CN104073803A - Etching composition for copper-based metal layer and method of preparing metal line - Google Patents
Etching composition for copper-based metal layer and method of preparing metal line Download PDFInfo
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- CN104073803A CN104073803A CN201410123681.0A CN201410123681A CN104073803A CN 104073803 A CN104073803 A CN 104073803A CN 201410123681 A CN201410123681 A CN 201410123681A CN 104073803 A CN104073803 A CN 104073803A
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- Prior art keywords
- acid
- copper
- etching agent
- etching
- metal level
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 217
- 239000010949 copper Substances 0.000 title claims abstract description 135
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 133
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 116
- 239000002184 metal Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 101
- -1 triazole compound Chemical class 0.000 claims abstract description 86
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims description 93
- 239000002253 acid Substances 0.000 claims description 57
- 150000003839 salts Chemical class 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 38
- 150000003851 azoles Chemical class 0.000 claims description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims description 25
- 150000004706 metal oxides Chemical class 0.000 claims description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 22
- 239000011707 mineral Substances 0.000 claims description 22
- 235000010755 mineral Nutrition 0.000 claims description 22
- 150000002978 peroxides Chemical class 0.000 claims description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 17
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- 239000012212 insulator Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 12
- 235000011164 potassium chloride Nutrition 0.000 claims description 12
- 159000000000 sodium salts Chemical class 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229960004643 cupric oxide Drugs 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010955 niobium Substances 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
- 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 9
- 239000004973 liquid crystal related substance Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- 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
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 150000003009 phosphonic acids Chemical class 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 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
- 229940120146 EDTMP Drugs 0.000 claims description 4
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-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
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 4
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004693 imidazolium salts Chemical class 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical class [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 claims description 3
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-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
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 241000545067 Venus Species 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 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
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229960003280 cupric chloride Drugs 0.000 claims description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 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
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical group [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 21
- 238000005452 bending Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 12
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- 238000004519 manufacturing process Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
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- 238000000206 photolithography Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002751 molybdenum Chemical class 0.000 description 3
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- TVNDPZYOQCCHTJ-UHFFFAOYSA-N 5-thiophen-2-yl-1h-pyrazole Chemical class C1=CSC(C=2NN=CC=2)=C1 TVNDPZYOQCCHTJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BVIAOQMSVZHOJM-UHFFFAOYSA-N N(6),N(6)-dimethyladenine Chemical compound CN(C)C1=NC=NC2=C1N=CN2 BVIAOQMSVZHOJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 230000004304 visual acuity Effects 0.000 description 2
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 1
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 1
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- ZPNWJGPRXXTUNI-UHFFFAOYSA-N 1-(1h-indol-2-yl)-2-phenylethanone Chemical class C=1C2=CC=CC=C2NC=1C(=O)CC1=CC=CC=C1 ZPNWJGPRXXTUNI-UHFFFAOYSA-N 0.000 description 1
- PWIXZDJDBSEIOY-UHFFFAOYSA-N 1-(benzotriazol-1-yl)propane-1,2-diol Chemical compound C1=CC=C2N(C(O)C(O)C)N=NC2=C1 PWIXZDJDBSEIOY-UHFFFAOYSA-N 0.000 description 1
- LRFHKHHUKGZIGE-UHFFFAOYSA-N 1-benzyl-2,5-dihydropyrrole Chemical compound C=1C=CC=CC=1CN1CC=CC1 LRFHKHHUKGZIGE-UHFFFAOYSA-N 0.000 description 1
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- ULIDRMKBVYYVIQ-UHFFFAOYSA-N 1-phenyltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC=C1 ULIDRMKBVYYVIQ-UHFFFAOYSA-N 0.000 description 1
- RLGAYEJPGHIHIB-UHFFFAOYSA-N 1h-indol-2-yl(phenyl)methanone Chemical class C=1C2=CC=CC=C2NC=1C(=O)C1=CC=CC=C1 RLGAYEJPGHIHIB-UHFFFAOYSA-N 0.000 description 1
- IYSPNYLFKSTATA-UHFFFAOYSA-N 1h-pyrazol-5-ylmethanamine Chemical class NCC=1C=CNN=1 IYSPNYLFKSTATA-UHFFFAOYSA-N 0.000 description 1
- CZHBXDSQJOQIHE-UHFFFAOYSA-N 2-(benzotriazol-1-yl)ethane-1,1-diol Chemical compound C1=CC=C2N(CC(O)O)N=NC2=C1 CZHBXDSQJOQIHE-UHFFFAOYSA-N 0.000 description 1
- JYBNOUMWGUMFBK-UHFFFAOYSA-N 2-(pyridine-3-carbonylamino)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1NC(=O)C1=CC=CN=C1 JYBNOUMWGUMFBK-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- DXFBKDSQMUFYLD-UHFFFAOYSA-N 2-pyrazol-1-ylethanol Chemical class OCCN1C=CC=N1 DXFBKDSQMUFYLD-UHFFFAOYSA-N 0.000 description 1
- YEALAJQPOVKTOH-UHFFFAOYSA-N 2-pyridin-4-ylacetamide Chemical compound NC(=O)CC1=CC=NC=C1 YEALAJQPOVKTOH-UHFFFAOYSA-N 0.000 description 1
- IDLHTECVNDEOIY-UHFFFAOYSA-N 2-pyridin-4-ylethanamine Chemical compound NCCC1=CC=NC=C1 IDLHTECVNDEOIY-UHFFFAOYSA-N 0.000 description 1
- GDMZHPUPLWQIBD-UHFFFAOYSA-N 2-pyrrol-1-ylaniline Chemical class NC1=CC=CC=C1N1C=CC=C1 GDMZHPUPLWQIBD-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical class C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- WVIXTJQLKOLKTQ-UHFFFAOYSA-N 3-(benzotriazol-1-yl)propane-1,2-diol Chemical compound C1=CC=C2N(CC(O)CO)N=NC2=C1 WVIXTJQLKOLKTQ-UHFFFAOYSA-N 0.000 description 1
- 150000002965 3-phenyl-1H-pyrazoles Chemical class 0.000 description 1
- JVQIKJMSUIMUDI-UHFFFAOYSA-N 3-pyrroline Chemical compound C1NCC=C1 JVQIKJMSUIMUDI-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 description 1
- XORHNJQEWQGXCN-UHFFFAOYSA-N 4-nitro-1h-pyrazole Chemical class [O-][N+](=O)C=1C=NNC=1 XORHNJQEWQGXCN-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 description 1
- QJTQKPNNQVLHHO-UHFFFAOYSA-N 9h-carbazole;1h-indole Chemical compound C1=CC=C2NC=CC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 QJTQKPNNQVLHHO-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- HYVABZIGRDEKCD-UHFFFAOYSA-N N(6)-dimethylallyladenine Chemical compound CC(C)=CCNC1=NC=NC2=C1N=CN2 HYVABZIGRDEKCD-UHFFFAOYSA-N 0.000 description 1
- YWNBTWJXAVFARK-UHFFFAOYSA-N N1C=CCC1.CC1=C(C(=O)O)C=CC=C1C(=O)O Chemical compound N1C=CCC1.CC1=C(C(=O)O)C=CC=C1C(=O)O YWNBTWJXAVFARK-UHFFFAOYSA-N 0.000 description 1
- CAMZCCDMGNIZTA-UHFFFAOYSA-O NC=1N=NN[N+]1C1=CC=CC2=CC=CC=C12 Chemical compound NC=1N=NN[N+]1C1=CC=CC2=CC=CC=C12 CAMZCCDMGNIZTA-UHFFFAOYSA-O 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004690 coupled electron pair approximation Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- SVEUVITYHIHZQE-UHFFFAOYSA-N n-methylpyridin-2-amine Chemical compound CNC1=CC=CC=N1 SVEUVITYHIHZQE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- NRTYMEPCRDJMPZ-UHFFFAOYSA-N pyridine;2,2,2-trifluoroacetic acid Chemical compound C1=CC=NC=C1.OC(=O)C(F)(F)F NRTYMEPCRDJMPZ-UHFFFAOYSA-N 0.000 description 1
- ZFCHNZDUMIOWFV-UHFFFAOYSA-N pyrimidine-2-carboxylic acid Chemical compound OC(=O)C1=NC=CC=N1 ZFCHNZDUMIOWFV-UHFFFAOYSA-N 0.000 description 1
- IIVUJUOJERNGQX-UHFFFAOYSA-N pyrimidine-5-carboxylic acid Chemical compound OC(=O)C1=CN=CN=C1 IIVUJUOJERNGQX-UHFFFAOYSA-N 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 229940074386 skatole Drugs 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to an etching composition for a copper-based metal layer and a method for preparing a metal line. The invention discloses an etching agent composition for the copper-based metal layer. The etching agent composition can represent an excellent cone angle profile. Furthermore the invention discloses a method of forming a wiring through the etching agent composition. The etching agent composition for the copper-based metal layer comprises the components of: 0.5-20% by weight of persulfate, 0.1-5% by weight of a triazole compound and the balance of water. Therefore the copper-based metal layer is selectively etched. An excellent straightness of the etched pattern is realized. Furthermore an improved cone angle profile is represented.
