WO2019180915A1 - Etching liquid for thick copper film - Google Patents
Etching liquid for thick copper film Download PDFInfo
- Publication number
- WO2019180915A1 WO2019180915A1 PCT/JP2018/011695 JP2018011695W WO2019180915A1 WO 2019180915 A1 WO2019180915 A1 WO 2019180915A1 JP 2018011695 W JP2018011695 W JP 2018011695W WO 2019180915 A1 WO2019180915 A1 WO 2019180915A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- etching
- hydrogen peroxide
- mass
- copper
- acid
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 211
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000010949 copper Substances 0.000 title claims abstract description 85
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 title abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 160
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 230000002378 acidificating effect Effects 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 38
- -1 amine compound Chemical class 0.000 claims abstract description 33
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012141 concentrate Substances 0.000 claims description 30
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 23
- 150000003851 azoles Chemical class 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 16
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 11
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 11
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 10
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 7
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 7
- 229940043276 diisopropanolamine Drugs 0.000 claims description 6
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 26
- 229910001431 copper ion Inorganic materials 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 98
- 239000010408 film Substances 0.000 description 51
- 239000002994 raw material Substances 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 15
- 239000003381 stabilizer Substances 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 150000003536 tetrazoles Chemical class 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
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- CEGRHPCDLKAHJD-UHFFFAOYSA-N 1,1,1-propanetricarboxylic acid Chemical compound CCC(C(O)=O)(C(O)=O)C(O)=O CEGRHPCDLKAHJD-UHFFFAOYSA-N 0.000 description 1
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- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
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- RDTCWQXQLWFJGY-UHFFFAOYSA-N 1-(methylamino)butan-2-ol Chemical compound CCC(O)CNC RDTCWQXQLWFJGY-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
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- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- DPEOTCPCYHSVTC-UHFFFAOYSA-N 2-aminohexan-1-ol Chemical compound CCCCC(N)CO DPEOTCPCYHSVTC-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- FBXBSCUQZWUZDD-UHFFFAOYSA-N 3-(ethylamino)propan-1-ol Chemical compound CCNCCCO FBXBSCUQZWUZDD-UHFFFAOYSA-N 0.000 description 1
- HNNZBZKURNBXOO-UHFFFAOYSA-N 3-(methylamino)butan-1-ol Chemical compound CNC(C)CCO HNNZBZKURNBXOO-UHFFFAOYSA-N 0.000 description 1
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 description 1
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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
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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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
Definitions
- the present invention relates to an etching solution for thick copper film used when etching copper used for wiring of flat panel displays such as liquid crystal and organic EL.
- Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPD) such as liquid crystal and organic EL (Electro-Luminescence).
- FPD Thin Film Transistors
- FPD flat panel displays
- the wiring material used has been required to have a resistance lower than that of aluminum.
- copper which has a lower resistance than aluminum, has been used as a wiring material.
- the FPD wiring is formed by wet etching a copper film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened. Here, the following points are important for wet etching of wiring. (1) Processing accuracy is high and uniform. (2) The wiring cross section after processing is a forward taper of a predetermined angle. (3) The etching rate does not change because copper ions are contained (the bath life is long).
- Patent Document 1 is disclosed as an etchant that satisfies such requirements.
- Hydrogen peroxide An acidic organic acid, An amine compound; A hydrogen peroxide decomposition inhibitor; Azoles, A multilayer film etching solution containing molybdenum and copper, characterized by containing a precipitation inhibitor containing an aluminum salt, is disclosed.
- This etchant has an etching rate of copper (Cu) and molybdenum (Mo), a taper angle of the etched boundary region, an undercut of molybdenum (Mo), a residue of molybdenum (Mo), resistance to overetching, precipitates, It has the performance that satisfies the level used in the production at the present time in the evaluation such as the rate of superhydrolysis.
- Patent Document 2 includes at least one selected from (A) hydrogen peroxide, (B) an inorganic acid not containing a fluorine atom, (C) succinic acid, glycolic acid, lactic acid, malonic acid, and malic acid. A kind of organic acid, (D) an amine compound having 2 to 10 carbon atoms and having an amino group and a hydroxyl group so that the total number of groups is 2 or more, (E) 5-amino-1H-tetrazole, and (F) A multilayer thin film etching solution containing a hydrogen peroxide stabilizer and a copper layer and a molybdenum layer having a pH of 2.5 to 5 is disclosed.
- the present invention has been conceived in order to solve the above problems, and provides an etching solution for a copper thick film that has a high etching rate and can be etched even under a high copper ion concentration.
- the etching solution for copper thick film according to the present invention is: Hydrogen peroxide, Strongly acidic substances, An amine compound; A hydrogen peroxide decomposition inhibitor; Azoles, Including water, pH is less than 2.
- the copper thick film etching solution according to the present invention has an etching rate of 380 nm / min or more as an etching rate. Further, even if the copper ion concentration is 20,000 ppm, the etching can be continued.
- the copper thick film etching solution according to the present invention can be processed in a conventional process time when etching copper in a thick film state, and a high concentration of copper ions is contained in the etching solution. Even if it remains, the etching can be continued.
- the copper thick film etching solution according to the present invention will be described.
- the following description shows an embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention.
- the numerical range is indicated by “A to B” or “A to B”, it means “A or more and B or less”. That is, it means a large range including the numerical value A and a small range including the numerical value B.
- greater than A means large without including the numerical value A
- “less than A” means small without including the numerical value A.
- the copper thick film etching solution according to the present invention contains hydrogen peroxide, a strongly acidic substance, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and water, and has a pH of less than 2.
- hydrogen peroxide a strongly acidic substance
- an amine compound a hydrogen peroxide decomposition inhibitor
- an azole a hydrogen peroxide decomposition inhibitor
- ⁇ Hydrogen peroxide> copper is oxidized to become copper oxide (CuO) and is dissolved by an acid. That is, hydrogen peroxide is used as an oxidizing agent that oxidizes copper. Hydrogen peroxide and overwater are synonymous. Hydrogen peroxide is preferably 4.0% by mass to 5.8% by mass with respect to the total amount of the etching solution.
- the copper thick film etching solution according to the present invention has a pH of less than 2 in order to increase the etching rate. Therefore, it is necessary to use a strongly acidic substance.
- the strongly acidic substance may be an inorganic strong acid or an organic strong acid. Moreover, even if it is weakly acidic, it is sufficient if the pH of the entire etching solution can be made less than 2.
- the strength of an acid is represented by an acid dissociation constant Ka.
- a value obtained by taking the negative logarithm of the acid dissociation constant Ka is referred to as pKa.
- Strongly acidic substances that can be used in the present invention include those having a pKa of 3 or less in addition to a substance called a strong acid having a pKa of 0 or less. This is because a plurality of types of substances are mixed in the etching solution, but if the pKa is 3 or less, the pH of the entire etching solution can be adjusted to less than 2. Therefore, the strongly acidic substance in the present invention is a substance having a pKa of 3 or less.
- examples of the strongly acidic substance inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid (hydrogen bromide aqueous solution), hydroiodic acid (hydrogen iodide aqueous solution), sulfamic acid, and the like.
- organic acids that are strongly acidic substances include glycine, asparagine, aspartic acid, alanine, glutamic acid, valine, glutamine, glutamic acid, leucine, arginine, isoleucine, lysine, serine, histidine, threonine, phenylalanine, cysteine, tyrosine, methionine, Amino acids such as tryptophan, proline, malonic acid, pyruvic acid, oxalic acid, tartaric acid, trans-aconitic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, vinylsulfonic acid, picric acid, trichloroacetic acid, Compounds such as acetamide, salicylic acid and 4-nitroaniline can be suitably used.
- the strongly acidic substance can be contained in an amount of 5% by mass to 15% by mass with respect to the total amount of the etching solution.
- a chemical described later may be prepared so that the total pH is less than 2.
- the copper thick film etching solution according to the present invention may contain a weakly acidic organic acid in addition to the strongly acidic substance in order to adjust the taper angle and suppress the decomposition of hydrogen peroxide.
- weak acid means a substance having an acid dissociation constant pKa larger than 3.
- organic acid examples include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, and amino acids having 1 to 10 carbon atoms.
- aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, butyric acid, hydroxybutyric acid, succinic acid, malic acid, maleic acid, fumaric acid, valeric acid, and glutar Preferred are acid, itaconic acid, adipic acid, caproic acid, citric acid, propanetricarboxylic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like.
- Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, mandelic acid, phthalic acid, isophthalic acid, and terephthalic acid.
- amino acid having 1 to 10 carbon atoms include carbamic acid, sarcosine, 4-aminobutyric acid, iminodibutyric acid, nitrilotriacetic acid and the like.
- the weakly acidic organic acid can be contained in an amount of 1 to 20% by mass with respect to the total amount of the etching solution.
- the amine compound is responsible for adjusting the taper angle of the copper film and adjusting the pH of the etching solution.
- the amine compound those having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethy
- 1-amino-2-propanol (CAS number 78-96-6: hereinafter also referred to as “1A2P”)
- N, N-diethyl-1,3-propanediamine (CAS number 104-78-9: (Hereinafter also referred to as “NNDPA”)
- NPDPA N-diethyl-1,3-propanediamine
- TIPA triisopropanolamine
- DIPA diisopropanolamine
- the amine compound is preferably contained in an amount of 0.05% to 5.5% by mass with respect to the total amount of the etching solution.
- Hydro peroxide decomposition inhibitor In the copper thick film etching solution according to the present invention, hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added.
- the hydrogen peroxide decomposition inhibitor is also referred to as a hydrogen peroxide stabilizer (or “super water stabilizer”).
- hydrogen peroxide decomposition inhibitor examples include urea-based hydrogen peroxide decomposition inhibitors such as urea, phenylurea, allylurea, 1,3-dimethylurea, thiourea, phenylacetamide, phenylethylene glycol, 1- Lower alcohols such as propanol and 2-propanol, ethylene glycol monobutyl ether, and the like can be used.
- urea CAS No. 57-13-6
- phenylurea CAS No. 64-10-8: hereinafter also referred to as “FN”
- 1-propanol CAS No. 71-23-8: hereinafter referred to as “1P”.
- ethylene glycol monobutyl ether (CAS No. 111-76-2: hereinafter also referred to as “BG”) is particularly preferred.
- the hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.1% by mass to 2.0% by mass with respect to the total amount of the etching solution.
- the copper thick film etching solution according to the present invention contains azoles in order to suppress the etching rate of Cu.
- the pH is set to less than 2 in order to increase the etching rate. In this pH region, the etching rate changes sharply due to a slight pH difference. Then, the etching rate may not be adjusted only by the composition ratio of the strongly acidic substance. Therefore, an etching rate inhibitor is used.
- azoles triazoles, tetrazoles, imidazoles, thiazoles and the like can be suitably used. More specifically, the following can be listed.
- triazole 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be preferably used.
- tetrazole 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and the like can be suitably used.
- imidazoles 1H-imidazole, 1H-benzimidazole and the like can be preferably used.
- thiazoles 1,3-thiazole, 4-methylthiazole and the like can be suitably used.
- tetrazoles are highly effective in suppressing the etching rate, and in particular, 5-amino-1H-tetrazole (CAS number 4418-61-5: hereinafter also referred to as “5A1HT”), 5-methyl-1H-tetrazole. (CAS number 4076-36-2: hereinafter also referred to as “5M1HT”), 5-phenyl-1H-tetrazole (CAS number 18039-42-4: hereinafter also referred to as “5phenyl1HT”) is preferred, and triazoles are preferred.
- 5-methyl-1H-benzotriazole (CAS number 136-85-6: hereinafter also referred to as “5M1HBTA”) and 1H-benzotriazole (CAS number 95-14-7: hereinafter also referred to as “BTA”) are preferable. .
- These azoles are preferably contained in an amount of 0.01% by mass to 0.10% by mass with respect to the total amount of the etching solution.
- etching solution for dilution is usually added to the copper etching solution so that the Cu ion concentration is about 2,000 ppm to 4,000 ppm. This is because when the copper ion concentration is increased, the decomposition rate of the excess water is increased, and thus the excess water concentration in the etching solution is decreased.
- the etching solution according to the present invention uses the hydrogen peroxide decomposition inhibitor in an environment with strong acidity, and therefore suppresses the decomposition rate of overwater. Therefore, it is not necessary to add an etching solution for diluting Cu ions even when the Cu ion concentration is higher. More specifically, it is not necessary to add an etching solution for dilution until the Cu concentration of the etching solution is 20,000 ppm.
- the copper thick film etching solution of the present invention may contain water and various commonly used additives as long as the etching performance is not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable. Water can be determined as the remaining component for each of the above components.
- the range of the content ratio of each component described above is appropriately adjusted so that the total amount of the etching solution becomes 100% by mass. Moreover, although copper ion may be contained from the beginning, since the amount is small relative to other compositions, the composition ratio as the total amount of the etching solution is ignored.
- the copper thick film etching solution according to the present invention is adjusted to a pH of less than 2.
- the etching solution can be used between 20 ° C. and 40 ° C. More preferably, it is 25 degreeC to 35 degreeC, Most preferably, 30 degreeC to 35 degreeC is good.
- Hydrogen peroxide is used in the copper thick film etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately.
