Metal ion acidic etching solution and preparation method thereof

Abstract

The invention relates to the technical field of etching solutions, in particular to a metal ion acid etching solution and a preparation method thereof.The metal ion acid etching solution is prepared from modified composite metal salt, a composite acid medium, a catalytic regenerant, a synergistic corrosion inhibitor, a surfactant, an antioxidant and a complexing agent.The preparation method comprises the steps that 1, the composite acid medium is added into deionized water, and stirring is conducted; an acidic substrate solution is obtained; and 2, adding a surfactant and the modified composite metal salt into the acidic substrate liquid, uniformly stirring, then adding a catalytic regeneration agent and a synergistic corrosion inhibitor, finally adding an antioxidant and a complexing agent, and homogenizing and aging to obtain the metal ion acidic etching liquid. The prepared metal ion acid etching solution has the advantages of remarkable performance advantages, high etching precision, high side wall perpendicularity, small key size loss, moderate etching rate, high etching factor and small lateral erosion, and takes both efficient production and quality stability into account.

Description

Technical Field

[0001] This application relates to the field of etching solution technology, and more specifically, to a metal ion acid etching solution and its preparation method. Background Technology

[0002] In the field of metal etching, performance optimization and environmentally friendly regeneration of acidic etching solutions have always been core challenges. Traditional acidic copper chloride systems (such as hydrochloric acid + sodium chlorate combination) have significant technical bottlenecks: the etching rate is low under low acid conditions, which cannot meet the etching requirements of industry; while high acid systems can improve the rate, they rely on strong oxidants to maintain copper ion regeneration, which easily leads to the risk of chlorine gas leakage and severe side corrosion. In addition, waste liquid treatment is costly, copper resource recovery rate is insufficient, and existing electrolytic regeneration equipment requires large investment and consumes a lot of energy.

[0003] With the surge in demand for precision circuitry (linewidth / spacing ≤25μm) from 5G communications and high-end consumer electronics, the industry urgently needs to overcome the triangular constraints of etching rate, etching stability, and etching safety. Based on the above, this application provides a metal ion acidic etching solution and its preparation method, which can improve etching rate and stability, reduce safety risks, and facilitate resource recycling. Summary of the Invention

[0004] To address the technical problems mentioned in the background art, this application provides a metal ion acid etching solution and its preparation method.

[0005] This application provides a metal ion acid etching solution, employing the following technical solution: A metal ion acid etching solution comprises the following raw materials in the following mass concentrations: modified composite metal salt 40-80 g / L, composite acidic medium 25-50 g / L, catalytic regenerator 3-8 g / L, synergistic corrosion inhibitor 2-6 g / L, surfactant 1-3 g / L, antioxidant 0.5-2 g / L, and complexing agent 3-7 g / L.

[0006] Preferably, the modified composite metal salt is composed of copper chloride, ferric chloride and cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5-8:3-5, and the cerium-zirconium MOFs composite accounts for 15-18% of the total mass of the modified composite metal salt.

[0007] Preferably, the preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, and trimesic acid was added. The mixture was reacted at 120-140℃ for 12-16 h, centrifuged, and dried to obtain MOF crystals. Copper nitrate and iron nitrate were dispersed in anhydrous ethanol at a metal ion molar ratio of 1:0.6-1 to prepare an impregnation solution with a concentration of 0.1-0.3 mol / L. The MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1-3:10-20. The mixture was stirred at room temperature for 6-12 h, centrifuged, and vacuum dried at 60-80℃ for 6-12 h. Under an inert atmosphere, the temperature was increased to 250-300℃ at a heating rate of 2-5℃ / min and calcined at a constant temperature for 2-4 h. After natural cooling, the mixture was washed three times with deionized water and vacuum dried at 60-80℃ for 5-8 h to obtain the cerium-zirconium MOF composite.

[0008] Preferably, the molar ratio of Ce:Zr metal ions in cerium acetylacetone and zirconium nitrate is 3-5:1-2.

[0009] Preferably, the amount of pyromellitic acid added is equal to the total molar amount of metal ions (Ce+Zr).

[0010] Preferably, the composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3-5:1-3:0.5-1.

[0011] Preferably, the catalytic regenerator is cobalt nitrate and / or lanthanum nitrate.

[0012] Preferably, the synergistic corrosion inhibitor is one or more of 2-mercaptobenzothiazole, 2-aminobenzothiazole, and benzotriazole.

[0013] Preferably, the surfactant is one or more of sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, cocamidopropyl betaine, and Tween-80.

