Micro-nano bubble assisted glass through hole processing method and system

Abstract

The invention provides a micro-nano bubble assisted glass through hole processing method and system, and the method comprises the steps: carrying out laser-induced modification treatment on a glass substrate, forming a modification area with a preset path in the glass substrate, and obtaining a to-be-processed glass substrate; performing micro-nano bubble auxiliary infiltration pretreatment on the modified area of the to-be-processed glass substrate in an infiltration solution containing micro-nano bubbles to obtain a pre-infiltrated glass substrate; in a corrosive liquid containing micro-nano bubbles, the micro-nano bubbles are used for assisting in corroding and pre-wetting the glass substrate, and the glass substrate with the through holes is obtained. In the process of chemically etching the glass through hole, the micro-nano bubbles are introduced into the pre-infiltration solution and the corrosive liquid respectively, so that a targeted improvement effect can be exerted according to the characteristics of the corrosive liquid, and accurate optimization of different corrosion requirements in the glass through hole processing is realized.

Description

Technical Field

[0001] This invention belongs to the field of glass substrate processing technology, specifically relating to a method and system for processing glass through holes using micro-nano bubbles. Background Technology

[0002] In the field of modern electronic packaging, through-glass via (TGV) technology is playing an increasingly important role as a key technology for realizing three-dimensional circuit interconnection. As electronic products continue to evolve towards miniaturization and high performance, traditional two-dimensional circuit board designs can no longer meet the challenges of higher performance requirements and smaller space constraints. Against this backdrop, TGV technology emerged, allowing electronic signals to be transmitted perpendicular to the planar circuit board direction, breaking through the limitations of traditional two-dimensional layouts and greatly improving the performance and packaging density of electronic devices. After years of development, the performance of TGV technology has gradually improved, and it is now widely used in sensors, central processing units (CPUs), graphics processing units (GPUs), artificial intelligence (AI) chips, display panels, medical devices, and advanced semiconductor packaging. For example, in 2.5D semiconductor packaging applications, TGV, as an intermediate layer, enables denser electrical interconnections, supporting the transmission of more signals within a limited space. In the implementation of TGV technology, the fabrication of vias on glass substrates is crucial. Currently, the method of laser-induced surface modification followed by chemical etching has attracted much attention. This method first uses a laser to induce surface modification of the glass, forming specific channels, and then uses chemical etching to amplify these channels, thereby forming the desired vias. Currently, chemical etching mainly uses two types of etching solutions: acidic and alkaline. These two etching solutions have different etching effects, each with its own advantages and disadvantages. In acidic etching solutions (represented by hydrofluoric acid or fluoride-containing solutions), the etching rate is relatively fast. However, during the etching process, insoluble products such as fluorosilicic acid formed by fluoride ions and glass easily adhere to the inner wall of the via, hindering the uniform distribution and circulation of the etching solution within the via, thus causing a significant difference in the etching rate. At the via exit point, because the etching solution can flow in and out relatively smoothly, the renewal efficiency is high, and the etching reaction can continue at a high speed, resulting in a continuous and rapid increase in the orifice diameter. Conversely, in the waist region of the through-hole, insoluble products accumulate in large quantities, forming a barrier-like structure that significantly hinders the deep penetration of the corrosive solution, resulting in a substantial reduction in the corrosion rate. Over time, the resulting through-hole exhibits a typical trumpet-shaped appearance with a wide opening and a narrow waist, which is detrimental to subsequent glass processing. Furthermore, the adhesion of insoluble substances and uneven localized corrosion on the hole wall lead to significantly higher roughness, resulting in a jagged appearance at the microscopic level and severely affecting the consistency of the overall morphology of the through-hole. While a more ideal through-hole can be obtained in alkaline solutions, the corrosion rate is extremely slow, greatly increasing production time and costs, severely impacting production efficiency, and posing significant limitations for large-scale production. Summary of the Invention

[0003] In view of the above-mentioned defects or improvement needs of the existing technology, the present invention proposes a glass through-hole processing method and system using micro-nano bubbles as an aid.

