Method for improving the bond between tgv product and line layer

Abstract

This invention provides a method for improving the adhesion between a TGV product and a circuit layer, comprising the steps of surface treating the TGV product with a surface treatment solution, wherein the surface treatment solution contains a solute and water by weight, the solute comprising 5-30 parts of acid, 8-35 parts of fluoride, 5-25 parts of fluorosilicate, 3-25 parts of fluorine-free soluble metal salt, and 0.3-2.0 parts of surfactant, the chemical formula of the fluoride being M1F or M2F2, where M1 is selected from K, Na, or NH4, and M2 is selected from NH4H, Mg, Ba, or Ca; and a circuit layer is formed on the surface of the TGV product after step (1). This method can improve the adhesion strength between the TGV product and the circuit layer, thereby providing a high-performance chip packaging structure.

Description

Technical Field

[0001] This invention relates to the field of integrated circuit packaging technology, and more particularly to the surface treatment of TGV products in integrated circuit packaging, and even more particularly to a method for improving the bonding force between TGV products and circuit layers. Background Technology

[0002] In the semiconductor industry, as Moore's Law approaches its physical limits, improving chip performance through 3D integration has become a core development direction. The widespread application of advanced packaging technologies such as 2.5D / 3D packaging and heterogeneous integration has placed higher demands on vertical interconnect density and substrate performance. The limitations of traditional silicon substrates in high-frequency signal transmission, manufacturing costs, and process complexity are becoming increasingly apparent. Meanwhile, glass, with its high dimensional stability, isotropy, high transparency, good insulation, and low dielectric loss, is gradually becoming the ideal choice for next-generation chip packaging substrates.

[0003] Against this backdrop, through-glass vias (TGV products) serve as a key technology for achieving three-dimensional integration of glass substrates, acting as "miniature channels" in the chip world and leading the transition of semiconductor packaging from the "silicon-based era" to the "glass-based era." TGV products are formed by laser modification, etching of through-holes, and electroplating filling of the glass core.

[0004] To improve the bonding strength between the circuit structure and the glass core board during subsequent fabrication of circuit structures on the glass core board surface, existing technologies involve laser modification, etching of through-holes, and electroplating to form a TGV product. A Ti, Cr, and Ni metal layer is then sputtered as a barrier layer. This layer not only prevents copper diffusion from the circuit layer onto the glass core board but also acts as an adhesive layer, enhancing the bonding force between the circuit layer and the glass core board. However, this metal layer only forms physical contact and electrostatic adsorption with the glass surface, exhibiting poor adhesion to the copper layer of the circuit layer. This can easily lead to delamination between the glass core board and the metal layer, resulting in metal layer curling or even detachment, affecting the lifespan of the chip device. In addition, some studies have used silane coupling agents to chemically bond organic thin films to glass core substrates, followed by chemical deposition or sputtering of Ti-Cu metal seed layers. In this method, the silane coupling agent connects the glass layer and combines with the organic thin film (such as ABF / ZIF thin films), and then the organic thin film is combined with Ti-Cu, achieving good results. However, this method is costly, and the significant difference in the coefficient of thermal expansion (CTE) between the organic thin film and the glass core substrate may lead to reliability risks such as device failure due to thermal expansion. Summary of the Invention

[0005] To address the aforementioned issues, the present invention aims to provide a method for improving the bonding strength between TGV products and circuit layers, thereby enhancing the bonding strength between TGV products and circuit layers and providing a high-performance chip packaging structure.

[0006] To achieve the above objectives, the present invention provides a method for improving the bonding strength between TGV products and the circuit layer, comprising the following steps: (1) The TGV product is surface treated with a surface treatment liquid. The surface treatment liquid contains a solute and water by weight. The solute contains 5-30 parts of acid, 8-35 parts of fluoride, 5-25 parts of fluorosilicate, 3-25 parts of fluorine-free soluble metal salt and 0.3-2.0 parts of surfactant. The chemical formula of the fluoride is M1F or M2F2, where M1 is selected from K, Na or NH4, and M2 is selected from NH4H, Mg, Ba or Ca. (2) The circuit layer is formed on the surface of the TGV product after step (1).

[0007] The method of the present invention can improve the bonding strength between the glass core board and the circuit layer in TGV products through a one-step glass core board surface treatment. It has wide applicability, simple operation and low cost, and has obvious advantages over the prior art.