Description
Technical field
The present invention relates to a kind of etching agent composite for excellent cone angle profile of can presenting of the metal level based on copper, and relate to the method that uses this etching agent composite to form wiring.
Background technology
For example, the representative semiconductor devices that is provided with the low resistance wiring that contains copper can comprise liquid-crystal display (LCD) device.
The flat-panel monitor (FPD) that aforementioned LCD device is the film type of lightweight and can substitute the existing display unit such as cathode ray tube (CRT), aforementioned LCD device utilizes the optical isotropy character of liquid crystal to express image, and can effectively be used in notebook computer or the desk-top computer with excellent resolving power, color displays and picture quality.
The liquid crystal layer that liquid crystal indicator conventionally has colored filter substrate, array substrate and forms between colored filter substrate and array substrate.
The driving method that is mainly used in LCD device is active matrix (AM), and it drives amorphous silicon film transistor (a-Si TFT) liquid crystal of pixel portion as switch device.
In LCD device, be selected for metal line if there is the metal of low-resistivity and high erosion resistance, the material that forms the metal line (for example, gate line or data line) in order to interference signal can improve reliability and the price competitiveness of product.Aluminium (Al) or Al alloy have mainly been used as metal line material as described above.
But along with the size of LCD device increases, for SVGA, XGA, SXGA, VXGA etc., it is higher that resolving power becomes, reduce synchronous signal processing sweep time and greatly accelerated.Therefore, must use the metallic substance of low-resistivity to form metal line, to process these situations.
Therefore, proposed recently to replace existing metal line material with the copper with the resistivity more excellent than current material and electromigration characteristic.
Under afore-mentioned, cause more concern in the application of new low resistivity metal film for the etching agent composite of copper layer or the metal level based on copper.Although the different types of etching agent composite for the metal level based on copper of current use, but the required performance of user can't be satisfactory.
For example, the open No.2005-0067934 of Korean Patent discloses for the etching reagent of etch copper metal level and stacking transparent semiconductor layer, and described etching reagent comprises nitric acid, hydrochloric acid, hydrogen peroxide and azole compounds.But the problem that above-mentioned patent has is that the copper metal layer on upper strata and the indium oxide layer of lower floor are etched, and electric short circuit or wiring trouble can occur thus.
Summary of the invention
Therefore, the object of this invention is to provide the etching agent composite of a kind of cone angle profile that can form improvement and excellent planeness.
Another object of the present invention is to provide a kind of etching agent composite for the metal level based on copper, and it can not leave the residue of the metal level based on copper.
Another object of the present invention is to provide a kind of for using etching agent composite to form the method for wiring.
Above-mentioned purpose of the present invention realizes by following feature:
(1) for an etching agent composite for the metal level based on copper, comprising: persulphate, 0.1 azole compounds of % by weight to 5 % by weight and the water of surplus of 0.5 % by weight to 20 % by weight.
(2) basis (1) described etching agent composite above, wherein, described persulphate is to be selected from Potassium Persulphate (K
2s
2o
8), Sodium Persulfate (Na
2s
2o
8) and ammonium persulphate ((NH
4)
2s
2o
8) at least one.
(3) basis (1) described etching agent composite above, wherein, described azole compounds is at least one being selected from triazole compounds, amino tetrazole compound, imidazolium compounds, benzazolyl compounds, purine compound, pyrazole compound, pyridine compounds, pyrimidine compound, azole compounds, pyrrolidine compound and pyrrolinium compound.
(4) basis (1) described etching agent composite above, also comprises: organic (peroxide) acid or its salt of 1 % by weight to 5 % by weight.
(5) basis (4) described etching agent composite above, wherein, described organic (peroxide) acid is at least one being selected from Peracetic Acid, benzoyl hydroperoxide, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, oxyacetic acid, propanedioic acid, valeric acid and oxalic acid.
(6), according to the etching agent composite above (4) described, wherein, the salt of described organic (peroxide) acid is at least one in the sodium salt of the sylvite that is selected from organic (peroxide) acid, organic (peroxide) acid and the ammonium salt of organic (peroxide) acid.
(7), according to the etching agent composite above (1) described, also comprise the phosphonate compound of 3 % by weight to 15 % by weight.
(8) basis (7) described etching agent composite above, wherein, described phosphonate compound is to be selected from phosphoric acid, 2-amino-ethyl phosphonic acids, dimethyl methyl phosphonate, 1-hydroxy ethylene-1, 1-di 2 ethylhexyl phosphonic acid, amino three (methylene phosphonic acids), EDTMP, tetramethylene-diamine four (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), phosphonic acids butane-tricarboxylic acid, N-((phosphonomethyl)) iminodiethanoic acid, 2-propyloic phosphonic acids, at least one in 2-hydroxy phosphinylidyne yl carboxylic acid and amino-tri--(methylene phosphonic acid).
(9) basis (7) described etching agent composite above, wherein, described phosphonate compound is at least one in sylvite, the sodium salt of phosphonate compound and the ammonium salt of phosphonate compound that is selected from phosphonate compound.