[0014] Preferably, the antioxidant is one or more of tea polyphenols and tert-butylhydroquinone.

[0015] Preferably, the complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonotriacetic acid in a mass ratio of 3-8:1-3:0.5-1.2.

[0016] This application also provides a method for preparing a metal ion acidic etching solution, using the following technical solution: A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 20-25℃ and 200-300 rpm for 10-15 minutes until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30-35℃, stir at 400-500 rpm for 20-25 minutes until homogeneous, then add modified composite metal salt in batches. After each addition, stir at 600-800 rpm for 5-10 minutes until homogeneous. Then add catalytic regenerator and synergistic corrosion inhibitor, maintain 30-35℃, and stir at 300-400 rpm for 20-30 minutes. Finally, add antioxidant and complexing agent, heat the system to 40-45℃, and stir at 500-800 rpm for 1-2 hours. After standing for 2-3 hours, the metal ion acidic etching solution is obtained. The entire preparation process is protected by inert gas.

[0017] In summary, this application has the following beneficial effects: This application uses a mixture of hydrochloric acid, methanesulfonic acid, and fluoroboric acid as the acidic medium. Hydrochloric acid can rapidly dissociate and release high concentrations of H+. + Methylsulfonic acid provides a sufficient proton environment for the dissolution reaction of metals (such as copper and iron), but its strong corrosiveness can easily lead to excessively intense local reactions on the metal surface, resulting in defects such as over-etching and edge burrs. Methylsulfonic acid, as a strong organic acid, has an acidity close to that of hydrochloric acid but is milder in corrosiveness. The CH3SO3⁻ in its molecule can react with metal ions (Cu... 2+ Fe 3+ This forms a weak complexation, reducing local H⁺ concentration fluctuations and balancing the strong corrosiveness of hydrochloric acid, making the etching process more gentle and controllable. (The text also mentions BF₄ in fluoroboric acid.) - The ions possess strong complexing capabilities, preferentially reacting with and dissolving the oxide film (such as CuO, Fe2O3) on the metal surface, allowing H⁺ to contact the metal surface more evenly and avoiding local reaction delays caused by uneven oxide film distribution. When the three are used synergistically, hydrochloric acid provides high reactivity to ensure the etching rate, methanesulfonic acid regulates the reaction rhythm through weak complexation, and fluoroboric acid eliminates oxide film barriers to ensure uniform reaction initiation, resulting in a significantly improved etching rate compared to a single acid. Hydrochloric acid, when used alone, is highly volatile and easily generates a large amount of acid mist, causing not only raw material loss but also equipment corrosion and harm to the health of operators. Methanesulfonic acid has low volatility, and its addition can reduce the volatility tendency of hydrochloric acid through intermolecular forces. Fluoroboric acid itself has low volatility, and its strong complexing effect with metal ions can reduce free H⁺. + The concentration further inhibits the formation of acid mist.

[0018] This application utilizes a compound of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozinotriacetic acid. These three compounds form a highly efficient complex network through structural and functional synergy. Disodium ethylenediaminetetraacetate strongly chelates Cu. 2+ Principal metal ions, 1,3-propanediaminetetraacetic acid specifically optimized Fe 3+Complexation efficiency, triacetic acid enhances complexation stability in acidic environments, the three complement each other to broaden the complexation range, synergistically inhibit the hydrolysis and precipitation of metal ions, buffer ion concentration fluctuations during etching, avoid the defects of insufficient complexation of specific ions by a single complexing agent, significantly extend the life of the etching solution, and at the same time ensure uniform and stable etching rate and improve the quality of the etched surface.

[0019] This application utilizes a cerium-zirconium MOF composite, whose porous structure allows for the uniform loading of Cu. 2+ Fe 3+ Increase etching active sites and improve etching rate, Ce 3+ / Ce 4+ The redox cycle synergistically promotes cobalt nitrate, which in turn promotes Fe 2+ Oxidized to Fe 3+ To maintain etching activity, Zr 4+ It enhances the structural stability of MOFs and prevents disintegration in acidic environments. It works synergistically with copper chloride and ferric chloride to regulate the release rate of metal ions, ensuring uniform etching, enhanced stability, extended lifespan, and reduced metal ion aggregation, thus optimizing the surface quality of the etched surface. Detailed Implementation

[0020] The present application will be further described in detail below with reference to the embodiments.

