A glass adapter plate and a method of filling glass vias thereof and a chip

Abstract

A glass adapter plate and a filling method of glass through hole and a chip thereof; the filling method comprises the following steps: ultrasonic cleaning is conducted on a glass substrate with a glass through hole; a seed layer is prepared by adopting a chemical copper plating method; vacuumizing treatment is conducted on the glass substrate; the glass substrate is placed in an electroplating solution for immersion pretreatment; a double-anode electroplating system is adopted; the glass substrate is placed between two anodes and serves as a cathode, and parallelism is maintained between the cathode and the anodes; a bidirectional asymmetric pulse current is adopted in the electroplating system, copper ions in the middle of the glass through hole are supplemented through a forward pulse current, and a protruding structure generated in the glass through hole during deposition is dissolved through a reverse pulse current; and copper ions in the glass through hole are supplemented when the forward and reverse pulse currents are both in a closed state. The scheme has the advantages of high efficiency, wide controllable range of process, high electroplating quality and simple operation, and solves the problems of gaps, holes and other defects in TGV electroplating.

Description

Technical Field

[0001] The present invention relates to the field of glass transfer plates, and in particular to a glass transfer plate and a method for filling a through-glass hole thereof, and a chip. Background Art

[0002] With the slowdown of Moore's Law and the diversification of integrated circuit applications, emerging fields such as the Internet of Things, high-performance computing, artificial intelligence, and 6G communications have placed higher demands on advanced packaging. 3D packaging technology, represented by transsilicon vias (TSVs), achieves high integration of multifunctional electronic devices by vertically stacking chips with different functions. It also has the advantages of small size, light weight, short interconnection distance, low transmission loss, and greatly improved signal transmission efficiency. However, since silicon is a semiconductor, high-frequency electrical signals experience significant electromagnetic coupling effects when transmitted through silicon-based transsilicon vias, which can easily lead to problems such as signal crosstalk. Glass, on the other hand, is an insulator, and crosstalk and other problems do not occur during signal transmission. Furthermore, glass has advantages such as a thermal expansion coefficient similar to that of silicon and low manufacturing cost, making it have broad application prospects in fields such as high-frequency communications.

[0003] The metallization of glass adapter plates is one of the key processes for achieving vertical interconnection in 3D packaging. Currently, the most commonly used TGV metallization method is electroplating deposition. When using conventional DC electroplating solutions for electroplating filling, ideally, the current density amplitude decreases from the center of the through-hole toward the two end openings. Because the electroplating deposition rate is directly proportional to the current amplitude, the deposition rate is highest in the center of the through-hole. This results in the center of the through-hole closing first, forming two blind vias with a small aspect ratio. Consequently, the subsequent electroplating process transitions to a superfill mode, achieving complete filling of the TGV.

[0004] However, due to the large current density gradient in geometrically sharp areas such as the corners and internal protrusions of the TGV orifice, the deposition rate in these areas also increases simultaneously, causing these areas to close first, resulting in defects such as gaps and holes. In addition, under DC electroplating conditions, the copper ions in the TGV are constantly consumed. Especially for TGVs with high aspect ratios, the copper ions cannot be replenished in a timely and sufficient manner through natural diffusion of concentration differences alone. As a result, the maximum deposition rate area of ​​the glass hole shifts to the two ends of the orifice and closes first, which is also very likely to cause defects such as gaps and holes. Summary of the Invention

[0005] The purpose of the present invention is to propose a method for filling glass through-holes in a glass transition plate, which adopts asymmetric bidirectional pulse current electroplating, divides the electroplating filling into different stages according to the electroplating filling rate, and adopts different pulse currents and duty cycles in different stages to realize the regulation of the electroplating filling morphology of high aspect ratio and large aperture glass through-holes, and ultimately achieve the purpose of efficient and defect-free electroplating filling.

[0006] The application further provides a glass adapter plate, a surface of which is processed by using the filling method.

[0007] The application further provides a chip, which uses the glass adapter plate.

