CN103890232A - 铜钼合金膜的蚀刻液组合物 - Google Patents
铜钼合金膜的蚀刻液组合物 Download PDFInfo
- Publication number
- CN103890232A CN103890232A CN201280051862.6A CN201280051862A CN103890232A CN 103890232 A CN103890232 A CN 103890232A CN 201280051862 A CN201280051862 A CN 201280051862A CN 103890232 A CN103890232 A CN 103890232A
- Authority
- CN
- China
- Prior art keywords
- acid
- etching
- molybdenum alloy
- alloy film
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000010949 copper Substances 0.000 title abstract description 24
- 229910000881 Cu alloy Inorganic materials 0.000 title abstract description 21
- 239000000203 mixture Substances 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- -1 dicyclic compound Chemical class 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003352 sequestering agent Substances 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 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 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
- 239000004471 Glycine Substances 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229960002449 glycine Drugs 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 2
- OMAFFHIGWTVZOH-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium Chemical compound C[N+]1=CN=NN1 OMAFFHIGWTVZOH-UHFFFAOYSA-O 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
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical compound SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 claims description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 2
- WYKHSBAVLOPISI-UHFFFAOYSA-N 2-phenyl-1,3-thiazole Chemical compound C1=CSC(C=2C=CC=CC=2)=N1 WYKHSBAVLOPISI-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
- YHEKBXQMXRLCCX-UHFFFAOYSA-N 2h-benzotriazol-4-ylmethanol Chemical compound OCC1=CC=CC2=C1N=NN2 YHEKBXQMXRLCCX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- ZBXNFTFKKOSPLD-UHFFFAOYSA-N 5-methylsulfanyl-2h-tetrazole Chemical compound CSC1=NN=NN1 ZBXNFTFKKOSPLD-UHFFFAOYSA-N 0.000 claims description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 229950006191 