KR102009250B1 - 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
- Publication number
- KR102009250B1 KR102009250B1 KR1020110091917A KR20110091917A KR102009250B1 KR 102009250 B1 KR102009250 B1 KR 102009250B1 KR 1020110091917 A KR1020110091917 A KR 1020110091917A KR 20110091917 A KR20110091917 A KR 20110091917A KR 102009250 B1 KR102009250 B1 KR 102009250B1
- Authority
- KR
- South Korea
- Prior art keywords
- copper
- acid
- film
- compound
- metal oxide
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 104
- 239000002184 metal Substances 0.000 title claims abstract description 104
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000010949 copper Substances 0.000 title claims abstract description 100
- 238000005530 etching Methods 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 64
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 27
- 229910000431 copper oxide Inorganic materials 0.000 title 1
- 229910052802 copper Inorganic materials 0.000 claims abstract description 98
- 239000004065 semiconductor Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000000059 patterning Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 78
- -1 cyclic amine compound Chemical class 0.000 claims description 41
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 31
- 235000002639 sodium chloride Nutrition 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 239000011575 calcium Substances 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 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
- 229910052735 hafnium Inorganic materials 0.000 claims description 15
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims description 13
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 150000001805 chlorine compounds Chemical class 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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 group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052767 actinium Inorganic materials 0.000 claims description 10
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-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
- 229910052790 beryllium Inorganic materials 0.000 claims description 10
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 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
- 229910052706 scandium Inorganic materials 0.000 claims description 10
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052716 thallium Inorganic materials 0.000 claims description 10
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 9
- 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 8
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 8
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 150000001879 copper Chemical class 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
- 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 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 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
- 239000011572 manganese Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010955 niobium Substances 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
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910052742 iron Inorganic materials 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-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
- 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
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-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
- 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
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 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
- 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
- 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
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 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
- 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
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 155
- 239000010409 thin film Substances 0.000 abstract description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- YSRUGFMGLKANGO-UHFFFAOYSA-N zinc hafnium(4+) indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[In+3].[Hf+4] YSRUGFMGLKANGO-UHFFFAOYSA-N 0.000 description 3
- 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 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- JWQMZGJKIAJVFE-UHFFFAOYSA-L azanium copper phosphate Chemical compound [NH4+].[Cu+2].[O-]P([O-])([O-])=O JWQMZGJKIAJVFE-UHFFFAOYSA-L 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 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 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000004807 localization 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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)
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- Crystallography & Structural Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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- Metallurgy (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Thin Film Transistor (AREA)
- Weting (AREA)
Abstract
본 발명은 표시장치의 제조방법 및 이에 이용되는 구리계 금속막/금속 산화물막의 식각액 조성물에 관한 것으로, 보다 상세하게는 구리계 금속막을 포함하는 데이터 금속층과 금속 산화물막을 포함하는 산화물 반도체층을 동시에 식각하는 식각액 조성물을 이용하여 패터닝함으로써 반도체 패턴과, 데이터 라인, 소스 전극 및 드레인 전극을 포함하는 소스 패턴을 형성할 수 있어 박막 트랜지스터 및 표시장치의 생산성 및 제조 공정의 신뢰성을 향상시킬 수 있는 표시장치의 제조방법 및 이에 이용되는 구리계 금속막/금속 산화물막의 식각액 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a display device and an etchant composition of a copper-based metal film / metal oxide film, and more particularly, to simultaneously etching a data metal layer including a copper-based metal film and an oxide semiconductor layer including a metal oxide film. By patterning using an etchant composition to form a semiconductor pattern, a source pattern including a data line, a source electrode and a drain electrode, thereby improving the productivity of the thin film transistor and the display device and the reliability of the manufacturing process of the display device. It relates to a manufacturing method and an etching liquid composition of the copper-based metal film / metal oxide film used therein.
Description
본 발명은 포토리소그래피(photolithography) 공정에 이용되는 구리계 금속막과 금속 산화물막으로 구성된 산화물 반도체층을 동시에 식각하는 식각액 조성물을 이용한 표시장치의 제조방법 및 이에 이용되는 구리계 금속막/금속 산화물막의 식각액 조성물에 관한 것이다.
The present invention provides a method of manufacturing a display device using an etchant composition for simultaneously etching an oxide semiconductor layer composed of a copper-based metal film and a metal oxide film used in a photolithography process, and a copper-based metal film / metal oxide film used therein. It relates to an etchant composition.
반도체 장치 및 평판표시장치를 구동하는 전자 회로로서 대표적인 것은 박막 트랜지스터(thin film transistor, TFT)이다. TFT의 제조 과정은 통상 기판 위에 게이트와 데이터 배선 재료로서 금속막을 형성하고, 이 금속막의 선택적인 영역에 포토레지스트를 형성한 후 이 포토레지스트를 마스크로 하여 위 금속막을 식각하는 공정으로 구성된다.Typical electronic circuits for driving semiconductor devices and flat panel displays are thin film transistors (TFTs). The manufacturing process of the TFT generally consists of forming a metal film as a gate and data wiring material on a substrate, forming a photoresist in an optional region of the metal film, and then etching the upper metal film using the photoresist as a mask.
하나의 금속막을 식각하기 위해서는 원하는 패턴을 포함하는 하나의 마스크를 사용하고 있으나, 최근에는 고가인 마스크의 사용을 최소화하고 공정을 단순화하기 위하여 하나의 마스크를 사용하여 적어도 2 이상의 금속막을 식각하기도 한다. 그러나, 하나의 마스크를 이용한다 하더라도 금속막의 성질이 다른 경우에는 서로 다른 방식으로 식각 공정이 수행되므로, 실질적으로 공정 수를 줄이기 어렵다.In order to etch one metal film, one mask including a desired pattern is used, but recently, at least two or more metal films are etched using one mask to minimize the use of expensive masks and simplify the process. However, even when one mask is used, since the etching processes are performed in different ways when the properties of the metal film are different, it is difficult to substantially reduce the number of processes.
통상, 게이트 및 데이터 배선 재료로는 전기 전도도가 좋고 저항이 낮은 구리를 포함하는 구리 단독막 또는 구리 합금막과, 이들 막과 계면 접착력이 우수한 금속 산화물막이 사용된다. 이 경우 두 금속막의 다른 성질에 의해 하나의 공정으로 식각 공정이 수행되기 어렵다.
Usually, as a gate and data wiring material, the copper single film | membrane or copper alloy film | membrane which consists of copper with good electrical conductivity, and low resistance, and the metal oxide film excellent in the interface adhesive force with these films are used. In this case, the etching process is difficult to be performed in one process due to the different properties of the two metal films.
본 발명은 생산성 및 제조 공정의 신뢰성을 향상시킬 수 있는 표시장치의 제조 방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a method of manufacturing a display device which can improve productivity and reliability of a manufacturing process.
또한, 본 발명은 상기 표시장치의 제조방법에 이용되는 구리계 금속막/금속 산화물막의 식각액 조성물을 제공하는 것을 다른 목적으로 한다.
Another object of the present invention is to provide an etching liquid composition of a copper-based metal film / metal oxide film used in the method of manufacturing the display device.
