CN117488302B - Circuit etching solution - Google Patents
Circuit etching solution Download PDFInfo
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- CN117488302B CN117488302B CN202311351923.7A CN202311351923A CN117488302B CN 117488302 B CN117488302 B CN 117488302B CN 202311351923 A CN202311351923 A CN 202311351923A CN 117488302 B CN117488302 B CN 117488302B
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- 238000005530 etching Methods 0.000 title claims abstract description 120
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229920002643 polyglutamic acid Polymers 0.000 claims abstract description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 21
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XUJNEKJLAYXESH-UHFFFAOYSA-N Cysteine Chemical compound SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 18
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229920001400 block copolymer Polymers 0.000 claims description 14
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 7
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 4
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 claims description 4
- 229960003540 oxyquinoline Drugs 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 claims description 4
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 3
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 57
- 239000010949 copper Substances 0.000 abstract description 57
- 229910052802 copper Inorganic materials 0.000 abstract description 57
- 238000000034 method Methods 0.000 abstract description 20
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract description 3
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005507 spraying Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910000912 Bell metal Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 102000004528 Mannose-Binding Protein-Associated Serine Proteases Human genes 0.000 description 1
- 108010042484 Mannose-Binding Protein-Associated Serine Proteases Proteins 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention discloses a circuit etching solution which comprises inorganic acid, an oxidant, copper ions, an etching uniformity agent, an etching solution stabilizer and an etching inhibitor. The etching uniformity agent of the circuit etching solution comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid segmented copolymer and dodecylphenol polyoxyethylene ether, different copper ion ligands can be applied to the circuit etching solution, and a synergistic effect is formed among the different copper ion ligands, so that the chemical condition of the metal copper surface is optimized, the dissolution process and the etching process of copper oxide in different areas under the microcosmic condition are adjusted, and the dissolution speed of different copper crystal faces is adjusted, so that the uniformity of a copper layer on the circuit surface in etching is improved, and the problems of pinholes, pits and the like are reduced. In combination with the specific embodiment part of the specification, the circuit etching solution can solve the problems of pinholes, pits and the like when the copper layer on the surface is thinned when the carrier-like circuit board is etched, and improve the quality of the circuit board.
Description
Technical Field
The invention relates to the field of circuit board manufacturing, in particular to a circuit etching solution.
Background
The advent of intelligent mobile communication products and their widespread use in our daily lives has led to the increasing miniaturization and microminiaturization of electronic devices, which have required to meet product design requirements through finer line manufacturing. The demand for finer wiring has driven the development of printed wiring board fabrication technology, with the advancement of printed wiring board High Density Interconnect (HDI) fabrication to higher levels, and the proliferation of finer-wiring board-like circuit boards (SLPs).
The circuit width (15-40 microns) of the carrier-like circuit board (SLP) is smaller than that of the conventional circuit board and the common HDI, and the circuit board needs to be manufactured by adopting a modified semi-additive process (MSAP). The improved semi-addition process uses copper-clad plate with thinner surface copper as base material, and processes electroless copper plating, hole filling, circuit copper electroplating, etching and the like on the copper-clad plate selectively to obtain the fine conductive circuit.
After the copper electroplating process, the total thickness of the copper layer of the circuit part on the resin substrate is about 25-30 microns, and the total thickness of the copper base of the copper-clad plate in the area to be etched, the copper layer of the chemical copper and the flash-plated copper is about 4-6 microns. Limited by the equipment and processing capabilities of the conventional etching process, if the desired circuit is to be etched, the total thickness of the copper layer in the circuit portion is typically controlled to less than 80% of the circuit width to ensure that the circuit is not excessively undercut.