[0021] The methanesulfonic acid used in the examples and comparative examples of this application was purchased from Jinan Zhengkang Chemical Co., Ltd., fluoroboric acid (concentration: 40%) was purchased from Shandong Xima Supply Chain Management Co., Ltd., 2-mercaptobenzothiazole was purchased from Shandong Xima Supply Chain Management Co., Ltd., disodium ethylenediaminetetraacetate was purchased from Shandong Yuxing Fine Chemical Co., Ltd., 1,3-propanediaminetetraacetic acid was purchased from Jinan Yuno Chemical Co., Ltd., hyponitrotriacetic acid was purchased from Shandong Xuchen Chemical Technology Co., Ltd., cerium acetylacetone was purchased from Hubei Xingyan New Material Technology Co., Ltd., zirconium nitrate was purchased from Shandong Xuchen Chemical Technology Co., Ltd., and pyromellitic acid was purchased from Shandong Xinghai Chemical Co., Ltd.

[0022] Examples 1-3 provide a metal ion acid etching solution and its preparation method.

[0023] Example 1 A metal ion acidic etching solution comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3:1:0.5. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 3:1:0.5. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0024] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Tristyric acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 3:1 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 120°C and 200 rpm for 12 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0025] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0026] Example 2 An acidic etching solution for metal ions comprises the following raw materials at the following mass concentrations: 60 g / L modified composite metal salt, 40 g / L composite acidic medium, 6 g / L catalytic regenerator, 4 g / L synergistic corrosion inhibitor, 2 g / L surfactant, 1 g / L antioxidant, and 5 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 4:2:0.8. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 5:2:0.8. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 6:4, and the cerium-zirconium MOFs composite accounts for 17% of the total mass of the modified composite metal salt.

[0027] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:8. Trimethylbenzene acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 4:1.5 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 300 rpm for 14 h at 130 °C, centrifuged, and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.8. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.2 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 2:15. The mixture was stirred at room temperature for 9 h at a stirring speed of 400 rpm, centrifuged, and dried under vacuum at 70 °C for 9 h. Under an inert atmosphere, the temperature was increased to 280 °C at a heating rate of 4 °C / min and calcined at a constant temperature for 3 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 70 °C for 7 h to obtain the cerium-zirconium MOF composite.

[0028] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 250 rpm for 12 minutes at 22°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 32℃, stir at 450 rpm for 22 min, and after stirring evenly, add modified composite metal salt in 4 batches, each batch containing 1 / 4 of the total mass of modified composite metal salt. After each addition, stir at 700 rpm for 8 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 32℃, and stir at 350 rpm for 25 min. Finally, add antioxidant and complexing agent, heat the system to 42℃, stir at 700 rpm for 1.5 h, and then let it stand for 2.5 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0029] Example 3 An acidic etching solution for metal ions comprises the following raw materials at the following mass concentrations: 80 g / L modified composite metal salt, 50 g / L composite acidic medium, 8 g / L catalytic regenerator, 6 g / L synergistic corrosion inhibitor, 3 g / L surfactant, 2 g / L antioxidant, and 7 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 5:3:1. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 8:3:1.2. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 8:5, and the cerium-zirconium MOFs composite accounts for 18% of the total mass of the modified composite metal salt.

[0030] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 2:15. Trimethylbenzene acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 5:2 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 140°C and 400 rpm for 16 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and ferric nitrate were then added according to a Cu:Fe molar ratio of 1:1. The MOFs were dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.3 mol / L. MOFs crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 3:20. The mixture was stirred at room temperature for 12 h at a stirring speed of 500 rpm, centrifuged, and dried under vacuum at 80 °C for 12 h. Under an inert atmosphere, the temperature was increased to 300 °C at a heating rate of 5 °C / min and calcined at a constant temperature for 4 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 80 °C for 8 h to obtain the cerium-zirconium MOFs composite.