(10) basis (1) described etching agent composite above, also comprises: the mineral acid of 0.5 % by weight to 3 % by weight or its salt (wherein, except persulphate).
(11) basis (10) described etching agent composite above, wherein, described mineral acid is at least one being selected from nitric acid, sulfuric acid, phosphoric acid, boric acid and perchloric acid.
(12) basis (10) described etching agent composite above, wherein, the salt of described mineral acid is at least one (wherein, except the persulphate) in sylvite, the sodium salt of mineral acid and the ammonium salt of mineral acid that is selected from mineral acid.
(13), according to the etching agent composite above (1) described, also comprise sulfonic acid or its salt of 0.5 % by weight to 5 % by weight.
(14) basis (13) described etching agent composite above, wherein, described sulfonic acid is at least one being selected from thionamic acid, methylsulphonic acid, ethylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, thionamic acid and polystyrolsulfon acid.
(15) basis (13) described etching agent composite above, wherein, the salt of described sulfonic acid is at least one being selected from sylvite, sodium salt and ammonium salt.
(16), according to the etching agent composite above (1) described, also comprise the mantoquita (wherein, except the persulphate of copper) of 0.5 % by weight to 3 % by weight.
(17) basis (16) described etching agent composite above, wherein, described mantoquita is at least one being selected from copper sulfate, cupric nitrate, cupric chloride, venus crystals and cupric fluoride.
(18) basis (1) described etching agent composite above, wherein, forms the described metal level based on copper, and the described metal level based on copper comprises: be selected from least one in copper, copper nitride and cupric oxide; Or comprise at least one and the alloy that is selected from least one metal in aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) of being selected from copper, copper nitride and cupric oxide.
(19) basis (18) described etching agent composite above, wherein, the described metal level based on copper comprises: copper molybdenum layer, the metal level based on copper that it has molybdenum layer and forms on this molybdenum layer; Or copper molybdenum alloy layer, the metal level based on copper that it has molybdenum alloy layer and forms on this molybdenum alloy layer.
(20) be used to form the method for wiring, comprise:
(S1) on substrate, form metal oxide layer;
(S2) on described metal oxide layer, form the metal level based on copper;
(S3) on the described metal level based on copper, form photoetching agent pattern alternatively; With
(S4) by using according to the etching agent composite described in any one in above-mentioned (1) to (19), the only described metal level based on copper on metal oxide layer described in etching.
(21) method according to above (20), wherein, forms described metal oxide layer, and described metal oxide layer comprises: pass through A
xb
yc
zwherein, A, B and C are respectively the metals being selected from zinc (Zn), titanium (Ti), cadmium (Cd), gallium (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum (Ta) to O(; X, y and z all represent metal ratio and are 0 or are greater than 0 integer or prime number) the three-component system oxide compound or the four component system oxide compounds that represent.
(22) basis (20) described method above, wherein, forms the described metal level based on copper, and the described metal level based on copper comprises: be selected from least one in copper, copper nitride and cupric oxide; Or comprise at least one and the alloy that is selected from least one metal in aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) of being selected from copper, copper nitride and cupric oxide.
(23) method according to above (22), wherein, the described metal level based on copper comprises: copper molybdenum layer, the metal level based on copper that it has molybdenum layer and forms on this molybdenum layer; Or copper molybdenum alloy layer, the metal level based on copper that it has molybdenum alloy layer and forms on this molybdenum alloy layer.
(24) manufacture, for a method for the array substrate of liquid crystal indicator, comprising:
A) on substrate, form grid wiring;
B) on the substrate that comprises described grid wiring, form gate insulator;
C) on described gate insulator, form semiconductor layer;
D) on described semiconductor layer, form source wiring and drain electrode wiring; With
E) form the pixel electrode that is connected to described drain electrode wiring,
Wherein, described a) step comprises: on described substrate, form the metal level based on copper, and use according to the metal level based on copper described in the etching agent composite etching described in any one in above-mentioned (1) to (19) to form described grid wiring.
(25) manufacture, for a method for the array substrate of liquid crystal indicator, comprising:
A) on substrate, form grid wiring;
B) on the substrate that comprises described grid wiring, form gate insulator;
C) on described gate insulator, form semiconductor layer;
D) on described semiconductor layer, form source wiring and drain electrode wiring; With
E) form the pixel electrode that is connected to described drain electrode wiring,
Wherein said d) step comprises: on described semiconductor layer, form the metal level based on copper, and use according to the metal level based on copper described in the etching agent composite etching described in any one in above-mentioned (1) to (19) to form described source wiring and drain electrode wiring.
The selectively metal level of etching based on copper and without the oxide skin of etching lower floor of etching agent composite of the present invention.
In addition, etching agent composite of the present invention can have excellent etched pattern planeness, present the cone angle profile of improvement and there is the beneficial effect that prevents the residue that forms metal level based on copper, therefore the excellent effect preventing such as electric short circuit, wiring trouble, brightness reduction etc. is provided.
Adopt wet etch process instead of adopt dry etching method according to the method for formation wiring of the present invention, therefore, it does not need expensive equipment, has thus economic advantages.
Embodiment
The invention discloses a kind of etching agent composite for the metal level based on copper, it comprises: persulphate, 0.1 azole compounds of % by weight to 5 % by weight and the water of surplus of 0.5 % by weight to 20 % by weight, the metal level of etching based on copper optionally thus, there is the planeness of excellent etched pattern, and present the cone angle profile of improvement.
Below will specifically describe the present invention.
Etching agent composite of the present invention comprises the water of persulphate, azole compounds and surplus, and this etching agent composite is the composition of the metal level based on copper for etching.
Metal level based on copper according to the present invention be as raw-material film to form metal line so that transmission electronic signal, and can be called the metal level of cupric.The metal level based on copper that can apply etching agent composite of the present invention can be the design that comprises unitary film or multilayer film, and is not particularly limited, as long as above-mentioned layer can be consistent with above-mentioned design.For example, aforementioned layers can refer to formed metal level, and this metal level comprises: be selected from least one in copper, copper nitride and cupric oxide; Or any one comprises and is selected from least one metal in aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) and is selected from least one the alloy in copper, copper nitride and cupric oxide, but is not limited to this.
In addition, the metal level based on copper can be the design that comprises unitary film and multilayer (for example, bilayer) film.The aforementioned metal level based on copper can be the film of single or multiple lift (for example, copper molybdenum layer or copper molybdenum alloy layer).Copper molybdenum layer refers to the metal level based on copper that comprises molybdenum layer and form on this molybdenum layer, and copper molybdenum alloy layer refers to the metal level based on copper that comprises molybdenum alloy layer and form on this molybdenum alloy layer.Molybdenum alloy can comprise molybdenum and the alloy that is selected from least one metal in Ti, Ta, Cr, Ni, Nd and In.
The persulphate comprising in etching agent composite of the present invention is the main component of the metal level of etching based on copper.With respect to the gross weight of composition, the weight percent content of the persulphate that can comprise is 0.5% to 20%, preferably 1% to 15%.If the content of persulphate is less than 0.5 % by weight, etching speed reduces, thereby cause insufficient etching of the metal level based on copper, and in the time that the content of persulphate exceedes 20 % by weight, total etching speed becomes suitable height and makes because the over etching of the metal level based on copper causes etching degree and controls the difficulty on etch process.
