TW201311934A - Method for manufacturing display device and an etching solution composition for metal layer containing copper/metal oxide layer - Google Patents
Method for manufacturing display device and an etching solution composition for metal layer containing copper/metal oxide layer Download PDFInfo
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- TW201311934A TW201311934A TW101131588A TW101131588A TW201311934A TW 201311934 A TW201311934 A TW 201311934A TW 101131588 A TW101131588 A TW 101131588A TW 101131588 A TW101131588 A TW 101131588A TW 201311934 A TW201311934 A TW 201311934A
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- Prior art keywords
- acid
- layer
- copper
- group
- composition
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 100
- 239000002184 metal Substances 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000005530 etching Methods 0.000 title claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010949 copper Substances 0.000 title claims abstract description 92
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 52
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910000431 copper oxide Inorganic materials 0.000 title 1
- 229910052802 copper Inorganic materials 0.000 claims abstract description 91
- 239000004065 semiconductor Substances 0.000 claims abstract description 46
- -1 and furnace Chemical compound 0.000 claims description 48
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 26
- 229910052712 strontium Inorganic materials 0.000 claims description 21
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 21
- 229910052762 osmium Inorganic materials 0.000 claims description 18
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 18
- 235000002639 sodium chloride Nutrition 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 150000007524 organic acids Chemical class 0.000 claims description 14
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 10
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 10
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims description 10
- 150000004767 nitrides Chemical class 0.000 claims description 10
- 229910052705 radium Inorganic materials 0.000 claims description 10
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000010755 mineral Nutrition 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-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 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 3
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 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 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- WSLQHGMJTGELSF-UHFFFAOYSA-L dipotassium;difluoride Chemical compound [F-].[F-].[K+].[K+] WSLQHGMJTGELSF-UHFFFAOYSA-L 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JWQMZGJKIAJVFE-UHFFFAOYSA-L azanium copper phosphate Chemical compound [NH4+].[Cu+2].[O-]P([O-])([O-])=O JWQMZGJKIAJVFE-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 8
- 238000000059 patterning Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 36
- 239000010408 film Substances 0.000 description 23
- 230000008901 benefit Effects 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- VSQAMHLYSYQSBM-UHFFFAOYSA-N [F].OB(O)O Chemical compound [F].OB(O)O VSQAMHLYSYQSBM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 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
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- KZRAXTQTJYXBNW-UHFFFAOYSA-N zinc cerium(3+) indium(3+) oxygen(2-) Chemical compound [O-2].[Ce+3].[O-2].[Zn+2].[O-2].[In+3] KZRAXTQTJYXBNW-UHFFFAOYSA-N 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
- C23F1/02—Local etching
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Weting (AREA)
- Thin Film Transistor (AREA)
Abstract
Description
相關申請案
此申請案主張於2011年9月9日在韓國智慧財產局申請的韓國專利申請案號10-2011-0091917的優先權，其全部揭露內容併入於本文中以作為參考。
本發明有關一種使用用於同時蝕刻以銅為基礎的金屬層（「銅金屬層」）以及氧化物半導體層的蝕刻溶液組成物來製造顯示裝置的方法，該氧化物半導體層由金屬氧化物層組成，以及一種用於該顯示裝置的銅金屬層/金屬氧化物層的蝕刻溶液組成物。
RELATED APPLICATIONS This application claims the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the disclosure.
The present invention relates to a method of manufacturing a display device using a composition of an etching solution for simultaneously etching a copper-based metal layer ("copper metal layer") and an oxide semiconductor layer, the oxide semiconductor layer being composed of a metal oxide layer Composition, and an etching solution composition for a copper metal layer/metal oxide layer of the display device.
驅動任何一種半導體裝置以及平面顯示裝置的代表性電子電路是薄膜電晶體（TFT）。藉由在基板上形成作為用於閘極以及資料的線路材料的金屬薄膜、在該金屬薄膜上的選擇區域上製備光阻、以及以該光阻作為遮罩來蝕刻該金屬薄膜，來典型地提供製造TFT的傳統製程。
雖然具有想要圖案的單一遮罩例行地被用以蝕刻一層金屬層，為了最小化相對高價的遮罩之使用，同時簡化該製程，近來常常只使用一個遮罩來蝕刻至少二或更多的金屬層。然而，即使使用單一遮罩，如果將該遮罩塗佈至具有不同特性的將被蝕刻的金屬層，這些層受到對於該金屬層的不同蝕刻模式，因此在減少製程次數上造成實質上的困難。
用於閘極以及資料的線路材料典型為只含銅或含有其銅合金的金屬薄膜以及對其具有極佳介面吸附的額外的金屬氧化物層，其中銅具有適合的電傳導性以及低電阻。在此方面，由於兩層金屬層不同的性質，這些金屬層難以藉由使用單一蝕刻製程而充分地蝕刻。
A representative electronic circuit that drives any of the semiconductor devices and the planar display device is a thin film transistor (TFT). Typically, the metal film is formed on a substrate by forming a metal film as a gate material for the gate and the material, preparing a photoresist on a selected region on the metal film, and etching the metal film with the photoresist as a mask. Provides a traditional process for manufacturing TFTs.
Although a single mask with the desired pattern is routinely used to etch a metal layer, in order to minimize the use of relatively expensive masks while simplifying the process, it has recently been common to use only one mask to etch at least two or more. Metal layer. However, even if a single mask is used, if the mask is applied to a metal layer to be etched having different characteristics, the layers are subjected to different etching modes for the metal layer, thereby causing substantial difficulty in reducing the number of processes. .
The circuit material for the gate and the material is typically a metal film containing only copper or a copper alloy thereof and an additional metal oxide layer having excellent interface adsorption, wherein copper has suitable electrical conductivity and low electrical resistance. In this regard, due to the different properties of the two metal layers, these metal layers are difficult to adequately etch by using a single etching process.