[0008] To achieve the above object, the application adopts the following technical scheme.

[0009] The application provides a filling method for a glass via of a glass adapter plate, which comprises the following steps.

[0010] S1: ultrasonic cleaning is performed on a glass substrate with a glass via processed thereon;

[0011] S2: a seed layer is prepared by using a chemical copper plating method;

[0012] S3: vacuumizing treatment is performed on the glass substrate;

[0013] S4: the glass substrate is immersed in an electroplating solution for pre-treatment;

[0014] S5: a double-anode electroplating system is used; the glass substrate is arranged between the two anodes and used as a cathode, and the cathode and the anodes are kept parallel; the electroplating system uses a bidirectional asymmetric pulse current; the copper ions in the middle of the glass via are supplemented by a forward pulse current, and the protruding structure generated in the glass via during the deposition process is dissolved by a reverse pulse current; when the forward pulse current and the reverse pulse current are both in the off state, the copper ions in the glass via are supplemented.

[0015] Optimally, in the step S5, the electroplating filling is performed in stages according to the filling rate F(t) and the filling rate f(t) of the glass via; the pulse current amplitude and the duty cycle are different in different electroplating filling stages; the filling rate f(t) is the first derivative of the filling rate F(t), and the function of the filling rate F(t) with respect to time t in different electroplating filling stages is as follows:

[0016] First stage: F(t)=a1t-b1t 2 , 0≤t<t1; the forward current amplitude is I on 1, and the reverse current amplitude is I rev 1;

[0017] The duty cycle is t on 1: t rev 1: t off 1; t on 1 is the forward current duration of the first stage, t rev 1 is the reverse current duration, t on 1 is the off time; a1 and b1 are coefficients related to the current in the first stage;

[0018] Second stage: t1≤t<t2; positive current amplitude is I on 2, reverse current amplitude is I rev 2;

[0019] duty cycle is t on 2: t rev 2: t off 2; t on 2 is the positive current duration of the second stage, t rev 2 is the reverse current duration, t off 2 is the off time; a2 and b2 are the current-related coefficients in the second stage;

[0020] n-th stage: t n-1 ≤t<t n ; positive current amplitude is I on n , reverse current amplitude is I rev n ;

[0021] duty cycle is t on n : t rev n : t off n ; t on n is the positive current duration of the n-th stage, t rev n is the reverse current duration, t on n is the off time; a n and b n are the current-related coefficients in the n-th stage.

[0022] Optimally, the step S2 comprises:

[0023] S21: placing the glass substrate in a solution containing stannous ions for sensitization treatment;

[0024] S22: placing the glass substrate in a solution containing palladium ions for activation treatment, so that the stannous ions attached to the surface of the glass and inside the through hole react with the palladium ions to form an activation layer;

[0025] S23: placing the glass substrate in a chemical copper plating solution to perform chemical copper plating to make a seed layer.

[0026] Optimally, the step S20 is performed before the step S21;

[0027] Step S20: placing the glass substrate in a bath containing a roughening solution for roughening treatment; the roughening solution comprises hydrofluoric acid and sulfuric acid.

[0028] Optimally, in steps S20-S22, ultrasonic assistance is applied at a frequency of 40-100 kHz and a power of 70-100 w.

[0029] Optimally, in step S20, the roughening solution comprises 5-15 wt% hydrofluoric acid, 50-70 wt% sulfuric acid, and the balance deionized water.

[0030] In step S21, the stannous ion concentration is 0.2-0.5 mol / L.

[0031] In step S22, the palladium ion concentration is 0.2-0.5 mol / L.

[0032] Optimally, during the execution of steps S20-S23, the glass substrate is cleaned with deionized water after each step is completed.

[0033] Optimally, the glass substrate is placed in the middle of the two anodes, the cathode and the anodes are kept parallel, and the distance between the cathode and the anodes is 15-30 mm.

