JP6793312B2 - Etching solution for multilayer film, etching concentrate and etching method - Google Patents
Etching solution for multilayer film, etching concentrate and etching method Download PDFInfo
- Publication number
- JP6793312B2 JP6793312B2 JP2019544111A JP2019544111A JP6793312B2 JP 6793312 B2 JP6793312 B2 JP 6793312B2 JP 2019544111 A JP2019544111 A JP 2019544111A JP 2019544111 A JP2019544111 A JP 2019544111A JP 6793312 B2 JP6793312 B2 JP 6793312B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- acid
- etching solution
- etching
- total amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005530 etching Methods 0.000 title claims description 256
- 239000012141 concentrate Substances 0.000 title claims description 42
- 238000000034 method Methods 0.000 title claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 192
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 72
- 239000010949 copper Substances 0.000 claims description 65
- 150000007524 organic acids Chemical class 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 57
- 229910052802 copper Inorganic materials 0.000 claims description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 52
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 40
- 239000004310 lactic acid Substances 0.000 claims description 35
- 235000014655 lactic acid Nutrition 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 25
- 239000003381 stabilizer Substances 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 17
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 17
- 150000003851 azoles Chemical class 0.000 claims description 17
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 16
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 16
- 235000005985 organic acids Nutrition 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000001384 succinic acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- POAOYUHQDCAZBD-IDEBNGHGSA-N 2-butoxyethanol Chemical group [13CH3][13CH2][13CH2][13CH2]O[13CH2][13CH2]O POAOYUHQDCAZBD-IDEBNGHGSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 149
- 239000010408 film Substances 0.000 description 54
- 229960000448 lactic acid Drugs 0.000 description 26
- 239000002994 raw material Substances 0.000 description 22
- -1 Fluorine ions Chemical class 0.000 description 20
- 230000002378 acidificating effect Effects 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 13
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 229940093915 gynecological organic acid Drugs 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 7
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- 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
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 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
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 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
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 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
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 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
- 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
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-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
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 150000003557 thiazoles Chemical class 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
- 150000003852 triazoles Chemical class 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
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 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
- PVPTUASRAVWKGX-UHFFFAOYSA-N 1,2-dihydrotriazol-3-amine Chemical compound NN1NNC=C1 PVPTUASRAVWKGX-UHFFFAOYSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- 229940057054 1,3-dimethylurea Drugs 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- JRLAKNMVEGRRGK-UHFFFAOYSA-N 1-(ethylamino)butan-2-ol Chemical compound CCNCC(O)CC JRLAKNMVEGRRGK-UHFFFAOYSA-N 0.000 description 1
- 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
- LXQMHOKEXZETKB-UHFFFAOYSA-N 1-amino-2-methylpropan-2-ol Chemical compound CC(C)(O)CN LXQMHOKEXZETKB-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
- MPGVRLGIUWFEPA-UHFFFAOYSA-N 1-aminooctan-2-ol Chemical compound CCCCCCC(O)CN MPGVRLGIUWFEPA-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QHBWSLQUJMHGDB-UHFFFAOYSA-N 2,3-diaminopropan-1-ol Chemical compound NCC(N)CO QHBWSLQUJMHGDB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- BMTAVLCPOPFWKR-UHFFFAOYSA-N 2-(ethylamino)butan-1-ol Chemical compound CCNC(CC)CO BMTAVLCPOPFWKR-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- SGBGCXQCQVUHNE-UHFFFAOYSA-N 2-(ethylamino)propan-1-ol Chemical compound CCNC(C)CO SGBGCXQCQVUHNE-UHFFFAOYSA-N 0.000 description 1
- HSHIHFMFJLIQDN-UHFFFAOYSA-N 2-(methylamino)butan-1-ol Chemical compound CCC(CO)NC HSHIHFMFJLIQDN-UHFFFAOYSA-N 0.000 description 1
- PXWASTUQOKUFKY-UHFFFAOYSA-N 2-(methylamino)propan-1-ol Chemical compound CNC(C)CO PXWASTUQOKUFKY-UHFFFAOYSA-N 0.000 description 1
- BCLSJHWBDUYDTR-UHFFFAOYSA-N 2-(propylamino)ethanol Chemical compound CCCNCCO BCLSJHWBDUYDTR-UHFFFAOYSA-N 0.000 description 1
- VPSSPAXIFBTOHY-UHFFFAOYSA-N 2-amino-4-methylpentan-1-ol Chemical compound CC(C)CC(N)CO VPSSPAXIFBTOHY-UHFFFAOYSA-N 0.000 description 1
- 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
- AXCSUIBUZBQBGT-UHFFFAOYSA-N 3-(ethylamino)butan-1-ol Chemical compound CCNC(C)CCO AXCSUIBUZBQBGT-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
- AGMZSYQMSHMXLT-UHFFFAOYSA-N 3-aminobutan-1-ol Chemical compound CC(N)CCO AGMZSYQMSHMXLT-UHFFFAOYSA-N 0.000 description 1
- LXHUAPWNXDAINJ-UHFFFAOYSA-N 3-aminoheptan-4-ol Chemical compound CCCC(O)C(N)CC LXHUAPWNXDAINJ-UHFFFAOYSA-N 0.000 description 1
- HBUXNNBOWNIKNE-UHFFFAOYSA-N 4-(3-carboxypropylamino)butanoic acid Chemical compound OC(=O)CCCNCCCC(O)=O HBUXNNBOWNIKNE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PVNNOLUAMRODAC-UHFFFAOYSA-N 4-(ethylamino)butan-1-ol Chemical compound CCNCCCCO PVNNOLUAMRODAC-UHFFFAOYSA-N 0.000 description 1
- DBKSSENEKWOVKL-UHFFFAOYSA-N 4-(methylamino)butan-1-ol Chemical compound CNCCCCO DBKSSENEKWOVKL-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- CTDFCRIOSLTKFQ-UHFFFAOYSA-N 5-aminooctan-4-ol Chemical compound CCCC(N)C(O)CCC CTDFCRIOSLTKFQ-UHFFFAOYSA-N 0.000 description 1
- VJGRDSFPHUTBBE-UHFFFAOYSA-N 5-aminopentan-2-ol Chemical compound CC(O)CCCN VJGRDSFPHUTBBE-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 102100037644 Kelch-like protein 41 Human genes 0.000 description 1
- 108050003242 Kelch-like protein 41 Proteins 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229960000310 isoleucine Drugs 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- HDCAZTXEZQWTIJ-UHFFFAOYSA-N n,n',n'-triethylethane-1,2-diamine Chemical compound CCNCCN(CC)CC HDCAZTXEZQWTIJ-UHFFFAOYSA-N 0.000 description 1
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- NPKKRSHVJIQBKU-UHFFFAOYSA-N ornogenin Natural products CC(OC(=O)C=Cc1ccccc1)C2(O)CCC3(O)C4(O)CC=C5CC(O)CCC5(C)C4CC(OC(=O)C=Cc6ccccc6)C23C NPKKRSHVJIQBKU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- JGQDLMSXMOGEMC-UHFFFAOYSA-N pentane-2,4-diamine Chemical compound CC(N)CC(C)N JGQDLMSXMOGEMC-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- VPJDULFXCAQHRC-UHFFFAOYSA-N prop-2-enylurea Chemical compound NC(=O)NCC=C VPJDULFXCAQHRC-UHFFFAOYSA-N 0.000 description 1
- PZZICILSCNDOKK-UHFFFAOYSA-N propane-1,2,3-triamine Chemical compound NCC(N)CN PZZICILSCNDOKK-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- KVZLHPXEUGJPAH-QNDGGIRCSA-N rac-lactic acid Chemical compound C[C@@H](O)C(O)=O.C[C@H](O)C(O)=O KVZLHPXEUGJPAH-QNDGGIRCSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
- Electrodes Of Semiconductors (AREA)
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およびチタンの多層膜をエッチングする際に用いる、多層膜用エッチング液とエッチング濃縮液およびエッチング方法に関する。 The present invention relates to an etching solution for a multilayer film, an etching concentrate, and an etching method used when etching a multilayer film of copper and titanium used for wiring a flat panel display such as a liquid crystal or an 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を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 (FPDs) such as liquid crystals and organic ELs (Electro-Luminessecence). In recent years, FPDs with large screens and high definition have become widespread, and the wiring materials used are required to have lower resistance than aluminum. Therefore, in recent years, copper, which has a lower resistance than aluminum, has come to be used as a wiring material.
