Glass etching device for laser induction and fluoride-free etching method

Abstract

The invention discloses a glass etching device for laser induction and a fluoride-free etching method, and belongs to the technical field of glass etching.The etching device comprises an etching tank and an oil bath heating device, the etching speed can be increased by heating alkaline fluoride-free etching liquid, and the etching efficiency is improved. A composite stirring system of a magnetic stirrer and a stirring paddle can enable the fluoride-free etching liquid to circularly flow, so that the etching uniformity is improved, and the etching reaction is more favorably and stably carried out; the fluoride-free etching method adopts fluoride-free etching liquid, does not contain hydrofluoric acid, is safe and environment-friendly, and can avoid deterioration of through hole characteristics. Under the action of the fluorocarbon surfactant, the etching liquid has excellent wettability, and sodium hydroxide and potassium hydroxide in the etching liquid can perform high-selectivity etching on the glass after laser induction; the glass subjected to fluoride-free etching is high in surface smoothness and higher in through hole roundness, the surface and the inner wall of the through hole are smooth, the roughness of the inner wall of the through hole is smaller than 1 micron, the taper of the through hole is smaller, and a good etching effect is achieved.

Description

Technical Field

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

[0002] In the era of the booming development of artificial intelligence and the semiconductor integrated circuit industry, the bottleneck encountered by semiconductor technology manufacturers at home and abroad is how to increase the number of transistors on semiconductor chips that can be packaged per unit area, while also having excellent electrical performance, heat dissipation performance, low-loss function, and the ability to withstand extreme environments. As an important means to improve chip performance in the post-Moore era, three-dimensional packaging integration technology has become a research hotspot in the semiconductor industry. Therefore, using glass to make multilayer interposer boards has become the core component of three-dimensional integrated systems, playing a connecting role. Glass has low manufacturing costs and is easier to achieve larger areas and thinner thicknesses. At the same time, glass has advantages such as high strength and excellent electrical insulation performance. Therefore, it is regarded as an excellent substitute for traditional silicon-based interposer boards in the field of semiconductor packaging applications.

[0003] Currently, how to achieve efficient and high-quality glass vias is the main factor restricting the development of glass interposer board technology. Laser-induced deep etching technology (LIDE) can achieve excellent glass vias with high efficiency and low cost, becoming a research hotspot in the industry.

[0004] Glass etching has high technical requirements. It is necessary to have a high etching selectivity and good isotropy to ensure the consistency of hole characteristics after etching and the smoothness of the glass surface. The glass etching solution for laser-induced etching technology usually uses 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 angles, and low depth-to-width ratios. More importantly, hydrofluoric acid has high corrosiveness and can strongly corrode metals, glass, and silicon-containing objects. Inhaling the vapor or contacting the skin can cause incurable burns, posing a great hazard to the physical and mental health of production personnel. At the same time, it also causes serious damage to the environment.

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

[0006] The purpose of the present invention is to provide a laser-induced glass etching device and a fluoride-free etching method. The etching device can improve the uniformity of etching and is more conducive to the stable progress of the etching reaction. The fluoride-free etching method uses a fluoride-free etching solution, does not contain hydrofluoric acid, is safe and environmentally friendly, and can avoid the deterioration of via characteristics.

[0007] The object of the present invention can be achieved by the following technical solutions: A glass etching device for laser induction includes an etching tank and an oil bath heating device. The oil bath heating device includes 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 stirrer that can be magnetically driven by the magnetic stirring heater is provided at the bottom of the etching tank.

[0008] Furthermore, the glass etching device further includes a bracket. A long crossbar and a short crossbar are provided on the bracket. A motor is fixed on the long crossbar, and a stirring paddle extending into the interior of the etching tank is fixed to the output shaft of the motor. A temperature sensor for monitoring the temperature of the heat-conducting oil is fixed on the short crossbar.