[0034] A glass adapter plate, the surface of which is processed by the above-mentioned glass adapter plate glass via hole filling method.

[0035] A chip using the above-mentioned glass adapter plate.

[0036] Compared with the prior art, one of the above technical solutions has the following beneficial effects:

[0037] The present application provides a glass adapter plate glass via hole filling method, which uses asymmetric bidirectional pulse current electroplating, divides the electroplating filling into different stages according to the electroplating filling rate, uses different pulse currents and duty cycles in different stages, realizes the control of the electroplating filling morphology of high aspect ratio large aperture glass via holes, and finally realizes the purpose of high-efficiency defect-free electroplating filling. The method has the advantages of high efficiency, wide process controllable range, high electroplating quality, and simple operation, and solves the problem of defects such as gaps and holes in TGV electroplating. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a flowchart of the glass adapter plate glass via hole filling method;

[0039] Figure 2 is a structural schematic diagram of one embodiment of a double-anode electroplating system;

[0040] Figure 3This is the electroplating morphology of the glass substrate surface under the metallographic microscope in the comparative example;

[0041] Figure 4 This is the cross section of the through hole observed under a metallographic microscope in the comparative example.

[0042] Figure 5 is the electroplating morphology of the glass substrate surface under the metallographic microscope in Example 1;

[0043] Figure 6 This is the cross section of the through hole observed under a metallographic microscope in Example 1.

[0044] Figure 7 is the electroplating morphology of the glass substrate surface under the metallographic microscope in Example 2;

[0045] Figure 8 This is the cross section of the through hole observed under a metallographic microscope in Example 2.

[0046] Figure 9 1 is a fitting curve diagram of Comparative Example 1, Example 1 and Example 2;

[0047] Figure 10 Schematic diagram of pulse current of comparative example 1;

[0048] Figure 11 is a pulse current schematic diagram of Example 1;

[0049] Figure 12 Schematic diagram of the pulse current of Example 2.

[0050] in:

[0051] Pulse power supply 1, adjustable fixing clamp 2, electrode clamp 3, 1# anode 4, electroplating tank 5, glass substrate 6 and 2# anode 7. DETAILED DESCRIPTION

[0052] The following describes embodiments of the present invention in detail. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present invention and are not to be construed as limiting the present invention.

[0053] like Figure 1-8 A method for filling a through-glass hole of a glass transfer plate comprises the following steps:

[0054] S1: Ultrasonic cleaning of the glass substrate with through-glass holes processed;

[0055] Ultrasonic cleaning can effectively remove impurities on the surface of glass substrates and prevent the influence of impurities on subsequent electroplating. For example, it can clean and remove oil stains on glass substrates, thereby improving the adhesion and uniformity of the plating solution on the glass substrate and improving the quality and hardness of the coating.

[0056] S2: A seed layer is prepared by electroless copper plating;

[0057] The seed layer can be made by using a known electroplating method instead;

[0058] S3: vacuuming the glass substrate;

[0059] The gas inside the through hole is discharged to prevent bubbles in the hole from forming defects during the electroplating process. Vacuuming is a well-known method. For example, a glass substrate clamped with an electrode clamp is placed in a container filled with a copper sulfate solution (with the same concentration as the electroplating solution). The container is fixed in a vacuum box and tilted at a certain angle so that the solution and the glass substrate do not contact each other in the initial stage. Vacuuming is then started to discharge the air in the glass through hole. When the vacuum reaches 0.1MPa, the vacuum box is returned to an upright position so that the glass substrate is immersed in the copper sulfate solution. This process is repeated 3-4 times. After the vacuum is completed, the entire small beaker is directly immersed in the electroplating tank and then removed from the electroplating tank (during the removal of the small beaker, the glass substrate is still immersed in the electroplating solution).