銅を配線材料として用いると、基板との間の接着力と、半導体基材への拡散という2つの問題が生じる。つまり、ゲート配線で用いる場合は、比較的基材への衝突エネルギーが大きいとされるスパッタリング法を用いても、ガラスなどの基板の間で接着力が十分でない場合がある。また、ソース・ドレイン配線で用いる場合は、付着した銅が下地となるシリコンへ拡散し、半導体の電気的設計値を変えてしまうという問題が生じる。 When copper is used as a wiring material, two problems arise: adhesive force between the substrate and diffusion into the semiconductor substrate. That is, when used for gate wiring, the adhesive force between substrates such as glass may not be sufficient even if the sputtering method, which is said to have a relatively large collision energy with the substrate, is used. Further, when used in the source / drain wiring, there arises a problem that the adhered copper diffuses into the underlying silicon and changes the electrical design value of the semiconductor.
この問題を解決するため、半導体基材上にモリブデン膜を最初に形成しておき、その上に銅膜を形成する多層構造が採用された。しかし、下地とのアイソレーションおよび接着性をより確実にするため、銅膜の下地層としてチタンが採用されてきている。 In order to solve this problem, a multilayer structure in which a molybdenum film is first formed on a semiconductor base material and a copper film is formed on the molybdenum film is adopted. However, titanium has been adopted as the base layer of the copper film in order to further ensure the isolation and adhesiveness with the base.
また、大型のFPDが普及に伴い、より抵抗の低い銅配線パターンが求められた。画面が広くなると、画素に給電するための配線長が長くなり、また高精細にするために線幅を狭くする必要がある。そこで、銅膜の厚みを厚くして抵抗を低下させることが検討されている。 Further, with the spread of large FPDs, a copper wiring pattern having lower resistance has been required. As the screen becomes wider, the wiring length for supplying power to the pixels becomes longer, and it is necessary to narrow the line width in order to obtain high definition. Therefore, it has been studied to increase the thickness of the copper film to reduce the resistance.
FPDの配線は、スパッタリング法で形成された多層膜をウエットエッチング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用のエッチング液には、以下の点が重要とされている。
(1)加工精度が高く基板全面にわたり一様に加工できること。
(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)。
(4)析出物の発生が少ないこと。The wiring of the FPD is formed by wet etching a multilayer film formed by a sputtering method. This is because a large area can be formed at once, so that the process can be shortened. Here, the following points are important for the etching solution for wet etching of wiring.
(1) High processing accuracy and uniform processing over the entire surface of the substrate.
(2) The processed wiring cross section has a forward taper of a predetermined angle.
(3) The etching rate does not change due to the inclusion of copper ions (long bath life).
(4) The generation of precipitates is small.
特許文献1には、銅/チタンの積層膜のエッチング液として、
(A)過酸化水素、
(B)硝酸、
(C)フッ素イオン供給源としてフッ化アンモニウム及び/又は酸性フッ化アンモニウム、
(D)5−アミノ−1H−テトラゾール、
(E)第四級アンモニウムヒドロキシドとしてテトラアルキルアンモニウムヒドロキシド及び/又は(ヒドロキシアルキル)トリアルキルアンモニウムヒドロキシド及び
(F)フェニル尿素及び/又はフェノールスルホン酸を含み、
pHが1.5〜2.5である多層膜用エッチング液が開示されている。In Patent Document 1, as an etching solution for a copper / titanium laminated film,
(A) Hydrogen peroxide,
(B) Nitric acid,
(C) Ammonium fluoride and / or acidic ammonium fluoride as a fluorine ion source,
(D) 5-amino-1H-tetrazole,
(E) Quaternary ammonium hydroxide contains tetraalkylammonium hydroxide and / or (hydroxyalkyl) trialkylammonium hydroxide and (F) phenylurea and / or phenolsulfonic acid.
Etching solutions for multilayer films having a pH of 1.5 to 2.5 are disclosed.
特許文献1のエッチング液は、下層のチタン膜および上層の銅膜のサイドエッチングの指標であるトップCDロス、ボトムCDロス、バリア膜テイリング、テーパー角などに関して好適な範囲でエッチングできることが示されている。 It has been shown that the etching solution of Patent Document 1 can be etched in a suitable range with respect to top CD loss, bottom CD loss, barrier film tailing, taper angle, etc., which are indicators of side etching of the lower titanium film and the upper copper film. There is.
一方、特許文献1のエッチング液は、上記の特性を維持できる範囲(バスライフ)を4000ppmとしている。金属イオン量がこの値以上になると、過酸化水素や硝酸の分解が進み、性能を維持できないからとされている。 On the other hand, the etching solution of Patent Document 1 has a range (bath life) of 4000 ppm that can maintain the above characteristics. It is said that when the amount of metal ions exceeds this value, hydrogen peroxide and nitric acid are decomposed and the performance cannot be maintained.
銅の膜厚が増えると、サイドエッチングの挙動も変化する。したがって、膜厚に応じたエッチング液組成の調整が必要となる。しかし、銅の膜厚が増えると、エッチング液中の金属イオン濃度の上昇も早くなる。結果、エッチング液の成分管理のための追添の手間が多く必要となるという課題が生じる。 As the copper film thickness increases, so does the side etching behavior. Therefore, it is necessary to adjust the etching solution composition according to the film thickness. However, as the film thickness of copper increases, the metal ion concentration in the etching solution also increases faster. As a result, there arises a problem that a lot of time and effort for addition is required for controlling the components of the etching solution.
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、エッチング液中の金属イオン濃度が高くなっても、エッチングの性能の変化を許容範囲に収めることができ、組成管理の手間を軽減することができる銅/チタン用エッチング液を提供することにある。 The present invention has been conceived in order to solve the above problems, and even if the metal ion concentration in the etching solution is high, the change in etching performance can be kept within an allowable range, and the labor of composition management can be saved. It is an object of the present invention to provide an etching solution for copper / titanium which can be reduced.
より具体的に、本発明に係る多層膜用エッチング液は、
銅とチタンの多層膜をエッチングするエッチング液であって、
(a)過酸化水素と、
(b)フッ素イオン供給源と、
(c)アゾール類と、
(d)過酸化水素安定剤と、
(e)有機酸と、
(f)アミン類と、
(g)水を含み、
前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、エッチング液全量に対して0.2質量%〜1.5質量%含み、
さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうち一種の有機酸が併用され、
前記併用される有機酸に乳酸を含む場合は、前記乳酸は、エッチング液全量に対して2.0質量%〜10.0質量%であり、
前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、エッチング液全量に対して4.5質量%〜5.5質量%であり、
前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、エッチング液全量に対して9.5質量%〜10.5質量%であり、
前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、エッチング液全量に対して4.5質量%〜5.5質量%であり、
前記有機酸が乳酸だけの場合は、前記乳酸はエッチング液全量に対して4.0質量%〜5.0質量%であることを特徴とする。More specifically, the etching solution for a multilayer film according to the present invention is
An etching solution that etches a multilayer film of copper and titanium.
(A) Hydrogen peroxide and
(B) Fluorine ion source and
(C) Azole and
(D) Hydrogen peroxide stabilizer and
(E) Organic acids and
(F) Amines and
(G) Contains water
The organic acid is selected from methanesulfonic acid and lactic acid with respect to the total amount of the etching solution.
When the organic acid contains methanesulfonic acid, the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
Furthermore, at least one of organic acids such as lactic acid, succinic acid, glutaric acid, and malonic acid is used in combination.
When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution.
When the organic acid used in combination contains succinic acid, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
When glutaric acid is contained in the organic acid used in combination, the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
When malonic acid is contained in the organic acid used in combination, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
When the organic acid is only lactic acid, the lactic acid is 4.0% by mass to 5.0% by mass with respect to the total amount of the etching solution.
また、本発明に係るエッチング方法は、
上記のエッチング液を銅とチタンの多層膜にレジストパターンが配された被処理基板に接触させる工程と、
前記接触させた状態を所定時間維持する工程を有することを特徴とする。Further, the etching method according to the present invention is
The process of bringing the above etching solution into contact with the substrate to be processed in which the resist pattern is arranged on the multilayer film of copper and titanium, and
It is characterized by having a step of maintaining the contacted state for a predetermined time.
