A laser-induced glass etching device and a fluorine-free etching method

Abstract

The present invention discloses a glass etching device and a fluorine-free etching method for laser induction, belonging to the field of glass etching technology. The etching device includes an etching tank and an oil bath heating device, which can increase the etching speed by heating an alkaline fluorine-free etching solution. The composite stirring system of a magnetic stirrer and a stirring paddle can circulate the fluorine-free etching solution, improve the uniformity of etching, and is more conducive to the stable progress of the etching reaction. The fluorine-free etching method uses a fluorine-free etching solution that does not contain hydrofluoric acid, is safe and environmentally friendly, and can avoid degradation of through-hole features. Under the action of a fluorocarbon surfactant, the etching solution has excellent wettability, and the sodium hydroxide and potassium hydroxide therein can perform highly selective etching on the glass after laser induction. The glass after fluorine-free etching has a high surface finish and a higher through-hole roundness. The surface and inner wall of the through-hole are smooth, the through-hole inner wall roughness is less than 1μm, and the through-hole taper is smaller, achieving a good etching effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass etching, and in particular relates to a laser-induced glass etching device and a fluorine-free etching method. Background Art

[0002] In an era of booming artificial intelligence and semiconductor integrated circuit industries, semiconductor technology manufacturers both domestically and internationally face the challenge of increasing the number of transistors that can be packed per unit area on semiconductor chips while maintaining excellent electrical performance, heat dissipation, low loss, and resistance to extreme environments. As a key approach to improving chip performance in the post-Moore era, three-dimensional packaging integration technology has become a research hotspot in the semiconductor industry. Therefore, multi-layered glass interposers have become a core component of three-dimensional integrated systems, serving as a bridge between the two. Glass offers low manufacturing costs, making it easier to achieve larger areas and thinner thicknesses. Furthermore, glass offers advantages such as high strength and excellent electrical insulation properties. Therefore, it is considered an excellent alternative to traditional silicon-based interposers in semiconductor packaging applications.

[0003] Currently, achieving efficient, high-quality through-glass vias (TGOs) is a major factor limiting the development of glass interposer technology. Laser-induced deep etching (LIDE) technology, which can achieve excellent TGOs efficiently and at low cost, has become a research hotspot within the industry.

[0004] Glass etching has high technical requirements. It must have a high etching selectivity and good isotropy to ensure the consistency of the hole characteristics after etching and the smoothness of the glass surface. The glass etching solution of laser-induced etching technology usually adopts an acidic medium containing hydrofluoric acid and HCL. Although it has a high etching selectivity, the hole characteristics of the glass after etching are usually poor. Currently, there are practical problems such as poor hole roundness, large taper angle, and low aspect ratio. More importantly, hydrofluoric acid is highly corrosive and can strongly corrode metals, glass, and silicon-containing objects. Inhalation of vapor or contact with skin can cause difficult-to-heal burns, causing great harm to the physical and mental health of production personnel. At the same time, it also seriously damages the environment.

[0005] Therefore, in order to solve some practical problems in the existing technical solutions, it is very meaningful to develop a new glass etching equipment and a fluorine-free etching method that does not contain hydrofluoric acid, has high selectivity and ideal pore-forming effect. Summary of the Invention

[0006] The purpose of the present invention is to provide a glass etching device and a fluorine-free etching method for laser induction. The etching device can improve the uniformity of etching and is more conducive to the stable progress of the etching reaction; the fluorine-free etching method uses a fluorine-free etching solution that does not contain hydrofluoric acid, is safe and environmentally friendly, and can avoid degradation of through-hole features.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] A laser-induced glass etching device comprises an etching tank and an oil bath heating device. The oil bath heating device comprises a magnetic stirring heater and an oil bath pot filled with heat-conducting oil. The oil bath pot is placed on the magnetic stirring heater, and the etching tank is placed in the oil bath pot. A magnetic stirring bar that can be magnetically driven by the magnetic stirring heater is provided at the bottom of the etching tank.

[0009] Furthermore, the glass etching device also includes a bracket, which is provided with a long cross bar and a short cross bar. The long cross bar is fixed with a motor, the output shaft of the motor is fixed with a stirring paddle extending into the etching tank, and the short cross bar is fixed with a temperature sensor for monitoring the temperature of the heat transfer oil.