The shape of the side surface of the circuit is ensured when the carrier-like circuit board is etched, and the shape of the surface of the etched copper circuit is ensured because the copper is thinned on the surface of the circuit during etching. When the circuit width of the carrier-like circuit board is finer, the thickness of the circuit copper layer is thinner correspondingly, so that when the circuit width is 25 microns, the etched line is always etched and the copper is thinned by acid etching of more than 5 microns on the surface of the circuit, and the etching process is different from the conventional process of etching only the non-circuit area but not the circuit surface of the circuit of the packaging substrate, and is not completely different from the flashing process of etching the circuit of the packaging substrate. In the process of electroplating copper in the pre-circuit procedure, the microscopic distribution of the power lines on the cathode and the influence of electroplating additives can cause the difference of grain structures and crystal orientations in different areas of the electroplated copper, and the problem of microscopic difference of copper layers on the surface of the circuit board can be solved.
The etching solution used in the conventional carrier-plate type circuit board MASP process mainly comprises hydrogen peroxide, sulfuric acid and a stabilizer, and the formula of the etching solution does not contain components for improving the surface morphology of the circuit, so that the copper layer can be etched indiscriminately, and the etching capability of the copper surfaces in different forms can be protected and adjusted indiscriminately. Therefore, when the conventional circuit etching solution is used for etching a carrier-like circuit board, the copper layer on the surface of the circuit is easy to generate pinholes, pits and other problems when the copper layer is thinned, so that the quality of the circuit board is greatly affected, and the improvement is needed.
Disclosure of Invention
Based on this, it is necessary to provide a line etching solution that can solve the above-described problems.
A circuit etching solution comprises 40 g/L-140 g/L of inorganic acid, 20 g/L-40 g/L of oxidant, 15 g/L-35 g/L of copper ion, 2 g/L-10 g/L of etching uniformity agent, 1 g/L-10 g/L of etching solution stabilizer and 2 g/L-5 g/L of etching inhibitor;
The etching uniformity agent comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid block copolymer and dodecylphenol polyoxyethylene ether.
In one embodiment, in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer and the dodecylphenol polyoxyethylene ether is 1:1 to 5:1 to 2.
In one embodiment, in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer and the dodecylphenol polyoxyethylene ether is 1:2.5:1.5.
In one embodiment, the polyacrylic acid-polyglutamic acid block copolymer has a molecular weight of 1000 to 3000.
In one embodiment, the etching solution stabilizer is selected from at least one of 2-ethylpyridine, 8-hydroxyquinoline, sodium p-hydroxybenzenesulfonate, and butanol phosphate.
In one embodiment, the etching inhibitor is selected from at least one of hydroxybenzotriazole and 2-mercapto-1-methylimidazole.
In one embodiment, the mineral acid is sulfuric acid.
In one embodiment, the oxidizing agent is hydrogen peroxide, potassium peroxide, or sodium peroxide.
In one embodiment, the copper ions are provided by copper sulfate or copper phosphate.
In one embodiment, the circuit etching solution is a circuit etching solution for a carrier-like circuit board.
The circuit etching solution comprises inorganic acid, oxidant, copper ion, etching uniformity agent, etching solution stabilizer and etching inhibitor; the etching uniformity agent comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid segmented copolymer and dodecylphenol polyoxyethylene ether, different copper ion ligands can be applied to the circuit etching solution, a synergistic effect is formed among the different copper ion ligands, the chemical condition of the metal copper surface is optimized, the dissolution process and the etching process of copper oxide in different areas under the microcosmic condition are adjusted, and the dissolution speed of copper crystal faces is adjusted, so that the uniformity of a copper layer on the circuit surface in etching is improved, and the problems of pinholes, pits and the like are reduced.
In combination with the specific embodiment part of the specification, the circuit etching solution can better solve the problems of pinholes, pits and the like when the copper layer on the surface of the circuit is thinned when the circuit board type circuit board is etched, and can improve the quality of the circuit board.
According to the circuit etching solution, the adsorption protection difference of copper layers with different properties on the circuit is achieved by using the composite etching uniform agent, the etching efficiency of the circuit etching solution on the copper layers with different properties is adjusted, and the problem that pinholes and pits are easy to occur on the circuit after etching in an MSAP process is solved by combining the interaction of other components in the system.