[0031] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 300 rpm for 15 minutes at 25°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 35℃, stir at 500 rpm for 25 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 800 rpm for 10 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 35℃, and stir at 400 rpm for 30 min. Finally, add antioxidant and complexing agent, heat the system to 45℃, stir at 800 rpm for 2 h, and then let it stand for 3 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0032] Comparative Example 1 A metal ion acidic etching solution comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid and fluoroboric acid in a mass ratio of 3:0.5. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 3:1:0.5. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0033] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Tristyric acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 3:1 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 120°C and 200 rpm for 12 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0034] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0035] Comparative Example 2 An acidic etching solution for metal ions comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid and methanesulfonic acid in a mass ratio of 3:1. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 3:1:0.5. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0036] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Tristyric acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 3:1 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 120°C and 200 rpm for 12 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0037] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0038] Comparative Example 3 A metal ion acid etching solution comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3:1:0.5. The catalytic regenerator is cobalt nitrate, the synergistic corrosion inhibitor is 2-mercaptobenzothiazole, the surfactant is sodium dodecyl sulfate, the antioxidant is tert-butylhydroquinone, and the complexing agent is composed of disodium ethylenediaminetetraacetate and hypotriacetic acid in a mass ratio of 3:0.5. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0039] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Tristyric acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 3:1 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 120°C and 200 rpm for 12 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0040] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0041] Comparative Example 4 A metal ion acidic etching solution comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3:1:0.5. The catalytic regenerator is cobalt nitrate, the synergistic corrosion inhibitor is 2-mercaptobenzothiazole, the surfactant is sodium dodecyl sulfate, the antioxidant is tert-butylhydroquinone, and the complexing agent is composed of disodium ethylenediaminetetraacetate and 1,3-propanediaminetetraacetic acid in a mass ratio of 3:1. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0042] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Tristyric acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of 3:1 in both cerium acetylacetone and zirconium nitrate. The mixture was stirred at 120°C and 200 rpm for 12 hours, then centrifuged and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0043] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0044] Comparative Example 5 An acidic etching solution for metal ions comprises the following raw materials in the following mass concentrations: 40 g / L of a composite metal salt, 25 g / L of a composite acidic medium, 3 g / L of a catalytic regenerator, 2 g / L of a synergistic corrosion inhibitor, 1 g / L of a surfactant, 0.5 g / L of an antioxidant, and 3 g / L of a complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3:1:0.5. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonotriacetic acid in a mass ratio of 3:1:0.5. The composite metal salt is composed of copper chloride and ferric chloride in a mass ratio of 5:3.

[0045] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0046] Comparative Example 6 A metal ion acidic etching solution comprises the following raw materials at the following mass concentrations: 40 g / L modified composite metal salt, 25 g / L composite acidic medium, 3 g / L catalytic regenerator, 2 g / L synergistic corrosion inhibitor, 1 g / L surfactant, 0.5 g / L antioxidant, and 3 g / L complexing agent. The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3:1:0.5. The catalytic regenerator is cobalt nitrate. The synergistic corrosion inhibitor is 2-mercaptobenzothiazole. The surfactant is sodium dodecyl sulfate. The antioxidant is tert-butylhydroquinone. The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozonyltriacetic acid in a mass ratio of 3:1:0.5. The modified composite metal salt is composed of copper chloride, ferric chloride, and a cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5:3, and the cerium-zirconium MOFs composite accounts for 15% of the total mass of the modified composite metal salt.

[0047] The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, with a solid-liquid mass ratio of 1:10. Trimethylbenzene acid, equal in molar amount to the total metal ions (Ce+Zr), was added, maintaining a Ce:Zr molar ratio of ions in the cerium acetylacetone and zirconium nitrate at 1:3. The mixture was stirred at 200 rpm for 12 h at 120 °C, centrifuged, and dried to obtain MOF crystals. Copper nitrate and nitrate were then added according to a Cu:Fe molar ratio of 1:0.6. Ferric acid was dispersed in anhydrous ethanol to prepare an impregnation solution with a concentration of 0.1 mol / L. MOF crystals were added to the impregnation solution, and the solid-liquid mass ratio was controlled at 1:10. The mixture was stirred at room temperature for 6 h at a stirring speed of 300 rpm, centrifuged, and dried under vacuum at 60 °C for 6 h. Under an inert atmosphere, the temperature was increased to 250 °C at a heating rate of 2 °C / min and calcined at a constant temperature for 2 h. After natural cooling, the mixture was washed three times with deionized water and dried under vacuum at 60 °C for 5 h to obtain the cerium-zirconium MOF composite.

[0048] A method for preparing a metal ion acidic etching solution, comprising the following steps: Step 1: Add the composite acidic medium to deionized water and stir at 200 rpm for 10 minutes at 20°C until homogeneous to obtain the acidic base solution for later use. Step 2: Add surfactant to acidic base solution, heat to 30℃, stir at 400 rpm for 20 min, and after stirring evenly, add modified composite metal salt in 3 batches, each batch containing 1 / 3 of the total mass of modified composite metal salt. After each addition, stir at 600 rpm for 5 min, and after stirring evenly, add catalytic regenerator and synergistic corrosion inhibitor, maintain 30℃, and stir at 300 rpm for 20 min. Finally, add antioxidant and complexing agent, heat the system to 40℃, stir at 500 rpm for 1 h, and then let it stand for 2 h to obtain metal ion acidic etching solution. The entire preparation process is protected by nitrogen.