- the hydrogen peroxide solution is an aqueous solution of hydrogen peroxide. Further, only hydrogen peroxide (or hydrogen peroxide solution), raw materials excluding water and copper ions (referred to as “etching solution raw material”) may be stored together.
- the thing of a liquid and a powder may exist in an etching liquid raw material. That is, the copper thick film etching solution according to the present invention may be completed by combining the etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide solution).
- an etchant raw material solution may be prepared by mixing an etchant raw material and water.
- a solution of the etchant raw material prepared with the etchant raw material and water is referred to as an “etching concentrate”.
- the etching concentrate has a smaller volume as compared with the etching liquid because there is no hydrogen peroxide, so it is convenient for storage and transport. Therefore, the copper thick film etching solution of the present invention may be completed by combining the etching concentrate, water, and hydrogen peroxide.
- the amount of water in the etching concentrate may be sufficient to dissolve the etching solution raw material.
- the water in the etching concentrate may be less than the water in the etching liquid. Accordingly, when it is considered that hydrogen peroxide is supplied as an aqueous hydrogen peroxide solution, the copper thick film etching solution of the present invention is completed by combining the etching concentrated solution, water, and hydrogen peroxide solution. be able to.
- each component ratio of an etching concentrate is represented by the ratio with respect to the whole quantity when an etching liquid is completed. Therefore, the total of the components of the etching concentrate is not 100% by mass.
- the object using the copper thick film etching solution according to the present invention is a copper film formed on a substrate with a thickness of 600 nm or more.
- An isolation layer made of another element may be formed between the substrate and the copper film.
- the etching method according to the present invention is performed by bringing a substrate on which a copper film is formed to a thickness of 600 nm or more into contact with an etching solution for copper thick film.
- the copper thick film etching solution according to the present invention can be stored for a long period of time by storing hydrogen peroxide, the etching solution raw material (or etching concentrate) and water separately during storage. Therefore, in actual use, these are mixed to complete the etching solution.
- the blending method is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
- an etching concentrate is prepared by mixing a raw material for etching with a certain amount of water.
- Hydrogen peroxide is normally supplied as a hydrogen peroxide solution having a concentration higher than the hydrogen peroxide concentration of the copper thick film etching solution according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate is prepared.
- This step may be called a step of preparing an etching solution for copper thick film.
- each component is prepared at a predetermined ratio, and the pH is less than 2.
- the etching solution is used under the condition of less than pH 2 and 20 ° C. to 40 ° C. Therefore, it is desirable that the object to be etched is also preheated to this temperature.
- the method for bringing the substrate to be processed into contact with the etching solution is not particularly limited. An etching solution may be sprayed on the substrate to be processed from above as in a shower type, or a method of dipping the substrate to be processed into a pool of etching solution may be used. This may be called a step of bringing the copper thick film etching solution into contact with the substrate to be processed.
- the substrate to be processed is a substrate in a state where at least a copper film is formed on a base material such as glass and a resist pattern for pattern formation is formed on the copper film.
- the copper thick film etchant according to the present invention was evaluated in terms of the copper etching rate (nm / min), the taper angle (°) of the cross section of the etched wiring, and the shape after etching.
- the etching rate was measured as follows. First, a copper film having a thickness of 600 nm was formed by sputtering on a silicon wafer on which a thermal oxide film of 100 nm was formed. This copper film was brought into contact with an etching solution at 30 ° C. (may be 35 ° C. in some comparative examples) for 20 to 60 seconds.
- the resistance value of the film before and after etching was measured using a constant current application type 4-terminal 4-probe resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-T610 type). The change in film thickness was calculated from the change in resistance value, and the etching rate was calculated.
- the etching rate of copper was 380 nm / min or more, it was judged as a circle ( ⁇ ). Other than that, it was judged as X (outside) as outside the specified range.
- the taper angle was measured as follows. First, a copper film with a thickness of 600 nm was formed on a glass substrate by sputtering to produce a copper thick film sample. A resist patterned into a wiring shape was formed on this copper film, and used as a base material for taper angle evaluation. That is, the base material includes a substrate, a copper film, and a patterned resist layer on the copper film. Etching was performed by immersing the base material in an etching solution for the time of just etching. After the etching sample was washed and dried, the wiring portion was cut and the cut surface was observed.
- the observation of the cut surface was performed using SEM (Hitachi: SU8020 type) under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times.
- the shape of the etched portion was also observed during the SEM observation. Note that just etching is the time from the start of etching until the film transmits light. The time when the film transmitted light was visually confirmed.
- FIG. 1 Schematic diagram of cut surface shape is shown in FIG.
- an angle 3 formed by the substrate 1 and the etched inclined surface 5 is a taper angle (°). If the taper angle 3 was 30 ° to 80 °, it was judged as a circle ( ⁇ ). If it was out of the range of this angle, it was judged as X (x).
- the Cu layer is represented by reference numeral 2 and the resist is represented by reference numeral 4.
- Example 1 As a strongly acidic substance, 8.33% by mass of nitric acid As an amine compound, 5.24% by mass of NNDPA (N, N-diethyl-1,3-propanediamine) As a water stabilizer, 0.12% by mass of FN (phenylurea) As azoles, 0.01% by mass of 5M1HT (5-methyl-1H-tetrazole) An etching solution raw material consisting of 72.41% by mass of water was prepared to prepare an etching concentrate. Each component ratio in the etching concentrate is expressed as a ratio to the total amount when the etching liquid is completed by mixing with a hydrogen peroxide solution described later. The same applies to the following examples and comparative examples.
- Example 2 As a strongly acidic substance, 9.88% by mass of malonic acid, As an amine compound, 1.35% by mass of 1A2P (1-amino-2-propanol) As a water stabilizer, 0.68% by mass of 1P (1-propanol), As azoles, 0.05% by mass of 5A1HT (5-amino-1H-tetrazole)
- the etching liquid raw material which consists of was mixed with 75.70 mass% of water, and the etching concentrated liquid was prepared.
- Example 3 As a strongly acidic substance, 6.93% by mass of sulfuric acid 1.84% by mass of glycine As an amine compound, 2.49% by mass of TIPA (triisopropanolamine) As a water stabilizer, 0.64% by mass of urea As azoles, 0.03% by mass of 5M1HBTA (5-methyl-1H-benzotriazole)
- the etching liquid raw material which consists of with 73.36 mass% of water was prepared, and the etching concentrated liquid was prepared.
- Example 4 As a strongly acidic substance, 7.20% by mass of malonic acid, 6.77% by mass of glutaric acid as organic acid As an amine compound, 0.06% by mass of DIPA (diisopropanolamine) As a water stabilizer, 0.96% by mass of BG (ethylene glycol monobutyl ether), As azoles, 0.03% by mass of 5-phenyl 1HT (5-phenyl-1H-tetrazole) An etching solution raw material consisting of 70.32% by mass of water was prepared to prepare an etching concentrate.
- DIPA diisopropanolamine
- BG ethylene glycol monobutyl ether
- 5-phenyl 1HT 5-phenyl 1HT
- Example 5 As a strongly acidic substance, 7.04% by mass of ethanesulfonic acid Malic acid as organic acid is 4.4% by mass As an amine compound, 1.04% by mass of TIPA (triisopropanolamine) As a water stabilizer, 0.85% by mass of BG (ethylene glycol monobutyl ether), As azoles, 0.02% by mass of BTA (benzotriazole)
- TIPA triisopropanolamine
- BG ethylene glycol monobutyl ether
- BTA benzotriazole
- Example 6 As a strongly acidic substance, 7.04% by mass of ethanesulfonic acid As an amine compound, 1.04% by mass of TIPA (triisopropanolamine) As a water stabilizer, 0.85% by mass of BG (ethylene glycol monobutyl ether), As azoles, 0.02% by mass of BTA (benzotriazole)
- TIPA triisopropanolamine
- BG ethylene glycol monobutyl ether
- BTA benzotriazole
- the pH of the entire etching solution can be adjusted to less than 2 if it is a strongly acidic substance.
- the copper thick film etching solution thus prepared can realize an etching rate of 380 nm / min or more under a copper ion environment of 20,000 ppm.
- the taper angle can be adjusted from 30 ° to 80 °. Also, there was no particular problem with its shape.
- the amine compound is preferably 0.05% by mass or more and less than 2.0% by mass (Examples 2, 4, 5, 6). reference). It is considered that the strongly acidic substance of the organic acid has a higher pKa than that of the inorganic acid, so that if the amine compound is added too much, the pH of the entire etching solution cannot be made less than 2.
- the etching solution for thick copper film according to the present invention can realize a high etching rate even under a high copper ion concentration, and etch thick film copper on a large area substrate at a processing speed of an actual mass production machine. can do.
- the etching solution according to the present invention can be suitably used when etching a thick copper film of 600 nm or more.
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Abstract
Provided is an etching liquid for a thick copper film, which has a high etching rate such that the same production speed as that achieved with conventional etching liquids can be maintained even when the copper film to be etched is thick, and which allows for etching under high copper ion concentrations. The etching liquid for a thick copper film contains hydrogen peroxide, a strongly acidic substance, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and water, and has a pH of less than 2. Even when the copper ion concentration is as high as 20,000 ppm, the etching liquid allows for etching of the copper film at an etching rate of 380 nm/min or higher. Additionally, with this etching liquid, the taper angle can be adjusted to 30º-80º.
Description
本発明は、液晶、有機EL等のフラットパネルディスプレイの配線用に用いられる銅をエッチングする際に用いる、銅厚膜用エッチング液に関する。
The present invention relates to an etching solution for thick copper film used when etching copper used for wiring of flat panel displays such as liquid crystal and organic EL.
液晶や有機EL(Electro-Luminescence)等のフラットパネルディスプレイ(FPD)のTFT(Thin Film Transistor)は、配線材料としてアルミニウムが使用されてきた。近年、大画面で高精細度のFPDが普及し、使用される配線材料には、アルミニウムよりも低抵抗のものが求められた。そこで、近年アルミニウムより低抵抗である銅が配線材料として用いられるようになった。
Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPD) such as liquid crystal and organic EL (Electro-Luminescence). In recent years, large-screen, high-definition FPDs have become widespread, and the wiring material used has been required to have a resistance lower than that of aluminum. In recent years, therefore, copper, which has a lower resistance than aluminum, has been used as a wiring material.
FPDの配線は、スパッタリング法で形成された銅膜をウエットエッチングすることによって形成される。大面積を一気に形成できるので、工程の短縮化が可能だからである。ここで、配線のウエットエッチングには、以下の点が重要とされている。
(1)加工精度が高く一様であること。
(2)加工後の配線断面が所定の角度の順テーパーであること。
(3)銅イオンが含まれることでエッチングレートが変化しないこと(バスライフが長いこと)。 The FPD wiring is formed by wet etching a copper film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened. Here, the following points are important for wet etching of wiring.
(1) Processing accuracy is high and uniform.
(2) The wiring cross section after processing is a forward taper of a predetermined angle.
(3) The etching rate does not change because copper ions are contained (the bath life is long).
(1)加工精度が高く一様であること。
(2)加工後の配線断面が所定の角度の順テーパーであること。
(3)銅イオンが含まれることでエッチングレートが変化しないこと(バスライフが長いこと)。 The FPD wiring is formed by wet etching a copper film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened. Here, the following points are important for wet etching of wiring.
(1) Processing accuracy is high and uniform.
(2) The wiring cross section after processing is a forward taper of a predetermined angle.
(3) The etching rate does not change because copper ions are contained (the bath life is long).
このような要求を満たすエッチング液として、特許文献1が開示されている。
ここでは、
過酸化水素と、
酸性有機酸と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
アルミニウム塩を含む析出防止剤を含むことを特徴とするモリブデンと銅を含む多層膜用エッチング液が開示されている。 Patent Document 1 is disclosed as an etchant that satisfies such requirements.
here,
Hydrogen peroxide,
An acidic organic acid,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
A multilayer film etching solution containing molybdenum and copper, characterized by containing a precipitation inhibitor containing an aluminum salt, is disclosed.
ここでは、
過酸化水素と、
酸性有機酸と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
アルミニウム塩を含む析出防止剤を含むことを特徴とするモリブデンと銅を含む多層膜用エッチング液が開示されている。 Patent Document 1 is disclosed as an etchant that satisfies such requirements.
here,
Hydrogen peroxide,
An acidic organic acid,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
A multilayer film etching solution containing molybdenum and copper, characterized by containing a precipitation inhibitor containing an aluminum salt, is disclosed.
このエッチング液は、銅(Cu)およびモリブデン(Mo)のエッチングレート、エッチングされた境界領域のテーパー角、モリブデン(Mo)のアンダーカット、モリブデン(Mo)の残渣、オーバーエッチングに対する耐性、析出物、過水分解速度といった評価において、現時点での製造に使用される水準を満たす性能を有している。
This etchant has an etching rate of copper (Cu) and molybdenum (Mo), a taper angle of the etched boundary region, an undercut of molybdenum (Mo), a residue of molybdenum (Mo), resistance to overetching, precipitates, It has the performance that satisfies the level used in the production at the present time in the evaluation such as the rate of superhydrolysis.
