TWI769216B - Etchant composition - Google Patents
Etchant composition Download PDFInfo
- Publication number
- TWI769216B TWI769216B TW107102105A TW107102105A TWI769216B TW I769216 B TWI769216 B TW I769216B TW 107102105 A TW107102105 A TW 107102105A TW 107102105 A TW107102105 A TW 107102105A TW I769216 B TWI769216 B TW I769216B
- Authority
- TW
- Taiwan
- Prior art keywords
- etching
- etchant composition
- acid
- copper
- molybdenum
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000005530 etching Methods 0.000 claims abstract description 123
- 239000010949 copper Substances 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 229910052750 molybdenum Inorganic materials 0.000 claims description 34
- 239000011733 molybdenum Substances 0.000 claims description 33
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 32
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 23
- 239000002738 chelating agent Substances 0.000 claims description 19
- 239000003112 inhibitor Substances 0.000 claims description 18
- -1 polycyclic heterocyclic compounds Chemical class 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 4
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052757 nitrogen Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 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 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- QEASJVYPHMYPJM-UHFFFAOYSA-N 1,2-dihydrotriazol-5-one Chemical compound OC1=CNN=N1 QEASJVYPHMYPJM-UHFFFAOYSA-N 0.000 claims 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims 1
- 229940120146 EDTMP Drugs 0.000 claims 1
- 229910017855 NH 4 F Inorganic materials 0.000 claims 1
- 229960003767 alanine Drugs 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims 1
- 229960002989 glutamic acid Drugs 0.000 claims 1
- 229960002449 glycine Drugs 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims 1
- 235000019799 monosodium phosphate Nutrition 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 101
- 229910021645 metal ion Inorganic materials 0.000 abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 abstract description 14
- 150000003624 transition metals Chemical class 0.000 abstract description 14
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 33
- 230000008569 process Effects 0.000 description 16
- 239000000758 substrate Substances 0.000 description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 229910001431 copper ion Inorganic materials 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002222 fluorine compounds Chemical class 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical compound [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 description 2
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- ZYVAQZSGKALVEU-UHFFFAOYSA-N 2-[2-[bis(2-hydroxy-2-oxoethyl)amino]ethyl-(2-hydroxy-2-oxoethyl)amino]ethanoic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O ZYVAQZSGKALVEU-UHFFFAOYSA-N 0.000 description 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-UHFFFAOYSA-N 0.000 description 1
- QJEINWXAHGQZHL-UHFFFAOYSA-N 2-aminoethanol;2-[bis(2-hydroxyethyl)amino]ethanol Chemical compound NCCO.OCCN(CCO)CCO QJEINWXAHGQZHL-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229910017971 NH4BF4 Inorganic materials 0.000 description 1
- 229910017665 NH4HF2 Inorganic materials 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000010599 Verbascum thapsus Nutrition 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Electroluminescent Light Sources (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
本發明係關於一種蝕刻劑組合物，更具體地，關於一種用於蝕刻作為TFT-LCD顯示器的電極等的過渡金屬膜(特別是含銅及/或鉬金屬膜)的蝕刻劑組合物。 The present invention relates to an etchant composition, more particularly, to an etchant composition for etching transition metal films (especially copper and/or molybdenum-containing metal films) used as electrodes of TFT-LCD displays and the like.
通常，薄膜電晶體(Thin Film Transistor，TFT)在液晶顯示裝置或有機電致發光(Electro Luminescence，EL)顯示裝置等中作為用於獨立驅動各個像素的電路板。TFT係由傳輸掃描信號的掃描信號線或柵極線和傳輸圖像信號的圖像信號線或資料線、與柵極線和資料線連接的薄膜電晶體以及與薄膜電晶體連接的像素電極等組成。形成所述TFT的佈線的形成製程通常包括：用於形成金屬膜的濺鍍製程；藉由光阻塗布、曝光及顯影形成所需圖案的光阻形成製程；用於形成佈線的蝕刻製程；及形成佈線後去除不必要的光阻的剝離製程。 Generally, a thin film transistor (TFT) is used as a circuit board for independently driving each pixel in a liquid crystal display device or an organic electroluminescence (Electro Luminescence, EL) display device or the like. TFT is composed of scanning signal lines or gate lines that transmit scanning signals, image signal lines or data lines that transmit image signals, thin film transistors connected to gate lines and data lines, and pixel electrodes connected to thin film transistors, etc. composition. The formation process for forming the wiring of the TFT generally includes: a sputtering process for forming a metal film; a photoresist forming process for forming a desired pattern by photoresist coating, exposure and development; an etching process for forming the wiring; and A lift-off process that removes unnecessary photoresist after wiring is formed.
以往，為了製造半導體裝置及TFT-LCD基板，TFT的柵極和資料線電極用佈線材料通常使用鋁或鋁合金層，但是為了實現大型顯示器必須減少電極用佈線的電阻，為此人們嘗試將電阻低的銅及/或鉬金屬用於佈線形成。從而對在含有銅及/或鉬的佈線蝕刻中使用的蝕刻劑組合物的研究也日益增多。 In the past, in order to manufacture semiconductor devices and TFT-LCD substrates, aluminum or aluminum alloy layers are generally used as wiring materials for TFT gates and data line electrodes. However, in order to realize large-scale displays, it is necessary to reduce the resistance of electrode wirings. Low copper and/or molybdenum metals are used for wiring formation. Therefore, the research on the etchant composition used for the wiring etching containing copper and/or molybdenum is also increasing day by day.
為了蝕刻含銅及/或鉬佈線，需要具有強氧化力的蝕刻劑組合物。因此，專利文獻1中揭露了一種銅膜蝕刻劑，其是含有過氧化氫(H2O2)和無機酸或中性鹽的混合物。專利文獻2中揭露了一種含有過氧化氫、銅反應抑制劑、雙氧水穩定劑和氟離子的蝕刻劑。此外，專利文獻3中揭露了一種將包括氟化合物、有機分子等的五種添加劑添加至過氧化氫的蝕刻劑。專利文獻4中揭露了一種鐵(III)六水合物和氟化氫(HF)的混合物。但是如上述的現有的蝕刻劑具有對銅膜和其他金屬膜的蝕刻速度過快，或蝕刻的金屬圖案的錐角(taper angle)超過約90°的問題，即具有倒錐形狀的問題。此外，銅離子濃度升高時，銅離子與過氧化氫反應形成自由基，而所形成的自由基係將組合物內含有的有機物分解從而改變蝕刻劑的特性，因此導致不良率提高等問題。 In order to etch copper and/or molybdenum-containing wirings, an etchant composition having strong oxidizing power is required. Therefore,
因此，本發明人旨在藉由本發明來解決上述現有技術中存在的問題，並同時提供一種蝕刻劑組合物，其藉由顯著提高處理件數，即使在蝕刻劑內金屬離子含量高的情況下也能夠在錐角、關鍵尺寸損失(Critical dimension loss，CD-loss)和蝕刻直線性等方面具有優異的蝕刻特性。 Therefore, the present inventors aim to solve the above-mentioned problems in the prior art by the present invention, and at the same time provide an etchant composition, which can significantly increase the number of processed pieces even in the case of high metal ion content in the etchant It can also have excellent etching characteristics in terms of taper angle, critical dimension loss (CD-loss) and etching linearity.