Preferably, the etching solution stabilizer is selected from at least one of 2-ethylpyridine, 8-hydroxyquinoline, sodium p-hydroxybenzenesulfonate, and butanol phosphate.
The etching solution stabilizer can slow down the catalysis and decomposition of copper ions on hydrogen peroxide by complexing with metal ions, thereby playing a role in stabilizing the solution.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Wherein:
fig. 1 is a microscopic view of a test example obtained by spraying a circuit etching solution prepared in example 1 on a copper surface of a board-like circuit board.
Fig. 2 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in example 2.
Fig. 3 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in example 3.
Fig. 4 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in comparative example 1.
Fig. 5 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in comparative example 2.
Fig. 6 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in comparative example 3.
Fig. 7 is a microscopic view of the copper surface of the board-like circuit board obtained in the test example after spraying the circuit etching solution prepared in comparative example 4.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship between the components, the movement condition, etc. in a specific gesture, if the specific gesture is changed, the directional indicators are correspondingly changed.
Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention discloses a circuit etching solution of an embodiment, which comprises 40g/L to 140g/L of inorganic acid, 20g/L to 40g/L of oxidant, 15g/L to 35g/L of copper ions, 2g/L to 10g/L of etching uniformity agent, 1g/L to 10g/L of etching solution stabilizer and 2g/L to 5g/L of etching inhibitor.
The etching uniformity agent comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid segmented copolymer and dodecylphenol polyoxyethylene ether.
The circuit etching solution comprises inorganic acid, an oxidant, copper ions, an etching uniformity agent, an etching solution stabilizer and an etching inhibitor, wherein the etching uniformity agent comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid segmented copolymer and dodecylphenol polyoxyethylene ether, different copper ion ligands can be applied to the circuit etching solution, and a synergistic effect is formed among the different copper ion ligands, so that the chemical condition of the surface of metal copper is optimized, the dissolution process and the etching process of copper oxide in different areas under the microscopic condition are regulated, and the dissolution speed of copper crystal faces is regulated, so that the uniformity of a copper layer on the surface of the circuit during etching is improved, and the problems of pinholes, pits and the like are reduced.
In combination with the specific embodiment part of the specification, the circuit etching solution can better solve the problems of pinholes, pits and the like when the copper layer on the surface of the circuit is thinned when the circuit board type circuit board is etched, and can improve the quality of the circuit board.
According to the circuit etching solution, the adsorption protection difference of copper layers with different properties on the circuit is achieved by using the composite etching uniform agent, the etching efficiency of the circuit etching solution on the copper layers with different properties is adjusted, and the problem that pinholes and pits are easy to occur on the circuit after etching in an MSAP process is solved by combining the interaction of other components in the system.
In this embodiment, the concentration of the etching uniformity agent is 2g/L to 10g/L, pinholes and pits are likely to occur when the concentration of the etching uniformity agent is too low, and the microetching rate is reduced when the concentration of the etching uniformity agent is too high.
Preferably, in the present embodiment, in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer and the dodecylphenol polyoxyethylene ether is 1:1 to 5:1 to 2.
More preferably, in the present embodiment, in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer, and the dodecylphenol polyoxyethylene ether is 1:2.5:1.5.
Specifically, in the present embodiment, the molecular weight of the polyacrylic acid-polyglutamic acid block copolymer is 1000 to 3000.
The uniformity becomes worse when the molecular weight of the polyacrylic acid-polyglutamic acid block copolymer is too small, and pinhole and pitting defects easily occur when the molecular weight of the polyacrylic acid-polyglutamic acid block copolymer is too large.
Preferably, in the present embodiment, the etching solution stabilizer is selected from at least one of 2-ethylpyridine, 8-hydroxyquinoline, sodium p-hydroxybenzenesulfonate, and butanol phosphate.
The etching solution stabilizer can slow down the catalysis and decomposition of copper ions on hydrogen peroxide by complexing with metal ions, thereby playing a role in stabilizing the solution.
