CN114752939A - Etching solution and preparation method and application thereof - Google Patents
Etching solution and preparation method and application thereof Download PDFInfo
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- CN114752939A CN114752939A CN202210568533.4A CN202210568533A CN114752939A CN 114752939 A CN114752939 A CN 114752939A CN 202210568533 A CN202210568533 A CN 202210568533A CN 114752939 A CN114752939 A CN 114752939A
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- Prior art keywords
- acid
- etching solution
- nickel
- etching
- copper
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- 238000005530 etching Methods 0.000 title claims abstract description 192
- 238000002360 preparation method Methods 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 claims abstract description 94
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000010949 copper Substances 0.000 claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005260 corrosion Methods 0.000 claims abstract description 49
- 230000007797 corrosion Effects 0.000 claims abstract description 45
- 239000003112 inhibitor Substances 0.000 claims abstract description 34
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 239000006184 cosolvent Substances 0.000 claims abstract description 19
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 17
- KHBQMWCZKVMBLN-IDEBNGHGSA-N benzenesulfonamide Chemical group NS(=O)(=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 KHBQMWCZKVMBLN-IDEBNGHGSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 182
- 229910052759 nickel Inorganic materials 0.000 claims description 91
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- DIRCLGLKRZLKHG-UHFFFAOYSA-N 4-hydroxybenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C(O)C=C1 DIRCLGLKRZLKHG-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 20
- JPVKCHIPRSQDKL-UHFFFAOYSA-N 3-aminobenzenesulfonamide Chemical compound NC1=CC=CC(S(N)(=O)=O)=C1 JPVKCHIPRSQDKL-UHFFFAOYSA-N 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 3,3, 5-trihydroxyvaleric acid Chemical compound 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 229960004063 propylene glycol Drugs 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 12
- OISQSDKFWKJEBA-UHFFFAOYSA-N 4-amino-n-methylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(N)C=C1 OISQSDKFWKJEBA-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- JPIJQSOTBSSVTP-UHFFFAOYSA-N 2,3,4-trihydroxybutanoic acid Chemical compound OCC(O)C(O)C(O)=O JPIJQSOTBSSVTP-UHFFFAOYSA-N 0.000 claims description 8
- VBUWJOHKCBQXNU-UHFFFAOYSA-N 2-Deoxypentonic acid Chemical compound OCC(O)C(O)CC(O)=O VBUWJOHKCBQXNU-UHFFFAOYSA-N 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- QXKAIJAYHKCRRA-UHFFFAOYSA-N l-lyxonate Chemical compound OCC(O)C(O)C(O)C(O)=O QXKAIJAYHKCRRA-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- CHUMGDDVFASTDV-UHFFFAOYSA-N 2,3,4-trihydroxypentanoic acid Chemical compound CC(O)C(O)C(O)C(O)=O CHUMGDDVFASTDV-UHFFFAOYSA-N 0.000 claims description 4
- RSKGLBJVIAQRMC-UHFFFAOYSA-N 2,4,5-trihydroxypentanoic acid Chemical compound OCC(O)CC(O)C(O)=O RSKGLBJVIAQRMC-UHFFFAOYSA-N 0.000 claims description 4
- UFYGCFHQAXXBCF-UHFFFAOYSA-N 2,4-dihydroxybutanoic acid Chemical compound OCCC(O)C(O)=O UFYGCFHQAXXBCF-UHFFFAOYSA-N 0.000 claims description 4
- IPFDALLIRXQJDG-UHFFFAOYSA-N 3,3-dihydroxypropanoic acid Chemical compound OC(O)CC(O)=O IPFDALLIRXQJDG-UHFFFAOYSA-N 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- GOCCREQJUBABAL-UHFFFAOYSA-N 2,2-dihydroxyacetic acid Chemical compound OC(O)C(O)=O GOCCREQJUBABAL-UHFFFAOYSA-N 0.000 claims description 3
- WLBZSUDERATLNN-UHFFFAOYSA-N 2,4,4-trihydroxybutanoic acid Chemical compound OC(O)CC(O)C(O)=O WLBZSUDERATLNN-UHFFFAOYSA-N 0.000 claims description 3
- WGSYQANIQMOSPL-UHFFFAOYSA-N 3,3,4,5-tetrahydroxypentanoic acid Chemical compound C(C(C(CC(=O)O)(O)O)O)O WGSYQANIQMOSPL-UHFFFAOYSA-N 0.000 claims description 3
- AYSPMZBNLBCWGY-UHFFFAOYSA-N 3,3-dihydroxypentanoic acid Chemical compound CCC(O)(O)CC(O)=O AYSPMZBNLBCWGY-UHFFFAOYSA-N 0.000 claims description 3
- DZAIOXUZHHTJKN-UHFFFAOYSA-N 3,4-dihydroxybutyric acid Chemical compound OCC(O)CC(O)=O DZAIOXUZHHTJKN-UHFFFAOYSA-N 0.000 claims description 3
- XMWHJMODTBOXDX-UHFFFAOYSA-N 4,5-dihydroxypentanoic acid Chemical compound OCC(O)CCC(O)=O XMWHJMODTBOXDX-UHFFFAOYSA-N 0.000 claims description 3
- LMVYYKVYJJLTES-UHFFFAOYSA-N 5,5-dihydroxypentanoic acid Chemical compound OC(O)CCCC(O)=O LMVYYKVYJJLTES-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000002184 metal Substances 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 42