本発明に係るエッチング液は、エッチング液中の金属イオン濃度が8,000ppmでもサイドエッチングの各パラメータを好適な範囲に維持することができる。したがって、銅の膜厚を厚くした基板をエッチングする際にも、これまで通りの組成管理(成分や全量の追添等の量や時期の決定)を行うことができる。 The etching solution according to the present invention can maintain each parameter of side etching in a suitable range even if the metal ion concentration in the etching solution is 8,000 ppm. Therefore, even when etching a substrate having a thick copper film thickness, it is possible to control the composition (determine the amount and timing of addition of components and the total amount) as before.
以下本発明に係る銅およびチタンの多層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」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。 Hereinafter, the etching solution for a multilayer film of copper and titanium according to the present invention will be described. In addition, the following description shows one 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", it means "A or more and B or less". That is, it means a range that is large including the numerical value A and small including the numerical value B.
本発明に係る多層膜用エッチング液は、過酸化水素と、フッ素イオン供給源と、アゾール類と、過酸化水素安定剤と、有機酸と、アミン類と、水を含む。以下、それぞれの成分について詳説する。 The etching solution for a multilayer film according to the present invention contains hydrogen peroxide, a fluorine ion source, azoles, a hydrogen peroxide stabilizer, an organic acid, amines, and water. Each component will be described in detail below.
<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(有機酸)により溶解される。過酸化水素は、銅を酸化する酸化剤として用いられる。過酸化水素は、エッチング液全量の4.0質量%〜8.8質量%が好ましく、5.0質量%〜7.0質量%であればより好ましく、5.5質量%〜6.5質量%であれば最も好ましい。<Hydrogen peroxide>
In the etching of copper, copper is oxidized to copper oxide (CuO), which is dissolved by an acid (organic acid). Hydrogen peroxide is used as an oxidant to oxidize copper. The amount of hydrogen peroxide is preferably 4.0% by mass to 8.8% by mass, more preferably 5.0% by mass to 7.0% by mass, and 5.5% by mass to 6.5% by mass, based on the total amount of the etching solution. % Is most preferable.
<フッ素イオン供給源>
チタンの溶解にはフッ素イオンが有用である。フッ素イオンの供給源としては、エッチング液中でフッ素がイオン化するものであれば特に限定はない。フッ化水素酸、フッ化アンモニウム、フッ化水素アンモニウム等が好適に利用できる。特にフッ化アンモニウム(NH4F:CAS番号12125−01−8)は好適に利用することができる。フッ素イオン供給源は、ガラスを侵食するため含有量が多すぎると基板自体を腐食させる。エッチング液全量に対して0.2質量%〜1.0質量%が好ましい。<Fluorine ion source>
Fluorine ions are useful for dissolving titanium. The source of fluorine ions is not particularly limited as long as fluorine is ionized in the etching solution. Hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride and the like can be preferably used. In particular, ammonium fluoride (NH4F: CAS No. 12125-01-8) can be preferably used. Since the fluorine ion source erodes the glass, if the content is too high, the substrate itself will be corroded. It is preferably 0.2% by mass to 1.0% by mass with respect to the total amount of the etching solution.
<アゾール類>
本発明に係る多層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。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。<Azole>
The etching solution for a multilayer film according to the present invention contains azoles in order to suppress the etching rate of Cu. As the azoles, triazoles, tetraazoles, imidazoles, thiazoles and the like can be preferably used. More specifically, the following can be listed. As the triazoles, 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 preferably used. Further, as the imidazoles, 1H-imidazole, 1H-benzimidazole and the like can be preferably used. Further, as the thiazoles, 1,3-thiazole, 4-methylthiazole and the like can be preferably 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。)が好ましい。 Of these, tetrazole is highly effective in suppressing the etching rate, and 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1HT") is particularly preferable.
これらのアゾール類は、エッチング液全量に対して、0.005質量%〜1.0質量%がよく、より好ましくは0.01質量%〜0.5質量%、最も好ましくは0.01質量%〜0.10質量%含有させるのがよい。 These azoles are preferably 0.005% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.5% by mass, and most preferably 0.01% by mass, based on the total amount of the etching solution. It is preferable to contain ~ 0.10% by mass.
<過酸化水素安定剤>
本発明に係る多層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、過酸化水素安定剤とも呼ぶ。<Hydrogen peroxide stabilizer>
Hydrogen peroxide is used as an oxidizing agent in the etching solution for a multilayer film according to the present invention. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. The hydrogen peroxide decomposition inhibitor is also called a hydrogen peroxide stabilizer.
特に、本発明に係るエッチング液の場合、Cu濃度が8,000ppmまでエッチングレートの変化がわずかであることが必要である。本発明では、2−ブトキシエタノール(CAS番号111−76−2:以下「BG」とも呼ぶ。)が好適に用いられる。 In particular, in the case of the etching solution according to the present invention, it is necessary that the change in the etching rate is small up to a Cu concentration of 8,000 ppm. In the present invention, 2-butoxyethanol (CAS No. 111-76-2: hereinafter also referred to as "BG") is preferably used.
従来、過酸化水素安定剤としては、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安定剤のほか、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などがよく用いられていた。しかし、BGはCu濃度が8,000ppm以上の高い濃度になっても、過酸化水素の分解を抑制する顕著な効果を発揮することがわかった。 Conventionally, as hydrogen peroxide stabilizers, urea-based hydrogen peroxide stabilizers such as phenylurea, allylurea, 1,3-dimethylurea, and thiourea, as well as phenylacetate amide, phenylethylene glycol, 1-propanol, and the like. Lower alcohols such as 2-propanol were often used. However, it was found that BG exerts a remarkable effect of suppressing the decomposition of hydrogen peroxide even when the Cu concentration is as high as 8,000 ppm or more.
なお、BGは、エッチング液に一定以上入れることで効果があり、多量に入れても効果は飽和する。他の必要成分量を確保できれば、多量に入れてもエッチング液としての効果は発揮する。しかし、BGを多く加えることで、コストは高くなる。効果と価格を考慮するとエッチング液全量に対して5.0質量%を超えて添加する意味はない。 It should be noted that BG is effective when it is added to the etching solution in a certain amount or more, and the effect is saturated even if it is added in a large amount. If the amount of other necessary components can be secured, the effect as an etching solution will be exhibited even if a large amount is added. However, adding a large amount of BG increases the cost. Considering the effect and price, there is no point in adding more than 5.0% by mass with respect to the total amount of the etching solution.
また、エッチング液中の過酸化水素の割合が上記に示した範囲内であれば、BGは、エッチング液全量に対して0.1質量%以上含有されていれば効果を奏する。したがって、過酸化水素安定剤としてのBGは、エッチング液全量に対して0.1質量%〜5.0質量%含有されていればよく、0.5質量%〜2.5質量%含有されていればより好ましく、0.7質量%〜1.5質量%含有されていれば最も好ましい。 Further, if the ratio of hydrogen peroxide in the etching solution is within the range shown above, BG is effective if it is contained in an amount of 0.1% by mass or more based on the total amount of the etching solution. Therefore, BG as a hydrogen peroxide stabilizer may be contained in an amount of 0.1% by mass to 5.0% by mass, and 0.5% by mass to 2.5% by mass, based on the total amount of the etching solution. It is more preferable, and it is most preferable that it is contained in an amount of 0.7% by mass to 1.5% by mass.
なお、従来過酸化水素分解抑制剤として使われていたフェニル尿素は、エッチング液全量に対して0.2質量%を超えて含有させると、フェニル基と過酸化水素が反応し、アゾール類と過酸化水素の反応物とは異なる析出物を生じた。一方、BGはそのような析出物を発生させない。したがって析出物の生成という点からも、BGは好適な過酸化水素安定剤である。 When phenylurea, which has been conventionally used as a hydrogen peroxide decomposition inhibitor, is contained in an amount of more than 0.2% by mass based on the total amount of the etching solution, the phenyl group reacts with hydrogen peroxide and is excessive with azoles. A precipitate different from the reaction product of hydrogen peroxide was produced. On the other hand, BG does not generate such precipitates. Therefore, BG is a suitable hydrogen peroxide stabilizer from the viewpoint of forming precipitates.
<有機酸>
有機酸は、銅膜をエッチングするとともに、エッチングされた配線の断面のテーパー角度を調整する役目を負う。また、過酸化水素の分解を抑制する機能もある程度有すると考えられる。有機酸には酸性有機酸を用いる。<Organic acid>
The organic acid has the role of etching the copper film and adjusting the taper angle of the cross section of the etched wiring. It is also considered to have a function of suppressing the decomposition of hydrogen peroxide to some extent. An acidic organic acid is used as the organic acid.