[0009] A fluorine-free etching method for glass by laser induction includes the following steps: Inject the fluorine-free etching solution into the etching tank, heat the etching solution to 50 - 70 °C by using the oil bath heating device, circulate the fluorine-free etching solution at a stirring speed of 1000 - 2000 r / min, immerse the laser-induced glass in the fluorine-free etching solution for etching for 30 - 120 min, continue etching for 10 - 20 min after cooling to room temperature, take out the glass, wash it with clear water and then dry it in vacuum to complete the fluorine-free etching method.

[0010] Furthermore, the fluorine-free etching solution includes 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.

[0011] Furthermore, the fluorine-free etching solution includes the following components by mass percentage: 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.

[0012] Furthermore, the bifunctional nanoparticles are prepared by the following steps: Step 1: Treat yttrium-doped zirconia nanopowder with 3-aminopropyltriethoxysilane to obtain amino-modified yttrium-doped zirconia nanopowder; add the amino-modified yttrium-doped zirconia nanopowder, pyridine, and toluene into a reaction kettle, stir and mix them, then add 2-bromo-2-methylpropionyl bromide, stir at 4 - 5 °C and 200 - 300 r / min for 50 - 60 min, then raise the temperature to 20 - 25 °C and stir for 10 - 12 h, centrifuge and filter, wash the precipitate, and dry it to obtain graft-modified yttrium-doped zirconia nanopowder grafted with 2-bromo-2-methylpropionamide.

[0013] Step 2: Add cupric bromide anhydrous, L-ascorbic acid and the mixed solvent into the reaction kettle, stir at 20 - 25 °C and 200 - 300 r / min for 10 - 15 min, then add tris(2-dimethylaminoethyl)amine and stir for 5 - 10 min. Under the protection of nitrogen and at 10 - 15 °C, add the graft-modified yttrium-doped zirconia nanopowder and 10 wt% 3-fluorostyrene solution into the reaction kettle, stir and react for 2 - 3 h, then add 27 wt% N-isopropylacrylamide solution and stir and react for 4 - 5 h. Centrifuge and filter, wash the filter cake, dry it to obtain the bifunctional nanoparticles.

[0014] Further, in Step 1, the dosage ratio of the amino-modified yttrium-doped zirconia nanopowder, pyridine, toluene and 2-bromoisobutyryl bromide is 0.5 - 0.6 g : 0.3 mL : 25 - 30 mL : 0.2 - 0.24 mL.

[0015] Further, in Step 2, the dosage ratio of cupric bromide anhydrous, L-ascorbic acid, the mixed solvent, tris(2-dimethylaminoethyl)amine, the 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.

[0016] Further, in Step 3, the solvents of both the 3-fluorostyrene solution and the N-isopropylacrylamide solution are the mixed solvent.

[0017] Further, the mixed solvent is composed of DMF and deionized water mixed in a volume ratio of 7 - 9 : 1 - 3.

[0018] Further, the yttrium-doped zirconia nanopowder is prepared through the following steps: Add yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water into the reaction kettle at 20 - 25 °C, stir to dissolve and then adjust the pH value to 9 - 10 with ammonia water, stir and react at 200 - 300 r / min for 50 - 60 min, filter by suction, wash the filter cake, dry it, grind and refine to obtain the precursor powder.

[0019] Disperse the precursor powder with deionized water into a 2 - 3 wt% precursor dispersion liquid and transfer it to a hydrothermal reaction kettle, adjust the pH value to 4 with hydrochloric acid, carry out hydrothermal reaction at 190 - 200 °C for 2.5 - 3.5 h, cool, centrifuge and filter, wash the precipitate, dry it, grind and refine to obtain the yttrium-doped zirconia nanopowder.

[0020] Further, the dosage ratio of yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water is 0.46 - 0.77 g : 12.88 g : 200 mL.

[0021] Advantages of the present invention: 1. The structure of the glass etching device induced by laser of the present invention is simple. The etching speed can be increased by heating the alkaline fluoride-free etching solution, and the composite stirring system of the magnetic stirrer and the stirring paddle can make the fluoride-free etching solution circulate, improving the etching uniformity and being more conducive to the stable progress of the etching reaction.