gluconic acid Drugs 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002473 indoazoles Chemical class 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940095574 propionic acid Drugs 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- AYNUCZFIHUUAIZ-UHFFFAOYSA-N s-(2h-triazol-4-yl)thiohydroxylamine Chemical compound NSC1=CNN=N1 AYNUCZFIHUUAIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 122
- 229910021645 metal ion Inorganic materials 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 125000004434 sulfur atom Chemical group 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- IOQLGFCIMRCCNA-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid Chemical compound OC(=O)CNCC(O)=O.OC(=O)CNCC(O)=O IOQLGFCIMRCCNA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000583 Nd alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Thin Film Transistor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Weting (AREA)
Abstract
本发明涉及一种铜钼合金膜的蚀刻液组合物，本发明的蚀刻液组合物，相对于整体组合物的总重量，包含：5%至40%重量百分比的过氧化氢，0.01%至5%重量百分比的同时含有氮原子和硫原子的化合物，0.1%至5%重量百分比的有机酸，0.1%至5%重量百分比的杂环化合物，0.1%至5%中重量百分比的螯合剂，0.01至1重量百分比%的氟化物及使整体组合物的总重量达到100%的水。本发明的蚀刻液组合物在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性，可有效地应用在TFT-LCD显示器电极制造上。
Description
技术领域
本发明涉及一种铜钼合金膜的蚀刻液组合物，尤其是用于TFT-LCD、OLED等显示器电极的铜钼合金膜的蚀刻液组合物。
背景技术
半导体装置、TFT-LCD、OLED等微电路是通过在基板上形成的铝、铝合金、铜及铜合金等导电性金属膜或二氧化硅膜、氮化硅薄膜等绝缘膜上，均匀地涂抹光刻胶，然后通过刻有图案的薄膜，进行光照射后成像，使所需的图案光刻胶成像，采用干式蚀刻或湿式蚀刻，在光刻胶下部的金属膜或绝缘膜上显示图案后，剥离去除不需要的光刻胶等一系列的光刻工程而完成的。
大型显示器的栅极及数据金属配线所使用的铜合金，与以往技术中的铝铬配线相比，阻抗低且没有环境问题。铜存在与玻璃基板及绝缘膜的贴附性较低，易扩散为氧化硅膜等问题，所以通常使用钛、钼等作为下部薄膜金属。
另外，随着显示器大型化的发展，湿式蚀刻中所使用的蚀刻液的用量也随之增多，为了降低制造成本，开发出可减少蚀刻液用量的相关技术是势在必行的。
在韩国专利公开公报第2003-0082375号、专利公开公报第2004-0051502号、专利公开公报第2006-0064881号及专利公开公报第2006-0099089号等中，公开了过氧化氢基板的铜/钼合金蚀刻液，但是在进行反复蚀刻，且蚀刻液中的金属含量有所增加时，就很难维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性，为了维持上述蚀刻特性，则需要降低金属含量，从而需要使用大量的蚀刻液。
发明内容
为了解决上述技术问题，本发明的目的在于提供一种在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性的铜钼合金膜的蚀刻液组合物。
为了实现上述目的，本发明提供一种在过氧化氢基础上的蚀刻液组合物，所述过氧化氢内添加有同时含有氮原子和硫原子化合物。