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、炭素数1〜10のスルホン酸などが好ましく挙げられる。 Preferred examples of the organic acid include an aliphatic carboxylic acid having 1 to 18 carbon atoms, an aromatic carboxylic acid having 6 to 10 carbon atoms, an amino acid having 1 to 10 carbon atoms, and a sulfonic acid 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、ジグリコール酸、ピルビン酸、マロン酸、酪酸、ヒドロキシ酪酸、酒石酸、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、trans−アコニット酸、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, diglycolic acid, pyruvate, malonic acid, butyric acid, hydroxybutyric acid, tartrate acid, succinic acid, malic acid, maleic acid, and fumaric acid. , Valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propantricarboxylic acid, trans-aconic acid, enanthic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linole Acids, linolenic acid and the like are preferably mentioned.
炭素数6〜10の芳香族カルボン酸としては、安息香酸、サリチル酸、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, salicylic 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、アラニン、グリシン、アスパラギン、アスパラギン酸、サルコシン、セリン、グルタミン、グルタミン酸、4−アミノ酪酸、イミノジ酪酸、アルギニン、ロイシン、イソロイシン、ニトリロ三酢酸などが好ましく挙げられる。
また、炭素数1〜10のスルホン酸としては、メタンスルホン酸、ベンゼンスルホン酸、p−トルエンスルホン酸等が好ましい。Examples of amino acids having 1 to 10 carbon atoms include carbamate, alanine, glycine, asparagine, aspartic acid, sarcosin, serine, glutamic acid, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, and nitrilotriacetic acid. Is preferably mentioned.
Further, as the sulfonic acid having 1 to 10 carbon atoms, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are preferable.
上記有機酸のなかでも、酸性有機酸として乳酸、コハク酸、グルタル酸、マロン酸、メタンスルホン酸が好適に利用できる。 Among the above organic acids, lactic acid, succinic acid, glutaric acid, malonic acid, and methanesulfonic acid can be preferably used as the acidic organic acid.
メタンスルホン酸(CAS番号:75−75−2)は、単独で用いられることはなく、必ず他の酸性有機酸と併用される。この場合、メタンスルホン酸はエッチング液全量に対して0.2質量%〜1.5質量%であるのが好ましい。 Methanesulfonic acid (CAS No .: 75-75-2) is not used alone, but is always used in combination with other acidic organic acids. In this case, the amount of methanesulfonic acid is preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
併用される酸性有機酸が乳酸(混合状態(DL−乳酸)CAS番号:50−21−5)の場合、乳酸はエッチング液全量に対して2.0質量%〜10.0質量%の範囲が好ましい。なお、乳酸はL−乳酸若しくはD−乳酸を単独で用いてもよい。 When the acidic organic acid used in combination is lactic acid (mixed state (DL-lactic acid) CAS number: 50-21-5), the range of lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution. preferable. As lactic acid, L-lactic acid or D-lactic acid may be used alone.
また、併用される酸性有機酸がコハク酸(CAS番号:110−15−6)の場合、コハク酸はエッチング液全量に対して4.5質量%〜5.5質量%の範囲が好ましい。 When the acidic organic acid used in combination is succinic acid (CAS number: 110-15-6), the amount of succinic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
また、併用される酸性有機酸がグルタル酸(CAS番号:110−94−1)の、グルタル酸はエッチング液全量に対して9.5質量%〜10.5質量%の範囲が好ましい。 The acidic organic acid used in combination is preferably glutaric acid (CAS number: 110-94-1), and the glutaric acid is preferably in the range of 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
また、併用される酸性有機酸がマロン酸(CAS番号:141−82−2)の場合、マロン酸はエッチング液全量に対して4.5質量%〜5.5質量%の範囲が好ましい。 When the acidic organic acid used in combination is malonic acid (CAS number: 141-82-2), the amount of malonic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
なお、乳酸は単独で用いることができる。乳酸を単独で用いた場合は、エッチング液全量に対して4.0質量%〜5.0質量%の範囲が好ましい。 Lactic acid can be used alone. When lactic acid is used alone, it is preferably in the range of 4.0% by mass to 5.0% 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、トリイソプロパノールアミン、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、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る。これらの有機酸は、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 pH of the etching solution. As the amine compound, those having 2 to 10 carbon atoms can be preferably 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) amine, tetra ( Aminomethyl) Polyamines such as methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene; ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N- Ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethyl Isopropanolamine, N-propylisopropanolamine, 2-aminopropane-1-ol, N-methyl-2-amino-propane-1-ol, N-ethyl-2-amino-propane-1-ol, 1-aminopropane -3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropane-3-ol, 1-aminobutane-2-ol, N-methyl-1-aminobutane-2-ol , N-ethyl-1-aminobutane-2ol, 2-aminobutane-1-ol, N-methyl-2-aminobutane-1-ol, N-ethyl-2-aminobutane-1-ol, 3-aminobutane-1-ol All, N-methyl-3-aminobutane-1-ol, N-ethyl-3-aminobutane-1-ol, 1-aminobutane-4-ol, N-methyl1-aminobutane-4-ol, N-ethyl-1 -Aminobutane-4-ol, 1-amino-2-methylpropan-2-ol, 2-Amino-2-methylpropan-1-ol, 1-aminopentane-4-ol, 2-amino-4-methylpentane-1-ol, 2-aminohexane-1-ol, 3-aminoheptane-4 -Ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminoppan-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, Alkanolamines such as 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, diglycolamine Is preferably mentioned. These organic acids can be used alone or in combination of two or more.
これらの中でも、トリイソプロパノールアミン(CAS番号122−20−3)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、0.5質量%〜3.0質量%含有させるのが好ましく、0.6質量%〜2.5質量%であればより好ましく、0.7〜2.0質量%なら最も好ましい。 Of these, triisopropanolamine (CAS No. 122-20-3) is particularly preferred. Further, the amine compound is preferably contained in an amount of 0.5% by mass to 3.0% by mass, more preferably 0.6% by mass to 2.5% by mass, and 0.7 to 0.7% by mass, based on the total amount of the etching solution. 2.0% by mass is most preferable.
<銅イオン>
通常の多層膜用エッチング液は、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。過酸化水素の分解速度が速くなるため、過酸化水素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、過酸化水素の分解速度を抑制するので、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濃度が少なくとも8,000ppm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 added to a normal etching solution for a multilayer film so that the Cu ion concentration becomes about 2,000 ppm to 4,000 ppm. This is because the decomposition rate of hydrogen peroxide becomes faster and the concentration of hydrogen peroxide decreases. However, since the etching solution according to the present invention suppresses the decomposition rate of hydrogen peroxide, it is not necessary to add an etching solution for diluting Cu ions even if the Cu ion concentration becomes higher. More specifically, it is not necessary to add an etching solution for dilution until the Cu concentration of the etching solution is at least 8,000 ppm.
<その他>
本発明の多層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。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。<Others>
In addition to these components, water and various additives usually used as long as the etching performance is not impaired may be added to the etching solution for a multilayer film of the present invention. Since water is intended for precision processing, it is desirable that water is free of foreign matter. Pure water or ultrapure water is preferable. Needless to say, the range of the content ratio of each component described above is appropriately adjusted so that the total amount of the etching solution is 100% by mass.
<pH、温度>
本発明に係る多層膜用エッチング液は、pH1〜4、より好ましくはpH1.5〜2.5の範囲で使用されるのが好ましい。また、エッチング液は、20℃から60℃の間で使用することができる。より好ましくは30℃から55℃であり、最も好ましくは35℃から50℃がよい。<pH, temperature>
The etching solution for a multilayer film according to the present invention is preferably used in the range of pH 1 to 4, more preferably pH 1.5 to 2.5. Further, the etching solution can be used between 20 ° C. and 60 ° C. More preferably, it is 30 ° C. to 55 ° C., and most preferably 35 ° C. to 50 ° C.