Preferably, in this embodiment, the etching inhibitor is selected from at least one of hydroxybenzotriazole and 2-mercapto-1-methylimidazole.
Preferably, in the present embodiment, the inorganic acid is sulfuric acid.
Preferably, in this embodiment, the oxidizing agent is hydrogen peroxide, potassium peroxide, or sodium peroxide.
Preferably, in the present embodiment, the copper ions are provided by copper sulfate or copper phosphate.
Preferably, in the present embodiment, the circuit etching solution is a circuit etching solution similar to a carrier board type circuit board.
The following are specific examples.
In a specific example, 2-amino-3-mercaptopropionic acid is purchased from Shanghai Meilin Corp; the polyacrylic acid-polyglutamic acid block copolymer was purchased from fei ril corporation, bergamot, and had a molecular weight of 2200; dodecyl phenol polyoxyethylene ether was purchased from Shanghai microphone company; both 2-ethylpyridine and hydroxybenzotriazole were purchased from the company Ara Ding Shiji.
Example 1
5.5Kg of 2-ethylpyridine, 3.5Kg of hydroxybenzotriazole, 90Kg of inorganic acid, 30Kg of oxidant, 20Kg of copper sulfate calculated by copper ions, 1.0Kg of 2-amino-3-mercaptopropionic acid, 2.5Kg of polyacrylic acid-polyglutamic acid segmented copolymer and 1.5Kg of dodecylphenol polyoxyethylene ether are weighed and respectively dissolved in 500L of pure water in sequence, uniformly mixed every time, accurately supplemented to 1000L, and fully stirred and mixed for standby.
Example 2
5.5Kg of 2-ethylpyridine, 3.5Kg of hydroxybenzotriazole, 90Kg of inorganic acid, 30Kg of oxidant, 20Kg of copper sulfate calculated by copper ions, 1.0Kg of 2-amino-3-mercaptopropionic acid, 1.0Kg of polyacrylic acid-polyglutamic acid segmented copolymer and 1.0Kg of dodecylphenol polyoxyethylene ether are weighed and respectively dissolved in 500L of pure water in sequence, and the mixture is uniformly mixed every time, accurately supplemented to 1000L, and fully stirred and mixed for standby.
Example 3
5.5Kg of 2-ethylpyridine, 3.5Kg of hydroxybenzotriazole, 90Kg of inorganic acid, 30Kg of oxidant, 20Kg of copper sulfate calculated by copper ions, 1.0Kg of 2-amino-3-mercaptopropionic acid, 5.0Kg of polyacrylic acid-polyglutamic acid segmented copolymer and 2.0Kg of dodecylphenol polyoxyethylene ether are weighed and respectively dissolved in 500L of pure water in sequence, and the mixture is uniformly mixed every time, accurately supplemented to 1000L, and fully stirred and mixed for standby.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that 2-amino-3-mercaptopropionic acid was not added in comparative example 1.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the polyacrylic acid-polyglutamic acid block copolymer was not added in comparative example 2.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that dodecylphenol polyoxyethylene ether was not added in comparative example 2.
Comparative example 4
90Kg of inorganic acid, 30Kg of oxidant and 20Kg of copper sulfate calculated by copper ions are weighed and dissolved in about 500L of pure water, 50Kg of commercial BTH-2066 additive of Ming's technology is added, and the mixture is uniformly mixed, accurately supplemented to 1000L, and fully stirred and mixed for later use.
Test case
The line etching solutions prepared in examples 1 to 3 and comparative examples 1 to 3 were each operated as follows: and spraying the circuit etching solution onto the copper surface (the line width and line distance are 25 micrometers/25 micrometers) of a carrier-like circuit board for a 5G mobile phone motherboard by adopting a vacuum double-fluid etching machine under the condition that the temperature of the circuit etching solution is 25-35 ℃, wherein the spraying pressure is 1.5kg/cm 2～2.0kg/cm2, and drying the circuit board after being washed clean by spraying water, and respectively detecting the copper etching amount and pinhole pits of the dried circuit board.