更详细地说，本发明供一种铜钼合金膜的蚀刻液组合物，相对于整体组合物的总重量，包含：5%至40%重量百分比的过氧化氢，0.01%至5%重量百分比的同时含有氮原子和硫原子的化合物，0.1%至5%重量百分比的有机酸，0.1%至5%重量百分比的杂环化合物，0.1%至5%中重量百分比的螯合剂，0.01%至1%重量百分比的氟化物及使整体组合物的总重量达到100%的水。
本发明的有益效果在于，依据本发明的铜钼合金膜的蚀刻液组合物，在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性。从而可减少用于蚀刻工程中的蚀刻液的用量，使TFT-LCD等的制造成本有显著的降低。
附图说明
图1是在本发明实施例1的蚀刻组合物中，溶解6000ppm的铜/钼合金粉末后，使用扫描电子显微镜观察到的铜/钼合金膜蚀刻截面的照片；
图2是在本发明实施例1的蚀刻组合物中，溶解4000ppm的铜/钼合金粉末后，使用扫描电子显微镜观察到的铜/钼合金膜蚀刻截面的照片。
具体实施方式
本发明的蚀刻液组合物可同时蚀刻铜/钼合金。这里的“铜/钼合金膜”是指铜膜和钼合金膜，钼合金是钼和多种金属的合金，优选为与钛、钽、铬、钕、镍、铟或锡的合金，更优选为与钛的合金。
本发明的铜钼合金膜的蚀刻液组合物，相对于整体组合物的总重量，包含：5%至40%重量百分比的过氧化氢，0.01%至5%重量百分比的同时含有氮原子和硫原子的化合物，0.1%至5%重量百分比的有机酸，0.1%至5%重量百分比的杂环化合物，0.1%至5%中重量百分比的螯合剂，0.01%至1%重量百分比的氟化物及使整体组合物的总重量达到100%的水。
上述蚀刻液组合物除了包含同时含有氮原子和硫原子的化合物以外，还包含有助于过氧化氢和蚀刻的有机酸、可控制螯合剂及氟化物等蚀刻添加剂和蚀刻速度，并在蚀刻后可形成金属膜轮廓的蚀刻抑制剂—杂环化合物。
在本发明的蚀刻液组合物中，同时含有氮原子和硫原子的添加剂不仅仅可以提高铜钼合金的蚀刻速度，还可以在反复进行蚀刻工程，蚀刻液内的金属离子含量增加时，维持蚀刻的速度。反复进行蚀刻工程，蚀刻液内的金属离子含量增加时，蚀刻液会发生变化，蚀刻锥角变大，蚀刻精度减小。随着蚀刻工程的反复，蚀刻液内的蚀刻添加剂与金属离子反应，持续消耗。但是蚀刻抑制剂被维持，相对于参与蚀刻的蚀刻添加剂，用于控制蚀刻速度的蚀刻抑制剂则有所增加，蚀刻速度变慢。
上述同时含有氮原子和硫原子的添加剂，在蚀刻工程反复进行，蚀刻液内的金属离子的含量有所增加时，可以控制蚀刻抑制剂被过度的吸附在金属表面而导致的蚀刻速度变慢。由此可见，即使在蚀刻液内的金属离子含量较高时，也可以维持蚀刻的速度。
同时含有氮原子和硫原子的添加剂，相对于整体组合物的总重量，其含量优选为0.01%至5%重量百分比，更优选为其含量为0.1%至3%重量百分比。若其不足0.01%重量百分比时，金属离子含量过高，无法发挥维持蚀刻速度的作用；若超出5%重量百分比时，蚀刻速度过快，难以控制工程进度。
在本发明的蚀刻液组合物中，同时包含氮原子和硫原子的化合物优选为同时包含氮原子和硫原子的1至10元的单环或双环化合物，更优选为5至10元的单环或双环化合物。具体来说，可为硫醇基咪唑啉、2-硫醇基-1-甲基咪唑啉、2-巯基噻唑、2-氨基噻唑、巯基三唑、氨基巯基三唑、巯基四氮唑、甲基巯基四氮唑、噻唑、苯基噻唑、2-甲基苯并噻唑、2-氨基苯并噻唑及2-巯基苯并噻唑等，也可以同时使用一种或两种以上的上述化合物。
在本发明的蚀刻液组合物中，过氧化氢为铜钼合金的主要酸化剂。相对于整体组合物的总重量，优选为含5%至40%重量百分比的过氧化氢，更优选为含10%至30%重量百分比的过氧化氢。过氧化氢不足5%重量百分比时，对铜钼合金的酸化不够充分，无法实现蚀刻；超出40%重量百分比时，蚀刻速度过快，难以控制工程的进度。
本发明的蚀刻液组合物中，有机酸是用于蚀刻铜钼合金的只要成分，可调节蚀刻速度。相对于整体组合物的总重量，优选为含有0.1%至5%重量百分比的有机酸，更优选为其含量为0.5%至3%重量百分比。若其不足0.1%重量百分比时，蚀刻速度变慢，在可控制的工程时间内无法实现蚀刻，若其超出5%重量百分比时，蚀刻速度过快，难以控制工程进展。
所述有机酸可为醋酸、甲酸、丁酸、柠檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、葡萄糖酸、甘氨酸、琥珀酸等水溶性有机酸，也可同时使用一种或两种以上的上述有机酸。
在本发明的蚀刻液组合物中，杂环化合物用于调节铜钼合金的蚀刻速度，从而形成具有适当锥角的蚀刻轮廓。杂环化合物的含量相对于整体组合物的总重量，优选为0.1%至5%重量百分比，更优选为0.5%至3%重量百分比。若不足0.1%重量百分比时，可调节锥角的性能减弱，若其超过5%重量百分比时，蚀刻速度变慢，工程效率受到影响。