因此，本發明的目的是提供一種製造顯示裝置的方法，該方法確保製程中提升的生產力以及可靠性。
本發明的另一個目的是提供一種使用於製造如上述顯示裝置的方法的用於銅金屬層/金屬氧化物層的蝕刻溶液組成物。
為了實現上述目的，本發明提供了下述。
（1）一種製造一顯示裝置的方法，包含：在一基板上形成包括一閘極線以及一閘極的一閘極圖案；在具有該閘極圖案形成於其上的該基板上提供一氧化物半導體層，其中該半導體層包括一金屬氧化物層；在該氧化物半導體層上提供一資料金屬層，其中該資料金屬層包括一銅金屬層；使用一蝕刻溶液組成物，藉由同時且完全地蝕刻該資料金屬層以及該氧化物半導體層來將該資料金屬層以及該氧化物半導體層形成圖案，以形成包括一半導體圖案、一資料線、一源極以及一漏極的一源極圖案；以及提供電連接至該漏極的一畫素電極，其中該蝕刻溶液組成物包含：0.5至20重量％的過硫酸鹽、0.01至2重量％的一氟化合物、1至10重量％的無機酸、0.5至5重量％的環胺化合物、0.001至5重量％的氯化合物、0.1至10重量％的有機酸、其鹽類或混合物以及形成該組成物之剩餘成分的水。
（2）根據上述第（1）項所述的組成物，該銅金屬層是一單一銅層，該單一銅層包含選自由銅、其氮化物以及氧化物所組成的群組至少其中之一；一銅合金層，該銅合金層包含選自由鋁、鎂、鈣、鈦、銀、鉻、錳、鐵、鋯、鈮、鉬、鈀、鉿、鉭以及鎢所組成的群組至少其中之一以及選自由銅、其氮化物以及氧化物所組成的群組至少其中之一；或一其薄板。
（3）根據上述第（2）項所述的組成物，該銅合金層是包含銅以及錳的一薄膜。
（4）根據上述第（1）項所述的組成物，該金屬氧化物層包含選自由鋅、錫、鎘、鎵、鋁、鈹、鎂、鈣、鍶、鋇、鐳、鉈、鈧、銦、釔、鑭、錒、鈦、鋯、鉿、鉭以及鑪所組成的群組中的至少其中兩者。
（5）根據上述第（4）項所述的組成物，該金屬氧化物層是一三種成分的薄膜，該三種成分的薄膜包含選自由錫、鎘、鎵、鋁、鈹、鎂、鈣、鍶、鋇、鐳、鉈、鈧、釔、鑭、錒、鈦、鋯、鉿、鉭以及鑪所組成的群組至少其中之一，以及銦以及鋅。
（6）根據上述第（1）項所述的組成物，該資料金屬層包含一銅合金層以及在該銅合金層上所提供的一單一銅層。
（7）根據上述第（1）項所述的組成物，該資料金屬層包含一銅合金層、在該銅合金層上所提供的一單一銅層以及在該單一銅層上所提供的另一銅合金層。
（8）一種用於銅金屬層/金屬氧化物層的蝕刻溶液組成物，包含：0.5至20重量％的過硫酸鹽；0.01至2重量％的一氟化合物；1至10重量％的無機酸；0.5至5重量％的一環胺化合物；0.001至5重量％的一氯化合物；0.1至10重量％的有機酸、其一鹽類或混合物；以及形成該組成物剩餘成分的水。
（9）根據上述第（8）項所述的組成物，該過硫酸鹽是選自由過硫酸銨、過硫酸鈉以及過硫酸鉀所組成的群組至少其中之一。
（10）根據上述第（8）項所述的組成物，該氟化合物是選自由氟酸、氟化銨、二氟化銨、氟硼酸銨、氟化鉀、二氟化鉀、氟硼酸鉀、氟化鈉、二氟化鈉、氟化鋁、氟硼酸、氟化鋰以及氟化鈣所組成的群組至少其中之一。
（11）根據上述第（8）項所述的組成物，該無機酸是選自由硝酸、硫酸、磷酸以及過氯酸所組成的群組至少其中之一。
（12）根據上述第（8）項所述的組成物，該環胺化合物是選自由5-胺基四氮唑、甲苯基三氮唑、苯並三氮唑、甲基苯並三氮唑、咪唑化合物、吲哚化合物、嘌呤化合物、吡唑化合物、吡啶化合物、嘧啶化合物、吡咯化合物、吡咯啶化合物以及吡咯啉化合物所組成的群組至少其中之一。
（13）根據上述第（8）項所述的組成物，該氯化合物是選自由氯酸、氯化鈉、氯化鉀以及氯化銨所組成的群組至少其中之一。
（14）根據上述第（8）項所述的組成物，該有機酸是選自由醋酸、亞胺基二醋酸、乙二胺四醋酸、丁酸、檸檬酸、異檸檬酸、甲酸、葡萄糖酸、乙醇酸、丙二酸、草酸、戊酸、磺基苯甲酸、琥珀酸、磺基琥珀酸、水楊酸、磺基水楊酸、苯甲酸、乳酸、甘油酸、蘋果酸、酒石酸以及丙烯酸所組成的群組至少其中之一。
（15）根據上述第（8）項所述的組成物，該鹽類是一鉀鹽、鈉鹽或銨鹽。
（16）根據上述第（8）項所述的組成物，更包含0.05至3重量％的一銅鹽。
（17）根據上述第（16）項所述的組成物，該銅鹽是選自由硝酸銅、硫酸銅以及磷酸銨銅組成的群組至少其中之一。
（18）根據上述第（8）項所述的組成物，該銅金屬層是一單一銅層，該單一銅層包含選自由銅、其氮化物以及氧化物所組成的群組至少其中之一；一銅合金層，該銅合金層包含選自由鋁、鎂、鈣、鈦、銀、鉻、錳、鐵、鋯、鈮、鉬、鈀、鉿、鉭以及鎢所組成的群組至少其中之一，以及選自由銅、其氮化物以及氧化物所組成的群組至少其中之一；或一其薄板。
（19）根據上述第（8）項所述的組成物，該金屬氧化物層包含選自由鋅、錫、鎘、鎵、鋁、鈹、鎂、鈣、鍶、鋇、鐳、鉈、鈧、銦、釔、鑭、錒、鈦、鋯、鉿、鉭以及鑪所組成的群組中的至少其中兩者。
（20）根據上述第（8）項所述的組成物，該金屬氧化物層是一三種成分的薄膜，該三種成分的薄膜包含選自由錫、鎘、鎵、鋁、鈹、鎂、鈣、鍶、鋇、鐳、鉈、鈧、釔、鑭、錒、鈦、鋯、鉿、鉭以及鑪所組成的群組至少其中之一，以及銦以及鋅。
根據製造本發明顯示裝置的方法，可將具有銅金屬層的資料金屬層以及具有金屬氧化物層的氧化物半導體層同時形成圖案，因此簡化了製程。此外，可能預防該氧化物半導體層被過切。因此，可改進製程中薄膜電晶體與顯示裝置的生產力以及可靠性。
Accordingly, it is an object of the present invention to provide a method of fabricating a display device that ensures increased productivity and reliability in a process.
Another object of the present invention is to provide an etching solution composition for a copper metal layer/metal oxide layer for use in a method of manufacturing a display device as described above.
In order to achieve the above object, the present invention provides the following.
(1) A method of manufacturing a display device comprising: forming a gate pattern including a gate line and a gate on a substrate; providing oxidation on the substrate having the gate pattern formed thereon a semiconductor layer, wherein the semiconductor layer comprises a metal oxide layer; a data metal layer is provided on the oxide semiconductor layer, wherein the data metal layer comprises a copper metal layer; and an etching solution composition is used, The material metal layer and the oxide semiconductor layer are completely etched to pattern the data metal layer and the oxide semiconductor layer to form a source including a semiconductor pattern, a data line, a source, and a drain. a pattern; and a pixel electrode electrically connected to the drain, wherein the etching solution composition comprises: 0.5 to 20% by weight of persulfate, 0.01 to 2% by weight of a fluorine compound, and 1 to 10% by weight a mineral acid, 0.5 to 5% by weight of a cyclic amine compound, 0.001 to 5% by weight of a chlorine compound, 0.1 to 10% by weight of an organic acid, a salt or mixture thereof, and a composition thereof Water over ingredients.
(2) The composition according to the above item (1), wherein the copper metal layer is a single copper layer, the single copper layer comprising at least one selected from the group consisting of copper, a nitride thereof, and an oxide. a copper alloy layer comprising at least one selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, hafnium, molybdenum, palladium, ruthenium, osmium, and tungsten. And at least one selected from the group consisting of copper, its nitrides, and oxides; or a thin plate thereof.
(3) The composition according to the above (2), wherein the copper alloy layer is a film containing copper and manganese.
(4) The composition according to the above item (1), wherein the metal oxide layer is selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, strontium, magnesium, calcium, strontium, barium, radium, strontium, barium, At least two of the group consisting of indium, lanthanum, cerium, lanthanum, titanium, zirconium, hafnium, tantalum, and furnaces.
(5) The composition according to the above item (4), wherein the metal oxide layer is a film of a three component, the film of the three components comprising selected from the group consisting of tin, cadmium, gallium, aluminum, strontium, magnesium, calcium At least one of the group consisting of ruthenium, osmium, iridium, radium, osmium, iridium, osmium, iridium, osmium, titanium, zirconium, lanthanum, cerium, and furnace, and indium and zinc.
(6) The composition according to the above item (1), wherein the data metal layer comprises a copper alloy layer and a single copper layer provided on the copper alloy layer.
(7) The composition according to the above item (1), wherein the data metal layer comprises a copper alloy layer, a single copper layer provided on the copper alloy layer, and another provided on the single copper layer A copper alloy layer.
(8) An etching solution composition for a copper metal layer/metal oxide layer comprising: 0.5 to 20% by weight of persulfate; 0.01 to 2% by weight of a monofluoro compound; and 1 to 10% by weight of a mineral acid 0.5 to 5% by weight of a monocyclic amine compound; 0.001 to 5% by weight of a monochloro compound; 0.1 to 10% by weight of an organic acid, a salt or mixture thereof; and water forming the remaining components of the composition.
(9) The composition according to the above item (8), wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate, and potassium persulfate.
(10) The composition according to the above item (8), which is selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium difluoride, ammonium fluoroborate, potassium fluoride, potassium difluoride, potassium fluoroborate At least one of the group consisting of sodium fluoride, sodium difluoride, aluminum fluoride, fluoroboric acid, lithium fluoride, and calcium fluoride.