- 239000008213 purified water Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 29
- 238000000034 method Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VLZDQMVCSFFDNB-UHFFFAOYSA-N 4,4-dihydroxybutanoic acid Chemical compound OC(O)CCC(O)=O VLZDQMVCSFFDNB-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/164—Sulfur-containing compounds containing a -SO2-N group
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides an etching solution, which comprises the following components: inorganic acid, oxidant, copper corrosion inhibitor, cosolvent and water; wherein the copper corrosion inhibitor comprises a mixture of a compound containing a benzenesulfonamide group and an organic carboxylic acid; the organic carboxylic acid has the formula R-COOH, R being a hydrocarbyl group having 2 to 5C atoms and substituted with 2 to 4 hydroxyl groups. The etching solution has high efficiency, stable performance, mild reaction conditions, small corrosion effect on copper and environmental protection.
Description
Technical Field
The invention relates to the technical field of PCB and chip packaging, in particular to an etching solution and a preparation method and application thereof.
Background
In the field of PCB and chip packaging, the nickel layer plays different roles in different locations. As shown in FIG. 1, if the seed layer is used, the metallization process can be performed on the non-metallic substrate; if the metal is used as a barrier layer, the diffusion prevention effect can be realized on two close metals; in the case of a resist layer, it can protect the underlying patterned metal.
When the nickel layer is used as an anti-corrosion layer, the nickel layer and the copper layer are electroplated on the copper layer of the substrate, and then a dielectric layer with patterns is formed by exposing, developing, line etching, film stripping, and pressing the dielectric layer. In the nickel etching process, a nickel etching solution with low copper corrosion is required, so that a nickel layer serving as an anti-corrosion layer is etched cleanly, and a pattern circuit of a dielectric layer can be effectively protected.
When the nickel layer is used as a seed layer, a seed nickel layer is generally plated on a base material EMC in a chemical plating mode, then a copper layer is plated, then the base material EMC is subjected to processes of exposure, development, circuit etching, film stripping and the like, and finally the required product with the pattern is formed through the nickel etching process.
Generally, the copper nickel stripping method is divided into acidic and alkaline methods. The traditional acid nickel-removing method adopts sulfuric acid, phosphoric acid or sodium persulfate and the like to dissolve a nickel layer. Wherein, the sulfuric acid has stronger corrosivity and strong dissolving power on nickel and copper, and is not easy to control; sodium persulfate has poor stability, is easy to decompose and damp, is not stable in deplating and has great damage to the surface of base material copper, especially for a circuit board with thin circuit and thin base material copper, the sodium persulfate is not applicable at all, nickel is usually completely removed, and thin copper wires on the circuit are broken; although the sulfuric acid and phosphoric acid system has a good nickel etching rate, copper is also unprotected, and phosphorus in phosphoric acid can cause serious pollution to the environment. The traditional alkaline stripping solution is often characterized by high alkali concentration and high use temperature, so that the ink and the solder mask of the circuit board cannot be corroded by the alkaline stripping solution. In addition, the adoption of the high-concentration strong-acid and strong-alkaline nickel-removing method also causes the problem of environmental pollution. The etching rate of the traditional ferric chloride nickel etching solution is too fast, so that the metal copper protected below a nickel layer cannot be ensured not to be corroded, and iron ions and halogen ions are introduced into an etching system, so that the etching process is not easy to control.
Therefore, there is an urgent need in the industry to find an etching solution that has a high nickel etching rate, hardly corrodes a copper metal layer, and has less environmental pollution.
Disclosure of Invention
Based on the etching solution, the etching solution provided by the invention is high in efficiency, stable in performance, mild in reaction condition, small in corrosion effect on copper and environment-friendly.
The invention is realized by the following technical scheme.