[0010] A method for laser-induced fluorine-free etching of glass comprises the following steps:

[0011] The fluorine-free etching solution is injected into the etching tank, and the etching solution is heated to 50-70°C using an oil bath heating device. The fluorine-free etching solution is circulated at a stirring speed of 1000-2000 r / min. The laser-induced glass is immersed in the fluorine-free etching solution and etched for 30-120 minutes. After cooling to room temperature, the etching is continued for 10-20 minutes. The glass is taken out, washed with clean water, and then vacuum-dried to complete the fluorine-free etching method.

[0012] Furthermore, the fluorine-free etching solution comprises the following components by mass percentage:

[0013] Sodium hydroxide 1-50%, potassium hydroxide 0.1-10%, fluorocarbon surfactant 0.1-5%, bifunctional nanoparticles 1-5%, and the balance is water.

[0014] Furthermore, the fluorine-free etching solution comprises the following components by mass percentage:

[0015] Sodium hydroxide 20-30%, potassium hydroxide 2-5%, fluorocarbon surfactant 0.5-1.5%, bifunctional nanoparticles 1.5-2.5%, and the balance is water.

[0016] Furthermore, the bifunctional nanoparticles are prepared by the following steps:

[0017] Step 1: Yttrium-doped zirconia nanopowder is treated with 3-aminopropyltriethoxysilane to obtain amino-modified yttrium-doped zirconia nanopowder; amino-modified yttrium-doped zirconia nanopowder, pyridine and toluene are added to a reactor and stirred and mixed, and then 2-bromoisobutyl bromide is added, and stirred at 4-5°C and 200-300r / min for 50-60min, and then heated to 20-25°C and stirred for 10-12h, centrifuged and filtered, and the precipitate is washed and dried to obtain grafted modified yttrium-doped zirconia nanopowder grafted with 2-bromoisobutylimide.

[0018] Step 2: Add anhydrous copper bromide, L-ascorbic acid and a mixed solvent to a reactor, stir at 20-25°C and 200-300 r / min for 10-15 minutes, then add tris(2-dimethylaminoethyl)amine and stir for 5-10 minutes. Under nitrogen protection and 10-15°C, add grafted modified yttrium-doped zirconia nanopowder and 10wt% 3-fluorostyrene solution to the reactor, stir and react for 2-3 hours, then add 27wt% N-isopropylacrylamide solution, stir and react for 4-5 hours, centrifuge and filter, wash the filter cake, and dry to obtain bifunctional nanoparticles.

[0019] Furthermore, in step 1, the usage ratio of the amino-modified yttrium-doped zirconia nanopowder, pyridine, toluene and 2-bromoisobutyl bromide is 0.5-0.6 g: 0.3 mL: 25-30 mL: 0.2-0.24 mL.

[0020] Furthermore, in step 2, the dosage ratio of anhydrous copper bromide, L-ascorbic acid, mixed solvent, tris(2-dimethylaminoethyl)amine, modified yttrium-doped zirconia nanopowder, 3-fluorostyrene solution and N-isopropylacrylamide solution is 0.14-0.145 g: 0.085-0.088 g: 15 mL: 1.22-1.27 g: 0.5 g: 14-15 mL: 15-18 mL.

[0021] Furthermore, in step 3, the solvents of the 3-fluorostyrene solution and the N-isopropylacrylamide solution are both mixed solvents.

[0022] Furthermore, the mixed solvent is prepared by mixing DMF and deionized water in a volume ratio of 7-9:1-3.

[0023] Furthermore, yttrium-doped zirconia nanopowder is prepared by the following steps:

[0024] Yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water are added to a reaction kettle at 20-25°C, stirred to dissolve, and then the pH value is adjusted to 9-10 with ammonia water. The mixture is stirred at 200-300 r / min for 50-60 minutes, filtered, and the filter cake is washed, dried, and ground to obtain a precursor powder.

[0025] The precursor powder is dispersed into a 2-3 wt% precursor dispersion with deionized water and transferred to a hydrothermal reactor. The pH value is adjusted to 4 with hydrochloric acid. The hydrothermal reaction is carried out at 190-200 ° C for 2.5-3.5 hours. The mixture is cooled and centrifuged. The precipitate is washed, dried, and ground to obtain yttrium-doped zirconia nanopowder.