[0022] 2. The fluoride-free etching method of the present invention uses a fluoride-free etching solution, which does not contain hydrofluoric acid, is safe and environmentally friendly, and can avoid the deterioration of the through-hole characteristics. Under the action of the fluorocarbon surfactant, the etching solution has excellent wettability, and sodium hydroxide and potassium hydroxide therein can perform highly selective etching on the laser-induced glass.

[0023] Under high-temperature etching, the polymer segments on the surface of the bifunctional nanoparticles will shrink, maintaining the particle hardness and enhancing the effect of mechanical grinding. Under low-temperature etching, the polymer segments on the surface of the bifunctional nanoparticles will swell, which can play roles such as adsorbing and removing silicate fragments, thereby playing an auxiliary etching role and reducing the roughness and taper of the inner wall of the through-hole. The poly(3-fluorostyrene) short chain in the bifunctional nanoparticles can improve the alkali resistance of the thermosensitive polymer long chain, enhancing its stability, and the fluorophenyl group has an electron-withdrawing ability, which can promote the cleavage of the silicon-oxygen bond and further improve the surface smoothness of the etched glass.

[0024] The glass surface after fluoride-free etching has high smoothness, higher through-hole roundness, and the surface and inner wall of the through-hole are smooth. The roughness of the inner wall of the through-hole is <1 μm, and the through-hole taper is smaller, achieving a good etching effect. Description of the drawings

[0025] Figure 1 is a schematic structural diagram of the etching device of the present invention; Figure 2 is a cross-sectional view of the etching tank and the oil bath of the present invention. Detailed implementation manners

[0026] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0027] Example 1: This example provides a fluoride-free etching solution, which includes the following components by mass percentage: Sodium hydroxide 1%, potassium hydroxide 10%, fluorocarbon surfactant 0.1%, bifunctional nanoparticles 1%, and the balance is water.

[0028] Among them, the bifunctional nanoparticles are prepared through the following steps: S1: Under the condition of 20 °C, add 0.46 kg of yttrium nitrate hexahydrate, 12.88 kg of zirconium oxychloride octahydrate and 200 L of deionized water into the reaction kettle. After stirring and dissolving, adjust the pH value to 9 with ammonia water with a concentration of 3 mol / L, stir and react at 200 r / min for 50 min, carry out suction filtration, wash the filter cake with deionized water until the last washing liquid is neutral, dry it in vacuum at 50 °C until constant weight, and grind it to obtain the precursor powder.

[0029] Disperse the precursor powder with deionized water to obtain a precursor dispersion with a mass concentration of 2%, transfer it to a hydrothermal reaction kettle, adjust the pH value to 4 with hydrochloric acid, carry out hydrothermal reaction at 190 °C for 2.5 h, cool to room temperature and then carry out centrifugal filtration. Wash the precipitate with deionized water until the last washing liquid is neutral, dry it in vacuum until constant weight, and grind it to obtain yttrium-doped zirconia nanometer powder with a tetragonal crystal form. The stability of its tetragonal crystal form can be improved by yttrium doping.

[0030] S2: Add 0.5 kg of yttrium-doped zirconia nanometer powder, 0.05 L of triethanolamine and 25 L of absolute ethanol into the reaction kettle, carry out ultrasonic dispersion for 5 min, then dissolve 0.3 kg of 3-aminopropyltriethoxysilane with 0.5 L of deionized water and add it into the reaction kettle. Adjust the pH value to 9 with ammonia water with a concentration of 3 mol / L, stir and react at 60 °C and 200 r / min for 10 h, naturally cool and then carry out centrifugal filtration. Wash the filter cake with absolute ethanol twice, dry it in vacuum until constant weight to obtain amino-modified yttrium-doped zirconia nanometer powder.

