JP2012508965A - Transparent conductive film etching solution - Google Patents
Transparent conductive film etching solution Download PDFInfo
- Publication number
- JP2012508965A JP2012508965A JP2011535523A JP2011535523A JP2012508965A JP 2012508965 A JP2012508965 A JP 2012508965A JP 2011535523 A JP2011535523 A JP 2011535523A JP 2011535523 A JP2011535523 A JP 2011535523A JP 2012508965 A JP2012508965 A JP 2012508965A
- Authority
- JP
- Japan
- Prior art keywords
- film
- transparent conductive
- etching
- conductive film
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 239000003112 inhibitor Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 230000032683 aging Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 iron ion Chemical class 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- ULIDRMKBVYYVIQ-UHFFFAOYSA-N 1-phenyltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC=C1 ULIDRMKBVYYVIQ-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 241001274216 Naso Species 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229960004109 potassium acetate Drugs 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 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 1
- TTWYBNLBVHMTBZ-UHFFFAOYSA-N CN1N=NN=C1N.CN1N=NN=C1N Chemical compound CN1N=NN=C1N.CN1N=NN=C1N TTWYBNLBVHMTBZ-UHFFFAOYSA-N 0.000 claims 1
- GQIIFFOTIPKTHB-UHFFFAOYSA-N NN1N=NN=C1N.NN1N=NN=C1N Chemical compound NN1N=NN=C1N.NN1N=NN=C1N GQIIFFOTIPKTHB-UHFFFAOYSA-N 0.000 claims 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000002123 temporal effect Effects 0.000 claims 1
- 229960000314 zinc acetate Drugs 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 192
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 35
- 229910052802 copper Inorganic materials 0.000 abstract description 35
- 239000010949 copper Substances 0.000 abstract description 35
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 21
- 239000000243 solution Substances 0.000 abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 19
- 239000011733 molybdenum Substances 0.000 abstract description 19
- 229910001182 Mo alloy Inorganic materials 0.000 abstract description 16
- 239000010409 thin film Substances 0.000 abstract description 9
- 239000003517 fume Substances 0.000 abstract description 4
- 230000009545 invasion Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000001473 noxious effect Effects 0.000 abstract description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 229910001069 Ti alloy Inorganic materials 0.000 description 11
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 235000006408 oxalic acid Nutrition 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 3
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229940116269 uric acid Drugs 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 2
- JZLMRQMUNCKZTP-UHFFFAOYSA-N molybdenum tantalum Chemical compound [Mo].[Ta] JZLMRQMUNCKZTP-UHFFFAOYSA-N 0.000 description 2
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XMGWNAIPGOPSNX-UHFFFAOYSA-N 1,5-diaminotetrazole Chemical compound NC1=NN=NN1N XMGWNAIPGOPSNX-UHFFFAOYSA-N 0.000 description 1
- CAMZCCDMGNIZTA-UHFFFAOYSA-N 1-naphthalen-1-yltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC2=CC=CC=C12 CAMZCCDMGNIZTA-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
本発明は、薄膜トランジスタ液晶表示装置などの平板ディスプレイ表示装置の薄膜トランジスタ製造工程において、微細パターンに形成された透明伝導膜のエッチング溶液組成物に関する。
本発明は、含ハロゲン化合物０．０５〜１５重量％、補助酸化剤０．１〜２０重量％、エッチング調節剤０．０５〜１５重量％、残渣抑制剤０．１〜１５重量％、腐食抑制剤０．３〜１０重量％及び全体組成物の総重量が１００重量％になるようにする水で構成され、銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜の侵害現象が発生しないようにする透明伝導膜エッチング組成物に関する。
本発明の透明伝導膜エッチング組成物は腐食抑制剤と経時変化抑制剤を含む水溶液であり、従来の透明伝導膜エッチング組成物で発生する側面エッチング現象、経時変化現象、エッチング時の残渣発生現象、銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜の侵害現象などの欠点を完全に解消することができる。特に本発明は、従来の透明伝導膜エッチング組成物の主要問題点であるエッチング時の残渣発生現象と銅膜、銅膜銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜の侵害現象を解消するため、透明伝導膜の選択的パターンエッチングが可能である。
また、本発明による透明伝導膜エッチング組成物は適切なエッチング速度及び適切な傾斜角を提供することができ、蒸発量を顕著に減少させてエッチング組成物の成分量の変動を減少させ、それによるヒューム（ｆｕｍｅ）発生量を減らすことにより、大気環境汚染を防止することができる長所を有している。
【選択図】図１The present invention relates to an etching solution composition for a transparent conductive film formed in a fine pattern in a thin film transistor manufacturing process of a flat panel display device such as a thin film transistor liquid crystal display device.
The present invention includes a halogen-containing compound of 0.05 to 15% by weight, an auxiliary oxidizing agent of 0.1 to 20% by weight, an etching regulator of 0.05 to 15% by weight, a residue inhibitor of 0.1 to 15% by weight, and corrosion inhibition. A copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these are laminated, each composed of 0.3 to 10% by weight of an agent and water that makes the total weight of the entire composition 100% by weight The present invention relates to a transparent conductive film etching composition that prevents the invasion phenomenon.
The transparent conductive film etching composition of the present invention is an aqueous solution containing a corrosion inhibitor and a aging inhibitor, a side etching phenomenon that occurs in a conventional transparent conductive film etching composition, a aging phenomenon, a residue generation phenomenon during etching, Defects such as a noxious phenomenon of a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film or a multilayer film in which these films are laminated can be completely eliminated. In particular, the present invention relates to a residue generation phenomenon during etching, which is a main problem of conventional transparent conductive film etching compositions, and a copper film, a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these are laminated. In order to eliminate the infringement phenomenon, selective pattern etching of the transparent conductive film is possible.