[0026] Furthermore, the usage ratio of yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water is 0.46-0.77 g:12.88 g:200 mL.

[0027] Beneficial effects of the present invention:

[0028] 1. The laser-induced glass etching device of the present invention has a simple structure and can increase the etching speed by heating the alkaline fluorine-free etching solution. The composite stirring system of the magnetic stirrer and the stirring paddle can circulate the fluorine-free etching solution, thereby improving the uniformity of etching and being more conducive to the stable progress of the etching reaction.

[0029] 2. The fluorine-free etching method of the present invention uses a fluorine-free etching solution that does not contain hydrofluoric acid, is safe and environmentally friendly, and can prevent degradation of through-hole features. Under the action of fluorocarbon surfactants, the etching solution has excellent wettability, and the sodium hydroxide and potassium hydroxide in it can etch the glass with high selectivity after laser induction.

[0030] Under high-temperature etching, the polymer chains on the surface of the bifunctional nanoparticles shrink, maintaining particle hardness and enhancing mechanical abrasion. Under low-temperature etching, the polymer chains swell, adsorbing and removing silicate fragments, thereby assisting etching and reducing the roughness and taper of the through-hole inner wall. The short poly(3-fluorostyrene) chains in the bifunctional nanoparticles enhance the alkali resistance and stability of the long thermosensitive polymer chains. Furthermore, the fluorophenyl groups possess electron-abstracting properties, promoting the breakage of silicon-oxygen bonds and further improving the surface finish of the etched glass.

[0031] The glass surface after fluorine-free etching has high smoothness and higher through-hole roundness. The surface and inner wall of the through-hole are smooth, the roughness of the inner wall of the through-hole is less than 1μm, and the through-hole taper is smaller, achieving a good etching effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Schematic diagram of the structure of the etching device of the present invention;

[0033] Figure 2 This is a cross-sectional view of the etching tank and oil bath pot of the present invention. DETAILED DESCRIPTION

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0035] Example 1: This example provides a fluorine-free etching solution comprising the following components by mass percentage:

[0036] Sodium hydroxide 1%, potassium hydroxide 10%, fluorocarbon surfactant 0.1%, bifunctional nanoparticles 1%, and the balance is water.

[0037] The bifunctional nanoparticles are prepared by the following steps:

[0038] S1: At 20°C, 0.46 kg of yttrium nitrate hexahydrate, 12.88 kg of zirconium oxychloride octahydrate and 200 L of deionized water were added to a reactor. After stirring and dissolving, the pH value was adjusted to 9 with 3 mol / L ammonia water. The mixture was stirred at 200 r / min for 50 min and filtered. The filter cake was washed with deionized water until the last washing liquid was neutral. The mixture was vacuum dried at 50°C to constant weight and ground into powder to obtain a precursor powder.

[0039] The precursor powder was dispersed with deionized water to obtain a precursor dispersion with a mass concentration of 2% and transferred to a hydrothermal reactor. The pH value was adjusted to 4 with hydrochloric acid, and the hydrothermal reaction was carried out at 190°C for 2.5 hours. After cooling to room temperature, the dispersion was centrifuged and filtered. The precipitate was washed with deionized water until the last washing liquid was neutral, vacuum dried to constant weight, and ground into a tetragonal yttrium-doped zirconia nanopowder. Yttrium doping can improve the stability of its tetragonal crystal.

[0040] S2: 0.5 kg of yttrium-doped zirconia nanopowder, 0.05 L of triethanolamine and 25 L of anhydrous ethanol were added to the reactor and ultrasonically dispersed for 5 minutes. Then, 0.3 kg of 3-aminopropyltriethoxysilane was dissolved in 0.5 L of deionized water and added to the reactor. The pH value was adjusted to 9 with 3 mol / L ammonia water. The reaction was stirred at 60°C and 200 r / min for 10 hours. After natural cooling, centrifugal filtration was carried out. The filter cake was washed twice with anhydrous ethanol and vacuum dried to constant weight to obtain amino-modified yttrium-doped zirconia nanopowder.

