WO2021251204A1 - 銅または銅合金の表面処理に用いられる化学研磨液および表面処理方法 - Google Patents

銅または銅合金の表面処理に用いられる化学研磨液および表面処理方法 Download PDF

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WO2021251204A1
WO2021251204A1 PCT/JP2021/020778 JP2021020778W WO2021251204A1 WO 2021251204 A1 WO2021251204 A1 WO 2021251204A1 JP 2021020778 W JP2021020778 W JP 2021020778W WO 2021251204 A1 WO2021251204 A1 WO 2021251204A1
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copper
chemical polishing
polishing liquid
copper alloy
component
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PCT/JP2021/020778
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English (en)
French (fr)
Japanese (ja)
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伸也 黒澤
裕嗣 松永
聡 玉井
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三菱瓦斯化学株式会社
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Priority to CN202180040575.4A priority Critical patent/CN115836143A/zh
Priority to JP2022530481A priority patent/JPWO2021251204A1/ja
Publication of WO2021251204A1 publication Critical patent/WO2021251204A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals

Definitions

  • the present invention relates to a chemical polishing liquid used for surface treatment of copper or copper alloy, a surface treatment method for copper or copper alloy using the chemical polishing liquid, and a method for producing surface-treated copper or copper alloy.
  • the surface of copper or copper alloy may be plated with nickel, gold, or the like.
  • a natural oxide film or an organic substance is usually present on the surface of copper or a copper alloy. If the plating process is performed without removing these, color unevenness (plating unevenness) may occur or the plating thickness may become non-uniform. Therefore, it is desirable to appropriately remove the natural oxide film and organic substances on the surface of copper or copper alloy in order to suppress the occurrence of color unevenness due to the plating treatment and to make the plating thickness uniform.
  • Patent Documents 1 to 3 there is a problem that a part of the natural oxide film and organic substances remains without being removed, and as a result, color unevenness occurs after the plating treatment. rice field.
  • Japanese Unexamined Patent Publication No. 9-184081 Japanese Unexamined Patent Publication No. 2017-031502 Japanese Unexamined Patent Publication No. 2017-195311
  • the present invention relates to the following chemical polishing liquids, surface treatment methods, and methods for producing surface-treated copper or copper alloys.
  • a chemical polishing liquid used for surface treatment of copper or copper alloys (A) Hydrogen peroxide is 0.1 to 3.5% by mass based on the total amount of the chemical polishing liquid. (B) One or more selected from the group consisting of sulfuric acid and nitric acid, 1 to 20% by mass based on the total amount of the chemical polishing liquid. (C) The content of fluoride in terms of fluorine atom is 0.05 to 0.8% by mass based on the total amount of the chemical polishing liquid.
  • (D) One or more selected from the group consisting of anthranilic acid, cyclohexylamine, cyclohexanol and 1,5-pentanediol, 0.01 to 4% by mass based on the total amount of the chemical polishing solution.
  • E a fluorine-based surfactant in an amount of 0.0005 to 0.005% by mass based on the total amount of the chemical polishing liquid
  • (F) water water.
  • the time for contacting the chemical polishing liquid with the surface of the copper or the copper alloy to perform the surface treatment of the copper or the copper alloy is 1 second or more and 10 minutes or less.
  • a surface treatment is performed, which comprises contacting the surface of the copper or the copper alloy with the chemical polishing liquid according to any one of the above [1] to [6] to perform the surface treatment of the copper or the copper alloy. How to make copper or copper alloy.
  • the above-mentioned [11] which comprises uniformly stirring at least the component (A), the component (B), the component (C), the component (D), the component (E) and the component (F).
  • the surface of the copper or the copper alloy is treated with the chemical polishing solution of the present invention so as to be present on the surface of the copper or the copper alloy while suppressing the amount of the copper or the copper alloy to be dissolved.
  • Natural oxides and organic substances can be appropriately removed, and a copper or copper alloy surface having no color unevenness or suppressed color unevenness can be obtained.