また、同様の目的で特許文献2には、(A)過酸化水素、(B)フッ素原子を含有しない無機酸、(C)コハク酸、グリコール酸、乳酸、マロン酸及びリンゴ酸から選ばれる少なくとも一種である有機酸、(D)炭素数2~10であり、かつアミノ基と水酸基とをその合計基数が二以上となるように有するアミン化合物、(E)5-アミノ-1H-テトラゾール、及び(F)過酸化水素安定剤を含み、pHが2.5~5である銅層及びモリブデン層を含む多層薄膜用エッチング液が開示されている。
For the same purpose, Patent Document 2 includes at least one selected from (A) hydrogen peroxide, (B) an inorganic acid not containing a fluorine atom, (C) succinic acid, glycolic acid, lactic acid, malonic acid, and malic acid. A kind of organic acid, (D) an amine compound having 2 to 10 carbon atoms and having an amino group and a hydroxyl group so that the total number of groups is 2 or more, (E) 5-amino-1H-tetrazole, and (F) A multilayer thin film etching solution containing a hydrogen peroxide stabilizer and a copper layer and a molybdenum layer having a pH of 2.5 to 5 is disclosed.
現在、4Kや8Kといった高解像度の規格が提唱されている。これらの規格は、小さな画面ではその能力が発揮されない。したがって、画面が従来よりさらに大きなディスプレイ(大画面FPD)が開発されてきている。大画面FPDでは、画素を駆動させるための配線の距離が長くなるため、より低抵抗な配線が要求される。銅配線において抵抗を少なくするには、配線の断面積を増やすことが考えられる。しかし、配線の幅を広げ1つの画素の面積を大きくすると高精細度という要求を満たせない。
Currently, high-resolution standards such as 4K and 8K have been proposed. These standards do not work on small screens. Therefore, a display (large screen FPD) having a larger screen than before has been developed. In the large screen FPD, since the distance of the wiring for driving the pixel becomes long, a wiring with lower resistance is required. In order to reduce the resistance in the copper wiring, it is conceivable to increase the cross-sectional area of the wiring. However, if the width of the wiring is increased and the area of one pixel is increased, the demand for high definition cannot be satisfied.
一方、配線材料の抵抗を下げるためには、銀や金といった銅より抵抗率の低い材料を使うことも考えれるが、コストが高くなりすぎ、普及という観点からは望ましくない。結果、銅配線の厚み方向を増やすことで断面積を大きくし、抵抗値を減らすことが必要となる。
On the other hand, in order to lower the resistance of the wiring material, it is possible to use a material having a lower resistivity than copper, such as silver or gold, but the cost becomes too high, which is not desirable from the viewpoint of diffusion. As a result, it is necessary to increase the cross-sectional area and increase the resistance value by increasing the thickness direction of the copper wiring.
銅の厚みを厚くした配線を形成するには、次のような技術的課題を解決する必要がある。
(1)従来同様の製造レートを維持するために、エッチング速度を早くする。
(2)エッチング液中には、エッチングされた銅イオン量が増えるので、高銅イオン濃度であっても、エッチングできる。 In order to form a wiring with thick copper, it is necessary to solve the following technical problems.
(1) In order to maintain the same manufacturing rate as before, the etching rate is increased.
(2) Since the amount of etched copper ions increases in the etching solution, etching can be performed even at a high copper ion concentration.
(1)従来同様の製造レートを維持するために、エッチング速度を早くする。
(2)エッチング液中には、エッチングされた銅イオン量が増えるので、高銅イオン濃度であっても、エッチングできる。 In order to form a wiring with thick copper, it is necessary to solve the following technical problems.
(1) In order to maintain the same manufacturing rate as before, the etching rate is increased.
(2) Since the amount of etched copper ions increases in the etching solution, etching can be performed even at a high copper ion concentration.
本発明は上記の課題を解決するために想到されたものであり、エッチング速度が速く、高銅イオン濃度下であってもエッチングが可能な銅厚膜用エッチング液を提供するものである。
The present invention has been conceived in order to solve the above problems, and provides an etching solution for a copper thick film that has a high etching rate and can be etched even under a high copper ion concentration.
より具体的に、本発明に係る銅厚膜用エッチング液は、
過酸化水素と、
強酸性物質と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
水を含み、
pHが2未満であることを特徴とする。 More specifically, the etching solution for copper thick film according to the present invention is:
Hydrogen peroxide,
Strongly acidic substances,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
Including water,
pH is less than 2.
過酸化水素と、
強酸性物質と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
水を含み、
pHが2未満であることを特徴とする。 More specifically, the etching solution for copper thick film according to the present invention is:
Hydrogen peroxide,
Strongly acidic substances,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
Including water,
pH is less than 2.
本発明に係る銅厚膜用エッチング液は、エッチングレートとして、380nm/min以上のエッチングレートを有する。また、銅イオン濃度が20,000ppmであっても、エッチングを継続することが可能である。
The copper thick film etching solution according to the present invention has an etching rate of 380 nm / min or more as an etching rate. Further, even if the copper ion concentration is 20,000 ppm, the etching can be continued.
したがって、本発明に係る銅厚膜用エッチング液は、厚膜状態の銅をエッチングする際にも、従来程度の工程時間で処理することができ、また、エッチング液中に高濃度の銅イオンが残留しても、エッチングを継続することができるという効果を有する。
Accordingly, the copper thick film etching solution according to the present invention can be processed in a conventional process time when etching copper in a thick film state, and a high concentration of copper ions is contained in the etching solution. Even if it remains, the etching can be continued.
以下本発明に係る銅厚膜用エッチング液について説明する。なお、以下の説明は本発明に係るエッチング液の一実施形態を示すものであり、本発明の趣旨を逸脱しない範囲で、以下の実施形態および実施例は改変されてもよい。なお、以下の説明において、数値範囲を「A~B」若しくは「AからB」で示した場合、「A以上、B以下」の意味である。すなわち、数値Aを含んで大きく、且つ数値Bを含んで小さい範囲を意味する。また、「Aより大きい」は数値Aを含まず大きく、「A未満」は数値Aを含まず小さいという意味である。
Hereinafter, the copper thick film etching solution according to the present invention will be described. The following description shows an embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention. In the following description, when the numerical range is indicated by “A to B” or “A to B”, it means “A or more and B or less”. That is, it means a large range including the numerical value A and a small range including the numerical value B. Further, “greater than A” means large without including the numerical value A, and “less than A” means small without including the numerical value A.
本発明に係る銅厚膜用エッチング液は、過酸化水素と、強酸性物質と、アミン化合物と、過酸化水素分解抑制剤と、アゾール類と、水を含み、pHは2未満である。以下それぞれの成分について詳説する。
The copper thick film etching solution according to the present invention contains hydrogen peroxide, a strongly acidic substance, an amine compound, a hydrogen peroxide decomposition inhibitor, an azole, and water, and has a pH of less than 2. Hereinafter, each component will be described in detail.
<過酸化水素>
銅のエッチングは、銅が酸化され、酸化銅(CuO)となり、酸により溶解される。すなわち、過酸化水素は、銅を酸化する酸化剤として用いられる。なお、過酸化水素と過水は同義語である。過酸化水素は、エッチング液全量の4.0質量%~5.8質量%が好ましい。 <Hydrogen peroxide>
In the etching of copper, copper is oxidized to become copper oxide (CuO) and is dissolved by an acid. That is, hydrogen peroxide is used as an oxidizing agent that oxidizes copper. Hydrogen peroxide and overwater are synonymous. Hydrogen peroxide is preferably 4.0% by mass to 5.8% by mass with respect to the total amount of the etching solution.
銅のエッチングは、銅が酸化され、酸化銅(CuO)となり、酸により溶解される。すなわち、過酸化水素は、銅を酸化する酸化剤として用いられる。なお、過酸化水素と過水は同義語である。過酸化水素は、エッチング液全量の4.0質量%~5.8質量%が好ましい。 <Hydrogen peroxide>
In the etching of copper, copper is oxidized to become copper oxide (CuO) and is dissolved by an acid. That is, hydrogen peroxide is used as an oxidizing agent that oxidizes copper. Hydrogen peroxide and overwater are synonymous. Hydrogen peroxide is preferably 4.0% by mass to 5.8% by mass with respect to the total amount of the etching solution.
<強酸性物質>
本発明に係る銅厚膜用エッチング液は、エッチングレートを高くするために、pHを2未満にする。したがって、酸性の強い物質を用いる必要がある。強酸性物質は無機強酸であっても有機強酸であってもよい。また、弱酸性であっても、エッチング液全体のpHを2未満にできるものであればよい。 <Strongly acidic substances>
The copper thick film etching solution according to the present invention has a pH of less than 2 in order to increase the etching rate. Therefore, it is necessary to use a strongly acidic substance. The strongly acidic substance may be an inorganic strong acid or an organic strong acid. Moreover, even if it is weakly acidic, it is sufficient if the pH of the entire etching solution can be made less than 2.
本発明に係る銅厚膜用エッチング液は、エッチングレートを高くするために、pHを2未満にする。したがって、酸性の強い物質を用いる必要がある。強酸性物質は無機強酸であっても有機強酸であってもよい。また、弱酸性であっても、エッチング液全体のpHを2未満にできるものであればよい。 <Strongly acidic substances>
The copper thick film etching solution according to the present invention has a pH of less than 2 in order to increase the etching rate. Therefore, it is necessary to use a strongly acidic substance. The strongly acidic substance may be an inorganic strong acid or an organic strong acid. Moreover, even if it is weakly acidic, it is sufficient if the pH of the entire etching solution can be made less than 2.
一般に酸の強度は、酸解離定数Kaによって表される。また、酸解離定数Kaのマイナス対数をとった値をpKaという。本発明に利用できる強酸性物質はpKaがゼロ以下である強酸と呼ばれる物質に加えて、pKaが3以下のものが利用できる。エッチング液は、複数種の物質が混入されるが、pKaが3以下の物質であれば、エッチング液全体のpHを2未満に調整することも可能だからである。したがって、本発明において強酸性物質とは、pKaが3以下の物質である。
Generally, the strength of an acid is represented by an acid dissociation constant Ka. A value obtained by taking the negative logarithm of the acid dissociation constant Ka is referred to as pKa. Strongly acidic substances that can be used in the present invention include those having a pKa of 3 or less in addition to a substance called a strong acid having a pKa of 0 or less. This is because a plurality of types of substances are mixed in the etching solution, but if the pKa is 3 or less, the pH of the entire etching solution can be adjusted to less than 2. Therefore, the strongly acidic substance in the present invention is a substance having a pKa of 3 or less.
具体的には強酸性物質の無機酸としては、塩酸、硫酸、硝酸、臭化水素酸(臭化水素の水溶液)、ヨウ化水素酸(ヨウ化水素の水溶液)、スルファミン酸等が挙げられる。
Specifically, examples of the strongly acidic substance inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid (hydrogen bromide aqueous solution), hydroiodic acid (hydrogen iodide aqueous solution), sulfamic acid, and the like.
また、強酸性物質の有機酸としては、グリシン、アスパラギン、アスパラギン酸、アラニン、グルタミン酸、バリン、グルタミン、グルタミン酸、ロイシン、アルギニン、イソロイシン、リシン、セリン、ヒスチジン、トレオニン、フェニルアラニン、システイン、チロシン、メチオニン、トリプトファン、プロリンといったアミノ酸や、マロン酸、ピルビン酸、シュウ酸、酒石酸、trans-アコニット酸、パラトルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、ビニルスルホン酸、ピクリン酸、トリクロロ酢酸、アセトアミド、サリチル酸、4-ニトロアニリンといった化合物が好適に利用できる。
In addition, organic acids that are strongly acidic substances include glycine, asparagine, aspartic acid, alanine, glutamic acid, valine, glutamine, glutamic acid, leucine, arginine, isoleucine, lysine, serine, histidine, threonine, phenylalanine, cysteine, tyrosine, methionine, Amino acids such as tryptophan, proline, malonic acid, pyruvic acid, oxalic acid, tartaric acid, trans-aconitic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, vinylsulfonic acid, picric acid, trichloroacetic acid, Compounds such as acetamide, salicylic acid and 4-nitroaniline can be suitably used.
なお、有機酸で強酸性を示すものとして、ハロゲンを骨格中に有するものが挙げられる。特にトリフルオロ酢酸といった強酸性物質はある。しかし、フッ素を骨格中に含むものは、フッ酸に変化する可能性があり、基板に損傷を与えるおそれがあるので、本発明に係る強酸性物質からは除くのが望ましい。
In addition, what has a halogen in a skeleton is mentioned as what shows strong acidity with an organic acid. There are particularly strongly acidic substances such as trifluoroacetic acid. However, those containing fluorine in the skeleton may be converted into hydrofluoric acid and may damage the substrate, so it is desirable to remove them from the strongly acidic substance according to the present invention.
強酸性物質は、エッチング液全量に対して5質量%~15質量%含有させることができる。エッチング対象箇所やエッチング後のテーパー角の調整のために、後述する薬剤を調製し、全体のpHが2未満になるように調製してよい。
The strongly acidic substance can be contained in an amount of 5% by mass to 15% by mass with respect to the total amount of the etching solution. In order to adjust the portion to be etched and the taper angle after etching, a chemical described later may be prepared so that the total pH is less than 2.