[0041] S3: Add 0.5 kg of amino-modified yttrium-doped zirconia nanopowder, 0.3 L of pyridine and 25 L of toluene into a reactor and stir to mix, then add 0.2 L of 2-bromoisobutylimide bromide and stir at 4 ° C and 200 r / min for 50 minutes, then heat to 20 ° C and stir for 10 hours, centrifuge and filter, wash the precipitate twice with toluene, and vacuum dry to constant weight to obtain grafted modified yttrium-doped zirconia nanopowder grafted with 2-bromoisobutylimide.

[0042] S4: DMF and deionized water are mixed in a volume ratio of 7:1 to obtain a mixed solvent, 3-fluorostyrene is dissolved in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%, and N-isopropylacrylamide is dissolved in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0043] 0.14 kg of anhydrous copper bromide as a catalyst, 0.085 kg of L-ascorbic acid as a reducing agent and 15 L of a mixed solvent were added to a reactor and stirred at 20°C and 200 r / min for 10 minutes. Then, 1.22 kg of tris(2-dimethylaminoethyl)amine was added and stirred for 5 minutes. Under nitrogen protection and 10°C, 0.5 kg of grafted modified yttrium-doped zirconia nanopowder and 14 L of 3-fluorostyrene solution were added to the reactor and stirred for 2 hours. Then, 15 L of N-isopropylacrylamide solution was added and stirred for 4 hours. Through the reaction, poly(3-fluorostyrene) short chains and thermosensitive polymer long chains were grafted onto the grafted modified yttrium-doped zirconia nanopowder in sequence. The mixture was centrifuged and filtered. The filter cake was washed three times with deionized water and vacuum dried at 40°C to constant weight to obtain bifunctional nanoparticles.

[0044] Example 2: This example provides a fluorine-free etching solution comprising the following components by mass percentage:

[0045] Sodium hydroxide 50%, potassium hydroxide 0.1%, fluorocarbon surfactant 5%, bifunctional nanoparticles 5%, and the balance is water.

[0046] The bifunctional nanoparticles are prepared by the following steps:

[0047] S1: At 22.5°C, 0.615 kg of yttrium nitrate hexahydrate, 12.88 kg of zirconium oxychloride octahydrate and 200 L of deionized water were added to a reactor. After stirring and dissolving, the pH value was adjusted to 9.5 with 3 mol / L ammonia water. The mixture was stirred at 250 r / min for 55 min, filtered, and the filter cake was washed with deionized water until the last washing liquid was neutral. The mixture was vacuum dried at 60°C to constant weight and ground into powder to obtain a precursor powder.

[0048] The precursor powder was dispersed with deionized water to obtain a precursor dispersion with a mass concentration of 2.5% and transferred to a hydrothermal reactor. The pH value was adjusted to 4 with hydrochloric acid, and the hydrothermal reaction was carried out at 195°C for 3 hours. After cooling to room temperature, the dispersion was centrifuged and filtered. The precipitate was washed with deionized water until the last washing liquid was neutral, vacuum dried to constant weight, and ground into fine powder to obtain tetragonal yttrium-doped zirconia nanopowder.

[0049] S2: 0.55 kg of yttrium-doped zirconia nanopowder, 0.05 L of triethanolamine and 27.5 L of anhydrous ethanol were added to the reactor and ultrasonically dispersed for 7.5 minutes. Then, 0.33 kg of 3-aminopropyltriethoxysilane was dissolved in 0.5 L of deionized water and added to the reactor. The pH value was adjusted to 9.5 with 3 mol / L ammonia water. The reaction was stirred at 65 ° C and 250 r / min for 11 hours. After natural cooling, centrifugal filtration was carried out. The filter cake was washed with anhydrous ethanol 2.5 times and vacuum dried to constant weight to obtain amino-modified yttrium-doped zirconia nanopowder.

[0050] S3: Add 0.55 kg of amino-modified yttrium-doped zirconia nanopowder, 0.3 L of pyridine and 27.5 L of toluene into a reactor and stir to mix, then add 0.22 L of 2-bromoisobutylimide bromide and stir at 4.5 ° C and 250 r / min for 55 minutes, then heat to 22.5 ° C and stir for 11 hours, centrifuge and filter, wash the precipitate with toluene 2.5 times, and vacuum dry to constant weight to obtain grafted modified yttrium-doped zirconia nanopowder grafted with 2-bromoisobutylimide.