[0004] To achieve the above objectives, according to one aspect of the present invention, a method for fabricating glass through-holes using micro / nano bubbles is provided, comprising: Laser-induced modification treatment is performed on a glass substrate to form a modification region with a preset path inside the glass substrate, thereby obtaining a glass substrate to be processed. In an impregnation solution containing micro-nano bubbles, the modified area of ​​the glass substrate to be processed is subjected to micro-nano bubble-assisted impregnation pretreatment to obtain a pre-impregnated glass substrate. In an etching solution containing micro- and nano-bubbles, a pre-wetted glass substrate is etched using the assistance of micro- and nano-bubbles to obtain a glass substrate with through holes.

[0005] According to the above scheme, the infiltration pretreatment specifically includes: The glass substrate to be processed is placed in an immersion solution containing micro-nano bubbles and kept for a first preset time to allow the immersion solution to fully fill the nano gaps in the modified region.

[0006] According to the above scheme, the wetting solution is deionized water or an aqueous solution containing 0.1%-5% surfactant; and / or, the first preset time is 1-45 minutes.

[0007] According to the above scheme, the etching solution is an acidic etching solution containing 5%-30% by volume of micro-nano bubbles, which helps to enhance the penetration ability of the acidic etching solution in the modified area and remove the corrosion products at the site where the through hole is to be formed.

[0008] According to the above scheme, the acidic corrosion solution is a mixed solution of hydrofluoric acid; wherein, the mass fraction of hydrofluoric acid is 0.1%-20%, the volume percentage of fluoride additive is 2%-20%, and the remainder is water.

[0009] According to the above scheme, the corrosive liquid is an alkaline corrosive liquid. The material exchange between the glass and the alkaline corrosive liquid is strengthened by micro-nano bubbles, thereby increasing the contact area for the corrosion reaction. The corrosion rate curve is preset based on the thickness of the glass substrate, and the preset corrosion rate is maintained by adjusting the content of micro-nano bubbles in the etching solution.

[0010] According to the above scheme, the alkaline corrosive solution is a strong alkali solution, which includes a strong alkali with a mass concentration of 15%-35%, a complexing agent with a mass concentration of 2%-20%, and the remainder is water.

[0011] According to the above scheme, the diameter range of micro-nano bubbles is 10nm-100μm.

[0012] According to the above scheme, micro-nano bubbles are obtained by pressure dissolution and ultrasonic cavitation generation, wherein the pressure is adjusted in the range of 0.2-0.6MPa and the ultrasonic frequency is 20-200kHz.

[0013] According to a second aspect of the present invention, a glass through-hole processing system assisted by micro / nano bubbles is provided, comprising: The laser-induced modification unit is used to perform laser-induced modification treatment on the glass substrate, forming a modification area with a preset path inside the glass substrate to obtain the glass substrate to be processed. Micro / nano bubble generation unit, used to generate micro / nano bubbles; The pre-wetting unit is used to perform micro-nano bubble-assisted wetting pretreatment on the modified area of ​​the glass substrate to be processed in a wetting solution containing micro-nano bubbles, so as to obtain a pre-wetted glass substrate. The etching unit is used to etch a pre-wetted glass substrate in an etching solution containing micro- and nano-bubbles, thereby obtaining a glass substrate with through holes.

[0014] According to a third aspect of the present invention, a glass substrate is provided having glass through-holes, the glass through-holes being processed by the glass through-hole processing method assisted by micro-nano bubbles.

[0015] In summary, compared with the prior art, the above-described technical solutions conceived by this invention can achieve the following beneficial effects: 1. In the process of chemically etching glass through holes, micro-nano bubbles are introduced into the wetting solution and the etching solution respectively. This can play a targeted improvement role in the characteristics of the etching solution, realize the precise optimization of different etching requirements in glass through hole processing, and provide a more flexible and efficient technical solution for glass through hole processing.