[0031] S3: Add 0.5 kg of amino-modified yttrium-doped zirconia nanometer powder, 0.3 L of pyridine and 25 L of toluene into the reaction kettle and stir to mix. Then add 0.2 L of 2-bromoisobutyryl bromide, stir at 4 °C and 200 r / min for 50 min, then raise the temperature to 20 °C and stir for 10 h, carry out centrifugal filtration, wash the precipitate with toluene twice, dry it in vacuum until constant weight to obtain graft-modified yttrium-doped zirconia nanometer powder grafted with 2-bromoisobutyramide.

[0032] S4: Mix DMF and deionized water according to a volume ratio of 7:1 to obtain a mixed solvent. Dissolve 3-fluorostyrene in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%. Dissolve N-isopropylacrylamide in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0033] 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 reaction kettle. The mixture was stirred for 10 min at 20 °C and 200 r / min, and then 1.22 kg of tris(2-dimethylaminoethyl)amine was added and stirred for 5 min. Under nitrogen protection and at 10 °C, 0.5 kg of graft-modified yttrium-doped zirconia nanopowder and 14 L of 3-fluorostyrene solution were added to the reaction kettle and stirred for 2 h. Then 15 L of N-isopropylacrylamide solution was added and stirred for 4 h. Through the reaction, short chains of poly(3-fluorostyrene) and long chains of thermosensitive polymer were successively grafted onto the graft-modified yttrium-doped zirconia nanopowder. After centrifugal filtration, the filter cake was washed 3 times with deionized water and vacuum dried at 40 °C to constant weight to obtain bifunctional nanoparticles.

[0034] Example 2: This example provides a fluorine-free etching solution, which includes the following components by mass percentage: Sodium hydroxide 50%, potassium hydroxide 0.1%, fluorocarbon surfactant 5%, bifunctional nanoparticles 5%, and the balance is water.

[0035] Among them, the bifunctional nanoparticles are prepared by the following steps: 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 reaction kettle. After stirring and dissolving, the pH value was adjusted to 9.5 with 3 mol / L ammonia water, and the mixture was stirred and reacted at 250 r / min for 55 min. After suction filtration, the filter cake was washed with deionized water until the last washing liquid was neutral, and then vacuum dried at 60 °C to constant weight and ground to obtain precursor powder.

[0036] 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 reaction kettle. The pH value was adjusted to 4 with hydrochloric acid, and the hydrothermal reaction was carried out at 195 °C for 3 h. After cooling to room temperature, centrifugal filtration was carried out. The precipitate was washed with deionized water until the last washing liquid was neutral, and then vacuum dried to constant weight and ground to obtain yttrium-doped zirconia nanopowder with a tetragonal crystal form.

[0037] S2: 0.55 kg of yttrium-doped zirconia nanopowder, 0.05 L of triethanolamine, and 27.5 L of absolute ethanol were added to a reaction kettle and ultrasonically dispersed for 7.5 min. Then 0.33 kg of 3-aminopropyltriethoxysilane was dissolved in 0.5 L of deionized water and added to the reaction kettle. The pH value was adjusted to 9.5 with 3 mol / L ammonia water, and the mixture was stirred and reacted at 65 °C and 250 r / min for 11 h. After natural cooling, centrifugal filtration was carried out. The filter cake was washed 2.5 times with absolute ethanol and vacuum dried to constant weight to obtain amino-modified yttrium-doped zirconia nanopowder.

[0038] S3: Add 0.55 kg of amino-modified yttrium-doped zirconia nanometer powder, 0.3 L of pyridine and 27.5 L of toluene into a reaction kettle, stir and mix them, then add 0.22 L of 2-bromoisobutyryl bromide, stir at 4.5 °C and 250 r / min for 55 min, then raise the temperature to 22.5 °C and stir for 11 h, centrifuge and filter, wash the precipitate with toluene for 2.5 times, and dry it in vacuum to constant weight to obtain graft-modified yttrium-doped zirconia nanometer powder grafted with 2-bromoisobutyramide.