[0060] S4: placing the glass substrate in the electroplating solution for immersion pretreatment;

[0061] The composition and ratio of the plating solution can be determined as needed. In a preferred embodiment, the plating solution includes the following components: 0.5-2 mol / L CuSO4, 0.1-0.7 mol / L H2SO4, 20-80 mg / L NaCl, and 20-80 mg / L NTBC. With this ratio, the plating solution diffuses at a moderate rate under concentration gradients, and the concentration gradient is evenly distributed, allowing the plating solution to be distributed throughout the glass through-hole within a mere 30 minutes of immersion. In the most preferred embodiment, the plating solution includes the following components: 1.0 mol / L CuSO4, 0.4 mol / L H2SO4, 50 mg / L NaCl, and 50 mg / L NTBC. NTBC: Nitro blue tetrazolium chloride, C 40 H 30 N 10 O6Cl2.

[0062] S5: A dual-anode electroplating system is used; the glass substrate is placed between the two anodes and serves as the cathode, and the cathode and anode are kept parallel; the electroplating system uses a bidirectional asymmetric pulse current, replenishing the copper ions in the middle of the glass hole through the forward pulse current, and dissolving the raised structure inside the glass hole generated during the deposition process through the reverse pulse current; when both the forward pulse current and the reverse pulse current are in the off state, the copper ions inside the glass hole are replenished.

[0063] This solution uses pulsed current for power supply, which can generate asymmetric bidirectional pulsed current. The forward pulse current provides a higher material (copper ion) transport rate while rapidly depositing, ensuring that the copper ions in the middle of the through-hole can be adequately replenished. When the reverse pulse current is turned on, the tips and protrusions generated in the glass through-hole during the deposition process are dissolved, avoiding defects caused by abnormal local morphology during the electroplating process. When both the forward and reverse pulse currents are in the off state, the copper ions in the glass through-hole are further well replenished.

[0064] This solution uses asymmetric bidirectional pulse current electroplating, dividing the electroplating filling into different stages according to the electroplating filling rate. Different pulse currents and duty cycles are used in different stages to achieve the regulation of the electroplating filling morphology of high-aspect-ratio and large-aperture glass through-holes, ultimately achieving the goal of efficient and defect-free electroplating filling. This method has the advantages of high efficiency, a wide range of process controllability, high electroplating quality, and simple operation. It solves the problem of defects such as gaps and holes that are prone to appearing during TGV electroplating.

[0065] Compared with DC electroplating, the pulse electroplating of this scheme can not only adjust the size of the forward current, but also adjust the parameters such as the forward and reverse current amplitude ratio, duty cycle (the ratio of the forward and reverse current on time and off time), pulse frequency and pulse number (forward and reverse pulse number), and pulse electroplating allows larger current for electroplating.

[0066] Optionally, in step S5, electroplating filling is performed in stages based on the through-glass via filling rate F(t) and filling rate f(t), with different pulse current amplitudes and duty cycles in different electroplating filling stages. The filling rate F(t) is determined based on actual measured data as it changes over time t. Adjusting the amplitude of the forward pulse current improves the transport efficiency of copper ions within the TGV, thereby improving filling efficiency. Adjusting the reverse pulse current dissolves protrusions and sharp tips during the filling process, resulting in a denser and more uniform coating and eliminating defects during the filling process. Adjusting the duty cycle ensures timely replenishment of copper ions within the TGV, thereby improving electroplating quality.

[0067] The filling rate f(t) is the first-order derivative of the filling rate F(t). The filling rate F(t) at different electroplating filling stages is a function of time t:

[0068] Phase 1: F(t) = a1t - b1t 2 , 0≤t <t1;

[0069] The forward current amplitude is I on 1. The reverse current amplitude is I rev 1; t1 is the time of the first stage deposition, that is, the time required for the central area of ​​the glass through hole to form a seal during the electroplating process, which is determined based on the aperture, aspect ratio, and filling rate.