專利文獻1：韓國專利申請案公開號第KR 2000-0079355號 Patent Document 1: Korean Patent Application Publication No. KR 2000-0079355
專利文獻2：韓國專利申請案公開號第KR 2005-0000682號 Patent Document 2: Korean Patent Application Publication No. KR 2005-0000682
專利文獻3：韓國專利申請案公開號第KR 2006-0064881號 Patent Document 3: Korean Patent Application Publication No. KR 2006-0064881
專利文獻4：韓國專利申請案公開號第KR 2000-0032999號 Patent Document 4: Korean Patent Application Publication No. KR 2000-0032999
本發明的目的在於，提供一種能夠有效地對用作TFT-LCD顯示器電極等的過渡金屬膜進行蝕刻的蝕刻劑組合物，具體地，提供一種相比現有技術以較高的選擇性對過渡金屬膜，特別是對含銅及/或鉬的金屬膜顯示優異蝕刻特性的蝕刻劑組合物；及一種利用該蝕刻劑組合物的蝕刻方法。 The object of the present invention is to provide an etchant composition that can efficiently etch transition metal films used as electrodes for TFT-LCD displays, etc. A film, particularly an etchant composition exhibiting excellent etching properties for metal films containing copper and/or molybdenum; and an etching method using the etchant composition.
為了解決上述問題，本發明的蝕刻劑組合物的特徵在於包含：蝕刻抑制劑，其選自分子內含有至少一種選自氧、硫和氮的雜原子的單環或多環的雜環化合物；螯合劑；及蝕刻調節劑，其選自硫酸鹽和磷酸鹽。 In order to solve the above problems, the etchant composition of the present invention is characterized by comprising: an etching inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing at least one heteroatom selected from oxygen, sulfur and nitrogen in the molecule; a chelating agent; and an etch modifier selected from the group consisting of sulfates and phosphates.
根據本發明一實施態樣的蝕刻劑組合物的特徵在於，以該蝕刻抑制劑1重量份為基準，包含20至60重量份的螯合劑及5至12重量份的蝕刻調節劑，且滿足下列關係式1和關係式2：[關係式1]△Ta<10°，在上述關係式1中，△Ta表示錐角變化幅度的絕對值；[關係式2]△Ebias<0.05微米， 在上述關係式2中，△Ebias表示蝕刻偏差(etch bias)變化幅度的絕對值。 The etchant composition according to an embodiment of the present invention is characterized in that, based on 1 part by weight of the etching inhibitor, it contains 20 to 60 parts by weight of a chelating agent and 5 to 12 parts by weight of an etching regulator, and satisfies the following
根據本發明一實施態樣，該蝕刻劑組合物較佳用於蝕刻銅、鉬或它們的合金膜。 According to an embodiment of the present invention, the etchant composition is preferably used for etching copper, molybdenum or their alloy films.
根據本發明一實施態樣的蝕刻劑組合物特別是對含銅及/或鉬或鉬合金膜的金屬膜賦予高選擇性，同時能夠顯著提高蝕刻處理件數。同時，即使蝕刻劑內的金屬離子濃度較高，也能夠更穩定地表現出所需的蝕刻特性。 The etchant composition according to one embodiment of the present invention imparts high selectivity especially to metal films containing copper and/or molybdenum or molybdenum alloy films, and can significantly increase the number of etching treatments. At the same time, even if the metal ion concentration in the etchant is high, the desired etching characteristics can be more stably exhibited.
此外，根據本發明一實施態樣的蝕刻劑組合物還可以包括通常習知的添加劑，其非限制性實例可以是氟化合物、底切(undercut)抑制劑等，但不限於此。 In addition, the etchant composition according to an embodiment of the present invention may further include commonly known additives, non-limiting examples of which may be fluorine compounds, undercut inhibitors, etc., but are not limited thereto.
本發明提供一種利用滿足上述條件的蝕刻劑組合物的蝕刻方法。此時，該蝕刻劑組合物的特徵為能夠選擇性地蝕刻銅、鉬或它們的合金膜。 The present invention provides an etching method using an etchant composition satisfying the above-mentioned conditions. At this time, the etchant composition is characterized by being able to selectively etch copper, molybdenum, or alloy films thereof.
本發明蝕刻劑組合物具有能夠長時間穩定地維持顯著提高的處理件數。因此，在蝕刻過渡金屬膜時，不僅能夠實現直線性優異的錐角輪廓(taper profile)，還顯著降低關鍵尺寸損失(CD loss)，從而能夠有效抑制殘渣的發生。此外，根據本發明的蝕刻劑組合物的儲存穩定性顯著提高，即使在長時間使用或儲存的情況下也顯示不會降低蝕刻處理件數的穩定性。 The etchant composition of the present invention has a significantly increased number of processed items that can be stably maintained over a long period of time. Therefore, when the transition metal film is etched, not only a taper profile with excellent linearity can be realized, but also CD loss can be significantly reduced, so that the generation of residues can be effectively suppressed. In addition, the storage stability of the etchant composition according to the present invention is remarkably improved, and even when used or stored for a long time, it is shown that the stability does not reduce the number of etching treatments.
此外，在製造液晶顯示裝置或有機EL顯示裝置等的基板時，根據本發明的蝕刻劑組合物能夠同時蝕刻柵極線及源極 /汲極線等，能夠使得製程非常簡便，特別是對電阻低的含銅及/或鉬或它們的合金膜的金屬膜具有優異的蝕刻效果。 In addition, when manufacturing substrates of liquid crystal display devices or organic EL display devices, the etchant composition according to the present invention can simultaneously etch gate lines and source/drain lines, etc., which can make the process very simple, especially for resistance A low metal film containing copper and/or molybdenum or their alloy films has an excellent etching effect.
總之，根據本發明能夠使得電路短路或佈線不良、亮度減少等問題的發生最小化，且使得蝕刻劑的使用量相對減少的同時能夠以非常經濟的方法提供高亮度的液晶顯示裝置或有機EL顯示裝置。 In conclusion, according to the present invention, the occurrence of problems such as short circuit, poor wiring, and brightness reduction can be minimized, and the amount of etchant used can be relatively reduced, and a high-brightness liquid crystal display device or organic EL display can be provided in a very economical method. device.
圖1是使用本發明的蝕刻劑組合物(實施例1)在處理件數達到30件時(銅離子濃度300ppm)進行蝕刻後的SEM分析照片。 FIG. 1 is a photograph of SEM analysis after etching was performed using the etchant composition of the present invention (Example 1) when the number of treatments reached 30 (copper ion concentration: 300 ppm).