[0051] S4: DMF and deionized water are mixed in a volume ratio of 8:2 to obtain a mixed solvent, 3-fluorostyrene is dissolved in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%, and N-isopropylacrylamide is dissolved in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0052] 0.1425 kg of anhydrous copper bromide as a catalyst, 0.0865 kg of L-ascorbic acid as a reducing agent and 15 L of a mixed solvent were added to a reactor and stirred at 22.5°C and 250 r / min for 12.5 min. Then, 1.245 kg of tris(2-dimethylaminoethyl)amine was added and stirred for 7.5 min. Under nitrogen protection and 12.5°C, 0.5 kg of grafted modified yttrium-doped zirconia nanopowder and 14.5 L of 3-fluorostyrene solution were added to the reactor and stirred for 2.5 h. Then, 16.5 L of N-isopropylacrylamide solution was added and stirred for 4.5 h. The mixture was centrifuged and filtered. The filter cake was washed four times with deionized water and dried in vacuo at 45°C to constant weight to obtain bifunctional nanoparticles.

[0053] Example 3: This example provides a fluorine-free etching solution comprising the following components by mass percentage:

[0054] Sodium hydroxide 20%, potassium hydroxide 2%, fluorocarbon surfactant 0.5%, bifunctional nanoparticles 1.5%, and the balance is water.

[0055] The bifunctional nanoparticles in Example 3 are the same as the bifunctional nanoparticles in Example 2.

[0056] Example 4: This example provides a fluorine-free etching solution comprising the following components by mass percentage:

[0057] Sodium hydroxide 30%, potassium hydroxide 5%, fluorocarbon surfactant 1.5%, bifunctional nanoparticles 2.5%, and the balance is water.

[0058] The bifunctional nanoparticles are prepared by the following steps:

[0059] S1: At 25°C, 0.77 kg of yttrium nitrate hexahydrate, 12.88 kg of zirconium oxychloride octahydrate and 200 L of deionized water were added to a reactor. After stirring and dissolving, the pH value was adjusted to 10 with 3 mol / L ammonia water. The mixture was stirred at 300 r / min for 60 min and filtered. The filter cake was washed with deionized water until the last washing liquid was neutral. The mixture was vacuum dried at 70°C to constant weight and ground into powder to obtain a precursor powder.

[0060] The precursor powder was dispersed with deionized water to obtain a precursor dispersion with a mass concentration of 3% and transferred to a hydrothermal reactor. The pH value was adjusted to 4 with hydrochloric acid, and the hydrothermal reaction was carried out at 200°C for 3.5 hours. After cooling to room temperature, the dispersion was centrifuged and filtered. The precipitate was washed with deionized water until the last washing liquid was neutral, vacuum dried to constant weight, and ground into fine powder to obtain tetragonal yttrium-doped zirconia nanopowder.

[0061] S2: 0.6 kg of yttrium-doped zirconia nanopowder, 0.05 L of triethanolamine and 30 L of anhydrous ethanol were added to the reactor and ultrasonically dispersed for 10 minutes. Then, 0.36 kg of 3-aminopropyltriethoxysilane was dissolved in 0.5 L of deionized water and added to the reactor. The pH value was adjusted to 10 with 3 mol / L ammonia water. The reaction was stirred at 70 ° C and 300 r / min for 12 hours. After natural cooling, centrifugal filtration was carried out. The filter cake was washed with anhydrous ethanol 3 times and vacuum dried to constant weight to obtain amino-modified yttrium-doped zirconia nanopowder.

[0062] S3: Add 0.6 kg of amino-modified yttrium-doped zirconia nanopowder, 0.3 L of pyridine and 30 L of toluene into a reactor and stir to mix, then add 0.24 L of 2-bromoisobutylimide bromide and stir at 5 ° C and 300 r / min for 60 minutes, then heat to 25 ° C and stir for 12 hours, centrifuge and filter, wash the precipitate with toluene three times, and vacuum dry to constant weight to obtain grafted modified yttrium-doped zirconia nanopowder grafted with 2-bromoisobutylimide.