1. 베이스 기판 상에 게이트 라인 및 게이트 전극을 포함하는 게이트 패턴을 형성하는 단계; 상기 게이트 패턴이 형성된 베이스 기판 상에 금속 산화물막을 포함하는 산화물 반도체층을 형성하는 단계; 상기 산화물 반도체층 상에 구리계 금속막을 포함하는 데이터 금속층을 형성하는 단계; 상기 데이터 금속층과 산화물 반도체층을 식각액 조성물로 동시에 일괄 식각하여 패터닝함으로써 반도체 패턴과, 데이터 라인, 소스 전극 및 드레인 전극을 포함하는 소스 패턴을 형성하는 단계; 및 상기 드레인 전극과 전기적으로 연결된 화소 전극을 형성하는 단계를 포함하는 표시장치의 제조방법에 있어서, 상기 식각액 조성물은 과황산염 0.5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 무기산 1 내지 10중량%; 고리형 아민 화합물 0.5 내지 5중량%; 염소 화합물 0.001 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 0.1 내지 10중량%; 및 잔량의 물을 포함하는 것인 표시장치의 제조방법.1. forming a gate pattern including a gate line and a gate electrode on a base substrate; Forming an oxide semiconductor layer including a metal oxide layer on the base substrate on which the gate pattern is formed; Forming a data metal layer including a copper-based metal film on the oxide semiconductor layer; Forming a source pattern including a semiconductor pattern, a data line, a source electrode, and a drain electrode by simultaneously collectively etching and patterning the data metal layer and the oxide semiconductor layer with an etchant composition; And forming a pixel electrode electrically connected to the drain electrode, wherein the etchant composition comprises 0.5 to 20 wt% of persulfate; 0.01 to 2 weight percent of a fluorine compound; 1 to 10% by weight of inorganic acid; 0.5 to 5% by weight of the cyclic amine compound; 0.001 to 5 wt% chlorine compound; 0.1 to 10% by weight of organic acid, salt thereof or mixture thereof; And a residual amount of water.
2. 위 1에 있어서, 상기 구리계 금속막은 구리, 이의 질화물 및 이의산화물로 이루어진 군으로부터 1종 이상을 함유하는 구리 단독막; 구리, 이의 질화물 및 이의 산화물로 이루어진 군으로부터 1종 이상과, 알루미늄, 마그네슘, 칼슘, 티타늄, 은, 크롬, 망간, 철, 지르코늄, 나이오븀, 몰리브덴, 팔라듐, 하프늄, 탄탈륨 및 텅스텐으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 구리 합금막; 또는 이들의 적층막인 표시장치의 제조방법.2. In the above 1, wherein the copper-based metal film is a copper single layer containing one or more from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or a laminated film thereof.
3. 위 2에 있어서, 상기 구리 합금막은 구리 및 망간을 함유하는 막인 표시장치의 제조방법.3. In the above 2, wherein the copper alloy film is a film containing copper and manganese manufacturing method of the display device.
4. 위 1에 있어서, 상기 금속 산화물막은 아연, 주석, 카드뮴, 갈륨, 알루미늄, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐, 탈륨, 스칸듐, 인듐, 이트륨, 란탄, 악티늄, 티타늄, 지르코늄, 하프늄, 탄탈륨 및 러더포늄으로 이루어진 군으로부터 선택된 2종 이상을 함유하는 막인 표시장치의 제조방법.4. In the above 1, the metal oxide film is zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, indium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium And a film containing at least two kinds selected from the group consisting of tantalum and rudderphonium.
5. 위 4에 있어서, 상기 금속 산화물막은 인듐 및 아연과, 주석, 카드뮴, 갈륨, 알루미늄, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐, 탈륨, 스칸듐, 이트륨, 란탄, 악티늄, 티타늄, 지르코늄, 하프늄, 탄탈륨 및 러더포늄으로 이루어진 군으로부터 선택된 1종을 함유하는 3성분계 막인 표시장치의 제조방법.5. In the above 4, the metal oxide film is indium and zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, yttrium, lanthanum, actinium, titanium, zirconium, A method of manufacturing a display device, which is a three-component film containing one selected from the group consisting of hafnium, tantalum, and ruthenium.
6. 위 1에 있어서, 상기 데이터 금속층은 구리 합금막, 상기 구리 합금막 상에 형성된 구리 단독막을 포함하는 것인 표시장치의 제조방법.6. In the above 1, wherein the data metal layer is a copper alloy film, a method of manufacturing a display device comprising a copper single layer formed on the copper alloy film.
7. 위 1에 있어서, 상기 데이터 금속층은 구리 합금막, 상기 구리 합금막 상에 형성된 구리 단독막 및 상기 구리 단독막 상에 형성된 구리 합금막을 포함하는 것인 표시장치의 제조방법.7. The method of claim 1, wherein the data metal layer includes a copper alloy layer, a copper single layer formed on the copper alloy layer, and a copper alloy layer formed on the copper single layer.
8. 과황산염 0.5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 무기산 1 내지 10중량%; 고리형 아민 화합물 0.5 내지 5중량%; 염소 화합물 0.001 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 0.1 내지 10중량%; 및 잔량의 물을 포함하는 구리계 금속막/금속 산화물막의 식각액 조성물.8. 0.5-20 wt% persulfate; 0.01 to 2 weight percent of a fluorine compound; 1 to 10% by weight of inorganic acid; 0.5 to 5% by weight of the cyclic amine compound; 0.001 to 5 wt% chlorine compound; 0.1 to 10% by weight of organic acid, salt thereof or mixture thereof; And a residual amount of water. An etching liquid composition of a copper-based metal film / metal oxide film.
9. 위 8에 있어서, 상기 과황산염은 과황산암모늄, 과황산나트륨 및 과황산칼륨으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.9. The etching solution composition of the above 8, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
10. 위 8에 있어서, 상기 불소 화합물은 불산, 불화암모늄, 중불화암모늄, 붕불화암모늄, 불화칼륨, 중불화칼륨, 붕불화칼륨, 불화나트륨, 중불화나트륨, 불화알루미늄, 불화붕소산, 불화리튬 및 불화칼슘으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.10. In the above 8, the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium fluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, fluoride An etching liquid composition of at least one copper-based metal film / metal oxide film selected from the group consisting of lithium and calcium fluoride.
11. 위 8에 있어서, 상기 무기산은 질산, 황산, 인산 및 과염소산으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.11. The etching liquid composition of the above 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. 위 8에 있어서, 상기 고리형 아민 화합물은 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸, 메틸벤조트리아졸, 이미다졸계 화합물, 인돌계 화합물, 푸린계 화합물, 피라졸계 화합물, 피리딘계 화합물, 피리미딘계 화합물, 피롤계 화합물, 피롤리딘계 화합물 및 피롤린계 화합물로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.12. In the above 8, wherein the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, An etching solution composition of a copper-based metal film / metal oxide film selected from the group consisting of a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound and a pyrroline compound.
13. 위 8에 있어서, 상기 염소 화합물은 염산, 염화나트륨, 염화칼륨 및 염화암모늄으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.13. The etching liquid composition of the above 8, wherein the chlorine compound is at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride.
14. 위 8에 있어서, 상기 유기산은 아세트산, 이미노디아세트산, 에틸렌디아민테트라아세트산, 부탄산, 시트르산, 이소시트르산, 포름산, 글루콘산, 글리콜산, 말론산, 옥살산, 펜탄산, 술포벤조산, 석신산, 술포석신산, 살리실산, 술포살리실산, 벤조산, 락트산, 글리세르산, 말산, 타르타르산 및 프로펜산으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.14. In the above 8, wherein the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, iso citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid Etching liquid composition of the copper-based metal film / metal oxide film of at least one selected from the group consisting of, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid and propenoic acid.
15. 위 8에 있어서, 상기 염은 칼륨염, 나트륨염 또는 암모늄염인 구리계 금속막/금속 산화물막의 식각액 조성물.15. The etching solution of claim 8, wherein the salt is a potassium salt, sodium salt or ammonium salt.