  • the chemical polishing liquid of the present invention is also excellent in storage stability. Further, according to a more preferable aspect of the present invention, the chemical polishing liquid of the present invention has stable removal performance of natural oxide film and organic substances even if the copper concentration in the chemical polishing liquid increases due to repeated use.
  • the chemical polishing liquid of the present invention is a chemical polishing liquid used for surface treatment of copper or a copper alloy.
  • Hydrogen peroxide is 0.1 to 3.5% by mass based on the total amount of the chemical polishing liquid.
  • B One or more selected from the group consisting of sulfuric acid and nitric acid, totaling 1 to 20% by mass based on the total amount of the chemical polishing liquid.
  • C The content of fluoride in terms of fluorine atom is 0.05 to 0.8% by mass based on the total amount of the chemical polishing liquid.
  • (D) One or more selected from the group consisting of anthranilic acid, cyclohexylamine, cyclohexanol and 1,5-pentanediol, 0.01 to 4% by mass based on the total amount of the chemical polishing solution.
  • the fluorosurfactant (E) is characterized by containing 0.0005 to 0.005% by mass based on the total amount of the chemical polishing liquid, and (F) water.
  • the chemical polishing liquid of the present invention is used for removing a natural oxide film and organic substances existing on the surface of copper or a copper alloy.
  • the "copper alloy” is not particularly limited as long as it is an alloy containing copper as a main component.
  • the copper content in the copper alloy is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and particularly preferably 90% by mass or more. It may be 95% by mass or more.
  • hydrogen peroxide (hereinafter, also referred to as “component (A)”) has an action of oxidizing copper or copper contained in a copper alloy as an oxidizing agent. It is generally preferable to use hydrogen peroxide as an aqueous solution of hydrogen peroxide in terms of availability and operability.
  • the grade of the hydrogen peroxide aqueous solution is not particularly limited, and various grades such as those for industrial use and those for the electronic industry can be used.
  • the content of hydrogen peroxide is 0.1 to 3.5% by mass, preferably 0.5 to 2.0% by mass, preferably 0. 7 to 1.6% by mass is more preferable, and 0.7 to 1.2% by mass is further preferable from the viewpoint of the solubility of copper.
  • the content of hydrogen peroxide is within the above range, the natural oxide film and organic substances can be appropriately removed from the surface of copper or the copper alloy.
  • the amount of copper dissolved can be suppressed to a small level, and local corrosion of copper or a copper alloy can be prevented from occurring.
  • the numerical range is shown in the present specification, the upper limit value and the lower limit value can be freely combined.
  • component (B) One or more selected from the group consisting of sulfuric acid and nitric acid
  • sulfuric acid and nitric acid are converted into copper oxidized by the component (A) or a copper alloy oxidized by the component (A).
  • the content of one or more selected from the group consisting of sulfuric acid and nitric acid (hereinafter, also referred to as "component (B)"), which promotes the dissolution of the contained copper or copper compound, is based on the total amount of the chemical polishing solution. It is 1 to 20% by mass, preferably 3 to 18% by mass, more preferably 4 to 16% by mass, still more preferably 5 to 15% by mass.
  • the total amount thereof may satisfy the above range.
  • the content of the component (B) is within the above range, the natural oxide film and the organic substance can be appropriately removed from the surface of the copper or the copper alloy.
  • the amount of copper dissolved can be suppressed to a small level, and local corrosion of copper or a copper alloy can be prevented from occurring.
  • Sulfuric acid is particularly preferable as the component (B) because the range of choices for the container when storing the chemical polishing liquid of the present invention is widened.
  • the fluoride (hereinafter, also referred to as “component (C)" is not particularly limited as long as it produces fluorine ions in the chemical polishing solution, but it is acidic. It is preferably one or more selected from the group consisting of potassium fluorinated, acidic ammonium fluoride and hydrogen fluoride. Among these, acidic potassium fluoride and acidic ammonium fluoride are more preferable, and acidic potassium fluoride is particularly preferable, from the viewpoint of low toxicity.