[0070] The duty cycle is t on 1:t rev 1:t off 1;t on 1 is the forward current duration of the first stage, t rev 1 is the reverse current duration, t on 1 is the shutdown time; a1 and b1 are the coefficients related to the current in the first stage;

[0071] Phase 2: t1≤t <t2;

[0072] The forward current amplitude is I on 2. The reverse current amplitudes are I rev 2. The forward current amplitude is determined based on the required current density; the reverse current amplitude is proportional to the forward current amplitude. The short-duration reverse current has the effect of dissolving the protruding parts deposited at both ends of the through-hole, making the coating more dense and uniform. The reverse current amplitude is generally 1-3 times that of the forward current.

[0073] The duty cycle is t on 2:t rev 2:t off 2;t on 2 is the forward current duration of the second stage, t rev 2 is the reverse current duration, t off 2 is the shutdown time; a2 and b2 are the coefficients related to the current in the second stage; t2 refers to the second stage deposition time, which is determined based on the filling rate and filling rate.

[0074] Stage n: t n-1 ≤t <t n ;

[0075] The forward current amplitude is I on n , the reverse current amplitude is I rev n ;

[0076] The duty cycle is t onn :t rev n :t off n ;t on n is the forward current duration of the nth stage, t rev n is the reverse current duration, t on n is the shutdown time, which is determined based on the filling rate, hole diameter, aspect ratio, etc.; a n and b n is the coefficient related to the current in the nth stage.

[0077] Among them, in multi-step electroplating, first perform polynomial curve fitting on the filling rate F(t) of the first step and the electroplating time t to obtain the quadratic polynomial function of F(t) with respect to t, and determine the coefficients a1 and b1, such as Figure 9 is the fitting curve of comparative example 1, embodiment 1 and embodiment 2; then the filling rate F(t) and electroplating time t of the second step are subjected to polynomial curve fitting to obtain the quadratic polynomial function of F(t) with respect to t, and the coefficients a2 and b2 are determined; similarly, the filling rate F(t) and electroplating time t of the nth step are subjected to polynomial curve fitting to obtain the quadratic polynomial function of F(t) with respect to t, and thus a is determined. n 、b n coefficient.

[0078] Electroplating filling is carried out in stages according to the filling rate F(t) and filling rate f(t) of the glass through hole, with different pulse current amplitudes and duty cycles in different stages. First, electroplating deposition is carried out under a small-amplitude pulse current to achieve defect-free filling and sealing of the middle part of the high-aspect-ratio glass through hole, forming two blind holes with a small aspect ratio. Thereafter, the filling efficiency is gradually improved by adjusting the pulse current amplitude and duty cycle, ultimately achieving efficient and defect-free filling.

[0079] Optimally, step S2 includes:

[0080] S21: placing the glass substrate in a solution containing stannous ions for sensitization treatment;

[0081] A layer of stannous ions adheres to the surface and interior of the through-glass hole, providing stannous ions for the next activation and reduction step;

[0082] S22: placing the glass substrate in a solution containing palladium ions for activation treatment, so that the stannous ions attached to the glass surface and inside the through-hole react with the palladium ions to form an activation layer;

[0083] The activation layer is mainly a single substance palladium colloid; after the activation layer is formed, it can provide a catalyst for the chemical copper plating reaction in the next step;

[0084] S23: placing the glass substrate in a chemical copper plating solution to perform chemical copper plating to form a seed layer.

[0085] Optimally, step S20 is performed before step S21 is performed;

[0086] Step S20: placing the glass substrate in a bath containing a roughening solution to perform roughening treatment; the roughening solution includes hydrofluoric acid and sulfuric acid.

[0087] The roughening solution can perform roughening treatment on the glass substrate, so that the glass via sidewall forms a hydrophilic microstructure, which can increase the adhesion between the subsequent seed layer and the glass via sidewall and surface, thereby ensuring that the structure of the subsequent deposition layer remains most stable.

[0088] Optimally, in steps S20-S22, ultrasonic assistance with a frequency of 40-100 kHz and a power of 70-100 W is applied.