Operable persulphate is not particularly limited in the present invention, and can comprise, for example, and Potassium Persulphate (K
2s
2o
8), Sodium Persulfate (Na
2s
2o
8), ammonium persulphate ((NH
4)
2s
2o
8), these materials can use separately or with two kinds or more than two kinds be used in combination.
The effect that the azole compounds comprising in etching agent composite of the present invention can play is: the CD(critical size of controlling etching speed and minimizing pattern) loss, increase thus process margin.With respect to the gross weight of composition, the content range of azole compounds can be from 0.1 % by weight to 5 % by weight, preferably from 0.5 % by weight to 2 % by weight.If the content of azole compounds is less than 0.1 % by weight, can there is too large CD loss; And in the time that the content of azole compounds exceedes 5 % by weight, it is too low that the etching speed of the metal level based on copper becomes, thereby greatly extend process period.
Azole compounds is not particularly limited, as long as it can be included in arbitrary conventional azole compounds used in correlation technique.For example, azole compounds preferably has 1 azole compounds to 30 carbon atoms.More specifically, triazole compounds, amino tetrazole compound, imidazolium compounds, benzazolyl compounds, purine compound, pyrazole compound, pyridine compounds, pyrimidine compound, azole compounds, pyrrolidine compound and pyrrolinium compound can use separately or with two kinds or more than two kinds be used in combination.
For example, triazole compounds can comprise the compound representing by following formula 1, and it can use separately or with two kinds or more than two kinds be used in combination.
[formula 1]
(wherein, R
1and R
2be respectively hydrogen atom; Carboxyl; Amino; Hydroxyl; Cyano group; Formyl radical; Or sulfonic group; Or there is 1 alkyl to 20 carbon atoms or alkylsulfonyl, described in there is 1 alkyl to 20 carbon atoms or alkylsulfonyl is not substituted or is replaced by carboxyl, amino, hydroxyl, cyano group, formyl radical or sulfonic group, and R
1and R
2can comprise ester group, and
Q is hydrogen atom; Hydroxyl; The substituting group representing by following formula 2; Or there is 1 alkyl to 10 carbon atoms or alkoxyl group, described in there is 1 alkyl to 10 carbon atoms or alkoxyl group is not substituted or had 6 aryl to 20 carbon atoms or hydroxyl replaces; And Q can comprise at least one in amino or ester group).
[formula 2]
(wherein R
3to there is 1 alkylidene group to 6 carbon atoms, and R
4and R
5it is respectively hydrogen atom; Hydroxyl; Or have 1 alkyl to 10 carbon atoms, hydroxyalkyl or alkoxyalkyl, it is not substituted or is replaced by hydroxyl).
The compound that through type 1 represents can comprise 1, 2, 3-benzotriazole, 5-Methylbenzotriazole, benzotriazole, 1-(2, 2-dihydroxy ethyl) benzotriazole, I-hydroxybenzotriazole, 1-methoxyl group benzo triazole, 1-(1, 2-dihydroxypropyl) benzotriazole, 1-(2, 3-dihydroxypropyl) benzotriazole, N, N-pair-(2-ethylhexyl)-arylmethyl-1H-benzotriazole-1-methylamine, 2, 2'-{[(4-methyl isophthalic acid H-benzotriazole-1-yl) methyl] imino-} di-alcohol, 2, 2'-{[(5-methyl isophthalic acid H-benzotriazole-1-yl) methyl] imino-} di-alcohol, 5-carboxyl benzotriazole butyl ester, 5-carboxyl benzotriazole monooctyl ester, 5-carboxyl benzotriazole dodecyl ester etc.
Except the compound that through type 1 represents, etching agent composite of the present invention also can be included in the triazole compounds of the arbitrary routine using in correlation technique.For example, triazole compounds can comprise 1,2,3-triazoles, 1,2,4-triazole, tolyl-triazole, 4-amino-1,2,4-triazole etc., and these triazole compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, imidazolium compounds can comprise: glyoxal ethyline, 2-ethyl imidazol(e), 2-propyl imidazole, 2-aminooimidazole, 4-methylimidazole, 4-ethyl imidazol(e), 4-propyl imidazole etc., these imidazolium compoundss are used alone or with two kinds or more than two kinds be used in combination.
For example, amino tetrazole compound can comprise: amino tetrazole, 5-amino-1-phenyltetrazole, 5-amino-1-(1-naphthyl) tetrazolium, 1-methyl-5-amino tetrazole, 1,5-diamino tetrazoliums etc., preferably use amino tetrazole.
For example, benzazolyl compounds can comprise: aminoalkyl indole, benzoyl indoles, skatole, phenylacetyl indoles, indole carbazole, these benzazolyl compounds use separately or with two kinds or more than two kinds be used in combination.
For example, purine compound can comprise: 6-dimethylaminopurine, 2, the chloro-7-methyl-7H-of 6-bis-purine, 6-(γ, γ-dimethyl-allyl amino) purine, the chloro-9H-purine-9-of 2-amino-6-acetic acid etc., these materials are used alone or with two kinds or more than two kinds be used in combination.
For example, pyrazole compound can comprise: 3-phenyl-1H-pyrazoles, 3-(amino methyl) pyrazoles, 5-(2-thienyl) pyrazoles, 1-(2-hydroxyethyl)-pyrazoles, 3-(2-thienyl) pyrazoles, 5-methyl isophthalic acid H-pyrazoles, 4-nitro-1H-pyrazoles, 1H-pyrazoles-5-boric acid etc., these pyrazole compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, pyridine compounds can comprise: 4-(amino-ethyl) pyridine, 2-(methylamino) pyridine, pyridine trifluoro-acetate, pyridine-4-ethanamide, 2-[(pyridine-3-carbonyl)-amino]-phenylformic acid etc., these pyridine compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, pyrimidine compound can comprise: pyrimidine-5-carboxylic acid, pyrimidine-2-carboxylic acid etc., these pyrimidine compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, azole compounds can comprise: pyrroles-2-carboxylic acid, pyrroles-3-carboxylic acid, 1-(2-aminophenyl) pyrroles, 1H-pyrroles-1-propionic acid etc., these azole compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, pyrrolidine compound can comprise: 1-(2-amino-ethyl) tetramethyleneimine, tetramethyleneimine-3-carboxylic acid, tetramethyleneimine-3-carboxylic acid hydrochloride, tetramethyleneimine-1,2-dicarboxylic acid 1-phenyl esters etc., these pyrrolidine compounds are used alone or with two kinds or more than two kinds be used in combination.
For example, pyrrolinium compound can comprise: 3-pyrroline, 2-methyl isophthalic acid-pyrroline, 1-benzyl-3-pyrroline etc., these pyrrolinium compounds are used alone or with two kinds or more than two kinds be used in combination.
Alternatively, etching agent composite of the present invention also can comprise organic (peroxide) acid or its salt.