[0008] In the method of this invention, the surface treatment solution used for surface treatment comprises 5-30 parts of acid, 8-35 parts of fluoride, 5-25 parts of fluorosilicate, 3-25 parts of fluorine-free soluble metal salt, and 0.3-2.0 parts of surfactant. The chemical formula of the fluoride is M1F or M2F2, where M1 is selected from K, Na, or NH4, and M2 is selected from NH4H, Mg, Ba, or Ca. The acid primarily provides the H2O required by the surface treatment solution. + Fluorides mainly react with acids, resulting in the presence of many fluoride active groups (HF2) in the surface treatment solution. - Fluorosilicates (HF, (HF)₂) provide sodium, potassium, barium, and ammonium ions required for the reaction. Fluorosilicates, in conjunction with other components (such as fluorides and acids), form a micron-scale uneven structure on the glass core surface, improving the stability and reaction efficiency of the surface treatment solution and reducing excessive action on the glass substrate. Soluble metal salts primarily promote crystal nucleation; their sodium or potassium ions also participate in the reaction to form sodium or potassium fluorosilicate, which adhere to the glass core surface to form crystal nuclei, protecting the glass from continuous etching. Surfactants mainly stabilize particle distribution and improve the surface roughness uniformity of the glass core.

[0009] When this surface treatment solution is used to treat TGV products, the H in the surface treatment solution... +It will first adsorb onto the surface of the glass core in TGV products, combining with the broken bonds in the Si-O structure of the glass surface to generate a certain concentration of Si-OH. The Si-OH will continuously react with H... + Combine to form SiOH2 + This causes the surface of the glass core to become positively charged, and the active ingredient HF2 in the surface treatment solution... - (HF)₂ is more easily adsorbed onto glass surfaces. - The nucleophilic etching of Si atoms by (HF)₂ causes a shift in the electron cloud of the adjacent Si-O bond, weakening and breaking the Si-O bond to form Si-F. Simultaneously, H₂ previously adsorbed on the surface of the glass core plate... + It binds oxygen atoms via hydrogen bonds, electrophilically erodes Si-O, further reducing the strength of the Si-O bond, and catalyzes the entire reaction. This catalytic and non-catalytic reaction occur simultaneously. After the above reaction, SiF4 is generated on the surface of the glass core board. When SiF4 enters the surface treatment solution, it undergoes hydrolysis to generate fluorosilicic acid (H2SiF6) and silicic acid (H2SiO3). The fluorosilicic acid anions combine with metal cations in the glass core board or the surface treatment solution to form fluorosilicate nuclei on the glass core board surface (e.g., ...). Figure 1 As shown in Figure a), fluorosilicate crystal nuclei slowly grow under the influence of soluble metal salts (e.g., Figure 1 As shown in Figure b), finally, a uniform and dense fluorosilicate crystal layer 30 with a certain roughness is formed on the surface of the glass core plate 10 (as shown in Figure b). Figure 1 (As shown in c). Since the surface treatment liquid only acts on the glass and does not react with the copper, it will not affect the copper holes. A circuit layer is formed on this fluorosilicate crystal layer. Its uniform, dense, and rough characteristics can greatly improve the bonding strength between the glass core board and the circuit layer of the TGV product, thereby obtaining a high-performance chip packaging structure.

[0010] As a technical solution of the present invention, the surface treatment includes immersing the TGV product in the surface treatment liquid and maintaining it at 25~50°C for 5~30 minutes.

[0011] As one technical solution of the present invention, the acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid and citric acid.

[0012] As a technical solution of the present invention, the fluorosilicate is selected from at least one of ammonium fluorosilicate, potassium fluorosilicate, calcium fluorosilicate, sodium fluorosilicate and barium fluorosilicate.

[0013] As one technical solution of the present invention, the fluorine-free soluble metal salt is selected from at least one of potassium sulfate, sodium sulfate, potassium chloride, sodium chloride and ferric chloride.

[0014] As one technical solution of the present invention, the surfactant is selected from at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and sodium dodecyl sulfonate.

[0015] As a technical solution of the present invention, the TGV product is first cleaned before the surface treatment. The cleaning treatment includes ultrasonic treatment of the TGV product followed by drying treatment. The ultrasonic treatment is performed at a temperature of 30~60℃ for 5~30min and a power of 20~100kHz. The drying temperature is 90~110℃ and the drying time is 5~20min.

[0016] As a technical solution of the present invention, the preparation of the TGV product includes the following steps: (i) Pre-treat the glass core board to remove dirt from the surface of the glass core board; (ii) The glass core plate is subjected to laser processing to form a through-hole pattern modification area on the glass core plate; (iii) Etching the modified area of ​​the through-hole pattern to form a through-hole structure; (iv) After forming a seed layer in the through-hole structure, electroplating is performed to fill the hole.

[0017] As a technical solution of the present invention, the pretreatment includes ultrasonic treatment and drying treatment. The ultrasonic treatment is performed at a temperature of 30~60℃ for 5~30min and a power of 20~100kHz. The drying temperature is 90~110℃ and the drying time is 5~20min.

[0018] As one technical solution of the present invention, the laser processing conditions are: energy 5~30W, pulse number 1~6, pulse width 1000~5000fs, frequency 100~400kHz, laser scanning speed 2~10mm / s, and laser processing acceleration 10~50mm / s. 2 .