And (3) detecting the copper etching amount: the copper loss of the circuit board after spraying is divided by the density of copper and then by the effective copper area and the operation time of the circuit board, the copper loss of the thickness gauge thinned by bell metal layers per minute is calculated by a weighing method, the copper loss per minute is controlled between 0.8 micrometers and 1.5 micrometers, and the test result is shown in table 1.
Pinhole pock detection: and (3) carrying out optical inspection on the etched circuit board in an optical inspection instrument, and counting the number of pinholes and pits on each board, wherein the test results are shown in fig. 1-7 and table 1.
Solution stability tests were performed on the line etching solutions prepared in examples 1 to 3 and comparative examples 1 to 3, respectively, as follows: the line etching solution was stored at room temperature for 24 hours, and the hydrogen peroxide content before and after analysis was judged to be acceptable within 2g/L, and the test results are shown in Table 1.
TABLE 1
| Copper etching quantity (micron) | Pinhole number of hemp | Solution stability | |
| Example 1 | 1.21 | 0 | Qualified product |
| Example 2 | 1.13 | 0 | Qualified product |
| Example 3 | 1.27 | 0 | Qualified product |
| Comparative example 1 | 1.33 | 6 | Qualified product |
| Comparative example 2 | 1.26 | 15 | Qualified product |
| Comparative example 3 | 1.12 | 7 | Qualified product |
| Comparative example 4 | 1.36 | 27 | Qualified product |
Referring to table 1, it can be seen that the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer and the dodecylphenol polyoxyethylene ether in the etching uniformity agent is 1:2.5:1.5, 1:1:1 and 1:5:2, the copper surface of the etched carrier-like circuit board has no pinholes and pits, and the components in the etching uniformity agent lack any one, and the copper surface of the etched carrier-like circuit board has pinholes and pits when the conventional additive is used.
From this, it can be seen that the circuit etching solutions prepared in examples 1 to 3 can better solve the problems of pinholes, pits, and the like of the copper layer on the circuit surface during thinning copper when etching the carrier-like circuit board, and can improve the quality of the circuit board.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. A circuit etching solution is characterized by comprising 40 g/L-140 g/L of inorganic acid, 20 g/L-40 g/L of oxidant, 15 g/L-35 g/L of copper ions, 2 g/L-10 g/L of etching uniformity agent, 1 g/L-10 g/L of etching solution stabilizer and 2 g/L-5 g/L of etching inhibitor;
The etching uniformity agent comprises 2-amino-3-mercaptopropionic acid, polyacrylic acid-polyglutamic acid block copolymer and dodecylphenol polyoxyethylene ether;
in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid segmented copolymer and the dodecylphenol polyoxyethylene ether is 1: 1-5: 1-2;
the molecular weight of the polyacrylic acid-polyglutamic acid segmented copolymer is 1000-3000.
2. The line etching solution according to claim 1, wherein in the etching uniformity agent, the mass ratio of the 2-amino-3-mercaptopropionic acid, the polyacrylic acid-polyglutamic acid block copolymer, and the dodecylphenol polyoxyethylene ether is 1:2.5:1.5.
3. The etching solution according to any one of claims 1 to 2, wherein the etching solution stabilizer is at least one selected from the group consisting of 2-ethylpyridine, 8-hydroxyquinoline, sodium p-hydroxybenzenesulfonate, and butanol phosphate.
4. The wiring etching solution according to claim 3, wherein the etching inhibitor is at least one selected from the group consisting of hydroxybenzotriazole and 2-mercapto-1-methylimidazole.
5. The line etching solution according to claim 3, wherein the inorganic acid is sulfuric acid.
6. A line etching solution according to claim 3, characterized in that the oxidizing agent is hydrogen peroxide, potassium peroxide or sodium peroxide.
7. A line etching solution according to claim 3, characterized in that the copper ions are provided by copper sulphate or copper phosphate.
8. The circuit etching solution of claim 3, wherein the circuit etching solution is a circuit etching solution of a carrier-like board type circuit board.
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