(11) The composition according to the above item (8), wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid.
(12) The composition according to the above item (8), which is selected from the group consisting of 5-aminotetrazolium, tolyltriazole, benzotriazole, and methylbenzotriazole At least one of the group consisting of an imidazole compound, an anthracene compound, an anthracene compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, and a pyrroline compound.
(13) The composition according to the above item (8), wherein the chlorine compound is at least one selected from the group consisting of chloric acid, sodium chloride, potassium chloride, and ammonium chloride.
(14) The composition according to the above item (8), which is selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid , glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid At least one of the groups formed.
(15) The composition according to the above item (8), which is a potassium salt, a sodium salt or an ammonium salt.
(16) The composition according to the above item (8), further comprising 0.05 to 3% by weight of a copper salt.
(17) The composition according to the above item (16), wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate, and ammonium ammonium phosphate.
(18) The composition according to the above item (8), wherein the copper metal layer is a single copper layer, the single copper layer comprising at least one selected from the group consisting of copper, a nitride thereof, and an oxide. a copper alloy layer comprising at least one selected from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, hafnium, molybdenum, palladium, ruthenium, osmium, and tungsten. And at least one selected from the group consisting of copper, a nitride thereof, and an oxide; or a thin plate thereof.
(19) The composition according to the above item (8), wherein the metal oxide layer is selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, strontium, magnesium, calcium, strontium, barium, radium, strontium, barium, At least two of the group consisting of indium, lanthanum, cerium, lanthanum, titanium, zirconium, hafnium, tantalum, and furnaces.
(20) The composition according to the above item (8), wherein the metal oxide layer is a film of a three component, the film of the three components comprising selected from the group consisting of tin, cadmium, gallium, aluminum, strontium, magnesium, calcium At least one of the group consisting of ruthenium, osmium, iridium, radium, osmium, iridium, osmium, iridium, osmium, titanium, zirconium, lanthanum, cerium, and furnace, and indium and zinc.
According to the method of manufacturing the display device of the present invention, the data metal layer having the copper metal layer and the oxide semiconductor layer having the metal oxide layer can be simultaneously patterned, thereby simplifying the process. Further, it is possible to prevent the oxide semiconductor layer from being overcut. Therefore, the productivity and reliability of the thin film transistor and the display device in the process can be improved.
本發明提供了一種製造顯示裝置的方法，該顯示裝置具有銅金屬層/金屬氧化物層，以及此外，一種用於銅金屬層/金屬氧化物層的蝕刻溶液組成物，該蝕刻溶液組成物被應用至如上所述的製造顯示裝置的方法。
此後，將更詳細地描述本發明。
蝕刻溶液組成物
本發明的蝕刻溶液組成物是用於同時蝕刻銅金屬層以及金屬氧化物層。
本發明的蝕刻溶液組成物可包含：過硫酸鹽；氟化合物；無機酸；環胺化合物；氯化合物；有機酸、其鹽類或混合物；以及水。
更特別的是，該具進步性的組成物可包含0.5至20重量％的過硫酸鹽；0.01至2重量％的氟化合物；1至10重量％的無機酸；0.5至5重量％的環胺化合物；0.001至5重量％的氯化合物；0.1至10重量％的有機酸、其鹽類或混合物；以及該組成物總重量剩餘部分的水。
過硫酸鹽是用以蝕刻銅金屬層的主成分。其特定的範例可包括過硫酸銨（(NH4)2S2O8）、過硫酸鈉（Na2S2O8）、過硫酸鉀（K2S2O8）或諸如此類，其可被單獨或與其二或更多個組合而使用。
過硫酸鹽可包括於總量100重量％的蝕刻溶液組成物中的0.5至20重量％的量。如果過硫酸鹽的含量少於5重量％，銅金屬層有時不被蝕刻，或可具有低蝕刻率。當該含量多於20重量％時，整體的蝕刻被非常快速地進行（也就是，蝕刻率較高），其隨之造成控制蝕刻過程的困難。
氟化合物是一種可能被蝕刻溶液組成物中的氟離子或多原子氟離子解離的化合物，其是用以移除在蝕刻期間產生的殘餘物，同時增加銅金屬層的蝕刻率的主成分。氟化合物的種類不特別受限制，但可包括，例如：氟酸（HF）、氟化銨（NH4F）、二氟化銨（NH4HF2）、氟硼酸銨（NH4BF4）、氟化鉀（KF）、二氟化鉀（KHF2）、氟硼酸鉀（KBF4）、氟化鈉（NaF）、二氟化鈉（NaHF2）、氟化鋁（AlF3）、氟硼酸（HBF4）、氟化鋰（LiF）、氟化鈣（CaF2）或諸如此類，其可被單獨或作為其二或更多個的混合物而使用。
氟化合物可包括於總量100重量％的蝕刻溶液組成物中的0.01至2重量％的量。如果氟化合物的含量少於0.01重量％，金屬氧化物層具有降低的蝕刻率，以造成殘餘物的產生。當該含量超過2重量％時，該金屬氧化物層被過度蝕刻，以造成該氧化物半導體層從基板「剝離」。
無機酸是一種氧化作用輔助物，以蝕刻銅金屬層以及金屬氧化物層。其特定的範例可包括硝酸、硫酸、磷酸、過氯酸等等，其被單獨或作為其二或更多個的混合物而使用。
無機酸可包括於總量100重量％的蝕刻溶液組成物中的1至10重量％的量。如果無機酸的含量少於1重量％，銅金屬層或金屬氧化物層的蝕刻率被降低而引起不佳的蝕刻輪廓，且殘餘物可殘留。當該含量超過10重量％時，發生過度蝕刻，光阻包括裂縫，且該蝕刻溶液組成物滲入該裂縫中，導致線路短路。