[0039] S4: Mix DMF and deionized water according to a volume ratio of 8:2 to obtain a mixed solvent, dissolve 3-fluorostyrene in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%, and dissolve N-isopropylacrylamide in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0040] Add 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 the mixed solvent into a reaction kettle, stir at 22.5 °C and 250 r / min for 12.5 min, then add 1.245 kg of tris(2-dimethylaminoethyl)amine, stir for 7.5 min, under the protection of nitrogen and at 12.5 °C, add 0.5 kg of graft-modified yttrium-doped zirconia nanometer powder and 14.5 L of 3-fluorostyrene solution into the reaction kettle, stir and react for 2.5 h, then add 16.5 L of N-isopropylacrylamide solution, stir and react for 4.5 h, centrifuge and filter, wash the filter cake with deionized water for 4 times, and dry it in vacuum at 45 °C to constant weight to obtain bifunctional nanoparticles.

[0041] Example 3: This example provides a fluorine-free etching solution, which includes the following components by mass percentage: Sodium hydroxide 20%, potassium hydroxide 2%, fluorocarbon surfactant 0.5%, bifunctional nanoparticles 1.5%, and the balance is water.

[0042] Among them, the bifunctional nanoparticles in Example 3 are the same as those in Example 2.

[0043] Example 4: This example provides a fluorine-free etching solution, which includes the following components by mass percentage: Sodium hydroxide 30%, potassium hydroxide 5%, fluorocarbon surfactant 1.5%, bifunctional nanoparticles 2.5%, and the balance is water.

[0044] Among them, the bifunctional nanoparticles are prepared by the following steps: S1: Under the condition of 25 °C, add 0.77 kg of yttrium nitrate hexahydrate, 12.88 kg of zirconium oxychloride octahydrate and 200 L of deionized water into the reaction kettle. After stirring and dissolving, adjust the pH value to 10 with ammonia water with a concentration of 3 mol / L, stir and react at 300 r / min for 60 min, carry out suction filtration, wash the filter cake with deionized water until the last washing liquid is neutral, dry it to constant weight under vacuum at 70 °C, and grind it to obtain the precursor powder.

[0045] Disperse the precursor powder with deionized water to obtain a precursor dispersion with a mass concentration of 3%, transfer it to a hydrothermal reaction kettle, adjust the pH value to 4 with hydrochloric acid, carry out hydrothermal reaction at 200 °C for 3.5 h, cool to room temperature and then carry out centrifugal filtration. Wash the precipitate with deionized water until the last washing liquid is neutral, dry it to constant weight under vacuum, and grind it to obtain yttrium-doped zirconia nanometer powder with a tetragonal crystal form.

[0046] S2: Add 0.6 kg of yttrium-doped zirconia nanometer powder, 0.05 L of triethanolamine and 30 L of absolute ethanol into the reaction kettle, carry out ultrasonic dispersion for 10 min, then dissolve 0.36 kg of 3-aminopropyltriethoxysilane with 0.5 L of deionized water and add it into the reaction kettle. Adjust the pH value to 10 with ammonia water with a concentration of 3 mol / L, stir and react at 70 °C and 300 r / min for 12 h, naturally cool and then carry out centrifugal filtration. Wash the filter cake with absolute ethanol three times, dry it to constant weight under vacuum to obtain amino-modified yttrium-doped zirconia nanometer powder.

[0047] S3: Add 0.6 kg of amino-modified yttrium-doped zirconia nanometer powder, 0.3 L of pyridine and 30 L of toluene into the reaction kettle and stir to mix, then add 0.24 L of 2-bromoisobutyryl bromide, stir at 5 °C and 300 r / min for 60 min, then raise the temperature to 25 °C and stir for 12 h, carry out centrifugal filtration, wash the precipitate with toluene three times, dry it to constant weight under vacuum to obtain graft-modified yttrium-doped zirconia nanometer powder grafted with 2-bromoisobutyramide.