[0089] Each sub-step in the preparation of the seed layer uses ultrasonic treatment, which can concentrate low-concentration components in the liquid to high-concentration areas through high-speed convection, and accelerate their precipitation, coagulation and sedimentation, thereby achieving plating solution concentration and purification to improve the stability of sensitization treatment, activation treatment and chemical copper plating.

[0090] Optimally, in step S20, the roughening solution includes 5-15 wt% hydrofluoric acid, 50-70 wt% sulfuric acid, and the balance deionized water;

[0091] In step S21, the stannous ion concentration is 0.2-0.5 mol / L;

[0092] In step S22, the palladium ion concentration is 0.2-0.5 mol / L.

[0093] The roughening solution only needs to contain 5-15 wt% hydrofluoric acid and 50-70 wt% sulfuric acid, which can reduce the roughening treatment time to 2 min, achieving the highest roughening efficiency; when the sensitization treatment is performed with a stannous ion solution concentration of 0.2 mol / L, the sensitization treatment time can be reduced to 5 min, achieving the highest sensitization treatment efficiency; when the activation treatment is performed with a palladium ion concentration of 0.2 mol / L, the activation treatment time can be reduced to 5 min, achieving the highest activation treatment efficiency.

[0094] Optimally, during the performance of steps S20-S23, the glass substrate is cleaned with deionized water after each step is completed.

[0095] The deionized water can remove the residual treatment solution, which is dissolved in the deionized water, preventing the residual treatment solution from affecting the subsequent step.

[0096] Optimally, the glass substrate is placed between the two anodes, the cathode and the anode are kept parallel, and the distance between the cathode and the anode is 15 to 30 mm.

[0097] The glass substrate is placed between two anodes. This dual-anode electroplating system facilitates symmetrical electric field distribution centered on the center of the through-glass hole, improving the efficiency of copper ion transport into the hole. The advantage of a 15-30mm spacing between the cathode and anode is that the current density is evenly distributed across the glass substrate, improving the efficiency of copper ion transport from the anode to the through-glass hole.

[0098] A glass transition plate, the surface of which is processed by the filling method of a glass through-hole of a glass transition plate according to any of the above embodiments.

[0099] A chip uses a glass transfer plate according to any of the above embodiments.

[0100] The following is a comparative example, Example 1 and Example 2 for further explanation.

[0101] Comparative Example:

[0102] S1: The glass substrate with the through-holes processed was ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 5 minutes respectively, with a total cleaning time of 15 minutes; the ultrasonic frequency was 40 kHz and the power was 70 W.

[0103] S2 includes:

[0104] S21: Rinse the glass substrate with a large amount of deionized water;

[0105] S22: transferring the glass substrate to a solution containing 0.2 mol / L palladium ions for activation treatment for 5 minutes while applying ultrasonic assistance at 40 kHz and 70 W power; rinsing the activated glass substrate with a large amount of deionized water;

[0106] S23: transferring the glass substrate to a chemical copper plating solution for chemical copper plating, wherein the chemical copper plating time is 10 minutes; and washing the glass substrate after the chemical copper plating with a large amount of deionized water.

[0107] S3: Use an electrode clamp to clamp and fix the glass substrate, and place it in an immersion tank for vacuum treatment. The vacuum degree is 0.1 kPa and the pressure holding time is 30 minutes.

[0108] S4: The glass substrate is quickly transferred to the electroplating solution for immersion pretreatment, so that the electroplating solution diffuses into the pores driven by the concentration difference to form a concentration gradient. The immersion pretreatment time is 30 minutes. At this time, the electroplating solution includes the following components: CuSO4 concentration is 1.0 mol / L, H2SO4 concentration is 0.4 mol / L, NaCl concentration is 50 mg / L, and NTBC concentration is 50 mg / L.