圖2是使用本發明的蝕刻劑組合物(實施例1)在處理件數達到700件時(銅離子濃度7000ppm)進行蝕刻後的SEM分析照片。可以確認處理件數從30件增加到700件時，在關鍵尺寸損失(CD-loss)和錐角不變的情況下維持蝕刻特性。 2 is a photograph of SEM analysis after etching was performed using the etchant composition of the present invention (Example 1) when the number of treatments reached 700 (copper ion concentration: 7000 ppm). It was confirmed that when the number of processed pieces was increased from 30 to 700 pieces, the etching characteristics were maintained without changing the critical dimension loss (CD-loss) and the taper angle.
下面參照附圖和實施例對本發明的優點和特徵及實現它們的方法進行詳細說明以使它們更加明確。但是本發明不限於下面將要揭露的實施例，本發明可以藉由其他多種形態實施。這些實施例僅用於例示性地說明本發明，對本領域技藝人士來說明確的是本發明的範圍不應由這些實施例限定，而是由隨附的申請專利範圍來限定。下面詳細說明本發明的蝕刻劑組合物。 The advantages and features of the present invention and the method for realizing them are described in detail below with reference to the drawings and examples to make them more clear. However, the present invention is not limited to the embodiments to be disclosed below, and the present invention can be implemented in other various forms. These embodiments are only used to illustrate the present invention, and it is clear to those skilled in the art that the scope of the present invention should not be limited by these embodiments, but by the scope of the appended claims. The etchant composition of the present invention will be described in detail below.
近來顯示器基板所需的高畫質及/或大型化需要係 增加佈線使用的金屬膜的厚度。具體地，由於高畫質導致像素大小減小，佈線幅度逐漸減少；由於大型化而需要佈線電阻降低。為此，不得不將用於佈線的金屬膜的厚度增加。由於上述原因等，用於目標蝕刻製程的時間變長，蝕刻劑內的金屬離子濃度急劇變高，因此需要努力提高維持蝕刻特性的有效區間，即處理件數。 Recently, the high image quality and/or size increase required for display substrates requires an increase in the thickness of metal films used for wiring. Specifically, the pixel size is reduced due to high image quality, and the wiring width is gradually reduced; due to the increase in size, the wiring resistance needs to be reduced. For this reason, the thickness of the metal film for wiring has to be increased. For the above reasons, etc., the time required for the target etching process becomes longer, and the metal ion concentration in the etchant rapidly increases. Therefore, efforts must be made to increase the effective range for maintaining the etching characteristics, that is, the number of processes.
以往的蝕刻劑組合物雖然蝕刻速度優異，但是在蝕刻時金屬離子濃度變高的話，存在有關鍵尺寸損失增加、錐角變大等問題。所述關鍵尺寸損失增加係導致金屬膜電阻值變化，由於高錐角而引起聚芳碸(polyarylsulfone，PAS)絕緣膜的裂痕，導致短路缺陷。 Although the conventional etchant composition has an excellent etching rate, when the metal ion concentration increases during etching, there are problems such as an increase in critical dimension loss and a large taper angle. The increase in the critical dimension loss leads to a change in the resistance value of the metal film, which causes cracks in the polyarylsulfone (PAS) insulating film due to the high taper angle, resulting in short-circuit defects.
為此，本發明人為了解決上述問題而深入研究具有更高處理件數的蝕刻劑組合物。結果確認特定蝕刻劑組合物能夠顯著提高蝕刻處理件數，並同時提高其穩定性，在長時間使用時也能夠展現較佳的蝕刻特性，由此完成了本發明。此時，根據本發明一實施態樣，顯示出優異的蝕刻偏差、錐角、尾巴長度(tail length)等蝕刻特性，但不限於此。 Therefore, in order to solve the above-mentioned problems, the present inventors have intensively studied an etchant composition having a higher number of processed items. As a result, it was confirmed that the specific etchant composition can remarkably increase the number of etching treatments, and at the same time improve its stability, and can exhibit favorable etching characteristics even when used for a long time, thereby completing the present invention. At this time, according to one embodiment of the present invention, excellent etching characteristics such as etching variation, taper angle, and tail length are exhibited, but the present invention is not limited thereto.
根據本發明的一實施態樣的蝕刻劑組合物，包括：蝕刻抑制劑，其選自分子內包含至少一種選自氧、硫及氮的雜原子的單環或多環的雜環化合物；螯合劑；及蝕刻調節劑，其選自硫酸鹽和磷酸。 An etchant composition according to an embodiment of the present invention includes: an etching inhibitor selected from monocyclic or polycyclic heterocyclic compounds containing at least one heteroatom selected from oxygen, sulfur and nitrogen in the molecule; chelate a mixture; and an etching regulator selected from sulfate and phosphoric acid.
具體地，根據本發明的蝕刻劑組合物的上述組分的特徵在於，以所述蝕刻抑制劑1重量份為基準，包括20至60重量份 的螯合劑和5至12重量份的蝕刻調節劑。因此，本發明的蝕刻劑組合物以組合物總重量為基準，具有高的螯合劑含量。這與包含同量程度的蝕刻抑制劑、螯合劑、蝕刻調節劑等的現有蝕刻劑組合物有區別。 Specifically, the above components of the etchant composition according to the present invention are characterized in that, based on 1 part by weight of the etching inhibitor, it includes 20 to 60 parts by weight of a chelating agent and 5 to 12 parts by weight of an etching regulator . Therefore, the etchant composition of the present invention has a high chelating agent content based on the total weight of the composition. This is in contrast to existing etchant compositions that contain the same levels of etch inhibitors, chelating agents, etch modifiers, and the like.
根據本發明一實施態樣的蝕刻劑組合物，在蝕刻過渡金屬膜時，特別是在蝕刻銅及/或鉬或銅-鉬合金膜時，在錐角(Ta)、蝕刻偏差(Ebias)等方面顯示顯著的蝕刻特性。 According to the etchant composition of an embodiment of the present invention, when etching transition metal films, especially when etching copper and/or molybdenum or copper-molybdenum alloy films, the taper angle (T a ), etching deviation (E bias ) ) and other aspects show remarkable etching characteristics.
根據本發明一實施態樣的蝕刻劑組合物在具有上述組合的同時，滿足下列關係式1和關係式2：[關係式1]△Ta<10°，在上述關係式1中，△Ta表示錐角變化幅度的絕對值；[關係式2]△Ebias<0.05微米，在上述關係式2中，△Ebias表示蝕刻偏差變化幅度的絕對值。 The etchant composition according to an embodiment of the present invention satisfies the following
特別是，根據本發明一實施態樣的蝕刻劑組合物，相對於組合物總重量具有高的螯合劑含量且給出螯合劑與蝕刻抑制劑、蝕刻調節劑之間的適當比例，因此能夠增加與蝕刻時生成的金屬離子之間的螯合效果，同時發現上述組合對蝕刻處理件數具有無法預期的提升效果。 In particular, the etchant composition according to one embodiment of the present invention has a high content of the chelating agent relative to the total weight of the composition and an appropriate ratio of the chelating agent to the etching inhibitor and the etching regulator is given, so that it is possible to increase the The chelation effect between the metal ions generated during etching, and the above combination is found to have an unexpected improvement effect on the number of etching treatments.