在本发明的蚀刻液组合物中，所述蚀刻抑制剂是含有选自氧、硫及氮中至少一个以上的杂原子，不同时包含氮原子和硫原子的1至10元杂环碳氢化合物。具体来说，可为呋喃、噻吩、吡咯、恶唑、咪唑、吡唑、1,2,4-三氮唑、四唑、氧茚、苯并噻吩、吲哚、苯并咪唑、苯并吡唑、氨基四唑、甲基四唑、甲基苯并三唑、氢甲基苯并三唑(hydro-tolutriazole)、羟甲基苯并三唑(hydroxye-tolutriazole)等杂环芳香族化合物及哌嗪、甲基哌嗪、羟乙基哌嗪、吡咯烷及四氧嘧啶等杂环脂肪族化合物；也可以同时使用一种或两种以上的上述化合物。
本发明的蚀刻液组合物中的螯合剂与在蚀刻过程中产生铜及钼合金离子形成螯合，并使其非活性化，从而抑制蚀刻液中过氧化氢的分解反应。若本发明的蚀刻液组合物中不添加螯合剂，那么在蚀刻进行过程中，被酸化的金属离子无法实现非活性化，其可促进蚀刻液组合物中的过氧化氢进行分解反应，可导致发热及爆炸。相对于整体组合物的总重量，优选为其含量为0.1%至5%重量百分比，更优选为0.5%至3%重量百分比。若不足0.1%重量百分比时，可进行非活性化的金属离子量很少，从而使其抑制过氧化氢进行分解反应的效能减弱；若超出5%重量百分比时，会形成多余的螯合，使金属离子非活性化的效果不佳，影响工程效率。
本发明的螯合剂优选为同时具备氨基和羧酸基的化合物，具体来说，可为亚氨基二乙酸、氨三乙酸、乙二胺四乙酸、二乙烯三胺五乙酸、氨基三亚甲基膦酸、1-羟基亚乙基-1,1-二磷酸、乙二胺四甲撑磷酸、二亚乙基三胺五亚甲基磷酸、肌氨酸、丙氨酸、谷氨酸、氨基丁酸及甘氨酸等。
本发明的蚀刻液组合物中的氟化物在铜钼合金同时蚀刻时，可提高钼合金的蚀刻速度，减少尾巴长度，去除在蚀刻时所产生的钼合金残渣。钼合金的尾部若增加则会降低明暗度，残渣若余留在基板及下部膜上的话，则会导致电短路、配线不良及明暗度降低，所以一定要去除残渣。相对于整体组合物的总重量，所述氟化物优选为其含量为0.01%至1%重量百分比，更优选为0.1%至1%重量百分比。若不足0.01%重量百分比时，钼合金的残渣不能有效去除，若超出1%重量百分比时，会蚀刻下部膜。
本发明的氟化物是离解出F-或HF2 -离子的化合物，可为铪、氟化钠、氟化钾、氟化铝、硼氟酸、氟化铵、氟化氢铵、氟化氢钠、氟氢化钾及氟硼酸铵等，也可以同时使用一种或两种以上的上述氟化物。
本发明的蚀刻液组合物中所使用的水没有特别的限定，优选为使用去离子水，更优选为使用水中去除离子后的比阻抗值为18MΩ/㎝以上的去离子水。
本发明的铜/钼合金蚀刻液组合物，为了提高其蚀刻性能，还可以包含本领域已公知的任意一种添加剂。该添加剂可为无机酸及双氧水稳定剂。
所述无机酸起到铜钼合金的辅助酸化剂的作用，双氧水稳定剂在蚀刻工程反复进行，蚀刻液内的金属离子的含量过高时，起到控制过氧化氢分解反应的作用。所述无机酸可为硫酸、硝酸及磷酸等，所述双氧水稳定剂可为磷酸盐、甘醇类及胺类。
利用本发明的蚀刻液组合物，可蚀刻用于TFT-LCD显示器等电极的铜/钼合金膜，在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性。从而可减少用于蚀刻工程中的蚀刻液的用量，使TFT-LCD等的制造成本有显著的降低。
接下来，通过本发明的实施例，对本发明进行详细的说明，实施例仅为说明本发明的内容，本发明不受实施例的局限。
实施例1至6及对比例1
以下列表1所记载的成分含量，混合各成份，制成本发明实施例1至6及对比例1的组合物。
表1
BTZ：苯并噻唑(benzothiazole)
ATZ：5-氨基四唑(5-aminotetrazole)
IDA：亚氨基二乙酸(iminodiacetic acid)
蚀刻性能测试
为了评价本发明蚀刻液的效果，在玻璃基板上沉积厚度为
的钼钛合金膜，然后沉积厚度为
的铜，制成试片。在上述试片上，进行光刻工程，制成图案化的玻璃。蚀刻在可喷涂的装置（Mini-etcher ME-001）上进行。蚀刻后利用扫描电子显微镜（日立集团制造，S-4800）对蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性进行观察。
在蚀刻液中添加铜/钼合金，对蚀刻进行评价，同时对维持蚀刻特性的铜/钼合金的含量进行评价。
如表2所示，本发明的实施例1至6的组合物，在铜/钼合金含量超出6000ppm时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性，并显示出良好的结果。图1是在本发明实施例1的蚀刻组合物中，溶解6000ppm的铜/钼合金粉末后，使用扫描电子显微镜观察到的铜/钼合金膜蚀刻截面的照片。
相反，对比例1的蚀刻液组合物，在铜/钼含量超出4000ppm时，会发生残渣，蚀刻锥角增大，蚀刻精度减小，并会失去直线度，其蚀刻特性难以维持，金属含量也变得非常低。图2是在本发明实施例1的蚀刻组合物中，溶解4000ppm的铜/钼合金粉末后，使用扫描电子显微镜观察到的铜/钼合金膜蚀刻截面的照片。