環胺化合物是一種用以控制蝕刻率、並在銅金屬層的蝕刻期間抑制過度蝕刻的成分，因此降低蝕刻損失（臨界尺寸，CD）。其特定的範例可包括，5-胺基四氮唑、甲苯基三氮唑、苯並三氮唑、甲基苯並三氮唑、咪唑化合物、吲哚化合物、嘌呤化合物、吡唑化合物、吡啶化合物、嘧啶化合物、吡咯化合物、吡咯啶化合物、吡咯啉化合物等等，其被單獨或作為其二或更多個的混合物而使用。
環胺化合物可包括於總量100重量％的蝕刻溶液組成物中的0.5至5重量％、較佳為0.5至3重量％的量。在這樣的含量範圍內，可提供想要的銅蝕刻率以及錐狀角，並可控制側邊蝕刻。如果該含量少於0.5重量％，難以適當地控制銅金屬層的蝕刻率，造成過度蝕刻。當該含量超過5重量％，該銅金屬層的蝕刻率降低，且製程的蝕刻時間延長，因此降低了生產力。
氯化合物是一種可能在蝕刻溶液組成物中解離成氯離子的化合物，其是氧化作用輔助物，以蝕刻銅金屬層，且也是用以藉由與過硫酸鹽關於該銅金屬層的蝕刻競爭而控制蝕刻率以及錐狀角的成分，以至於控制過硫酸鹽局部過度腐蝕該銅金屬層。其特定的範例可包括氫氯酸（HCl）、氯化鈉（NaCl）、氯化鉀（KCl）、氯化銨(NH4Cl)等等，其被單獨或作為其二或更多個的混合物而使用。
氯化合物可包括於總量100重量％的蝕刻溶液組成物中的0.001至5重量％的量。如果氯化合物的含量少於0.001重量％，該蝕刻溶液可造成銅金屬層的局部過度腐蝕，因此導致其品質的惡化。當含量超過5重量％時，藉由以想要的含量蝕刻要被處理的片數減少，且蝕刻率非常快，以至於引起不佳的蝕刻輪廓。
有機酸、其鹽類或混合物是一種關於藉由蝕刻要被處理的片數而隨時間確保固定之蝕刻輪廓的成分，以至於控制了銅金屬層的錐狀角以及蝕刻率，因此提供了想要的側邊蝕刻。此外，上述成分可預防與所蝕刻金屬離子的嵌合反應受到蝕刻溶液組成物的影響，因此能夠在一固定含量下增加要被處理的片數。有機酸、其鹽類或混合物的特定範例可包括醋酸、亞胺基二醋酸、乙二胺四醋酸、丁酸、檸檬酸、異檸檬酸、甲酸、葡萄糖酸、乙醇酸、丙二酸、草酸、戊酸、磺基苯甲酸、琥珀酸、磺基琥珀酸、水楊酸、磺基水楊酸、苯甲酸、乳酸、甘油酸、蘋果酸、酒石酸、丙烯酸或諸如此類，其被單獨或作為其二或更多個的混合物而使用。此外，有機酸的鹽類可包括，例如，上述有機酸的鉀鹽、鈉鹽、銨鹽等等，其被單獨或作為其二或更多個的混合物而使用。
有機酸、其鹽類或混合物可包括於總量100重量％的蝕刻溶液組成物中的0.1至10重量％的量。如果有機酸的含量少於0.1重量％，關於要被處理的片數難以隨時間維持固定的蝕刻輪廓，且對於增加要被處理的片數的效果很小。當該含量多於10重量％時，發生了過度蝕刻而增加了側邊蝕刻，且要被處理的片數增加的進一步效果並無法預期，因此承擔了經濟上的缺點。
蝕刻溶液組成物可更包括銅鹽。
銅鹽可控制CD變異（偏斜）。其特定的範例可包括硝酸銅、硫酸銅、磷酸銨銅等等，其被單獨或作為其二或更多個的混合物而使用。
銅鹽可包括於總量100重量％的蝕刻溶液組成物中的少於3重量％、較佳為0.05至3重量％的量。如果銅鹽的含量超過3重量％，主要氧化劑的氧化作用效能降低而減少了要被處理的片數。
水是溶劑，且其類型不特別受限制，然而，可包括去離子蒸餾水，且更特別的是，用於半導體製程的去離子蒸餾水，且其特定的電阻可為18ΜΩ/cm或更高。
水可包括作為總量100重量％的蝕刻溶液組成物的剩餘部分。
本發明的蝕刻溶液組成物可更包括至少一添加物，例如蝕刻調節劑、界面活性劑、金屬離子隔離劑（或螯合劑）、腐蝕抑制劑、pH調整劑等等，以及上述成分。
具有如上述技術配置的蝕刻溶液組成物特別有用於均勻且同時地蝕刻銅金屬層以及金屬氧化物層。因此，可能簡化蝕刻過程，同時提升生產力。此外，減少了進入氧化物半導體層底部的滲透作用，且該滲透作用不引起氧化物半導體層底部的過切，藉此預防半導體圖案的剝離。
本發明的「銅金屬層/金屬氧化物層」可包括，例如，以此順序做成薄板之包含銅金屬層/金屬氧化物層的雙薄膜，以及以此順序做成薄板之包含金屬氧化物層/銅金屬層的雙薄膜。此外，也可包括包含將銅金屬層以及金屬氧化物層交替地做成三或多層薄板的多層金屬薄膜，例如，包含銅金屬層/金屬氧化物層/銅金屬層的三重薄膜、包含金屬氧化物層/銅金屬層/金屬氧化物層的三重薄膜、包含銅金屬層/金屬氧化物層/銅金屬層/金屬氧化物層/銅金屬層的多層薄膜，或諸如此類。在本文中，不特別限制每層銅金屬層以及金屬氧化物層的厚度。
同樣地，本發明的「銅金屬層」在薄膜的組成中是含有銅的薄膜，且特別的是，可包含單一銅層，該單一銅層包括選自由純銅以及其氮化物或氧化物所組成的群組至少其中之一。此外，該銅金屬層可為由銅合金製成的銅合金層，該銅合金包含選自由純銅、其氮化物以及氧化物所組成的群組至少其中之一，以及選自由鋁（Al）、鎂（Mg）、鈣（Ca）、鈦（Ti）、銀（Ag）、鉻（Cr）、錳（Mn）、鐵（Fe）、鋯（Zr）、鈮（Nb）、鉬（Mo）、鈀（Pd）、鉿（Hf）、鉭（Ta）以及鎢（W）所組成的群組至少其中之一。此外，該銅金屬層可為包含單一銅層以及銅合金層的薄板。此後，該銅金屬層以Cu-X表示。
本文中所使用的「金屬氧化物層」是含有至少2種成分氧化物的薄膜，例如2種至4種成分的氧化物，其可以表示。在本文中，A、B、C以及D彼此不同，且每個可為鋅（Zn）、錫（Sn）、鎘（Cd）、鎵（Ga）、鋁（Al）、鈹（Be）、鎂（Mg）、鈣（Ca）、鍶（Sr）、鋇（Ba）、鐳（Ra）、鉈（Tl）、鈧（Sc）、銦（In）、釔（Y）、鑭（La）、錒（Ac）、鈦（Ti）、鋯（Zr）、鉿（Hf）、鉭（Ta）或鑪（Rf），且a、b、c以及d每個為至少0的數字，前提是當中的至少兩個每個為0之外的數字。較佳地，該金屬氧化物層可包含2種成分的金屬氧化物層，該包含2種成分的金屬氧化物層含有鎵，以(Ga)aBbC0D0O表示，或3種成分的金屬氧化物層，該3種成分的金屬氧化物含有銦以及鋅，以AaInbZncD0O表示。其特定的範例可包括，氧化鎵-氧化鋅（Ga2O3-ZnO，GZO）、氧化鎵-氧化銦-氧化鋅（Ga2O3-In2O3-ZnO，GIZO）、氧化鉿-氧化銦-氧化鋅（HfO2-In2O3-ZnO，HIZO）等等。該金屬氧化物層的厚度範圍可為300至500。
顯示裝置的製造
本發明可提供一種使用如上所述的蝕刻溶液組成物來製造顯示裝置的方法。
第1圖是示例一顯示裝置的平面圖，以及第2圖是取自沿著第1圖中所示的線I-I’的截面圖。
顯示裝置100可包括閘極線GL、資料線DL、薄膜電晶體SW以及畫素電極170，以及，此外，閘極絕緣層120以及鈍化層160。
製造顯示裝置的方法可包括：在基板上形成包括閘極線以及閘極的閘極圖案；在具有該閘極圖案形成於其上的該基板上提供氧化物半導體層，其中該半導體層包括金屬氧化物層；在該氧化物半導體層上提供資料金屬層，其中該資料金屬層包括銅金屬層；以本發明的蝕刻溶液組成物，藉由同時且完全地蝕刻該資料金屬層以及該氧化物半導體層來將該資料金屬層以及該氧化物半導體層形成圖案，以至於形成包括半導體圖案、資料線、源極以及漏極的源極圖案；以及提供電連接至該漏極的畫素電極。
第3至5圖分別是解釋根據本發明一個範例的製造顯示裝置的方法的截面圖。
首先，如第3圖中所示，在基板110上形成具有閘極線GL以及閘極GE的閘極圖案，並在具有該閘極圖案形成於其上的該基板110上提供閘極絕緣層120。
閘極圖案可藉由在基板110上提供閘極金屬層以及經由蝕刻將該閘極金屬層形成圖案而形成。也就是說，該閘極金屬層可含有銅。
然後，如第4圖中所示，以金屬氧化物層提供的氧化物半導體層130以及資料金屬層140提供依序地提供在包括閘極絕緣層120的基板110上。
氧化物半導體層130可包含金屬氧化物層，該金屬氧化物層包括選自由鋅、錫、鎘、鎵、鋁、鈹、鎂、鈣、鍶、鋇、鐳、鉈、鈧、銦、釔、鑭、錒、鈦、鋯、鉿、鉭以及鑪所組成的群組中的至少其中兩者。例如，該金屬氧化物可包括氧化鎵-氧化銦-氧化鋅（Ga2O3-In2O3-ZnO，GIZO）、氧化鉿-氧化銦-氧化鋅（HfO2-In2O3-ZnO，HIZO）等等。該氧化物半導體層130的厚度範圍可為300至500。
可在氧化物半導體層130以及資料金屬層140之間提供蝕刻阻擋層ES，使其與閘極GE重疊。
可藉由在氧化物半導體層130上提供絕緣層，然後經由蝕刻將該絕緣層形成圖案來形成蝕刻阻擋層ES。該絕緣層可由二氧化矽或氮化矽製成，且可藉由移除除了與形成閘極GE的部分重疊的部分以外的所有部分來形成該蝕刻阻擋層ES。
資料金屬層140可包含銅金屬層，特別是，含有銅與錳的合金以及被穩定地提供在氧化物半導體層130上的銅合金層，因為其具有極佳的界面吸附。該資料金屬層140實質上可為由銅合金層所組成的單一薄膜，且包含該銅合金層以及形成於其上的單一銅層。或者，其可包含銅合金層、提供在該銅合金層上的單一銅層以及提供在該單一銅層上的另一銅合金層。該資料金屬層140的厚度範圍可為2,000至4,000。
接下來，如第5圖中所示，在資料金屬層140上形成光阻圖案152。該光阻圖案152可形成在源極區域10、漏極區域20以及源極線區域30上，而該資料金屬層140是從包括通道區域40的其他區域曝露出。
使用光阻圖案152作為一蝕刻預防薄膜以及具進步性的蝕刻溶液組成物，可同時且完全地蝕刻資料金屬層140以及氧化物半導體層130。
經由資料金屬層140以及氧化物半導體層130同時且完全的蝕刻，分別在源極區域10以及漏極區域20上提供源極SE以及漏極DE。同樣地，將資料線DL提供給源極線區域30。在如上述形成源極圖案的情況下，形成了半導體圖案132。通道區域40中的該資料金屬層140由光阻圖案152曝露，並由蝕刻溶液組成物移除。同時，由於蝕刻阻擋層ES，該通道區域40中的該半導體圖案132仍可留下而未被移除。