[0063] S4: DMF and deionized water are mixed in a volume ratio of 9:3 to obtain a mixed solvent, 3-fluorostyrene is dissolved in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%, and N-isopropylacrylamide is dissolved in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0064] 0.145 kg of anhydrous copper bromide as a catalyst, 0.088 kg of L-ascorbic acid as a reducing agent and 15 L of a mixed solvent were added to a reactor and stirred at 25°C and 300 r / min for 15 minutes. Then, 1.27 kg of tris(2-dimethylaminoethyl)amine was added and stirred for 10 minutes. Under nitrogen protection and 15°C, 0.5 kg of grafted modified yttrium-doped zirconia nanopowder and 15 L of 3-fluorostyrene solution were added to the reactor and stirred for 3 hours. Then, 18 L of N-isopropylacrylamide solution was added and stirred for 5 hours. The mixture was centrifuged and filtered. The filter cake was washed with deionized water 5 times and vacuum dried at 50°C to constant weight to obtain bifunctional nanoparticles.

[0065] The fluorocarbon surfactants in Examples 1 to 4 were purchased from Hubei Zhongnuoyaxing Biotechnology Co., Ltd. with the brand name FC-20.

[0066] Example 5: Please refer to Figure 1-Figure 2 This embodiment provides a glass etching device for laser induction, including an etching tank 4 and an oil bath heating device. The oil bath heating device includes a magnetic stirring heater 1 and an oil bath pot 3 filled with thermal oil. The oil bath pot 3 is placed on the magnetic stirring heater 1, and the etching tank 4 is placed in the oil bath pot 3. A magnetic stirring bar 8 that can be magnetically driven by the magnetic stirring heater 1 is provided at the bottom of the etching tank 4.

[0067] The glass etching device also includes a bracket 2, which is provided with a long crossbar and a short crossbar. A motor 5 is fixed on the long crossbar. The output shaft of the motor 5 is fixed with a stirring paddle 7 extending into the etching tank 4. A temperature sensor 6 for monitoring the temperature of the heat transfer oil is fixed on the short crossbar.

[0068] During the application of the etching device, the rotation directions of the stirring paddle 7 and the magnetic stirring bar 8 can be the same or opposite, and can rotate at the same speed or at a differential speed. The following embodiment takes the stirring paddle 7 and the magnetic stirring bar 8 rotating in the same direction and at the same speed as an example.

[0069] Example 6: This example provides a method for laser-induced fluorine-free etching of glass, comprising the following steps:

[0070] Using the etching device in Example 5, the fluorine-free etching solution in Example 1 was injected into the etching tank 4, and the etching solution was heated to 50° C. using an oil bath heating device. The fluorine-free etching solution was circulated at a stirring speed of 1000 r / min. The laser-induced glass was immersed in the fluorine-free etching solution to avoid contact with the stirring paddle 7 and the magnetic stirring bar 8. The etching was carried out for 120 minutes. After cooling to room temperature, the etching was continued for 10 minutes. The glass was taken out, washed with clean water, and then vacuum-dried to complete the fluorine-free etching method.

[0071] Example 7: This example provides a method for laser-induced fluorine-free etching of glass, comprising the following steps:

[0072] Using the etching device in Example 5, the fluorine-free etching solution in Example 2 was injected into the etching tank 4, and the etching solution was heated to 60° C. using an oil bath heating device. The fluorine-free etching solution was circulated at a stirring speed of 1500 r / min. The glass after laser induction was immersed in the fluorine-free etching solution to avoid contact with the stirring paddle 7 and the magnetic stirring bar 8. The etching was carried out for 30 minutes, and the etching was continued for 15 minutes after cooling to room temperature. The glass was taken out, washed with clean water, and then vacuum-dried to complete the fluorine-free etching method.

[0073] Example 8: This example provides a method for laser-induced fluorine-free etching of glass, comprising the following steps:

[0074] Using the etching device in Example 5, the fluorine-free etching solution in Example 3 was injected into the etching tank 4, and the etching solution was heated to 60°C using an oil bath heating device. The fluorine-free etching solution was circulated at a stirring speed of 1500 r / min, and the glass after laser induction was immersed in the fluorine-free etching solution to avoid contact with the stirring paddle 7 and the magnetic stirring bar 8. The etching was carried out for 90 minutes, and the etching was continued for 15 minutes after cooling to room temperature. The glass was taken out, washed with clean water, and then vacuum-dried to complete the fluorine-free etching method.