具體地，藉由高含量的螯合劑，隨著蝕刻進行組合物內銅金屬離子持續增加，也會將銅離子螯合，從而有效抑制過 氧化氫的自由基反應，以減少分解程度。此外，藉由給定的螯合劑和蝕刻抑制劑、蝕刻調節劑之間的適當比例，即使處理件數增加，關鍵尺寸損失(CD-loss)和錐角變化幅度也相比先前的蝕刻劑組合物有顯著的減少，確認上述蝕刻劑組合物可適用的處理件數達到700件。 Specifically, with a high content of chelating agent, as the etching proceeds, the copper metal ions in the composition continue to increase, and the copper ions are also chelated, thereby effectively suppressing the free radical reaction of hydrogen peroxide to reduce the degree of decomposition. In addition, with a given appropriate ratio between chelating agent and etch inhibitor, etch modifier, even with an increase in the number of processed pieces, the magnitude of the critical dimension loss (CD-loss) and taper angle changes compared to previous etchant combinations There was a significant reduction in the number of etchants, and it was confirmed that the above-mentioned etchant composition was applicable to 700 pieces of processing.
根據本發明的一實施態樣的蝕刻劑組合物，還可以包括氟化合物。此時，該氟化合物蝕刻雙重金屬膜時，例如同時蝕刻銅/鉬或銅/鉬合金膜時，係提高鉬或鉬合金膜的蝕刻速度，減少尾巴長度，起到去除在蝕刻時必然發生的銅或鉬合金膜的殘渣的作用。 The etchant composition according to an embodiment of the present invention may further include a fluorine compound. At this time, when the fluorine compound etches the dual metal film, for example, when etching the copper/molybdenum or copper/molybdenum alloy film at the same time, the etching speed of the molybdenum or molybdenum alloy film is increased, and the length of the tail is reduced, so as to remove the inevitable occurrence during etching. The role of residues of copper or molybdenum alloy films.
根據本發明，不僅具有錐角、蝕刻偏差等蝕刻特性，還能夠有效抑制在蝕刻時發生的鉬或鉬合金膜的尾巴長度，提供優異的亮度特性，且防止產生鉬或鉬合金膜的殘渣，從而有效抑制在基板及/或下部膜可能發生的電路短路、佈線不良等問題。 According to the present invention, not only has the etching characteristics such as taper angle and etching deviation, but also can effectively suppress the tail length of the molybdenum or molybdenum alloy film that occurs during etching, provide excellent brightness characteristics, and prevent the generation of residues of the molybdenum or molybdenum alloy film, Thereby, problems such as short circuit and poor wiring that may occur on the substrate and/or the lower film are effectively suppressed.
本發明一實施態樣的氟化物只要是可解離產生F-或HF2-的化合物均可，具體實例可以是選自以下群組之至少一者：HF、NaF、KF、AlF3、HBF4、NH4F、NH4HF2、NaHF2、KHF2和NH4BF4。此時，根據本發明的一實施態樣的蝕刻劑組合物，該氟化合物的用量不受特別限制，較佳相對於組合物總重量含有0.01至5重量%；從銅/鉬或銅/鉬合金膜中有效去除鉬或鉬合金殘渣及抑制玻璃基板等下部膜的蝕刻等方面來看，較佳為0.01至1重量%；更佳為0.05至0.5重量%。 The fluoride of an embodiment of the present invention can be any compound that can be dissociated to generate F- or HF 2 -, and a specific example can be at least one selected from the following group: HF, NaF, KF, AlF 3 , HBF 4 , NH4F , NH4HF2 , NaHF2 , KHF2 and NH4BF4 . At this time, according to the etchant composition of an embodiment of the present invention, the amount of the fluorine compound is not particularly limited, and preferably contains 0.01 to 5% by weight relative to the total weight of the composition; from copper/molybdenum or copper/molybdenum From the viewpoint of effectively removing molybdenum or molybdenum alloy residues in the alloy film and inhibiting the etching of lower films such as glass substrates, it is preferably 0.01 to 1 wt %; more preferably 0.05 to 0.5 wt %.
根據本發明一實施態樣的蝕刻劑組合物，該蝕刻抑制劑係藉由調節過渡金屬的蝕刻速度來減少圖案的關鍵尺寸損失(CD loss)、提高製程利潤、並形成具有適當錐角的蝕刻剖面(etch profile)，其可以是分子內包含至少一種選自氧、硫及氮的雜原子的雜環化合物。在此，根據本發明的該雜環化合物可包括單環的雜環化合物及含有單環的雜環和苯環縮合結構的多環的雜環化合物。 According to an etchant composition of an embodiment of the present invention, the etch inhibitor reduces the critical dimension loss (CD loss) of the pattern, improves the process profit, and forms an etch with a proper taper angle by adjusting the etch rate of the transition metal. The etch profile may be a heterocyclic compound containing at least one heteroatom selected from oxygen, sulfur and nitrogen in the molecule. Here, the heterocyclic compound according to the present invention may include a monocyclic heterocyclic compound and a polycyclic heterocyclic compound containing a condensed structure of a monocyclic heterocycle and a benzene ring.
雜環化合物的具體例有噁唑(oxazole)、咪唑(imidazole)、吡唑(pyrazole)、三唑(triazole)、四唑(tetrazole)、5-胺基四唑(5-aminotetrazole)、5-甲基四唑(methyltetrazole)、哌嗪(piperazine)、甲基哌嗪(methylpiperazine)、羥基乙基哌嗪(hydroxyethylpiperazine)、苯并咪唑(benzimidazole)、苯并吡唑(benzpyrazole)、甲苯三唑(tolutriazole)、氫甲苯三唑(hydrotolutriazole)、羥基甲苯三唑(hydroxytolutriazole)、吲哚(indole)、嘌呤(purine)、吡啶(pyridine)、嘧啶(pyrimidine)、吡咯(pyrrole)和吡咯啉(pyrroline)等，較佳為選自以下群組之至少一者：四唑、5-胺基四唑和5-甲基四唑。 Specific examples of the heterocyclic compound include oxazole, imidazole, pyrazole, triazole, tetrazole, 5-aminotetrazole, 5- Methyltetrazole, piperazine, methylpiperazine, hydroxyethylpiperazine, benzimidazole, benzpyrazole, toltriazole ( tolutriazole, hydrotolutriazole, hydroxytolutriazole, indole, purine, pyridine, pyrimidine, pyrrole and pyrroline etc., preferably at least one selected from the group consisting of tetrazole, 5-aminotetrazole and 5-methyltetrazole.
在此，蝕刻抑制劑的含量不受特別限制，為了容易調節蝕刻速度且實現經濟的量產性，以組合物的總重量為基準，可以為0.01至5重量%；較佳為0.05至5重量%；更佳為0.05至3重量%。 Here, the content of the etching inhibitor is not particularly limited, but may be 0.01 to 5% by weight, preferably 0.05 to 5% by weight, based on the total weight of the composition in order to easily adjust the etching rate and achieve economical mass production. %; more preferably 0.05 to 3% by weight.