<保存>
本発明に係る多層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。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、液体のものと液体以外の形態のものが存在してもよい。すなわち、本発明に係る多層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 etching solution for a multilayer film according to the present invention. Hydrogen peroxide autolyzes. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, at the time of storage, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. Further, only the raw materials excluding hydrogen peroxide (or hydrogen peroxide solution), water and copper ions (referred to as “etching liquid raw materials”) may be stored together. The etching solution raw material may include a liquid one and a non-liquid form. That is, the etching solution for a multilayer film 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製しておいてよい。この溶液は、後述する実施例で示すエッチング液の水の割合より少ない割合の水であってもよい。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。これに対して過酸化水素を所定の割合で混合し完成されたエッチング液を「完全エッチング液」と呼んでもよい。エッチング濃縮液は、完全エッチング液と比べると過酸化水素および水の一部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、本発明の多層膜用エッチング液(完全エッチング液)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。 Further, the etching solution raw material and water may be mixed to prepare a solution of the etching solution raw material. This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in Examples described later. The solution of the etching solution raw material and the etching solution raw material prepared from water is called an "etching concentrate". On the other hand, the etching solution completed by mixing hydrogen peroxide in a predetermined ratio may be called a "complete etching solution". Compared to a complete etching solution, the etching concentrate has a smaller volume due to the absence of hydrogen peroxide and a part of water, and is convenient for storage and transfer. Therefore, the etching solution for a multilayer film (complete etching solution) of the present invention may be completed by combining an etching concentrate, water, and hydrogen peroxide.
したがって、エッチング濃縮液は、本発明に係る完全エッチング液から過酸化水素を除いた成分で構成され、過酸化水素と水を所定の濃度になるように添加すれば、本発明のエッチング液が完成する。すなわち、エッチング濃縮液は、過酸化水素を所定の濃度になるように調製した完全エッチング液にした時の各成分の組成比を規定することで表すことができる。 Therefore, the etching concentrate is composed of components obtained by removing hydrogen peroxide from the complete etching solution according to the present invention, and the etching solution of the present invention is completed by adding hydrogen peroxide and water to a predetermined concentration. To do. That is, the etching concentrate can be expressed by defining the composition ratio of each component when the complete etching solution is prepared by adding hydrogen peroxide to a predetermined concentration.
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。つまり、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、本発明の多層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. That is, considering that hydrogen peroxide is supplied as an aqueous solution of hydrogen peroxide, the etching solution for a multilayer film of the present invention is completed by combining the etching concentrate, water, and hydrogen peroxide solution. Can be done.
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。 Further, if water is included in the etching concentrate or the hydrogen peroxide solution, the etching concentrate and the hydrogen peroxide solution can be combined to complete the process. Further, in the present specification, each component ratio of the etching concentrate is expressed as a ratio to the total amount of the etching solution when it is completed. Therefore, the total of each component of the etching concentrate is not 100% by mass.
<エッチング方法>
本発明に係る多層膜用エッチング液を用いる対象は、チタン若しくはチタン合金(チタン合金を含め単に「チタン」とも呼ぶ。)が下層で、銅若しくは銅合金(銅合金を含め単に「銅」とも呼ぶ。)が上層となった銅/チタンの多層膜である。下層のチタンの厚みは、上層の銅の厚みより薄い。下層の厚みをt0とし上層の厚みをt1とすると、t1/t0の範囲が16から32までの範囲の構成である。t1/t0の範囲がこの範囲を外れて、チタン層が厚すぎると、チタン層の残渣が生じやすく、逆に薄すぎるとCu層の下地層としての役割を果たさなくなる。<Etching method>
The object to which the etching solution for a multilayer film according to the present invention is used is titanium or a titanium alloy (including a titanium alloy, also simply referred to as "titanium") as a lower layer, and copper or a copper alloy (including a copper alloy, also simply referred to as "copper"). ) Is the upper layer of the copper / titanium multilayer film. The thickness of titanium in the lower layer is thinner than the thickness of copper in the upper layer. Assuming that the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t1 / t0 is the range from 16 to 32. If the range of t1 / t0 is out of this range and the titanium layer is too thick, a residue of the titanium layer is likely to be generated, and conversely, if it is too thin, it does not serve as a base layer of the Cu layer.
本発明に係る多層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。そして、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 etching solution for a multilayer film according to the present invention can be stored for a long period of time by separately storing hydrogen peroxide, the etching solution raw material, and water at the time of storage. Then, when actually used, these are mixed to complete the etching solution. The method of preparation 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多層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(さらに水があってもよい)を所定量ずつ調合する。この工程を多層膜用エッチング液を調合する工程と呼んでもよい。なお、この工程は、エッチングの直前に行う必要はなく、予め過酸化水素を含めて調製されたエッチング液を用いてエッチングしてもよい。 As an example, an etching concentrate prepared by mixing a certain amount of water with an etching solution raw material is prepared. Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than that of the etching solution for a multilayer film according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and an etching concentrate (which may further contain water) are mixed. This step may be called a step of preparing an etching solution for a multilayer film. It should be noted that this step does not have to be performed immediately before etching, and may be etched using an etching solution prepared in advance containing hydrogen peroxide.
エッチングを行う際は、上記の通り、pH1〜4で、20℃から60℃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(被処理基板)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。これを多層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, as described above, the etching solution is used at pH 1 to 4 under the conditions of 20 ° C. to 60 ° C. Therefore, it is desirable that the object to be etched (the substrate to be processed) is also preheated to this temperature. The method of bringing the substrate to be treated into contact with the etching solution is not particularly limited. The etching solution may be sprayed onto the substrate to be processed from above as in the shower type, or the substrate to be processed may be dip into a pool of etching solutions. This may be called a step of bringing the etching solution for a multilayer film into contact with the substrate to be processed.
またエッチングは、被処理基板とエッチング液の接触を所定の時間維持しなければならない。これは被処理基板とエッチング液の接触を所定の時間維持する工程である。 Further, in the etching, the contact between the substrate to be processed and the etching solution must be maintained for a predetermined time. This is a step of maintaining the contact between the substrate to be processed and the etching solution for a predetermined time.
なお、被処理基板とは、ガラス等の基材の上にチタン層と銅層が積層され、この積層膜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 treated is a substrate in which a titanium layer and a copper layer are laminated on a base material such as glass, and a resist pattern for pattern formation is formed on the laminated film.
<各種評価方法の説明>
本発明に係る多層膜用エッチング液に対しては、ジャストエッチングの際の、被処理基板を切断し、SEMによる観察でサイドエッチングの指標を調べた。<Explanation of various evaluation methods>
For the etching solution for a multilayer film according to the present invention, the substrate to be processed was cut at the time of just etching, and the index of side etching was examined by observation by SEM.
より具体的には、まず、ガラス基板上にスパッタ法でチタンを25nmの厚みで成膜し、その上に続けて銅を600nmの厚みで成膜し、Cu/Tiの多層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、ガラス基板とチタン膜とその上の銅膜と、銅膜上のパター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、配線部分を配線方向に直角に切断し、切断面を観察した。 More specifically, first, titanium was formed on a glass substrate by a sputtering method to a thickness of 25 nm, and then copper was formed on a glass substrate to a thickness of 600 nm to prepare a Cu / Ti multilayer film sample. .. A resist patterned in a wiring shape was formed on this copper film and used as a base material for taper angle evaluation. That is, the base material comprises a glass substrate, a titanium film, a copper film on the glass substrate, and a patterned resist layer on the copper film. This substrate was immersed in an etching solution for a period of time for just etching to perform etching. After the etched sample was washed and dried, the wiring portion was cut at right angles to the wiring direction, 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。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。ただし、エッチングを開始してから3分経過しても、まだ膜が残っている場合は、「測定不可」とした。 The cut surface was observed using an SEM (Hitachi: SU8020 type) under the condition of an accelerating voltage of 1 kV and 30,000 to 50,000 times. The 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. However, if the film still remains even after 3 minutes have passed since the etching was started, it was judged as "not measurable".