藉由使用去除組成物來移除光阻圖案152，可在基板110上提供包括閘極GE、半導體圖案132、蝕刻阻擋層ES、源極SE以及漏極DE的薄膜電晶體SW。
在此之後，在如上述製備的基板110上提供鈍化層160，接著將該鈍化層160形成圖案，以形成接觸孔，經由該接觸孔，曝露了該漏極DE的一端。隨後，在具有該接觸孔形成於其上的該基板110上提供了透明電極層，接著將該透明電極層形成圖案，以形成經由該接觸孔而電連接至該漏極DE的畫素電極170。
根據上述方法，可製造於第1圖所示出的顯示裝置100。特別是，可使用本發明的蝕刻溶液組成物來同時且完全地蝕刻具有銅金屬層以及由金屬氧化物層組成的氧化物半導體層130的資料金屬層140，藉此簡化蝕刻過程，並提升生產力。
此後，將描述較佳具體實施例，以參照範例以及比較性範例來更具體地了解本發明。然而，本領域的技術人員將領略，這樣的具體實施例僅提供用於示例的目的，且不限制如詳細描述以及附隨申請專利範例中所揭露將要保護的標的。因此，對於本領域的技術人員而言，將顯而易見的是，在本發明的範圍以及精神內，具體實施例的各種替代方案以及修飾是可能的，且充分地包括在附隨申請專利範圍所定義的範圍內。
範例
範例1
將10重量％的過硫酸鈉（SPS）、1重量％的二氟化銨（ABF）、4重量％的硝酸（HNO3）、1.5重量％的5-胺基四氮唑（ATZ）、1重量％的氯化鈉（NaCl）、3重量％的醋酸以及總量100重量％混合物的剩餘部分的水混合在一起，以製備180 kg的蝕刻溶液組成物。
比較性範例1至4
除了使用下面表1中所列出的個別成分以及含量之外，重覆範例1中所描述的相同程序。在本文中，含量以重量％表示。
表1
實驗範例
<蝕刻性質的評估>
藉由提供氧化物半導體層（該氧化物半導體層依序包含含有氧化鉿-氧化銦-氧化鋅（HfO2-In2O3-ZnO，HIZO）的金屬氧化物層以及含有銅與錳的銅合金層，然後以想要的形式在該銅合金層上形成光阻圖案）而製備的基板係藉由鑽石刀來切割成樣品，每個樣品具有550 mm× 650 mm的大小。
將所製備的蝕刻溶液組成物放置在注射蝕刻模式中的測試儀器（ETCHER（TFT），SEMES公司）中，並加熱至30℃的預設溫度。然後，在溫度到達30±0.1℃之後，進行蝕刻過程。在參照EPD（終點偵測器）時間的總蝕刻時間期間，進行了200％的過度蝕刻。將每個樣品被導入該測試儀器中，接著開始注射。在完成蝕刻之後，將處理過的樣品移出該儀器，以去離子水沖洗，使用熱吹風機乾燥，並使用光阻去除劑而從乾燥的樣品移除光阻。在沖洗以及乾燥之後，利用掃瞄式電子顯微鏡（SEM）（S-4700，日立公司）將該樣品進行蝕刻性質的評估，包括側邊蝕刻損失（臨界尺寸（CD））、錐狀角、金屬薄膜損害等等。
<評估標準>
◎ – 極佳（CD偏斜1μm，錐狀角：40至60°）。
○ – 優（1μm<CD偏斜1.5μm，錐狀角：30至60°）。
△ – 良（1.5μm<CD偏斜2μm，錐狀角：30至60°）。
× - 故障（金屬薄膜的損失或殘餘物的出現）。
表2
如表2中所示，確認了：相較於根據比較性範例1至4的蝕刻溶液組成物，根據本發明範例1中所製備的蝕刻溶液組成物（其包含：過硫酸鹽；氟化合物；無機酸；環胺化合物；氯化合物；有機酸、其鹽類或混合物；以及在其最佳含量所剩餘部分的水）在銅金屬層以及金屬氧化物層被完全蝕刻時，可達到極佳的蝕刻性質。The present invention provides a method of manufacturing a display device having a copper metal layer/metal oxide layer, and further, an etching solution composition for a copper metal layer/metal oxide layer, the etching solution composition being It is applied to the method of manufacturing a display device as described above.
Hereinafter, the present invention will be described in more detail.
Etching Solution Composition The etching solution composition of the present invention is for simultaneously etching a copper metal layer and a metal oxide layer.
The etching solution composition of the present invention may comprise: a persulfate; a fluorine compound; an inorganic acid; a cyclic amine compound; a chlorine compound; an organic acid, a salt or a mixture thereof;
More particularly, the progressive composition may comprise from 0.5 to 20% by weight of persulfate; from 0.01 to 2% by weight of fluorine compound; from 1 to 10% by weight of mineral acid; from 0.5 to 5% by weight of cyclic amine a compound; 0.001 to 5% by weight of a chlorine compound; 0.1 to 10% by weight of an organic acid, a salt or a mixture thereof; and water remaining in the total weight of the composition.
Persulfate is the main component used to etch the copper metal layer. Specific examples thereof may include ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ) or the like, which may be Used alone or in combination with two or more thereof.
The persulfate salt may be included in an amount of from 0.5 to 20% by weight based on the total of 100% by weight of the etching solution composition. If the content of persulfate is less than 5% by weight, the copper metal layer is sometimes not etched, or may have a low etching rate. When the content is more than 20% by weight, the overall etching is performed very rapidly (that is, the etching rate is high), which in turn causes difficulty in controlling the etching process.
The fluorine compound is a compound which may be dissociated by fluoride ions or polyatomic fluoride ions in the composition of the etching solution, which is a principal component for removing residues generated during etching while increasing the etching rate of the copper metal layer. The kind of the fluorine compound is not particularly limited, but may include, for example, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium difluoride (NH 4 HF 2 ), ammonium fluoroborate (NH 4 BF 4 ). , potassium fluoride (KF), potassium difluoride (KHF 2 ), potassium fluoroborate (KBF 4 ), sodium fluoride (NaF), sodium difluoride (NaHF 2 ), aluminum fluoride (AlF 3 ), fluorine Boric acid (HBF 4 ), lithium fluoride (LiF), calcium fluoride (CaF 2 ) or the like may be used singly or as a mixture of two or more thereof.