[0019] As a technical solution of the present invention, the etching is performed using an acidic etching solution or an alkaline etching solution. By weight, the acidic etching solution comprises 2-30 parts hydrofluoric acid, 0.5-5.0 parts ammonium fluoride, 0.5-8.0 parts hydrochloric acid, 0.6-9.0 parts sulfuric acid, 0.2-5.0 parts nitric acid, 0.2-4.0 parts surfactant and water. The alkaline etching solution comprises 8-60 parts sodium hydroxide, 1-10 parts inorganic salt and 0.5-2.0 parts surfactant and water.

[0020] As one technical solution of the present invention, the seed layer is formed by chemical plating or magnetron sputtering, wherein the conditions for chemical plating are: current density of 0.02~0.5A / dm³. 2The pulse frequency is 0.5~6.0kHz, the temperature is 0~35℃, and the magnetron sputtering conditions are: at 2×10 -4 ~8×10 -4 Magnetron sputtering of Ti or Cu is performed at a vacuum of Pa, with argon gas of not less than 99.99% introduced at a flow rate of 5~50 sccm, working pressure of 0.1~0.5 Pa, DC power supply of 1000~6000W, RF bias of 200~800V, and temperature of 120~300℃.

[0021] As one technical solution of the present invention, the current density used for electroplating and filling the holes is 0.025~1.000A / dm. 2 The pulse frequency is 0.5~5.0kHz, and the temperature is 0~35℃.

[0022] As a technical solution of the present invention, the circuit layer is formed by magnetron sputtering and / or electroplating, wherein the magnetron sputtering conditions are: at 5 × 10⁻⁶ ppm. -4 Argon gas with a purity of not less than 99.99% is introduced at a flow rate of 10~100 sccm under a vacuum of 0.1~0.6 Pa, with a DC power supply of 1000~6000W, an RF bias of 200~800V, and a temperature of 120~200℃. Magnetron sputtering is performed using a target material selected from Ti-Cu, Cr-Cu, or Ni-Cu. The electroplating conditions are: current density of 0.025~1.000 A / dm³. 2 The pulse frequency is 0.5~5.0kHz, and the temperature is 0~35℃. Attached Figure Description

[0023] Figure 1 A schematic diagram illustrating the process of generating fluorosilicate crystal layers.

[0024] Figure 2 This is a microscope image of the TGV product in Example 1 after treatment with a surface treatment solution. Detailed Implementation

[0025] To improve the bonding strength between TGV products and circuit layers, this invention provides a method that involves surface treating the TGV product with a surface treatment liquid to form a uniform, dense fluorosilicate crystal layer with a certain roughness on the surface of the glass core board. Then, a circuit layer is formed on this fluorosilicate crystal layer. The uniform, dense, and rough characteristics of the fluorosilicate crystal can greatly improve the bonding strength between the glass core board and the circuit layer of the TGV product, thereby obtaining a high-performance chip packaging structure.

[0026] The preparation of TGV products includes the following steps: (a) Pre-treat the glass core board to remove dirt from its surface; (ii) Laser treatment is performed on the glass core board to form a through-hole pattern modification area on the glass core board; (iii) Etching the modified area of ​​the through-hole pattern to form a through-hole structure; (iv) After forming a seed layer in the through-hole structure, electroplating is then used to fill the hole.

[0027] This glass core board is suitable for various glass core board substrates, including borosilicate glass, borosilicate-like glass, alkali-free glass, soda-lime glass, and high-alumina glass. Pretreatment includes ultrasonic treatment and drying. Ultrasonic treatment uses a temperature of 30-60℃ for 5-30 minutes and a power of 20-100kHz. Drying uses a temperature of 90-110℃ for 5-20 minutes. Ultrasonic cleaning removes dirt from the glass core board surface and dries it, preventing stains from affecting laser induction. The cleaning agent used for ultrasonic treatment can be an alkaline cleaning agent, which may include sodium hydroxide, nonionic surfactants, and organic bases, with a mass ratio of 1-5:1-5:0.1-1.0. Nonionic surfactants can be fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, or fatty acid polyoxyethylene esters. Organic bases can be triethanolamine or triethylamine.