切断面形状の模式図を図1に示す。図1を参照して、切断面は、ガラス基板10と、チタン層12と、銅層14と、レジスト層16で構成される。レジスト層16の端16aからガラス基板10との間にできるガラス基板10に垂直な仮想面18が理想的なエッジ面である。現実のエッジ面は、膜の上面と下面でエッチング速度が異なり、図に示すような傾斜面となる。
A schematic view of the cut surface shape is shown in FIG. With reference to FIG. 1, the cut surface is composed of a
レジスト層16の端16aの直下方の銅層14は、エッチングが進行し存在しない。したがって、レジスト層16の端16aは庇形状になっている。
The
また、銅層14は、ガラス基板10に近い方よりレジスト層16に近い方が仮想面18から深く浸食されている。銅層14の下層であるチタン層12は、銅とのエッチングレートの違いで仮想面18からの浸食具合は浅い。
Further, the
ここで、銅層14の上面14aの端14aaと仮想面18(レジスト層16の端16a)との間の距離aを「トップCD(Critical Dimension:線幅)ロス」と呼ぶ。また、銅層14の下面14bの端14baと仮想面18との距離bを「ボトムCDロス」と呼ぶ。また、銅層14の下面14bの端14baから上面14aの端14aaまでの斜面の角度θを「テーパー角」と呼ぶ。
Here, the distance a between the end 14aa of the
トップCDロス、ボトムCDロス、テーパー角は、それぞれ記号「a」、「b」、「θ」とする。なお、通常トップCDロス、ボトムCDロスは、線幅の両側で生じるため、測定値の2倍の値を評価値とする。すなわち、あるサンプルの断面を観測したときに、トップCDロスが0.5μmであったとすると、トップCDロスの評価値は、1.0μmとする。しかし、ここでは、配線の片側だけのトップCDロスaとボトムCDロスbの測定値を表に表記した。 The top CD loss, bottom CD loss, and taper angle are represented by the symbols "a", "b", and "θ", respectively. Since top CD loss and bottom CD loss usually occur on both sides of the line width, a value twice the measured value is used as the evaluation value. That is, assuming that the top CD loss is 0.5 μm when observing the cross section of a certain sample, the evaluation value of the top CD loss is 1.0 μm. However, here, the measured values of the top CD loss a and the bottom CD loss b on only one side of the wiring are shown in the table.
なお、トップCDロスaは、0.5μm〜2.0μm、ボトムCDロスbは0.3μm〜1.0μmであるのが望ましい。またテーパー角θは、30°から80°であればよい。 It is desirable that the top CD loss a is 0.5 μm to 2.0 μm and the bottom CD loss b is 0.3 μm to 1.0 μm. The taper angle θ may be 30 ° to 80 °.
「ガラス腐食速度」は、エッチング実験を行ったサンプルの浸食部分と非浸食部分の段差を段差測定器で測定し求めた。単位はnm/minである。ガラス腐食速度は30〜60nm/minであればよい。 The "glass corrosion rate" was determined by measuring the step between the eroded portion and the non-eroded portion of the sample in which the etching experiment was performed with a step measuring device. The unit is nm / min. The glass corrosion rate may be 30 to 60 nm / min.
「評価Cu濃度」は、サンプルとするエッチング液に、銅を所定量ずつ溶解させながらエッチングを行い、テーパー角θ、トップCDロスa、ボトムCDロスbの何れかが好ましい範囲からはずれた場合、若しくは他の原因で継続してエッチングができなくなった濃度の直前の濃度とした。「評価Cu濃度」が高いということはバスライフが長いと言ってもよい。 The "evaluation Cu concentration" is determined when the taper angle θ, the top CD loss a, or the bottom CD loss b deviates from the preferable range by performing etching while dissolving copper in a predetermined amount of the etching solution as a sample. Alternatively, the concentration immediately before the concentration at which etching cannot be continuously performed due to other causes is used. It can be said that a high "evaluation Cu concentration" means a long bath life.
以下に実施例および比較例の組成を示す。
(実施例1)
酸性有機酸として、
メタンスルホン酸を0.3質量%、
乳酸を9.0質量%、
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水72.04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。The compositions of Examples and Comparative Examples are shown below.
(Example 1)
As an acidic organic acid
0.3% by mass of methanesulfonic acid,
9.0% by mass of lactic acid,
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of this was mixed with 72.04% by mass of water to prepare an etching concentrate. The ratio of each component in the etching concentrate is expressed as a ratio to the total amount when the etching solution is completed by mixing with hydrogen peroxide solution described later. The same applies to the following examples and comparative examples.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で82.81質量%となる。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。なお、表1では、水の全量は「残部」と記載した。以下表2を含め同様である。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 82.81% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item. In Table 1, the total amount of water is described as "remaining portion". The same applies to Table 2 below.
(実施例2)
酸性有機酸として、
メタンスルホン酸を1.0質量%、
乳酸を2.7質量%、
アミン化合物として、
トリイソプロパノールアミンを2.0質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.8質量%
からなるエッチング液原料を水75.99質量%と調合し、エッチング濃縮液を調製した。(Example 2)
As an acidic organic acid
1.0% by mass of methanesulfonic acid,
2.7% by mass of lactic acid,
As an amine compound
2.0% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.8% by mass of ammonium fluoride
An etching solution raw material made of the above was mixed with 75.99% by mass of water to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で86.76質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 86.76% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(実施例3)
酸性有機酸として、
メタンスルホン酸を0.3質量%、
コハク酸を5.0質量%、
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水76.04質量%と調合し、エッチング濃縮液を調製した。(Example 3)
As an acidic organic acid
0.3% by mass of methanesulfonic acid,
5.0% by mass of succinic acid,
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material made of the above was mixed with 76.04% by mass of water to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で86.81質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 86.81% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(実施例4)
酸性有機酸として、
メタンスルホン酸を0.5質量%、
グルタル酸を10.0質量%、
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水70.84質量%と調合し、エッチング濃縮液を調製した。(Example 4)
As an acidic organic acid
0.5% by mass of methanesulfonic acid,
Glutaric acid 10.0% by mass,
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material made of the above was mixed with 70.84% by mass of water to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で81.61質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 81.61% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(実施例5)
酸性有機酸として、
メタンスルホン酸を0.3質量%、
マロン酸を5.0質量%、
アミン化合物として、
トリイソプロパノールアミンを1.5質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水75.29質量%と調合し、エッチング濃縮液を調製した。(Example 5)
As an acidic organic acid
0.3% by mass of methanesulfonic acid,
5.0% by mass of malonic acid,
As an amine compound
1.5% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of 75.29% by mass of water was mixed to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で86.06質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 86.06% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(実施例6)
酸性有機酸として、
乳酸を4.5質量%、
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水76.84質量%と調合し、エッチング濃縮液を調製した。(Example 6)
As an acidic organic acid
4.5% by mass of lactic acid,
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of this was mixed with 76.84% by mass of water to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で87.61質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 87.61% by mass. The liquid temperature was 35 ° C. Table 1 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(比較例1)
酸性有機酸として、
マロン酸を20.0質量%、
アミン化合物として、
水酸化テトラメチルアンモニウム(TMAH:CAS番号75−59−2)を5.7質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.2質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.26質量%
からなるエッチング液原料を水56.37質量%と調合し、エッチング濃縮液を調製した。(Comparative Example 1)
As an acidic organic acid
20.0% by mass of malonic acid,
As an amine compound
Tetramethylammonium hydroxide (TMAH: CAS No. 75-59-2) in 5.7% by mass,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.2% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.26% by mass of ammonium fluoride
An etching solution raw material composed of 56.37% by mass of water was mixed to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で67.14質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 67.14% by mass. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(比較例2)
酸性有機酸として、
メタンスルホン酸を2.3質量%
マロン酸を10.0質量%、
アミン化合物として、
水酸化テトラメチルアンモニウムを3.3質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.1質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.26質量%
からなるエッチング液原料を水66.57質量%と調合し、エッチング濃縮液を調製した。(Comparative Example 2)
As an acidic organic acid
2.3% by mass of methanesulfonic acid
10.0% by mass of malonic acid,
As an amine compound
Tetramethylammonium hydroxide in 3.3% by mass,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.1% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.26% by mass of ammonium fluoride
An etching solution raw material composed of 66.57% by mass of water was mixed to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で77.34質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 77.34% by mass. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(比較例3)
酸性有機酸として、
メタンスルホン酸を0.3質量%
乳酸を13.5質量%、
アミン化合物として、
トリイソプロパノールアミンを1.5質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.01質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水66.82質量%と調合し、エッチング濃縮液を調製した。(Comparative Example 3)
As an acidic organic acid
0.3% by mass of methanesulfonic acid
13.5% by mass of lactic acid,
As an amine compound
1.5% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.01% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of 66.82% by mass of water was mixed to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で77.59質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 77.59% by mass. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(比較例4)
酸性有機酸として、
メタンスルホン酸を0.5質量%
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水80.84質量%と調合し、エッチング濃縮液を調製した。(Comparative Example 4)
As an acidic organic acid
0.5% by mass of methanesulfonic acid
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of 80.84% by mass of water was mixed to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で91.61質量%となる。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。 A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 91.61% by mass. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
(比較例5)
酸性有機酸として、
メタンスルホン酸を0.3質量%
グリコール酸を9.0質量%
アミン化合物として、
トリイソプロパノールアミンを0.75質量%、
過酸化水素安定剤として、
2−ブトキシエタノールを0.90質量%、
アゾール類として、
5−アミノ−1H−テトラゾールを0.04質量%
フッ素イオン供給源として、
フッ化アンモニウムを0.4質量%
からなるエッチング液原料を水72.04質量%と調合し、エッチング濃縮液を調製した。(Comparative Example 5)
As an acidic organic acid
0.3% by mass of methanesulfonic acid
9.0% by mass of glycolic acid
As an amine compound
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
2-Butoxyethanol 0.90% by mass,
As azoles
0.04% by mass of 5-amino-1H-tetrazole
As a fluorine ion source
0.4% by mass of ammonium fluoride
An etching solution raw material composed of this was mixed with 72.04% by mass of water to prepare an etching concentrate.
35%過酸化水素水16.57重量%(エッチング液の全量に対して過酸化水素が5.8質量%と水分が10.77質量%)とエッチング濃縮液を混合し、過酸化水素濃度が5.8質量%のエッチング液を調製した。なお、水は全量で82.81質量%となる。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。
A 35% hydrogen peroxide solution of 16.57% by mass (5.8% by mass of hydrogen peroxide and 10.77% by mass of water content with respect to the total amount of the etching solution) and an etching concentrate are mixed to increase the concentration of hydrogen peroxide. An etching solution of 5.8% by mass was prepared. The total amount of water is 82.81% by mass. The liquid temperature was 35 ° C. Table 2 shows the concentration of each component in the entire etching solution and the results of each evaluation item.
表1を参照する。実施例1乃至5は、有機酸としてメタンスルホン酸とその他の有機酸を併用したものである。これらの実施例においては、テーパー角、トップCDロスおよびボトムCDロスとも、好ましい範囲内でエッチングすることができた。また、これらの組成では、評価Cu濃度も8,000ppm以上であった。 See Table 1. In Examples 1 to 5, methanesulfonic acid and other organic acids are used in combination as organic acids. In these examples, both the taper angle, the top CD loss and the bottom CD loss could be etched within a preferable range. Further, in these compositions, the evaluated Cu concentration was 8,000 ppm or more.
実施例6は有機酸として乳酸だけのものである。本発明に係るエッチング液では有機酸は、乳酸だけでも銅/チタンの多層膜を好適にエッチングすることができた。 Example 6 is only lactic acid as an organic acid. In the etching solution according to the present invention, the organic acid could suitably etch the copper / titanium multilayer film with lactic acid alone.
次に表2を参照する。表2は比較例を掲載したものである。比較例1および比較例2はいずれもフッ化アンモニウムが0.26質量%であり、表1に示した各実施例よりも少ない場合である。比較例1および2ともに、規定時間内にジャストエッチの状態になることができず、エッチング残りが生じた。したがって、テーパー角等のサイドエッチングの指標は測定できなかった。表2の備考には「時間切れ」と記載した。 Next, refer to Table 2. Table 2 shows comparative examples. In both Comparative Example 1 and Comparative Example 2, ammonium fluoride was 0.26% by mass, which was less than each of the examples shown in Table 1. In both Comparative Examples 1 and 2, the state of just etching could not be achieved within the specified time, and etching residue was generated. Therefore, the index of side etching such as the taper angle could not be measured. In the remarks of Table 2, "time out" is described.
比較例3は、有機酸としてメタンスルホン酸と乳酸を含んだ組成である。サイドエッチングの指標は値を掲載しているが、テーパー部分がテーパーになっておらず、形状が非常に乱れたエッチ面となっていた。表2の備考には「θ不良」と記載した。 Comparative Example 3 has a composition containing methanesulfonic acid and lactic acid as organic acids. The index of side etching shows the value, but the tapered part was not tapered, and the shape was a very disordered etched surface. In the remarks of Table 2, "θ defect" is described.
比較例4は、有機酸としてメタンスルホン酸だけのものである。また比較例5は、有機酸としてメタンスルホン酸とグリコール酸を併用したものである。いずれの場合も、規定時間内にジャストエッチングの状態にならず、溶け残りがあった。表2の備考には「時間切れ」と記載した。 In Comparative Example 4, only methanesulfonic acid is used as the organic acid. Further, Comparative Example 5 is a combination of methanesulfonic acid and glycolic acid as organic acids. In either case, the state of just etching was not achieved within the specified time, and there was undissolved residue. In the remarks of Table 2, "time out" is described.
以上のことより、メタンスルホン酸は全量に対して0.2質量%〜1.5質量%の範囲であって、乳酸を併用する場合は乳酸は2.0質量%〜10.0質量%が望ましい。 From the above, methanesulfonic acid is in the range of 0.2% by mass to 1.5% by mass with respect to the total amount, and when lactic acid is used in combination, lactic acid is 2.0% by mass to 10.0% by mass. desirable.
また、コハク酸を併用する場合、コハク酸は4.5質量%〜5.5質量%がよく、グルタル酸を併用する場合、グルタル酸は9.5質量%〜10.5質量%がよく、マロン酸を併用する場合、マロン酸は4.5質量%〜5.5質量%が望ましい。 When succinic acid is used in combination, succinic acid is preferably 4.5% by mass to 5.5% by mass, and when glutaric acid is used in combination, glutaric acid is preferably 9.5% by mass to 10.5% by mass. When malonic acid is used in combination, the amount of malonic acid is preferably 4.5% by mass to 5.5% by mass.
また、有機酸として乳酸は単独で使用することもできる。その際の乳酸は4.0質量%〜5.0質量%が好適である。 Lactic acid can also be used alone as the organic acid. The lactic acid at that time is preferably 4.0% by mass to 5.0% by mass.
以上のように、過酸化水素と、フッ素イオン供給源と、アゾールと、過酸化水素安定剤と、有機酸と、アミンと水で構成されるエッチング液であって、有機酸は、メタンスルホン酸と乳酸、コハク酸、グルタン酸、マロン酸から選ばれる少なくとも1種を含むものは、銅/チタンの多層膜を好適にエッチングすることができ、また、バスライフも長い。したがって、銅の膜厚が厚くなっても、頻繁にエッチング液の組成調整を行う必要がない。 As described above, the etching solution is composed of hydrogen peroxide, a fluorine ion source, azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water, and the organic acid is methanesulfonic acid. And those containing at least one selected from lactic acid, succinic acid, glutanic acid and malonic acid can suitably etch a copper / titanium multilayer film and have a long bath life. Therefore, even if the copper film thickness is increased, it is not necessary to frequently adjust the composition of the etching solution.
本発明に係るエッチング液は、チタンと銅の多層膜をエッチングする際に好適に利用することができる。特に、銅イオン濃度が非常に高くなっても、サイドエッチングの特性を維持することができるので、銅の膜厚が厚くなっても長期間にわたって所定のエッチングレートの範囲を維持することができる。 The etching solution according to the present invention can be suitably used when etching a multilayer film of titanium and copper. In particular, since the side etching characteristics can be maintained even when the copper ion concentration becomes very high, the predetermined etching rate range can be maintained for a long period of time even when the copper film thickness becomes thick.
ガラス基板10
チタン層12
銅層14
(銅層14の)上面14a
(銅層14の上面14aの)端14aa
(銅層14の)下面14b
(銅層14の下面14bの)端14ba
レジスト層16
端16a
仮想面18
角度θ
Edge 14aa (on the
Edge 14ba (on the
Resist
Angle θ
Claims (8)
(a)過酸化水素と、
(b)フッ素イオン供給源と、
(c)アゾール類と、
(d)過酸化水素安定剤と、
(e)有機酸と、
(f)アミン類と、
(g)水を含み、
前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、エッチング液全量に対して0.2質量%〜1.5質量%含み、
さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうち一種の有機酸が併用され、
前記併用される有機酸に乳酸を含む場合は、前記乳酸は、エッチング液全量に対して2.0質量%〜10.0質量%であり、
前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、エッチング液全量に対して4.5質量%〜5.5質量%であり、
前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、エッチング液全量に対して9.5質量%〜10.5質量%であり、
前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、エッチング液全量に対して4.5質量%〜5.5質量%であり、
前記有機酸が乳酸だけの場合は、前記乳酸はエッチング液全量に対して4.0質量%〜5.0質量%であるエッチング液。An etching solution that etches a multilayer film of copper and titanium.