The pH value that organic (peroxide) acid or its salt can be controlled etching reagent, to increase the activity of persulphate, is controlled the etching speed of the metal level based on copper thus, and for suppressing the degraded of persulphate, and the oxygenizement of the metal level of performance assisted etch based on copper.In the present invention, organic (peroxide) acid refers to organic acid, organic peroxide acid or its combination.
With respect to the gross weight of composition, the amount that organic (peroxide) acid or its salt can be included is 1 % by weight to 5 % by weight, preferably 1 % by weight to 3 % by weight.If the content of organic (peroxide) acid or its salt is less than 1 % by weight, in the metal level based on copper, can there is not etched part; And in the time that the content of organic (peroxide) acid or its salt exceedes 5 % by weight, thereby etching speed becomes the very high difficulty causing in technology controlling and process.
The concrete example of organic (peroxide) acid can comprise at least one being selected from Peracetic Acid, benzoyl hydroperoxide, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, oxyacetic acid, propanedioic acid, valeric acid and oxalic acid.The salt of organic (peroxide) acid is selected from least one in sylvite, sodium salt and ammonium salt.
Alternatively, etching agent composite of the present invention also can comprise phosphonate compound.
Phosphonate compound can be combined into inner complex to control the activity of cupric ion with the cupric ion being eluted in etching reagent during etched copper, suppresses thus the degraded of persulphate.Owing to having reduced the activity of cupric ion, therefore this technique can stably be carried out during using etching reagent.With respect to the gross weight of composition, the amount that phosphonate compound can be included is 3 % by weight to 15 % by weight, preferably 5 % by weight to 10 % by weight.If the content of phosphonate compound is less than 3 % by weight, the degraded of etched homogeneity reduction and persulphate is accelerated, and has reduced thus working ability; And in the time that the content of phosphonate compound exceedes 15 % by weight, thereby total etching speed becomes the very high difficulty causing in technology controlling and process, and the viscosity of etching reagent increases.
Phosphonate compound comprises phosphonic acid ester, phosphate derivatives and its salt.The concrete example of phosphonate compound can comprise and is selected from phosphoric acid, 2-amino-ethyl phosphonic acids (2-AEP), dimethyl methyl phosphonate (DMMP), 1-hydroxy ethylene-1, 1-di 2 ethylhexyl phosphonic acid (HEDP), amino three (methylene phosphonic acids) (ATMP), EDTMP (EDTMP), tetramethylene-diamine four (methylene phosphonic acid) (TDTMP), hexamethylene-diamine four (methylene phosphonic acid) (HDTMP), diethylene triamine penta(methylene phosphonic acid) (DTPMP), phosphonic acids butane-tricarboxylic acid (PBTC), N-((phosphonomethyl)) iminodiethanoic acid (PMIDA), 2-propyloic phosphonic acids (CEPA), 2-hydroxy phosphinylidyne yl carboxylic acid (HPAA) and amino-tri--(methylene phosphonic acid) are (AMP), or at least one in its salt.
The salt of phosphonate compound can comprise at least one in sylvite, the sodium salt of phosphonate compound and the ammonium salt of phosphonate compound that is selected from phosphonate compound.
Alternatively, etching agent composite of the present invention also can comprise mineral acid or its salt (wherein, except persulphate).
The pH value that mineral acid or its salt (wherein, persulphate except) can be controlled etching reagent, to increase the activity of persulphate, is controlled the etching speed of the metal level based on copper thus, and for increasing the cone angle of etched surfaces.With respect to the gross weight of composition, the amount that mineral acid or its salt can be included is 0.5 % by weight to 3.0 % by weight, preferably 1.0 % by weight to 2.0 % by weight.If the content of mineral acid or its salt is less than 0.5 % by weight, etching speed reduces, and in the time that the content of mineral acid or its salt exceedes 3.0 % by weight, thereby etching speed causes over etching problem and the damage to photoresist material very soon.
The concrete example of mineral acid or its salt can comprise at least one being selected from nitric acid, sulfuric acid, phosphoric acid, boric acid and perchloric acid.Aspect this, because hydrochloric acid can damage the metal level based on copper and the metal oxide layer in some situation described below, therefore mineral acid or its salt cannot comprise hydrochloric acid.The salt of mineral acid can comprise at least one being selected from sylvite, sodium salt and ammonium salt, still, and except persulphate.
Alternatively, etching agent composite of the present invention also can comprise sulfonic acid or its salt.
Sulfonic acid or its salt in the aqueous solution by dissociation (RSO
3h →-RSO
3 -+ H
+) to present sour performance.The acidity ratio of sulfonic acid is much better than such as the carboxylic acid of acetic acid, and is substantially similar to sulfuric acid.Sulfonic acid in etching agent composite of the present invention can be controlled the pH value of etching reagent to increase the activity of persulphate, controls thus the etching speed of the metal level based on copper, and for suppressing the degraded of persulphate and the cone angle of reduction etched surfaces.In the present invention, sulfonic acid all refers to have-SO
3the compound of H, and comprise inorganic sulfonic acid and organic sulfonic acid.
With respect to the gross weight of composition, the amount that sulfonic acid or its salt can be included is 0.5 % by weight to 5 % by weight, preferably 1 % by weight to 3 % by weight.If the content of sulfonic acid or its salt is less than 0.5 % by weight, etching speed reduces, and in the time that the content of sulfonic acid or its salt exceedes 5 % by weight, thereby etching speed causes the difficulty in technology controlling and process very soon.
The concrete example of sulfonic acid can comprise at least one being selected from thionamic acid, methylsulphonic acid, ethylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, thionamic acid and polystyrolsulfon acid.The salt of sulfonic acid can comprise at least one being selected from sylvite, sodium salt and ammonium salt.
Alternatively, etching agent composite of the present invention also can comprise mantoquita (wherein, except the persulphate of copper).
Mantoquita can be controlled the pH value of etching reagent to increase the activity of persulphate, and the etching speed of controlling thus the metal level based on copper changes (deflection) to control CD, and for suppressing the degraded of persulphate and the cone angle of reduction etched surfaces.
With respect to the gross weight of composition, the amount that mantoquita can be included is 0.5 % by weight to 3 % by weight, preferred 1 % by weight to 2 % by weight.If the content of mantoquita is less than 0.5 % by weight, the CD that pending many sheet materials can seriously occur changes (deflection), and in the time that the content of mantoquita exceedes 3 % by weight, thereby the oxidation susceptibility of primary oxidant is lowered the quantity reduction that causes pending sheet material.
The concrete example of mantoquita can comprise at least one being selected from copper sulfate, cupric nitrate, cupric chloride, venus crystals and cupric fluoride.
In etching agent composite of the present invention, can also comprise the water of the surplus except the content of aforementioned composition of the composition that amounts to 100 % by weight.Water used is not particularly limited in the present invention, but preferred deionized water.In addition, more preferably using resistivity value is 18M Ω cm or the deionized water that is greater than 18M Ω cm.The degree of ion is removed in resistivity value instruction from water.