An etching solution comprises the following components: inorganic acid, oxidant, copper corrosion inhibitor, cosolvent and water;
wherein the copper corrosion inhibitor comprises a mixture of a compound containing a benzenesulfonamide group and an organic carboxylic acid;
the organic carboxylic acid has the formula R-COOH, R being a hydrocarbon radical having 2 to 5C atoms and substituted with 2 to 4 hydroxyl groups.
In one embodiment, the etching solution comprises the following components in parts by weight: 10 to 200 portions of inorganic acid, 5 to 100 portions of oxidant, 1 to 20 portions of copper corrosion inhibitor, 10 to 100 portions of cosolvent and 480 to 980 portions of water.
In one embodiment, in the copper corrosion inhibitor, the mass ratio of the compound containing the benzene sulfonamide group to the organic carboxylic acid is 1 (0.1-10).
In one embodiment, the benzenesulfonamide group-containing compound is selected from one or more of 4-hydroxybenzenesulfonamide, 3-aminobenzenesulfonamide, and 4-amino-N-methylbenzenesulfonamide.
In one embodiment, the organic carboxylic acid is selected from the group consisting of 2, 2-dihydroxyacetic acid, 3, 3-dihydroxypropionic acid, 2, 3-dihydroxypropionic acid, 3, 4-dihydroxybutyric acid, 4-dihydroxybutyric acid, 2, 4-dihydroxybutyric acid, 5-dihydroxyvaleric acid, 4, 5-dihydroxyvaleric acid, 3, 3-dihydroxyvaleric acid, 2,3, 4-trihydroxybutyric acid, 2, 4-trihydroxybutyric acid, 2,3, 4-trihydroxyvaleric acid, 3,4, 5-trihydroxyvaleric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3,3, 5-tetrahydroxyvaleric acid, 2,3, 5-tetrahydroxyvaleric acid, 2,3,4, 5-tetrahydroxyvaleric acid, 3,4, 5-tetrahydroxyvaleric acid, 2,4,4, 5-tetrahydroxyvaleric acid, 2,3,5, 5-tetrahydroxyvaleric acid and 3,4,5, 5-tetrahydroxyvaleric acid.
In one embodiment, the inorganic acid is selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and phosphoric acid.
In one embodiment, the oxidizing agent is selected from one or more of sodium persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide, t-butyl hydroperoxide, and ammonium persulfate.
In one embodiment, the co-solvent is selected from one or more of 1, 2-propanediol, glycerol, monoethanolamine, diethanolamine, and triethanolamine.
The invention also provides a preparation method of the etching solution, which comprises the following steps: mixing the components of the etching solution.
The invention also provides application of the etching solution in etching nickel-containing parts.
Compared with the prior art, the etching solution has the following beneficial effects:
the nickel etching solution with the inorganic acid system has a larger etching coefficient, and can efficiently etch a nickel metal barrier layer, an anti-corrosion layer and a seed layer in the PCB manufacturing and chip packaging processes. Under the action of the oxidant, the nickel metal can be quickly corroded at normal temperature, the metal residue on the surface is effectively removed, and the production efficiency and cost are reduced. Meanwhile, the organic carboxylic acid and the compound containing the benzene sulfonamide group are used as copper corrosion inhibitors, so that the corrosion of metal copper is reduced to a great extent, the etching of metal nickel can be accelerated synergistically, and the carboxylic acid containing polyhydroxy can increase the solubility of organic matters such as the compound containing the benzene sulfonamide group.
The etching solution has the characteristic of low copper corrosivity, can etch copper metal very little, has no pore corrosion phenomenon on the surface, can ensure the integrity of a circuit, and avoids the waste of metal copper resources. In addition, the etching solution provided by the invention is simple in use method, only a nickel-containing material needs to be immersed in the etching solution in the application process, the etching time is short, the action effect is good, the environmental pollution is low, and the application prospect is wide.
Furthermore, the etching solution disclosed by the invention is simple to prepare, simple and convenient to operate, high in production efficiency, capable of saving time and energy consumption and reducing production cost, and suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of the effect of a nickel metal layer in different positions;
FIG. 2 is a schematic process flow diagram of a nickel metal layer as a resist layer;
FIG. 3 is a schematic view of a process flow of using a nickel metal layer as a seed layer;
FIG. 4 is a diagram showing the etching solution of example 2 of the present invention after nickel etching;
FIG. 5 is a diagram showing an etching solution of comparative example 6 of the present invention after nickel etching.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, singular terms may include the plural and are not to be construed as being one in number.
In the present invention, at least one means one kind or a mixture of plural kinds. For example, the copper corrosion inhibitor is selected from at least one of 4-hydroxybenzenesulfonamide and 3-aminobenzenesulfonamide, and comprises the following components: the copper corrosion inhibitor is 4-hydroxybenzenesulfonamide, or the copper corrosion inhibitor is 3-aminobenzenesulfonamide, and the copper corrosion inhibitor is 3 cases of a mixture of 4-hydroxybenzenesulfonamide and 3-aminobenzenesulfonamide.