表2
由上述结果可知，对用在TFT-LCD显示器电极制造上的铜钼合金膜进行蚀刻时，本发明的蚀刻液组合物在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性，可有效地提高TFT-LCD阵列基板的生产性，并可显著地降低制造费用和成本。
产业上的适用性
本发明在对用于在TFT-LCD显示器电极制造上的铜钼合金膜进行蚀刻时，即使在反复进行蚀刻工程、蚀刻液内的金属离子的含量较高时，也可以维持蚀刻锥角、蚀刻精度及蚀刻直线度等蚀刻特性，可有效地提高TFT-LCD阵列基板的生产性，并可显著地降低制造费用和成本。
Claims (9)
1.一种铜钼合金膜的蚀刻液组合物，其特征在于，相对于整体组合物的总重量，包含：5%至40%重量的过氧化氢，0.01%至5%重量的同时含有氮原子和硫原子的化合物，0.1%至5%重量百分比的有机酸，0.1%至5%重量百分比的杂环化合物，0.1%至5%中重量百分比的螯合剂，0.01%至1%重量百分比的氟化物及使整体组合物的总重量达到100%的水。
2.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述同时含有氮原子和硫原子的化合物是五元至十元的单环或双环化合物。
3.根据权利要求2所述的铜钼合金膜蚀刻液组合物，其特征在于，所述同时含有氮原子和硫原子的化合物选自硫醇基咪唑啉、2-硫醇基-1-甲基咪唑啉、2-巯基噻唑、2-氨基噻唑、巯基三唑、氨基巯基三唑、巯基四氮唑、甲基巯基四氮唑、噻唑、苯基噻唑、2-甲基苯并噻唑、2-氨基苯并噻唑及2-巯基苯并噻唑中的至少一种。
4.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述有机酸选自醋酸、甲酸、丁酸、柠檬酸、乙醇酸、草酸、丙二酸、戊酸、丙酸、酒石酸、葡萄糖酸、甘氨酸、琥珀酸中的至少一种。
5.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述杂环化合物是含有选自氧、硫及氮中至少一个以上的杂原子，不同时包含氮原子和硫原子的1至10元杂环芳香族化合物或杂环脂肪族化合物。
6.根据权利要求5所述的铜钼合金膜蚀刻液组合物，其特征在于，所述杂环芳香族化合物选自由呋喃、噻吩、吡咯、恶唑、咪唑、吡唑、1,2,4-三氮唑、四唑、氧茚、苯并噻吩、吲哚、苯并咪唑、苯并吡唑、氨基四唑、甲基四唑、甲基苯并三唑、氢甲基苯并三唑(hydro-tolutriazole)、羟甲基苯并三唑(hydroxye-tolutriazole)构成的群，所述杂环脂肪族化合物选自由哌嗪、甲基哌嗪、羟乙基哌嗪、吡咯烷及四氧嘧啶构成的群。
7.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述螯合剂为同时具备氨基和羧酸基的化合物。
8.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述螯合剂选自亚氨基二乙酸、氨三乙酸、乙二胺四乙酸、二乙烯三胺五乙酸、氨基三亚甲基膦酸、1-羟基亚乙基-1,1-二磷酸、乙二胺四甲撑磷酸、二亚乙基三胺五亚甲基磷酸、肌氨酸、丙氨酸、谷氨酸、氨基丁酸及甘氨酸中的至少一种。
9.根据权利要求1所述的铜钼合金膜蚀刻液组合物，其特征在于，所述氟化物选自铪、氟化钠、氟化钾、氟化铝、硼氟酸、氟化铵、氟化氢铵、氟化氢钠、氟氢化钾及氟硼酸铵中的至少一种。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0123513 | 2011-11-24 | ||
| KR1020110123513A KR101333551B1 (ko) | 2011-11-24 | 2011-11-24 | 구리와 몰리브덴 합금막의 식각액 조성물 |
| PCT/KR2012/009507 WO2013077580A1 (ko) | 2011-11-24 | 2012-11-12 | 구리와 몰리브덴 합금막의 식각액 조성물 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103890232A true CN103890232A (zh) | 2014-06-25 |
| CN103890232B CN103890232B (zh) | 2016-01-06 |
Family
ID=48469984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280051862.6A Active CN103890232B (zh) | 2011-11-24 | 2012-11-12 | 铜钼合金膜的蚀刻液组合物 |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR101333551B1 (zh) |