<有機酸>
本発明に係る銅厚膜用エッチング液は、テーパー角の調整や、過酸化水素の分解抑制といった役割から強酸性物質以外に弱酸性の有機酸が含まれていてもよい。なお、ここで弱酸性とは酸解離定数pKaが3より大きい物質を言う。 <Organic acid>
The copper thick film etching solution according to the present invention may contain a weakly acidic organic acid in addition to the strongly acidic substance in order to adjust the taper angle and suppress the decomposition of hydrogen peroxide. Here, weak acid means a substance having an acid dissociation constant pKa larger than 3.
本発明に係る銅厚膜用エッチング液は、テーパー角の調整や、過酸化水素の分解抑制といった役割から強酸性物質以外に弱酸性の有機酸が含まれていてもよい。なお、ここで弱酸性とは酸解離定数pKaが3より大きい物質を言う。 <Organic acid>
The copper thick film etching solution according to the present invention may contain a weakly acidic organic acid in addition to the strongly acidic substance in order to adjust the taper angle and suppress the decomposition of hydrogen peroxide. Here, weak acid means a substance having an acid dissociation constant pKa larger than 3.
具体的には有機酸としては、炭素数1~18の脂肪族カルボン酸、炭素数6~10の芳香族カルボン酸のほか、炭素数1~10のアミノ酸などが好ましく挙げられる。
Specifically, preferred examples of the organic acid include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, and amino acids having 1 to 10 carbon atoms.
炭素数1~18の脂肪族カルボン酸としては、ギ酸、酢酸、プロピオン酸、乳酸、グリコール酸、ジグリコール酸、酪酸、ヒドロキシ酪酸、コハク酸、リンゴ酸、マレイン酸、フマル酸、吉草酸、グルタル酸、イタコン酸、アジピン酸、カプロン酸、クエン酸、プロパントリカルボン酸、エナント酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸などが好ましく挙げられる。
Examples of aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, butyric acid, hydroxybutyric acid, succinic acid, malic acid, maleic acid, fumaric acid, valeric acid, and glutar Preferred are acid, itaconic acid, adipic acid, caproic acid, citric acid, propanetricarboxylic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like.
炭素数6~10の芳香族カルボン酸としては、安息香酸、マンデル酸、フタル酸、イソフタル酸、テレフタル酸などが好ましく挙げられる。
Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, mandelic acid, phthalic acid, isophthalic acid, and terephthalic acid.
また、炭素数1~10のアミノ酸としては、カルバミン酸、サルコシン、4-アミノ酪酸、イミノジ酪酸、ニトリロ三酢酸などが好ましく挙げられる。弱酸性の有機酸はエッチング液全量に対して1~20質量%含有させることができる。
Preferred examples of the amino acid having 1 to 10 carbon atoms include carbamic acid, sarcosine, 4-aminobutyric acid, iminodibutyric acid, nitrilotriacetic acid and the like. The weakly acidic organic acid can be contained in an amount of 1 to 20% by mass with respect to the total amount of the etching solution.
<アミン化合物>
アミン化合物は銅膜のテーパー角の調整および、エッチング液のpH調整を担う。アミン化合物としては、炭素数2~10のものが好適に利用できる。より具体的には、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、1,2-プロパンジアミン、1,3-プロパンジアミン、N,N-ジメチル-1,3-プロパンジアミン、N,N-ジエチル-1,3-プロパンジアミン、1,3-ジアミノブタン、2,3-ジアミノブタン、ペンタメチレンジアミン、2,4-ジアミノペンタン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、N-メチルエチレンジアミン、N,N-ジメチルエチレンジアミン、トリメチルエチレンジアミン、N-エチルエチレンジアミン、N,N-ジエチルエチレンジアミン、トリエチルエチレンジアミン、1,2,3-トリアミノプロパン、ヒドラジン、トリス(2-アミノエチル)アミン、テトラ(アミノメチル)メタン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチルペンタミン、ヘプタエチレンオクタミン、ノナエチレンデカミン、ジアザビシクロウンデセンなどのポリアミン;エタノールアミン、N-メチルエタノールアミン、N-メチルジエタノールアミン、N-エチルエタノールアミン、N-アミノエチルエタノールアミン、N-プロピルエタノールアミン、N-ブチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、1-アミノ-2-プロパノール、N-メチルイソプロパノールアミン、N-エチルイソプロパノールアミン、トリイソプロパノールアミン、ジイソプロパノールアミン、N-プロピルイソプロパノールアミン、2-アミノプロパン-1-オール、N-メチル-2-アミノ-プロパン-1-オール、N-エチル-2-アミノ-プロパン-1-オール、1-アミノプロパン-3-オール、N-メチル-1-アミノプロパン-3-オール、N-エチル-1-アミノプロパン-3-オール、1-アミノブタン-2-オール、N-メチル-1-アミノブタン-2-オール、N-エチル-1-アミノブタン-2オール、2-アミノブタン-1-オール、N-メチル-2-アミノブタン-1-オール、N-エチル-2-アミノブタン-1-オール、3-アミノブタン-1-オール、N-メチル-3-アミノブタン-1-オール、N-エチル-3-アミノブタン-1-オール、1-アミノブタン-4-オール、N-メチル1-アミノブタン-4-オール、N-エチル-1-アミノブタン-4-オール、1-アミノ-2-メチルプロパン-2-オール、2-アミノ-2-メチルプロパン-1-オール、1-アミノペンタン-4-オール、2-アミノ-4-メチルペンタン-1-オール、2-アミノヘキサン-1-オール、3-アミノヘプタン-4-オール、1-アミノオクタン-2-オール、5-アミノオクタン-4-オール、1-アミノプロパン-2,3-ジオール、2-アミノプロパン-1,3-ジオール、トリス(オキシメチル)アミノメタン、1,2-ジアミノプロパン-3-オール、1,3-ジアミノプロパン-2-オール、2-(2-アミノエトキシ)エタノール、2-(2-アミノエチルアミノ)エタノール、ジグリコールアミンなどのアルカノールアミンが好ましく挙げられ、これらを単独で又は複数を組み合わせて用いることができる。 <Amine compound>
The amine compound is responsible for adjusting the taper angle of the copper film and adjusting the pH of the etching solution. As the amine compound, those having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) amino , Tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene, etc .; ethanolamine, N-methylethanolamine, N-methyldiethanolamine N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanol Amine, triisopropanolamine, diisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2 Amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1- Aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutan-1-ol, N-methyl- 2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutane-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutane-1- All, 1-aminobutane-4-ol, N-methyl 1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol, 1-amino-2-me Tilpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (Oxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, Preferred examples include alkanolamines such as diglycolamine, and these can be used alone or in combination.
アミン化合物は銅膜のテーパー角の調整および、エッチング液のpH調整を担う。アミン化合物としては、炭素数2~10のものが好適に利用できる。より具体的には、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、1,2-プロパンジアミン、1,3-プロパンジアミン、N,N-ジメチル-1,3-プロパンジアミン、N,N-ジエチル-1,3-プロパンジアミン、1,3-ジアミノブタン、2,3-ジアミノブタン、ペンタメチレンジアミン、2,4-ジアミノペンタン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、N-メチルエチレンジアミン、N,N-ジメチルエチレンジアミン、トリメチルエチレンジアミン、N-エチルエチレンジアミン、N,N-ジエチルエチレンジアミン、トリエチルエチレンジアミン、1,2,3-トリアミノプロパン、ヒドラジン、トリス(2-アミノエチル)アミン、テトラ(アミノメチル)メタン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチルペンタミン、ヘプタエチレンオクタミン、ノナエチレンデカミン、ジアザビシクロウンデセンなどのポリアミン;エタノールアミン、N-メチルエタノールアミン、N-メチルジエタノールアミン、N-エチルエタノールアミン、N-アミノエチルエタノールアミン、N-プロピルエタノールアミン、N-ブチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、1-アミノ-2-プロパノール、N-メチルイソプロパノールアミン、N-エチルイソプロパノールアミン、トリイソプロパノールアミン、ジイソプロパノールアミン、N-プロピルイソプロパノールアミン、2-アミノプロパン-1-オール、N-メチル-2-アミノ-プロパン-1-オール、N-エチル-2-アミノ-プロパン-1-オール、1-アミノプロパン-3-オール、N-メチル-1-アミノプロパン-3-オール、N-エチル-1-アミノプロパン-3-オール、1-アミノブタン-2-オール、N-メチル-1-アミノブタン-2-オール、N-エチル-1-アミノブタン-2オール、2-アミノブタン-1-オール、N-メチル-2-アミノブタン-1-オール、N-エチル-2-アミノブタン-1-オール、3-アミノブタン-1-オール、N-メチル-3-アミノブタン-1-オール、N-エチル-3-アミノブタン-1-オール、1-アミノブタン-4-オール、N-メチル1-アミノブタン-4-オール、N-エチル-1-アミノブタン-4-オール、1-アミノ-2-メチルプロパン-2-オール、2-アミノ-2-メチルプロパン-1-オール、1-アミノペンタン-4-オール、2-アミノ-4-メチルペンタン-1-オール、2-アミノヘキサン-1-オール、3-アミノヘプタン-4-オール、1-アミノオクタン-2-オール、5-アミノオクタン-4-オール、1-アミノプロパン-2,3-ジオール、2-アミノプロパン-1,3-ジオール、トリス(オキシメチル)アミノメタン、1,2-ジアミノプロパン-3-オール、1,3-ジアミノプロパン-2-オール、2-(2-アミノエトキシ)エタノール、2-(2-アミノエチルアミノ)エタノール、ジグリコールアミンなどのアルカノールアミンが好ましく挙げられ、これらを単独で又は複数を組み合わせて用いることができる。 <Amine compound>
The amine compound is responsible for adjusting the taper angle of the copper film and adjusting the pH of the etching solution. As the amine compound, those having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) amino , Tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene, etc .; ethanolamine, N-methylethanolamine, N-methyldiethanolamine N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanol Amine, triisopropanolamine, diisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2 Amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1- Aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutan-1-ol, N-methyl- 2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutane-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutane-1- All, 1-aminobutane-4-ol, N-methyl 1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol, 1-amino-2-me Tilpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (Oxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, Preferred examples include alkanolamines such as diglycolamine, and these can be used alone or in combination.
これらの中でも、1-アミノ-2-プロパノール(CAS番号78-96-6:以下「1A2P」とも呼ぶ。)、N,N-ジエチル-1,3-プロパンジアミン(CAS番号104-78-9:以下「NNDPA」とも呼ぶ。)、トリイソプロパノールアミン(CAS番号122-20-3:以下「TIPA」とも呼ぶ。)およびジイソプロパノールアミン(CAS番号110-97-4:以下「DIPA」とも呼ぶ。)が特に好ましい。また、アミン化合物はエッチング液全量に対して、0.05質量%~5.5質量%含有させるのが好ましい。
Among these, 1-amino-2-propanol (CAS number 78-96-6: hereinafter also referred to as “1A2P”), N, N-diethyl-1,3-propanediamine (CAS number 104-78-9: (Hereinafter also referred to as “NNDPA”), triisopropanolamine (CAS number 122-20-3: hereinafter also referred to as “TIPA”) and diisopropanolamine (CAS number 110-97-4: hereinafter also referred to as “DIPA”) Is particularly preferred. Further, the amine compound is preferably contained in an amount of 0.05% to 5.5% by mass with respect to the total amount of the etching solution.
<過酸化水素分解抑制剤>
本発明に係る銅厚膜用エッチング液では、酸化剤として過酸化水素を利用している。過酸化水素は、自己分解するため、その分解を抑制する分解抑制剤を添加する。過酸化水素分解抑制剤は、過酸化水素安定剤(若しくは「過水安定剤」)とも呼ぶ。 <Hydrogen peroxide decomposition inhibitor>
In the copper thick film etching solution according to the present invention, hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. The hydrogen peroxide decomposition inhibitor is also referred to as a hydrogen peroxide stabilizer (or “super water stabilizer”).
本発明に係る銅厚膜用エッチング液では、酸化剤として過酸化水素を利用している。過酸化水素は、自己分解するため、その分解を抑制する分解抑制剤を添加する。過酸化水素分解抑制剤は、過酸化水素安定剤(若しくは「過水安定剤」)とも呼ぶ。 <Hydrogen peroxide decomposition inhibitor>
In the copper thick film etching solution according to the present invention, hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. The hydrogen peroxide decomposition inhibitor is also referred to as a hydrogen peroxide stabilizer (or “super water stabilizer”).
過酸化水素分解抑制剤としては、尿素、フェニル尿素、アリル尿素、1,3-ジメチル尿素、チオ尿素などの尿素系過酸化水素分解抑制剤のほか、フェニル酢酸アミド、フェニルエチレングリコールや、1-プロパノール、2-プロパノール等の低級アルコールや、エチレングリコールモノブチルエーテルなどが用いることができる。これらの中でも、尿素(CAS番号57-13-6)、フェニル尿素(CAS番号64-10-8:以下「FN」とも呼ぶ。)、1-プロパノール(CAS番号71-23-8:以下「1P」とも呼ぶ。)、エチレングリコールモノブチルエーテル(CAS番号111-76-2:以下「BG」とも呼ぶ。)が特に好ましい。過酸化水素分解抑制剤は、エッチング液全量に対して、0.1質量%~2.0質量%含有させるのが好ましい。
Examples of the hydrogen peroxide decomposition inhibitor include urea-based hydrogen peroxide decomposition inhibitors such as urea, phenylurea, allylurea, 1,3-dimethylurea, thiourea, phenylacetamide, phenylethylene glycol, 1- Lower alcohols such as propanol and 2-propanol, ethylene glycol monobutyl ether, and the like can be used. Among these, urea (CAS No. 57-13-6), phenylurea (CAS No. 64-10-8: hereinafter also referred to as “FN”), 1-propanol (CAS No. 71-23-8: hereinafter referred to as “1P”). And ethylene glycol monobutyl ether (CAS No. 111-76-2: hereinafter also referred to as “BG”) is particularly preferred. The hydrogen peroxide decomposition inhibitor is preferably contained in an amount of 0.1% by mass to 2.0% by mass with respect to the total amount of the etching solution.