[0049] Performance testing Etching characteristics: The glass substrate was etched under a constant temperature water bath at 35°C. A molybdenum metal film with a thickness of 300 Å and a copper metal film with a thickness of 6000 Å were deposited sequentially on the glass substrate. The etching was performed using the metal ion acid etching solutions prepared in Examples 1-3 and Comparative Examples 1-6. The etching time was 120 s. The substrate was then washed with water and dried completely with a nitrogen gun. The etching characteristics were recorded. The specific test results are shown in Table 1.

[0050] Table 1. Etching effect parameters of the metal ion acidic etching solutions prepared in Examples 1-3 and Comparative Examples 1-6. As shown in Table 1, the metal ion acidic etching solution prepared in this application exhibits significant performance advantages. It has a taper angle close to 90°, high sidewall perpendicularity, minimal CD loss, controllable critical dimension deviations, and can precisely match design requirements. The etching rate is moderate, balancing efficient production with quality stability. It also has a high etching factor and minimal lateral erosion. In summary, it combines high-precision pattern control, excellent dimensional consistency, and efficient etching capabilities, reducing process deviations, improving product yield, and meeting the needs of precision metal etching scenarios.

[0051] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A metal ion acid etching solution, characterized in that, The raw materials include the following mass concentrations: modified composite metal salt 40-80 g / L, composite acidic medium 25-50 g / L, catalytic regenerator 3-8 g / L, synergistic corrosion inhibitor 2-6 g / L, surfactant 1-3 g / L, antioxidant 0.5-2 g / L, and complexing agent 3-7 g / L.

2. The metal ion acid etching solution according to claim 1, characterized in that, The modified composite metal salt is composed of copper chloride, ferric chloride and cerium-zirconium MOFs composite, wherein the mass ratio of copper chloride to ferric chloride is 5-8:3-5, and the cerium-zirconium MOFs composite accounts for 15-18% of the total mass of the modified composite metal salt.

3. The metal ion acid etching solution according to claim 2, characterized in that, The preparation method of the cerium-zirconium MOFs composite is as follows: Cerium acetylacetone and zirconium nitrate were dispersed in N,N-dimethylformamide, and trimesic acid was added. The mixture was reacted at 120-140℃ for 12-16 h, centrifuged, and dried to obtain MOF crystals. Copper nitrate and ferric nitrate were dispersed in anhydrous ethanol to prepare an impregnation solution. The MOF crystals were added to the impregnation solution, stirred at room temperature for 6-12 h, centrifuged, and dried under vacuum. Under an inert atmosphere, the temperature was increased to 250-300℃ at a rate of 2-5℃ / min, and calcined at a constant temperature for 2-4 h. After natural cooling, the mixture was washed and dried under vacuum to obtain cerium-zirconium MOF composites.

4. The acidic etching solution with metal ions according to claim 3, characterized in that, The molar ratio of metal ions Ce:Zr in cerium acetylacetone and zirconium nitrate is 3-5:1-2; the amount of pyromellitic acid added is equal to the total molar amount of metal ions (Ce+Zr).

5. The metal ion acid etching solution according to claim 1, characterized in that, The composite acidic medium is composed of hydrochloric acid, methanesulfonic acid, and fluoroboric acid in a mass ratio of 3-5:1-3:0.5-1.

6. The metal ion acid etching solution according to claim 1, characterized in that, The catalytic regenerator is one or more of cobalt nitrate and / or lanthanum nitrate.

7. The metal ion acid etching solution according to claim 1, characterized in that, The synergistic corrosion inhibitor is one or more of 2-mercaptobenzothiazole, 2-aminobenzothiazole, and benzotriazole.

8. The metal ion acid etching solution according to claim 1, characterized in that, The complexing agent is composed of disodium ethylenediaminetetraacetate, 1,3-propanediaminetetraacetic acid, and hypozinotriacetic acid in a mass ratio of 3-8:1-3:0.5-1.

2.

9. A method for preparing a metal ion acidic etching solution as described in any one of claims 1-8, characterized in that, The preparation steps include the following: Step 1: Add the composite acidic medium to deionized water, stir evenly to obtain an acidic base solution, and set aside. Step 2: Add surfactant to acidic base solution and stir evenly. Then add modified composite metal salt in batches and stir evenly after each addition. Then add catalytic regenerator and synergistic corrosion inhibitor. Finally add antioxidant and complexing agent. After homogenization and aging, the metal ion acidic etching solution is obtained. The entire preparation process is protected by inert gas.

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