16. 위 8에 있어서, 구리염 0.05 내지 3중량%를 더 포함하는 구리계 금속막/금속 산화물막의 식각액 조성물.16. The etching liquid composition of the above 8, wherein the copper-based metal film / metal oxide film further comprises 0.05 to 3% by weight of copper salt.
17. 위 16에 있어서, 상기 구리염은 질산구리, 황산구리 및 인산구리암모늄으로 이루어진 군으로부터 선택된 1종 이상인 구리계 금속막/금속 산화물막의 식각액 조성물.17. The etching solution composition of the above 16, wherein the copper salt is at least one selected from the group consisting of copper nitrate, copper sulfate and ammonium copper phosphate.
18. 위 8에 있어서, 상기 구리계 금속막은 구리, 이의 질화물 및 이의산화물로 이루어진 군으로부터 1종 이상을 함유하는 구리 단독막; 구리, 이의 질화물 및 이의 산화물로 이루어진 군으로부터 1종 이상과, 알루미늄, 마그네슘, 칼슘, 티타늄, 은, 크롬, 망간, 철, 지르코늄, 나이오븀, 몰리브덴, 팔라듐, 하프늄, 탄탈륨 및 텅스텐으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 구리 합금막; 또는 이들의 적층막인 구리계 금속막/금속 산화물막의 식각액 조성물.18. In the above 8, the copper-based metal film is a copper single layer containing one or more from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or an etching liquid composition of a copper-based metal film / metal oxide film which is a laminated film thereof.
19. 위 8에 있어서, 상기 금속 산화물막은 아연, 주석, 카드뮴, 갈륨, 알루미늄, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐, 탈륨, 스칸듐, 인듐, 이트륨, 란탄, 악티늄, 티타늄, 지르코늄, 하프늄, 탄탈륨 및 러더포늄으로 이루어진 군으로부터 선택된 2종 이상을 함유하는 막인 구리계 금속막/금속 산화물막의 식각액 조성물.19. In the above 8, the metal oxide film is zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, indium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium And a copper-based metal film / metal oxide film, which is a film containing two or more selected from the group consisting of tantalum and ruthenium.
20. 위 8에 있어서, 상기 금속 산화물막은 인듐 및 아연과, 주석, 카드뮴, 갈륨, 알루미늄, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐, 탈륨, 스칸듐, 이트륨, 란탄, 악티늄, 티타늄, 지르코늄, 하프늄, 탄탈륨 및 러더포늄으로 이루어진 군으로부터 선택된 1종을 함유하는 3성분계 막인 구리계 금속막/금속 산화물막의 식각액 조성물.
20. In the above 8, the metal oxide film is indium and zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, yttrium, lanthanum, actinium, titanium, zirconium, An etching liquid composition of a copper-based metal film / metal oxide film, which is a three-component film containing one kind selected from the group consisting of hafnium, tantalum, and ruthenium.
본 발명의 표시장치의 제조방법에 따르면, 구리계 금속막을 포함하는 데이터 금속층과 금속 산화물막을 포함하는 산화물 반도체층을 동시에 패터닝할 수 있어 제조 공정을 단순화시킬 수 있다. 또한, 상기 산화물 반도체층에 언더 컷이 형성되는 것을 방지할 수 있다. 이를 통하여, 박막 트랜지스터 및 표시장치의 생산성 및 제조 공정의 신뢰성을 향상시킬 수 있다.
According to the method of manufacturing the display device of the present invention, the data metal layer including the copper-based metal film and the oxide semiconductor layer including the metal oxide film can be patterned at the same time, thereby simplifying the manufacturing process. In addition, an undercut may be prevented from being formed in the oxide semiconductor layer. Through this, productivity of the thin film transistor and the display device and reliability of the manufacturing process may be improved.
도 1은 표시장치의 평면도이고,
도 2는 도 1의 I-I' 따라 절단한 단면도이며,
도 3 내지 5는 본 발명의 일 실시예에 따른 표시장치의 제조방법을 설명하기 위한 단면도들이다.1 is a plan view of a display device;
FIG. 2 is a cross-sectional view taken along line II ′ of FIG. 1;
3 to 5 are cross-sectional views illustrating a method of manufacturing a display device according to an exemplary embodiment of the present invention.
본 발명은 구리계 금속막/금속 산화물막이 구비된 표시장치의 제조방법 및 이에 이용되는 구리계 금속막/금속 산화물막의 식각액 조성물에 관한 것이다.
The present invention relates to a method of manufacturing a display device provided with a copper-based metal film / metal oxide film, and to an etching liquid composition of a copper-based metal film / metal oxide film used therein.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
식각액Etchant 조성물 Composition
본 발명의 식각액 조성물은 구리계 금속막과 금속 산화물막을 동시에 일괄 식각하기 위한 것이다.The etchant composition of the present invention is for collectively etching the copper-based metal film and the metal oxide film at the same time.
본 발명의 구리계 금속막/금속 산화물막의 식각액 조성물은 과황산염; 불소 화합물; 무기산; 고리형 아민 화합물; 염소 화합물; 유기산, 이의 염 또는 이들의 혼합물; 및 물을 포함하는 것을 특징으로 한다.The etchant composition of the copper-based metal film / metal oxide film of the present invention is persulfate; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Chlorine compounds; Organic acids, salts thereof or mixtures thereof; And water.
보다 상세하게, 과황산염 0.5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 무기산 1 내지 10중량%; 고리형 아민 화합물 0.5 내지 5중량%; 염소 화합물 0.001 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 0.1 내지 10중량%; 및 잔량의 물을 포함하는 것을 특징으로 한다.More specifically, 0.5 to 20% by weight persulfate; 0.01 to 2 weight percent of a fluorine compound; 1 to 10% by weight of inorganic acid; 0.5 to 5% by weight of the cyclic amine compound; 0.001 to 5 wt% chlorine compound; 0.1 to 10% by weight of organic acid, salt thereof or mixture thereof; And a residual amount of water.
과황산염은 구리계 금속막을 식각하는 주성분이다. 구체적인 예로는 과황산암모늄((NH4)2S2O8), 과황산나트륨(Na2S2O8), 과황산칼륨(K2S2O8) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Persulfate is the main component for etching the copper-based metal film. Specific examples thereof 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 ), and the like. It can mix and use species.
과황산염은 식각액 조성물 총 100중량% 중에 0.5 내지 20중량%로 포함되는 것이 바람직하다. 함량이 5중량% 미만인 경우 구리계 금속막이 식각되지 않거나 식각 속도가 느릴 수 있고, 20중량% 초과인 경우 식각 속도가 전체적으로 빨라져 공정을 제어하기 어려울 수 있다.Persulfate is preferably included in 0.5 to 20% by weight in 100% by weight of the total etching composition. If the content is less than 5% by weight, the copper-based metal film may not be etched or the etching rate may be slow, and when the content is more than 20% by weight, the etching rate may be faster to control the process.