The fluorine compound may be included in an amount of 0.01 to 2% by weight in a total of 100% by weight of the etching solution composition. If the content of the fluorine compound is less than 0.01% by weight, the metal oxide layer has a reduced etching rate to cause generation of a residue. When the content exceeds 2% by weight, the metal oxide layer is excessively etched to cause the oxide semiconductor layer to "peel" from the substrate.
The mineral acid is an oxidation aid to etch the copper metal layer as well as the metal oxide layer. Specific examples thereof may include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like, which are used singly or as a mixture of two or more thereof.
The inorganic acid may be included in an amount of from 1 to 10% by weight in the total of 100% by weight of the etching solution composition. If the content of the inorganic acid is less than 1% by weight, the etching rate of the copper metal layer or the metal oxide layer is lowered to cause a poor etching profile, and the residue may remain. When the content exceeds 10% by weight, over-etching occurs, the photoresist includes cracks, and the etching solution composition penetrates into the crack, causing a short circuit.
The cyclic amine compound is a component for controlling the etching rate and suppressing excessive etching during etching of the copper metal layer, thereby reducing etching loss (critical dimension, CD). Specific examples thereof may include 5-aminotetrazolium, tolyltriazole, benzotriazole, methylbenzotriazole, imidazole compound, hydrazine compound, hydrazine compound, pyrazole compound, pyridine. A compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, a pyrroline compound or the like, which is used singly or as a mixture of two or more thereof.
The cyclic amine compound may be included in an amount of from 0.5 to 5% by weight, preferably from 0.5 to 3% by weight, based on the total of 100% by weight of the etching solution composition. Within such a range of contents, a desired copper etch rate as well as a tapered angle can be provided and side etching can be controlled. If the content is less than 0.5% by weight, it is difficult to appropriately control the etching rate of the copper metal layer, resulting in over etching. When the content exceeds 5% by weight, the etching rate of the copper metal layer is lowered, and the etching time of the process is prolonged, thereby reducing productivity.
A chlorine compound is a compound that may dissociate into chloride ions in an etching solution composition, which is an oxidation aid to etch a copper metal layer, and is also used to compete with persulfate for etching of the copper metal layer. The composition of the etch rate and the tapered angle is controlled such that the persulfate is locally controlled to locally corrode the copper metal layer. Specific examples thereof may include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH 4 Cl), and the like, either alone or as two or more thereof. Use as a mixture.
The chlorine compound may be included in an amount of 0.001 to 5% by weight in a total of 100% by weight of the etching solution composition. If the content of the chlorine compound is less than 0.001% by weight, the etching solution may cause local excessive corrosion of the copper metal layer, thus causing deterioration in quality thereof. When the content exceeds 5% by weight, the number of sheets to be processed is reduced by etching at a desired level, and the etching rate is so fast that a poor etching profile is caused.
An organic acid, a salt thereof or a mixture is a component for ensuring a fixed etching profile with time by etching the number of sheets to be processed, so that the tapered angle of the copper metal layer and the etching rate are controlled, thus providing an idea The desired side etches. Further, the above components can prevent the chimeric reaction with the etched metal ions from being affected by the etching solution composition, and therefore the number of sheets to be processed can be increased at a fixed level. Specific examples of organic acids, salts or mixtures thereof may include acetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid. , valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, acrylic acid or the like, alone or as a Two or more mixtures are used. Further, the salts of the organic acid may include, for example, a potassium salt, a sodium salt, an ammonium salt or the like of the above organic acid, which is used singly or as a mixture of two or more thereof.
The organic acid, a salt thereof or a mixture thereof may be included in an amount of from 0.1 to 10% by weight based on 100% by weight of the total of the etching solution composition. If the content of the organic acid is less than 0.1% by weight, it is difficult to maintain a fixed etching profile with time with respect to the number of sheets to be processed, and the effect of increasing the number of sheets to be processed is small. When the content is more than 10% by weight, excessive etching occurs to increase the side etching, and further effects of an increase in the number of sheets to be processed are not expected, and thus an economic disadvantage is assumed.
The etching solution composition may further include a copper salt.
Copper salts control CD variation (skew). Specific examples thereof may include copper nitrate, copper sulfate, copper ammonium phosphate, and the like, which are used singly or as a mixture of two or more thereof.
The copper salt may be included in an amount of less than 3% by weight, preferably 0.05 to 3% by weight, based on the total of 100% by weight of the etching solution composition. If the content of the copper salt exceeds 3% by weight, the oxidation efficiency of the main oxidizing agent is lowered to reduce the number of sheets to be treated.
Water is a solvent, and its type is not particularly limited, however, it may include deionized distilled water, and more particularly, deionized distilled water for a semiconductor process, and its specific electric resistance may be 18 ΜΩ/cm or more.
Water may include the remainder of the composition of the etching solution as a total of 100% by weight.
The etching solution composition of the present invention may further include at least one additive such as an etching regulator, a surfactant, a metal ion release agent (or a chelating agent), a corrosion inhibitor, a pH adjuster, and the like, and the above components.
The etching solution composition having the configuration as described above is particularly useful for uniformly and simultaneously etching a copper metal layer and a metal oxide layer. Therefore, it is possible to simplify the etching process while increasing productivity. Further, the permeation into the bottom of the oxide semiconductor layer is reduced, and the permeation does not cause overcutting of the bottom of the oxide semiconductor layer, thereby preventing peeling of the semiconductor pattern.
The "copper metal layer/metal oxide layer" of the present invention may include, for example, a double film comprising a copper metal layer/metal oxide layer as a thin plate in this order, and a metal oxide containing thin film in this order Double film of layer/copper metal layer. In addition, a multilayer metal film including a copper metal layer and a metal oxide layer alternately formed into three or more thin plates may be included, for example, a triple film including a copper metal layer/metal oxide layer/copper metal layer, including metal oxide A triple film of a layer/copper metal layer/metal oxide layer, a multilayer film comprising a copper metal layer/metal oxide layer/copper metal layer/metal oxide layer/copper metal layer, or the like. Herein, the thickness of each layer of the copper metal layer and the metal oxide layer is not particularly limited.
Similarly, the "copper metal layer" of the present invention is a film containing copper in the composition of the film, and in particular, may comprise a single copper layer comprising a layer selected from the group consisting of pure copper and its nitride or oxide. At least one of the groups. Further, the copper metal layer may be a copper alloy layer made of a copper alloy containing at least one selected from the group consisting of pure copper, a nitride thereof, and an oxide, and selected from aluminum (Al), Magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), At least one of a group consisting of palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W). Further, the copper metal layer may be a thin plate including a single copper layer and a copper alloy layer. Thereafter, the copper metal layer is represented by Cu-X.
The "metal oxide layer" as used herein is a film containing at least two component oxides, for example, oxides of two to four components, which may Said. Herein, A, B, C, and D are different from each other, and each may be zinc (Zn), tin (Sn), cadmium (Cd), gallium (Ga), aluminum (Al), bismuth (Be), magnesium. (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), strontium (Tl), strontium (Sc), indium (In), yttrium (Y), lanthanum (La), lanthanum (Ac), titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta) or furnace (Rf), and each of a, b, c, and d is a number of at least 0, provided that at least Both are numbers other than 0. Preferably, the metal oxide layer may comprise a metal oxide layer of two components, the metal oxide layer containing the two components containing gallium, represented by (Ga) a B b C 0 D 0 O, or three The metal oxide layer of the component, the metal oxide of the three components contains indium and zinc, and is represented by A a In b Zn c D 0 O. Specific examples thereof may include gallium oxide-zinc oxide (Ga 2 O 3 -ZnO, GZO), gallium oxide-indium oxide-zinc oxide (Ga 2 O 3 -In 2 O 3 -ZnO, GIZO), yttrium oxide- Indium oxide-zinc oxide (HfO 2 -In 2 O 3 -ZnO, HIZO) and the like. The metal oxide layer may have a thickness ranging from 300 to 500 .
Manufacture of Display Device The present invention can provide a method of manufacturing a display device using the etching solution composition as described above.
Fig. 1 is a plan view showing an example of a display device, and Fig. 2 is a cross-sectional view taken along line I-I' shown in Fig. 1.
The display device 100 may include a gate line GL, a data line DL, a thin film transistor SW, and a pixel electrode 170, and, in addition, a gate insulating layer 120 and a passivation layer 160.