The invention provides an etching solution, which comprises the following components: inorganic acid, oxidant, copper corrosion inhibitor, cosolvent and water;
wherein the copper corrosion inhibitor comprises a mixture of a compound containing a benzene sulfonamide group and an organic carboxylic acid;
the organic carboxylic acid has the formula R-COOH, R being a hydrocarbon radical having 2 to 5C atoms and substituted with 2 to 4 hydroxyl groups.
In a specific example, the etching solution comprises the following components in parts by weight: 10 to 200 portions of inorganic acid, 5 to 100 portions of oxidant, 1 to 20 portions of copper corrosion inhibitor, 10 to 100 portions of cosolvent and 480 to 980 portions of water.
In a specific example, the etching solution comprises the following components in parts by weight: 50 to 150 portions of inorganic acid, 30 to 80 portions of oxidant, 5 to 20 portions of copper corrosion inhibitor, 10 to 100 portions of cosolvent and 650 to 910 portions of water.
In a specific example, each liter of etching solution comprises 10g to 200g of water, 5g to 100g of oxidizing agent, 1g to 20g of copper corrosion inhibitor and 10g to 100g of cosolvent.
In a specific example, each liter of etching solution comprises 50-150 g of water, 30-80 g of inorganic acid, 5-20 g of copper corrosion inhibitor and 10-100 g of cosolvent.
In a specific example, in the copper corrosion inhibitor, the mass ratio of the compound containing the benzene sulfonamide group to the organic carboxylic acid is 1 (0.1-10).
It is understood that in the present invention, the mass ratio of the compound containing a benzenesulfonamide group to the organic carboxylic acid in the copper corrosion inhibitor includes, but is not limited to, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.5, 1:3.0, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.
Preferably, in the copper corrosion inhibitor, the mass ratio of the compound containing the benzene sulfonamide group to the organic carboxylic acid is 1 (0.5-2).
In a specific example, the benzenesulfonamide group-containing compound is selected from one or more of 4-hydroxybenzenesulfonamide, 3-aminobenzenesulfonamide, and 4-amino-N-methylbenzenesulfonamide.
In one particular example, the organic carboxylic acid is selected from the group consisting of 2, 2-dihydroxyacetic acid, 3, 3-dihydroxypropionic acid, 2, 3-dihydroxypropionic acid, 3, 4-dihydroxybutyric acid, 4-dihydroxybutyric acid, 2, 4-dihydroxybutyric acid, 5-dihydroxyvaleric acid, 4, 5-dihydroxyvaleric acid, 3, 3-dihydroxyvaleric acid, 2,3, 4-trihydroxybutyric acid, 2, 4-trihydroxybutyric acid, 2,3, 4-trihydroxyvaleric acid, 3,4, 5-trihydroxyvaleric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3,3, 5-tetrahydroxyvaleric acid, 2,3, 5-tetrahydroxyvaleric acid, 2,3,4, 5-tetrahydroxyvaleric acid, 3,4, 5-tetrahydroxyvaleric acid, 2,4,4, 5-tetrahydroxyvaleric acid, 2,3,5, 5-tetrahydroxyvaleric acid and 3,4,5, 5-tetrahydroxyvaleric acid.
More preferably, the organic carboxylic acid has 4 to 5C atoms and is substituted with 3 hydroxyl groups.
In a specific example, the inorganic acid is selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and phosphoric acid.
In a particular example, the oxidizing agent is selected from one or more of sodium persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide, t-butyl hydroperoxide, and ammonium persulfate.
In one particular example, the co-solvent is selected from one or more of 1, 2-propanediol, glycerol, monoethanolamine, diethanolamine, and triethanolamine.
In one particular example, the mineral acid is sulfuric acid, the oxidizing agent is sodium persulfate, the copper corrosion inhibitor is a mixture of 3-aminobenzenesulfonamide and 2,4, 5-trihydroxyvaleric acid, and the cosolvent is glycerol.
In one particular example, the mineral acid is hydrochloric acid, the oxidizing agent is m-chloroperoxybenzoic acid, the copper corrosion inhibitor is a mixture of 4-amino-N-methylbenzenesulfonamide and 2, 3-dihydroxypropionic acid, and the cosolvent is monoethanolamine.
In one particular example, the inorganic acid is hydrofluoric acid, the oxidizing agent is t-butyl hydroperoxide, the copper corrosion inhibitor is a mixture of 3-aminobenzenesulfonamide and 2,3,4, 5-tetrahydroxypentanoic acid, and the cosolvent is diethanolamine.