불소 화합물은 식각액 조성물 내에서 불소 이온 또는 다원자 불소 이온으로 해리될 수 있는 화합물로서, 금속 산화물막을 식각하는 주성분이며 식각 시 발생하는 잔사를 제거하고 구리계 금속막의 식각 속도도 증가시키는 성분이다. 불소 화합물의 종류는 특별히 한정되지 않으며, 구체적인 예로는 불산(HF), 불화암모늄(NH4F), 중불화암모늄(ammonium bifluoride, NH4HF2), 붕불화암모늄(NH4BF4), 불화칼륨(KF), 중불화칼륨(potassium bifluoride, KHF2), 붕불화칼륨(KBF4), 불화나트륨(NaF), 중불화나트륨(sodium bifluoride, NaHF2), 불화알루미늄(AlF3), 불화붕소산(HBF4), 불화리튬(LiF), 불화칼슘(CaF2) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The fluorine compound is a compound capable of dissociating into fluorine ions or polyatomic fluorine ions in the etching liquid composition. The fluorine compound is a main component for etching the metal oxide film, and removes residues generated during etching and increases the etching rate of the copper-based metal film. The type of the fluorine compound is not particularly limited, and specific examples thereof include hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), ammonium fluoride (NH 4 BF 4 ), and fluoride Potassium (KF), Potassium Bifluoride (KHF 2 ), Potassium Borofluoride (KBF 4 ), Sodium Fluoride (NaF), Sodium Bifluoride (NaHF 2 ), Aluminum Fluoride (AlF 3 ), Boron Fluoride Acids (HBF 4 ), lithium fluoride (LiF), calcium fluoride (CaF 2 ), and the like, and these may be used alone or in combination of two or more thereof.
불소 화합물은 식각액 조성물 총 100중량% 중에 0.01 내지 2중량%로 포함되는 것이 바람직하다. 함량이 0.01중량% 미만인 경우 금속 산화물막의 식각 속도가 저하되어 잔사가 발생할 수 있고, 2중량% 초과인 경우 금속 산화물막이 과다하게 식각되어 산화물 반도체층이 기판으로부터 리프트-오프(lift-off)될 수 있다.The fluorine compound is preferably included in an amount of 0.01 to 2% by weight in 100% by weight of the etching liquid composition. If the content is less than 0.01% by weight, the etching rate of the metal oxide film may be lowered, and residues may occur. If the content is more than 2% by weight, the metal oxide film may be excessively etched, and the oxide semiconductor layer may be lifted off from the substrate. have.
무기산은 구리계 금속막과 금속 산화물막의 식각을 위한 보조 산화제 성분이다. 구체적인 예로는 질산, 황산, 인산, 과염소산 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The inorganic acid is an auxiliary oxidant component for etching the copper-based metal film and the metal oxide film. Specific examples include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like, which may be used alone or in combination of two or more thereof.
무기산은 식각액 조성물 총 100중량% 중에 1 내지 10중량%로 포함되는것이 바람직하다. 함량이 1중량% 미만인 경우 구리계 금속막 또는 금속 산화물막의 식각 속도가 저하되어 식각 프로파일이 불량해지고 잔사가 발생할 수 있으며, 10중량% 초과인 경우 과식각이 발생할 수 있고 포토레지스트에 크랙(crack)이 발생하고 이 크랙으로 식각액 조성물이 침투하여 배선이 단락될 수 있다.The inorganic acid is preferably included in an amount of 1 to 10% by weight in 100% by weight of the etching liquid composition. If the content is less than 1% by weight copper-based metal film Alternatively, the etching rate of the metal oxide film may be lowered, resulting in poor etching profiles and residues. If the etching rate is greater than 10% by weight, cracks may occur in the photoresist, and the etching liquid composition may penetrate the cracks. The wiring may be shorted.
고리형 아민 화합물은 구리계 금속막의 식각 시 식각 속도를 조절하고 과식각을 억제하여 식각 손실(critical demension, CD)을 감소시키는 성분이다. 구체적인 예로는 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸, 메틸벤조트리아졸, 이미다졸계 화합물, 인돌계 화합물, 푸린계 화합물, 피라졸계 화합물, 피리딘계 화합물, 피리미딘계 화합물, 피롤계 화합물, 피롤리딘계 화합물, 피롤린계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The cyclic amine compound is a component that reduces the etching loss (critical demension (CD)) by controlling the etching rate during the etching of the copper-based metal film and inhibits over-etching. Specific examples include 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, An imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, a pyrroline compound, and the like. It can be mixed and used.
고리형 아민 화합물은 식각액 조성물 총 100중량% 중에 0.5 내지 5중량%로 포함될 수 있고, 바람직하게는 0.5 내지 3중량%인 것이 좋다. 이 함량 범위에서는 적정한 구리계 금속막의 식각율과 테이퍼 각도를 형성할 수 있고 측면 식각량을 조절할 수 있다. 함량이 0.5중량% 미만인 경우 구리계 금속막의 식각 속도를 충분히 조절하기 어려워 과식각이 발생할 수 있고, 5중량% 초과인 경우 구리계 금속막의 식각 속도가 저하되어 공정 상 식각 시간이 길어져 생산성을 저하시킬 수 있다.The cyclic amine compound may be included in an amount of 0.5 to 5% by weight in 100% by weight of the etching liquid composition, and preferably 0.5 to 3% by weight. In this content range, a suitable copper-based metal film Etch rate and taper angle can be formed and side etch rate can be adjusted. If the content is less than 0.5% by weight, it is difficult to sufficiently control the etching rate of the copper-based metal film, which may cause over-etching. When the content is more than 5% by weight, the etching speed of the copper-based metal film is lowered, resulting in longer etching time and lower productivity. Can be.
염소 화합물은 식각액 조성물 내에서 염소 이온으로 해리될 수 있는 화합물로서, 구리계 금속막을 식각하는 보조 산화제이자 구리계 금속막의 식각에 대하여 과황산염과 경쟁반응을 하여 과황산염의 구리계 금속막에 대한 국부적 과침식을 제어하는 식각 속도 조절과 테이퍼 각도를 조절하는 성분이다. 구체적인 예로는 염산(HCl), 염화나트륨(NaCl), 염화칼륨(KCl), 염화암모늄(NH4Cl) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The chlorine compound is a compound capable of dissociating into chlorine ions in the etching liquid composition, and is an auxiliary oxidant for etching the copper-based metal film, and competes with the persulfate for the etching of the copper-based metal film, thereby allowing the localization of the persulfate to the copper-based metal film. It controls the etch rate and taper angle to control over erosion. Specific examples include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH 4 Cl) and the like, these may be used alone or in combination of two or more.
염소 화합물은 식각액 조성물 총 100중량% 중에 0.001 내지 5중량%로 포함되는 것이 바람직하다. 함량이 0.001중량% 미만인 경우 식각액에 의한 구리계 금속막의 국부적 과침식으로 불량을 유발시킬 수 있고, 5중량% 초과인 경우 일정 함량에 대한 처리매수를 감소시키고 식각 속도가 과도하게 빨라져 식각 프로파일이 불량해질 수 있다.The chlorine compound is preferably included in 0.001 to 5% by weight in 100% by weight of the total etching solution composition. If the content is less than 0.001% by weight, it may cause defects by local over erosion of the copper-based metal film by the etching solution.If the content is more than 5% by weight, the etching number is reduced due to the decrease of the number of treatments for a certain content and the etching rate is excessively fast. Can be done.