  • the content of fluorine is 0.05 to 0.8% by mass based on the total amount of the chemical polishing liquid as the content in terms of fluorine atom, and is 0.1 to 0. 6% by mass is preferable, 0.15 to 0.5% by mass is more preferable, and 0.2 to 0.4% by mass is further preferable.
  • the total amount thereof may satisfy the above range.
  • the content of fluoride is within the above range, the natural oxide film and organic substances can be appropriately removed from the surface of copper or a copper alloy.
  • the amount of copper dissolved can be suppressed to a small level, and local corrosion of copper or a copper alloy can be prevented from occurring.
  • anthranilic acid cyclohexylamine, cyclohexanol and 1,5-pentanediol
  • anthranilic acid, cyclohexylamine, cyclohexanol and 1,5-pentanediol Is adsorbed on the surface of copper and copper alloys and acts on the removability of natural oxide films and organic substances, and the solubility of copper.
  • the content of one or more selected from the group consisting of anthranilic acid, cyclohexylamine, cyclohexanol and 1,5-pentanediol (hereinafter, also referred to as “component (D)”) is 0. It is 01 to 4% by mass, preferably 0.05 to 3.5% by mass, more preferably 0.1 to 3.3% by mass, still more preferably 0.2 to 3% by mass.
  • component (D) When two or more kinds are used as the component (D), the total amount thereof may satisfy the above range.
  • the content of the component (D) is within the above range, the natural oxide film and organic substances can be appropriately removed from the surface of copper or the copper alloy.
  • the amount of copper dissolved can be suppressed to a small level, and local corrosion of copper or a copper alloy can be prevented from occurring.
  • cyclohexylamine, cyclohexanol or a combination thereof is preferable as the component (D).
  • the fluorine-based surfactant (hereinafter, also referred to as “component (E)”) is adsorbed on the surface of copper and copper alloys, and is a natural oxide film or an organic substance. It affects the removability and the solubility of copper. Since the chemical polishing liquid of the present invention contains the component (E), the removal performance of the natural oxide film and organic substances tends to be stable even if the copper concentration in the chemical polishing liquid increases due to repeated use.
  • the fluorine-based surfactant preferably contains one or more groups selected from the group consisting of a perfluoroalkyl group, a perfluoroalkenyl group and a perfluorophenyl group, and more preferably contains a perfluoroalkyl group.
  • Fluorosurfing agents include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl quaternary ammonium salts, perfluoroalkyl phosphates, perfluoroalkyl phosphonates, and perfluoroalkyl ethylene oxide additions.
  • the content of the fluorine-based surfactant is 0.0005 to 0.005% by mass, preferably 0.0006 to 0.004% by mass, preferably 0, based on the total amount of the chemical polishing liquid. It is more preferably .0007 to 0.003% by mass, and even more preferably 0.0007 to 0.002% by mass.
  • the total amount thereof may satisfy the above range.
  • the content of the fluorine-based surfactant is within the above range, the wettability of the surface of copper or a copper alloy is improved, and the surface treatment can be performed more uniformly. Further, even if the copper concentration in the chemical polishing liquid increases due to repeated use, the removal performance of the natural oxide film and organic substances tends to be stable.
  • the chemical polishing liquid of the present invention contains water (hereinafter, also referred to as “component (F)”) as a diluent.
  • Water is preferably water from which metal ions, organic impurities, particle particles and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments and the like, and pure water or ultrapure water is particularly preferable.
  • the water content is the balance of the above components (A) to (E) and any component, and is preferably 40% by mass or more, more preferably 40 to 99% by mass, based on the total amount of the chemical polishing liquid. It is preferable, more preferably 50 to 97% by mass, still more preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass.