In one particular example, the inorganic acid is phosphoric acid, the oxidizing agent is ammonium persulfate, the copper corrosion inhibitor is a mixture of 4-amino-N-methylbenzenesulfonamide and 3,4, 5-trihydroxypentanoic acid, and the cosolvent is triethanolamine.
In one particular example, the mineral acid is sulfuric acid, the oxidizing agent is t-butyl hydroperoxide, the copper corrosion inhibitor is a mixture of 3-aminobenzenesulfonamide, 4-amino-N-methylbenzenesulfonamide, and 4, 4-dihydroxybutyric acid, and the cosolvent is triethanolamine.
In one particular example, the inorganic acid is phosphoric acid, the oxidizing agent is ammonium persulfate, the copper corrosion inhibitor is a mixture of 3-aminobenzenesulfonamide, 4-hydroxybenzenesulfonamide, 3-dihydroxypropionic acid, and 3,3,4, 5-tetrahydroxypentanoic acid, and the cosolvent is glycerol.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, 10g to 100g of nitric acid, 5g to 100g of hydrogen peroxide, 1g to 20g of a mixture of 4-hydroxybenzenesulfonamide and 2,3, 4-trihydroxybutyric acid, and 10g to 50g of 1, 2-propanediol.
In a specific example, each liter of etching solution comprises 10g to 200g of water, sulfuric acid, 5g to 100g of sodium persulfate, 1g to 20g of a mixture of 3-aminobenzenesulfonamide and 2,4, 5-trihydroxy valeric acid, and 10g to 50g of glycerol.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, 10g to 100g of hydrochloric acid, 5g to 100g of m-chloroperoxybenzoic acid, 1g to 20g of a mixture of 4-amino-N-methylbenzenesulfonamide and 2, 3-dihydroxypropionic acid, and 10g to 50g of monoethanolamine.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, 10g to 100g of hydrofluoric acid, 5g to 100g of tert-butyl hydroperoxide, 1g to 20g of a mixture of 3-aminobenzenesulfonamide and 2,3,4, 5-tetrahydroxyvaleric acid, and 10g to 50g of diethanolamine.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, 10g to 100g of phosphoric acid, 5g to 100g of ammonium persulfate, 1g to 20g of a mixture of 4-amino-N-methylbenzenesulfonamide and 3,4, 5-trihydroxy valeric acid, and 10g to 50g of triethanolamine.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, sulfuric acid, 5g to 100g of tert-butyl hydroperoxide, 1g to 20g of a mixture of 3-aminobenzenesulfonamide, 4-amino-N-methylbenzenesulfonamide and 4, 4-dihydroxybutyric acid, and 10g to 50g of triethanolamine.
In a specific example, each liter of the etching solution comprises 10g to 200g of water, 10g to 100g of phosphoric acid, 5g to 100g of ammonium persulfate, 3-aminobenzenesulfonamide, 4-hydroxybenzenesulfonamide, 1g to 20g of a mixture of 3, 3-dihydroxypropionic acid and 3,3,4, 5-tetrahydroxyvaleric acid, and 10g to 50g of glycerol.
The invention also provides a preparation method of the etching solution, which comprises the following steps: the components of the etching solution are mixed.
The invention also provides application of the etching solution in etching nickel-containing parts.
In one particular example, nickel-containing components are used as nickel seed layers in the field of PCB and chip packaging.
In one particular example, nickel-containing components are used as nickel barrier layers in the PCB and chip packaging fields.
In one particular example, nickel-containing components are used as a nickel resist layer in the PCB and chip packaging fields.
The invention also provides a method of etching a nickel-containing component, comprising the steps of:
the nickel-containing member is immersed in the etching solution.
The schematic flow chart of the nickel metal layer etching process of the invention can refer to fig. 2 and fig. 3:
the nickel layer in fig. 2 is used as an anti-corrosion layer, the nickel layer and the copper layer are firstly electroplated on the copper layer of the substrate, then a dielectric layer with a pattern is formed by exposing, developing, circuit etching, film stripping and pressing the dielectric layer, and finally the dielectric layer with the pattern is formed by utilizing the processes of copper etching and nickel etching.
The nickel layer in fig. 3 is used as a seed layer, a seed nickel layer is firstly plated on the base material EMC, then a copper layer is electroplated, and finally the required product with patterns is formed through the processes of exposure, development, circuit etching, film stripping and the like and nickel etching.
The etching solution and the preparation method thereof according to the present invention will be described in further detail with reference to specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
The embodiment provides a nickel etching solution and a preparation method thereof, and the preparation method specifically comprises the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-trihydroxy butyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 2
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-trihydroxy butyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 3
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2-dihydroxyacetic acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred and stands for standby.