유기산, 이의 염 또는 이들의 혼합물은 구리계 금속막의 테이퍼 각도를 조절하고 식각 속도를 조절하여 원하는 측면 식각을 얻기 위하여 처리매수의 경시 진행 시 일정한 식각 프로파일을 유지할 수 있게 하는 성분이다. 또한, 식각된 금속 이온과의 킬레이팅 작용에 의해 식각액 조성물에 영향을 주는 것을 방지하여 일정 함량에 대한 처리매수를 증가시키는 역할도 한다. 구체적인 예로는, 아세트산, 이미노디아세트산, 에틸렌디아민테트라아세트산, 부탄산, 시트르산, 이소시트르산, 포름산, 글루콘산, 글리콜산, 말론산, 옥살산, 펜탄산, 술포벤조산, 석신산, 술포석신산, 살리실산, 술포살리실산, 벤조산, 락트산, 글리세르산, 말산, 타르타르산, 프로펜산 등을 들 수 있다. 또한, 유기산의 염으로는 위 유기산의 칼륨염, 나트륨염, 암모늄염 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.An organic acid, a salt thereof, or a mixture thereof is a component capable of maintaining a constant etching profile during the course of treatment, in order to obtain a desired side etching by adjusting the taper angle of the copper-based metal film and controlling the etching rate. In addition, the chelating action with the etched metal ions to prevent affecting the etching liquid composition also serves to increase the number of treatment for a certain amount. Specific examples include acetic acid, imino diacetic acid, ethylenediaminetetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid And sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, propenoic acid, and the like. In addition, examples of the salts of the organic acids include potassium salts, sodium salts and ammonium salts of the above organic acids. These can be used individually or in mixture of 2 or more types.
유기산, 이의 염 또는 이들의 혼합물은 식각액 조성물 총 100중량% 중에 0.1 내지 10중량%로 포함되는 것이 바람직하다. 함량이 0.1중량% 미만인 경우 처리매수의 경시 진행 시 일정한 식각 프로파일의 유지가 어렵고 처리매수 증가 효과가 미미하며, 10중량% 초과인 경우 과식각이 발생하여 측면 식각이 커지는 현상이 발생하고 더 이상의 처리매수의 증가 효과가 없어 비경제적이다.The organic acid, salts thereof or mixtures thereof are preferably included in an amount of 0.1 to 10% by weight in 100% by weight of the etching liquid composition. If the content is less than 0.1% by weight, it is difficult to maintain a constant etching profile over time, and the effect of increasing the number of treatments is insignificant.If the content is more than 10% by weight, overetching occurs, causing side etching to increase, and further treatment. It is uneconomical as there is no increase in buying.
식각액 조성물은 구리염을 더 포함할 수 있다.The etchant composition may further include a copper salt.
구리염은 CD 변화(skew)를 조절하는 역할을 한다. 구체적인 예로는 질산구리, 황산구리, 인산구리암모늄 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Copper salts play a role in regulating CD skew. Specific examples include copper nitrate, copper sulfate, copper ammonium phosphate, and the like, which may be used alone or in combination of two or more thereof.
구리염은 식각액 조성물 총 100중량% 중에 3중량% 이하로 포함될 수 있으며, 바람직하게 0.05 내지 3중량%인 것이 좋다. 함량이 3중량% 초과인 경우 주산화제의 산화력을 감소시켜 처리매수를 감소시킬 수 있다.The copper salt may be included in 3% by weight or less in 100% by weight of the total etchant composition, preferably 0.05 to 3% by weight. If the content is more than 3% by weight can reduce the number of treatment by reducing the oxidation power of the main oxidizing agent.
물은 용매로서 그 종류는 특별히 한정되지 않으며, 탈이온 증류수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.The kind of water is not specifically limited as a solvent, It is preferable that it is deionized distilled water, More preferably, it is good that the specific resistance value is 18 kPa / cm or more as deionized distilled water for a semiconductor process.
물은 식각액 조성물 총 100중량% 중에 잔량으로 포함될 수 있다.Water may be included in the balance in a total of 100% by weight of the etchant composition.
본 발명의 식각액 조성물은 상기 성분과 함께 식각 조절제, 계면활성제, 금속 이온 봉쇄제, 부식방지제, pH 조절제 등의 첨가제를 1종 이상 더 포함할 수 있다.The etchant composition of the present invention may further include one or more additives such as an etching regulator, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH regulator, etc. together with the above components.
이와 같이 구성된 본 발명의 식각액 조성물은 구리계 금속막과 금속 산화물막을 동시에 일괄 식각할 수 있어, 제조 공정을 단순화하고 생산성을 향상시킬 수 있다. 또한, 산화물 반도체층의 하부에 침투되는 정도가 낮아 언더컷을 형성하지 않으며, 이로 인하여 반도체 패턴의 리프트-오프도 방지할 수 있다.The etching liquid composition of the present invention configured as described above can simultaneously etch the copper-based metal film and the metal oxide film, thereby simplifying the manufacturing process and improving productivity. In addition, the degree of penetration into the lower portion of the oxide semiconductor layer is low, so that the undercut is not formed, thereby preventing lift-off of the semiconductor pattern.
본 발명에서 '구리계 금속막/금속 산화물막'은 구리계 금속막/금속 산화물막의 순으로 적층된 이중막, 금속 산화물막/구리계 금속막의 순으로 적층된 이중막을 포함한다. 또한, 구리계 금속막과 금속 산화물막이 3층 이상으로 교대로 적층된 다중 금속막, 예컨대 구리계 금속막/금속 산화물막/구리계 금속막의 삼중막, 금속 산화물막/구리계 금속막/금속 산화물막의 삼중막, 구리계 금속막/금속 산화물막/구리계 금속막/금속 산화물막/구리계 금속막의 다중막 등도 포함한다. 이때, 구리계 금속막과 금속 산화물막의 두께는 특별히 한정되지 않는다.In the present invention, the 'copper-based metal film / metal oxide film' includes a double film laminated in the order of the copper-based metal film / metal oxide film, and a double film stacked in the order of the metal oxide film / copper-based metal film. Further, a multilayer metal film in which a copper metal film and a metal oxide film are alternately stacked in three or more layers, for example, a triple film of a copper metal film / metal oxide film / copper metal film, a metal oxide film / copper metal film / metal oxide The film includes a triple film, a copper-based metal film / metal oxide film / copper-based metal film / metal oxide film / copper-based metal film, and the like. At this time, the thickness of a copper metal film and a metal oxide film is not specifically limited.
또한, 본 발명에서 '구리계 금속막'은 막의 구성 성분 중에 구리를 포함하는 막으로서, 순수 구리, 이의 질화물 및 이의 산화물로 이루어진 군으로부터 선택된 1종 이상으로 구성된 구리 단독막일 수 있다. 또한, 순수 구리, 이의 질화물 및 이의 산화물로 이루어진 군으로부터 선택된 1종 이상과, 알루미늄(Al), 마그네슘(Mg), 칼슘(Ca), 티타늄(Ti), 은(Ag), 크롬(Cr), 망간(Mn), 철(Fe), 지르코늄(Zr), 나이오븀(Nb), 몰리브덴(Mo), 팔라듐(Pd), 하프늄(Hf), 탄탈륨(Ta) 및 텅스텐(W)으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 구리 합금으로 구성된 구리 합금막, 예컨대 구리와 망간으로 구성된 구리 합금막일 수 있다. 또한, 구리계 금속막은 구리 단독막과 구리 합금막의 적층막일 수 있다. 이하에서는 구리계 금속막을 Cu-X로 표시한다. In addition, in the present invention, the copper-based metal film is a film containing copper in the constituents of the film, and may be a copper single film composed of one or more selected from the group consisting of pure copper, nitrides thereof, and oxides thereof. In addition, at least one selected from the group consisting of pure copper, nitrides thereof and oxides thereof, aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), Selected from the group consisting of manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) It may be a copper alloy film composed of a copper alloy containing one or more, such as a copper alloy film composed of copper and manganese. In addition, the copper-based metal film may be a laminated film of a copper single film and a copper alloy film. Hereinafter, a copper metal film is represented by Cu-X.
또한, 본 발명에서 '금속 산화물막'은 2성분계 이상, 예컨대 2 내지 4성분계 산화물을 함유하여 구성된 막으로서, AaBbCcDdO로 표시될 수 있다. A, B, C 및 D는 서로 다르며 각각 아연(Zn), 주석(Sn), 카드뮴(Cd), 갈륨(Ga), 알루미늄(Al), 베릴륨(Be), 마그네슘(Mg), 칼슘(Ca), 스트론튬(Sr), 바륨(Ba), 라듐(Ra), 탈륨(Tl), 스칸듐(Sc), 인듐(In), 이트륨(Y), 란탄(La), 악티늄(Ac), 티타늄(Ti), 지르코늄(Zr), 하프늄(Hf), 탄탈륨(Ta) 또는 러더포늄(Rf)이고, a, b, c 및 d는 0 이상의 수로서 이들 중 적어도 2개는 0이 아닌 수이다. 바람직하게, (Ga)aBbC0D0O로 표시되는 갈륨 함유 2성분계 금속 산화물막 또는 AaInbZncD0O로 표시되는 인듐 및 아연 함유 3성분계 금속 산화물막이 좋다. 구체적인 예로는, 갈륨-아연 산화물(Ga2O3-ZnO, GZO), 갈륨-인듐-아연 산화물(Ga2O3-In2O3-ZnO, GIZO), 하프늄-인듐-아연 산화물(HfO2-In2O3-ZnO, HIZO) 등을 들 수 있다. 금속 산화물막의 두께는 약 300 내지 500Å일 수 있다.
In addition, in the present invention, the 'metal oxide film' is a film composed of two or more components, for example, two to four component oxides, and may be represented as A a B b C c D d O. A, B, C and D are different from each other, zinc (Zn), tin (Sn), cadmium (Cd), gallium (Ga), aluminum (Al), beryllium (Be), magnesium (Mg), calcium (Ca) , Strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), scandium (Sc), indium (In), yttrium (Y), lanthanum (La), actinium (Ac), titanium (Ti) , Zirconium (Zr), hafnium (Hf), tantalum (Ta) or rutherfonium (Rf), a, b, c and d are zero or more numbers, at least two of which are non-zero numbers. Preferably, a gallium-containing bicomponent metal oxide film represented by (Ga) a B b C 0 D 0 O or an indium and zinc containing tricomponent metal oxide film represented by A a In b Zn c D 0 O is preferable. Specific examples include gallium-zinc oxide (Ga 2 O 3 -ZnO, GZO), gallium-indium-zinc oxide (Ga 2 O 3 -In 2 O 3 -ZnO, GIZO), hafnium-indium-zinc oxide (HfO 2 -In 2 O 3 -ZnO, HIZO). The metal oxide film may have a thickness of about 300 to 500 kPa.
표시장치의 제조방법Manufacturing method of display device
본 발명은 상기 식각액 조성물을 이용한 표시장치의 제조방법을 제공한다.The present invention provides a method of manufacturing a display device using the etchant composition.
도 1은 표시장치의 평면도이며, 도 2는 도 1의 I-I' 라인을 따라 절단한 단면도이다.1 is a plan view of the display device, and FIG. 2 is a cross-sectional view taken along the line II ′ of FIG. 1.
표시장치(100)는 게이트 라인(GL), 데이터 라인(DL), 박막 트랜지스터(SW) 및 화소 전극(170)을 포함하며, 이와 함께 게이트 절연층(120) 및 패시베이션층(160)을 더 포함할 수 있다.The
표시장치의 제조방법은 베이스 기판 상에 게이트 라인 및 게이트 전극을 포함하는 게이트 패턴을 형성하는 단계; 상기 게이트 패턴이 형성된 베이스 기판 상에 금속 산화물막을 포함하는 산화물 반도체층을 형성하는 단계; 상기 산화물 반도체층 상에 구리계 금속막을 포함하는 데이터 금속층을 형성하는 단계; 상기 데이터 금속층과 산화물 반도체층을 본 발명의 식각액 조성물로 동시에 식각하여 패터닝함으로써 반도체 패턴과, 데이터 라인, 소스 전극 및 드레인 전극을 포함하는 소스 패턴을 형성하는 단계; 및 상기 드레인 전극과 전기적으로 연결된 화소 전극을 형성하는 단계를 포함한다.A method of manufacturing a display device includes forming a gate pattern including a gate line and a gate electrode on a base substrate; Forming an oxide semiconductor layer including a metal oxide layer on the base substrate on which the gate pattern is formed; Forming a data metal layer including a copper-based metal film on the oxide semiconductor layer; Simultaneously etching and patterning the data metal layer and the oxide semiconductor layer with the etchant composition of the present invention to form a semiconductor pattern and a source pattern including a data line, a source electrode and a drain electrode; And forming a pixel electrode electrically connected to the drain electrode.
도 3 내지 6은 본 발명의 일 실시예에 따른 표시장치의 제조방법을 설명하기 위한 단면도들이다.3 to 6 are cross-sectional views illustrating a method of manufacturing a display device according to an exemplary embodiment of the present invention.
먼저, 도 3에 나타낸 바와 같이, 베이스 기판(110) 상에 게이트 라인(GL) 및 게이트 전극(GE)을 포함하는 게이트 패턴을 형성하고, 상기 게이트 패턴을 포함하는 베이스 기판(110) 상에 게이트 절연층(120)을 형성한다.First, as shown in FIG. 3, a gate pattern including a gate line GL and a gate electrode GE is formed on a
게이트 패턴은 베이스 기판(110) 상에 게이트 금속층을 형성하고, 상기 게이트 금속층을 식각 공정을 통해 패터닝함으로써 형성할 수 있다. 예컨대, 게이트 금속층은 구리를 포함할 수 있다.The gate pattern may be formed by forming a gate metal layer on the
그 다음, 도 4에 나타낸 바와 같이, 게이트 절연층(120)을 포함하는 베이스 기판(110) 상에 금속 산화물막을 포함하는 산화물 반도체층과(130)과 데이터 금속층(140)을 순서대로 형성한다.Next, as shown in FIG. 4, the
산화물 반도체층(130)은 아연, 주석, 카드뮴, 갈륨, 알루미늄, 베릴륨, 마그네슘, 칼슘, 스트론튬, 바륨, 라듐, 탈륨, 스칸듐, 인듐, 이트륨, 란탄, 악티늄, 티타늄, 지르코늄, 하프늄, 탄탈륨 및 러더포늄으로 이루어진 군으로부터 선택된 2종 이상을 함유하는 금속 산화물막으로 구성될 수 있다. 예컨대, 금속 산화물로는 갈륨-인듐-아연 산화물(Ga2O3-In2O3-ZnO, GIZO), 하프늄-인듐-아연 산화물(HfO2-In2O3-ZnO, HIZO) 등을 들 수 있다. 산화물 반도체층(130)의 두께는 300 내지 500Å일 수 있다.The
산화물 반도체층(130)과 데이터 금속층(140) 사이에는 게이트 전극(GE)과 중첩되도록 에치-스토퍼(ES)를 형성할 수 있다.An etch stopper ES may be formed between the