Alternatively, etching agent composite of the present invention also can comprise tensio-active agent.Tensio-active agent can play and reduce surface tension to increase the effect of etching uniformity coefficient.Tensio-active agent is not particularly limited, as long as it can have resistibility and compatible with etching agent composite of the present invention to etching agent composite of the present invention, but, for example, preferably include, be selected from least one or two kinds or more kinds of in anion surfactant, cats product, amphoterics, nonionogenic tenside and EPE polyol EPE.
Except aforementioned composition, etching agent composite of the present invention also can comprise the additive of arbitrary routine.For example, this additive can be metal ion chelation agent, corrosion inhibitor etc.
Aforementioned etching agent composite of the present invention can be pressed into the block metal level based on copper and metal oxide layer by etch layer, and forms the tapered profiles with excellent planeness, is therefore effectively used in the formation of wiring.
Be used to form according to the method for wiring of the present invention embodiment and can comprise: (S1) on substrate, form metal oxide layer; (S2) on described metal oxide layer, form the metal level based on copper; (S3) on the described metal level based on copper, form photoetching agent pattern alternatively; (S4) by using according to aforementioned etching agent composite of the present invention, be only etched in the described metal level based on copper on described metal oxide layer.
According to the method being used to form according to wiring of the present invention, use conventional photoresist material, can form photoetching agent pattern by exposure and the developing process of arbitrary routine.
According to the method that is used to form wiring of the present invention, metal oxide layer is the film that can form oxide semiconductor layer, and can be arbitrary common metal oxide skin used in correlation technique.For example, metal oxide layer can comprise: adopt A
xb
yc
zwherein, A, B and C are respectively the metals being selected from zinc (Zn), titanium (Ti), cadmium (Cd), gallium (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum (Ta) to O(independently; X, y and z all refer to metal ratio and are 0 or are greater than 0 integer or prime number) the three-component system oxide compound or the four component system oxide compounds that represent.
Be used to form according to the method for wiring of the present invention and can be applied to the array substrate of manufacturing LCD device.Hereinafter by the method specifically describing for the manufacture of the array substrate of LCD device according to the present invention.
First, on substrate, form grid wiring.The effect that grid wiring can play is, according to the electrical signal being transmitted by grid lead, to be controlled at the electric current between source/drain.The material of grid wiring can comprise the aforementioned metal level based on copper, therefore, by using according to etching agent composite of the present invention, can form the metal level based on copper with required pattern.
Then, on grid wiring, form gate insulator.The effect that gate insulator can play is: the active layer at grid wiring and top is separated, to prevent that the electric current that flows into active layer from flowing into grid wiring.
Form as follows gate insulator.For example, plasma activated chemical vapour deposition (CVD) method is used to be formed uniformly gate insulator on the substrate that comprises grid wiring.Use by being selected from silicon-dioxide (SiO
2), at least one insulating material of making in silicon nitride (SiNx) and silicon oxynitride (SiONx) etc., can form gate insulator.
Then, on gate insulator, form semiconductor layer.Semiconductor layer becomes according to the path of the electric current of the electrical signal from grid wiring.Use aforementioned metal oxide material (A
xb
yc
zo), can on gate insulator, be formed uniformly active layer by plasma CVD method.
After this, on semiconductor layer, form source wiring and drain electrode wiring.Source wiring and drain electrode wiring can be used for electrical signal to be transformed into pixel.The material of source/drain wiring used can comprise the aforementioned metal level based on copper in this article, therefore, by using according to etching agent composite of the present invention, can form source/drain wiring with required pattern.
Then, form the pixel electrode that is connected to drain electrode wiring.
According to preceding method, can manufacture the array substrate for LCD device.
Hereinafter, describe preferred embodiment in connection with embodiment, more clearly to understand the present invention.But, it will be appreciated by those skilled in the art that, such embodiment is provided for illustrative object, can make multiple modification and variation and not depart from the scope of the present invention and spirit, such modification and variation are suitably included in the present invention who limits by appending claims.
Embodiment
1-1. embodiment 1 to embodiment 5 and comparing embodiment 1 are to comparing embodiment 4
According to the component of enumerating in following table 1, to comparing embodiment 4, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 1 to embodiment 5 and comparing embodiment 1.
[table 1]
1-2. EXPERIMENTAL EXAMPLE 2
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 1 to embodiment 5 and comparing embodiment 1 to every kind of prepared composition in comparing embodiment 4, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the temperature of approximately 30 DEG C at during etching etching agent composite.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(scanning electronic microscope, by the manufacturing of Hitachi company, model name: S-4700) detect, and detected result is as shown in table 2 below.
< evaluates the standard > of etching outline
Zero: 35 °≤cone angle≤60 °
△: cone angle <35 ° or cone angle >60 °
Х: undercutting or back taper
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 2]
As shown in table 2, the etching agent composite in embodiment 1 to 5 all presents favourable etch features.
But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 1(comparing embodiment 1 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 2(comparing embodiment 2), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 3(comparing embodiment 3), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 4(comparing embodiment 4), the etching of copper layer is impossible.
2-1. embodiment 6 to embodiment 11 and comparing embodiment 5 are to comparing embodiment 10
According to the component of enumerating in following table 3, to comparing embodiment 10, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 6 to embodiment 11 and comparing embodiment 5.
[table 3]
2-2. EXPERIMENTAL EXAMPLE 2
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 6 to embodiment 11 and comparing embodiment 5 to every kind of prepared composition in comparing embodiment 10, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the etching agent composite of during etching at the temperature of approximately 30 DEG C.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(by the manufacturing of Hitachi company, model name: S-4700) detect, detected result is as shown in table 4 below.
< evaluates the standard > of etching outline
60 ° of zero: 35 °≤cone angle <
△: 35 ° of 30 °≤cone angle <; Or 60 °≤cone angle≤65 °
Х: cone angle≤30 ° or cone angle >65 °
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 4]
As shown in table 4, the etching agent composite in embodiment 6 to embodiment 11 all presents favourable etch features.
But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 5(comparing embodiment 5 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 6(comparing embodiment 6), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 7(comparing embodiment 7), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 8(comparing embodiment 8), the etching of copper layer is impossible.In addition, there is a large amount of organic (peroxide) acid or its salt in comparing embodiment 9(comparing embodiment 9), confirm over etching situation, and there is a small amount of organic (peroxide) acid or its salt in comparing embodiment 10(comparing embodiment 10), etching speed is low and etching outline is poor.
3-1. embodiment 12 to embodiment 17 and comparing embodiment 11 are to comparing embodiment 16
According to the component of listing in following table 5, to comparing embodiment 16, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 12 to embodiment 17 and comparing embodiment 11.
[table 5]
3-2. EXPERIMENTAL EXAMPLE 3
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 12 to embodiment 17 and comparing embodiment 11 to every kind of prepared composition in comparing embodiment 16, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the etching agent composite of during etching at the temperature of approximately 30 DEG C.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(by the manufacturing of Hitachi company, model name: S-4700) detect, detected result is as shown in table 6 below.