[0028] The conditions for laser processing are: energy 5~30W, pulse number 1~6, pulse width 1000~5000fs, frequency 100~400kHz, laser scanning speed 2~10mm / s, and laser processing acceleration 10~50mm / s. 2 The laser is focused at the center of the pre-formed through-hole area, forming a corresponding through-hole pattern modification area on the glass core plate. Etching is performed using an acidic or alkaline etching solution. The aperture of the through-hole can be controlled according to the etching time, such as 30μm, 50μm, 60μm, etc. By weight, the acidic etching solution includes 2-30 parts hydrofluoric acid, 0.5-5.0 parts ammonium fluoride, 0.5-8.0 parts hydrochloric acid, 0.6-9.0 parts sulfuric acid, 0.2-5.0 parts nitric acid, 0.2-4.0 parts surfactant, and water. The water content can be determined according to the actual situation. The surfactant in the acidic etching solution can be sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, Tween 20, Tween 21, Tween 40, Tween 60, Tween 61, Tween 80, Tween 81, Tween 85, etc. The alkaline etching solution comprises 8-60 parts sodium hydroxide, 1-10 parts inorganic salt, 0.5-2.0 parts surfactant, and water. The water content can be determined according to actual conditions. The inorganic salt can be at least one of potassium sulfate, sodium sulfate, potassium chloride, and sodium chloride. The surfactant in the alkaline etching solution can be sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, etc. The seed layer is formed by chemical plating or magnetron sputtering. The conditions for chemical plating are a current density of 0.02-0.5 A / dm³.2 The pulse frequency is 0.5~6.0kHz, and the temperature is 0~35℃. The magnetron sputtering conditions are: at 2×10 -4 ~8×10 -4 Under a vacuum of 0.1 Pa, argon gas with a purity of not less than 99.99% is introduced at a flow rate of 5-50 sccm. The working pressure is 0.1-0.5 Pa, the DC power supply power is 1000-6000W, the RF bias voltage is 200-800V, and the temperature is 120-300℃ for magnetron sputtering of Ti or Cu. The electroplating solution used for filling the holes can be a self-developed copper plating solution or a commercially available solution, such as Anmet's InPro®THF / InPro®THF2, etc., with a current density of 0.025-1.000 A / dm³. 2 The pulse frequency is 0.5~5.0kHz, and the temperature is 0~35℃. After electroplating and filling the holes, the metal layer on the surface of the glass core board can be removed for the next process.

[0029] Before surface treatment with a surface treatment liquid, TGV products undergo a cleaning process, which includes ultrasonic treatment followed by drying. The ultrasonic treatment is performed at a temperature of 30-60℃ for 5-30 minutes at a power of 20-100kHz. The drying process is performed at a temperature of 90-110℃ for 5-20 minutes. Using an ultrasonic cleaner to remove dirt from the TGV product surface and then drying further improves the surface treatment effect. The cleaning agent used for ultrasonic treatment can be an alkaline cleaning agent, which may include sodium hydroxide, a nonionic surfactant, and an organic base, with a mass ratio of 1-5:1-5:0.1-1.0. The nonionic surfactant can be fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, or fatty acid polyoxyethylene ester. The organic base can be triethanolamine or triethylamine.

[0030] During surface treatment, TGV products can be immersed in the surface treatment solution and kept at 25-50℃ for 5-30 minutes. By weight, the surface treatment solution contains solute and water. The solute contains 5-30 parts acid, 8-35 parts fluoride, 5-25 parts fluorosilicate, 3-25 parts fluorine-free soluble metal salt, and 0.3-2.0 parts surfactant. The fluoride mainly reacts with the acid to provide a small amount of HF, while also providing sodium, potassium, barium, and ammonium ions required for the reaction. Its chemical formula is M1F or M2F2, where M1 is selected from K, Na, or NH4, and M2 is selected from NH4H, Mg, Ba, or Ca. The acid mainly provides the H2O required by the surface treatment solution. +The components are selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid. Fluorosilicates, in combination with other components (such as fluorides and acids), form a micron-scale uneven structure on the glass core surface, improving the stability and reaction efficiency of the surface treatment solution and reducing excessive action on the glass substrate. They are selected from at least one of ammonium fluorosilicate, potassium fluorosilicate, calcium fluorosilicate, sodium fluorosilicate, and barium fluorosilicate. Fluorine-free soluble metal salts primarily promote crystal nucleation growth; these are selected from at least one of potassium sulfate, sodium sulfate, potassium chloride, sodium chloride, and ferric chloride. Surfactants primarily stabilize particle distribution and improve the uniformity of the glass core surface roughness. They are selected from at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfonate. After mixing the components of the surface treatment solution and preheating at 50-80°C, the solution is naturally cooled to the surface treatment temperature before surface treatment of the TGV product.

[0031] TGV products undergo surface treatment with a surface treatment solution before a circuit layer is formed on the surface. The circuit layer is formed by magnetron sputtering and / or electroplating. The magnetron sputtering conditions are: 2 × 10⁻⁶ -4 ~8×10 -4 Argon gas with a purity of not less than 99.99% was introduced at a flow rate of 10~100 sccm under a vacuum of PPa. The working pressure was 0.1~0.6Pa, the DC power supply power was 1000~6000W, the RF bias voltage was 200~800V, and the temperature was 120~200℃. Magnetron sputtering was performed with a target material selected from Ti-Cu, Cr-Cu, or Ni-Cu. The thickness of the metal layer formed by magnetron sputtering was 1~3μm. The electroplating conditions were as follows: the electroplating solution could be a self-developed copper plating solution or a commercial electroplating solution, such as Anmet's InPro®THF / InPro®THF2, etc., and the current density was 0.025~1.000A / dm³. 2 The pulse frequency is 0.5~5.0kHz, the temperature is 0~35℃, and a coating with a thickness of 15~30μm can be formed by electroplating.

[0032] To better illustrate the purpose, technical solution, and beneficial effects of this invention, the invention will be further described below with reference to specific embodiments. It should be noted that the methods described below are further explanations of this invention and should not be construed as limiting it.

[0033] Part 1: Preparation of TGV Products The preparation of TGV products includes the following steps: (a) Place the 550μm glass core board into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) to ultrasonically clean for 10 minutes at a temperature of 50℃ and a power of 80kHz. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 15 minutes to remove dirt from the surface of the glass core board.

[0034] (ii) Place it on the platform of the infrared femtosecond laser equipment, adjust the height of the platform, and set the laser energy to 12W, pulse number 1, pulse width 3000fs, frequency 320kHz, laser scanning speed 6mm / s, and laser processing acceleration 20mm / s. 2 Laser processing is performed under certain conditions to form through-hole pattern modification areas on the glass core plate.

[0035] (III) The laser-modified glass core board is placed in an acidic etching solution bath to etch the modified areas of the through-hole pattern to form a through-hole structure with a pore diameter of 50 μm. The acidic etching solution includes 20 wt.% hydrofluoric acid, 2.0 wt.% ammonium fluoride, 3.0 wt.% hydrochloric acid, 3.0 wt.% sulfuric acid, 3.0 wt.% nitric acid, 2.0 wt.% additives, and the balance being deionized water.

[0036] (iv) Place the glass core board into the PVD equipment and heat it at 5×10 -4 Ti-Cu magnetron sputtering was performed at a vacuum of 0.15 Pa, with 99.999% pure argon gas introduced at a flow rate of 20 sccm, a working pressure of 0.15 Pa, a DC power supply of 2000 W, an RF bias of 400 V, and a temperature of 160 °C to form a seed layer with a thickness of 2 μm. After cleaning, a current density of 0.03 A / dm³ was applied. 2 Electroplating was performed at a pulse frequency of 0.6kHz and a temperature of 20℃ (using Anmet's InPro®THF plating solution) to fill the holes and remove the metal layer on the surface of the glass core board to obtain the TGV product.

[0037] Part Two: Surface Treatment of TGV Products Example 1 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 20 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 20 minutes.

[0038] (II) Prepare a surface treatment solution according to the following composition: 25 wt.% citric acid, 12 wt.% ammonium bifluoride, 10 wt.% sodium fluorosilicate, 6 wt.% sodium sulfate, 9 wt.% potassium chloride, 0.5 wt.% sodium dodecyl sulfonate, with the balance being deionized water. After mixing all components of the surface treatment solution evenly in a tank, preheat it to 70°C, then allow it to cool naturally to 40°C. Immerse the TGV product treated in step (I) in the tank and maintain the temperature for 10 minutes.

[0039] The surface morphology of the TGV products that have undergone surface treatment was observed using a 3D microscope, such as... Figure 2 As shown, a uniform and dense covering layer with a certain roughness is formed on the surface, exposing each copper-plated hole, indicating that surface treatment with surface treatment liquid can indeed form a fluorosilicate crystal layer.

[0040] Example 2 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:2:3:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 65℃ and 70kHz for 25 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 120℃ for 5 minutes.

[0041] (II) Prepare a surface treatment solution according to the following proportions: 10 wt.% hydrochloric acid, 10 wt.% sodium fluoride, 15 wt.% potassium fluorosilicate, 10 wt.% sodium sulfate, 8 wt.% potassium chloride, 0.6 wt.% sodium dodecyl sulfate, with the balance being deionized water. After mixing all components of the surface treatment solution evenly in a tank, preheat it to 70°C, then allow it to cool naturally to 35°C. Immerse the TGV product treated in step (I) in the tank and maintain the temperature for 10 minutes.

[0042] Example 3 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 30 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 20 minutes.

[0043] (II) Prepare a surface treatment solution according to the following composition: 15 wt.% sulfuric acid, 15 wt.% potassium fluoride, 18 wt.% ammonium fluorosilicate, 12 wt.% sodium chloride, 5 wt.% potassium sulfate, 0.4 wt.% sodium dodecylbenzenesulfonate, with the balance being deionized water. After mixing all components of the surface treatment solution evenly in a tank, preheat it to 65°C, then allow it to cool naturally to 30°C. Immerse the TGV product treated in step (I) in the tank and maintain the temperature for 20 minutes.

[0044] Example 4 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:2 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 20 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 15 minutes.

[0045] (II) Prepare a surface treatment solution according to the following composition: 20 wt.% citric acid, 15 wt.% potassium fluoride, 10 wt.% sodium fluorosilicate, 10 wt.% sodium chloride, 6 wt.% potassium sulfate, 0.4 wt.% sodium dodecylbenzenesulfonate, with the balance being deionized water. After mixing all components of the surface treatment solution evenly in a tank, preheat it to 70°C, then allow it to cool naturally to 30°C. Immerse the TGV product treated in step (I) in the tank and maintain the temperature for 20 minutes.

[0046] Example 5 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 20 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 20 minutes.

[0047] (II) Prepare a surface treatment solution according to the following formula: 9 wt.% nitric acid, 20 wt.% sodium fluoride, 15 wt.% potassium fluorosilicate, 10 wt.% sodium chloride, 12 wt.% potassium chloride, 1.0 wt.% sodium dodecyl sulfonate, with the balance being deionized water. After mixing all components of the surface treatment solution evenly in a tank, preheat it to 70°C, then allow it to cool naturally to 30°C. Immerse the TGV product treated in step (I) in the tank and maintain the temperature for 30 minutes.

[0048] Comparative Example 1 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 20 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 20 minutes.

[0049] (II) Prepare a surface treatment solution with the following composition: 25 wt.% citric acid, 10 wt.% sodium fluorosilicate, 6 wt.% sodium sulfate, 9 wt.% potassium chloride, 0.5 wt.% sodium dodecyl sulfonate, and the balance being deionized water. Mix all components of the surface treatment solution evenly in a tank, preheat at 70°C, and then allow to cool naturally to 40°C. Immerse the TGV product treated in step (I) in the tank and maintain for 10 minutes.

[0050] Comparative Example 2 (i) Place the TGV product prepared in the first part into an ultrasonic cleaning machine and use an alkaline cleaning agent with a mass ratio of 6:3:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) for ultrasonic cleaning at 55℃ and 70kHz for 20 minutes. After cleaning, rinse twice with deionized water at room temperature and dry at 100℃ for 20 minutes.

[0051] (II) Prepare a surface treatment solution with the following composition: 25 wt.% citric acid, 12 wt.% ammonium bifluoride, 6 wt.% sodium sulfate, 9 wt.% potassium chloride, 0.5 wt.% sodium dodecyl sulfonate, and the balance being deionized water. Mix all components of the surface treatment solution evenly in a tank, preheat at 70°C, and then allow to cool naturally to 40°C. Immerse the TGV product treated in step (I) in the tank and maintain for 10 minutes.

[0052] Part Three: Forming the Circuit Layer Example 6 (a) Place the TGV product that has undergone surface treatment in Example 1 into an ultrasonic cleaning machine. Use an alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) and ultrasonically clean it for 10 minutes at a temperature of 50°C and a power of 80kHz. After cleaning, rinse twice with deionized water at room temperature and dry at 100°C for 15 minutes to remove the treatment liquid from the surface.

[0053] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ti-Cu magnetron sputtering was performed at a vacuum of 0.3 Pa, with 99.999% pure argon gas introduced at a flow rate of 30 sccm. The working pressure was 0.3 Pa, the DC power supply was 2000 W, the RF bias was 300 V, and the temperature was 140 °C, forming a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, and the current density was 0.75 A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0054] Example 7 (a) Place the TGV product that has undergone surface treatment in Example 2 into an ultrasonic cleaning machine. Use an alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) and ultrasonically clean it for 10 minutes at a temperature of 50°C and a power of 80kHz. After cleaning, rinse twice with deionized water at room temperature and dry at 100°C for 25 minutes to remove the treatment liquid from the surface.

[0055] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Under a vacuum of 0.3 Pa, 99.999% pure argon gas was introduced at a flow rate of 30 sccm, with a working pressure of 0.3 Pa, a DC power supply of 3000 W, an RF bias of 420 V, and a temperature of 160 °C. Cr-Cu magnetron sputtering was then performed to form a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.80 A / dm³. 2 The pulse frequency is 3.0kHz and the temperature is 30℃.

[0056] Example 8 (a) The TGV product that has undergone surface treatment in Example 3 is placed in an ultrasonic cleaning machine. An alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) is used. The ultrasonic cleaning is performed at 45°C and 80kHz for 10 minutes. After cleaning, the product is rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the surface treatment liquid.

[0057] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ni-Cu magnetron sputtering was performed under the following conditions: a vacuum of 0.3 Pa, a flow rate of 30 sccm for 99.999% pure argon gas, a working pressure of 1500W DC power supply, a radio frequency bias of 360V, and a temperature of 150℃, to form a 2μm metal layer. The Cu layer was then thickened to 30μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.75A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0058] Example 9 (a) The TGV product that has undergone surface treatment in Example 4 is placed in an ultrasonic cleaning machine. An alkaline cleaning agent with a mass ratio of 6:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) is used. The ultrasonic cleaning is performed at 50°C and 80kHz for 10 minutes. After cleaning, the product is rinsed three times with deionized water at room temperature and dried at 100°C for 15 minutes to remove the treatment liquid from the surface.

[0059] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ni-Cu magnetron sputtering was performed under the following conditions: a vacuum of 0.3 Pa, a flow rate of 25 sccm for 99.999% pure argon gas, a working pressure of 1500W DC power supply, a radio frequency bias of 360V, and a temperature of 150℃, to form a 2μm metal layer. The Cu layer was then thickened to 30μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.75A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0060] Example 10 (a) The TGV product that has undergone surface treatment in Example 5 is placed in an ultrasonic cleaning machine. An alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) is used. The ultrasonic cleaning is performed at 50°C and 80kHz for 15 minutes. After cleaning, the product is rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the treatment liquid from the surface.

[0061] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Under a vacuum of 0.3 Pa, 99.999% pure argon gas was introduced at a flow rate of 30 sccm, with a working pressure of 0.3 Pa, a DC power supply of 2500 W, an RF bias of 420 V, and a temperature of 150 °C. Cr-Cu magnetron sputtering was then performed to form a 3 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.75 A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0062] Comparative Example 3 (a) The TGV product of Comparative Example 1, which has undergone surface treatment, was placed in an ultrasonic cleaning machine. An alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) was used for ultrasonic cleaning at 50°C and 80kHz for 10 minutes. After cleaning, the product was rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the treatment liquid from the surface.

[0063] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ti-Cu magnetron sputtering was performed at a vacuum of 0.3 Pa, with 99.999% pure argon gas introduced at a flow rate of 30 sccm. The working pressure was 0.3 Pa, the DC power supply was 2000 W, the RF bias was 300 V, and the temperature was 140 °C, forming a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, and the current density was 0.75 A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0064] Comparative Example 4 (a) The TGV product of Comparative Example 2, which has undergone surface treatment, was placed in an ultrasonic cleaning machine. An alkaline cleaning agent with a mass ratio of 5:2:2:1 (deionized water:sodium hydroxide:fatty alcohol polyoxyethylene ether:triethanolamine) was used for ultrasonic cleaning at 50°C and 80kHz for 10 minutes. After cleaning, the product was rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the surface treatment liquid.

[0065] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ti-Cu magnetron sputtering was performed at a vacuum of 0.3 Pa, with 99.999% pure argon gas introduced at a flow rate of 30 sccm. The working pressure was 0.3 Pa, the DC power supply was 2000 W, the RF bias was 300 V, and the temperature was 140 °C, forming a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, and the current density was 0.75 A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0066] Comparative Example 5 (i) The TGV product prepared in the first part without surface treatment solution is placed in an ultrasonic cleaning machine and ultrasonically cleaned for 10 minutes at 50°C and 80 kHz using an alkaline cleaning agent with a mass ratio of 5:2:2:1 of deionized water: sodium hydroxide: fatty alcohol polyoxyethylene ether: triethanolamine. After cleaning, it is rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the surface treatment solution.

[0067] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ti-Cu magnetron sputtering was performed at a vacuum of 0.3 Pa, with 99.999% pure argon gas introduced at a flow rate of 30 sccm. The working pressure was 0.3 Pa, the DC power supply was 2000 W, the RF bias was 300 V, and the temperature was 140 °C, forming a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, and the current density was 0.75 A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0068] Comparative Example 6 (i) The TGV product prepared in the first part without surface treatment solution is placed in an ultrasonic cleaning machine and ultrasonically cleaned for 10 minutes at 50°C and 80 kHz using an alkaline cleaning agent with a mass ratio of 5:2:2:1 of deionized water: sodium hydroxide: fatty alcohol polyoxyethylene ether: triethanolamine. After cleaning, it is rinsed twice with deionized water at room temperature and dried at 100°C for 25 minutes to remove the surface treatment solution.

[0069] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Under a vacuum of 0.3 Pa, 99.999% pure argon gas was introduced at a flow rate of 30 sccm, with a working pressure of 0.3 Pa, a DC power supply of 3000 W, an RF bias of 420 V, and a temperature of 160 °C. Cr-Cu magnetron sputtering was then performed to form a 2 μm metal layer. The Cu layer was then thickened to 30 μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.80 A / dm³. 2 The pulse frequency is 3.0kHz and the temperature is 30℃.

[0070] Comparative Example 7 (a) The TGV product prepared in the first part without surface treatment solution was placed in an ultrasonic cleaning machine and ultrasonically cleaned for 10 minutes at 45°C and 80 kHz using an alkaline cleaning agent with a mass ratio of 5:2:2:1 of deionized water: sodium hydroxide: fatty alcohol polyoxyethylene ether: triethanolamine. After cleaning, it was rinsed twice with deionized water at room temperature and dried at 100°C for 15 minutes to remove the surface treatment solution.

[0071] (ii) Place the cleaned and surface-treated TGV product into the PVD equipment and heat it at 5×10⁻⁶ rpm. -4 Ni-Cu magnetron sputtering was performed under the following conditions: a vacuum of 0.3 Pa, a flow rate of 30 sccm for 99.999% pure argon gas, a working pressure of 1500W DC power supply, a radio frequency bias of 360V, and a temperature of 150℃, to form a 2μm metal layer. The Cu layer was then thickened to 30μm using electroplating. The electroplating solution was Anmet's InPro® THF, with a current density of 0.75A / dm³. 2 The pulse frequency is 3.5kHz and the temperature is 30℃.

[0072] The bonding strength of Examples 6-10 and Comparative Examples 3-7 was tested at 90°C using a universal testing machine to determine the bonding strength between the TGV product and the circuit layer. The results are shown in Table 1.