[0048] S4: Mix DMF and deionized water according to a volume ratio of 9:3 to obtain a mixed solvent. Dissolve 3-fluorostyrene in the mixed solvent to obtain a 3-fluorostyrene solution with a mass fraction of 10%. Dissolve N-isopropylacrylamide in the mixed solvent to obtain an N-isopropylacrylamide solution with a mass concentration of 27%.

[0049] Add 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 into a reaction kettle. Stir for 15 min at 25 °C and 300 r / min, then add 1.27 kg of tris(2-dimethylaminoethyl)amine and stir for 10 min. Under nitrogen protection and at 15 °C, add 0.5 kg of graft-modified yttrium-doped zirconia nanopowder and 15 L of 3-fluorostyrene solution into the reaction kettle, stir and react for 3 h, then add 18 L of N-isopropylacrylamide solution and stir and react for 5 h. Centrifuge and filter, wash the filter cake 5 times with deionized water, and vacuum dry at 50 °C to constant weight to obtain bifunctional nanoparticles.

[0050] In Examples 1-4, the fluorocarbon surfactant was purchased from Hubei Zhongnuoyaxing Biotechnology Co., Ltd., and the product number was FC-20.

[0051] Example 5: Please refer to Figure 1 - Figure 2 , this example 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 heat-conducting 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 stirrer 8 that can be magnetically driven by the magnetic stirring heater 1 is provided at the bottom of the etching tank 4.

[0052] The glass etching device further includes a bracket 2. A long crossbar and a short crossbar are provided on the bracket 2. A motor 5 is fixed on the long crossbar, a stirring paddle 7 extending into the interior of the etching tank 4 is fixed on the output shaft of the motor 5, and a temperature sensor 6 for monitoring the temperature of the heat-conducting oil is fixed on the short crossbar.

[0053] During the application of this etching device, the rotation directions of the stirring paddle 7 and the magnetic stirrer 8 can be the same or opposite, and they can rotate at the same speed or at different speeds. In the following examples, the case where the stirring paddle 7 and the magnetic stirrer 8 rotate in the same direction and at the same speed is taken as an example.

[0054] Example 6: This example provides a method for laser-induced fluoride-free glass etching, including the following steps: Use the etching device in Example 5, inject the fluoride-free etching solution in Example 1 into the etching tank 4, heat the etching solution to 50 °C by using the oil bath heating device, make the fluoride-free etching solution circulate and flow at a stirring speed of 1000 r / min, immerse the laser-induced glass into the fluoride-free etching solution, avoiding contact with the stirring paddle 7 and the magnetic stirrer 8, etch for 120 min, continue to etch for 10 min after cooling to room temperature, take out the glass, wash it with water and then vacuum dry to complete this fluoride-free etching method.

[0055] Example 7: This example provides a method for laser-induced fluoride-free glass etching, including the following steps: Using the etching device in Example 5, inject the fluoride-free etching solution in Example 2 into the etching tank 4. Heat the etching solution to 60 °C using an oil bath heating device. Circulate the fluoride-free etching solution at a stirring speed of 1500 r / min. Immerse the laser-induced glass into the fluoride-free etching solution, avoiding contact with the stirring paddle 7 and the magnetic stirrer 8. Etch for 30 min, continue etching for 15 min after cooling to room temperature, take out the glass, wash it with clear water and then dry it in vacuum to complete this fluoride-free etching method.

[0056] Example 8: This example provides a method for fluoride-free etching of laser-induced glass, including the following steps: Using the etching device in Example 5, inject the fluoride-free etching solution in Example 3 into the etching tank 4. Heat the etching solution to 60 °C using an oil bath heating device. Circulate the fluoride-free etching solution at a stirring speed of 1500 r / min. Immerse the laser-induced glass into the fluoride-free etching solution, avoiding contact with the stirring paddle 7 and the magnetic stirrer 8. Etch for 90 min, continue etching for 15 min after cooling to room temperature, take out the glass, wash it with clear water and then dry it in vacuum to complete this fluoride-free etching method.

[0057] Example 9: This example provides a method for fluoride-free etching of laser-induced glass, including the following steps: Using the etching device in Example 5, inject the fluoride-free etching solution in Example 4 into the etching tank 4. Heat the etching solution to 70 °C using an oil bath heating device. Circulate the fluoride-free etching solution at a stirring speed of 2000 r / min. Immerse the laser-induced glass into the fluoride-free etching solution, avoiding contact with the stirring paddle 7 and the magnetic stirrer 8. Etch for 60 min, continue etching for 20 min after cooling to room temperature, take out the glass, wash it with clear water and then dry it in vacuum to complete this fluoride-free etching method.

[0058] Comparative Example 1: On the basis of Example 4, do not add 3-fluorostyrene solution in step S4, and keep the other conditions unchanged. Prepare the bifunctional nanoparticles, and after formulating the fluoride-free etching solution, then perform fluoride-free etching on the laser-induced glass according to the method in Example 9.

[0059] Comparative Example 2: On the basis of Example 4, formulate the fluoride-free etching solution without adding bifunctional nanoparticles, and then perform fluoride-free etching on the laser-induced glass according to the method in Example 9.

[0060] Comparative Example 3: On the basis of Example 9, replace the fluoride-free etching solution with a 10% hydrofluoric acid solution by mass concentration, and keep the other conditions unchanged to complete the etching of the laser-induced glass.

[0061] The base material of the laser-induced glass used in Examples 6-9 and Comparative Examples 1-3 was a BF33 glass sheet with a thickness of 300 μm, the laser-induced power was 20 W, the energy was 150 μJ, and the shape of the laser-induced area was a circle with a diameter of 50 μm.

[0062] Quality inspection was carried out on the etched glass in Examples 6-9 and Comparative Examples 1-4, and the results are shown in Table 1.

[0063] Table 1 Quality inspection results of each etched glass Item Through - hole roundness / % Through - hole diameter / μm Inner wall roughness of through - hole / 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 As can be seen from Table 1, the etched peeling in Examples 6-9 has a higher through-hole roundness, the inner wall roughness of the through-hole < 1 μm, and a smaller through-hole taper.

[0064] Comparative Example 3 shows that the etching rate becomes faster under hydrofluoric acid etching conditions, but the through-hole characteristics of the glass deteriorate. Through the analysis of Comparative Example 2, the polymer segments on the surface of the bifunctional nanoparticles will shrink under high-temperature etching to 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 adsorbing and removing silicate fragments, etc., thereby reducing the inner wall roughness and taper of the through-hole. In Comparative Example 1, the inner wall roughness and through-hole taper of the through-hole increase, probably because the bifunctional nanoparticles lack the 3-fluorostyrene polymerization chain segment, and the temperature-sensitive polymer segment is hydrolyzed or degraded under alkaline conditions, the stability of the bifunctional nanoparticles decreases, the cleaning function of the polymer segment is lost, and the electron-withdrawing ability of the fluorophenyl group is lacking, and the promotion of the cleavage of the glass silicon-oxygen bond is lacking, resulting in a decrease in the smoothness.

[0065] It should be noted that in this article, terms such as "including", "comprising" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0066] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

Claims

1. A laser-induced glass etching device, comprising an etching tank (4) and an oil bath heating device, characterized in that, The oil bath heating device includes 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), 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).

2. The glass etching device for laser induction according to claim 1, wherein The glass etching device further includes a long crossbar bracket (2), and a motor (5) is fixed on the long crossbar. A stirring paddle (7) extending into the interior of the etching tank (4) is fixed to the output shaft of the motor (5).

3. A method for laser-induced fluorine-free etching of glass, characterized in that, Using the etching device described in any one of claims 1-2, the fluorine-free etching method includes the following steps: Inject the fluorine-free etching solution into the etching tank (4), heat the etching solution to 50-70 °C using the oil bath heating device, circulate the fluorine-free etching solution at a stirring speed of 1000-2000 r / min, immerse the laser-induced glass in the fluorine-free etching solution for etching for 30-120 min, continue etching for 10-20 min after cooling to room temperature, take out the glass, wash it with water and then dry it under vacuum to complete the fluorine-free etching method.

4. A fluoride-free etching method for glass induced by laser according to claim 3, characterized in that The fluorine-free etching solution includes 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.

5. A method for laser-induced fluorine-free etching of glass according to claim 4, characterized in that The bifunctional nanoparticles are prepared by the following steps: Add anhydrous copper bromide, L-ascorbic acid and a mixed solvent into a reaction kettle, stir at 20-25 °C and 200-300 r / min for 10-15 min, add tris(2-dimethylaminoethyl)amine, stir for 5-10 min, under nitrogen protection and at 10-15 °C, add the graft-modified yttrium-doped zirconia nanopowder and a 10 wt% 3-fluorostyrene solution into the reaction kettle, stir and react for 2-3 h, then add a 27 wt% N-isopropylacrylamide solution, stir and react for 4-5 h, centrifuge and filter, wash the filter cake, and dry to obtain the bifunctional nanoparticles; The dosage ratios of the anhydrous copper bromide, L-ascorbic acid, mixed solvent, tris(2-dimethylaminoethyl)amine, modified yttrium-doped zirconia nanopowder, 3-fluorostyrene solution and N-isopropylacrylamide solution are 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.

6. A method for laser-induced fluoride-free etching of glass according to claim 5, characterized in that, The mixed solvent is composed of DMF and deionized water mixed in a volume ratio of 7-9:1-3.

7. A method for laser-induced fluorine-free etching of glass according to claim 5, characterized in that, The graft-modified yttrium-doped zirconia nanopowder is prepared by the following steps: The yttrium-doped zirconia nanopowder is treated with 3-aminopropyltriethoxysilane to obtain an amino-modified yttrium-doped zirconia nanopowder; the amino-modified yttrium-doped zirconia nanopowder, pyridine and toluene are added to a reaction kettle, stirred and mixed, 2-bromo-2-methylpropionyl bromide is added, and the mixture is stirred at 4-5 °C and 200-300 r / min for 50-60 min, then stirred at 20-25 °C for 10-12 h, centrifuged and filtered, and the precipitate is washed and dried to obtain a graft-modified yttrium-doped zirconia nanopowder grafted with 2-bromo-2-methylpropionamide; The dosage ratio of the amino-modified yttrium-doped zirconia nanopowder, pyridine, toluene and 2-bromo-2-methylpropionyl bromide is 0.5-0.6 g: 0.3 mL: 25-30 mL: 0.2-0.24 mL.

8. A method for laser-induced fluorine-free etching of glass according to claim 7, characterized in that, The yttrium-doped zirconia nanopowder is prepared by the following steps: The precursor powder is dispersed in deionized water into a 2-3 wt% precursor dispersion and transferred to a hydrothermal reaction kettle, the pH value is adjusted to 4 with hydrochloric acid, and the hydrothermal reaction is carried out at 190-200 °C for 2.5-3.5 h, cooled, centrifuged and filtered, and the precipitate is washed, dried and ground to obtain the yttrium-doped zirconia nanopowder.

9. A method for laser-induced fluoride-free etching of glass according to claim 8, characterized in that, The precursor powder is prepared by the following steps: At 20-25 °C, yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water are added to a reaction kettle, stirred and dissolved, and then the pH value is adjusted to 9-10 with ammonia water, stirred and reacted at 200-300 r / min for 50-60 min, filtered by suction, and the filter cake is washed, dried and ground to obtain the precursor powder.

10. A method for laser-induced fluoride-free etching of glass according to claim 9, characterized in that, The dosage ratio of yttrium nitrate hexahydrate, zirconium oxychloride octahydrate and deionized water is 0.46-0.77 g: 12.88 g: 200 mL.

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