릴트리아졸(tolyltriazole), 피라졸(pyrazole), 피롤(pyrrole), 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸 및 4-프로필이미다졸로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 하는 구리계 금속막 및 금속산화물막의 식각액 조성물.The method according to claim 1,
The azole compound is aminotetrazole, benzotriazole, tolyltriazole, pyrazole, pyrrole, imidazole, 2-methylimidazole, 2-ethyl Midazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole and 4-propylimidazole comprising at least one selected from the group consisting of An etchant composition of a copper-based metal film and a metal oxide film.
상기 킬레이트 화합물은 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군에서 선택되는 1 종 이상을 포함하는 것을 특징으로 하는 구리계 금속막 및 금속산화물막의 식각액 조성물.The method according to claim 1,
The chelate compound is composed of alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid and sarcosine. An etchant composition for a copper-based metal film and a metal oxide film, comprising at least one selected from the group.
상기 과수안정제는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol), 폴리에틸렌 글리콜(polyethylene glycol), 프로판디올(propandiol) 및 부탄디올(butanediol)로 이루어진 군에서 선택되는 1 종 이상을 포함하는 것을 특징으로 하는 구리계 금속막 및 금속산화물막의 식각액 조성물.The method according to claim 1,
The fruit water stabilizer comprises at least one selected from the group consisting of glycerol, triethylene glycol, polyethylene glycol, propandiol and butanediol. An etchant composition for a copper-based metal film and a metal oxide film.
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 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 a)단계는 기판 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 청구항 1의 식각액 조성물로 식각하여 게이트 전극을 형성하는 단계를 포함하고,
상기 d)단계는 반도체층 상에 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 형성하고 상기 구리계 금속막 또는 구리계 금속막과 금속산화물막의 다층막을 청구항 1의 식각액 조성물로 식각하여 소스/드레인 전극을 형성하는 단계를 포함하며,
상기 a) 단계 및 d) 단계에서 형성되는 구리계 금속막은 두께가 5000Å이상인 후막인 것을 특징으로 하는 액정표시장치용 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 a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer, and
e) a method of manufacturing an array substrate for a liquid crystal display comprising the step of forming a pixel electrode connected to the drain electrode,
In step a), a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film is formed on a substrate, and the copper-based metal film or a multilayer film of the copper-based metal film and a metal oxide film is etched with the etchant composition of claim 1 to gate the gate. forming an electrode;
In step d), a copper-based metal film or a multilayer film of a copper-based metal film and a metal oxide film is formed on the semiconductor layer, and the copper-based metal film or a multilayer film of the copper-based metal film and a metal oxide film is etched with the etchant composition of claim 1, forming source/drain electrodes;
The method of manufacturing an array substrate for a liquid crystal display, characterized in that the copper-based metal film formed in steps a) and d) is a thick film having a thickness of 5000 Å or more.
상기 액정표시장치용 어레이 기판이 박막트랜지스터(TFT) 어레이 기판인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.9. The method of claim 8,
The method of manufacturing an array substrate for a liquid crystal display, characterized in that the array substrate for the liquid crystal display is a thin film transistor (TFT) array substrate.
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