[0075] Example 9: This example provides a method for laser-induced fluorine-free etching of glass, comprising the following steps:

[0076] Using the etching device in Example 5, the fluorine-free etching solution in Example 4 was injected into the etching tank 4, and the etching solution was heated to 70°C using an oil bath heating device. The fluorine-free etching solution was circulated at a stirring speed of 2000 r / min, and the glass after laser induction was immersed in the fluorine-free etching solution to avoid contact with the stirring paddle 7 and the magnetic stirring bar 8. The glass was etched for 60 minutes, cooled to room temperature, and then etched for another 20 minutes. The glass was taken out, washed with clean water, and then vacuum-dried to complete the fluorine-free etching method.

[0077] Comparative Example 1: Based on Example 4, 3-fluorostyrene solution was not added in step S4, and other conditions remained unchanged. Bifunctional nanoparticles were prepared, and a fluorine-free etching solution was prepared. Then, the laser-induced glass was fluorine-free etched according to the method in Example 9.

[0078] Comparative Example 2: Based on Example 4, a fluorine-free etching solution was prepared without adding bifunctional nanoparticles, and then the laser-induced glass was etched with fluorine-free etching according to the method in Example 9.

[0079] Comparative Example 3: Based on Example 9, the fluorine-free etching solution was replaced with a hydrofluoric acid solution with a mass concentration of 10%, and the other conditions remained unchanged to complete the laser-induced etching of the glass.

[0080] The substrate of the laser-induced glass used in Examples 6 to 9 and Comparative Examples 1 to 3 is a BF33 glass sheet with a thickness of 300 μm, the laser-induced power is 20 W, the energy is 150 μJ, and the laser-induced shape is a circle with a diameter of 50 μm.

[0081] The quality of the etched glasses in Examples 6 to 9 and Comparative Examples 1 to 4 was tested, and the results are shown in Table 1.

[0082] Table 1 Glass quality test results after each etching

[0083] project Through hole roundness / % Through hole diameter / μm Through hole inner wall roughness / μm Through hole taper / ° Glass thinning amount / μm Example 6 98 52.8 ＜1 0.18 23 Example 7 97 52.3 ＜1 0.34 19 Example 8 98 53.5 ＜1 0.10 34 Example 9 98 52.6 ＜1 0.15 26 Comparative Example 1 97 53.4 2.2 0.35 32 Comparative Example 2 96 52.3 2.9 0.87 23 Comparative Example 3 94 54.6 5.4 1.32 45

[0084] It can be seen from Table 1 that the stripping after etching in Examples 6 to 9 has a higher through-hole roundness, and the through-hole inner wall roughness is less than 1 μm, and the through-hole taper is smaller.

[0085] Comparative Example 3 shows that the etching speed becomes faster under hydrofluoric acid etching conditions, but the through-hole characteristics of the glass deteriorate. According to the analysis of Comparative Example 2, the polymer segments on the surface of the bifunctional nanoparticles will shrink under high-temperature etching, maintain their particle hardness, and improve the effect of mechanical grinding, while the polymer segments on the surface will swell under low-temperature etching, which can play a role in adsorption and removal of silicate fragments, thereby reducing the roughness and taper of the through-hole inner wall. The increase in the roughness of the through-hole inner wall and the through-hole taper in Comparative Example 1 may be because the bifunctional nanoparticles lack 3-fluorostyrene polymer segments, which are hydrolyzed or degraded under alkaline conditions. The stability of the bifunctional nanoparticles decreases, the cleaning function of the polymer segments is lost, and the lack of the electron-abstracting ability of the fluorophenyl group promotes the breakage of the silicon-oxygen bond of the glass, resulting in a decrease in smoothness.