[0016] 2. In acidic etching solutions, micro- and nano-bubbles enhance the penetration of the etching solution in the modified area and promptly remove local corrosion products, effectively solving the problem of blocked pores and incomplete penetration that is common in traditional acidic etching, thus significantly improving the pore formation rate. In alkaline etching solutions, micro- and nano-bubbles enhance the material exchange at the solid-liquid interface and increase the contact area of ​​the corrosion reaction, thereby greatly increasing the rate of alkaline etching and shortening the processing cycle.

[0017] 3. During the etching process of alkaline etching solution, the content of micro-nano bubbles in the etching solution is adjusted in real time to maintain the preset etching rate and thus control the degree of etching; the preset etching rate is preset according to the thickness of the glass substrate. Attached Figure Description

[0018] Figure 1 This is a flowchart of a method provided in an embodiment of the present invention.

[0019] Figure 2 This is a schematic diagram of a corrosion state provided in an embodiment of the present invention.

[0020] In the figure: 100 - etching solution; 200 - pre-wetted glass substrate; 300 - micro / nano bubbles. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0022] In the description of this invention, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified. In the description of this application, it should be noted that, unless otherwise specified and limited, the term "micro-nanobubble" refers to tiny bubbles with a diameter of less than 100 μm, which are further divided into microbubbles with a diameter of 1-100 μm and nanobubbles with a diameter of less than 1 μm. They possess characteristics such as large specific surface area, high surface charge, and strong mass transfer efficiency, and exhibit unique motion patterns. Ordinary bubbles (with a diameter greater than 100 μm) are typically elliptical, rising in water in a zigzag or spiral motion, bursting upon contact with the water surface and dissolving into the atmosphere. In contrast, micro-nanobubbles rise more slowly, remain stable in water for a longer period, have a larger specific surface area, and carry a negative surface charge, enabling them to adsorb colloidal particles, chemicals, oils, etc., from the water.

[0023] In the description of this application, it should be noted that, unless otherwise specified and limited, the term "through-hole penetration rate" refers to the ratio of the number of through-holes that completely penetrate the glass substrate to the total number of through-holes processed on the glass substrate. "Etching rate improvement ratio" refers to the reciprocal of the etching time ratio of the micro / nano bubble-assisted process to the conventional process. "Waist-to-hole ratio" refers to the ratio of the narrowest point of the through-hole to the widest point of the through-hole. Taper is the angle (usually acute) formed between the radial cross-section of the through-hole and the sidewall.

[0024] In the glass through-hole processing technology combining laser-induced modification and chemical etching, acidic etching solutions easily form funnel-shaped through-holes due to the adhesion of corrosion products, while alkaline etching solutions suffer from efficiency limitations due to slow reaction rates. This application addresses these shortcomings by introducing micro-nano bubbles to assist etching, specifically optimizing the core defects of both etching systems: in the acidic system, micro-nano bubbles are used to agitate and remove corrosion product blockages, while in the alkaline system, micro-nano bubbles enhance mass transfer and increase the rate, achieving precise control over through-hole morphology and processing efficiency. To achieve the aforementioned technical effects, one aspect of this application provides a method for processing glass through-holes using micro / nano bubbles as an aid, such as... Figure 1 As shown, it includes the following steps: S1. Laser-induced modification treatment is performed on the glass substrate to form a modification area with a preset path inside the glass substrate, thereby obtaining the glass substrate to be processed.

[0025] During through-hole processing, a laser-modified carrier, namely a laser-treated glass substrate, is first prepared. The glass substrate can be made of materials such as quartz glass, high borosilicate glass, or alkali-free borosilicate glass, as long as the morphology of the through-hole can be controlled by this method. The formation mechanism of the modified region on the glass substrate is as follows: The surface of the glass substrate is irradiated with an infrared laser (e.g., a wavelength of 1030 nm), with a laser power set to 5-30 W and a pulse repetition frequency of 10 Hz-300 kHz. After the laser energy is absorbed by the irradiated area, the Si-O bonds inside the glass break and recombine, forming a silicon-rich modified region. This is accompanied by the generation of nanoscale gaps (50-500 nm in width), which constitute the preferential reaction area for subsequent corrosion. The three-dimensional distribution of the modified region is consistent with the laser scanning path, providing a preset path for through-hole processing.