此外，根據本發明一實施態樣的蝕刻劑組合物，所 述蝕刻調節劑可以是選自以下群組之至少一者：硫酸鹽和磷酸鹽。此處，根據本發明的蝕刻劑組合物的特徵在pH於1至5的範圍內。 Furthermore, according to the etchant composition of an embodiment of the present invention, the etch modifier may be at least one selected from the group consisting of sulfate and phosphate. Here, the etchant composition according to the present invention is characterized by a pH in the range of 1 to 5.
蝕刻調節劑起到過渡金屬或金屬的輔助氧化劑作用，並改善錐角輪廓，其可以是選自硫酸氫鉀(potassium hydrogen sulfate)、硫酸氫鈉(sodium hydrogen sulfate)、硫酸鈉(sodium sulfate)、過硫酸鈉(sodium persulfate)、硫酸鉀(potassium sulfate)、過硫酸鉀(potassium persulfate)、硫酸銨(ammonium sulfate)、過硫酸銨(ammonium persulfate)等的硫酸鹽；選自磷酸二氫銨(ammonium phosphate monobasic)、磷酸氫二銨(ammonium phosphate dibasic)、磷酸二氫鈉(sodium phosphate monobasic)、磷酸氫二鈉(sodium phosphate dibasic)、磷酸二氫鉀(potassium phosphate monobasic)及磷酸氫二鉀(potassium phosphate dibasic)等中的磷酸鹽等。從蝕刻特性改善效果方面來講，該蝕刻調節劑較佳包括含有選自上述至少一種硫酸鹽及至少一種磷酸鹽的混合物，但不限於此。 The etch modifier acts as a transition metal or metal auxiliary oxidant and improves the cone angle profile, and can be selected from the group consisting of potassium hydrogen sulfate, sodium hydrogen sulfate, sodium sulfate, Sulfate of sodium persulfate, potassium sulfate, potassium persulfate, ammonium sulfate, ammonium persulfate, etc.; selected from ammonium dihydrogen phosphate phosphate monobasic), ammonium phosphate dibasic, sodium phosphate monobasic, sodium phosphate dibasic, potassium dihydrogen phosphate (potassium phosphate monobasic) and dipotassium phosphate Phosphate etc. in phosphate dibasic) etc. In terms of the effect of improving the etching characteristics, the etching modifier preferably includes a mixture containing at least one sulfate and at least one phosphate selected from the above, but is not limited thereto.
根據本發明一實施態樣的蝕刻劑組合物中，所述螯合劑係與蝕刻進行期間所生成的金屬離子形成螯合物，使其非活性化，從而防止由這些金屬離子引起的副反應的發生，結果可以在反覆的蝕刻製程中也能夠維持蝕刻特性。特別是，蝕刻銅層時，若蝕刻劑組合物中殘存大量銅離子，將形成鈍化膜並氧化，從而存在有無法蝕刻的問題，然而當使用本發明的蝕刻劑組合物時， 能夠有效防止銅離子的鈍化膜形成，同時防止蝕刻劑組合物自身的分解反應，可以實現組合物的穩定性的提高。 In the etchant composition according to an aspect of the present invention, the chelating agent forms a chelate compound with metal ions generated during etching to inactivate them, thereby preventing side reactions caused by these metal ions. occurs, and as a result, the etching characteristics can be maintained even in the repeated etching process. In particular, when a copper layer is etched, if a large amount of copper ions remain in the etchant composition, a passivation film is formed and oxidized, and there is a problem that etching cannot be performed. However, when the etchant composition of the present invention is used, it is possible to effectively prevent copper The formation of a passivation film of ions and the prevention of the decomposition reaction of the etchant composition itself can improve the stability of the composition.
特別是，根據本發明，不同於現有使用等量程度的蝕刻抑制劑、蝕刻調節劑、螯合劑的蝕刻劑組合物，係使用蝕刻抑制劑的用量的10倍以上的螯合劑，不僅能夠顯著提高蝕刻特性，且能夠顯著抑制在蝕刻進行期間由於氧化金屬離子的分解反應促進而發生的發熱及/或爆炸現象。另外，由於上述的過量的螯合劑與蝕刻抑制劑、蝕刻調節劑的適當比例組合，在蝕刻偏差、錐角、尾巴長度等蝕刻特性上顯示驚人的提升效果。 In particular, according to the present invention, different from the existing etchant composition using the same amount of etching inhibitor, etching regulator, and chelating agent, the amount of the chelating agent used is more than 10 times the amount of the etching inhibitor, which can not only significantly improve the Etching characteristics, and can significantly suppress the generation of heat generation and/or explosion phenomenon due to the promotion of decomposition reaction of oxide metal ions during the progress of etching. In addition, due to the combination of the above-mentioned excess chelating agent, etching inhibitor, and etching regulator in an appropriate ratio, the etching characteristics such as etching deviation, taper angle, and tail length are surprisingly improved.
根據本發明的一實施態樣的蝕刻劑組合物的螯合劑係不受特別限制，較佳為選自以下群組之至少一者：亞胺基二乙酸(iminodiacetic acid)、次氮基三乙酸(nitrilotriacetic acid)、乙二胺四乙酸(ethylenediaminetetraacetic acid)、二乙烯三腈五乙酸(diethylenetrinitrilepentaacetic acid)、胺基三亞甲基膦酸、羥基伸乙基二膦酸、乙二胺四亞甲基膦酸(ethylene diamine tetra(methylene phosphonic acid))、二乙烯三胺五亞甲基膦酸(diethylenetriaminepenta(methylenephosphonic acid))、丙胺酸、麩胺酸、胺基丁酸及甘胺酸。更佳為選自以下群組之具有二個以上的酸根的至少一者：亞胺基二乙酸、次氮基三乙酸、乙二胺四乙酸、二乙烯三腈五乙酸。特別更佳是使用二個以上的醋酸根。 The chelating agent of the etchant composition according to an embodiment of the present invention is not particularly limited, and is preferably at least one selected from the following group: iminodiacetic acid, nitrilotriacetic acid (nitrilotriacetic acid), ethylenediaminetetraacetic acid (ethylenediaminetetraacetic acid), diethylenetrinitrilepentaacetic acid (diethylenetrinitrilepentaacetic acid), aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphine Acid (ethylene diamine tetra (methylene phosphonic acid)), diethylenetriaminepenta (methylenephosphonic acid), alanine, glutamic acid, aminobutyric acid and glycine. More preferably, it is at least one selected from the group consisting of at least two acid groups: iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and diethylenetrinitrile pentaacetic acid. It is particularly preferable to use two or more acetate groups.
根據本發明一實施態樣的蝕刻劑組合物是以過氧化氫(雙氧水，H2O2)為主成分的過氧化氫類蝕刻劑組合物，其對 過渡金屬膜，特別是對電阻低的含銅及鉬或鉬合金膜的金屬膜蝕刻具有優異的效果。通常對過氧化氫類蝕刻劑組合物而言，蝕刻時生成的金屬離子係與過氧化氫反應而生成自由基，由此生成的自由基係分解組合物內含有的有機成分，導致蝕刻特性的降低、過量分解產物的析出而導致的壓力差等問題。但是根據本發明，能夠有效螯合金屬離子，能夠將該問題得到前所未有的改善。在此，過氧化氫的用量不受特別限制，以組合物的總重量為基準，可含有10至30重量份；較佳為15至30重量%；更佳為20至30重量%。 An etchant composition according to an embodiment of the present invention is a hydrogen peroxide-based etchant composition containing hydrogen peroxide (hydrogen peroxide, H 2 O 2 ) as the main component, which is effective for transition metal films, especially for those with low resistance. The etching of metal films containing copper and molybdenum or molybdenum alloy films has excellent effects. Generally, for hydrogen peroxide-based etchant compositions, metal ions generated during etching react with hydrogen peroxide to generate radicals, and the generated radicals decompose organic components contained in the composition, resulting in poor etching characteristics. problems such as pressure drop caused by the precipitation of excessive decomposition products. However, according to the present invention, metal ions can be effectively chelated, and this problem can be improved unprecedentedly. Here, the amount of hydrogen peroxide used is not particularly limited, and based on the total weight of the composition, it may contain 10 to 30 parts by weight; preferably 15 to 30% by weight; more preferably 20 to 30% by weight.
特別是，可以確認根據本發明，就含銅及/或鉬的金屬膜而言，以往僅僅為450件(銅離子濃度4500至5000ppm)的處理件數可以提高至最少700件(銅離子濃度7000至7500ppm)(最大2000件)。同時，根據本發明不僅能夠顯著地改善錐角、關鍵尺寸損失(CD loss)、蝕刻各異向性等蝕刻特性，還可以保護雙重金屬膜或多重金屬膜的介面，抑制介面的過度蝕刻，從而使得高選擇性的蝕刻為可能的。 In particular, according to the present invention, it was confirmed that, for metal films containing copper and/or molybdenum, the number of treatments that was previously only 450 (copper ion concentration 4500 to 5000 ppm) can be increased to at least 700 (copper ion concentration 7000 ppm) to 7500ppm) (maximum 2000 pieces). At the same time, according to the present invention, not only can the etching characteristics such as taper angle, CD loss, and etching anisotropy be significantly improved, but also the interface of double metal films or multiple metal films can be protected, and the over-etching of the interface can be suppressed, thereby Enables highly selective etching.
此外，根據本發明一實施態樣的蝕刻劑組合物還可以包括過氧化氫穩定劑等添加劑。這將有助於在蝕刻製程時穩定過氧化氫，使蝕刻特性以高穩定性發揮。 In addition, the etchant composition according to an embodiment of the present invention may further include additives such as hydrogen peroxide stabilizer. This will help stabilize the hydrogen peroxide during the etching process, so that the etching characteristics can be exhibited with high stability.
過氧化氫穩定劑具有醇基或胺基或同時具有它們，只要其是本領域通常使用的並不受特別限制，具體實例為甲醇胺、乙醇胺、丙醇胺、丁醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺、N-甲基乙醇胺、甲胺、乙胺、丙胺、丁胺、戊胺、己胺等， 但不限於此。 The hydrogen peroxide stabilizer has an alcohol group or an amine group or both, as long as it is commonly used in the art and is not particularly limited, and specific examples are methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine Ethanolamine, dimethylethanolamine, N-methylethanolamine, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, etc., but not limited thereto.
根據本發明一實施態樣的蝕刻劑組合物能夠根據目標過渡金屬膜的種類及其厚度等而適當調整，但是從本發明的目標效果來看較佳以蝕刻抑制劑1重量份為基準，蝕刻調節劑和螯合劑的重量比以1：10至1：30混合，但不限於此。 The etchant composition according to one embodiment of the present invention can be appropriately adjusted according to the type and thickness of the target transition metal film. However, from the viewpoint of the target effect of the present invention, it is preferable to use 1 part by weight of the etching inhibitor as the basis for etching The weight ratio of the conditioner and the chelating agent is mixed at 1:10 to 1:30, but not limited thereto.
根據本發明的蝕刻劑組合物在過渡金屬或金屬膜蝕刻時，容易調節蝕刻速度，且蝕刻剖面特性優異，佈線的直線性優異。此外，能夠完全去除蝕刻時發生的鉬或鉬合金膜殘渣等，可以有效用作TFT-LCD柵極和源極/汲極用過渡金屬膜，特別是含銅/鉬或鉬合金膜的金屬膜蝕刻劑組合物。 The etchant composition according to the present invention can easily adjust the etching rate during etching of a transition metal or a metal film, and is excellent in etching cross-sectional properties and linearity of wiring. In addition, it can completely remove molybdenum or molybdenum alloy film residues generated during etching, and can be effectively used as transition metal films for TFT-LCD gates and source/drain electrodes, especially metal films containing copper/molybdenum or molybdenum alloy films Etchant composition.
進一步地，相比現有的蝕刻劑組合物具有顯著提高的儲存穩定性，且即使在蝕刻製程中生成的金屬離子濃度高達7000ppm的情況下，也不會發生過氧化氫的分解，能夠穩定地進行蝕刻。 Further, compared with the existing etchant composition, it has significantly improved storage stability, and even when the concentration of metal ions generated in the etching process is as high as 7000 ppm, the decomposition of hydrogen peroxide does not occur, and can be stably performed. etching.
根據本發明一實施態樣的蝕刻劑組合物可以用於金屬膜的蝕刻，本發明記載的金屬膜是包括金屬、非金屬或過渡金屬。較佳係該金屬膜為單金屬膜、金屬合金膜或金屬氧化膜，具體實例為以銅及/或鉬為主成分，還包括選自以下金屬或過渡金屬之至少一者的金屬膜：鈦、銦、鋅、錫、鎢、銦、金、鉻、錳、鐵、鈷、鎳和鈮；較佳為銅膜、銅/鉬膜、銅/鈦膜、銅/鉬合金膜、銅/銦合金膜，更佳為銅/鉬膜、銅/鉬合金膜，但不限於此。 The etchant composition according to an embodiment of the present invention can be used for etching metal films, and the metal films described in the present invention include metals, non-metals or transition metals. Preferably, the metal film is a single metal film, a metal alloy film or a metal oxide film, a specific example is a metal film with copper and/or molybdenum as the main component, and also includes a metal film selected from at least one of the following metals or transition metals: titanium , indium, zinc, tin, tungsten, indium, gold, chromium, manganese, iron, cobalt, nickel and niobium; preferably copper film, copper/molybdenum film, copper/titanium film, copper/molybdenum alloy film, copper/indium film The alloy film is more preferably a copper/molybdenum film or a copper/molybdenum alloy film, but is not limited thereto.