A method of manufacturing a display device may include: forming a gate pattern including a gate line and a gate on a substrate; providing an oxide semiconductor layer on the substrate having the gate pattern formed thereon, wherein the semiconductor layer comprises a metal An oxide layer; a data metal layer is provided on the oxide semiconductor layer, wherein the data metal layer comprises a copper metal layer; and the material layer and the oxide are simultaneously and completely etched by the etching solution composition of the present invention A semiconductor layer is patterned to form the material metal layer and the oxide semiconductor layer such that a source pattern including a semiconductor pattern, a data line, a source, and a drain is formed; and a pixel electrode electrically connected to the drain is provided.
3 to 5 are respectively sectional views explaining a method of manufacturing a display device according to an example of the present invention.
First, as shown in FIG. 3, a gate pattern having a gate line GL and a gate GE is formed on the substrate 110, and a gate insulating layer is provided on the substrate 110 having the gate pattern formed thereon. 120.
The gate pattern can be formed by providing a gate metal layer on the substrate 110 and patterning the gate metal layer via etching. That is, the gate metal layer may contain copper.
Then, as shown in FIG. 4, the oxide semiconductor layer 130 and the material metal layer 140 provided with the metal oxide layer are sequentially provided on the substrate 110 including the gate insulating layer 120.
The oxide semiconductor layer 130 may include a metal oxide layer including a layer selected from the group consisting of zinc, tin, cadmium, gallium, aluminum, lanthanum, magnesium, calcium, lanthanum, cerium, radium, lanthanum, cerium, indium, lanthanum, At least two of the group consisting of ruthenium, osmium, titanium, zirconium, hafnium, tantalum, and furnaces. For example, the metal oxide may include gallium oxide-indium oxide-zinc oxide (Ga 2 O 3 -In 2 O 3 -ZnO, GIZO), yttrium oxide-indium oxide-zinc oxide (HfO 2 -In 2 O 3 -ZnO) , HIZO) and so on. The oxide semiconductor layer 130 may have a thickness ranging from 300 to 500 .
An etch stop layer ES may be provided between the oxide semiconductor layer 130 and the data metal layer 140 to overlap the gate GE.
The etching stopper layer ES can be formed by providing an insulating layer on the oxide semiconductor layer 130 and then patterning the insulating layer by etching. The insulating layer may be made of hafnium oxide or tantalum nitride, and the etching stopper layer ES may be formed by removing all portions except a portion overlapping with a portion where the gate GE is formed.
The data metal layer 140 may include a copper metal layer, in particular, an alloy containing copper and manganese, and a copper alloy layer stably provided on the oxide semiconductor layer 130 because it has excellent interface adsorption. The data metal layer 140 can be substantially a single film composed of a copper alloy layer and includes the copper alloy layer and a single copper layer formed thereon. Alternatively, it may comprise a copper alloy layer, a single copper layer provided on the copper alloy layer, and another copper alloy layer provided on the single copper layer. The data metal layer 140 can range in thickness from 2,000 to 4,000 .
Next, as shown in FIG. 5, a photoresist pattern 152 is formed on the material metal layer 140. The photoresist pattern 152 may be formed on the source region 10, the drain region 20, and the source line region 30, and the data metal layer 140 is exposed from other regions including the channel region 40.
Using the photoresist pattern 152 as an etch-preventive film and a progressive etching solution composition, the material metal layer 140 and the oxide semiconductor layer 130 can be simultaneously and completely etched.
The source electrode SE and the drain electrode DE are provided on the source region 10 and the drain region 20, respectively, through simultaneous and complete etching of the data metal layer 140 and the oxide semiconductor layer 130. Likewise, the data line DL is supplied to the source line region 30. In the case where the source pattern is formed as described above, the semiconductor pattern 132 is formed. The data metal layer 140 in the channel region 40 is exposed by the photoresist pattern 152 and removed by the etching solution composition. At the same time, the semiconductor pattern 132 in the channel region 40 can remain without being removed due to the etch stop layer ES.
The thin film transistor SW including the gate GE, the semiconductor pattern 132, the etch barrier layer ES, the source electrode SE, and the drain electrode DE may be provided on the substrate 110 by using the removal composition to remove the photoresist pattern 152.
After that, a passivation layer 160 is provided on the substrate 110 prepared as described above, and then the passivation layer 160 is patterned to form a contact hole through which one end of the drain electrode DE is exposed. Subsequently, a transparent electrode layer is provided on the substrate 110 having the contact hole formed thereon, and then the transparent electrode layer is patterned to form a pixel electrode 170 electrically connected to the drain DE via the contact hole. .
According to the above method, the display device 100 shown in Fig. 1 can be manufactured. In particular, the etching solution composition of the present invention can be used to simultaneously and completely etch the data metal layer 140 having the copper metal layer and the oxide semiconductor layer 130 composed of the metal oxide layer, thereby simplifying the etching process and increasing productivity .
Hereinafter, preferred embodiments will be described, and the present invention will be more specifically understood by referring to the examples and comparative examples. However, those skilled in the art will appreciate that such specific embodiments are provided for the purpose of illustration only, and are not to be construed as limited. It will be apparent to those skilled in the art that various alternatives and modifications of the specific embodiments are possible, and are fully included in the scope of the appended claims. In the range.
Sample example 1
10% by weight of sodium persulfate (SPS), 1% by weight of ammonium difluoride (ABF), 4% by weight of nitric acid (HNO 3 ), 1.5% by weight of 5-aminotetrazolium (ATZ), 1 The water of sodium chloride (NaCl), 3% by weight of acetic acid, and the remainder of the total 100% by weight mixture were mixed together to prepare a 180 kg etching solution composition.
Comparative Examples 1 to 4
The same procedure as described in Example 1 was repeated except that the individual ingredients and contents listed in Table 1 below were used. In this context, the content is expressed in % by weight.
Table 1
Experimental example
<Evaluation of etching properties>
Providing an oxide semiconductor layer containing a metal oxide layer containing cerium oxide-indium oxide-zinc oxide (HfO 2 -In 2 O 3 -ZnO, HIZO) and copper containing copper and manganese in this order The alloy layer, which is then formed into a photoresist pattern on the copper alloy layer in a desired form, was prepared by cutting a sample into a sample by a diamond knife, each sample having a size of 550 mm × 650 mm.
The prepared etching solution composition was placed in a test apparatus (ETCHER (TFT), SEMES) in an injection etching mode, and heated to a preset temperature of 30 °C. Then, after the temperature reached 30 ± 0.1 ° C, an etching process was performed. During the total etching time with reference to the EPD (end point detector) time, 200% over etching was performed. Each sample was introduced into the test instrument and then the injection was started. After the etching is completed, the treated sample is removed from the instrument, rinsed with deionized water, dried using a thermal blower, and the photoresist removed from the dried sample using a photoresist remover. After rinsing and drying, the sample was evaluated for etching properties using a scanning electron microscope (SEM) (S-4700, Hitachi, Inc.), including side etching loss (critical dimension (CD)), cone angle, metal Film damage and so on.
<Evaluation criteria>
◎ – Excellent (CD skew) 1 μm, cone angle: 40 to 60°).
○ – excellent (1μm<CD skew) 1.5 μm, cone angle: 30 to 60°).
△ – good (1.5μm<CD skew) 2 μm, cone angle: 30 to 60°).
× - Failure (loss of metal film or appearance of residue).
Table 2
As shown in Table 2, it was confirmed that the etching solution composition (which contains: persulfate; fluorine compound) prepared according to Example 1 of the present invention, compared to the etching solution composition according to Comparative Examples 1 to 4; An inorganic acid; a cyclic amine compound; a chlorine compound; an organic acid, a salt or a mixture thereof; and water remaining in an optimum amount thereof can be excellently obtained when the copper metal layer and the metal oxide layer are completely etched. Etching properties.