(A) Hydrogen peroxide and
(B) Fluorine ion source and
(C) Azole and
(D) Hydrogen peroxide stabilizer and
(E) Organic acids and
(F) Amines and
(G) Contains water
The organic acid is selected from methanesulfonic acid and lactic acid with respect to the total amount of the etching solution.
When the organic acid contains methanesulfonic acid, the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
Furthermore, at least one of organic acids such as lactic acid, succinic acid, glutaric acid, and malonic acid is used in combination.
When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution.
When the organic acid used in combination contains succinic acid, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
When glutaric acid is contained in the organic acid used in combination, the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
When malonic acid is contained in the organic acid used in combination, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
When the organic acid is only lactic acid, the etching solution contains 4.0% by mass to 5.0% by mass of the total amount of the etching solution.
(b)フッ素イオン供給源と、
(c)アゾール類と、
(d)過酸化水素安定剤と、
(e)有機酸と、
(f)アミン類と、
(g)水を含み、
前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、過酸化水素を全量の4.0質量%〜8.8質量%になるように混合した請求項1乃至5の何れかに記載された完全エッチング液の全量に対して0.2質量%〜1.5質量%含み、
さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうちもう一種の有機酸が併用され、
前記併用される有機酸に乳酸を含む場合は、前記乳酸は、前記完全エッチング液の全量に対して2.0質量%〜10.0質量%であり、
前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、前記完全エッチング液の全量に対して4.5質量%〜5.5質量%であり、
前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、前記完全エッチング液の全量に対して9.5質量%〜10.5質量%であり、
前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、前記完全エッチング液全量に対して4.5質量%〜5.5質量%であり、
前記有機酸が乳酸だけの場合は、前記乳酸は前記完全エッチング液の全量に対して4.0質量%〜5.0質量%であるエッチング濃縮液。It is an etching concentrate that concentrates the etching solution that etches the laminated film of copper and titanium.
(B) Fluorine ion source and
(C) Azole and
(D) Hydrogen peroxide stabilizer and
(E) Organic acids and
(F) Amines and
(G) Contains water
The organic acid is selected from methanesulfonic acid and lactic acid with respect to the total amount of the etching solution.
When the organic acid contains methanesulfonic acid, the methanesulfonic acid is any of claims 1 to 5 in which hydrogen peroxide is mixed so as to be 4.0% by mass to 8.8% by mass of the total amount. Contains 0.2% by weight to 1.5% by weight based on the total amount of the described complete etching solution.
Furthermore, at least another organic acid among lactic acid, succinic acid, glutaric acid, and malonic acid is used in combination.
When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the complete etching solution.
When the organic acid used in combination contains succinic acid, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the complete etching solution.
When glutaric acid is contained in the organic acid used in combination, the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the complete etching solution.
When malonic acid is contained in the organic acid used in combination, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the complete etching solution.
When the organic acid is only lactic acid, the etching concentrate is 4.0% by mass to 5.0% by mass with respect to the total amount of the complete etching solution.
前記接触させた状態を所定時間維持する工程を有するエッチング方法。A step of bringing the etching solution according to any one of claims 1 to 5 into contact with a substrate to be treated in which a resist pattern is arranged on a multilayer film of copper and titanium.
An etching method including a step of maintaining the contacted state for a predetermined time.
前記エッチング液を銅とチタンの多層膜にレジストパターンが配された被処理基板に接触させる工程と
前記接触させた状態を所定時間維持する工程を有するエッチング方法。A step of mixing the etching concentrate according to claim 6 with hydrogen peroxide and water to prepare the etching solution according to claims 1 to 5.
An etching method including a step of bringing the etching solution into contact with a substrate to be processed in which a resist pattern is arranged on a multilayer film of copper and titanium, and a step of maintaining the contacted state for a predetermined time.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2017/035529 WO2019064506A1 (en) | 2017-09-29 | 2017-09-29 | Etching solution and etching concentrate for multilayer film, and etching method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2019064506A1 JPWO2019064506A1 (en) | 2020-04-09 |
JP6793312B2 true JP6793312B2 (en) | 2020-12-02 |
Family
ID=65900929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019544111A Active JP6793312B2 (en) | 2017-09-29 | 2017-09-29 | Etching solution for multilayer film, etching concentrate and etching method |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6793312B2 (en) |
CN (1) | CN111094627B (en) |
WO (1) | WO2019064506A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110904456B (en) * | 2019-12-28 | 2022-01-14 | 上海天承化学有限公司 | Copper etching solution and preparation method and application thereof |
CN111286738A (en) * | 2020-01-17 | 2020-06-16 | 江阴江化微电子材料股份有限公司 | Production process of acidic copper etching solution |
CN112420606B (en) * | 2020-11-04 | 2023-02-03 | 深圳市华星光电半导体显示技术有限公司 | Preparation method of array substrate and array substrate |
CN112663064A (en) * | 2020-12-16 | 2021-04-16 | 江苏艾森半导体材料股份有限公司 | Copper-molybdenum metal etching solution and preparation method and application thereof |
CN112981404B (en) * | 2021-02-05 | 2022-10-28 | 四川和晟达电子科技有限公司 | Titanium alloy etching solution composition and use method thereof |
CN114751385B (en) * | 2022-04-21 | 2024-02-06 | 盛隆资源再生(无锡)有限公司 | Regeneration method of sulfuric acid microetching waste liquid |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102834547B (en) * | 2010-01-28 | 2014-08-20 | 三菱瓦斯化学株式会社 | Etching liquid for a copper/titanium multilayer thin film |
JP2012189725A (en) * | 2011-03-09 | 2012-10-04 | Kobe Steel Ltd | WIRING FILM AND ELECTRODE USING Ti ALLOY BARRIER METAL AND Ti ALLOY SPUTTERING TARGET |
JP6207248B2 (en) * | 2013-06-17 | 2017-10-04 | 株式会社Adeka | Etching solution composition and etching method |
JP6494254B2 (en) * | 2014-11-18 | 2019-04-03 | 関東化學株式会社 | Copper / molybdenum metal laminated film etching solution composition, etching method using the composition, and method for extending the life of the composition |
JP6531612B2 (en) * | 2014-11-27 | 2019-06-19 | 三菱瓦斯化学株式会社 | Liquid composition and etching method using the same |
JP6777420B2 (en) * | 2016-04-21 | 2020-10-28 | 関東化学株式会社 | Etching composition of single-layer film or laminated film or etching method using the composition |
CN106086891B (en) * | 2016-08-11 | 2018-10-26 | 江阴江化微电子材料股份有限公司 | A kind of advanced lines tablet copper titanium film acidic etching liquid |
-
2017
- 2017-09-29 WO PCT/JP2017/035529 patent/WO2019064506A1/en active Application Filing
- 2017-09-29 CN CN201780094862.7A patent/CN111094627B/en active Active
- 2017-09-29 JP JP2019544111A patent/JP6793312B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
WO2019064506A1 (en) | 2019-04-04 |
CN111094627A (en) | 2020-05-01 |
JPWO2019064506A1 (en) | 2020-04-09 |
CN111094627B (en) | 2022-04-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6793312B2 (en) | Etching solution for multilayer film, etching concentrate and etching method | |
JP6443649B1 (en) | Etching solution for copper thick film | |
TWI666301B (en) | Etching solution compositions for copper-molybdenum metal laminated films, etching methods using said compositions, and methods for extending life-span of said compositions | |
JP5051323B2 (en) | Etching solution for multilayer thin film containing copper layer and molybdenum layer | |
JP5866566B2 (en) | Etching solution, etching concentrate and etching method for multilayer film containing molybdenum and copper | |
JP6036691B2 (en) | Manufacturing method of semiconductor device | |
JP6167444B1 (en) | Etching solution for multilayer film, etching concentrated solution, and etching method | |
WO2015075765A1 (en) | Multilayer-film etchant, concentrated etchant, and etching method | |
JP6516214B2 (en) | Etching solution for multilayer film, etching solution and etching method | |
JP6862817B2 (en) | A liquid composition for etching a multilayer thin film containing copper and molybdenum, an etching method using the liquid composition, and a method for manufacturing a display device. | |
JP2022052909A (en) | Etchant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191202 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201020 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201021 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 6793312 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |