TGV through hole etching solution and application thereof

Abstract

The invention discloses a TGV through hole etching solution and application thereof, and belongs to the technical field of TGV through hole etching. The TGV through hole etching liquid comprises the following components in percentage by mass: 12-18% of sodium hydroxide and / or potassium hydroxide, 4-10% of D-sodium gluconate, 1-2% of alkyl glycoside, 1-2% of sodium polyacrylate and the balance of water. According to the invention, the laser is adopted to punch the glass; and putting the glass subjected to laser drilling treatment into an etching solution, and carrying out etching processing. The TGV through hole etching liquid does not contain highly toxic hydrofluoric acid, and the etching rate is constant; the TGV through hole has good waist diameter ratio and good long-term use effect, can be etched to obtain a good TGV through hole, and saves the production cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of TGV via etching, and particularly relates to a TGV via etching solution and application thereof. BACKGROUND

[0002] With the development of semiconductor technology, glass substrates are increasingly applied in the fields of display and packaging. Glass substrate via technology can realize vertical interconnection, expand the integration technology to three-dimensional space, and significantly improve the space utilization, and has cost and performance advantages. Glass substrate via processing is a difficulty in process and manufacturing.

[0003] The laser-induced etching method can form a via by modifying glass through a pulsed laser and then selectively etching the via with an etching solution, and has the advantages of low cost and high efficiency, and has a large-scale application prospect. Currently, liquid hydrofluoric acid is generally used to etch the via, and the molecular weight of hydrofluoric acid is small, and it can easily penetrate, and the harm to the human body is even greater than that of mixed acid such as hydrochloric acid and sulfuric acid.

[0004] With the tightening of environmental regulations, HF acid etching glass is gradually abandoned due to its toxicity and strong corrosiveness. Generally, alkaline etching solution is often used for surface polishing or recess etching.

[0005] The applicant optimized the formula of the alkaline etching solution in the early stage, and can realize uniform etching rate and good waist diameter ratio, but the applicant found that the long-term use effect of the alkaline etching solution is not good, and the etching effect becomes poor and the rate becomes slow after long-term use. SUMMARY

[0006] In order to overcome the shortcomings of the prior art, the application provides a TGV via etching solution and application thereof.

[0007] The applicant used an alkaline concentration ratio in the middle in the early stage by improving the adding method, ensured the uniform etching rate, and slowly etched to obtain a TGV via etching solution with uniform etching rate and good waist diameter ratio, but the long-term use effect of the alkaline etching solution is not good; the application further adds sodium polyacrylate to significantly improve the long-term use effect of the TGV via etching solution, and the etching effect is still good and the rate does not become slow after long-term use, and the waist diameter ratio is further improved, which has significant economic value in actual production.

[0008] The technical scheme adopted by the application to solve the technical problems is:

[0009] The application provides a TGV via etching solution, which comprises, by mass percentage, 12-18% of sodium hydroxide and / or potassium hydroxide, 4-10% of sodium D-gluconate, 1-2% of alkyl glycoside, 1-2% of sodium polyacrylate, and the balance of water.

[0010] Preferably, the TGV via etching solution is composed of the following components in percentage by mass: sodium hydroxide and / or potassium hydroxide 12-18%, sodium D-gluconate 4-10%, alkyl glycoside 1-2%, sodium polyacrylate 1-2%, and the rest is water.

[0011] Preferably, the TGV via etching solution includes the following components in percentage by mass: sodium hydroxide and / or potassium hydroxide 15%, sodium D-gluconate 6%, alkyl glycoside 1%, sodium polyacrylate 1%, and the rest is water.

[0012] Further preferably, the TGV via etching solution is composed of the following components in percentage by mass: sodium hydroxide and / or potassium hydroxide 15%, sodium D-gluconate 6%, alkyl glycoside 1%, sodium polyacrylate 1%, and the rest is water.

[0013] Preferably, the alkyl glycoside is at least one of octyl to hexadecyl glycoside.

[0014] The present application provides a TGV via etching process, comprising the following steps:

[0015] (1) using laser to punch holes on the glass;

[0016] (2) placing the glass after laser punching treatment in the etching solution for etching processing; the etching solution is the TGV via etching solution described above.

[0017] Preferably, the glass in step (1) is borosilicate glass or quartz glass.

[0018] Preferably, the thickness of the glass in step (1) is 0.5-2mm.

[0019] Preferably, the temperature of the etching solution in step (2) is 90-100℃; such as 90℃, 91℃, 92℃, 93℃, 94℃, 95℃, 96℃, 97℃, 98℃, 99℃, 100℃; the etching rate increases by about 10% for every 1℃ increase in temperature, but the solution volatilization needs to be avoided.

[0020] Further preferably, the temperature of the etching solution in step (2) is 94℃.

[0021] Preferably, the etching solution in step (2) does not need stirring treatment, and weak circulation can be started when the volume is large.

[0022] Preferably, the etching processing time in step (2) is 10-30h; the etching processing time is adjusted according to the aperture requirement, and the etching rate is generally 4-7μm / h (much lower than 300-600μm / h of HF and 20-60μm / h of concentrated alkali).

[0023] Preferably, the etching solution in step (2) can be reused.

[0024] The core principle of the basic etching process of the present application

[0025] 1. Chemical reaction mechanism

[0026] Main reaction: Glass (take silicon dioxide as an example) reacts in a strong alkaline solution to generate soluble silicate:

[0027] SiO2 + 2NaOH → Na2SiO3 + H2O

[0028] This reaction gradually corrodes the glass to achieve the purpose of etching. However, concentrated alkali etching has problems such as too fast rate, unstable rate, poor uniformity, easy to produce uneven etching marks or excessive corrosion, etc., so additives need to be added to control the reaction.

[0029] 2. Additive auxiliary action

[0030] By adding an appropriate amount of complexing agent (sodium D-gluconate), the influencing factors that interfere with the reaction rate are controlled.

[0031] ① Complexing of metal impurities in the solution: D-gluconate sodium and free metal ions Al 3+ form a stable complex, reducing the concentration of free metal ions and inhibiting their catalytic effect on etching, avoiding excessive local etching rate.

[0032] ② Surface adsorption corrosion inhibition: The hydroxyl group of D-gluconate sodium can be adsorbed on the active sites on the glass surface (such as Si-OH groups), forming a temporary protective film that prevents NaOH from directly contacting Si, further controlling the etching rate and making the etching more uniform.

[0033] ③ Improve the dispersibility of sodium silicate colloid: Sodium silicate generated during etching is prone to form a colloid in concentrated alkali, which adheres to the glass surface and causes uneven etching. By adding a certain amount of D-gluconate sodium, the sodium silicate colloid is dispersed through charge repulsion and steric hindrance effect, making it difficult to deposit, thereby keeping the glass etching interface clean and achieving stable etching process.

[0034] 3. Add an appropriate amount of alkyl polyglycoside (APG):

[0035] ① Enhance the wettability and penetration ability of the etching solution. APG can significantly reduce the surface tension of the alkali solution (from about 72 mN / m to 30-40 mN / m), making the alkali solution more easily spread and penetrate into the micropores on the glass surface, improving the uniformity of through-hole etching.

[0036] ②Disperse etching products. Sodium silicate colloid is easy to form flocs by agglomeration, and APG disperses it into fine particles by micellar encapsulation, preventing the etching interface from being blocked and ensuring the continuous reaction. At the same time, the hydrophobic chain of APG can adsorb the hydrophobic groups in the sodium silicate colloid, further enhancing the dispersion effect.

[0037] ③Inhibit foam and adjust interface reaction. Traditional anionic surfactants (such as LAS) are prone to produce a large amount of foam in high-temperature concentrated alkali, while APG has low foam stability and is suitable for high-temperature processes. In addition, the adsorption layer of APG can fine-tune the contact area of NaOH and glass, avoiding excessive local reaction and assisting in controlling the etching depth.

[0038] 4, Add an appropriate amount of sodium polyacrylate:

[0039] Sodium polyacrylate prevents crystalline deposition through steric hindrance and electrostatic repulsion, while adjusting the viscosity of the system, improving the mass transfer effect, making the distribution of alkali liquor in the micropores more uniform, improving the uniformity of through-hole etching, and improving the long-term use effect of alkali liquor.

[0040] The beneficial effects of the present application are:

[0041] The TGV through-hole etching solution of the present application does not contain highly toxic hydrofluoric acid, is environmentally friendly, safe, and pollution-free, has a constant etching rate, has a good waist diameter ratio, has a good long-term use effect, can etch a good TGV through-hole, and saves production cost. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 The fitting curve of the through-hole diameter and time of the glass etched for different times after laser drilling treatment according to Example 1 of the present application.

[0043] Figure 2 The cross-sectional view of the through-hole 1 after etching of the glass etched after laser drilling treatment according to Example 1 of the present application.

[0044] Figure 3 The curve of the etching speed changing with time (days) of Example 1 and Comparative Example 1 of the present application.

[0045] Figure 4 The fitting curve of the through-hole diameter and time of the glass etched for different times after laser drilling treatment according to Comparative Example 1 of the present application.

[0046] Figure 5 The cross-sectional view of the through-hole 1 after etching of the glass etched according to Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0047] The present application will be further described below in conjunction with examples.

[0048] The concept, specific scheme and generated technical effects of the present application will be described clearly and completely in combination with the embodiments, so as to fully understand the purpose, features and effects of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, but not all the embodiments. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application. Each technical feature in the present application can be combined with each other as long as they are not contradictory.

[0049] Embodiment 1

[0050] A TGV via etching solution:

[0051] According to mass percentage, it comprises: water 77%, sodium hydroxide 15%, D-sodium gluconate 6%, alkyl glycoside (dodecyl glycoside) 1%, and sodium polyacrylate 1%.

[0052] A TGV via etching process, comprising the following steps:

[0053] (1) Laser drilling treatment is performed on the glass;

[0054] The glass is Schott BF33 (main components include 78.4% SiO2, 15.0% B2O3, 2.3% Al2O3, 3.5% Na2O, and 0.6% K2O by weight percentage), 0.7mm thick, and length-width (50x50mm).

[0055] (2) The laser-drilled glass is placed in the 94℃ etching solution for etching processing for 12h (the next batch is processed after stopping for 12h).

[0056] (3) The above steps (1) and (2) are repeated every day for 14 consecutive days.

[0057] The glass is taken out at different time points every day during the etching processing to measure the via hole diameter, and the average value is calculated by taking 4 via hole diameters.

[0058] The hole diameter change data with time during the etching processing on the first day are shown in Table 1; the fitting curve of the average hole diameter and time is shown in Figure 1 The curve fitting is linear, indicating that the etching process is carried out at a constant rate.

[0059] Table 1:

[0060] Time (h) 1.5 3 6 7.5 9 10.5 12 Measurement aperture 1 8.067 15.391 29.801 36.691 44.427 51.464 58.539 Measurement aperture 2 8.117 15.593 30.171 37.127 44.661 51.087 57.923 Measurement aperture 3 8.139 15.369 30.213 37.186 44.57 51.193 58.034 Measurement aperture 4 8.088 15.331 30.133 36.749 44.286 51.604 58.491 Average aperture (pm) 8.103 15.421 30.080 36.938 44.486 51.337 58.247

[0061] The cross-sectional view of via hole 1 after etching processing for 11.5h on the first day is shown in Figure 2The top diameter, middle aperture diameter, bottom diameter and waist diameter ratio data are shown in Table 2. As can be seen from Example 1 and Comparative Example 1, the waist diameter ratio is improved by 31% after adding sodium polyacrylate, and the waist diameter ratio is obviously improved.

[0062] Table 2:

[0063]

[0064] The etching speed change over time (days) is shown in Table 3 and Figure 3 As shown, it is shown that the long-term use effect of the etching solution with the addition of sodium polyacrylate is better.

[0065] Table 3:

[0066]

[0067] Comparative Example 1

[0068] A TGV via etching solution:

[0069] By mass percentage: water 78%, sodium hydroxide 15%, D-sodium gluconate 6%, alkyl glycoside (dodecyl glycoside) 1%.

[0070] A TGV via etching process, comprising the following steps:

[0071] (1) Laser drilling treatment is performed on the glass;

[0072] The glass is Schott BF33 (main components include 78.4% SiO2, 15.0% B2O3, 2.3% Al2O3, 3.5% Na2O, 0.6% K2O by weight percentage), 0.7mm thick, length and width (50x50mm).

[0073] (2) The laser drilling treated glass is placed in the 94℃ etching solution for etching processing for 12h (the next batch is performed after 12h of stoppage).

[0074] (3) The above steps (1) and (2) are repeated every day for 14 consecutive days.

[0075] The glass is taken out at different time points every day during the etching processing to measure the via aperture, and the average value is calculated from 4 via apertures.

[0076] The via aperture change over time during the etching processing on the first day is shown in Table 4; the fitting curve of the average aperture and time is shown in Figure 4 .

[0077] Table 4:

[0078] Time (h) 1.5 3 6 7.5 9 10.5 12 Through hole 1 8.191 16.782 32.19 39.96 46.911 54.049 60.777 Through hole 2 8.441 16.953 32.182 40.059 46.831 53.944 61.063 Through hole 3 8.398 16.646 32.215 40.043 46.785 54.129 60.955 Through hole 4 8.479 16.764 32.216 40.056 46.769 53.875 60.895 Average aperture (pm) 8.377 16.786 32.201 40.030 46.824 53.999 60.923

[0079] A cross-sectional view of the via 1 etched for 12h on day 1 is shown in Figure 5 The top diameter, middle aperture, bottom diameter and waist diameter ratio data are shown in Table 5.

[0080] Table 5:

[0081]

[0082]

[0083] The etching rate change with time (day) is shown in Table 6 and Figure 3 It is shown that the long-term use effect of the etching solution without adding sodium polyacrylate is poor, and the etching rate decreases significantly over a long period of time.

[0084] Table 6:

[0085]

[0086] Example 2

[0087] A TGV via etching solution:

[0088] It includes, by mass percentage: water 82%, sodium hydroxide 12%, sodium D-gluconate 4%, alkyl glycoside (dodecyl glycoside) 1%, sodium polyacrylate 1%.

[0089] A TGV via etching process, comprising the following steps:

[0090] (1) Laser drilling treatment is performed on the glass;

[0091] The glass is Schott BF33 (main components include, by weight percentage: 78.4% SiO2, 15.0% B2O3, 2.3% Al2O3, 3.5% Na2O, 0.6% K2O), 0.7mm thick, length and width (50x50mm).

[0092] (2) The glass after laser drilling treatment is placed in the 94℃ etching solution for etching processing for 12h (the next batch is performed after 12h of stop).

[0093] (3) The above steps (1) and (2) are repeated every day for 14 consecutive days.

[0094] The etching rate is different from that of Example 1, and the waist diameter ratio and long-term use effect are similar to those of Example 1.

[0095] Example 3

[0096] A TGV via etching solution:

[0097] By mass percentage: water 68%, sodium hydroxide 18%, D-glucose sodium 10%, alkyl glycoside (dodecyl glycoside) 2%, sodium polyacrylate 2%.

[0098] A TGV via etching process, comprising the steps of:

[0099] (1) Laser drilling of glass;

[0100] The glass is Schott BF33 (main components include 78.4% SiO2, 15.0% B2O3, 2.3% Al2O3, 3.5% Na2O, 0.6% K2O by weight percentage), 0.7mm thick, length-width (50x50mm).

[0101] (2) The laser-drilled glass is placed in a 94℃ etching solution for etching processing for 12h (the next batch is processed after 12h of stoppage).

[0102] (3) The above steps (1) and (2) are repeated every day for 14 consecutive days.

[0103] The etching rate is different from that of Example 1, and the waist diameter ratio and long-term use effect are similar to those of Example 1.

[0104] The above is a specific description of the preferred implementation of the present application, but the present application is not limited to the described embodiments. Those skilled in the art can make various equivalent modifications or replacements without departing from the spirit of the present application. These equivalent modifications or replacements are all included in the scope defined by the claims of the present application.

Claims

1. A TGV via etching solution, characterized by, Comprising by mass percentage: sodium and / or potassium hydroxide 12-18%, sodium D-glucuronate 4-10%, alkyl glycoside 1-2%, sodium polyacrylate 1-2%, and the balance being water.

2. The TGV via etching solution according to claim 1, wherein Comprising by mass percentage: sodium and / or potassium hydroxide 12-18%, sodium D-glucuronate 4-10%, alkyl glycoside 1-2%, sodium polyacrylate 1-2%, and the balance being water.

3. The TGV via etch liquid of claim 1, wherein, Comprising by mass percentage: sodium and / or potassium hydroxide 15%, sodium D-glucuronate 6%, alkyl glycoside 1%, sodium polyacrylate 1%, and the balance being water.

4. The TGV via etch liquid of claim 1, wherein, The alkyl glycoside is at least one of octyl to hexadecyl glycoside.

5. A TGV via etch process, characterized in that, Comprising the following steps: (1) performing laser drilling on the glass; (2) placing the laser-drilled glass in an etching solution to perform etching processing; the etching solution is the TGV through-hole etching solution according to any one of claims 1-4.

6. The TGV via etch process of claim 5, wherein, The glass in step (1) is borosilicate glass or quartz glass.

7. The TGV via etch process of claim 5, wherein, The thickness of the glass in step (1) is 0.5-2 mm.

8. The TGV via etch process of claim 5, wherein, The temperature of the etching solution in step (2) is 90-100°C.

9. The TGV via etch process of claim 5, wherein, The etching processing time in step (2) is 10-30 h.

10. The TGV via etch process of claim 5, wherein, The etching solution in step (2) can be reused.

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