[0026] S2. In an impregnation solution containing micro-nano bubbles, the modified area of ​​the glass substrate to be processed is subjected to micro-nano bubble-assisted impregnation pretreatment to obtain a pre-impregnated glass substrate.

[0027] A micro / nano bubble-assisted wetting pretreatment is performed on the laser-modified glass substrate. Specifically, the glass substrate is placed in an impregnation solution containing micro / nano bubbles for a predetermined time. Utilizing the interfacial activity and permeability of the micro / nano bubbles, the impregnation solution fully fills the nano-gap in the modified area. The pretreated glass substrate forms a uniform liquid adhesion layer in the modified area, laying the foundation for the rapid diffusion of the subsequent etching solution.

[0028] In this embodiment, the wetting solution is deionized water or an aqueous solution containing 0.1%-5% surfactant to enhance the stability of the micro / nano bubbles. Optionally, the surfactant is anionic surfactant (e.g., sodium dodecyl sulfate, sodium dodecylbenzene sulfonate) or nonionic surfactant (e.g., fatty alcohol polyoxyethylene ether).

[0029] The initial preset duration is 1-45 minutes, preferably 5-20 minutes. The temperature of the wetting solution is maintained at 25-40℃, and the micro-nano bubbles are evenly distributed by a stirring device. S3. In an etching solution containing micro-nano bubbles, the pre-wetted glass substrate is etched with the assistance of micro-nano bubbles to obtain a glass substrate with through holes.

[0030] The modified area of ​​the pre-wetted glass substrate has formed a uniform wetting layer, which is conducive to the rapid diffusion of the subsequent etching solution. With the assistance of micro-nano bubbles, efficient forming of through holes can be achieved: in acidic systems, corrosion products are removed with the help of micro-nano bubbles; in alkaline systems, mass transfer is enhanced by micro-nano bubbles, and through holes that meet the morphology requirements are finally obtained.

[0031] The micro- and nanobubbles, ranging in diameter from 10 nm to 100 μm, are obtained using a pressure dissolution and ultrasonic cavitation generator. The applied pressure is adjusted within the range of 0.2–0.6 MPa, and the ultrasonic frequency is 20–200 kHz. Specifically, the micro- and nanobubbles are generated in an immersion solution or corrosive solution using a pressure dissolution and ultrasonic cavitation generator.

[0032] It is understood that the micro- and nano-bubbles in the wetting solution and the etching solution can all be nano-bubbles, all be micro-bubbles, or include both micro-bubbles and nano-bubbles. Preferably, the micro- and nano-bubbles in the wetting solution and the etching solution include both micro-bubbles and nano-bubbles.

[0033] The specific processes for the two corrosion systems will be explained in detail below, depending on the choice of corrosion system.

[0034] Option 1: The corrosive solution is an acidic corrosive solution.

[0035] In some embodiments, the acidic etching solution may be a fluorine-containing acidic etching solution. Specifically, the acidic etching solution is a hydrofluoric acid-based mixed solution, comprising 0.1%-20% hydrofluoric acid by mass, 2%-20% fluoride, and the remainder being water (i.e., water is the solvent). The fluoride includes, but is not limited to, ammonium fluoride, ammonium hydrogen fluoride, etc.

[0036] At a first temperature, an acidic etching solution is used to etch the modified area of ​​the pre-wetted glass substrate. The acidic etching solution contains 5%-30% by volume of micro / nano bubbles to enhance its penetration into the modified area and remove corrosion products from the areas where through-holes are to be formed. The first temperature is 0℃-60℃. Preferably, the first temperature is 10℃-40℃.

[0037] In acidic corrosion systems, the action time of micro- and nano-bubbles is synchronized with the corrosion time.

[0038] Option 2: The corrosive solution is an alkaline corrosive solution.

[0039] In some possible embodiments of this scheme, the alkaline corrosive solution is a strong alkali solution, comprising a strong alkali with a mass concentration of 15%-35%, a complexing agent with a mass concentration of 2%-20%, and the remainder being water (i.e., the solvent is water). The strong alkali includes one or more of potassium hydroxide, sodium hydroxide, barium hydroxide, lithium hydroxide, calcium hydroxide, tetramethylammonium hydroxide, or quaternary ammonium bases; the complexing agent includes one or more of organic amines (such as triethanolamine), hydroxycarboxylic acids (such as sodium tartrate), organophosphonic acid complexing agents (such as sodium ethylenediaminetetramethylidene phosphate), and aminocarboxylic acids (such as ethylenediaminetetraacetic acid). Preferably, the strong alkali is sodium hydroxide, and the complexing agent is ethylenediaminetetraacetic acid.

[0040] At a second temperature, an alkaline etching solution is used to etch the modified area of ​​the pre-wetted glass substrate. Micro-nano bubbles enhance the material exchange at the interface between the glass and the alkaline etching solution, increasing the contact area for the etching reaction. The second temperature is 40℃-200℃. Preferably, the second temperature is 60℃-160℃.

[0041] In alkaline etching systems, micro-nano bubbles can be introduced into the alkaline etching solution 5-10 minutes before etching to activate the substrate, and then the pre-wetted glass substrate can be placed into the etching solution containing micro-nano bubbles.

[0042] The preset corrosion rate is maintained by adjusting the content of micro-nano bubbles in the etching solution according to the thickness of the glass substrate (e.g., the preset corrosion rate for a glass substrate with a thickness of 1 mm is 15-20 μm / h, and the preset corrosion rate for a glass substrate with a thickness of 0.5 mm is 10-15 μm / h).

[0043] According to a second aspect of the present invention, a glass through-hole processing system assisted by micro / nano bubbles is provided, comprising: The laser-induced modification unit is used to perform laser-induced modification treatment on the glass substrate, forming a modification area with a preset path inside the glass substrate to obtain the glass substrate to be processed.

[0044] Micro / nano bubble generation unit, used to generate micro / nano bubbles.

[0045] The pre-wetting unit is used to perform micro-nano bubble-assisted wetting pretreatment on the modified area of ​​the glass substrate to be processed in a wetting solution containing micro-nano bubbles, so as to obtain a pre-wetted glass substrate.

[0046] The etching unit is used to etch a pre-wetted glass substrate in an etching solution containing micro- and nano-bubbles, utilizing the micro- and nano-bubbles to assist in etching, thereby obtaining a glass substrate with through holes. For example... Figure 2 As shown, the pre-wetted glass substrate 200 is placed in a corrosion-resistant reaction tank and immersed in an etching solution 100 containing micro-nano bubbles 300. After etching for a certain period of time, it is removed.

[0047] According to a third aspect of the present invention, a glass substrate is provided having glass through-holes, which are processed by the aforementioned glass through-hole processing method assisted by micro / nano bubbles. The glass substrate processed using an acidic etching system has a through-hole throughput ≥95% and a through-hole diameter deviation of -4μm to 4μm; the glass substrate processed using an alkaline etching system exhibits an etching rate improvement of ≥30% for its through-holes. The following describes in detail a micropore fabrication method provided in this application with reference to various embodiments.

[0048] Example 1 Alkali-free borosilicate glass was used as the glass substrate, and the area of ​​the glass substrate to be formed with through holes was laser modified to obtain the glass substrate to be processed. Ultrasonic cleaning is performed on the glass substrate to be processed. The cleaned glass substrate to be processed is placed in an impregnation solution containing micro-nano bubbles, wherein the impregnation solution includes sodium dodecylbenzenesulfonate with a mass fraction of 2% and kept for 15 minutes to obtain a pre-wetted glass substrate. The pre-wetted glass substrate is placed in an acidic etching solution containing micro- and nano-bubbles and etched at 25°C for approximately 1-3 hours. Specifically, the acidic etching solution comprises 6% hydrofluoric acid and 3% ammonium fluoride by mass. During the generation of micro- and nano-bubbles in the acidic etching solution, compressed air or nitrogen is introduced into the micro- and nano-bubble generation unit. The diameter of the micro- and nano-bubbles is stabilized at 10 nm-100 μm, and the volume fraction of the micro- and nano-bubbles is 5%-30%. The micro- and nano-bubbles uniformly surround the surface of the pre-wetted glass substrate. Remove the glass substrate and ultrasonically clean it with deionized water for 5-10 minutes to remove residual fluoride.

[0049] The parameters for Example 1 are detailed in Table 1. Furthermore, Table 1 also shows the parameters for Examples 2 to 8. It should be understood that the sequence of steps in Examples 2 to 8 can be referenced from Example 1.

[0050] Table 1

[0051] Comparative Example 1 Alkali-free borosilicate glass was used as the glass substrate, and the area of ​​the glass substrate to be formed with through holes was laser modified to obtain the glass substrate to be processed. Ultrasonic cleaning is performed on the glass substrate to be processed. The cleaned glass substrate to be processed is placed in an immersion solution, which includes 2% sodium dodecylbenzenesulfonate by mass, and kept for 15 minutes to obtain a pre-wetted glass substrate. The pre-wetted glass substrate is immersed in an acidic etching solution and etched at 25°C for approximately 1-5 hours. The acidic etching solution comprises 6% hydrofluoric acid and 3% ammonium fluoride by mass. Remove the glass substrate and ultrasonically clean it with deionized water for 5-10 minutes to remove residual fluoride.

[0052] Table 2

[0053] Table 2 shows the performance parameters and corrosion time of the final glass through-holes formed in the above eight embodiments and Comparative Example 1.

[0054] As shown in Table 2, the taper and waist-to-hole ratio of the through holes obtained in Examples 1-8 are superior to those obtained in Comparative Example 1. This demonstrates that when using an acidic etching solution, introducing micro / nano bubbles during the wetting and etching process can effectively improve the taper and waist-to-hole ratio of the through holes, significantly improving the through hole forming quality. Furthermore, introducing micro / nano bubbles during the wetting and etching process can also significantly shorten the etching time and improve processing efficiency.

[0055] Examples 1-3 compared different pre-impregnation times. The experiments showed that as the impregnation time increased, the taper and waist-to-hole ratio of the through-hole exhibited a trend of "first increasing and then decreasing", with 15 minutes being the optimal impregnation time.

[0056] Examples 1, 4, and 5 compared the effects of different bubble sizes in the etching solution. The experiments showed that when 0.01-1μm nanobubbles were the dominant system, although the taper and waist-to-hole ratio of the through-holes were good, the etching time was short and the etching rate was too fast, resulting in poor consistency of the through-holes. When 10-100μm microbubbles were the dominant system, the waist-to-hole ratio and taper were poor, and the etching time was long. However, when 10nm-100μm micro-nanobubbles (microbubbles and nanobubbles coexisting) were the dominant system, the taper and waist-to-hole ratio of the through-holes were good, and the etching time was more suitable, resulting in through-holes with better consistency.

[0057] Examples 6-8 used different glass materials, and all of them could achieve the purpose of improving the taper and waist-hole ratio under the micro-nano bubble-assisted glass through-hole processing method of this application, and could also effectively shorten the etching time.