<アゾール類>
本発明に係る銅厚膜用エッチング液では、Cuのエッチングレートを抑制するために、アゾール類を含有する。本発明に係る銅厚膜用エッチング液は、エッチングレートを高くするために、pHを2未満に設定する。このpHの領域では、わずかなpHの違いによって、エッチングレートが急峻に変化する。すると、強酸性物質の組成比だけではエッチングレートを調整できない場合も生じる。そこで、エッチングレートの抑制剤を利用する。 <Azoles>
The copper thick film etching solution according to the present invention contains azoles in order to suppress the etching rate of Cu. In the copper thick film etching solution according to the present invention, the pH is set to less than 2 in order to increase the etching rate. In this pH region, the etching rate changes sharply due to a slight pH difference. Then, the etching rate may not be adjusted only by the composition ratio of the strongly acidic substance. Therefore, an etching rate inhibitor is used.
本発明に係る銅厚膜用エッチング液では、Cuのエッチングレートを抑制するために、アゾール類を含有する。本発明に係る銅厚膜用エッチング液は、エッチングレートを高くするために、pHを2未満に設定する。このpHの領域では、わずかなpHの違いによって、エッチングレートが急峻に変化する。すると、強酸性物質の組成比だけではエッチングレートを調整できない場合も生じる。そこで、エッチングレートの抑制剤を利用する。 <Azoles>
The copper thick film etching solution according to the present invention contains azoles in order to suppress the etching rate of Cu. In the copper thick film etching solution according to the present invention, the pH is set to less than 2 in order to increase the etching rate. In this pH region, the etching rate changes sharply due to a slight pH difference. Then, the etching rate may not be adjusted only by the composition ratio of the strongly acidic substance. Therefore, an etching rate inhibitor is used.
アゾール類としては、トリアゾール類、テトラゾール類、イミダゾール類、チアゾール類等が好適に利用することができる。より具体的には、以下のものが列挙できる。トリアゾール類としては、1H-ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、3-アミノ-1H-トリアゾール等が好適に利用できる。
As the azoles, triazoles, tetrazoles, imidazoles, thiazoles and the like can be suitably used. More specifically, the following can be listed. As the triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be preferably used.
テトラゾール類としては、1H-テトラゾール、5-メチル-1H-テトラゾール、5-フェニル-1H-テトラゾール、5-アミノ-1H-テトラゾール等が好適に利用できる。また、イミダゾール類としては、1H-イミダゾール、1H-ベンゾイミダゾール等が好適に利用できる。また、チアゾール類としては、1,3-チアゾール、4-メチルチアゾール等が好適に利用できる。
As the tetrazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and the like can be suitably used. As imidazoles, 1H-imidazole, 1H-benzimidazole and the like can be preferably used. As thiazoles, 1,3-thiazole, 4-methylthiazole and the like can be suitably used.
なお、これらのうち、テトラゾール類はエッチングレート抑制に効果が高く、とりわけ5-アミノ-1H-テトラゾール(CAS番号4418-61-5:以後「5A1HT」とも呼ぶ。)、5-メチル-1H-テトラゾール(CAS番号4076-36-2:以後「5M1HT」とも呼ぶ。)、5-フェニル-1H-テトラゾール(CAS番号18039-42-4:以後「5フェニル1HT」とも呼ぶ。)が好ましく、トリアゾール類では、5-メチル-1H-ベンゾトリアゾール(CAS番号136-85-6:以後「5M1HBTA」とも呼ぶ。)、1H-ベンゾトリアゾール(CAS番号95-14-7:以後「BTA」とも呼ぶ。)が好ましい。
Of these, tetrazoles are highly effective in suppressing the etching rate, and in particular, 5-amino-1H-tetrazole (CAS number 4418-61-5: hereinafter also referred to as “5A1HT”), 5-methyl-1H-tetrazole. (CAS number 4076-36-2: hereinafter also referred to as “5M1HT”), 5-phenyl-1H-tetrazole (CAS number 18039-42-4: hereinafter also referred to as “5phenyl1HT”) is preferred, and triazoles are preferred. 5-methyl-1H-benzotriazole (CAS number 136-85-6: hereinafter also referred to as “5M1HBTA”) and 1H-benzotriazole (CAS number 95-14-7: hereinafter also referred to as “BTA”) are preferable. .
これらのアゾール類は、エッチング液全量に対して、0.01質量%~0.10質量%含有させるのが好ましい。
These azoles are preferably contained in an amount of 0.01% by mass to 0.10% by mass with respect to the total amount of the etching solution.
<銅イオン>
銅のエッチング液は、通常Cuイオン濃度が2,000ppmから4,000ppm程度になるように、希釈用のエッチング液が追添される。銅イオン濃度が高くなると、過水の分解速度が速くなるため、エッチング液中の過水濃度が低下してしまうからである。しかし、本発明に係るエッチング液は、酸性が強い環境で過酸化水素分解抑制剤を使用するため、過水の分解速度を抑制する。したがって、より高いCuイオン濃度になっても、Cuイオンの希釈のためのエッチング液の追添は不要である。より具体的には、エッチング液のCu濃度が20,000ppmまでは、希釈のためのエッチング液を追添する必要はない。 <Copper ion>
An etching solution for dilution is usually added to the copper etching solution so that the Cu ion concentration is about 2,000 ppm to 4,000 ppm. This is because when the copper ion concentration is increased, the decomposition rate of the excess water is increased, and thus the excess water concentration in the etching solution is decreased. However, the etching solution according to the present invention uses the hydrogen peroxide decomposition inhibitor in an environment with strong acidity, and therefore suppresses the decomposition rate of overwater. Therefore, it is not necessary to add an etching solution for diluting Cu ions even when the Cu ion concentration is higher. More specifically, it is not necessary to add an etching solution for dilution until the Cu concentration of the etching solution is 20,000 ppm.
銅のエッチング液は、通常Cuイオン濃度が2,000ppmから4,000ppm程度になるように、希釈用のエッチング液が追添される。銅イオン濃度が高くなると、過水の分解速度が速くなるため、エッチング液中の過水濃度が低下してしまうからである。しかし、本発明に係るエッチング液は、酸性が強い環境で過酸化水素分解抑制剤を使用するため、過水の分解速度を抑制する。したがって、より高いCuイオン濃度になっても、Cuイオンの希釈のためのエッチング液の追添は不要である。より具体的には、エッチング液のCu濃度が20,000ppmまでは、希釈のためのエッチング液を追添する必要はない。 <Copper ion>
An etching solution for dilution is usually added to the copper etching solution so that the Cu ion concentration is about 2,000 ppm to 4,000 ppm. This is because when the copper ion concentration is increased, the decomposition rate of the excess water is increased, and thus the excess water concentration in the etching solution is decreased. However, the etching solution according to the present invention uses the hydrogen peroxide decomposition inhibitor in an environment with strong acidity, and therefore suppresses the decomposition rate of overwater. Therefore, it is not necessary to add an etching solution for diluting Cu ions even when the Cu ion concentration is higher. More specifically, it is not necessary to add an etching solution for dilution until the Cu concentration of the etching solution is 20,000 ppm.
<その他>
本発明の銅厚膜用エッチング液には、これらの成分の他、水と、エッチング性能を阻害しない範囲で通常用いられる各種添加剤が添加されてもよい。水は、精密加工を目的とするため、異物が存在しない物が望ましい。純水若しくは超純水であれば好ましい。水は上記各成分に対する残りの成分として決めることができる。 <Others>
In addition to these components, the copper thick film etching solution of the present invention may contain water and various commonly used additives as long as the etching performance is not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable. Water can be determined as the remaining component for each of the above components.
本発明の銅厚膜用エッチング液には、これらの成分の他、水と、エッチング性能を阻害しない範囲で通常用いられる各種添加剤が添加されてもよい。水は、精密加工を目的とするため、異物が存在しない物が望ましい。純水若しくは超純水であれば好ましい。水は上記各成分に対する残りの成分として決めることができる。 <Others>
In addition to these components, the copper thick film etching solution of the present invention may contain water and various commonly used additives as long as the etching performance is not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable. Water can be determined as the remaining component for each of the above components.
また、上記に説明した各成分の含有比率の範囲は、エッチング液総量で100質量%になるように適宜それぞれ調整されるのは言うまでもない。また、銅イオンは最初から含まれていてもよいが、他の組成物に対して量が少ないので、エッチング液総量としての組成比は無視する。
Further, it goes without saying that the range of the content ratio of each component described above is appropriately adjusted so that the total amount of the etching solution becomes 100% by mass. Moreover, although copper ion may be contained from the beginning, since the amount is small relative to other compositions, the composition ratio as the total amount of the etching solution is ignored.
<pH、温度>
本発明に係る銅厚膜用エッチング液は、pH2未満の範囲に調整される。また、エッチング液は、20℃から40℃の間で使用することができる。より好ましくは25℃から35℃であり、最も好ましくは30℃から35℃がよい。 <PH, temperature>
The copper thick film etching solution according to the present invention is adjusted to a pH of less than 2. The etching solution can be used between 20 ° C. and 40 ° C. More preferably, it is 25 degreeC to 35 degreeC, Most preferably, 30 degreeC to 35 degreeC is good.
本発明に係る銅厚膜用エッチング液は、pH2未満の範囲に調整される。また、エッチング液は、20℃から40℃の間で使用することができる。より好ましくは25℃から35℃であり、最も好ましくは30℃から35℃がよい。 <PH, temperature>
The copper thick film etching solution according to the present invention is adjusted to a pH of less than 2. The etching solution can be used between 20 ° C. and 40 ° C. More preferably, it is 25 degreeC to 35 degreeC, Most preferably, 30 degreeC to 35 degreeC is good.
<保存>
本発明に係る銅厚膜用エッチング液には、過酸化水素が用いられる。過酸化水素は自己分解する。そのためエッチング液には、過酸化水素分解抑制剤が含まれている。しかし、保存の際には、過酸化水素(若しくは過酸化水素水)とその他の液体を分けて保存しても良い。なお、過酸化水素水は、過酸化水素の水溶液である。また、過酸化水素(若しくは過酸化水素水)、水および銅イオンを除いた原料(「エッチング液原料」と呼ぶ。)だけをまとめて保存してもよい。なお、エッチング液原料には、液体のものと粉体のものが存在してもよい。すなわち、本発明に係る銅厚膜用エッチング液は、エッチング液原料と、水と、過酸化水素(若しくは過酸化水素水)を合わせて完成させてもよい。 <Save>
Hydrogen peroxide is used in the copper thick film etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. The hydrogen peroxide solution is an aqueous solution of hydrogen peroxide. Further, only hydrogen peroxide (or hydrogen peroxide solution), raw materials excluding water and copper ions (referred to as “etching solution raw material”) may be stored together. In addition, the thing of a liquid and a powder may exist in an etching liquid raw material. That is, the copper thick film etching solution according to the present invention may be completed by combining the etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide solution).
本発明に係る銅厚膜用エッチング液には、過酸化水素が用いられる。過酸化水素は自己分解する。そのためエッチング液には、過酸化水素分解抑制剤が含まれている。しかし、保存の際には、過酸化水素(若しくは過酸化水素水)とその他の液体を分けて保存しても良い。なお、過酸化水素水は、過酸化水素の水溶液である。また、過酸化水素(若しくは過酸化水素水)、水および銅イオンを除いた原料(「エッチング液原料」と呼ぶ。)だけをまとめて保存してもよい。なお、エッチング液原料には、液体のものと粉体のものが存在してもよい。すなわち、本発明に係る銅厚膜用エッチング液は、エッチング液原料と、水と、過酸化水素(若しくは過酸化水素水)を合わせて完成させてもよい。 <Save>
Hydrogen peroxide is used in the copper thick film etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. The hydrogen peroxide solution is an aqueous solution of hydrogen peroxide. Further, only hydrogen peroxide (or hydrogen peroxide solution), raw materials excluding water and copper ions (referred to as “etching solution raw material”) may be stored together. In addition, the thing of a liquid and a powder may exist in an etching liquid raw material. That is, the copper thick film etching solution according to the present invention may be completed by combining the etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide solution).