< evaluates the standard > of etching outline
60 ° of zero: 35 °≤cone angle <
△: 35 ° of 30 °≤cone angle <; Or 60 °≤cone angle≤65 °
Х: cone angle≤30 ° or cone angle >65 °
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 6]
As shown in table 6, the etching agent composite in embodiment 12 to embodiment 17 all presents favourable etch features.
But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 11(comparing embodiment 11 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 12(comparing embodiment 12), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 13(comparing embodiment 13), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 14(comparing embodiment 14), the etching of copper layer is impossible.In addition, there is a small amount of phosphonate compound in comparing embodiment 15(comparing embodiment 15), etching speed is low and etching outline is poor; And there is a large amount of phosphonate compounds in comparing embodiment 16(comparing embodiment 16), confirm to occur over etching situation.
4-1. embodiment 18 to embodiment 23 and comparing embodiment 17 are to comparing embodiment 22
According to the component of listing in following table 7, to comparing embodiment 22, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 18 to embodiment 23 and comparing embodiment 17.
[table 7]
4-2. EXPERIMENTAL EXAMPLE 4
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 18 to embodiment 23 and comparing embodiment 17 to every kind of prepared composition in comparing embodiment 22, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the etching agent composite of during etching at the temperature of approximately 30 DEG C.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(by the manufacturing of Hitachi company, model name: S-4700) detect, and detected result is as shown in table 8 below.
< evaluates the standard > of etching outline
Zero: 35 °≤cone angle≤60 °
△: cone angle <35 ° or cone angle >60 °
Х: undercutting or back taper
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 8]
As shown in table 8, the etching agent composite in embodiment 18 to 23 all presents favourable etch features.But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 17(comparing embodiment 17 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 18(comparing embodiment 18), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 19(comparing embodiment 19), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 20(comparing embodiment 20), the etching of copper layer is impossible.In addition, there is a small amount of mineral acid or its salt in comparing embodiment 21(comparing embodiment 21), etching outline and planeness are poor; And there is a large amount of mineral acids or its salt in comparing embodiment 22(comparing embodiment 22), because Cu pattern degree of lacking appears in photoresist material (PR) rise phenomenon.
5-1. embodiment 24 to embodiment 29 and comparing embodiment 23 are to comparing embodiment 28
According to the component of listing in following table 9, to comparing embodiment 28, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 24 to embodiment 29 and comparing embodiment 23.
[table 9]
5-2. EXPERIMENTAL EXAMPLE 5
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 24 to embodiment 29 and comparing embodiment 23 to every kind of prepared composition in comparing embodiment 28, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the temperature of approximately 30 DEG C at during etching etching agent composite.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(by the manufacturing of Hitachi company, model name: S-4700) detect, and detected result is as shown in table 10 below.
< evaluates the standard > of etching outline
60 ° of zero: 35 °≤cone angle <
△: 35 ° of 30 °≤cone angle <; Or 60 °≤cone angle≤65 °
Х: cone angle≤30 ° or cone angle >65 °
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 10]
As shown in table 10, the etching agent composite in embodiment 24 to embodiment 29 all presents favourable etch features.
But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 23(comparing embodiment 23 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 24(comparing embodiment 24), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 25(comparing embodiment 25), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 26(comparing embodiment 26), the etching of copper layer is impossible.In addition, there is a large amount of sulfonic acid or its salt in comparing embodiment 27(comparing embodiment 27), over etching situation be there is; And there is a small amount of sulfonic acid or its salt in comparing embodiment 28(comparing embodiment 28), etching speed is low and etching outline is poor.
6-1. embodiment 30 to embodiment 35 and comparing embodiment 29 are to comparing embodiment 34
According to the component of listing in following table 11, to comparing embodiment 34, prepare etching agent composite (unit: with respect to the weight percent of total weight percent 100%) at embodiment 30 to embodiment 35 and comparing embodiment 29.
[table 11]
6-2. EXPERIMENTAL EXAMPLE 6
After metal oxide materials (ITO) being deposited on glass substrate (100mm × 100mm) and copper being deposited upon on above-mentioned layer, by photolithography, the photoresist material with required pattern is formed on substrate.Then, use respectively in embodiment 30 to embodiment 35 and comparing embodiment 29 to every kind of prepared composition in comparing embodiment 34, the metal level based on copper is carried out to etch process.
Use the equipment (model name: ETCHER(TFT) of injection etching pattern, SEMES company), and be maintained at the temperature of approximately 30 DEG C at during etching etching agent composite.But, if needed, can, according to other processing condition and other factors, suitably change temperature.Etching is carried out approximately 100 seconds conventionally, and this time can change according to etch temperature.During etch process the profile of the etched metal level based on copper adopt section S EM(by the manufacturing of Hitachi company, model name: S-4700) detect, and detected result is as shown in table 12 below.
< evaluates the standard > of etching outline
Zero: 35 °≤cone angle≤60 °
△: cone angle <35 ° or cone angle >60 °
Х: undercutting or back taper
Unetched: not etching
< is for evaluating the standard > of etching planeness
Zero: straight pattern
△: 20% or be less than 20% bending pattern
Х: exceed 20% bending pattern
Unetched: not etching
[table 12]
As shown in table 12, the etching agent composite in embodiment 30 to embodiment 35 all presents favourable etch features.
But, the content concn of the persulphate that the content concn of the persulphate having in comparing embodiment 29(comparing embodiment 29 has lower than the present invention), the etching of copper layer is impossible; There is a large amount of persulphates in comparing embodiment 30(comparing embodiment 30), confirm to occur over etching situation.In addition, there is a small amount of azole compounds in comparing embodiment 31(comparing embodiment 31), confirm to occur over etching situation.In addition, there is a large amount of azole compounds in comparing embodiment 32(comparing embodiment 32), the etching of copper layer is impossible.In addition, there is a large amount of mantoquitas in comparing embodiment 33(comparing embodiment 33), etching outline and planeness variation; And there is a small amount of mantoquita in comparing embodiment 34(comparing embodiment 34), because etching outline and planeness variation also appear in low etching speed.
Claims (25)
1. for an etching agent composite for the metal level based on copper, comprising: persulphate, 0.1 azole compounds of % by weight to 5 % by weight and the water of surplus of 0.5 % by weight to 20 % by weight.
2. etching agent composite according to claim 1, wherein, described persulphate is to be selected from Potassium Persulphate (K
2s
2o
8), Sodium Persulfate (Na
2s
2o
8) and ammonium persulphate ((NH
4)
2s
2o
8) at least one.
3. etching agent composite according to claim 1, wherein, described azole compounds is at least one being selected from triazole compounds, amino tetrazole compound, imidazolium compounds, benzazolyl compounds, purine compound, pyrazole compound, pyridine compounds, pyrimidine compound, azole compounds, pyrrolidine compound and pyrrolinium compound.
4. etching agent composite according to claim 1, also comprises: organic (peroxide) acid or its salt of 1 % by weight to 5 % by weight.
5. etching agent composite according to claim 4, wherein, described organic (peroxide) acid is at least one being selected from Peracetic Acid, benzoyl hydroperoxide, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, oxyacetic acid, propanedioic acid, valeric acid and oxalic acid.