[0086] It should be noted that, in this document, terms such as "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0087] While the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions, and alterations can be made to the embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for laser-induced fluorine-free etching of glass, characterized in that: The steps include: Injecting fluorine-free etching liquid into the etching tank (4), heating the etching liquid to 50-70°C using an oil bath heating device, circulating the fluorine-free etching liquid at a stirring speed of 1000-2000 r / min, immersing the laser-induced glass in the fluorine-free etching liquid for 30-120 minutes, and continuing to etch for 10-20 minutes after cooling to room temperature, taking out the glass, washing it with clean water, and then vacuum drying it to complete the fluorine-free etching method; The glass etching device comprises an etching tank (4) and an oil bath heating device, characterized in that the oil bath heating device comprises a magnetic stirring heater (1) and an oil bath pot (3) filled with heat-conducting oil, the oil bath pot (3) is placed on the magnetic stirring heater (1), the etching tank (4) is placed in the oil bath pot (3), and a magnetic stirring bar (8) that can be driven by the magnetic force of the magnetic stirring heater (1) is provided at the bottom of the etching tank (4); The glass etching device further comprises a long crossbar support (2), a motor (5) being fixed on the long crossbar, and a stirring paddle (7) extending into the interior of the etching tank (4) being fixed to the output shaft of the motor (5); The fluorine-free etching solution comprises the following components by mass percentage: Sodium hydroxide 1-50%, potassium hydroxide 0.1-10%, fluorocarbon surfactant 0.1-5%, bifunctional nanoparticles 1-5%, and the balance is water; The dual-functional nanoparticles are prepared by the following steps: Yttrium-doped zirconia nanopowder is treated with 3-aminopropyltriethoxysilane to obtain amino-modified yttrium-doped zirconia nanopowder; the amino-modified yttrium-doped zirconia nanopowder, pyridine, and toluene are added to a reaction kettle and stirred and mixed; 2-bromoisobutylimide bromide is added, and the mixture is stirred at 4-5° C. and 200-300 r / min for 50-60 minutes, and then at 20-25° C. for 10-12 hours, and the mixture is centrifuged and filtered; the precipitate is washed and dried to obtain graft-modified yttrium-doped zirconia nanopowder grafted with 2-bromoisobutylimide; Anhydrous copper bromide, L-ascorbic acid and a mixed solvent are added to a reactor, stirred at 20-25°C and 200-300 r / min for 10-15 minutes, tris(2-dimethylaminoethyl)amine is added, and stirred for 5-10 minutes. Under nitrogen protection and 10-15°C, grafted modified yttrium-doped zirconia nanopowder and 10wt% 3-fluorostyrene solution are added to the reactor, stirred for 2-3 hours, and then 27wt% N-isopropylacrylamide solution is added, stirred for 4-5 hours, and centrifuged. The filter cake is washed and dried to obtain bifunctional nanoparticles.

2. The method for laser-induced fluorine-free etching of glass according to claim 1, characterized in that: The usage ratio of the anhydrous copper bromide, L-ascorbic acid, mixed solvent, tris(2-dimethylaminoethyl)amine, modified yttrium-doped zirconium oxide nanopowder, 3-fluorostyrene solution and N-isopropylacrylamide solution is 0.14-0.145 g: 0.085-0.088 g: 15 mL: 1.22-1.27 g: 0.5 g: 14-15 mL: 15-18 mL.

3. The method for laser-induced fluorine-free etching of glass according to claim 1, characterized in that: The mixed solvent is prepared by mixing DMF and deionized water in a volume ratio of 7-9:1-3.

4. The method for laser-induced fluorine-free etching of glass according to claim 1, characterized in that: The usage ratio of the amino-modified yttrium-doped zirconium oxide nanopowder, pyridine, toluene and 2-bromoisobutyl bromide is 0.5-0.6 g: 0.3 mL: 25-30 mL: 0.2-0.24 mL.

5. The method for laser-induced fluorine-free etching of glass according to claim 1, characterized in that: The yttrium-doped zirconia nanopowder is prepared by the following steps: The precursor powder is dispersed into a 2-3 wt% precursor dispersion with deionized water and transferred to a hydrothermal reactor. The pH value is adjusted to 4 with hydrochloric acid. The hydrothermal reaction is carried out at 190-200 ° C for 2.5-3.5 hours. The mixture is cooled and centrifuged. The precipitate is washed, dried, and ground to obtain yttrium-doped zirconia nanopowder.

6. The method for laser-induced fluorine-free etching of glass according to claim 5, characterized in that: The precursor powder is prepared by the following steps: Yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water are added to a reaction kettle at 20-25°C, stirred to dissolve, and then the pH value is adjusted to 9-10 with ammonia water. The mixture is stirred at 200-300 r / min for 50-60 minutes, filtered, and the filter cake is washed, dried, and ground to obtain a precursor powder.

7. The method for laser-induced fluorine-free etching of glass according to claim 6, characterized in that: The usage ratio of the yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water is 0.46-0.77 g:12.88 g:200 mL.

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