また、エッチング液原料と水を混ぜ合わせ、エッチング液原料の溶液を作成しておいてよい。エッチング液原料と水で作製したエッチング液原料の溶液を「エッチング濃縮液」と呼ぶ。エッチング濃縮液は、エッチング液と比べると過酸化水素が無い分だけ体積が少ないので、保存や移送の際には便利である。したがって、本発明の銅厚膜用エッチング液は、エッチング濃縮液と水と過酸化水素を合わせて完成させてもよい。
Also, an etchant raw material solution may be prepared by mixing an etchant raw material and water. A solution of the etchant raw material prepared with the etchant raw material and water is referred to as an “etching concentrate”. The etching concentrate has a smaller volume as compared with the etching liquid because there is no hydrogen peroxide, so it is convenient for storage and transport. Therefore, the copper thick film etching solution of the present invention may be completed by combining the etching concentrate, water, and hydrogen peroxide.
ここで、エッチング濃縮液の水は、エッチング液原料が溶解するだけの量があればよい。言い換えると、エッチング濃縮液中の水は、エッチング液中の水より少なくてもよい。したがって、過酸化水素が水溶液である過酸化水素水として供給されると考えると、本発明の銅厚膜用エッチング液は、エッチング濃縮液と水と過酸化水素水の3つを合わせて完成させることができる。
Here, the amount of water in the etching concentrate may be sufficient to dissolve the etching solution raw material. In other words, the water in the etching concentrate may be less than the water in the etching liquid. Accordingly, when it is considered that hydrogen peroxide is supplied as an aqueous hydrogen peroxide solution, the copper thick film etching solution of the present invention is completed by combining the etching concentrated solution, water, and hydrogen peroxide solution. be able to.
また、水はエッチング濃縮液若しくは過酸化水素水に含めてしまえば、エッチング濃縮液と過酸化水素水の2つを合わせて完成させることもできる。また、本明細書において、エッチング濃縮液の各成分比率は、エッチング液が完成したときの全量に対する比率で表す。したがって、エッチング濃縮液の各成分の合計は、100質量%にはならない。
Also, if water is included in the etching concentrate or hydrogen peroxide solution, it can be completed by combining the etching concentrate and hydrogen peroxide solution. Moreover, in this specification, each component ratio of an etching concentrate is represented by the ratio with respect to the whole quantity when an etching liquid is completed. Therefore, the total of the components of the etching concentrate is not 100% by mass.
<エッチング方法>
本発明に係る銅厚膜用エッチング液を用いる対象は、基板上に形成された厚さ600nm以上の厚みで形成された銅膜である。基板と銅膜の間に他の元素からなるアイソレート層が形成されていてもよい。本発明に係るエッチング方法は、600nm以上の厚みに銅膜が形成された基板を、銅厚膜用エッチング液に接触させることで行われる。 <Etching method>
The object using the copper thick film etching solution according to the present invention is a copper film formed on a substrate with a thickness of 600 nm or more. An isolation layer made of another element may be formed between the substrate and the copper film. The etching method according to the present invention is performed by bringing a substrate on which a copper film is formed to a thickness of 600 nm or more into contact with an etching solution for copper thick film.
本発明に係る銅厚膜用エッチング液を用いる対象は、基板上に形成された厚さ600nm以上の厚みで形成された銅膜である。基板と銅膜の間に他の元素からなるアイソレート層が形成されていてもよい。本発明に係るエッチング方法は、600nm以上の厚みに銅膜が形成された基板を、銅厚膜用エッチング液に接触させることで行われる。 <Etching method>
The object using the copper thick film etching solution according to the present invention is a copper film formed on a substrate with a thickness of 600 nm or more. An isolation layer made of another element may be formed between the substrate and the copper film. The etching method according to the present invention is performed by bringing a substrate on which a copper film is formed to a thickness of 600 nm or more into contact with an etching solution for copper thick film.
本発明に係る銅厚膜用エッチング液は、保存の際に、過酸化水素とエッチング液原料(若しくはエッチング濃縮液)および水を分けて保存しておくことで長期保存が可能になる。そこで、実際に使用する際には、これらを調合してエッチング液を完成させる。調合の方法は、最終的に過酸化水素の濃度が所定の濃度になれば、限定されるものではない。
The copper thick film etching solution according to the present invention can be stored for a long period of time by storing hydrogen peroxide, the etching solution raw material (or etching concentrate) and water separately during storage. Therefore, in actual use, these are mixed to complete the etching solution. The blending method is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
一例を示すと、一定量の水にエッチング液原料を混ぜたエッチング濃縮液を調製しておく。過酸化水素は通常本発明に係る銅厚膜用エッチング液の過酸化水素濃度より高い濃度の過酸化水素水として供給される。そこで、過酸化水素水とエッチング濃縮液を所定量ずつ調合する。この工程は、銅厚膜用エッチング液を調合する工程と呼んでもよい。調合された銅厚膜用エッチング液は、各成分が所定の割合に調合され、pHが2未満になっている。
As an example, an etching concentrate is prepared by mixing a raw material for etching with a certain amount of water. Hydrogen peroxide is normally supplied as a hydrogen peroxide solution having a concentration higher than the hydrogen peroxide concentration of the copper thick film etching solution according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate is prepared. This step may be called a step of preparing an etching solution for copper thick film. In the prepared etching solution for thick copper film, each component is prepared at a predetermined ratio, and the pH is less than 2.
エッチングを行う際は、上記の通り、pH2未満で、20℃から40℃の条件でエッチング液を使用する。したがって、エッチングの被対象物も、この温度に余熱されるのが望ましい。被処理基板をエッチング液に接触させる方法は、特に限定されない。シャワー式のように上方からエッチング液を被処理基板に対して散布してもよいし、エッチング液のプールに被処理基板をディップさせる方法でもよい。これを、銅厚膜用エッチング液を被処理基板に接触させる工程と呼んでも良い。
When etching is performed, as described above, the etching solution is used under the condition of less than pH 2 and 20 ° C. to 40 ° C. Therefore, it is desirable that the object to be etched is also preheated to this temperature. The method for bringing the substrate to be processed into contact with the etching solution is not particularly limited. An etching solution may be sprayed on the substrate to be processed from above as in a shower type, or a method of dipping the substrate to be processed into a pool of etching solution may be used. This may be called a step of bringing the copper thick film etching solution into contact with the substrate to be processed.
なお、被処理基板とは、ガラス等の基材の上に少なくとも銅膜が形成され、この銅膜上にパターン形成のためのレジストパターンが形成されている状態の基板である。
The substrate to be processed is a substrate in a state where at least a copper film is formed on a base material such as glass and a resist pattern for pattern formation is formed on the copper film.
<各種評価方法の説明>
本発明に係る銅厚膜用エッチング液に対しては、銅のエッチングレート(nm/min)、エッチングされた配線の断面のテーパー角(°)およびエッチング後の形状の項目で評価を行った。 <Description of various evaluation methods>
The copper thick film etchant according to the present invention was evaluated in terms of the copper etching rate (nm / min), the taper angle (°) of the cross section of the etched wiring, and the shape after etching.
本発明に係る銅厚膜用エッチング液に対しては、銅のエッチングレート(nm/min)、エッチングされた配線の断面のテーパー角(°)およびエッチング後の形状の項目で評価を行った。 <Description of various evaluation methods>
The copper thick film etchant according to the present invention was evaluated in terms of the copper etching rate (nm / min), the taper angle (°) of the cross section of the etched wiring, and the shape after etching.
エッチングレートは、以下のようにして測定した。まず、熱酸化膜100nmが形成されたシリコンウエハー上にスパッタ法により、銅膜を600nmの厚みで形成した。この銅膜を30℃(比較例によっては35℃の場合もある。)のエッチング液に20秒から60秒間接触させた。
The etching rate was measured as follows. First, a copper film having a thickness of 600 nm was formed by sputtering on a silicon wafer on which a thermal oxide film of 100 nm was formed. This copper film was brought into contact with an etching solution at 30 ° C. (may be 35 ° C. in some comparative examples) for 20 to 60 seconds.
エッチング前後の膜の抵抗値を、定電流印加方式の4端子4探針法抵抗率計(三菱化学アナリテック製:MCP-T610型)を用いて測定した。この抵抗値の変化より膜厚変化を算出し、エッチングレートを算出した。
The resistance value of the film before and after etching was measured using a constant current application type 4-terminal 4-probe resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-T610 type). The change in film thickness was calculated from the change in resistance value, and the etching rate was calculated.
なお、銅のエッチングレートは380nm/min以上であれば、丸(○)と判断した。それ以外は規定範囲外としてバツ(×)と判断した。
In addition, if the etching rate of copper was 380 nm / min or more, it was judged as a circle (◯). Other than that, it was judged as X (outside) as outside the specified range.
なお、「丸」は規格範囲内、成功若しくは合格を意味し、「バツ」は規格範囲外、失敗若しくは不合格を意味する。以下の評価でも同じである。
"Maru" means within the standard range, success or success, and "X" means out of standard range, failure or failure. The same applies to the following evaluations.
テーパー角は以下のようにして測定した。まず、ガラス基板上にスパッタ法で銅膜を600nmの厚みで成膜し、銅厚膜サンプルを作製した。この銅膜の上に配線形状にパターンニングしたレジストを形成し、テーパー角評価用の基材とした。つまり、基材は、基板と銅膜と、銅膜上のパターンニングされたレジスト層からなる。この基材をジャストエッチングする時間の間エッチング液に浸漬させ、エッチングを行った。エッチング後のサンプルを洗浄し、乾燥させた後、配線部分を切断し、切断面を観察した。
The taper angle was measured as follows. First, a copper film with a thickness of 600 nm was formed on a glass substrate by sputtering to produce a copper thick film sample. A resist patterned into a wiring shape was formed on this copper film, and used as a base material for taper angle evaluation. That is, the base material includes a substrate, a copper film, and a patterned resist layer on the copper film. Etching was performed by immersing the base material in an etching solution for the time of just etching. After the etching sample was washed and dried, the wiring portion was cut and the cut surface was observed.
切断面の観測は、SEM(日立製:SU8020型)を用い、加速電圧1kV、30,000~50,000倍の条件で行った。このSEM観測の際にエッチングされた部分の形状観察も行った。なお、ジャストエッチングは、エッチング開始から膜が光を透過するまでの時間である。膜が光を透過した時点は目視で確認した。
The observation of the cut surface was performed using SEM (Hitachi: SU8020 type) under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times. The shape of the etched portion was also observed during the SEM observation. Note that just etching is the time from the start of etching until the film transmits light. The time when the film transmitted light was visually confirmed.
切断面形状の模式図を図1に示す。図1に示すように、基板1とエッチングされた傾斜面5のなす角度3をテーパー角(°)とする。テーパー角3は30°~80°であれば丸(○)と判断した。この角度の範囲外であれば、バツ(×)と判断した。なお、図1では、Cu層は符号2、レジストは符号4で表した。
Schematic diagram of cut surface shape is shown in FIG. As shown in FIG. 1, an angle 3 formed by the substrate 1 and the etched inclined surface 5 is a taper angle (°). If the taper angle 3 was 30 ° to 80 °, it was judged as a circle (◯). If it was out of the range of this angle, it was judged as X (x). In FIG. 1, the Cu layer is represented by reference numeral 2 and the resist is represented by reference numeral 4.
(実施例1)
強酸性物質として、
硝酸を8.33質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を5.24質量%
過水安定剤として、
FN(フェニル尿素)を0.12質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.01質量%
からなるエッチング液原料を水72.41質量%と調合し、エッチング濃縮液を調製した。なお、エッチング濃縮液での各成分比率は、後述する過酸化水素水と混合しエッチング液が完成したときの総量に対する比率で表す。以下の実施例および比較例についても同様である。 (Example 1)
As a strongly acidic substance,
8.33% by mass of nitric acid
As an amine compound,
5.24% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.12% by mass of FN (phenylurea)
As azoles,
0.01% by mass of 5M1HT (5-methyl-1H-tetrazole)
An etching solution raw material consisting of 72.41% by mass of water was prepared to prepare an etching concentrate. Each component ratio in the etching concentrate is expressed as a ratio to the total amount when the etching liquid is completed by mixing with a hydrogen peroxide solution described later. The same applies to the following examples and comparative examples.
強酸性物質として、
硝酸を8.33質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を5.24質量%
過水安定剤として、
FN(フェニル尿素)を0.12質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.01質量%
からなるエッチング液原料を水72.41質量%と調合し、エッチング濃縮液を調製した。なお、エッチング濃縮液での各成分比率は、後述する過酸化水素水と混合しエッチング液が完成したときの総量に対する比率で表す。以下の実施例および比較例についても同様である。 (Example 1)
As a strongly acidic substance,
8.33% by mass of nitric acid
As an amine compound,
5.24% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.12% by mass of FN (phenylurea)
As azoles,
0.01% by mass of 5M1HT (5-methyl-1H-tetrazole)
An etching solution raw material consisting of 72.41% by mass of water was prepared to prepare an etching concentrate. Each component ratio in the etching concentrate is expressed as a ratio to the total amount when the etching liquid is completed by mixing with a hydrogen peroxide solution described later. The same applies to the following examples and comparative examples.