6. etching agent composite according to claim 4, wherein, the salt of described organic (peroxide) acid is at least one in the sodium salt of the sylvite that is selected from organic (peroxide) acid, organic (peroxide) acid and the ammonium salt of organic (peroxide) acid.
7. etching agent composite according to claim 1, also comprises the phosphonate compound of 3 % by weight to 15 % by weight.
8. etching agent composite according to claim 7, wherein, described phosphonate compound is to be selected from phosphoric acid, 2-amino-ethyl phosphonic acids, dimethyl methyl phosphonate, 1-hydroxy ethylene-1, 1-di 2 ethylhexyl phosphonic acid, amino three (methylene phosphonic acids), EDTMP, tetramethylene-diamine four (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), phosphonic acids butane-tricarboxylic acid, N-((phosphonomethyl)) iminodiethanoic acid, 2-propyloic phosphonic acids, at least one in 2-hydroxy phosphinylidyne yl carboxylic acid and amino-tri--(methylene phosphonic acid).
9. etching agent composite according to claim 7, wherein, described phosphonate compound is at least one in sylvite, the sodium salt of phosphonate compound and the ammonium salt of phosphonate compound that is selected from phosphonate compound.
10. etching agent composite according to claim 1, also comprises: the mineral acid of 0.5 % by weight to 3 % by weight or its salt, wherein, except persulphate.
11. etching agent composites according to claim 10, wherein, described mineral acid is at least one being selected from nitric acid, sulfuric acid, phosphoric acid, boric acid and perchloric acid.
12. etching agent composites according to claim 10, wherein, the salt of described mineral acid is at least one in sylvite, the sodium salt of mineral acid and the ammonium salt of mineral acid that is selected from mineral acid, wherein, except persulphate.
13. etching agent composites according to claim 1, also comprise sulfonic acid or its salt of 0.5 % by weight to 5 % by weight.
14. etching agent composites according to claim 13, wherein, described sulfonic acid is at least one being selected from thionamic acid, methylsulphonic acid, ethylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid, thionamic acid and polystyrolsulfon acid.
15. etching agent composites according to claim 13, wherein, the salt of described sulfonic acid is at least one being selected from sylvite, sodium salt and ammonium salt.
16. etching agent composites according to claim 1, also comprise the mantoquita of 0.5 % by weight to 3 % by weight, wherein, and except persulphate.
17. etching agent composites according to claim 16, wherein, described mantoquita is at least one being selected from copper sulfate, cupric nitrate, cupric chloride, venus crystals and cupric fluoride.
18. etching agent composites according to claim 1, wherein, form the described metal level based on copper, and the described metal level based on copper comprises: be selected from least one in copper, copper nitride and cupric oxide; Or comprise at least one and the alloy that is selected from least one metal in aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) of being selected from copper, copper nitride and cupric oxide.
19. etching agent composites according to claim 18, wherein, the described metal level based on copper comprises: copper molybdenum layer, the metal level based on copper that described copper molybdenum layer has molybdenum layer and forms on described molybdenum layer; Or copper molybdenum alloy layer, the metal level based on copper that described copper molybdenum alloy layer has molybdenum alloy layer and forms on described molybdenum alloy layer.
20. 1 kinds are used to form the method for wiring, comprise:
(S1) on substrate, form metal oxide layer;
(S2) on described metal oxide layer, form the metal level based on copper;
(S3) on the described metal level based on copper, form photoetching agent pattern alternatively; With
(S4) by using according to the etching agent composite described in any one in claim 1 to 19, the only described metal level based on copper on metal oxide layer described in etching.
21. methods according to claim 20, wherein, form described metal oxide layer, and described metal oxide layer comprises: pass through A
xb
yc
zthe three-component system oxide compound that O represents or four component system oxide compounds, wherein, A, B and C are respectively the metals that is selected from zinc (Zn), titanium (Ti), cadmium (Cd), gallium (Ga), indium (In), tin (Sn), hafnium (Hf), zirconium (Zr) and tantalum (Ta); X, y and z all represent metal ratio and are 0 or are greater than 0 integer or prime number.
22. methods according to claim 20, wherein, form the described metal level based on copper, and the described metal level based on copper comprises: be selected from least one in copper, copper nitride and cupric oxide; Or comprise at least one and the alloy that is selected from least one metal in aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W) of being selected from copper, copper nitride and cupric oxide.
23. methods according to claim 22, wherein, the described metal level based on copper comprises: copper molybdenum layer, the metal level based on copper that described copper molybdenum layer has molybdenum layer and forms on described molybdenum layer; Or copper molybdenum alloy layer, the metal level based on copper that described copper molybdenum alloy layer has molybdenum alloy layer and forms on described molybdenum alloy layer.
24. 1 kinds of manufactures are used for the method for the array substrate of liquid crystal indicator, comprising:
A) on substrate, form grid wiring;
B) on the described substrate that comprises described grid wiring, form gate insulator;
C) on described gate insulator, form semiconductor layer;
D) on described semiconductor layer, form source wiring and drain electrode wiring; With
E) form the pixel electrode that is connected to described drain electrode wiring,
Wherein, described a) step comprises: on described substrate, form the metal level based on copper, and use according to the metal level based on copper described in the etching agent composite etching described in any one in claim 1 to 19 to form described grid wiring.
25. 1 kinds of manufactures are used for the method for the array substrate of liquid crystal indicator, comprising:
A) on substrate, form grid wiring;
B) on the described substrate that comprises described grid wiring, form gate insulator;
C) on described gate insulator, form semiconductor layer;
D) on described semiconductor layer, form source wiring and drain electrode wiring; With
E) form the pixel electrode that is connected to described drain electrode wiring,
Wherein said d) step comprises: on described semiconductor layer, form the metal level based on copper, and use according to the metal level based on copper described in the etching agent composite etching described in any one in claim 1 to 19 to form described source wiring and described drain electrode wiring.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130033687A KR20140119885A (en) | 2013-03-28 | 2013-03-28 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR1020130033685A KR20140119884A (en) | 2013-03-28 | 2013-03-28 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR10-2013-0033687 | 2013-03-28 | ||
| KR10-2013-0033685 | 2013-03-28 | ||
| KR1020130034519A KR20140119937A (en) | 2013-03-29 | 2013-03-29 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR10-2013-0034517 | 2013-03-29 | ||
| KR1020130034520A KR20140118493A (en) | 2013-03-29 | 2013-03-29 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR1020130034515A KR20140118491A (en) | 2013-03-29 | 2013-03-29 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR10-2013-0034515 | 2013-03-29 | ||
| KR10-2013-0034520 | 2013-03-29 | ||
| KR1020130034517A KR20140118492A (en) | 2013-03-29 | 2013-03-29 | Etching composition for copper-based metal layer and method of preparing metal line |
| KR10-2013-0034519 | 2013-03-29 |
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| Publication Number | Publication Date |
|---|---|
| CN104073803A true CN104073803A (en) | 2014-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410123681.0A Pending CN104073803A (en) | 2013-03-28 | 2014-03-28 | Etching composition for copper-based metal layer and method of preparing metal line |
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| TW (1) | TW201445008A (en) |
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Application publication date: 20141001 |