  • the chemical polishing solution of the present invention is known to be stable with hydrogen peroxide such as alcohols, ureas, and organic carboxylic acids usually used in the chemical polishing solution.
  • Various additives such as agents can be contained within a range that does not impair the effect of the chemical polishing liquid.
  • the chemical polishing liquid of the present invention is preferably a dissolution liquid and does not contain solid particles such as polishing particles.
  • the pH range of the chemical polishing liquid of the present invention is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
  • the pH can be measured, for example, by the method described in Examples.
  • the lower limit of the pH of the chemical polishing liquid of the present invention is preferably -2.
  • a pH adjuster may be added to the chemical polishing liquid of the present invention in order to adjust the pH range.
  • pH adjuster for example, potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, triethylamine, ammonia, tetramethylammonium hydroxide, ethanolamine, 1-amino-2-propanol and the like can be used.
  • the pH adjuster may be used alone or in combination of two or more.
  • the chemical polishing liquid of the present invention can be prepared by uniformly stirring the component (A) to the component (F) and, if necessary, other components.
  • the stirring method for these components is not particularly limited, and a stirring method usually used in the preparation of a chemical polishing liquid can be adopted.
  • a part or all of the water of the component (F) may be added later.
  • the balance of the component (F) at the time of use is used. It may be diluted before use.
  • ⁇ Dissolved amount of copper or copper alloy> By surface-treating with the chemical polishing liquid of the present invention, it is possible to remove the natural oxide film and organic substances existing on the surface of copper or a copper alloy. At this time, it is preferable that the amount of copper or the copper alloy dissolved is as small as possible. If the amount of copper or the copper alloy dissolved is large, the thickness of the copper or the copper alloy tends to be different, and it becomes difficult to make the plating thickness uniform when the plating treatment is subsequently performed. Further, if the amount of dissolved copper or the copper alloy is large, color unevenness may occur on the surface of the copper or the copper alloy, which is not preferable.
  • the amount of copper or copper alloy dissolved in the surface treatment is preferably 4 ⁇ m or less, more preferably 2 ⁇ m or less, still more preferably 1 ⁇ m or less, from an economical point of view.
  • the amount of copper or copper alloy dissolved can be measured by the method described in Examples.
  • the dissolution rate of copper or copper alloy associated with the surface treatment using the chemical polishing liquid of the present invention is not particularly limited, but in order to keep the treatment time in an appropriate range, 0.1 to 24 ⁇ m / min is preferable, and 0. 2 to 10 ⁇ m / min is more preferred, and 0.4 to 5 ⁇ m / min is even more preferred.
  • the surface of the copper or the copper alloy is treated with the chemical polishing solution of the present invention so as to be present on the surface of the copper or the copper alloy while suppressing the amount of the copper or the copper alloy to be dissolved.
  • Natural oxides and organic substances can be appropriately removed, and a copper or copper alloy surface having no color unevenness or suppressed color unevenness can be obtained.
  • the surface treatment method of the present invention includes contacting the above-mentioned chemical polishing liquid of the present invention with the surface of copper or a copper alloy to perform surface treatment of copper or a copper alloy.
  • the surface treatment of the copper or the copper alloy is performed using the chemical polishing solution of the present invention, so that the copper or the copper alloy is present on the surface of the copper or the copper alloy while suppressing the dissolved amount of the copper or the copper alloy. Since natural oxides and organic substances can be appropriately removed, it is possible to obtain a copper or copper alloy surface having no color unevenness or suppressing the occurrence of color unevenness.
  • the method of bringing the chemical polishing liquid into contact with the surface of copper or a copper alloy is not particularly limited.
  • a method of bringing the chemical polishing liquid into contact with the surface of copper or a copper alloy by a form such as dropping (single-wafer spin treatment) or spraying, or a method of immersing the surface of copper or a copper alloy in the chemical polishing liquid is preferable. Will be adopted.