| CN (1) | CN103890232B (zh) |
| WO (1) | WO2013077580A1 (zh) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105060727A (zh) * | 2015-07-31 | 2015-11-18 | 安徽和润特种玻璃有限公司 | 一种高透过率防眩玻璃用蚀刻液及其制备方法 |
| CN105369249A (zh) * | 2014-08-25 | 2016-03-02 | 乐金显示有限公司 | 蚀刻剂组合物和制造薄膜晶体管阵列基板的方法 |
| CN105755472A (zh) * | 2015-01-05 | 2016-07-13 | 东友精细化工有限公司 | 银蚀刻液组合物和利用它的显示基板 |
| CN105803459A (zh) * | 2016-05-03 | 2016-07-27 | 苏州晶瑞化学股份有限公司 | 一种微电子用多层金属膜蚀刻液及其应用 |
| CN105986270A (zh) * | 2015-03-19 | 2016-10-05 | 东友精细化工有限公司 | 蚀刻剂组合物、液晶显示器阵列基板制作方法和阵列基板 |
| CN106148961A (zh) * | 2015-03-27 | 2016-11-23 | 东友精细化工有限公司 | 蚀刻剂组合物、形成金属线图案方法和制造阵列基板方法 |
| CN107587135A (zh) * | 2016-07-08 | 2018-01-16 | 深圳新宙邦科技股份有限公司 | 一种钼铝钼蚀刻液 |
| TWI679307B (zh) * | 2015-03-19 | 2019-12-11 | 南韓商東友精細化工有限公司 | 蝕刻劑組合物、液晶顯示器陣列基板製作方法和陣列基板 |
| CN112415799A (zh) * | 2020-11-10 | 2021-02-26 | Tcl华星光电技术有限公司 | 阵列基板及其制备方法 |
| CN113106453A (zh) * | 2020-02-26 | 2021-07-13 | 江苏艾森半导体材料股份有限公司 | 一种蚀刻液组合物及其应用 |
| CN114107991A (zh) * | 2021-11-29 | 2022-03-01 | 清华大学 | 一种钼-铜双层膜材料蚀刻方法及腐蚀液 |
| CN114318338A (zh) * | 2020-09-29 | 2022-04-12 | 上海飞凯材料科技股份有限公司 | 一种铜镍金结构的铜种子层蚀刻液及其应用 |
| CN116497355A (zh) * | 2023-04-10 | 2023-07-28 | 珠海市裕洲环保科技有限公司 | 一种酸性铜蚀刻液及其应用 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101972630B1 (ko) * | 2015-01-05 | 2019-04-26 | 동우 화인켐 주식회사 | 은 식각액 조성물 및 이를 이용한 표시 기판 |
| KR102281191B1 (ko) * | 2015-03-19 | 2021-07-23 | 동우 화인켐 주식회사 | 식각액 조성물 및 액정표시장치용 어레이 기판의 제조방법 |
| KR102455790B1 (ko) * | 2015-12-22 | 2022-10-19 | 주식회사 이엔에프테크놀로지 | 구리 식각액 조성물 |
| CN111719156A (zh) * | 2019-03-20 | 2020-09-29 | 易安爱富科技有限公司 | 蚀刻组合物及利用其的蚀刻方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040118814A1 (en) * | 2002-12-12 | 2004-06-24 | Seong-Su Kim | Etching solution for multiple layer of copper and molybdenum and etching method using the same |
| KR20050122122A (ko) * | 2004-06-23 | 2005-12-28 | 테크노세미켐 주식회사 | 평판디스플레이용 투명도전막의 에칭액 조성물 |
| KR20060099089A (ko) * | 2005-03-10 | 2006-09-19 | 엘지.필립스 엘시디 주식회사 | 금속배선 식각용액 및 이를 이용한 금속배선 식각방법과 상기 식각용액을 이용한 액정표시장치의 제조방법 |