所述銅/鉬膜或銅/鉬合金膜可以是一個以上的銅(Cu)膜和一個以上的鉬(Mo)膜及/或鉬合金膜(Mo-alloy)相互層積的多重膜，所述多重膜包括Cu/Mo(Mo合金)雙重膜、Cu/Mo(Mo合金)/Cu或Mo(Mo合金)/Cu/Mo(合金)的三重膜。膜的順序可以根據基板的物質、適合度來適當調整。 The copper/molybdenum film or copper/molybdenum alloy film may be a multi-layer film in which more than one copper (Cu) film and more than one molybdenum (Mo) film and/or molybdenum alloy film (Mo-alloy) are laminated on each other, so the The multiple films include Cu/Mo (Mo alloy) double film, Cu/Mo (Mo alloy)/Cu or Mo (Mo alloy)/Cu/Mo (alloy) triple film. The order of the films can be appropriately adjusted according to the substance and suitability of the substrate.
根據本發明一實施態樣的鉬合金膜可以由鉬-鎢(Mo-W)、鉬-鈦(Mo-Ti)、鉬-鈮(Mo-Nb)、鉬-鉻(Mo-Cr)或鉬-鉭(Mo-Ta)構成，鉬膜或鉬合金膜從不留殘渣且有效實施蝕刻的方面考慮，可以蒸鍍為100至500埃之厚度，銅膜可以蒸鍍為1000至10000埃之厚度。 The molybdenum alloy film according to an embodiment of the present invention may be composed of molybdenum-tungsten (Mo-W), molybdenum-titanium (Mo-Ti), molybdenum-niobium (Mo-Nb), molybdenum-chromium (Mo-Cr) or molybdenum -Constructed of tantalum (Mo-Ta), the molybdenum film or molybdenum alloy film can be vapor-deposited to a thickness of 100 to 500 angstroms, and the copper film can be vapor-deposited to a thickness of 1000 to 10,000 angstroms in terms of leaving no residue and efficiently performing etching .
此外，本發明還提供一種利用上述蝕刻劑組合物的金屬膜蝕刻方法。根據本發明的金屬膜蝕刻方法可以藉由通常的方法實施，利用根據本發明的特定組合的蝕刻劑組合物，在蝕刻偏差、錐角、尾巴長度等蝕刻特性上顯示出顯著的優異性。 In addition, the present invention also provides a metal film etching method using the above-mentioned etchant composition. The metal film etching method according to the present invention can be carried out by an ordinary method, and the etchant composition according to the specific combination of the present invention exhibits remarkable excellence in etching characteristics such as etching deviation, taper angle, and tail length.
具體地，根據本發明的該蝕刻方法可以包括：在基板上蒸鍍金屬膜的步驟；在該金屬膜上形成光阻膜後，進行圖案化的步驟；及使用本發明的蝕刻劑組合物對形成有該圖案化的光阻膜的金屬膜進行蝕刻的步驟。此處，在該基板上形成的金屬膜可以是單層膜、雙重金屬膜或多重金屬膜(多層金屬膜)，在雙重金屬膜或多重金屬膜時，其層積順序不受特別限制。 Specifically, the etching method according to the present invention may include: a step of evaporating a metal film on a substrate; a step of patterning after forming a photoresist film on the metal film; and using the etchant composition of the present invention to The step of etching the metal film formed with the patterned photoresist film. Here, the metal film formed on the substrate may be a single-layer film, a double metal film or a multi-metal film (multi-layer metal film), and the stacking order of the double metal film or the multi-metal film is not particularly limited.
此外，該金屬膜蝕刻方法還可以包括在基板和金屬膜之間，例如為銅/鉬膜時，在基板和銅膜之間或基板和鉬膜之 間形成半導體結構物的步驟。該半導體結構可以是液晶顯示裝置、電漿顯示器板等顯示裝置用半導體結構物。具體地，可以是包括該半導體結構物可以係選自以下群組之至少一層：介電層、導電層及非晶或多晶等二氧化矽膜，這些半導體結構物可以按照習知的方法製造。 In addition, the metal film etching method may further include the step of forming a semiconductor structure between the substrate and the metal film, for example, in the case of a copper/molybdenum film, between the substrate and the copper film or between the substrate and the molybdenum film. The semiconductor structure may be a semiconductor structure for display devices such as liquid crystal display devices and plasma display panels. Specifically, it can include at least one layer of the semiconductor structure, which can be selected from the following group: a dielectric layer, a conductive layer, and an amorphous or polycrystalline silicon dioxide film. These semiconductor structures can be manufactured according to conventional methods. .
以下藉由實施例進一步詳細說明本發明。但是這些實施例僅是為了更加具體地說明本發明，本發明的範圍並不由這些實施例限定。明確的是，下面這些實施例可以藉由本領域技藝人士在本發明的範圍內進行適當的修改或變更。 The present invention is further described in detail below by means of examples. However, these Examples are only for illustrating the present invention more specifically, and the scope of the present invention is not limited by these Examples. It is clear that the following embodiments can be appropriately modified or changed within the scope of the present invention by those skilled in the art.
此外，在本發明沒有單獨進行說明的情況下，溫度單位均為℃，使用的組合物的用量單位為重量%。 In addition, when the present invention is not individually described, the unit of temperature is °C, and the unit of the amount of the composition used is % by weight.
實施例1至7和比較例1至6 Examples 1 to 7 and Comparative Examples 1 to 6
將下表1中記載的組成的各成分混合，製備了本發明實施例1至7及比較例1至6的蝕刻劑組合物。 Etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 6 of the present invention were prepared by mixing each component of the composition described in Table 1 below.
為了評估藉由上述方法製備的蝕刻劑組合物的效果，在TFT-LCD GLS上用位障金屬(barrier metal)蒸鍍100埃的鉬膜，在其上蒸鍍5000埃之厚度的銅膜，然後進行光刻(photolithography)製程，形成圖案，從而製備了試片(2200毫米×2500毫米)。為了確認各個蝕刻劑組合物的蝕刻特性(錐角、蝕刻偏差)，利用迷你蝕刻機設備，將各個試片以蝕刻缺陷密度(etch pit density，EPD)基準為50%進行蝕刻，為了觀察蝕刻處理件數，將銅粉累計溶解300ppm、5000ppm、7000ppm而評估的試片，係利用掃描電子顯微鏡(日立公司製造，SU8010)觀察(參照圖1至圖2)。 In order to evaluate the effect of the etchant composition prepared by the above method, a molybdenum film with a thickness of 100 angstroms was vapor-deposited on the TFT-LCD GLS with a barrier metal, and a copper film with a thickness of 5000 angstroms was vapor-deposited thereon, Then, a photolithography process was performed to form a pattern, thereby preparing a test piece (2200 mm×2500 mm). In order to confirm the etching characteristics (taper angle, etching deviation) of each etchant composition, each test piece was etched on the basis of 50% etch pit density (EPD) using a mini-etcher device, and in order to observe the etching process The number of pieces, the test pieces evaluated by dissolving 300 ppm, 5000 ppm, and 7000 ppm of copper powder cumulatively were observed with a scanning electron microscope (manufactured by Hitachi, Ltd., SU8010) (see FIGS. 1 to 2 ).
此外，上述方法所製備的蝕刻劑組合物的蝕刻特性的確認方法是藉由析出物生成與否來確認，此是藉由各個實施例和比較例的蝕刻劑組合物在32℃條件下，添加7000ppm銅粉，確認析出物生成與否來實施。 In addition, the method of confirming the etching characteristics of the etchant composition prepared by the above method is to confirm whether the precipitate is formed or not. 7000ppm of copper powder was used to confirm the formation of precipitates.