35%過酸化水素水13.89質量%(エッチング液の全量に対して過酸化水素が4.86質量%と水分が9.03質量%)とエッチング濃縮液を混合し、過酸化水素濃度が4.86質量%のエッチング液を調合した。なお、水は全量で81.44質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 13.89% by mass (hydrogen peroxide 4.86% by mass and moisture 9.03% by mass with respect to the total amount of the etchant) and the etching concentrate were mixed, and the hydrogen peroxide concentration was 4.86 mass% etching liquid was prepared. The total amount of water is 81.44% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(実施例2)
強酸性物質として、
マロン酸を9.88質量%、
アミン化合物として、
1A2P(1-アミノ-2-プロパノール)を1.35質量%、
過水安定剤として、
1P(1-プロパノール)を0.68質量%、
アゾール類として、
5A1HT(5-アミノ-1H-テトラゾール)を0.05質量%
からなるエッチング液原料を水75.70質量%と調合し、エッチング濃縮液を調製した。 (Example 2)
As a strongly acidic substance,
9.88% by mass of malonic acid,
As an amine compound,
1.35% by mass of 1A2P (1-amino-2-propanol)
As a water stabilizer,
0.68% by mass of 1P (1-propanol),
As azoles,
0.05% by mass of 5A1HT (5-amino-1H-tetrazole)
The etching liquid raw material which consists of was mixed with 75.70 mass% of water, and the etching concentrated liquid was prepared.
強酸性物質として、
マロン酸を9.88質量%、
アミン化合物として、
1A2P(1-アミノ-2-プロパノール)を1.35質量%、
過水安定剤として、
1P(1-プロパノール)を0.68質量%、
アゾール類として、
5A1HT(5-アミノ-1H-テトラゾール)を0.05質量%
からなるエッチング液原料を水75.70質量%と調合し、エッチング濃縮液を調製した。 (Example 2)
As a strongly acidic substance,
9.88% by mass of malonic acid,
As an amine compound,
1.35% by mass of 1A2P (1-amino-2-propanol)
As a water stabilizer,
0.68% by mass of 1P (1-propanol),
As azoles,
0.05% by mass of 5A1HT (5-amino-1H-tetrazole)
The etching liquid raw material which consists of was mixed with 75.70 mass% of water, and the etching concentrated liquid was prepared.
35%過酸化水素水12.34重量%(エッチング液の全量に対して過酸化水素が4.32質量%と水分が8.02質量%)とエッチング濃縮液を混合し、過酸化水素濃度が4.32質量%のエッチング液を調合した。なお、水は全量で83.72質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 12.34% by weight (4.32% by mass of hydrogen peroxide and 8.02% by mass of water with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was An etching solution of 4.32% by mass was prepared. The total amount of water is 83.72% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(実施例3)
強酸性物質として、
硫酸を6.93質量%
グリシンを1.84質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を2.49質量%
過水安定剤として、
尿素を0.64質量%
アゾール類として、
5M1HBTA(5-メチル-1H-ベンゾトリアゾール)を0.03質量%
からなるエッチング液原料を水73.36質量%と調合し、エッチング濃縮液を調製した。 (Example 3)
As a strongly acidic substance,
6.93% by mass of sulfuric acid
1.84% by mass of glycine
As an amine compound,
2.49% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.64% by mass of urea
As azoles,
0.03% by mass of 5M1HBTA (5-methyl-1H-benzotriazole)
The etching liquid raw material which consists of with 73.36 mass% of water was prepared, and the etching concentrated liquid was prepared.
強酸性物質として、
硫酸を6.93質量%
グリシンを1.84質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を2.49質量%
過水安定剤として、
尿素を0.64質量%
アゾール類として、
5M1HBTA(5-メチル-1H-ベンゾトリアゾール)を0.03質量%
からなるエッチング液原料を水73.36質量%と調合し、エッチング濃縮液を調製した。 (Example 3)
As a strongly acidic substance,
6.93% by mass of sulfuric acid
1.84% by mass of glycine
As an amine compound,
2.49% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.64% by mass of urea
As azoles,
0.03% by mass of 5M1HBTA (5-methyl-1H-benzotriazole)
The etching liquid raw material which consists of with 73.36 mass% of water was prepared, and the etching concentrated liquid was prepared.
35%過酸化水素水14.71重量%(エッチング液の全量に対して過酸化水素が5.15質量%と水分が9.56質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.15質量%のエッチング液を調合した。なお、水は全量で82.92質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 14.71% by weight (hydrogen peroxide is 5.15% by mass and moisture is 9.56% by mass with respect to the total amount of the etching solution) and the etching concentrate are mixed, and the hydrogen peroxide concentration is An etching solution of 5.15% by mass was prepared. The total amount of water is 82.92% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(実施例4)
強酸性物質として、
マロン酸を7.20質量%、
有機酸として
グルタル酸を6.77質量%
アミン化合物として、
DIPA(ジイソプロパノールアミン)を0.06質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.96質量%、
アゾール類として、
5フェニル1HT(5-フェニル-1H-テトラゾール)を0.03質量%
からなるエッチング液原料を水70.32質量%と調合し、エッチング濃縮液を調製した。 Example 4
As a strongly acidic substance,
7.20% by mass of malonic acid,
6.77% by mass of glutaric acid as organic acid
As an amine compound,
0.06% by mass of DIPA (diisopropanolamine)
As a water stabilizer,
0.96% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.03% by mass of 5-phenyl 1HT (5-phenyl-1H-tetrazole)
An etching solution raw material consisting of 70.32% by mass of water was prepared to prepare an etching concentrate.
強酸性物質として、
マロン酸を7.20質量%、
有機酸として
グルタル酸を6.77質量%
アミン化合物として、
DIPA(ジイソプロパノールアミン)を0.06質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.96質量%、
アゾール類として、
5フェニル1HT(5-フェニル-1H-テトラゾール)を0.03質量%
からなるエッチング液原料を水70.32質量%と調合し、エッチング濃縮液を調製した。 Example 4
As a strongly acidic substance,
7.20% by mass of malonic acid,
6.77% by mass of glutaric acid as organic acid
As an amine compound,
0.06% by mass of DIPA (diisopropanolamine)
As a water stabilizer,
0.96% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.03% by mass of 5-phenyl 1HT (5-phenyl-1H-tetrazole)
An etching solution raw material consisting of 70.32% by mass of water was prepared to prepare an etching concentrate.
35%過酸化水素水14.66重量%(エッチング液の全量に対して過酸化水素が5.13質量%と水分が9.53質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.13質量%のエッチング液を調合した。なお、水は全量で79.85質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 14.66% by weight (5.13% by weight of hydrogen peroxide and 9.53% by weight of water with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was An etching solution of 5.13% by mass was prepared. The total amount of water is 79.85% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(実施例5)
強酸性物質として、
エタンスルホン酸を7.04質量%
有機酸として
リンゴ酸を4.4質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を1.04質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.85質量%、
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水71.56質量%と調合し、エッチング濃縮液を調製した。 (Example 5)
As a strongly acidic substance,
7.04% by mass of ethanesulfonic acid
Malic acid as organic acid is 4.4% by mass
As an amine compound,
1.04% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.85% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 71.56 mass% of water was prepared, and the etching concentrated liquid was prepared.
強酸性物質として、
エタンスルホン酸を7.04質量%
有機酸として
リンゴ酸を4.4質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を1.04質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.85質量%、
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水71.56質量%と調合し、エッチング濃縮液を調製した。 (Example 5)
As a strongly acidic substance,
7.04% by mass of ethanesulfonic acid
Malic acid as organic acid is 4.4% by mass
As an amine compound,
1.04% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.85% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 71.56 mass% of water was prepared, and the etching concentrated liquid was prepared.
35%過酸化水素水15.09重量%(エッチング液の全量に対して過酸化水素が5.28質量%と水分が9.81質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.28質量%のエッチング液を調合した。なお、水は全量で81.37質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 15.09% by weight (hydrogen peroxide 5.28% by mass and moisture 9.81% by mass with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was 5.28 mass% etching liquid was prepared. The total amount of water is 81.37% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(実施例6)
強酸性物質として、
エタンスルホン酸を7.04質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を1.04質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.85質量%、
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水75.96質量%と調合し、エッチング濃縮液を調製した。 (Example 6)
As a strongly acidic substance,
7.04% by mass of ethanesulfonic acid
As an amine compound,
1.04% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.85% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of was mixed with 75.96 mass% of water, and the etching concentrated liquid was prepared.
強酸性物質として、
エタンスルホン酸を7.04質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を1.04質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.85質量%、
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水75.96質量%と調合し、エッチング濃縮液を調製した。 (Example 6)
As a strongly acidic substance,
7.04% by mass of ethanesulfonic acid
As an amine compound,
1.04% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.85% by mass of BG (ethylene glycol monobutyl ether),
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of was mixed with 75.96 mass% of water, and the etching concentrated liquid was prepared.
35%過酸化水素水15.09重量%(エッチング液の全量に対して過酸化水素が5.28質量%と水分が9.81質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.28質量%のエッチング液を調合した。なお、水は全量で85.77質量%となる。さらに、銅粉末を加えて銅イオン濃度が20,000ppmになるように調整した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表1に示す。
35% hydrogen peroxide solution 15.09% by weight (hydrogen peroxide 5.28% by mass and moisture 9.81% by mass with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was 5.28 mass% etching liquid was prepared. The total amount of water is 85.77% by mass. Further, copper powder was added to adjust the copper ion concentration to 20,000 ppm. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(比較例1)
強酸性物質として、
硝酸を10.00質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を12.50質量%
過水安定剤として、
FN(フェニル尿素)を0.10質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.10質量%
からなるエッチング液原料を水65.87質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 1)
As a strongly acidic substance,
10.00 mass% nitric acid
As an amine compound,
12.50% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.10% by mass of FN (phenyl urea)
As azoles,
0.10% by mass of 5M1HT (5-methyl-1H-tetrazole)
An etching liquid raw material consisting of 65.87% by mass of water was prepared to prepare an etching concentrated liquid.
強酸性物質として、
硝酸を10.00質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を12.50質量%
過水安定剤として、
FN(フェニル尿素)を0.10質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.10質量%
からなるエッチング液原料を水65.87質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 1)
As a strongly acidic substance,
10.00 mass% nitric acid
As an amine compound,
12.50% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.10% by mass of FN (phenyl urea)
As azoles,
0.10% by mass of 5M1HT (5-methyl-1H-tetrazole)
An etching liquid raw material consisting of 65.87% by mass of water was prepared to prepare an etching concentrated liquid.
35%過酸化水素水11.43重量%(エッチング液の全量に対して過酸化水素が4.00質量%と水分が7.43質量%)とエッチング濃縮液を混合し、過酸化水素濃度が4.00質量%のエッチング液を調合した。なお、水は全量で73.30質量%となる。さらに、銅粉末を加えて銅イオン濃度を20,000ppmになるように溶解しようとしたが、溶解しきれなかった。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表2に示す。
35% hydrogen peroxide solution 11.43% by weight (hydrogen peroxide is 4.00% by mass and moisture is 7.43% by mass with respect to the total amount of the etching solution) and the etching concentrate are mixed, and the hydrogen peroxide concentration is An etching solution of 4.00% by mass was prepared. The total amount of water is 73.30% by mass. Furthermore, although it tried to melt | dissolve so that copper powder might be added and a copper ion density | concentration might be set to 20,000 ppm, it was not able to melt | dissolve. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(比較例2)
強酸性物質として、
エタンスルホン酸を6.00質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を9.70質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.70質量%
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水68.49質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 2)
As a strongly acidic substance,
Ethanesulfonic acid 6.00% by mass
As an amine compound,
9.70% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
BG (ethylene glycol monobutyl ether) 0.70% by mass
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 68.49 mass% of water was prepared, and the etching concentrated liquid was prepared.
強酸性物質として、
エタンスルホン酸を6.00質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を9.70質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.70質量%
アゾール類として、
BTA(ベンゾトリアゾール)を0.02質量%
からなるエッチング液原料を水68.49質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 2)
As a strongly acidic substance,
Ethanesulfonic acid 6.00% by mass
As an amine compound,
9.70% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
BG (ethylene glycol monobutyl ether) 0.70% by mass
As azoles,
0.02% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 68.49 mass% of water was prepared, and the etching concentrated liquid was prepared.
35%過酸化水素水15.09重量%(エッチング液の全量に対して過酸化水素が5.28質量%と水分が9.81質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.28質量%のエッチング液を調合した。なお、水は全量で78.30質量%となる。さらに、銅粉末を加えて銅イオン濃度を20,000ppmになるように溶解しようとしたが、溶解しきれなかった。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表2に示す。
35% hydrogen peroxide solution 15.09% by weight (hydrogen peroxide 5.28% by mass and moisture 9.81% by mass with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was 5.28 mass% etching liquid was prepared. The total amount of water is 78.30% by mass. Furthermore, although it tried to melt | dissolve so that copper powder might be added and a copper ion density | concentration might be set to 20,000 ppm, it was not able to melt | dissolve. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(比較例3)
強酸性物質として、
マロン酸を15.80質量%
アミン化合物として、
1A2P(1-アミノ-2-プロパノール)を8.40質量%
過水安定剤として、
1P(1-プロパノール)を0.60質量%
アゾール類として、
5A1HT(5-アミノ-1H-テトラゾール)を0.05質量%
からなるエッチング液原料を水62.86質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 3)
As a strongly acidic substance,
15.80% by mass of malonic acid
As an amine compound,
8.40% by mass of 1A2P (1-amino-2-propanol)
As a water stabilizer,
0.60% by mass of 1P (1-propanol)
As azoles,
0.05% by mass of 5A1HT (5-amino-1H-tetrazole)
An etching liquid raw material consisting of 62.86% by mass of water was prepared to prepare an etching concentrated liquid.