에치-스토퍼(ES)는 산화물 반도체층(130) 상에 절연층을 형성한 후, 이 절연층을 식각 공정을 통해 패터닝함으로써 형성할 수 있다. 절연층은 산화 실리콘 또는 질화 실리콘 등으로 형성될 수 있으며, 게이트 전극(GE)이 형성된 부분과 중첩되는 영역을 제외하고는 모두 제거되어 에치-스토퍼(ES)를 형성한다.The etch stopper ES may be formed by forming an insulating layer on the
데이터 금속층(140)은 구리계 금속막, 구체적으로 구리 및 망간 합금을 포함하는 구리 합금막으로 구성되며, 산화물 반도체층(130)과의 계면 접착력이 우수하여 산화물 반도체층(130) 상에 안정적으로 형성될 수 있다. 데이터 금속층(140)은 실질적으로 구리 합금막으로 구성된 단일막일 수 있고, 구리 합금막과 상기 구리 합금막 상에 형성된 구리 단독막으로 구성될 수 있다. 또한, 구리 합금막, 상기 구리 합금막 상에 형성된 구리 단독막 및 상기 구리 단독막 상에 형성된 구리 합금막으로 구성될 수도 있다. 데이터 금속층(140)의 두께는 2,000 내지 4,000Å일 수 있다.The
그 다음, 도 5에 나타낸 바와 같이, 데이터 금속층(140) 상에 포토레지스트 패턴(152)을 형성한다. 포토레지스트 패턴(152)은 소스 영역(10), 드레인 영역(20) 및 소스 라인 영역(30) 상에 형성되고, 채널 영역(40)을 포함한 다른 영역들 상에 형성된 데이터 금속층(140)을 노출시킨다.Next, as shown in FIG. 5, a
포토레지스트 패턴(152)을 식각 방지막으로 이용하고, 본 발명의 식각액 조성물을 이용하여 데이터 금속층(140)과 산화물 반도체층(130)을 동시에 일괄 식각한다.The
데이터 금속층(140)과 산화물 반도체층(130)을 동시에 일괄 식각함에 따라 소스 영역(10) 및 드레인 영역(20)에는 각각 소스 전극(SE) 및 드레인 전극(DE)이 형성되고, 소스 라인 영역(30)에는 데이터 라인(DL)이 형성된다. 이와 같이 형성된 소스 패턴의 하부에는 반도체 패턴(132)이 형성된다. 채널 영역(40)의 데이터 금속층(140)이 포토레지스트 패턴(152)에 의해 노출되고, 식각액 조성물에 의해서 채널 영역(40)의 데이터 금속층(140)이 제거된다. 채널 영역(40)의 반도체 패턴(132)은 식각 시 에치-스토퍼(ES)에 의해 제거되지 않고 잔류할 수 있다.As the
포토레지스트 패턴(152)을 박리 조성물을 이용하여 제거함으로써 게이트 전극(GE), 반도체 패턴(132), 에치-스토퍼(ES), 소스 전극(SE), 드레인 전극(DE)을 포함하는 박막 트랜지스터(SW)가 베이스 기판(110) 상에 형성된다.By removing the
그 다음, 위에서 얻어진 기판(110) 상에 패시베이션층(160)을 형성한 후 패시베이션층(160)을 패터닝하여 드레인 전극(DE)의 일단을 노출시키는 콘택홀을 형성한다. 이 콘택홀이 형성된 베이스 기판(110) 상에 투명 전극층을 형성한 후 이 투명 전극층을 패터닝하여 드레인 전극(DE)과 콘택홀을 통해서 전기적으로 연결된 화소 전극(170)을 형성한다.Next, after forming the
이와 같은 방법으로 도 1의 표시장치(100)를 제조할 수 있다. 특히, 구리계 금속막을 포함하는 데이터 금속층(140)과 금속 산화물막으로 구성된 산화물 반도체층(130)을 본 발명의 식각액 조성물로 동시에 일괄 식각함으로써 식각 공정을 단순화하고 생산성을 향상시킬 수 있다.In this manner, the
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
실시예Example
실시예 1Example 1
과황산나트륨(sodium persulfate, SPS) 10중량%, 중불화암모늄(ammonium bifluoride, ABF) 1중량%, 질산(HNO3) 4중량%, 5-아미노테트라졸(aminotetrazole, ATZ) 1.5중량%, 염화나트륨(NaCl) 1중량%, 아세트산 3중량% 및 잔량의 물이 혼합된 식각액 조성물을 180㎏이 되도록 제조하였다.
10% by weight sodium persulfate (SPS), 1% by weight ammonium bifluoride (ABF), 4% by weight nitric acid (HNO 3 ), 1.5% by weight 5-aminotetrazole (ATZ), sodium chloride ( An etchant composition in which NaCl) 1% by weight, acetic acid 3% by weight and the balance of water were mixed was prepared to be 180 kg.
비교예 1-4Comparative Example 1-4
상기 실시예 1과 동일하게 실시하되, 하기 표 1에 나타낸 바와 같은 성분 및 함량을 사용하였다.
The same procedure as in Example 1, except that the ingredients and contents as shown in Table 1 were used.
(중량%)SPS
(weight%)
(중량%)ABF
(weight%)
(중량%)HNO 3
(weight%)
(중량%)ATZ
(weight%)
(중량%)NaCl
(weight%)
(중량%)AcOH
(weight%)
(중량%)water
(weight%)
ABF: 중불화암모늄
ATZ: 5-아미노테트라졸
AcOH: 아세트산SPS: Ammonium Persulfate
ABF: Ammonium Bifluoride
ATZ: 5-aminotetrazole
AcOH: acetic acid
시험예Test Example
<식각 특성 평가><Etch Characteristic Evaluation>
하프늄-인듐-아연 산화물(HfO2-In2O3-ZnO, HIZO)을 포함하는 금속 산화물막으로 구성된 산화물 반도체층과 구리 및 망간을 포함하는 구리 합금막이 순서대로 형성되고, 구리 합금막 상에 일정한 형태의 모양으로 포토레지스트 패턴이 형성된 기판을 다이아몬드 칼을 이용하여 550㎜×650㎜ 크기로 잘라 시편으로 제작하였다.An oxide semiconductor layer composed of a metal oxide film containing hafnium-indium-zinc oxide (HfO 2 -In 2 O 3 -ZnO, HIZO), and a copper alloy film containing copper and manganese are formed in this order, and on the copper alloy film The substrate on which the photoresist pattern was formed in a shape of a certain shape was cut into a size of 550 mm × 650 mm using a diamond knife to prepare a specimen.
분사식 식각 방식의 실험장비(ETCHER(TFT), SEMES사) 내에 제조된 식각액 조성물을 넣고 온도를 30℃로 세팅하여 가온하였다. 그 후, 온도가 30±0.1℃에 도달한 후 식각 공정을 수행하였다. 총 식각 시간을 EPD(Ending point detector) 시간을 기준으로 하여 오버에치를 200% 실시하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍 건조장치를 이용하여 건조하고, 포토레지스트 박리기(stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM)(S-4700, HITACHI사)을 이용하여 측면 식각 손실(critical dimension, CD), 테이퍼 각도, 금속막 손상 등과 같은 식각 특성을 평가하였다.Etching liquid composition prepared in a spray etching experiment equipment (ETCHER (TFT), SEMES Co., Ltd.) was put and warmed by setting the temperature to 30 ℃. Thereafter, an etching process was performed after the temperature reached 30 ± 0.1 ° C. The total etching time was based on the EPD (Ending point detector) time over 200%. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper. After washing and drying, the electron scanning microscope (SEM) (S-4700, HITACHI Co., Ltd.) was used to evaluate the etching characteristics such as lateral etching loss (CD), taper angle, metal film damage, and the like.
<평가 기준><Evaluation Criteria>
◎: 매우 우수(CD Skew ≤ 1㎛, 테이퍼각: 40-60°) ◎: very good (CD Skew ≤ 1 μm, taper angle: 40-60 °)
○: 우수(1㎛ < CD Skew ≤ 1.5㎛, 테이퍼각: 30-60°)○: excellent (1 μm <CD Skew ≤ 1.5 μm, taper angle: 30-60 °)
△: 양호(1.5㎛ < CD Skew ≤ 2㎛, 테이퍼각: 30-60°)(Triangle | delta): Good (1.5 micrometer <CD Skew <2 micrometers, taper angle: 30-60 degrees)
×: 불량(금속막 소실 또는 잔사 발생)
X: defective (metal film loss or residue)
위 표 2와 같이, 본 발명에 따라 과황산염; 불소 화합물; 무기산; 고리형 아민 화합물; 염소 화합물; 유기산, 이의 염 및 이의 혼합물; 및 잔량의 물을 최적의 함량으로 포함하는 실시예 1의 식각액 조성물은 비교예 1 내지 4의 식각액 조성물과 비교하여 구리계 금속막과 금속 산화물막의 일괄 식각 시 우수한 식각특성을 얻을 수 있었다.
As shown in Table 2, persulfate according to the present invention; Fluorine compounds; Inorganic acids; Cyclic amine compounds; Chlorine compounds; Organic acids, salts thereof and mixtures thereof; And the etching liquid composition of Example 1 containing the remaining amount of the optimum amount of water was able to obtain excellent etching characteristics when batch etching of the copper-based metal film and the metal oxide film compared to the etching solution composition of Comparative Examples 1 to 4.
100: 표시 장치 GL: 게이트 라인
DL: 데이터 라인 SW: 박막 트랜지스터
GE: 게이트 전극 SE: 소스 전극
DE: 드레인 전극 ES: 에치-스토퍼
110: 베이스 기판 120: 게이트 절연층
130: 산화물 반도체층 132: 반도체 패턴
140: 데이터 금속층 152: 포토레지스트 패턴
160: 패시베이션층 170: 화소 전극100: display device GL: gate line
DL: data line SW: thin film transistor
GE: gate electrode SE: source electrode
DE: drain electrode ES: etch-stopper
110: base substrate 120: gate insulating layer
130: oxide semiconductor layer 132: semiconductor pattern
140: data metal layer 152: photoresist pattern
160: passivation layer 170: pixel electrode
Claims (20)
상기 게이트 패턴이 형성된 베이스 기판 상에 금속 산화물막을 포함하는 산화물 반도체층을 형성하는 단계;
상기 산화물 반도체층 상에 구리계 금속막을 포함하는 데이터 금속층을 형성하는 단계;
상기 데이터 금속층과 산화물 반도체층을 식각액 조성물로 동시에 일괄 식각하여 패터닝함으로써 반도체 패턴과, 데이터 라인, 소스 전극 및 드레인 전극을 포함하는 소스 패턴을 형성하는 단계; 및
상기 드레인 전극과 전기적으로 연결된 화소 전극을 형성하는 단계를 포함하는 표시장치의 제조방법에 있어서,
상기 식각액 조성물은 과황산염 0.5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 무기산 1 내지 10중량%; 고리형 아민 화합물 0.5 내지 5중량%; 염소 화합물 0.001 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 0.1 내지 10중량%; 및 잔량의 물을 포함하고,
상기 과황산염은 과황산암모늄, 과황산나트륨 및 과황산칼륨으로 이루어진 군으로부터 선택된 적어도 하나를 포함하며,
상기 염소 화합물은 염화나트륨을 포함하며,
상기 식각액 조성물은 구리염은 포함하지 않는 표시장치의 제조방법.
Forming a gate pattern including a gate line and a gate electrode on the base substrate;
Forming an oxide semiconductor layer including a metal oxide layer on the base substrate on which the gate pattern is formed;
Forming a data metal layer including a copper-based metal film on the oxide semiconductor layer;
Forming a source pattern including a semiconductor pattern, a data line, a source electrode, and a drain electrode by simultaneously collectively etching and patterning the data metal layer and the oxide semiconductor layer with an etchant composition; And
A method of manufacturing a display device, comprising: forming a pixel electrode electrically connected to the drain electrode;
The etchant composition is 0.5 to 20% by weight persulfate; 0.01 to 2% by weight of a fluorine compound; 1 to 10% by weight of inorganic acid; 0.5 to 5% by weight of the cyclic amine compound; 0.001 to 5 wt% chlorine compound; 0.1 to 10% by weight of organic acid, salt thereof or mixture thereof; And remaining water,
The persulfate includes at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate,
The chlorine compound comprises sodium chloride,
The etchant composition does not contain a copper salt.
The method of claim 1, wherein the copper-based metal film is a copper single layer containing at least one member from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or a laminated film thereof.
The method of claim 2, wherein the copper alloy film is a film containing copper and manganese.
The method of claim 1, wherein the metal oxide film is zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, indium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, tantalum And a film containing two or more selected from the group consisting of rudderphonium.
The method of claim 4, wherein the metal oxide film is indium and zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, A method of manufacturing a display device, which is a three-component film containing one selected from the group consisting of tantalum and rudderphonium.
The method of claim 1, wherein the data metal layer comprises a copper alloy layer and a copper single layer formed on the copper alloy layer.
The method of claim 1, wherein the data metal layer comprises a copper alloy film, a copper single layer formed on the copper alloy layer, and a copper alloy layer formed on the copper single layer.
불소 화합물 0.01 내지 2중량%;
무기산 1 내지 10중량%;
고리형 아민 화합물 0.5 내지 5중량%;
염화나트륨을 포함하는 염소 화합물 0.001 내지 5중량%;
유기산, 이의 염 또는 이들의 혼합물 0.1 내지 10중량%; 및
잔량의 물을 포함하며,
구리염은 포함하지 않는, 구리계 금속막/금속 산화물막의 식각액 조성물.
0.5-20 wt% persulfate comprising at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of inorganic acid;
0.5 to 5% by weight of the cyclic amine compound;
0.001 to 5% by weight of a chlorine compound including sodium chloride;
0.1 to 10% by weight of organic acid, salt thereof or mixture thereof; And
Contains residual amount of water,
The etching liquid composition of a copper type metal film / metal oxide film which does not contain a copper salt.
The method of claim 8, wherein the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium fluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, lithium fluoride and An etching liquid composition of at least one copper-based metal film / metal oxide film selected from the group consisting of calcium fluoride.
The etching solution composition of claim 8, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and perchloric acid.
The method according to claim 8, wherein the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine An etching liquid composition of a copper-based metal film / metal oxide film selected from the group consisting of a compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound and a pyrroline compound.
The method of claim 8, wherein the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, sulf Etching composition of a copper-based metal film / metal oxide film of at least one selected from the group consisting of succinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid and propene acid.
The etching solution composition of claim 8, wherein the salt of the organic acid is a potassium salt, a sodium salt, or an ammonium salt.
The method according to claim 8, wherein the copper-based metal film is a copper single layer containing at least one member from the group consisting of copper, nitrides thereof and oxides thereof; At least one from the group consisting of copper, nitrides thereof and oxides thereof, and from the group consisting of aluminum, magnesium, calcium, titanium, silver, chromium, manganese, iron, zirconium, niobium, molybdenum, palladium, hafnium, tantalum and tungsten A copper alloy film containing at least one selected; Or an etching liquid composition of a copper-based metal film / metal oxide film which is a laminated film thereof.
The method of claim 8, wherein the metal oxide film is zinc, tin, cadmium, gallium, aluminum, beryllium, magnesium, calcium, strontium, barium, radium, thallium, scandium, indium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, tantalum And a copper-based metal film / metal oxide film which is a film containing two or more selected from the group consisting of rudderphonium.
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| WO2014178426A1 (en) * | 2013-05-02 | 2014-11-06 | 富士フイルム株式会社 | Etching method, etching liquid and etching liquid kit to be used in said method, and semiconductor substrate product manufacturing method |
| 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 |
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