[0073] Table 1. Results of bonding strength tests for Examples 6-10 and Comparative Examples 3-7

[0074] As can be seen from the results in Table 1, the surface treatment of TGV products using the method of the present invention significantly improves the bonding strength between the glass core and the metal layer.

[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, it is not limited to those listed in the embodiments. Those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for improving the bonding strength between TGV products and the circuit layer, characterized in that, Including the following steps: (1) The TGV product is surface treated with a surface treatment liquid. The surface treatment liquid contains a solute and water by weight. The solute contains 5-30 parts of acid, 8-35 parts of fluoride, 5-25 parts of fluorosilicate, 3-25 parts of fluorine-free soluble metal salt and 0.3-2.0 parts of surfactant. The chemical formula of the fluoride is M1F or M2F2, where M1 is selected from K, Na or NH4, and M2 is selected from NH4H, Mg, Ba or Ca. (2) The circuit layer is formed on the surface of the TGV product after step (1).

2. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The surface treatment includes immersing the TGV product in the surface treatment solution and maintaining it at 25~50°C for 5~30 minutes.

3. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, and citric acid.

4. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The fluorosilicate is selected from at least one of ammonium fluorosilicate, potassium fluorosilicate, calcium fluorosilicate, sodium fluorosilicate, and barium fluorosilicate.

5. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The fluorine-free soluble metal salt is selected from at least one of potassium sulfate, sodium sulfate, potassium chloride, sodium chloride, and ferric chloride.

6. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The surfactant is selected from at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and sodium dodecyl sulfonate.

7. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The TGV product undergoes a cleaning process before surface treatment. The cleaning process includes ultrasonic treatment followed by drying. The ultrasonic treatment is performed at a temperature of 30-60°C for 5-30 minutes and a power of 20-100 kHz. The drying process is performed at a temperature of 90-110°C for 5-20 minutes.

8. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The preparation of the TGV product includes the following steps: (i) Pre-treat the glass core board to remove dirt from the surface of the glass core board; (ii) The glass core plate is subjected to laser processing to form a through-hole pattern modification area on the glass core plate; (iii) Etching the modified area of ​​the through-hole pattern to form a through-hole structure; (iv) After forming a seed layer in the through-hole structure, electroplating is performed to fill the hole.

9. The method for improving the bonding strength between TGV products and the circuit layer according to claim 8, characterized in that, Includes at least one of the following features (I) and (V): (I) The pretreatment includes ultrasonic treatment and drying treatment. The ultrasonic treatment is performed at a temperature of 30~60℃ for 5~30min and a power of 20~100kHz. The drying temperature is 90~110℃ and the drying time is 5~20min. (II) The laser processing conditions are: energy 5~30W, pulse number 1~6, pulse width 1000~5000fs, frequency 100~400kHz, laser scanning speed 2~10mm / s, and laser processing acceleration 10~50mm / s. 2 ; (III) The etching is performed using an acidic etching solution or an alkaline etching solution. By weight, the acidic etching solution comprises 2-30 parts hydrofluoric acid, 0.5-5.0 parts ammonium fluoride, 0.5-8.0 parts hydrochloric acid, 0.6-9.0 parts sulfuric acid, 0.2-5.0 parts nitric acid, 0.2-4.0 parts surfactant and water. The alkaline etching solution comprises 8-60 parts sodium hydroxide, 1-10 parts inorganic salt and 0.5-2.0 parts surfactant and water. (IV) The seed layer is formed by chemical plating or magnetron sputtering, wherein the chemical plating conditions are: a current density of 0.02~0.5 A / dm². 2 The pulse frequency is 0.5~6.0kHz, the temperature is 0~35℃, and the magnetron sputtering conditions are: at 2×10 -4 ~8×10 -4 Under a vacuum of Pa, argon gas with a purity of not less than 99.99% is introduced at a flow rate of 5~50 sccm, with a working pressure of 0.1~0.5 Pa, a DC power supply of 1000~6000W, an RF bias of 200~800V, and a temperature of 120~300℃ for magnetron sputtering of Ti or Cu. (V) The current density used for electroplating and filling the holes is 0.025~1.000A / dm. 2 The pulse frequency is 0.5~5.0kHz, and the temperature is 0~35℃.

10. The method for improving the bonding strength between TGV products and the circuit layer according to claim 1, characterized in that, The circuit layer is formed by magnetron sputtering and / or electroplating, wherein the magnetron sputtering conditions are: at 5 × 10⁻⁶ ppm. -4 Argon gas with a purity of not less than 99.99% is introduced at a flow rate of 10~100 sccm under a vacuum of 0.1~0.6 Pa, with a DC power supply of 1000~6000W, an RF bias of 200~800V, and a temperature of 120~200℃. Magnetron sputtering is performed using a target material selected from Ti-Cu, Cr-Cu, or Ni-Cu. The electroplating conditions are: current density of 0.025~1.000 A / dm³. 2 The pulse frequency is 0.5~5.0kHz, and the temperature is 0~35℃.

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