Example 4
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-tetrahydroxybutyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 5
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-trihydroxy valeric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 6
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction container, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2, 4-dihydroxybutyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred and stands for standby.
Example 7
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3,3, 5-tetrahydroxyvaleric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 8
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-trihydroxy butyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 9
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 2,3, 4-trihydroxy butyric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 10
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide, 4-hydroxybenzenesulfonamide, 3,4, 5-trihydroxy valeric acid and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 11
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, sulfuric acid, sodium persulfate, 3-aminobenzenesulfonamide, 2,4, 5-trihydroxy valeric acid and glycerol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred and stands for standby.
Example 12
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction container, hydrochloric acid, m-chloroperoxybenzoic acid, 4-amino-N-methylbenzenesulfonamide, 2, 3-dihydroxypropionic acid and monoethanolamine are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 13
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction container, hydrofluoric acid, tert-butyl hydroperoxide, 3-aminobenzenesulfonamide, 2,3,4, 5-tetrahydroxyvaleric acid and diethanol amine are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
Example 14
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, phosphoric acid, ammonium persulfate, 4-amino-N-methylbenzenesulfonamide, 3,4, 5-trihydroxy valeric acid and triethanolamine are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for later use.
Example 15
The embodiment provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction container, sulfuric acid, tert-butyl hydroperoxide, 3-aminobenzenesulfonamide, 4-amino-N-methylbenzenesulfonamide, 4-dihydroxybutyric acid and triethanolamine are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for later use.
Example 16
The embodiment provides an etching solution and a preparation method thereof, which specifically comprise the following steps:
(1) the composition of each liter of etching solution is as follows:
(2) the preparation method of the nickel etching solution in the embodiment comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction container, hydrochloric acid, ammonium persulfate, 3-aminobenzenesulfonamide, 4-hydroxybenzenesulfonamide, 3-dihydroxypropionic acid, 3,4, 5-tetrahydroxyvaleric acid and glycerol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for later use.
Comparative example 1
The comparative example provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
20g of hydrochloric acid, namely hydrochloric acid,
250g of ferric trichloride;
the balance being water.
(2) The preparation method of the etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of deionized water is added into a reaction vessel, hydrochloric acid is slowly added, ferric trichloride is slowly added after cooling, then stirring is carried out until the solution is clear, deionized water is added to 1L, stirring is carried out uniformly, and standing is carried out for standby.
Comparative example 2
The comparative example provides an etching solution and a preparation method thereof, and specifically comprises the following steps:
(1) the composition of each liter of etching solution is as follows:
100g of phosphoric acid is added to the solution,
50g of hydrogen peroxide;
the balance being water.
(2) The preparation method of the etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of deionized water is added into a reaction vessel, phosphoric acid is slowly added, hydrogen peroxide is slowly added after cooling, then stirring is carried out until the solution is clear, deionized water is added to 1L, stirring is carried out uniformly, and standing is carried out for standby.
Comparative example 3
The comparative example provides an etching solution and a preparation method thereof, and specifically comprises the following steps:
(1) the composition of each liter of etching solution is as follows:
100g of sulfuric acid is added into the mixture,
40g of hydrogen peroxide;
the balance being water.
(2) The preparation method of the etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of deionized water is added into a reaction vessel, sulfuric acid is slowly added, hydrogen peroxide is slowly added after cooling, then stirring is carried out until the solution is clear, deionized water is added to 1L, stirring is carried out uniformly, and standing is carried out for standby.
Comparative example 4
The comparative example provides an etching solution and a preparation method thereof, and specifically comprises the following steps:
(1) the composition of each liter of etching solution is as follows:
150g of sulfuric acid, 150g of,
60g of sodium persulfate;
the balance being water.
(2) The preparation method of the etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of deionized water is added into a reaction vessel, sulfuric acid is slowly added, sodium persulfate is slowly added after cooling, then stirring is carried out until the solution is clear, deionized water is added to 1L, stirring is carried out uniformly, and standing is carried out for standby.
Comparative example 5
The comparative example provides an etching solution and a preparation method thereof, and the etching solution comprises the following specific steps:
(1) the composition of each liter of etching solution is as follows:
650g of ammonia water (ammonia water),
100g of ammonium chloride is added into the solution,
120g of copper chloride dihydrate;
the balance being water.
(2) The preparation method of the etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of deionized water is added into a reaction vessel, ammonia water, ammonium chloride and copper chloride dihydrate are slowly added, then the mixture is stirred until the solution is clear, deionized water is added to 1L, the mixture is stirred uniformly and stands for standby.