DE．．．漏極DE. . . Drain
DL．．．資料線DL. . . Data line
ES．．．蝕刻阻擋層ES. . . Etch barrier
GE．．．閘極GE. . . Gate
GL．．．閘極線GL. . . Gate line
SE．．．源極SE. . . Source
SW．．．薄膜電晶體SW. . . Thin film transistor
10．．．源極區域10. . . Source area
20．．．漏極區域20. . . Drain region
30．．．源極線區域30. . . Source line area
40．．．通道區域40. . . Channel area
100．．．顯示裝置100. . . Display device
110．．．基板110. . . Substrate
120．．．閘極絕緣層120. . . Gate insulation
130．．．氧化物半導體層130. . . Oxide semiconductor layer
132．．．半導體圖案132. . . Semiconductor pattern
140．．．資料金屬層140. . . Data metal layer
152．．．光阻圖案152. . . Resistive pattern
160．．．鈍化層160. . . Passivation layer
170．．．畫素電極170. . . Pixel electrode
從下述詳細的描述結合伴隨的圖示，將更清楚地了解本發明上述以及其他的目的、特徵與優勢，其中：
第1圖是示例一顯示裝置的平面圖；
第2圖是取自沿著第1圖中所示的線I-I’的截面圖；以及
第3至5圖分別是解釋根據本發明一個範例的製造顯示裝置的方法的截面圖。
The above and other objects, features and advantages of the present invention will become more <RTIgt;
Figure 1 is a plan view showing an example of a display device;
2 is a cross-sectional view taken along line I-I' shown in FIG. 1; and FIGS. 3 to 5 are respectively cross-sectional views explaining a method of manufacturing a display device according to an example of the present invention.
DE．．．漏極DE. . . Drain
DL．．．資料線DL. . . Data line
ES．．．蝕刻阻擋層ES. . . Etch barrier
GE．．．閘極GE. . . Gate
GL．．．閘極線GL. . . Gate line
SE．．．源極SE. . . Source
SW．．．薄膜電晶體SW. . . Thin film transistor
10．．．源極區域10. . . Source area
20．．．漏極區域20. . . Drain region
30．．．源極線區域30. . . Source line area
40．．．通道區域40. . . Channel area
110．．．基板110. . . Substrate
120．．．閘極絕緣層120. . . Gate insulation
132．．．半導體圖案132. . . Semiconductor pattern
152．．．光阻圖案152. . . Resistive pattern
Claims (20)
在一基板上形成包括一閘極線以及一閘極的一閘極圖案；
在具有該閘極圖案形成於其上的該基板上提供一氧化物半導體層，其中該半導體層包括一金屬氧化物層；
在該氧化物半導體層上提供一資料金屬層，其中該資料金屬層包括一銅金屬層；
使用一蝕刻溶液組成物，藉由同時且完全地蝕刻該資料金屬層以及該氧化物半導體層來將該資料金屬層以及該氧化物半導體層形成圖案，以形成包括一半導體圖案、一資料線、一源極以及一漏極的一源極圖案；以及
提供電連接至該漏極的一畫素電極，
其中該蝕刻溶液組成物包含：0.5至20重量％的過硫酸鹽、0.01至2重量％的一氟化合物、1至10重量％的無機酸、0.5至5重量％的一環胺化合物、0.001至5重量％的一氯化合物、0.1至10重量％的有機酸、其一鹽類或混合物以及形成該組成物之剩餘成分的水。A method of manufacturing a display device comprising:
Forming a gate pattern including a gate line and a gate on a substrate;
Providing an oxide semiconductor layer on the substrate having the gate pattern formed thereon, wherein the semiconductor layer comprises a metal oxide layer;
Providing a data metal layer on the oxide semiconductor layer, wherein the data metal layer comprises a copper metal layer;
Using an etching solution composition, the data metal layer and the oxide semiconductor layer are patterned by simultaneously and completely etching the data metal layer and the oxide semiconductor layer to form a semiconductor pattern, a data line, a source pattern of a source and a drain; and a pixel electrode electrically connected to the drain,
Wherein the etching solution composition comprises: 0.5 to 20% by weight of persulfate, 0.01 to 2% by weight of a fluorine compound, 1 to 10% by weight of a mineral acid, 0.5 to 5% by weight of a monoamine compound, 0.001 to 5 A wt% monochloro compound, 0.1 to 10 wt% of an organic acid, a salt or mixture thereof, and water forming the remaining components of the composition.
0.5至20重量％的過硫酸鹽；
0.01至2重量％的一氟化合物；
1至10重量％的無機酸；
0.5至5重量％的一環胺化合物；
0.001至5重量％的一氯化物；
0.1至10重量％的有機酸、其一鹽類或混合物；以及
形成該組成物剩餘成分的水。An etching solution composition for a copper metal layer/metal oxide layer, comprising:
0.5 to 20% by weight of persulfate;
0.01 to 2% by weight of a monofluoro compound;
1 to 10% by weight of a mineral acid;
0.5 to 5% by weight of a monocyclic amine compound;
0.001 to 5% by weight of monochloride;
0.1 to 10% by weight of an organic acid, a salt or mixture thereof; and water forming the remaining components of the composition.
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| TW201445008A (en) * | 2013-03-28 | 2014-12-01 | Dongwoo Fine Chem Co Ltd | Etching composition for copper-based metal layer and method of preparing metal line |
| KR102175313B1 (en) | 2013-09-24 | 2020-11-09 | 삼성디스플레이 주식회사 | Etchant and fabrication method of metal wiring and thin film transistor substrate using the same |
| CN103474439B (en) * | 2013-09-26 | 2016-08-24 | 合肥京东方光电科技有限公司 | A kind of display device, array base palte and preparation method thereof |
| US9472420B2 (en) | 2013-12-20 | 2016-10-18 | Air Products And Chemicals, Inc. | Composition for titanium nitride hard mask and etch residue removal |
| CN104045241B (en) * | 2014-06-16 | 2016-09-14 | 刘存海 | A kind of micro-fluorine glass etching finishing method |
| US9222018B1 (en) * | 2014-07-24 | 2015-12-29 | Air Products And Chemicals, Inc. | Titanium nitride hard mask and etch residue removal |
| US10332784B2 (en) * | 2015-03-31 | 2019-06-25 | Versum Materials Us, Llc | Selectively removing titanium nitride hard mask and etch residue removal |
| KR102433385B1 (en) * | 2015-11-10 | 2022-08-17 | 동우 화인켐 주식회사 | Etching solution composition for silver layer and display substrate using the same |
| KR102546796B1 (en) * | 2016-05-16 | 2023-06-22 | 동우 화인켐 주식회사 | Etchant composition |
| TWI785591B (en) * | 2021-05-04 | 2022-12-01 | 台灣上村股份有限公司 | Copper surface microetch |
| CN115613032A (en) * | 2022-10-11 | 2023-01-17 | 苏州华星光电技术有限公司 | Etching solution |
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| CN1195895C (en) * | 1997-01-29 | 2005-04-06 | 美克株式会社 | Micro etching agent of copper and copper alloy |
| KR20070017762A (en) * | 2005-08-08 | 2007-02-13 | 엘지.필립스 엘시디 주식회사 | Etchant composition, method of patterning electroconductive film using the same and method of fabricating flat panel display using the same |
| KR101310310B1 (en) * | 2007-03-15 | 2013-09-23 | 주식회사 동진쎄미켐 | Etchant for thin film transistor-liquid crystal displays |
| KR100983060B1 (en) * | 2008-05-26 | 2010-09-20 | (주)이그잭스 | Echant without hydrogen peroxide for layers of copper or copper alloy |
| KR101495683B1 (en) * | 2008-09-26 | 2015-02-26 | 솔브레인 주식회사 | Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in Liquid Crystal Display system |
| KR101531688B1 (en) * | 2008-11-12 | 2015-06-26 | 솔브레인 주식회사 | Etchant for transparent conductive ITO films |
| KR101619380B1 (en) * | 2009-05-14 | 2016-05-11 | 삼성디스플레이 주식회사 | Etchant and method of array substrate using the same |
| KR101805185B1 (en) * | 2009-08-13 | 2017-12-06 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| KR101687311B1 (en) * | 2009-10-07 | 2016-12-16 | 삼성디스플레이 주식회사 | Display device and method of manufacturing the same |
| KR101107545B1 (en) * | 2009-11-27 | 2012-01-31 | 솔브레인 주식회사 | Copper thick metal patterning etchant for low resistance TFT |
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| TWI613329B (en) | 2018-02-01 |
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