強酸性物質として、
マロン酸を15.80質量%
アミン化合物として、
1A2P(1-アミノ-2-プロパノール)を8.40質量%
過水安定剤として、
1P(1-プロパノール)を0.60質量%
アゾール類として、
5A1HT(5-アミノ-1H-テトラゾール)を0.05質量%
からなるエッチング液原料を水62.86質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 3)
As a strongly acidic substance,
15.80% by mass of malonic acid
As an amine compound,
8.40% by mass of 1A2P (1-amino-2-propanol)
As a water stabilizer,
0.60% by mass of 1P (1-propanol)
As azoles,
0.05% by mass of 5A1HT (5-amino-1H-tetrazole)
An etching liquid raw material consisting of 62.86% by mass of water was prepared to prepare an etching concentrated liquid.
35%過酸化水素水12.29重量%(エッチング液の全量に対して過酸化水素が4.30質量%と水分が7.99質量%)とエッチング濃縮液を混合し、過酸化水素濃度が4.30質量%のエッチング液を調合した。なお、水は全量で70.85質量%となる。さらに、銅粉末を加えて銅イオン濃度を1,000ppmになるように溶解した。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表2に示す。
35% hydrogen peroxide solution 12.29% by weight (hydrogen peroxide is 4.30% by mass and moisture is 7.99% by mass with respect to the total amount of etching solution) and the etching concentrate are mixed, and the hydrogen peroxide concentration is 4. 30 mass% etching liquid was prepared. The total amount of water is 70.85% by mass. Further, copper powder was added and dissolved so that the copper ion concentration became 1,000 ppm. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(比較例4)
強酸性物質として、
硝酸を6.90質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を8.34質量%
過水安定剤として、
FN(フェニル尿素)を0.10質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.10質量%
からなるエッチング液原料を水71.99質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 4)
As a strongly acidic substance,
6.90 mass% nitric acid
As an amine compound,
8.34% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.10% by mass of FN (phenyl urea)
As azoles,
0.10% by mass of 5M1HT (5-methyl-1H-tetrazole)
The etching liquid raw material which consists of was mixed with 71.99 mass% of water, and the etching concentrated liquid was prepared.
強酸性物質として、
硝酸を6.90質量%
アミン化合物として、
NNDPA(N,N-ジエチル-1,3-プロパンジアミン)を8.34質量%
過水安定剤として、
FN(フェニル尿素)を0.10質量%
アゾール類として、
5M1HT(5-メチル-1H-テトラゾール)を0.10質量%
からなるエッチング液原料を水71.99質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 4)
As a strongly acidic substance,
6.90 mass% nitric acid
As an amine compound,
8.34% by mass of NNDPA (N, N-diethyl-1,3-propanediamine)
As a water stabilizer,
0.10% by mass of FN (phenyl urea)
As azoles,
0.10% by mass of 5M1HT (5-methyl-1H-tetrazole)
The etching liquid raw material which consists of was mixed with 71.99 mass% of water, and the etching concentrated liquid was prepared.
35%過酸化水素水12.57重量%(エッチング液の全量に対して過酸化水素が4.40質量%と水分が8.17質量%)とエッチング濃縮液を混合し、過酸化水素濃度が4.40質量%のエッチング液を調合した。なお、水は全量で80.16質量%となる。さらに、銅粉末を加えて銅イオン濃度を1,000ppmになるように溶解しようとしたが、溶解しきれなかった。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表2に示す。
35% hydrogen peroxide solution 12.57% by weight (hydrogen peroxide is 4.40% by mass and moisture is 8.17% by mass with respect to the total amount of the etching solution) and the etching concentrate are mixed, and the hydrogen peroxide concentration is 4. An etching solution of 40% by mass was prepared. The total amount of water is 80.16% by mass. Furthermore, although copper powder was added and it tried to melt | dissolve so that copper ion concentration might be set to 1,000 ppm, it was not able to melt | dissolve completely. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
(比較例5)
強酸性物質として、
エタンスルホン酸を6.00質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を5.96質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.82質量%
アゾール類として、
BTA(ベンゾトリアゾール)を0.04質量%
からなるエッチング液原料を水72.09質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 5)
As a strongly acidic substance,
Ethanesulfonic acid 6.00% by mass
As an amine compound,
5.96% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.82% by mass of BG (ethylene glycol monobutyl ether)
As azoles,
0.04% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 72.09 mass% of water was prepared, and the etching concentrated liquid was prepared.
強酸性物質として、
エタンスルホン酸を6.00質量%
アミン化合物として、
TIPA(トリイソプロパノールアミン)を5.96質量%
過水安定剤として、
BG(エチレングリコールモノブチルエーテル)を0.82質量%
アゾール類として、
BTA(ベンゾトリアゾール)を0.04質量%
からなるエッチング液原料を水72.09質量%と調合し、エッチング濃縮液を調製した。 (Comparative Example 5)
As a strongly acidic substance,
Ethanesulfonic acid 6.00% by mass
As an amine compound,
5.96% by mass of TIPA (triisopropanolamine)
As a water stabilizer,
0.82% by mass of BG (ethylene glycol monobutyl ether)
As azoles,
0.04% by mass of BTA (benzotriazole)
The etching liquid raw material which consists of with 72.09 mass% of water was prepared, and the etching concentrated liquid was prepared.
35%過酸化水素水15.09重量%(エッチング液の全量に対して過酸化水素が5.28質量%と水分が9.81質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.28質量%のエッチング液を調合した。なお、水は全量で81.90質量%となる。さらに、銅粉末を加えて銅イオン濃度を1,000ppmになるように溶解しようとしたが、溶解しきれなかった。また、液温は35℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表2に示す。
35% hydrogen peroxide solution 15.09% by weight (hydrogen peroxide 5.28% by mass and moisture 9.81% by mass with respect to the total amount of the etching solution) and the etching concentrate were mixed, and the hydrogen peroxide concentration was 5.28 mass% etching liquid was prepared. The total amount of water is 81.90% by mass. Furthermore, although copper powder was added and it tried to melt | dissolve so that copper ion concentration might be set to 1,000 ppm, it was not able to melt | dissolve completely. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the result of each evaluation item.
表1を参照して、無機酸および有機酸を用いた場合でも、強酸性物質であれば、エッチング液全体のpHを2未満に調整することができる。また、そのようにして作成された銅厚膜用エッチング液は、380nm/min以上のエッチングレートを、20,000ppmという銅イオン環境の下で実現することができる。また、テーパー角度は、30°から80°まで調整することができる。また、その形状も特に問題はなかった。
Referring to Table 1, even when an inorganic acid and an organic acid are used, the pH of the entire etching solution can be adjusted to less than 2 if it is a strongly acidic substance. In addition, the copper thick film etching solution thus prepared can realize an etching rate of 380 nm / min or more under a copper ion environment of 20,000 ppm. The taper angle can be adjusted from 30 ° to 80 °. Also, there was no particular problem with its shape.
一方、表2を参照する。使用した材料は表1で示した実施例と同じであるが、エッチング液全体のpHが2未満に設定しなければ、そもそも20,000ppmといった高イオン濃度にすらならなかった。銅イオンを溶解できないので、エッチングもできなかった。
Meanwhile, refer to Table 2. The materials used were the same as those shown in Table 1. However, unless the pH of the entire etching solution was set to less than 2, the ion concentration could not be as high as 20,000 ppm. Etching was not possible because copper ions could not be dissolved.
また、強酸性物質を有機酸だけで構成した場合は、アミン化合物は、0.05質量%以上、2.0質量%未満にすることが好適であった(実施例2、4、5、6参照)。有機酸の強酸性物質は、無機酸の場合よりpKaが高めになるため、アミン化合物を入れすぎると、エッチング液全体のpHを2未満にできないからと考えられる。
Further, when the strongly acidic substance is composed only of an organic acid, the amine compound is preferably 0.05% by mass or more and less than 2.0% by mass (Examples 2, 4, 5, 6). reference). It is considered that the strongly acidic substance of the organic acid has a higher pKa than that of the inorganic acid, so that if the amine compound is added too much, the pH of the entire etching solution cannot be made less than 2.
以上のように本発明に係る銅厚膜用エッチング液は、高いエッチングレートを高銅イオン濃度下でも実現することができ、大面積基板上の厚膜銅を実際の量産機の処理速度でエッチングすることができる。
As described above, the etching solution for thick copper film according to the present invention can realize a high etching rate even under a high copper ion concentration, and etch thick film copper on a large area substrate at a processing speed of an actual mass production machine. can do.
本発明に係るエッチング液は、600nm以上の厚い銅膜をエッチングする際に好適に利用することができる。
The etching solution according to the present invention can be suitably used when etching a thick copper film of 600 nm or more.
1 基板
2 Cu層
3 テーパー角
4 レジスト
5 傾斜面
1substrate 2 Cu layer 3 taper angle 4 resist 5 inclined surface
2 Cu層
3 テーパー角
4 レジスト
5 傾斜面
1
Claims (8)
- 過酸化水素と、
強酸性物質と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
水を含み、
pHが2未満である銅厚膜用エッチング液。 Hydrogen peroxide,
Strongly acidic substances,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
Including water,
Etching solution for copper thick film whose pH is less than 2. - さらに弱酸性の有機酸を含有する請求項1に記載された銅厚膜用エッチング液。 The copper thick film etching solution according to claim 1, further comprising a weakly acidic organic acid.
- 前記アゾール類は、5-アミノ-1H-テトラゾール、5-メチル-1H-テトラゾール、5-フェニル-1H-テトラゾール、5-メチル-1H-ベンゾトリアゾール、ベンゾトリアゾールから選択される1種若しくは複数種である請求項1または2に記載された銅厚膜用エッチング液。 The azole is one or more selected from 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-methyl-1H-benzotriazole, and benzotriazole. The copper thick film etching solution according to claim 1 or 2.
- 前記アミン化合物は、1-アミノ-2-プロパノール、N,N-ジエチル-1,3-プロパンジアミン、トリイソプロパノールアミン、ジイソプロパノールアミンから選択される1種若しくは複数種である請求項1乃至3のいずれか一の請求項に記載された銅厚膜用エッチング液。 4. The amine compound according to claim 1, wherein the amine compound is one or more selected from 1-amino-2-propanol, N, N-diethyl-1,3-propanediamine, triisopropanolamine, and diisopropanolamine. Etching solution for copper thick film according to any one of claims.
- 前記過酸化水素分解抑制剤は、尿素、フェニル尿素、1-プロパノール、エチレングリコールモノブチルエーテルから選択される1種若しくは複数種である請求項1乃至4のいずれか一の請求項に記載された銅厚膜用エッチング液。 The copper according to any one of claims 1 to 4, wherein the hydrogen peroxide decomposition inhibitor is one or more selected from urea, phenylurea, 1-propanol, and ethylene glycol monobutyl ether. Thick film etchant.
- 強酸性物質と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
水を含み、過酸化水素を含まない銅厚膜用エッチング濃縮液であって、
全体の4.0質量%から5.8質量%になるように過酸化水素を加えることで
pHが2未満となる銅厚膜用エッチング濃縮液。 Strongly acidic substances,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
An etching concentrate for copper thick film containing water and free of hydrogen peroxide,
Etching concentrate for copper thick film that has a pH of less than 2 by adding hydrogen peroxide so that the total amount is 4.0 to 5.8% by mass. - さらに弱酸性の有機酸を含有する請求項6に記載された銅厚膜用エッチング濃縮液。 The copper concentrate thick film etching concentrate according to claim 6, further comprising a weakly acidic organic acid.
- 強酸性物質と、
アミン化合物と、
過酸化水素分解抑制剤と、
アゾール類と、
水を含み、
全体の4.0質量%から5.8質量%になるように過酸化水素を加えることで
pHが2未満となる銅厚膜用エッチング濃縮液に過酸化化水素を全体の4.0質量%から5.8質量%になるように加えて銅厚膜用エッチング液を調合する工程と、
銅膜が600nm以上の厚みで形成された基板を前記銅厚膜用エッチング液に接触させる工程を含む銅厚膜用エッチング方法。
Strongly acidic substances,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
Azoles,
Including water,
Hydrogen peroxide is added so that the pH becomes less than 2 by adding hydrogen peroxide so that the total amount is 4.0% to 5.8% by mass. To prepare an etching solution for copper thick film in addition to 5.8% by mass from
A method for etching a copper thick film, comprising a step of bringing a substrate on which a copper film has a thickness of 600 nm or more into contact with the copper thick film etching solution.
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CN113079628A (en) * | 2021-03-30 | 2021-07-06 | 东莞市科佳电路有限公司 | Processing method of resistance copper foil material for mobile phone vibration motor PCB |
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Also Published As
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CN118223024A (en) | 2024-06-21 |
CN118223023A (en) | 2024-06-21 |
TW201940742A (en) | 2019-10-16 |
TWI678435B (en) | 2019-12-01 |
JPWO2019180915A1 (en) | 2020-04-30 |
CN109415818A (en) | 2019-03-01 |
JP6443649B1 (en) | 2018-12-26 |
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