Comparative example 6
The comparative example provides an etching solution and a preparation method thereof, and specifically comprises the following steps:
(1) the composition of each liter of etching solution is as follows:
100g of nitric acid is added into the mixture,
50g of hydrogen peroxide is added into the solution,
30g of 1, 2-propylene glycol;
the balance being water.
(2) The preparation method of the nickel etching solution in the comparative example comprises the following steps:
at normal temperature, 0.5L of purified water is added into a reaction vessel, nitric acid, hydrogen peroxide and 1, 2-propylene glycol are slowly added, then the mixture is stirred until the solution is clear, the purified water is added to 1L, the mixture is uniformly stirred, and the mixture is kept stand for standby.
The formulations of the etching solutions of examples 1 to 16 and comparative examples 1 to 6 are shown in table 1, and the total volume of the etching solutions is 1L, and all contain purified water (raw material 1).
TABLE 1
Test examples:
the test method is as follows:
after preparing the nickel etching solution, weighing the dried pure metal nickel block and the dried pure metal copper block respectively at normal temperature, measuring the areas of the pure metal nickel block and the pure metal copper block respectively, then putting the pure metal nickel block and the pure metal copper block into the etching solutions of the examples 1 to 16 and the comparative examples 1 to 6 respectively, soaking the pure metal nickel block and the pure metal copper block for 5 minutes, taking out the pure metal nickel block and the pure metal copper block, respectively cleaning the pure metal nickel block and the pure metal copper block with purified water, drying and weighing the pure metal nickel block and the pure metal copper block, calculating the weight loss, and respectively calculating the nickel etching rate and the copper etching rate by using a formula.
Calculating the formula: lost weight (g)/{2 } etched metal area (cm)2) Metal density (g/cm)3) Etch time (min) } 10000 ═ etch rate (μm/min).
Wherein the metal density of the pure metal nickel block is 8.9g/cm3The metal density of the pure metal copper block is 8.9g/cm3。
The selectivity is the ratio of the nickel etching rate to the copper etching rate, and the larger the value of the selectivity is, the better the selectivity is represented, which shows that the etching solution is more prone to etch nickel and less corrosive to copper, and the nickel etching performance is better. The etching rate of nickel is high, and the etching rate of copper is low, so that the selectivity is good, and the etching effect is optimal.
The test results are shown in table 2:
TABLE 2
As can be seen from table 2 above, the etching solutions of examples 1 to 16 of the present invention have strong etching effect on nickel metal, fast etching rate, and less etching effect on copper metal, and the etching solutions are more prone to etching nickel and less etching copper, and have better etching performance on nickel.
The experimental results shown in the above examples show that the etching rate of copper is related to the content of the corrosion inhibitor of copper, and the etching rate of copper is lower, which proves that the nickel etching solution of the invention has high selectivity.
As can be seen from the above examples 1-16, the increased contents of the inorganic acid and the oxidizing agent improve the etching rate of metallic nickel and copper, but when the organic carboxylic acid containing 3 hydroxyl substituents and having a carbon chain length of C4-C5 is mixed with the organic compound containing the benzene sulfonamide parent nucleus, the etching rate of copper is lower, and the effects of different proportions of the corrosion inhibitor are different. The etching solution has high selectivity to nickel and extremely small corrosion to a copper metal layer, and can meet the application requirement of etching the nickel metal layer in the fields of PCB manufacturing and chip packaging.
Comparative example 1 is a nickel etching solution of ferric trichloride, comparative example 2 is a nickel etching solution of phosphoric acid system, comparative example 3 is a nickel etching solution of sulfuric acid system, comparative example 4 is a nickel etching solution of sodium persulfate system, comparative example 5 is an alkaline nickel etching solution, and comparative example 6 is a nickel etching solution without adding a copper corrosion inhibitor. The etching effects of the comparative examples 1-6 are not ideal, the copper metal layer is corroded in different degrees while the nickel metal layer is etched, the copper corrosion degree is high, and the production requirements cannot be met.
Fig. 4 is a diagram of the etching solution of example 2 after nickel etching, and it can be seen from fig. 4 that, when the etching solution of the present invention is used for etching, after the reaction is completed, the copper surface has no pore corrosion, and the copper surface remains intact without severe corrosion.
FIG. 5 is a diagram of the etching solution of comparative example 6 after nickel etching, and it can be seen from FIG. 5 that relatively large corrosion and pitting corrosion occur on the copper surface after the etching reaction is completed without adding a copper corrosion inhibitor.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, which is convenient for specific and detailed understanding of the technical solutions of the present invention, but the present invention should not be construed as being limited to the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present patent shall be subject to the content of the appended claims, and the description and drawings can be used to explain the content of the claims.