[0058] Example 9 Alkali-free borosilicate glass was used as the glass substrate, and the area of ​​the glass substrate to be formed with through holes was laser modified to obtain the glass substrate to be processed. Ultrasonic cleaning is performed on the glass substrate to be processed. The cleaned glass substrate to be processed is placed in an impregnation solution containing micro-nano bubbles, wherein the impregnation solution includes sodium dodecylbenzenesulfonate with a mass fraction of 2% and kept for 15 minutes to obtain a pre-wetted glass substrate. The pre-wetted glass substrate is placed in an alkaline etching solution containing micro / nano bubbles and etched at 30-70℃ for approximately 30-150 minutes (a water bath can be used to maintain a stable etching temperature). The alkaline etching solution comprises 15%-35% sodium hydroxide (by mass), 2%-10% ethylenediaminetetraacetic acid (EDTA) as a complexing agent, and the remainder is deionized water. The specific process involves injecting the alkaline etching solution into the reaction tank of the etching unit, activating the micro / nano bubble generation unit, and introducing an inert gas to control the diameter of the micro / nano bubbles at 500nm-1μm and the density at 1×10⁻⁶.5 -5×10 6 The volume ratio of micro-nano bubbles to etching solution is 1:4-1:15. After generating micro-nano bubbles in alkaline etching solution, maintain for 5-10 minutes to activate the etching solution with micro-nano bubbles. Then, place the pre-wetted glass substrate into the reaction tank for etching. During the etching process, maintain the micro-nano bubble generation frequency at 5-50kHz. Remove the glass substrate, rinse it with deionized water to remove residual alkali, and perform neutralization treatment if necessary.

[0059] The parameters for Example 9 are detailed in Table 3. Furthermore, Table 3 also shows the parameters for Examples 10 to 16. It should be understood that the sequence of steps in Examples 10 to 16 can be referenced to that in Example 9.

[0060] Table 3

[0061] Comparative Example 2 Alkali-free borosilicate glass was used as the glass substrate, and the area of ​​the glass substrate to be formed with through holes was laser modified to obtain the glass substrate to be processed. Ultrasonic cleaning is performed on the glass substrate to be processed. The cleaned glass substrate to be processed is placed in an immersion solution, which includes 2% sodium dodecylbenzenesulfonate by mass, and kept for 15 minutes to obtain a pre-wetted glass substrate. The pre-wetted glass substrate is placed in an alkaline etching solution and etched at 30-70℃ for approximately 30-150 minutes (a water bath can be used to maintain a stable etching temperature). The alkaline etching solution comprises 15%-35% sodium hydroxide by mass, 2%-10% ethylenediaminetetraacetic acid (EDTA) as a complexing agent, and the remainder is deionized water. Remove the glass substrate and rinse it with deionized water to remove any residual alkaline solution.

[0062] Table 4

[0063] Table 4 shows the performance parameters and corrosion rates of the glass through-holes finally formed in Examples 9-16 and Comparative Example 2.

[0064] As shown in Table 4, the taper and waist-to-hole ratio of the through holes obtained in Examples 9-16 are superior to those obtained in Comparative Example 2. This demonstrates that when using an alkaline etching solution, introducing micro-nano bubbles during the wetting and etching process can effectively improve the taper and waist-to-hole ratio of the through holes, significantly improving the through hole forming quality. Furthermore, introducing micro-nano bubbles during the wetting and etching process can also significantly increase the etching rate and improve processing efficiency.

[0065] Examples 9-11 compared different pre-wetting times. The experiments showed that as the wetting time increased, the taper, the waist-hole ratio, and the corrosion rate first increased and then decreased, with 15 minutes being the optimal wetting time.

[0066] Examples 9, 12, and 13 compared the effect of bubble size in alkaline etching solutions. The results showed that when 0.01-0.5 μm nanobubbles were the dominant system, the corrosion rate was fast but the waist-to-hole ratio and taper were poor. When 10-100 μm microbubbles were the dominant system, the waist-to-hole ratio, taper, and corrosion rate were all unsatisfactory. When 10 nm-100 μm micro-nanobubbles (coexistence of micro-bubbles and nanobubbles) were the dominant system, the taper and waist-to-hole ratio of the through holes were good, and the corrosion rate was also good.

[0067] Examples 14-16 used different glass materials, and all of them could achieve the purpose of increasing the taper and waist-hole ratio under the micro-nano bubble-assisted glass through-hole processing method of this application, and could also effectively improve the corrosion rate.

[0068] It should be noted that both acidic and alkaline corrosive solutions can be fed through the micro-nano bubble generation unit using a circulating pump, forming a mixed flow of "micro-nano bubbles + corrosive solution" to improve mass transfer efficiency.

[0069] It should be noted that, depending on the implementation needs, the various steps / components described in this application can be broken down into more steps / components, or two or more steps / components or parts of the operation of steps / components can be combined into new steps / components to achieve the purpose of this invention.

[0070] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for glass via processing assisted by micro-nano bubbles, characterized in that: The method comprises the following steps: A laser-induced modification treatment is performed on a glass substrate to form a modification region with a preset path inside the glass substrate, thereby obtaining a glass substrate to be processed; A micro-nano bubble assisted immersion pretreatment is performed on the modification region of the glass substrate to be processed in a immersion liquid containing micro-nano bubbles, thereby obtaining a pre-immersed glass substrate; A micro-nano bubble assisted etching pretreatment is performed on the pre-immersed glass substrate in an etching liquid containing micro-nano bubbles, thereby obtaining a glass substrate with a through hole.

2. The glass via fabrication method of claim 1, wherein: The immersion pretreatment specifically comprises: The glass substrate to be processed is placed in the immersion liquid containing micro-nano bubbles, and the immersion liquid is allowed to fully fill the nano gap of the modification region for a first preset time period.

3. The glass via fabrication method of claim 2, wherein: The immersion liquid is deionized water or an aqueous solution containing 0.1%-5% surfactant; and / or, the first preset time period is 1-45 minutes.

4. The glass via fabrication method of any of claims 1-3, wherein: The etching liquid is an acidic etching liquid containing 5%-30% by volume of micro-nano bubbles, which can assist in enhancing the penetration ability of the acidic etching liquid in the modification region and removing the etching products at the position where the through hole is to be formed.

5. The glass via fabrication method of claim 4, wherein: The acidic etching liquid is a hydrofluoric acid-based mixed solution, wherein the mass fraction of hydrofluoric acid is 0.1%-20%, the mass fraction of fluoride additive is 2%-20%, and the rest is water.

6. The glass via fabrication method of any of claims 1-3, wherein: The etching liquid is an alkaline etching liquid, which can strengthen the material exchange between the glass and the alkaline etching liquid through micro-nano bubbles, thereby increasing the contact area of the etching reaction. The etching rate curve is preset according to the thickness of the glass substrate, and the content of micro-nano bubbles in the etching liquid is adjusted to maintain the preset etching rate.

7. The glass via fabrication method of claim 6, wherein: The alkaline etching liquid is a strong alkali solution, which comprises a strong alkali with a mass concentration of 15%-35%, a complexing agent with a mass concentration of 2%-20%, and the rest is water.

8. The glass via fabrication method of claim 1, wherein: The diameter of the micro-nano bubbles ranges from 10 nm to 100 μm.

9. The glass via fabrication method of claim 1, wherein: The micro-nano bubbles are generated by a pressurized dissolution and ultrasonic cavitation device, wherein the added pressure is adjusted to a range of 0.2-0.6 MPa, and the ultrasonic frequency is 20-200 kHz.

10. A glass via processing system assisted by micro-nano bubbles, characterized in that: The method comprises the following steps: A laser-induced modification unit is used to perform a laser-induced modification treatment on a glass substrate to form a modification region with a preset path inside the glass substrate, thereby obtaining a glass substrate to be processed; A micro-nano bubble generating unit is used to generate micro-nano bubbles; A pre-immersion unit is used to perform a micro-nano bubble assisted immersion pretreatment on the modification region of the glass substrate to be processed in a immersion liquid containing micro-nano bubbles, thereby obtaining a pre-immersed glass substrate; An etching unit is used to perform a micro-nano bubble assisted etching pretreatment on the pre-immersed glass substrate in an etching liquid containing micro-nano bubbles, thereby obtaining a glass substrate with a through hole.

11. A glass substrate, characterized by: The glass substrate with a through hole is processed by the method for processing a glass through hole assisted by micro-nano bubbles according to any one of claims 1-9.

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