此外，為了確認上述方法製備的蝕刻劑組合物的保存穩定性，藉由迷你蝕刻機評估，根據經時天數來確認(經時變 化確認：0至30天)。 In addition, in order to confirm the storage stability of the etchant composition prepared by the above-mentioned method, it was evaluated by a mini-etcher and confirmed according to the number of days over time (confirmation over time: 0 to 30 days).
下表2示出實施例和比較例的上述評估結果。 Table 2 below shows the above evaluation results of Examples and Comparative Examples.
如表2所示，根據本發明的蝕刻方法，即使在蝕刻製程反覆進行蝕刻劑內金屬離子含量高的情況下，也能夠維持蝕刻特性，還具有顯著改善的錐角變化幅度、蝕刻偏差變化幅度，從而實現直線性優異的錐角輪廓，顯著降低關鍵尺寸損失(CD loss)，從而能夠有效抑制殘渣發生。 As shown in Table 2, according to the etching method of the present invention, even when the etching process is repeatedly performed with a high metal ion content in the etchant, the etching characteristics can be maintained, and the taper angle variation range and the etching deviation variation range are remarkably improved. , so as to achieve a tapered angle profile with excellent linearity, significantly reduce the critical dimension loss (CD loss), and effectively suppress the occurrence of residues.
此外，使用比較例的蝕刻劑組合物時，其處理件數 為450件(約4500ppm至5000ppm)，而本發明的蝕刻劑組合物的處理件數為700件(約7000ppm至7500ppm)，相較於比較例提高56%。如上述的處理件數的顯著提高效果能夠解決現有技術中存在的如下的固有問題：當銅離子濃度提高時(處理件數增加時)，銅離子與過氧化氫反應生成自由基，所形成的自由基係分解組合物內包含的有機物，從而降低蝕刻劑的特性，由此顯示出高的不良率。 In addition, when the etchant composition of the comparative example was used, the number of processed pieces was 450 pieces (about 4500 ppm to 5000 ppm), while the number of processed pieces of the etchant composition of the present invention was 700 pieces (about 7000 ppm to 7500 ppm), compared with Compared with the comparative example, it is increased by 56%. The effect of significantly improving the number of treated items can solve the following inherent problems in the prior art: when the concentration of copper ions increases (when the number of treated items increases), the copper ions react with hydrogen peroxide to generate free radicals, and the resulting The radicals decompose the organic substances contained in the composition, thereby reducing the characteristics of the etchant, thereby showing a high defect rate.
同時，根據本發明的蝕刻劑組合物在保存30天後，顯示出優異的保存經時特性，沒有蝕刻劑組合物自身的經時分解。相反，比較例在保存7天後發生變化，或保存30天後發生變化，發生自身分解導致的蝕刻劑組合物的處理件數顯著降低的問題。 At the same time, the etchant composition according to the present invention exhibits excellent preservation time-dependent characteristics after being stored for 30 days, and there is no time-dependent decomposition of the etchant composition itself. On the contrary, the comparative example changed after 7 days of storage, or changed after 30 days of storage, and the problem that the number of processed etchant compositions due to self-decomposition was remarkably decreased.
根據本發明的特定組成的蝕刻劑組合物不僅能夠顯著提高蝕刻處理件數，甚至在金屬離子增加時也能夠抑制蝕刻劑組合物分解，能夠長時間維持蝕刻特性，由於穩定性高而即使處理時間增加也不會導致蝕刻速度和蝕刻處理件數降低，由此顯示出優異的蝕刻特性。由此，根據本發明能夠使電路短路或佈線的不良、亮度的減少等問題的發生最小化，蝕刻劑的使用量相對減少，且以非常經濟的方法提供用作高亮度液晶顯示裝置或有機EL顯示裝置等的電極的高品質過渡金屬膜，特別是含銅及/或鉬或鉬合金膜的金屬膜。 The etchant composition of the specific composition according to the present invention can not only remarkably increase the number of etching treatments, but also suppress the decomposition of the etchant composition even when metal ions increase, maintain the etching characteristics for a long time, and can maintain the etching characteristics for a long time due to its high stability. The increase also does not result in a decrease in the etching rate and the number of etching processes, thereby exhibiting excellent etching characteristics. Therefore, according to the present invention, the occurrence of problems such as short circuits, wiring defects, and reduction in brightness can be minimized, the amount of etchant used can be relatively reduced, and an extremely economical method can be provided for use as a high-brightness liquid crystal display device or an organic EL. High-quality transition metal films for electrodes of display devices, etc., especially metal films containing copper and/or molybdenum or molybdenum alloy films.
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| KR10-2018-0005973 | 2018-01-17 | ||
| KR1020180005973A KR20180088282A (en) | 2017-01-26 | 2018-01-17 | ETCHANT composition |
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| KR102665340B1 (en) * | 2018-09-18 | 2024-05-14 | 삼성전자주식회사 | Etching composition and method for manufacturing semiconductor device using the same |
| KR102562490B1 (en) * | 2018-10-29 | 2023-08-03 | 솔브레인 주식회사 | Etchant composition and method for methal layer etching method using the same |
| KR102769911B1 (en) * | 2019-08-07 | 2025-02-20 | 주식회사 이엔에프테크놀로지 | Etchant Composition |
| KR102830564B1 (en) * | 2020-01-06 | 2025-07-09 | 주식회사 이엔에프테크놀로지 | Etchant Composition |
| CN116288351B (en) * | 2023-03-23 | 2025-10-21 | 艾森半导体材料(南通)有限公司 | Etching liquid composition and application thereof |
| CN117286498A (en) * | 2023-09-27 | 2023-12-26 | 上海盛剑微电子有限公司 | Etching solution and its application in etching copper/molybdenum titanium nickel films |
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| TWI404825B (en) * | 2008-09-26 | 2013-08-11 | Techno Semichem Co Ltd | Cu or cu/mo or cu/mo alloy electrode etching liquid in liquid crystal display system |
| CN103668208A (en) * | 2012-09-04 | 2014-03-26 | 易安爱富科技有限公司 | Etchant composition of copper-molybdenum alloy film |
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| KR100960687B1 (en) | 2003-06-24 | 2010-06-01 | 엘지디스플레이 주식회사 | Etch solution for collective etching of a double metal layer containing copper (or copper alloy layer) |
| KR100708970B1 (en) | 2004-12-09 | 2007-04-18 | 주식회사 엘지화학 | Etch solution composition for copper molybdenum wiring |
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| TWI404825B (en) * | 2008-09-26 | 2013-08-11 | Techno Semichem Co Ltd | Cu or cu/mo or cu/mo alloy electrode etching liquid in liquid crystal display system |
| CN103668208A (en) * | 2012-09-04 | 2014-03-26 | 易安爱富科技有限公司 | Etchant composition of copper-molybdenum alloy film |
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| KR20230039621A (en) | 2023-03-21 |
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