Claims (10)
1. The etching solution is characterized by comprising the following components: inorganic acid, oxidant, copper corrosion inhibitor, cosolvent and water;
wherein the copper corrosion inhibitor comprises a mixture of a compound containing a benzenesulfonamide group and an organic carboxylic acid;
the organic carboxylic acid has the formula R-COOH, R being a hydrocarbon radical having 2 to 5C atoms and substituted with 2 to 4 hydroxyl groups.
2. The etching solution of claim 1, wherein the etching solution comprises the following components in parts by weight: 10 to 200 portions of inorganic acid, 5 to 100 portions of oxidant, 1 to 20 portions of copper corrosion inhibitor, 10 to 100 portions of cosolvent and 480 to 980 portions of water.
3. The etching solution according to claim 1, wherein the mass ratio of the compound containing a benzenesulfonamide group to the organic carboxylic acid in the copper corrosion inhibitor is 1 (0.1-10).
4. The etching solution according to claim 1, wherein the benzenesulfonamide group-containing compound is one or more selected from the group consisting of 4-hydroxybenzenesulfonamide, 3-aminobenzenesulfonamide, and 4-amino-N-methylbenzenesulfonamide.
5. The etching solution of claim 1, wherein the organic carboxylic acid is selected from the group consisting of 2, 2-dihydroxyacetic acid, 3, 3-dihydroxypropionic acid, 2, 3-dihydroxypropionic acid, 3, 4-dihydroxybutyric acid, 4-dihydroxybutyric acid, 2, 4-dihydroxybutyric acid, 5-dihydroxyvaleric acid, 4, 5-dihydroxyvaleric acid, 3, 3-dihydroxyvaleric acid, 2,3, 4-trihydroxybutyric acid, 2, 4-trihydroxybutyric acid, 2,3, 4-trihydroxyvaleric acid, 3,4, 5-trihydroxyvaleric acid, 2,4, 5-trihydroxyvaleric acid, 3,3, 5-trihydroxyvaleric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3, 4-tetrahydroxybutyric acid, 2,3,3, 5-tetrahydroxyvaleric acid, 2,3, 5-tetrahydroxyvaleric acid, 2,3,4, 5-tetrahydroxyvaleric acid, 3,3,4, 5-tetrahydroxyvaleric acid, 2,4,4, 5-tetrahydroxyvaleric acid, 2,3,5, 5-tetrahydroxyvaleric acid and one or more of 3,4,5, 5-tetrahydroxyvaleric acid.
6. The etching solution according to any one of claims 1 to 5, wherein the inorganic acid is one or more selected from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, and phosphoric acid.
7. The etching solution according to any one of claims 1 to 5, wherein the oxidant is one or more selected from sodium persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide, tert-butyl hydroperoxide and ammonium persulfate.
8. The etching solution of any one of claims 1 to 5, wherein the cosolvent is selected from one or more of 1, 2-propanediol, glycerol, monoethanolamine, diethanolamine, and triethanolamine.
9. A preparation method of the etching solution according to any one of claims 1 to 8, comprising the steps of: mixing the components of the etching solution.
10. Use of the etching solution according to any one of claims 1 to 8 for etching nickel-containing parts.
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| CN202210568533.4A CN114752939B (en) | 2022-05-24 | Etching solution and preparation method and application thereof |
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| CN105603425A (en) * | 2016-01-25 | 2016-05-25 | 熙腾电子科技（上海）有限公司 | Copper-selective etching solution and titanium-selective etching solution |
| CN106011826A (en) * | 2016-08-11 | 2016-10-12 | 苏州欣天新精密机械有限公司 | Method for protecting surface of copper-aluminium composite cover plate |
| US20180130706A1 (en) * | 2014-09-14 | 2018-05-10 | Entegris, Inc. | Cobalt deposition selectivity on copper and dielectrics |
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| JPH0657454A (en) * | 1992-08-17 | 1994-03-01 | Hitachi Chem Co Ltd | Etchant for nickel or nickel alloy, method for using the same and production of wiring board using the same |
| CN1506496A (en) * | 2002-12-06 | 2004-06-23 | 美格株式会社 | Etchant |
| US20180130706A1 (en) * | 2014-09-14 | 2018-05-10 | Entegris, Inc. | Cobalt deposition selectivity on copper and dielectrics |
| CN105603425A (en) * | 2016-01-25 | 2016-05-25 | 熙腾电子科技（上海）有限公司 | Copper-selective etching solution and titanium-selective etching solution |
| CN106011826A (en) * | 2016-08-11 | 2016-10-12 | 苏州欣天新精密机械有限公司 | Method for protecting surface of copper-aluminium composite cover plate |
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