  • the temperature of the chemical polishing liquid when surface-treating copper or a copper alloy is not particularly limited, but is usually, for example, 0 to 70 ° C, preferably 25 to 50 ° C, and more preferably 25 to 50 ° C. It is 45 ° C, more preferably 30 to 40 ° C.
  • the temperature of the chemical polishing liquid is 25 ° C. or higher, the chemical polishing rate does not become too slow, so that a decrease in production efficiency can be suppressed.
  • the temperature is 50 ° C. or lower, the change in liquid composition can be suppressed and the surface treatment conditions can be kept constant.
  • the chemical polishing rate is increased by raising the temperature of the chemical polishing liquid, the optimum treatment temperature may be appropriately determined in consideration of suppressing the composition change of the chemical polishing liquid to be small.
  • the time (treatment time) for contacting the chemical polishing liquid with the surface of the copper or the copper alloy to perform the surface treatment of the copper or the copper alloy is not particularly limited, but is usually preferably 1 second or more and 10 minutes or less. , More preferably 10 seconds or more and 5 minutes or less, still more preferably 20 seconds or more and 3 minutes or less.
  • the optimum treatment time may be appropriately selected according to the contact method between the surface of the copper or the copper alloy and the chemical polishing liquid, the temperature of the chemical polishing liquid, and the like.
  • the surface of the copper or the copper alloy may be degreased with an organic solvent such as alcohol or acetone before the surface treatment of the copper or the copper alloy is performed using the chemical polishing liquid of the present invention.
  • the chemical polishing liquid of the present invention may be brought into contact with the surface of the copper or the copper alloy to perform the surface treatment of the copper or the copper alloy, it may be appropriately washed with water or sulfuric acid, if necessary. Further, a neutralization treatment with sodium carbonate or a rust preventive treatment with an aqueous solution containing a rust preventive agent may be performed.
  • the present invention comprises surface-treating copper or copper alloy by contacting the chemical polishing liquid with the surface of copper or copper alloy. It also includes a method for manufacturing a copper alloy. By contacting the chemical polishing liquid of the present invention with the surface of copper or a copper alloy to perform surface treatment on copper or a copper alloy, it is possible to remove natural oxide films and organic substances existing on the surface of copper or a copper alloy. It is possible to obtain copper or a copper alloy having no surface color unevenness or suppressing the occurrence of surface color unevenness.
  • the methods for measuring the physical properties of the chemical polishing liquid, the physical properties of copper and the copper alloy, the method for evaluating the dissolution amount of copper or the copper alloy in the surface-treated product, and the method for evaluating the treatment unevenness of the surface-treated product in Examples and Comparative Examples are as follows. ..
  • FIG. 1 is a photograph showing an example in which color unevenness of a surface-treated product due to a chemical polishing liquid was observed.
  • FIG. 2 is a photograph showing an example in which color unevenness of the surface-treated product due to the chemical polishing liquid was not observed.
  • Example 1 (1) Preparation of chemical polishing solution Hydrogen peroxide (manufactured by Mitsubishi Gas Chemicals Co., Ltd., 60% by mass aqueous solution) 1.6 parts by mass (effective component ratio as hydrogen peroxide, "overwater” in Examples and Comparative Example tables (Notation), sulfuric acid (manufactured by Mitsubishi Gas Chemicals Co., Ltd., 46% by mass aqueous solution) 14.1 parts by mass (ratio of active ingredient as sulfuric acid), acid potassium fluoride (manufactured by Daiwa Kasei Co., Ltd.) 0.9 parts by mass (fluorine) 0.4 parts by mass in atomic equivalent), 0.09 parts by mass of anthranic acid (manufactured by Samsung Chemical Industry Co., Ltd.), and fluorine-based surfactant "Surflon S-243" (manufactured by AGC Seimi Chemical Co., Ltd., perfluoroalkyl group) 0.0018 parts by mass of a fluorine-based nonionic sur
  • Examples 2 to 12 A chemical polishing liquid was prepared in the same manner as in Example 1 except that the composition of the chemical polishing liquid was changed to that shown in Table 1-1, and surface treatment of copper and a copper alloy was carried out.
  • Table 1-1 (A), (B), (C), (D), (E) and (F) are the above-mentioned components (A), component (B) and component (F), respectively.
  • Table 1-2 shows the evaluation results of the amount of copper or copper alloy dissolved in the surface treatment and the treatment unevenness of the surface-treated product.
  • Examples 13 to 15 A chemical polishing liquid was prepared in the same manner as in Example 1 except that the composition of the chemical polishing liquid was changed to that shown in Table 2, and surface treatment of copper and a copper alloy was carried out.
  • Table 2 shows the evaluation results of the amount of copper or copper alloy dissolved in the surface treatment and the treatment unevenness of the surface-treated product.
  • Comparative Examples 1 to 15 A chemical polishing liquid was prepared in the same manner as in Example 1 except that the composition of the chemical polishing liquid was changed to that shown in Table 3, and surface treatment of copper and a copper alloy was carried out.
  • Table 3 shows the evaluation results of the amount of copper or copper alloy dissolved in the surface treatment and the treatment unevenness of the surface-treated product.
  • Examples 16-21 The composition of the chemical polishing liquid was changed to that shown in Table 4 to obtain a surface-treated product. Specifically, a storage solution prepared by mixing the components (A) to (F) is stored at room temperature (20 ° C. ⁇ 5 ° C.) for 3 months, and then diluted with water to prepare a chemical polishing solution. Surface treatment of copper and copper alloy was carried out in the same manner as in No. 1 to obtain a surface-treated product. Table 4 shows the evaluation results of the amount of copper or copper alloy dissolved in the surface treatment and the treatment unevenness of the surface-treated product.
  • Example 22 A chemical polishing liquid was prepared in the same manner as in Example 1 except that the composition of the chemical polishing liquid was changed to that shown in Table 5 and the copper alloy (NKC-4419-H) was further dissolved in an amount of 5 g / L. Then, the surface treatment of the copper alloy (NKC-4419-H) was carried out to obtain a surface-treated product.
  • Table 5 shows the evaluation results of the amount of copper dissolved in the surface treatment and the treatment unevenness of the surface-treated product. In Table 5, the amount of copper dissolved in the surface treatment of the chemical polishing solution of Example 5 having the same composition as that of Example 22 except that the copper alloy (NKC-4419-H) was not dissolved for comparison. The results of the treatment unevenness evaluation of the surface-treated product are also shown.
  • Comparative Examples 16 and 17 The composition of the chemical polishing liquid was changed to that shown in Table 5, and Comparative Example 17 was the same as in Example 1 except that the copper alloy (NKC-4419-H) was further dissolved in an amount of 5 g / L. A chemical polishing liquid was prepared, and a surface treatment of a copper alloy (NKC-4419-H) was carried out to obtain a surface-treated product. Table 5 shows the evaluation results of the amount of copper dissolved in the surface treatment and the treatment unevenness of the surface-treated product.
  • the chemical polishing liquid of the present invention can suppress the occurrence of processing unevenness even if the amount of copper dissolved in the liquid increases, and the chemical polishing liquid with stable removal performance can be obtained. Can be provided.

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PCT/JP2021/020778 2020-06-08 2021-06-01 銅または銅合金の表面処理に用いられる化学研磨液および表面処理方法 WO2021251204A1 (ja)

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CN115613043A (zh) * 2022-11-11 2023-01-17 安徽鑫科铜业有限公司 一种铜镍硅合金带材表面处理溶液及铜镍硅合金带材表面处理方法

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CN116497355B (zh) * 2023-04-10 2024-03-22 珠海市裕洲环保科技有限公司 一种酸性铜蚀刻液及其应用
CN117328066B (zh) * 2023-10-07 2024-03-22 江苏贺鸿电子有限公司 一种线路板用粗化微蚀剂及其制备方法

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