| JP2011099624A (ja) * | 2009-11-06 | 2011-05-19 | Kobelco Eco-Solutions Co Ltd | 冷却塔 |
| WO2011099624A1 (ja) * | 2010-02-15 | 2011-08-18 | 三菱瓦斯化学株式会社 | 銅層及びモリブデン層を含む多層薄膜用エッチング液 |
-
2011
- 2011-11-24 KR KR1020110123513A patent/KR101333551B1/ko active IP Right Grant
-
2012
- 2012-11-12 CN CN201280051862.6A patent/CN103890232B/zh active Active
- 2012-11-12 WO PCT/KR2012/009507 patent/WO2013077580A1/ko active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040118814A1 (en) * | 2002-12-12 | 2004-06-24 | Seong-Su Kim | Etching solution for multiple layer of copper and molybdenum and etching method using the same |
| KR20050122122A (ko) * | 2004-06-23 | 2005-12-28 | 테크노세미켐 주식회사 | 평판디스플레이용 투명도전막의 에칭액 조성물 |
| KR20060099089A (ko) * | 2005-03-10 | 2006-09-19 | 엘지.필립스 엘시디 주식회사 | 금속배선 식각용액 및 이를 이용한 금속배선 식각방법과 상기 식각용액을 이용한 액정표시장치의 제조방법 |
| JP2011099624A (ja) * | 2009-11-06 | 2011-05-19 | Kobelco Eco-Solutions Co Ltd | 冷却塔 |
| WO2011099624A1 (ja) * | 2010-02-15 | 2011-08-18 | 三菱瓦斯化学株式会社 | 銅層及びモリブデン層を含む多層薄膜用エッチング液 |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105369249B (zh) * | 2014-08-25 | 2018-05-29 | 乐金显示有限公司 | 蚀刻剂组合物和制造薄膜晶体管阵列基板的方法 |
| CN105369249A (zh) * | 2014-08-25 | 2016-03-02 | 乐金显示有限公司 | 蚀刻剂组合物和制造薄膜晶体管阵列基板的方法 |
| CN105755472B (zh) * | 2015-01-05 | 2019-12-17 | 东友精细化工有限公司 | 银蚀刻液组合物和利用它的显示基板 |
| CN105755472A (zh) * | 2015-01-05 | 2016-07-13 | 东友精细化工有限公司 | 银蚀刻液组合物和利用它的显示基板 |
| CN105986270A (zh) * | 2015-03-19 | 2016-10-05 | 东友精细化工有限公司 | 蚀刻剂组合物、液晶显示器阵列基板制作方法和阵列基板 |
| TWI679307B (zh) * | 2015-03-19 | 2019-12-11 | 南韓商東友精細化工有限公司 | 蝕刻劑組合物、液晶顯示器陣列基板製作方法和陣列基板 |
| CN105986270B (zh) * | 2015-03-19 | 2019-08-16 | 东友精细化工有限公司 | 蚀刻剂组合物、液晶显示器阵列基板制作方法和阵列基板 |
| CN106148961A (zh) * | 2015-03-27 | 2016-11-23 | 东友精细化工有限公司 | 蚀刻剂组合物、形成金属线图案方法和制造阵列基板方法 |
| CN105060727B (zh) * | 2015-07-31 | 2018-03-02 | 安徽和润特种玻璃有限公司 | 一种高透过率防眩玻璃用蚀刻液及其制备方法 |
| CN105060727A (zh) * | 2015-07-31 | 2015-11-18 | 安徽和润特种玻璃有限公司 | 一种高透过率防眩玻璃用蚀刻液及其制备方法 |
| CN105803459B (zh) * | 2016-05-03 | 2019-01-15 | 苏州晶瑞化学股份有限公司 | 一种微电子用多层金属膜蚀刻液及其应用 |
| CN105803459A (zh) * | 2016-05-03 | 2016-07-27 | 苏州晶瑞化学股份有限公司 | 一种微电子用多层金属膜蚀刻液及其应用 |
| CN107587135A (zh) * | 2016-07-08 | 2018-01-16 | 深圳新宙邦科技股份有限公司 | 一种钼铝钼蚀刻液 |
| CN113106453A (zh) * | 2020-02-26 | 2021-07-13 | 江苏艾森半导体材料股份有限公司 | 一种蚀刻液组合物及其应用 |
| CN114318338A (zh) * | 2020-09-29 | 2022-04-12 | 上海飞凯材料科技股份有限公司 | 一种铜镍金结构的铜种子层蚀刻液及其应用 |
| CN112415799A (zh) * | 2020-11-10 | 2021-02-26 | Tcl华星光电技术有限公司 | 阵列基板及其制备方法 |
| CN114107991A (zh) * | 2021-11-29 | 2022-03-01 | 清华大学 | 一种钼-铜双层膜材料蚀刻方法及腐蚀液 |
| CN116497355A (zh) * | 2023-04-10 | 2023-07-28 | 珠海市裕洲环保科技有限公司 | 一种酸性铜蚀刻液及其应用 |
| CN116497355B (zh) * | 2023-04-10 | 2024-03-22 | 珠海市裕洲环保科技有限公司 | 一种酸性铜蚀刻液及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130057656A (ko) | 2013-06-03 |
| KR101333551B1 (ko) | 2013-11-28 |
| WO2013077580A1 (ko) | 2013-05-30 |
| CN103890232B (zh) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103890232B (zh) | 铜钼合金膜的蚀刻液组合物 | |
| CN103924244A (zh) | 铜/钼膜或铜/钼合金膜的蚀刻液组合物 | |
| CN103668208B (zh) | 铜钼合金膜的蚀刻液组合物 | |
| CN104513981A (zh) | 铜及钼含有膜的蚀刻液组合物 | |
| CN103814432B (zh) | 增大蚀刻液蚀刻用量的铜/钼合金膜的蚀刻方法 | |
| CN103890234B (zh) | 钼合金膜及铟氧化膜的蚀刻液组合物 | |
| CN103924242B (zh) | 铜/钼膜或铜/钼合金膜的蚀刻液组合物 | |
| CN104513983B (zh) | 铜及钼含有膜的蚀刻液组合物 | |
| TWI503451B (zh) | 用以蝕刻金屬層之組成物 | |
| CN107475715A (zh) | 双氧水稳定剂及包含其的蚀刻组合物 | |
| CN107090581A (zh) | 蚀刻液组合物 | |
| CN103572292B (zh) | 蚀刻剂组合物以及用于蚀刻多层金属膜的方法 | |
| TWI632670B (zh) | 用於銅基金屬膜的蝕刻劑組合物及製造液晶顯示器用陣列基板的方法 | |
| CN112663064A (zh) | 一种铜钼金属蚀刻液及其制备方法和应用 | |
| CN108359987A (zh) | 蚀刻组合物 | |
| CN107630219A (zh) | 金属膜蚀刻液组合物及显示装置用阵列基板的制造方法 | |
| WO2022095262A1 (zh) | 用于铜钼膜层的蚀刻剂与铜钼膜层的蚀刻方法 | |
| CN110230059B (zh) | 显示面板的金属图案制作方法 | |
| CN103107130A (zh) | 用于液晶显示器的阵列基板及其制造方法，蚀刻液组合物和形成金属配线的方法 | |
| CN107236956A (zh) | 用于铜基金属层的蚀刻剂组合物及用其制造显示设备的阵列基板的方法 | |
| JPWO2018074279A1 (ja) | エッチング液組成物及びエッチング方法 | |
| CN108950556B (zh) | 蚀刻液组合物 | |
| KR101621545B1 (ko) | 액정표시장치용 어레이 기판의 제조 방법 | |
| CN102648269A (zh) | 用于单层钼膜的蚀刻剂组合物 | |
| CN103824808A (zh) | 蚀刻剂组合物、形成lcd布线的方法、阵列基板及其制法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |