CN115679321A - Metal etching liquid - Google Patents
Metal etching liquid Download PDFInfo
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- CN115679321A CN115679321A CN202211235091.8A CN202211235091A CN115679321A CN 115679321 A CN115679321 A CN 115679321A CN 202211235091 A CN202211235091 A CN 202211235091A CN 115679321 A CN115679321 A CN 115679321A
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- Prior art keywords
- acid
- etching
- structural formula
- etching solution
- metal
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- 238000005530 etching Methods 0.000 title claims abstract description 142
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 86
- -1 alcohol amine compounds Chemical class 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000002738 chelating agent Substances 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 4
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- YHEKBXQMXRLCCX-UHFFFAOYSA-N 2h-benzotriazol-4-ylmethanol Chemical compound OCC1=CC=CC2=C1N=NN2 YHEKBXQMXRLCCX-UHFFFAOYSA-N 0.000 claims description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 3
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 3
- 229930024421 Adenine Natural products 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229960000643 adenine Drugs 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229960003540 oxyquinoline Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 159000000001 potassium salts Chemical class 0.000 claims description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000004925 denaturation Methods 0.000 abstract description 3
- 230000036425 denaturation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000003814 drug Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 2
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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Abstract
In order to solve the problem that in the prior art, the residual removing effect is weak due to the denaturation of alcohol amine compounds in the etching solution, the application provides the metal etching solution; the etching solution comprises the following components: the hydrogen peroxide, an auxiliary oxidant, a metal chelating agent, a solubilizer, a residue remover and water, wherein the residue remover comprises a compound shown in a structural formula I and an alcohol amine compound shown in a structural formula II; according to the etching solution provided by the application, the compound shown in the structural formula I inhibits the reaction and decomposition of the alcamines compound shown in the structural formula II and hydrogen peroxide, so that the residue removal effect in the etching process is ensured, no residue is left in etching, and the reliability and the service life of the etching solution are ensured.
Description
Technical Field
The invention belongs to the technical field of etching solutions for semiconductors and panels, and particularly relates to a metal etching solution.
Background
Wet etching is a means of patterning a metal layer in the manufacturing process of semiconductors and panel displays, in which the purpose of etching is achieved by chemical reaction using a chemical reagent. In recent years, while the demand of displays is increasing, the quality and picture accuracy of products are also required to be higher from liquid crystal display screens to OLED display screens, and the etching effect can directly influence the accuracy and quality of high-density thin-wire images. While aluminum or an aluminum alloy is used for the metal wiring of the conventional liquid crystal display, the gate line and the data line connected to the thin film transistor increase in length and the response resistance increases with the increase in size, resolution, and refresh rate of the liquid crystal display, thereby causing problems such as signal delay. Therefore, studies have been conducted on a combination of copper or an alloy wiring mainly composed of copper, which is a material having a lower electric resistance. Molybdenum and titanium are specially produced to have high adhesion to a substrate such as glass, low diffusion efficiency, and barrier properties, and therefore, the process is upgraded to form a film on a substrate such as glass by a film formation process such as sputtering of a laminated film of an alloy such as copper or copper molybdenum/copper titanium containing copper as a main component, and then to form an electrode pattern by an etching step of etching using a resist or the like as a mask. However, in order to realize high-precision etching, the lateral etching depth of the copper, copper molybdenum and copper titanium composite wires must be controlled. The lateral etching depth and the etching time show positive correlation change. The compressive etching time can reduce the lateral etching, but at the same time, can cause residue problems. The addition of the alcohol amine compound has a good effect on removing residues, but during storage or use of the etching solution, the alcohol amine is easy to slowly react with hydrogen peroxide to cause denaturation, so that the residue removing effect is weakened, and the reliability and the service life of the liquid medicine are influenced.
Disclosure of Invention
To the problem that the effect of removing etching solution residue is weak and the effect of removing is unstable among the prior art, the application provides a metal etching solution.
In order to solve the technical problem, the application provides a metal etching solution, which comprises the following components: hydrogen peroxide, an auxiliary oxidant, a metal chelating agent, a solubilizer, a residue remover and water, wherein the residue remover contains an alcohol amine compound shown in a structural formula II and a compound shown in a structural formula I:
wherein R is 1 、R 2 、R 3 Each is independently selected from C n H 2n ，n≤3；
Wherein R is 4 、R 5 、R 6 Each independently selected from C1-C4 substituted or unsubstituted alkyl, and R 4 、R 5 And R 6 At least one hydrogen in the carbon is replaced by a hydroxyl group.
Preferably, the compound shown in the structural formula I is selected from one or more of triethanolamine amine oxide and triisopropanolamine amine oxide.
Preferably, the alcamines shown in the structural formula II comprise one or more of ethanolamine, isopropanolamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-dimethylethanolamine and N, N-dimethylisopropanolamine
Preferably, the total weight of the etching solution is 100%, and the mass percentage of the hydrogen peroxide is 5-25%; the mass percentage of the auxiliary oxidant is 0.01-6%; the mass percentage of the metal chelating agent is 1-10%; the mass percentage content of the solubilizer is 0.1-5%; the mass percentage of the residual remover is 2-15%, wherein the mass percentage of the alcohol amine compound is 1.5-10%, and the mass percentage of the compound shown in the structural formula I is 0.1-5%; the balance being water.
Preferably, the auxiliary oxidant comprises one or more of an organic acid, an inorganic acid or a salt thereof, the organic acid is a linear carboxylic acid, and the organic acid comprises one or more of oxalic acid, malonic acid, succinic acid, glutaric acid and glycolic acid; the inorganic acid or salt thereof includes one or more of phosphoric acid, sulfuric acid, nitric acid, and their corresponding ammonium, sodium or potassium salts.
Preferably, the metal chelating agent is a compound containing two or more groups selected from hydroxyl, carboxyl and amino;
the metal chelating agent comprises one or more of citric acid, malic acid, 2, 3-dihydroxy succinic acid, iminodiacetic acid and ethylenediamine tetraacetic acid.
Preferably, the solubilizer comprises one or more of ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol, ethylene glycol, and polyethylene glycol.
Preferably, the etching solution further comprises a hydrogen peroxide stabilizer with the mass percentage of 0.01-2%;
the hydrogen peroxide stabilizer comprises one or more of phenylurea, hexylamine, octylamine, ethylenediamine, cyclohexylamine, aniline, N-dimethylaniline and diethylaniline.
Preferably, the etching solution further comprises an etching regulator with the mass percentage content of 0.001-1%, wherein the etching regulator is a nitrogen-containing heterocyclic compound, and the nitrogen-containing heterocyclic compound comprises one or more of 8-hydroxyquinoline, benzotriazole, hydroxymethylbenzotriazole, 5-aminotetrazole, 3-amino-1, 2,4 triazole, methyltetrazole, guanine and adenine.
Has the advantages that:
according to the metal etching solution, the composition of the alcohol amine compound shown in the structural formula II and the compound shown in the structural formula I is used as a residue remover, so that residues generated in the etching process can be effectively removed, and the short circuit problem is avoided; in addition, compared with the alcohol amine compound only added with the alcohol amine compound shown in the structural formula II, the compound shown in the structural formula I contained in the residue remover can inhibit the reaction of the alcohol amine compound and hydrogen peroxide, thereby ensuring the residue removal effect in the etching process, improving the reliability of the liquid medicine and prolonging the service life. The etching solution provided by the application has the advantages that the residual remover has stable effect, no residual is left in etching, and the etching solution has higher reliability and longer service life.
Drawings
FIG. 1 is a SEM photograph of example 1 after etching;
FIG. 2 is a SEM photograph of example 2 after etching;
FIG. 3 is a SEM photograph of example 3 after etching;
FIG. 4 is a SEM image of example 5 after etching;
FIG. 5 is an SEM image of comparative example 1 after etching;
FIG. 6 is a SEM photograph of comparative example 2 after etching;
fig. 7 is an SEM image after etching of comparative example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application provides a metal etching solution, the etching solution includes following components: the hydrogen peroxide, an auxiliary oxidant, a metal chelating agent, a solubilizer, a residue remover and water, wherein the residue remover comprises a compound shown in a structural formula I and an alcohol amine compound shown in a structural formula II;
the compound represented by the structural formula I:
wherein R is 1 、R 2 、R 3 Each is independently selected from C n H 2n ，n≤3；
The alcamines represented by the structural formula II are as follows:
wherein R is 4 、R 5 、R 6 Each independently selected from C1-C4 substituted or unsubstituted alkyl, and R 4 、R 5 And R 6 At least one hydrogen in the carbon is replaced by a hydroxyl group.
In the metal etching solution, the alcohol amine compound has a good effect on removing residues, but the alcohol amine compound is easy to slowly react with hydrogen peroxide to cause denaturation, so that the effect of removing the residues is weakened. The inventor finds that the composition of the alcohol amine compound shown in the structural formula II and the compound shown in the structural formula I is added into the etching solution as a residue remover, so that residues generated in the etching process can be effectively removed, and the short circuit problem is avoided; compared with the alcohol amine compound shown in the structural formula II, the compound shown in the structural formula I can inhibit the reaction of the alcohol amine compound and hydrogen peroxide, so that the residue removal effect in the etching process is ensured, the reliability of the liquid medicine is improved, and the service life of the liquid medicine is prolonged.
Specifically, R in the compound shown in the structural formula 1 1 、R 2 、R 3 Each is independently selected from C n H 2n N is less than or equal to 3, e.g. R 1 、R 2 、R 3 Can be independently selected from CH 2 、CH 2 CH 2 、CH(CH 3 )CH 2 。
In the alcamines compounds represented by the structural formula II, R 4 、R 5 、R 6 May each be independently selected from C1-C4 substituted or unsubstituted alkyl, and R 4 、R 5 And R 6 At least one hydrogen in the carbon is replaced by a hydroxyl group; for example, unsubstituted C1-C4 alkyl can be methyl, ethyl, propyl, butyl, isopropyl; by substitution, i.e. at least one hydrogen atom of a carbon in a C1-C4 alkyl group is replaced by a hydroxyl group.
In some preferred embodiments, the compound of formula 1 comprises one or more of triethanolamine amine oxide and triisopropanolamine amine oxide.
In some preferred embodiments, the alcohol amine compound of formula II comprises one or more of ethanolamine, isopropanolamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-dimethylethanolamine, and N, N-dimethylisopropanolamine.
In some embodiments, the total weight of the etching solution is 100%, the mass percentage of the hydrogen peroxide is 2% to 25%, the mass percentage of the auxiliary oxidant is 0.01% to 6%, the mass percentage of the metal chelating agent is 1% to 10%, the mass percentage of the solubilizer is 0.1% to 5%, and the mass percentage of the residual remover is 2% to 15%, wherein the mass percentage of the alcohol amine compound represented by the structural formula ii is 1.5% to 10%, and the mass percentage of the compound represented by the structural formula i is 0.1% to 5%; the balance being water.
The compound shown in the structural formula I is not ideal in use effect when being used as a residual remover alone, but can inhibit the reaction of an alcamines compound and hydrogen peroxide due to the N-O bond, ensures the residual removal effect in the etching process by being used in combination with the alcamines compound, and can effectively prevent the residual remover from weakening the residual removal performance along with the change of time. The inventor finds that the addition of 0.1-5 wt% of the compound shown in the structural formula I into the etching solution can effectively inhibit the reaction of the alcohol amine compound and the hydrogen peroxide, ensure that the residue is removed in the etching process of the etching solution, and ensure that no residue is left after etching. If the mass content of the compound shown in the structural formula I is less than 0.1%, the content of N-O bonds in the etching solution is low, and the inhibition effect is reduced; if the mass content of the compound shown in the structural formula I is higher than 5%, steric effect is caused due to the increase of the concentration, and the inhibition effect is poor.
In some preferred embodiments, the mass content of the compound of formula i is greater than 10% of the mass content of the residual remover.
The hydrogen peroxide is mainly an oxidant of copper and copper alloy and plays a role of oxidizing the copper and copper alloy, and the hydrogen peroxide with the mass content of 5-25% is added into the etching solution, so that the oxidizing capability of the hydrogen peroxide is ensured, the etching is effectively carried out, meanwhile, the etching rate can be controlled to be maintained in a proper range, and the effective operation of the etching process is controlled. The content of hydrogen peroxide in the etching solution may be, for example, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25% by mass or the like, as long as it is 5% to 25%.
In some preferred embodiments, the hydrogen peroxide is present in an amount of 5% to 20% by mass.
The secondary oxidant serves primarily to provide H + And dissolving the metal oxide. The auxiliary oxidant comprises one or more of organic acid, inorganic acid or salt thereof, and the organic acid is straightA chain carboxylic acid, the organic acid comprising one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, and glycolic acid; the inorganic acid or salt thereof includes one or more of phosphoric acid, sulfuric acid and nitric acid, and their corresponding ammonium, sodium or potassium salts. For example, the corresponding ammonium salts of phosphoric acid include monoammonium phosphate, diammonium phosphate, etc.; the potassium salt corresponding to phosphoric acid includes potassium dihydrogen phosphate and the like.
The mass content of the auxiliary oxidant added into the etching solution is 0.01-6%, so that hydrogen ions for dissolving metal oxides can be provided, and the ordered proceeding of the etching process is ensured. Specifically, the auxiliary oxidizing agent may be contained in the etching solution in an amount of 0.01%, 0.05%, 0.08%, 0.1%, 0.5%, 0.6%, 0.8%, 1.0%, 1.5%, 1.8%, 2.0%, 2.4%, 2.8%, 3.2%, 3.6%, 3.8%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0% by mass or the like.
In some preferred embodiments, the mass content of the auxiliary oxidant is 0.05% to 3%.
The metal chelating agent can chelate free metal ions in the etching solution, so that the self-decomposition reaction of the hydrogen peroxide is slowed down, and the stability of the etching solution is enhanced. The metal chelating agent is a compound containing two or more of hydroxyl, carboxyl and amino, and comprises one or more of citric acid, malic acid, 2, 3-dihydroxysuccinic acid, iminodiacetic acid and ethylenediamine tetraacetic acid.
In some embodiments, the metal chelating agent is present in an amount of between 1% and 10%, preferably between 2% and 8% by weight. The content of the metal chelating agent is lower than 1%, so that the metal chelating capacity is poor, the hydrogen peroxide is decomposed too fast, and the problems of cone angle etching, etching deviation and uniformity reduction are caused while the potential safety hazard is high; the content of the chelating agent is higher than 10%, which easily causes the problem of incomplete dissolution of the chelating agent. The content of the metal chelating agent in the etching solution may be 1% to 10% by mass, for example, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0% by mass.
The solubilizer with the mass content of 0.5-5% is added into the etching solution, and the solubilizer is mainly used for prolonging the service life of the etching solution and improving the etching uniformity of the liquid medicine. The solubilizer comprises one or more of ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol, ethylene glycol and polyethylene glycol. For example, the content of the solubilizer may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The etching solution contains 1.5-10% of alcohol amine compound shown in the structural formula II by mass, and amino in the alcohol amine compound shown in the structural formula II can be chelated with etched metal ions, so that metal residues are easy to remove, the etching rate of the etching solution can be maintained, and the etching can be performed stably. The alcohol amine compound represented by the structural formula II may be contained in an amount of 1.5%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0% or the like, by mass.
In some preferred embodiments, the alcohol amine compound of formula II comprises one or more of ethanolamine, isopropanolamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-dimethylethanolamine, and N, N-dimethylisopropanolamine.
The etching solution also comprises 0.01-2% of hydrogen peroxide stabilizer by mass. The hydrogen peroxide stabilizer can prevent hydrogen peroxide from being decomposed violently in the etching process, prevent the hydrogen peroxide from decomposing into peroxide radicals and hydrogen ions too quickly, reduce the decomposition activity of the hydrogen peroxide to be 10% or less of the original decomposition activity, maintain the etching rate of the etching solution, enable the etching to be carried out stably, ensure the safety of the etching operation and prolong the service life of the etching solution. The hydrogen peroxide stabilizer is mainly a nitrogen-containing compound, and comprises one or more of phenylurea, hexylamine, octylamine, ethylenediamine, cyclohexylamine, aniline, N-dimethylaniline and diethylaniline. The hydrogen peroxide may be contained in an amount of, for example, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0% by mass.
In some preferred embodiments, the hydrogen peroxide stabilizer is 0.1 to 1% by weight.
In order to adjust the etching rate of the etching solution, thereby effectively improving the etching cone angle and reducing the etching deviation, the etching solution is also added with an etching regulator with the mass percentage of 0.001-1%. The etching regulator is a heterocyclic compound containing nitrogen. The nitrogen-containing heterocyclic compound comprises one or more of 8-hydroxyquinoline, benzotriazole, hydroxymethyl benzotriazole, 5-aminotetrazole, 3-amino-1, 2,4 triazole, methyl tetrazole, guanine and adenine.
The etching regulator may be contained in the etching solution in an amount of, for example, 0.001%, 0.005%, 0.008%, 0.01%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% by mass.
The preparation method of the metal etching solution provided by the invention is simple, and only needs to uniformly mix the components in corresponding parts by weight at room temperature.
According to the invention, hydrogen peroxide is used as an oxidant, so that the oxidizing property is strong, the environment is protected, metals such as copper oxide and nickel can be well oxidized, residues are removed by the residual remover, and the etching is facilitated; the composition of the alcohol amine compound shown in the structural formula II and the compound shown in the structural formula I is added to serve as a residue remover, so that residues generated in the etching process can be effectively removed, and the short circuit problem is avoided; compared with the alcohol amine compound shown in the structural formula II, the compound shown in the structural formula I can inhibit the reaction of the alcohol amine compound and hydrogen peroxide, so that the residue removal effect in the etching process is ensured, the reliability of the liquid medicine is improved, and the service life of the liquid medicine is prolonged. In order to ensure the operation safety and the etching effect, an auxiliary oxidant, a metal chelating agent for dissolving metal, a hydrogen peroxide stabilizer and an etching regulator are used for inhibiting the decomposition of hydrogen peroxide, controlling the etching rate and the etching cone angle, reducing the etching deviation, enabling the etching to be stably carried out and ensuring the etching quality.
The following examples are intended to illustrate specific embodiments of the present invention without limiting the scope of the invention to those described in the examples.
Example 1
At normal temperature, 12% of hydrogen peroxide by mass, 1.2% of ammonium dihydrogen phosphate and 1% of potassium dihydrogen phosphate by mass as auxiliary oxidants, 7.2% of citric acid by mass as metal chelating agents, 0.005% of 5-aminotetrazole by mass as etching regulators, 0.25% of phenylurea as hydrogen peroxide stabilizers, 5% of ethanolamine and 0.1% of triethanolamine amine oxide as residual removers, 0.5% of diethylene glycol as solubilizers and water by mass as residual removers are mixed and stirred uniformly to obtain the etching solution.
Examples 2 to 6 and comparative examples 1 to 3
Examples 2 to 6 and comparative examples 1 to 3 and comparative example 1 differ in the kind and mass content of hydrogen peroxide, auxiliary oxidizing agent, metal chelating agent, etching regulator, hydrogen peroxide stabilizer, residue remover, solubilizer, as shown in table 1.
TABLE 1 parameters of etching solutions for examples 1-3 and comparative examples 1-3
The etching solutions prepared in examples 1-6 and comparative examples 1-3 were left for 12 days and etched for the same time and temperature, and the etching residue results are shown in Table 2, wherein the scanning electron micrographs of the metal etched by the etching solutions are shown in FIGS. 1-7. The SEM picture of the etching result of example 1 is shown in fig. 1, the SEM picture of the etching result of example 2 is shown in fig. 2, and the SEM picture of the etching result of example 3 is shown in fig. 3; example 5 etched structure SEM figure is shown in fig. 4; the SEM of the etching results of comparative example 1 is shown in fig. 5, and the etching results of comparative example 2 is shown in fig. 6, and the etching results of comparative example 3 is shown in fig. 7, and the etching results of comparative example 1 is shown in fig. 5.
TABLE 2 etching results of examples 1 to 6 and comparative examples 1 to 3
| Group of | Residual condition after etching |
| Example 1 | Has no residue |
| Example 2 | Has no residue |
| Example 3 | Has no residue |
| Example 4 | Has no residue |
| Example 5 | Trace amount of residue |
| Example 6 | Has no residue |
| Comparative example 1 | A large amount of residues |
| Comparative example 2 | Small amount of residue |
| Comparative example 3 | A large amount of residues |
As shown in tables 1 to 2 and FIGS. 1 to 7, comparative example 1 in which the compound represented by formula 1 was not added had residues after etching with the etching solution; compared with the comparative example 1, 0.1% of the compound shown in the structural formula 1 is added into the etching solution prepared in the example 1, and the etching solution prepared in the example 1 has no residue after etching, which indicates that the compound shown in the structural formula 1 is added into the etching solution, and the compound shown in the structural formula 1 is supposed to be capable of inhibiting the reaction of the alcohol amine compound shown in the structural formula II and the hydrogen peroxide, inhibiting the decomposition of the residue remover, ensuring the residue removing effect of the residue remover, and improving the reliability and the service life of the liquid medicine. In comparative example 2, the content of the alcohol amine compound represented by the structural formula ii was increased and a small amount of residue was left after etching, which indicates that increasing the content of the alcohol amine compound can achieve the effect of reducing the residue, but the residue cannot be completely removed due to the decomposition of the alcohol amine compound. In comparative example 3, the content of the alcohol amine compound represented by the structural formula II was reduced, and a large amount of residue remained after etching. Compared with the example 2, the comparative example 3 is compared with the example 3, and no residue exists in the examples 2 and 3, which shows that the compound shown in the structural formula 1 added into the etching solution can inhibit the reaction of the alcohol amine compound shown in the structural formula II and the hydrogen peroxide, and ensures the effect of completely removing the residue by the residue remover. In the embodiments 1-4 and 6, the compound shown in the structural formula 1 is added, wherein the mass content of the compound shown in the structural formula 1 is 0.1-5%, and the obtained etching solution has no residue after etching; the mass content of the compound represented by the structural formula 1 added in example 5 is 6% and is more than 5%, and the etching solution prepared in example 5 has a trace amount of residue after etching, and it is estimated that the etching solution contains the compound represented by the structural formula 1 in an amount of more than 5% by mass, and the steric effect is caused by an increase in concentration, the inhibition effect is deteriorated, and the residue is caused after etching.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. The metal etching solution is characterized by comprising the following components: the hydrogen peroxide, an auxiliary oxidant, a metal chelating agent, a solubilizer, a residue remover and water, wherein the residue remover comprises a compound shown in a structural formula I and an alcohol amine compound shown in a structural formula II;
the compound shown in the structural formula I is as follows:
wherein R is 1 、R 2 、R 3 Each is independently selected from C n H 2n ，n≤3；
The alcohol amine compound shown in the structural formula II is as follows:
wherein R is 4 、R 5 、R 6 Each independently selected from C1-C4 substituted or unsubstituted alkyl, and R 4 、R 5 And R 6 At least one hydrogen in the carbon is replaced by a hydroxyl group.
2. The metal etchant of claim 1, wherein the compound of formula 1 comprises one or more of triethanolamine amine oxide and triisopropanolamine amine oxide.
3. The metal etchant according to claim 1, wherein the alcohol amine compound represented by the structural formula ii comprises one or more of ethanolamine, isopropanolamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-dimethylethanolamine, and N, N-dimethylisopropanolamine.
4. The metal etching solution of claim 1, wherein the total weight of the etching solution is 100%, the mass percentage of the hydrogen peroxide is 5% to 25%, the mass percentage of the auxiliary oxidant is 0.01% to 6%, the mass percentage of the metal chelating agent is 1% to 10%, the mass percentage of the solubilizer is 0.1% to 5%, and the mass percentage of the residual remover is 2% to 15%, wherein the mass percentage of the alcohol amine compound represented by the structural formula II is 1.5% to 10%, and the mass percentage of the compound represented by the structural formula I is 0.1% to 5%; the balance being water.
5. The metal etchant of claim 1, wherein the auxiliary oxidizer comprises one or more of an organic acid, an inorganic acid or a salt thereof, wherein the organic acid is a linear carboxylic acid, and wherein the organic acid comprises one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, and glycolic acid; the inorganic acid or salt thereof includes one or more of phosphoric acid, sulfuric acid and nitric acid, and their corresponding ammonium, sodium or potassium salts.
6. The metal etchant according to claim 1, wherein the metal chelating agent is a compound containing two or more of a hydroxyl group, a carboxyl group, and an amino group;
the metal chelating agent comprises one or more of citric acid, malic acid, 2, 3-dihydroxy succinic acid, iminodiacetic acid and ethylenediamine tetraacetic acid.
7. The metal etching solution of claim 1, wherein the solubilizer comprises one or more of ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol, ethylene glycol, and polyethylene glycol.
8. The metal etching solution of claim 1, further comprising 0.01-2% by mass of a hydrogen peroxide stabilizer;
the hydrogen peroxide stabilizer comprises one or more of phenylurea, hexylamine, octylamine, ethylenediamine, cyclohexylamine, aniline, N-dimethylaniline and diethylaniline.
9. The metal etching solution of claim 1, further comprising an etching regulator in an amount of 0.001-1% by mass, wherein the etching regulator is a nitrogen-containing heterocyclic compound, and the nitrogen-containing heterocyclic compound comprises one or more of 8-hydroxyquinoline, benzotriazole, hydroxymethylbenzotriazole, 5-aminotetrazole, 3-amino-1, 2,4 triazole, methyltetrazole, guanine, and adenine.
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| US20040180300A1 (en) * | 2002-12-20 | 2004-09-16 | Minsek David W. | Photoresist removal |
| US20060249482A1 (en) * | 2003-05-12 | 2006-11-09 | Peter Wrschka | Chemical mechanical polishing compositions for step-ll copper line and other associated materials and method of using same |
| CN101366107A (en) * | 2005-10-05 | 2009-02-11 | 高级技术材料公司 | Oxidizing aqueous cleaner for the removal of post-etch residues |
| US20150162213A1 (en) * | 2012-05-11 | 2015-06-11 | Advanced Technology Materials, Inc. | Formulations for wet etching nipt during silicide fabrication |
| WO2019180915A1 (en) * | 2018-03-23 | 2019-09-26 | パナソニックＩｐマネジメント株式会社 | Etching liquid for thick copper film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180300A1 (en) * | 2002-12-20 | 2004-09-16 | Minsek David W. | Photoresist removal |
| US20060249482A1 (en) * | 2003-05-12 | 2006-11-09 | Peter Wrschka | Chemical mechanical polishing compositions for step-ll copper line and other associated materials and method of using same |
| CN101366107A (en) * | 2005-10-05 | 2009-02-11 | 高级技术材料公司 | Oxidizing aqueous cleaner for the removal of post-etch residues |
| US20150162213A1 (en) * | 2012-05-11 | 2015-06-11 | Advanced Technology Materials, Inc. | Formulations for wet etching nipt during silicide fabrication |
| WO2019180915A1 (en) * | 2018-03-23 | 2019-09-26 | パナソニックＩｐマネジメント株式会社 | Etching liquid for thick copper film |
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