In addition, the transparent conductive film etching composition according to the present invention can provide an appropriate etching rate and an appropriate inclination angle, thereby significantly reducing the evaporation amount and reducing the variation of the component amount of the etching composition. It has an advantage that air environment pollution can be prevented by reducing the generation amount of fumes.
[Selection] Figure 1
Description
本発明は、平板表示装置（ＦＰＤ、Ｆｌａｔ Ｐａｎｅｌ Ｄｉｓｐｌａｙ）の製造工程における透明電極用微細パターンである透明伝導膜のエッチング組成物に関する。 The present invention relates to an etching composition for a transparent conductive film, which is a fine pattern for a transparent electrode, in a manufacturing process of a flat panel display (FPD, Flat Panel Display).
透明伝導膜は、薄膜トランジスタ液晶表示装置、プラズマディスプレイパネル表示装置、エレクトロルミネッセンス表示装置などに幅広く用いられている薄膜であり、前記平板ディスプレイ用表示装置に透明伝導膜を形成するためには、所望の微細パターンを形成させるエッチング工程が必要である。 The transparent conductive film is a thin film that is widely used in thin film transistor liquid crystal display devices, plasma display panel display devices, electroluminescence display devices, and the like. An etching process for forming a fine pattern is necessary.
その時に用いられる透明電極膜としては、酸化インジウムスズ膜、酸化インジウム亜鉛膜、酸化亜鉛膜が用いられており、前記酸化インジウムスズ膜、酸化インジウム亜鉛膜、酸化亜鉛膜の使用は、保護膜上に酸化インジウムスズ膜、酸化インジウム亜鉛膜、酸化亜鉛膜を形成し、フォトレジストをマスクとして塗布した後、酸化インジウムスズ膜、酸化インジウム亜鉛膜、酸化亜鉛膜をエッチングさせる。 As the transparent electrode film used at that time, an indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are used. The use of the indium tin oxide film, the indium zinc oxide film, and the zinc oxide film is performed on the protective film. Then, an indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are formed and applied using a photoresist as a mask, and then the indium tin oxide film, the indium zinc oxide film, and the zinc oxide film are etched.
従来の透明伝導膜エッチング溶液としては、塩酸／硝酸混合水溶液（王水）、塩酸／酢酸混合水溶液、塩化第二鉄水溶液、尿酸水溶液、リン酸水溶液、シュウ酸水溶液などが用いられているが、このような従来の透明伝導膜用エッチング溶液は、次のような問題点を有している。 As the conventional transparent conductive film etching solution, hydrochloric acid / nitric acid mixed aqueous solution (aqua regia), hydrochloric acid / acetic acid mixed aqueous solution, ferric chloride aqueous solution, uric acid aqueous solution, phosphoric acid aqueous solution, oxalic acid aqueous solution, etc. are used. Such a conventional transparent conductive film etching solution has the following problems.
第一に、塩酸／硝酸混合水溶液（王水）、塩酸／酢酸混合水溶液は、エッチング速度が早くて安定的であるが、塩酸や硝酸が揮発するためエッチング溶液組成物の成分量の変動が激しく、それによるヒューム（ｆｕｍｅ）発生が多くて作業環境を汚染させ、薄膜トランジスタ液晶表示装置の薄膜トランジスタ製造工程において電極材料として主に用いられている銅または銅合金を侵害するという欠点がある。 First, hydrochloric acid / nitric acid mixed aqueous solution (aqua regia) and hydrochloric acid / acetic acid mixed aqueous solution are fast and stable, but the amount of components in the etching solution composition varies greatly because hydrochloric acid and nitric acid volatilize. As a result, the generation of fumes is large, polluting the working environment, and invading copper or a copper alloy mainly used as an electrode material in the thin film transistor manufacturing process of the thin film transistor liquid crystal display device.
第二に、塩化第二鉄水溶液は、エッチング速度が早くて安定的であるが、相対的に側面エッチング量が大きく、鉄の汚染を誘発させるという欠点がある。 Secondly, the aqueous ferric chloride solution has a high etching rate and is stable, but has a disadvantage that the side etching amount is relatively large and iron contamination is induced.
第三に、尿酸水溶液は、側面エッチング量が少なくて良好なエッチング特性を有するが、液の経時変化が大きいという欠点がある。 Thirdly, the aqueous uric acid solution has good etching characteristics with a small amount of side etching, but has a drawback that the change with time of the solution is large.
第四に、リン酸水溶液は、電極材料として主に用いられる銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害し、透明伝導膜中の酸化インジウムスズ膜のエッチングを妨害するという欠点がある。 Fourth, the phosphoric acid aqueous solution invades the copper film, copper alloy film, molybdenum film, molybdenum alloy film or the multilayer film in which these are laminated mainly used as the electrode material, and the indium tin oxide film in the transparent conductive film There is a disadvantage that the etching is disturbed.
第五に、シュウ酸水溶液は、エッチング特性が安定的であり、液の経時変化も起こらないため良好であるが、エッチング時に残渣が発生しやすく、エッチング装備でエッチング溶液を用いた後に装置内壁に残遺物（シュウ酸結晶）が発生するという欠点を有している。 Fifth, the aqueous oxalic acid solution is good because it has stable etching characteristics and does not change over time, but it is easy to generate residues during etching. There is a disadvantage that a residue (oxalic acid crystal) is generated.
本発明は、従来の透明伝導膜エッチング組成物である塩酸／硝酸混合水溶液（王水）、塩酸／酢酸混合水溶液、塩化第二鉄水溶液、尿酸水溶液、リン酸水溶液、シュウ酸水溶液の使用時に発生する側面エッチング現象、経時変化現象、エッチング時の残渣発生現象、銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜の侵害現象などの欠点を解決することができる透明伝導膜用の選択的エッチング組成物を提供するためのものであり、本発明の透明伝導膜エッチング組成物は腐食抑制剤と経時変化抑制剤を含んでいる水溶液であり、従来の透明伝導膜エッチング組成物の欠点を完全に解消することができる。特に、本発明は、従来の透明伝導膜エッチング組成物の主な問題点であるエッチング時の残渣発生現象と銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害する現象を解消し、透明伝導膜の選択的パターンエッチングを可能にしたものである。 The present invention occurs when a conventional transparent conductive film etching composition, hydrochloric acid / nitric acid mixed aqueous solution (aqua regia), hydrochloric acid / acetic acid mixed aqueous solution, ferric chloride aqueous solution, uric acid aqueous solution, phosphoric acid aqueous solution, oxalic acid aqueous solution is used. Transparency that can solve defects such as side etching phenomenon, aging phenomenon, residue generation phenomenon during etching, invasion phenomenon of copper film, copper alloy film, molybdenum film, molybdenum alloy film or multilayer film in which these are laminated The transparent conductive film etching composition of the present invention is an aqueous solution containing a corrosion inhibitor and a aging inhibitor, and is a conventional transparent conductive film etch. The drawbacks of the composition can be completely eliminated. In particular, the present invention relates to a residue generation phenomenon during etching, which is a main problem of conventional transparent conductive film etching compositions, and a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these are laminated. This eliminates the infringing phenomenon and enables selective pattern etching of the transparent conductive film.
上述の問題点を解決するための本発明は、含ハロゲン化合物、補助酸化剤、エッチング調節剤、残渣調節剤、腐食抑制剤、経時変化抑制剤及び水を含む透明導電膜エッチング組成物であって、平板表示装置（ＦＰＤ、Ｆｌａｔ Ｐａｎｅｌ Ｄｉｓｐｌａｙ）の製造工程における透明電極用微細パターンである透明伝導膜の選択的エッチング溶液組成物に関する。 The present invention for solving the above-mentioned problems is a transparent conductive film etching composition comprising a halogen-containing compound, an auxiliary oxidant, an etching regulator, a residue regulator, a corrosion inhibitor, a aging inhibitor and water. The present invention relates to a selective etching solution composition for a transparent conductive film which is a fine pattern for a transparent electrode in a manufacturing process of a flat panel display (FPD).
より具体的には、本発明は、薄膜トランジスタの電極材料として主に用いられる銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜のエッチングさせる現象を解消し、透明伝導膜の選択的パターンエッチングのためのエッチング組成物を提供する。 More specifically, the present invention eliminates the etching phenomenon of a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these films are mainly used as an electrode material of a thin film transistor, and provides transparent conduction. An etching composition for selective pattern etching of a film is provided.
そして、前記夫々の金属膜の厚さは互いに制限されず、必要に応じて適宜調節することができるが、より具体的には、前記銅膜は約１０００〜５０００Åの厚さを有するように蒸着することができる。前記モリブデン合金膜は、タングステン、チタン、ニオブ、クロム、タンタルなど、モリブデンと合金をなすことができる金属成分を含んだモルリブデン膜を意味し、その例として、モリブデン−タングステン（Ｍｏ−Ｗ）、モリブデン−チタン（Ｍｏ−Ｔｉ）、モリブデン−ニオブ（Ｍｏ−Ｎｂ）、モリブデン−クロム（Ｍｏ−Ｃｒ）、モリブデン−タンタル（Ｍｏ−Ｔａ）などが挙げられる。前記モリブデン膜またはモリブデン合金膜は、１００〜５００Åの厚さを有するように蒸着することができる。 The thicknesses of the respective metal films are not limited to each other and can be appropriately adjusted as necessary. More specifically, the copper film is deposited to have a thickness of about 1000 to 5000 mm. can do. The molybdenum alloy film means a molribden film containing a metal component capable of forming an alloy with molybdenum, such as tungsten, titanium, niobium, chromium, and tantalum. Examples thereof include molybdenum-tungsten (Mo-W) and molybdenum. -Titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr), molybdenum-tantalum (Mo-Ta), etc. are mentioned. The molybdenum film or the molybdenum alloy film can be deposited to have a thickness of 100 to 500 mm.
本発明は、含ハロゲン化合物０．０５〜１５重量％、補助酸化剤０．１〜２０重量％、エッチング調節剤０．０５〜１５重量％、残渣抑制剤０．１〜１５重量％、腐食抑制剤０．３〜１０重量％及び全体組成物の総重量が１００重量％になるようにする水で構成され、より具体的には、銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜に対する侵害現象がないようにする透明伝導膜エッチング組成物に関する。 The present invention includes a halogen-containing compound of 0.05 to 15% by weight, an auxiliary oxidizing agent of 0.1 to 20% by weight, an etching regulator of 0.05 to 15% by weight, a residue inhibitor of 0.1 to 15% by weight, and corrosion inhibition. Composed of 0.3 to 10% by weight of the agent and water so that the total weight of the total composition becomes 100% by weight, more specifically, a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or these The present invention relates to a transparent conductive film etching composition that prevents a noxious phenomenon with respect to a multi-layered film.
本発明のエッチング組成物に含まれる含ハロゲン化合物は、透明伝導膜をエッチングする主要酸化剤としての機能をする。前記含ハロゲン化合物は、特に限定されず、溶液内でハロゲンイオンまたは多原子ハロゲンイオンに解離されることができる化合物であれば使用可能であり、具体的には、下記化学式１の構造を有することができる。 The halogen-containing compound contained in the etching composition of the present invention functions as a main oxidant for etching the transparent conductive film. The halogen-containing compound is not particularly limited and may be used as long as it is a compound that can be dissociated into a halogen ion or a polyatomic halogen ion in a solution. Specifically, the halogen-containing compound has a structure represented by the following chemical formula 1. Can do.
［化１］
ＡＸｍ
（前記式で、Ａは水素イオン（Ｈ＋）、アンモニウムイオン（ＮＨ４＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）、アルミニウムイオン（Ａｌ３＋）または酸化数が１〜３価であるアルキル金属イオン、Ｘはハロゲン元素、ｍはＡの酸化数である。）
[Chemical 1]
AX m
(In the above formula, A is a hydrogen ion (H + ), an ammonium ion (NH 4 + ), an iron ion (Fe 2+ , Fe 3+ ), an aluminum ion (Al 3+ ), or an alkyl metal ion having an oxidation number of 1 to 3. , X is a halogen element, and m is the oxidation number of A.)
具体的には、前記含ハロゲン化合物は、ハロゲン化水素、アンモニウムハライド、ハロゲン化鉄またはアルカリハライド等があり、より具体的な例示として、塩化水素（ＨＣｌ）、塩化アルミニウム（ＡｌＣｌ３）、フッ化アンモニウム（ＮＨ４Ｆ）、ヨウ化カリウム（ＫＩ）、塩化カリウム（ＫＣｌ）及び塩化アンモニウム（ＮＨ４Ｃｌ）からなる群から一つ以上選択されることができる。 Specific examples of the halogen-containing compound include hydrogen halide, ammonium halide, iron halide, and alkali halide. More specific examples include hydrogen chloride (HCl), aluminum chloride (AlCl 3 ), fluoride, and the like. One or more can be selected from the group consisting of ammonium (NH 4 F), potassium iodide (KI), potassium chloride (KCl), and ammonium chloride (NH 4 Cl).
前記含ハロゲン化合物は、全体組成物の総重量に対して０．０５〜１５重量％で含むことができる。前記含ハロゲン化合物の含量が多すぎると銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害する現象が発生する可能性があり、含量が少ないと透明伝導膜のエッチング速度が遅くなる可能性がある。 The halogen-containing compound may be included at 0.05 to 15% by weight based on the total weight of the entire composition. If the content of the halogen-containing compound is too large, there is a possibility that a phenomenon in which a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film or a multilayer film in which these are laminated is infringed may occur. There is a possibility that the etching rate of the film becomes slow.
本発明のエッチング組成物に含まれる補助酸化剤は透明伝導膜のエッチングを補助する機能をする。前記補助酸化剤は、全体組成物の総重量に対して０．１〜２０重量％で含むことができ、含量が多すぎると銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜をエッチングさせる現象が発生する可能性があり、含量が少ないと透明伝導膜のエッチング速度が遅くなる可能性がある。前記補助酸化剤は、硝酸アンモニウム（ＮＨ４ＮＯ３）、硝酸カリウム（ＫＮＯ３）、硝酸（ＨＮＯ３）、硝酸銅（ＣｕＮＯ３）及び硝酸ナトリウム（ＮａＮＯ３）からなる群から一つ以上選択された化合物を用いることができ、溶液内で硝酸イオン（ＮＯ３ −）に解離されることができる化合物は全て使用できる。 The auxiliary oxidizing agent contained in the etching composition of the present invention functions to assist the etching of the transparent conductive film. The auxiliary oxidant may be included in an amount of 0.1 to 20% by weight with respect to the total weight of the entire composition. If the content is too large, a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a laminate of these may be used. There is a possibility that a phenomenon of etching the formed multilayer film may occur, and if the content is small, the etching rate of the transparent conductive film may be slow. The auxiliary oxidant is one or more compounds selected from the group consisting of ammonium nitrate (NH 4 NO 3 ), potassium nitrate (KNO 3 ), nitric acid (HNO 3 ), copper nitrate (CuNO 3 ), and sodium nitrate (NaNO 3 ). Any compound that can be dissociated into nitrate ions (NO 3 − ) in solution can be used.
本発明のエッチング組成物に含まれるエッチング調節剤としては、硫酸及び硫酸塩化合物を用いることができ、より具体的には、硫酸（Ｈ２ＳＯ４）、硫酸アンモニウム（（ＮＨ４）２ＳＯ４）、硫酸ナトリウム（Ｎａ２ＳＯ４）、硫酸カリウム（Ｋ２ＳＯ４）、重硫酸アンモニウム（ＮＨ４ＳＯ４Ｈ）、重硫酸ナトリウム（ＮａＳＯ４Ｈ）、重硫酸カリウム（ＫＳＯ４Ｈ）、過硫酸アンモニウム（（ＮＨ４）２Ｓ２Ｏ８）、過硫酸ナトリウム（Ｎａ２Ｓ２Ｏ８）及び過硫酸カリウム（Ｋ２Ｓ２Ｏ８）からなる群から一つ以上選択された化合物を用いることができ、溶液内で硫酸イオン（ＳＯ４ −）に解離されることができる化合物は全て使用できる。 As an etching regulator contained in the etching composition of the present invention, sulfuric acid and a sulfate compound can be used, and more specifically, sulfuric acid (H 2 SO 4 ), ammonium sulfate ((NH 4 ) 2 SO 4 ). , Sodium sulfate (Na 2 SO 4 ), potassium sulfate (K 2 SO 4 ), ammonium bisulfate (NH 4 SO 4 H), sodium bisulfate (NaSO 4 H), potassium bisulfate (KSO 4 H), ammonium persulfate ( One or more compounds selected from the group consisting of (NH 4 ) 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), and potassium persulfate (K 2 S 2 O 8 ) can be used. Any compound that can be dissociated into sulfate ions (SO 4 − ) in the solution can be used.
前記エッチング調節剤は、全体組成物の総重量に対して０．０５〜１５重量％で添加され、その含量が多すぎるとエッチング速度が速くなり、また銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害する現象が発生する可能性があり、エッチング調節剤を含まないかまたはその含量が少ないと、透明伝導膜のエッチング速度が遅くなるという欠点がある。 The etching regulator is added in an amount of 0.05 to 15% by weight based on the total weight of the entire composition. If the content is too large, the etching rate is increased, and a copper film, a copper alloy film, a molybdenum film, and molybdenum. There is a possibility that a phenomenon of infringing the alloy film or the multilayer film in which these films are laminated may occur. If the etching control agent is not included or its content is low, the etching rate of the transparent conductive film is slow.
本発明のエッチング組成物に含まれる残渣抑制剤は、エッチング組成物のぬれ性を向上させて透明伝導膜のエッチングを円滑にし、残渣を抑制させる役割をする。残渣抑制剤は、全体組成物の総重量に対して０．１〜１５重量％で添加され、前記範囲で残渣を抑制させ、エッチング組成物を使用した後にも残遺物が発生せず、経時変化が起らない効果がある。残渣抑制剤は水溶性の酢酸基を有する全ての化合物などが使用でき、具体的には下記化学式２の構造を有することができる。 The residue inhibitor contained in the etching composition of the present invention plays a role of improving the wettability of the etching composition, smoothing the etching of the transparent conductive film, and suppressing the residue. Residue inhibitor is added in an amount of 0.1 to 15% by weight with respect to the total weight of the entire composition. Residues are suppressed within the above range, and no residue is generated even after using the etching composition. There is an effect that does not occur. As the residue inhibitor, any compound having a water-soluble acetic acid group can be used, and specifically, it can have a structure of the following chemical formula 2.
［化２］
Ｂ（ＣＨ３ＣＯＯ）ｎ
（前記式で、Ｂは水素イオン（Ｈ＋）、アンモニウムイオン（ＮＨ４＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）、アルミニウムイオン（Ａｌ３＋）または酸化数が１〜３価であるアルキル金属イオン、ｎはＢの酸化数、より具体的には１〜３の整数である。）
[Chemical formula 2]
B (CH 3 COO) n
(In the above formula, B is a hydrogen ion (H + ), an ammonium ion (NH 4 + ), an iron ion (Fe 2+ , Fe 3+ ), an aluminum ion (Al 3+ ), or an alkyl metal ion having an oxidation number of 1 to 3. , N is the oxidation number of B, more specifically an integer of 1 to 3.)
前記残渣抑制剤はより具体的に、酢酸（ａｃｅｔｉｃ ａｃｉｄ）、酢酸カリウム（ｐｏｔａｓｓｉｕｍ ａｃｅｔａｔｅ）、酢酸アンモニウム（ａｍｍｏｎｉｕｍ ａｃｅｔａｔｅ）、酢酸ナトリウム（ｓｏｄｉｕｍ ａｃｅｔａｔｅ）、酢酸マグネシウム（ｍａｇｎｅｓｉｕｍ ａｃｅｔａｔｅ）、酢酸マンガン（ｍａｎｇａｎｅｓｅ ａｃｅｔａｔｅ）及び酢酸亜鉛（ｚｉｎｃ ａｃｅｔａｔｅ）からなる群から一つ以上選択された化合物を用いることができる More specifically, the residue inhibitor includes acetic acid, potassium acetate, ammonium acetate, sodium acetate, magnesium acetate, and manganese acetate. And one or more compounds selected from the group consisting of zinc acetate
本発明のエッチング組成物に含まれる腐食抑制剤は、銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害する現象を抑制させる機能をする。前記腐食抑制剤は、全体組成物の総重量に対して０．３〜１０重量％で含まれ、含量が多すぎると透明伝導膜のエッチング速度が遅くなる現象が発生し、含量が少ないと銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜を侵害する現象が発生する可能性がある。 The corrosion inhibitor contained in the etching composition of the present invention functions to suppress a phenomenon of infringing on a copper film, a copper alloy film, a molybdenum film, a molybdenum alloy film, or a multilayer film in which these are laminated. The corrosion inhibitor is included in an amount of 0.3 to 10% by weight with respect to the total weight of the entire composition. If the content is too large, a phenomenon that the etching rate of the transparent conductive film is slowed occurs. There is a possibility that a phenomenon in which a film, a copper alloy film, a molybdenum film, a molybdenum alloy film or a multilayer film in which these films are laminated is infringed may occur.
前記腐食抑制剤は特に制限されないが、ベンゾトリアゾール（Ｂｅｎｚｏｔｒｉａｚｏｌｅ）、アミノテトラゾール（ａｍｉｎｏｔｅｔｒａｚｏｌｅ）、５−アミノ−１−フェニルテトラゾール（５−ａｍｉｎｏ−１−ｐｈｅｎｙｌｔｅｔｒａｚｏｌｅ）、５−アミノ−１−（１−ナフチル）テトラゾール（５−ａｍｉｎｏ−１−（１−ｎａｐｈｔｈｙｌ）ｔｅｔｒａｚｏｌｅ、１−メチル−５−アミノテトラゾール（１−ｍｅｔｈｙｌ−５−ａｍｉｎｏｔｅｔｒａｚｏｌｅ）、１，５−ジアミノテトラゾール（１，５−ｄｉａｍｉｎｏｔｅｔｒａｚｏｌｅ）、イミダゾール（ｉｍｉｄａｚｏｌｅ）、インドール（ｉｎｄｏｌｅ）、プリン（ｐｕｒｉｎｅ）、ピラゾール（ｐｙｒａｚｏｌｅ）、ピリジン（ｐｙｒｉｄｉｎｅ）、ピリミジン（ｐｙｒｉｍｉｄｉｎｅ）、ピロール（ｐｙｒｒｏｌｅ）、ピロリジン（ｐｙｒｒｏｌｉｄｉｎｅ）、ピロリン（ｐｙｒｒｏｌｉｎｅ）、２級アミン（ｓｅｃｏｎｄａｒｙ ａｍｉｎｅ）系化合物及びアミノ酸（ａｍｉｎｏ ａｃｉｄ）系化合物からなる群から一つ以上選択されることができる。 The corrosion inhibitor is not particularly limited, but is benzotriazole, aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1- (1-naphthyl). ) Tetrazole (5-amino-1- (1-naphthyl) tetrazole, 1-methyl-5-aminotetrazole (1,5-diaminotetrazole), 1,5-diaminotetrazole, imidazole ( imidazole, indole, purine, pyrazole, pyridine, pyrimidine ( yrimidine), pyrrole (pyrrole), pyrrolidine (pyrrolidine), pyrroline (pyrroline), can be selected secondary amine (secondary- Amine) compounds and amino acids (amino acid) one or more from the group consisting of compounds.
本発明のエッチング組成物に含まれる経時変化抑制剤は、エッチング組成物の蒸発量を減少させてエッチング組成物の成分量の変動を減少させ、それによるヒューム（ｆｕｍｅ）発生量を減少させる。前記経時変化抑制剤は、全体組成物の総重量に対して０〜５０重量％で添加されることができる。前記経時変化抑制剤の含量が多すぎると透明伝導膜のエッチング速度が遅くなる現象が発生し、エチレングリコール、テトラエチレングリコール、プロピレングリコール、ブチレングリコール、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレングリコールからなる群から一つ以上選択されて用いることができ、特にこれに制限されるものではない。 The aging inhibitor contained in the etching composition of the present invention reduces the amount of evaporation of the etching composition to reduce fluctuations in the component amount of the etching composition, thereby reducing the amount of generation of fume. The aging inhibitor may be added at 0 to 50% by weight based on the total weight of the entire composition. When the content of the aging inhibitor is too large, a phenomenon that the etching rate of the transparent conductive film is slow occurs, and it is composed of ethylene glycol, tetraethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. One or more selected from the group can be used, and is not particularly limited thereto.
本発明による透明伝導膜エッチング組成物は平板ディスプレイ用透明電極を形成するために用いることができる。この際、用いられる透明電極膜としては、インジウム酸化スズ膜、インジウム酸化亜鉛膜、酸化亜鉛膜などを用いることができ、前記インジウム酸化スズ膜、インジウム酸化亜鉛膜、酸化亜鉛膜の使用は、保護膜上にインジウム酸化スズ膜、インジウム酸化亜鉛膜、酸化亜鉛膜を形成し、フォトレジストをマスクとして塗布した後、インジウム酸化スズ膜、インジウム酸化亜鉛膜、酸化亜鉛膜をエッチングさせることができる。 The transparent conductive film etching composition according to the present invention can be used to form a transparent electrode for a flat panel display. At this time, as the transparent electrode film used, an indium tin oxide film, an indium zinc oxide film, a zinc oxide film, etc. can be used, and the use of the indium tin oxide film, the indium zinc oxide film, the zinc oxide film is a protection After an indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are formed on the film and applied using a photoresist as a mask, the indium tin oxide film, the indium zinc oxide film, and the zinc oxide film can be etched.
本発明の透明伝導膜エッチング組成物は腐食抑制剤と経時変化抑制剤を含む水溶液であり、従来の透明伝導膜エッチング組成物で発生する側面エッチング現象、経時変化現象、エッチング時の残渣発生現象、銅または銅合金とモリブデンまたはモリブデン合金の金属膜の侵害現象などの欠点を完全に解消することができる。特に、本発明は従来の透明伝導膜エッチング組成物の主要問題点であるエッチング時の残渣発生現象と銅または銅合金の薄膜を侵害する現象を解消するため、透明伝導膜の選択的パターンエッチングが可能である。 The transparent conductive film etching composition of the present invention is an aqueous solution containing a corrosion inhibitor and a aging inhibitor, a side etching phenomenon that occurs in a conventional transparent conductive film etching composition, a aging phenomenon, a residue generation phenomenon during etching, It is possible to completely eliminate the drawbacks such as the invasion phenomenon of copper or copper alloy and molybdenum or molybdenum alloy metal film. In particular, the present invention eliminates the phenomenon of residue generation during etching, which is a major problem of the conventional transparent conductive film etching composition, and the phenomenon of invading the thin film of copper or copper alloy. Is possible.
また、本発明による透明伝導膜エッチング組成物は適切なエッチング速度及び適切な傾斜角を提供することができ、蒸発量を顕著に減少させてエッチング組成物の成分量の変動を減少させ、それによるヒューム（ｆｕｍｅ）発生量を減らすことにより、大気環境汚染を防止することができる長所を有している。 In addition, the transparent conductive film etching composition according to the present invention can provide an appropriate etching rate and an appropriate inclination angle, thereby significantly reducing the evaporation amount and reducing the variation of the component amount of the etching composition. It has an advantage that air environment pollution can be prevented by reducing the generation amount of fumes.
本発明による透明伝導膜エッチング組成物は、微細パターンに形成された透明伝導膜のパターンエッチングのために適用する場合、従来の透明伝導膜エッチング組成物と異なって、薄膜トランジスタの電極材料として主に用いられる銅膜、銅合金膜、モリブデン膜、モリブデン合金膜またはこれらが積層された多重膜に対する侵害現象が殆ど発生しないため、コスト低減及び工程収率を向上させることができる長所がある。 Unlike the conventional transparent conductive film etching composition, the transparent conductive film etching composition according to the present invention is mainly used as an electrode material of a thin film transistor when applied for pattern etching of a transparent conductive film formed in a fine pattern. Since the copper film, the copper alloy film, the molybdenum film, the molybdenum alloy film, or the multi-layer film in which these films are laminated, almost no infringement phenomenon occurs, there is an advantage that the cost can be reduced and the process yield can be improved.
以下、実施例を用いて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
しかし、本発明の実施例は様々な形態に変形されることができ、本発明の範囲が以下で後述する実施例によって限定されて解釈されてはならない。 However, the embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited by the embodiments described below.
＜実施例１＞
エッチング溶液の製造
５重量％のＮＨ４Ｃｌ、１３重量％のＨＮＯ３、５重量％のＫ２ＳＯ４、３重量％の酢酸アンモニウム、２重量％のアミノテトラゾール、１５重量％のエチレングリコール及び全体組成物の総重量が１００重量％になるようにする水で構成されるエッチング組成物を製造した。
<Example 1>
NH 4 Cl, 13 wt% of HNO 3, 5 wt% of K 2 SO 4, 3% by weight of ammonium acetate Preparation 5 wt% of the etching solution, 2 wt% of aminotetrazole, 15% by weight of ethylene glycol and the whole An etching composition composed of water was prepared so that the total weight of the composition was 100% by weight.
本発明で用いられたエッチング膜の試料は、ガラス基板（１００ｍｍＸ１００ｍｍ）にインジウム酸化スズ膜、銅膜／モリブデンチタン合金膜、インジウム酸化スズ膜／銅膜／モリブデンチタン合金膜を蒸着したものであり、蒸着された膜の厚さは以下表１の通りである。 The etching film sample used in the present invention is a glass substrate (100 mm × 100 mm) in which an indium tin oxide film, a copper film / molybdenum titanium alloy film, an indium tin oxide film / copper film / molybdenum titanium alloy film are deposited, The thickness of the deposited film is as shown in Table 1 below.
表１ Table 1
インジウム酸化スズ膜のエッチング
前記インジウム酸化スズ膜の試料に写真現象工程を行ってエッチング試料を準備した後、本実施例により製造したエッチング組成物を用いてスプレー方式でエッチング工程を行った。エッチング工程時のエッチング溶液の温度は４０℃に維持し、夫々の総エッチング時間はエッチング終了時間から７０％超過された時間であり、エッチング後の結果を表２、図１、図２に示した。
Etching of indium tin oxide film A sample of the indium tin oxide film is subjected to a photographic phenomenon process to prepare an etching sample, and then an etching process is performed by a spray method using the etching composition manufactured according to this example. It was. The temperature of the etching solution during the etching process was maintained at 40 ° C., and the total etching time was 70% exceeding the etching end time. The results after etching are shown in Table 2, FIG. 1 and FIG. .
銅膜／モリブデンチタン合金膜のエッチング
銅または銅合金の侵害程度を評価するために、ガラス基板に蒸着された積層構造にパターニングされた前記表１の銅膜／モリブデンチタン合金膜を、前記と同一のエッチング組成物５００ｍｌに温度を４０℃前後に維持しながら４８時間浸漬（ｄｉｐｐｉｎｇ）した後、溶液を採取してＩＣＰ−ＭＳ（Ｉｎｄｕｃｔｉｖｅｌｙ ｃｏｕｐｌｅｄ ｐｌａｓｍａ ｍａｓｓ ｓｐｅｃｔｒｏｓｃｏｐｙ）で溶出した銅イオン濃度を測定した。銅または銅合金の侵害がもっとも少ないシュウ酸（５％）水溶液を基準にするために前記と同一の方法で実施し、その結果は下記表２に示した。
Etching of copper film / molybdenum titanium alloy film In order to evaluate the degree of invasion of copper or copper alloy, the copper film / molybdenum titanium alloy film of Table 1 patterned into a laminated structure deposited on a glass substrate was used. Then, after dipping in 500 ml of the same etching composition as described above for 48 hours while maintaining the temperature at around 40 ° C., the solution was collected and the concentration of copper ions eluted with ICP-MS (Inductively coupled plasma mass spectroscopy) was measured. It was measured. In order to use an aqueous solution of oxalic acid (5%) with the least infringement of copper or copper alloy, the same method as described above was used, and the results are shown in Table 2 below.
図１、図２及び表２に示したように、本発明による透明伝導膜エッチング組成物はエッチング速度が早く、残渣もなく、傾斜角が４０°前後の良好なプロフィール結果を示した。 As shown in FIG. 1, FIG. 2, and Table 2, the transparent conductive film etching composition according to the present invention showed a good profile result with a high etching rate, no residue, and an inclination angle of around 40 °.
多層膜試料であるインジウム酸化スズ膜／銅膜／モリブデンチタン合金膜のエッチング
前記表１のように準備した試料であるインジウム酸化スズ膜／銅膜／モリブデンチタン合金膜に、金属膜である銅膜／モリブデンチタン合金膜をエッチングしてパターンを形成した後、実施例１のエッチング液でエッチングした。その結果を図３に示し、銅膜／モリブデンチタン合金膜はエッチングされないことを確認した。
Etching of indium tin oxide film / copper film / molybdenum titanium alloy film as multilayer film sample Indium tin oxide film / copper film / molybdenum titanium alloy film as a sample prepared as shown in Table 1 was added to metal film. After the copper film / molybdenum titanium alloy film was etched to form a pattern, it was etched with the etching solution of Example 1. The results are shown in FIG. 3, and it was confirmed that the copper film / molybdenum titanium alloy film was not etched.
＜実施例２〜１２＞
実施例１と同様に実施するが、下記表２のように含ハロゲン化合物、補助酸化剤、エッチング調節剤、残渣抑制剤、腐食抑制剤及び経時変化抑制剤の組成比を変化させるか、または、含ハロゲン化合物、補助酸化剤、エッチング調節剤、残渣抑制剤、腐食抑制剤、経時変化抑制剤の種類を変化させ、全体組成物の総重量が１００重量％になるように水を添加した後、前記実施例１と同様にエッチング工程を行って、その結果を下記表２に示した。
<Examples 2 to 12>
Although it is carried out in the same manner as in Example 1, the composition ratio of the halogen-containing compound, the auxiliary oxidant, the etching regulator, the residue inhibitor, the corrosion inhibitor and the aging inhibitor is changed as shown in Table 2 below, or After changing the type of halogen-containing compound, auxiliary oxidant, etching regulator, residue inhibitor, corrosion inhibitor, aging inhibitor, and adding water so that the total weight of the entire composition becomes 100 wt%, The etching process was performed in the same manner as in Example 1, and the results are shown in Table 2 below.
下記表２は、実施例１〜１２における組成物に対する透明伝導膜（インジウム酸化スズ膜）のエッチング速度及び傾斜角の結果を示したものである。そして、銅または銅合金の侵害程度を評価するために、ガラス基板に蒸着された積層構造にパターニングされた前記表１の銅膜／モリブデンチタン合金膜を前記と同一のエッチング液でエッチングし、銅イオン濃度を測定して下記表２に示した。 Table 2 below shows the results of the etching rate and the inclination angle of the transparent conductive film (indium tin oxide film) for the compositions in Examples 1 to 12. Then, in order to evaluate the infringement degree of copper or copper alloy, the copper film / molybdenum titanium alloy film patterned in the laminated structure deposited on the glass substrate is etched with the same etching solution as described above. The ion concentration was measured and shown in Table 2 below.
夫々の総エッチング時間はエッチング終了時間から７０％超過された時間である。表２に示したように、各成分の含量がここに記載された組成範囲に該当する本発明による透明伝導膜エッチング組成物は、エッチング速度が早く、残渣もなく、傾斜角が４０°以下の良好なプロフィール結果を示し、銅に対する侵害評価結果もシュウ酸適用結果に対比して良好な特性を示した。 Each total etching time is a time exceeding 70% from the etching end time. As shown in Table 2, the transparent conductive film etching composition according to the present invention in which the content of each component falls within the composition range described herein has a high etching rate, no residue, and an inclination angle of 40 ° or less. The profile results were good, and the results of the infringement evaluation for copper also showed good properties compared to the results of oxalic acid application.
表２ Table 2
＜比較例１〜５＞
実施例１〜１２と同様に進行するが、下記表３のように含ハロゲン化合物、補助酸化剤、エッチング調節剤、残渣抑制剤、腐食抑制剤及び経時変化抑制剤の組成比を本発明の範囲を外れて変化させ、全体組成物の総重量が１００重量％になるように水を添加した後、実施例１〜１２のようにエッチング工程を行った。
<Comparative Examples 1-5>
Although it progresses similarly to Examples 1-12, the composition ratio of a halogen-containing compound, an auxiliary oxidizing agent, an etching regulator, a residue inhibitor, a corrosion inhibitor, and a aging inhibitor as shown in Table 3 below is within the scope of the present invention. After removing water and adding water so that the total weight of the entire composition was 100% by weight, an etching process was performed as in Examples 1-12.
下記表３は比較例１〜５による透明伝導膜（インジウム酸化スズ膜）のエッチング速度及び傾斜角の結果を示したものである。そして、銅または銅合金の侵害程度を評価するために、ガラス基板に蒸着された積層構造にパターニングされた前記表１の銅膜／モリブデンチタン合金膜を前記と同一のエッチング液でエッチングし、銅イオン濃度を測定して下記表２に示した。下記表３の結果から分かるように、比較例１〜３の場合、エッチング速度が速すぎて銅に対する選択性が低下し、比較例４の場合、エッチング速度が遅すぎて傾斜角が大きくなる問題点が発生した。 Table 3 below shows the results of the etching rate and the inclination angle of the transparent conductive films (indium tin oxide films) according to Comparative Examples 1 to 5. Then, in order to evaluate the infringement degree of copper or copper alloy, the copper film / molybdenum titanium alloy film patterned in the laminated structure deposited on the glass substrate is etched with the same etching solution as described above. The ion concentration was measured and shown in Table 2 below. As can be seen from the results in Table 3 below, in the case of Comparative Examples 1 to 3, the etching rate is too fast and the selectivity to copper is lowered, and in the case of Comparative Example 4, the etching rate is too slow and the tilt angle becomes large. A point occurred.
表３ Table 3
Claims (10)
［化１］
ＡＸｍ
（前記式で、Ａは水素イオン（Ｈ＋）、アンモニウムイオン（ＮＨ４＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）、アルミニウムイオン（Ａｌ３＋）または酸化数が１〜３価であるアルカリ金属イオン、Ｘはハロゲン元素、ｍはＡの酸化数である。） The transparent conductive film etching composition according to claim 1, wherein the halogen-containing compound has a structure represented by the following chemical formula 1.
[Chemical 1]
AX m
(In the above formula, A is hydrogen ion (H + ), ammonium ion (NH 4 + ), iron ion (Fe 2+ , Fe 3+ ), aluminum ion (Al 3+ ), or an alkali metal ion having an oxidation number of 1 to 3 , X is a halogen element, and m is the oxidation number of A.)
［化２］
Ｂ（ＣＨ３ＣＯＯ）ｎ
（前記式で、Ｂは水素イオン（Ｈ＋）、アンモニウムイオン（ＮＨ４＋）、鉄イオン（Ｆｅ２＋、Ｆｅ３＋）、アルミニウムイオン（Ａｌ３＋）または酸化数が１〜３価であるアルカリ金属イオン、ｎはＢの酸化数である。） The transparent conductive film etching composition according to claim 1, wherein the residue inhibitor has a structure represented by the following chemical formula 2.
[Chemical formula 2]
B (CH 3 COO) n
(In the above formula, B is hydrogen ion (H + ), ammonium ion (NH 4 + ), iron ion (Fe 2+ , Fe 3+ ), aluminum ion (Al 3+ ), or an alkali metal ion having an oxidation number of 1 to 3 , N is the oxidation number of B.)
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| KR1020080112176A KR101531688B1 (en) | 2008-11-12 | 2008-11-12 | Etchant for transparent conductive ITO films |
| PCT/KR2009/006657 WO2010056051A2 (en) | 2008-11-12 | 2009-11-12 | Etching solution for a transparent conductive film |
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| WO2010056051A3 (en) | 2010-08-19 |
| TW201035290A (en) | 2010-10-01 |
| CN102177219A (en) | 2011-09-07 |
| WO2010056051A8 (en) | 2011-04-21 |
| KR101531688B1 (en) | 2015-06-26 |
| CN102177219B (en) | 2014-06-11 |
| TWI419957B (en) | 2013-12-21 |
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| WO2010056051A2 (en) | 2010-05-20 |
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