[0109] S5: A dual-anode electroplating system is used; the glass substrate is placed between the two anodes and serves as a cathode, with the cathode and anode kept parallel; the wires are connected and electroplating begins; this embodiment performs electroplating filling in stages based on the filling rate F(t) and filling rate f(t) of the glass through hole of this solution, specifically, electroplating is performed in two stages, such as Figure 10 The filling rate f(t) is directly obtained from the derivative of the filling rate F(t); the pulse current setting of the first stage is: forward current density amplitude 0.1ASD, forward and reverse current density amplitude ratio 1:2, duty cycle t on 1:t rev 1:t off 1; = 100:20:100, electroplating time is 120min; the pulse current setting of the second stage is: forward current density amplitude 0.3ASD, forward and reverse current density amplitude ratio 1:2, duty cycle t on2 :t rev 2:t off 2=100:10:100, electroplating time is 120min.

[0110] After the electroplating is completed, the glass substrate is cleaned with deionized water and dried. The electroplated morphology of the glass substrate surface is observed under a metallographic microscope. The surface results are shown in Figure 3 Since the glass substrate has not been roughened, the adhesion between the deposited layer and the glass is poor, and the deposited layer on the surface has some defects such as falling off and bulging. The glass substrate was cut into small pieces of 10mm×10mm and cured with epoxy resin. The through-hole cross section was made using a metallographic grinding and polishing machine. The through-hole cross section was observed using a metallographic microscope to see if there were any plating defects. The results are shown in Figure 2. Figure 4 , the coating is uniform and has no defects.

[0111] Example 1:

[0112] S1: The glass substrate with the through-holes processed was ultrasonically cleaned with acetone, anhydrous ethanol, and deionized water for 5 minutes respectively, with a total cleaning time of 15 minutes; the ultrasonic frequency was 40 kHz and the power was 70 W.

[0113] S2 includes:

[0114] S20: placing the cleaned glass substrate in a roughening solution consisting of 50 wt % sulfuric acid, 10 wt % hydrofluoric acid, and the balance deionized water for roughening treatment, while applying ultrasonic assistance at 100 kHz and a power of 100 W, the roughening temperature being 60° C., and the roughening treatment time being 3 minutes; and rinsing the roughened glass substrate with a large amount of deionized water;

[0115] S21: transferring the glass substrate to a solution containing 0.2 mol / L stannous ions for sensitization treatment for 5 minutes while applying ultrasonic assistance at 40 kHz and 70 W power; rinsing the sensitized glass substrate with a large amount of deionized water;

[0116] S22: transferring the glass substrate to a solution containing 0.2 mol / L palladium ions for activation treatment for 5 minutes while applying ultrasonic assistance at 40 kHz and 70 W power; rinsing the activated glass substrate with a large amount of deionized water;

[0117] S23: transferring the glass substrate to a chemical copper plating solution for chemical copper plating, wherein the chemical copper plating time is 10 minutes; and washing the glass substrate after the chemical copper plating with a large amount of deionized water.

[0118] S3: Use an electrode clamp to clamp and fix the glass substrate, and place it in an immersion tank for vacuum treatment. The vacuum degree is 0.1 kPa and the pressure holding time is 30 minutes.

[0119] S4: The glass substrate is quickly transferred to the electroplating solution for immersion pretreatment, so that the electroplating solution diffuses into the pores driven by the concentration difference to form a concentration gradient. The immersion pretreatment time is 30 minutes. At this time, the electroplating solution includes the following components: CuSO4 concentration is 1.0 mol / L, H2SO4 concentration is 0.4 mol / L, NaCl concentration is 50 mg / L, and NTBC concentration is 50 mg / L.

[0120] S5: A dual-anode electroplating system is used; a glass substrate is placed between two anodes and serves as a cathode, with the cathode and anode kept parallel; a wire is connected and electroplating begins; this embodiment performs electroplating filling in stages based on the filling rate F(t) and filling rate f(t) of the glass through hole of this solution, specifically, electroplating is performed in three stages, such as Figure 11 ; Filling rate f(t) is directly obtained through the derivative of filling rate F(t);

[0121] The pulse current settings for the first stage are: forward current density amplitude 0.1ASD, forward and reverse current density amplitude ratio 1:3, duty cycle t on 1:t rev 1:t off1=100:10:100, electroplating time is 120min;

[0122] The pulse current setting of the second stage is: forward current density amplitude 0.2ASD, forward and reverse current density amplitude ratio 1:2, duty cycle t on 2:t rev 2:t off 2 = 100:10:100, electroplating time is 60 min;

[0123] The pulse current setting of the third stage is: forward current density amplitude 0.3ASD, forward and reverse current density amplitude ratio 1:1, duty cycle t on 3:t rev 3:t off 3=100:10:100, electroplating time is 30min.

[0124] After the electroplating is completed, the glass substrate is cleaned with deionized water and dried. The electroplated morphology of the glass substrate surface is observed under a metallographic microscope. The surface results are shown in Figure 5 The glass substrate was cut into 10mm×10mm pieces and cured with epoxy resin. A metallographic grinding and polishing machine was used to make the through-hole cross section. A metallographic microscope was used to observe whether there were any electroplating defects in the through-hole cross section. The results are shown in Fig. Figure 6 The coating is uniform and has no defects. This shows that the first embodiment solves the problem of defects such as gaps and holes that are prone to occur during TGV electroplating.

[0125] Example 2:

[0126] S1: The glass substrate with the through-holes processed was ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 5 minutes respectively. The total cleaning time was 15 minutes. The ultrasonic frequency was 40 kHz and the power was 70 W.

[0127] S2 includes:

[0128] S20: placing the cleaned glass substrate in a roughening solution containing 50 wt % sulfuric acid, 10 wt % hydrofluoric acid, and the balance deionized water for roughening treatment, while applying ultrasonic assistance at 100 kHz and a power of 100 W, the roughening temperature being 70° C., and the roughening treatment time being 2 minutes; and rinsing the roughened glass substrate with a large amount of deionized water;

[0129] S21: transferring the glass substrate to a solution containing 0.2 mol / L stannous ions for sensitization treatment for 5 minutes while applying ultrasonic assistance at 40 kHz and 70 W power; rinsing the sensitized glass substrate with a large amount of deionized water;

[0130] S22: The glass substrate is transferred to a solution containing 0.2 mol / L palladium ions for activation treatment, the activation treatment time is 5 min, and ultrasonic assistance with a frequency of 40 kHz and a power of 70 w is applied; the glass substrate after activation treatment is washed with a large amount of deionized water;

[0131] S23: The glass substrate is transferred to a solution for chemical copper plating for chemical copper plating, the chemical copper plating time is 10 min; the glass substrate after chemical copper plating is cleaned with a large amount of deionized water.

[0132] S24: The glass substrate is clamped and fixed by using an electrode clamp, and is placed in a soaking tank for vacuumizing treatment, the vacuum degree is 0.1 kPa, and the pressure maintaining time is 30 min.

[0133] S4: The glass substrate is quickly transferred to an electroplating solution for soaking pretreatment, so that the electroplating solution diffuses into the hole under the driving of the concentration difference to form a concentration gradient, and the soaking pretreatment time is 30 min; at this time, the electroplating solution includes the following components: the concentration of CuSO4 is 1.0 mol / L, the concentration of H2SO4 is 0.4 mol / L, the concentration of NaCl is 50 mg / L, and the concentration of NTBC is 50 mg / L.

[0134] S5: A double-anode electroplating system is adopted; the glass substrate is placed between the two anodes and serves as a cathode, and the cathode and the anode are kept parallel; the connecting wire is connected, and the electroplating is started; this embodiment is based on the filling rate F(t) and the filling rate f(t) of the glass via hole of the scheme to carry out stage-by-stage electroplating filling, and the electroplating is carried out in four stages, such as Figure 12 ;

[0135] The pulse current setting of the first stage: the forward current density amplitude is 0.1 ASD, the forward and reverse current density amplitude ratio is 1:2, and the duty cycle t on 1: t rev 1: t off 1 = 100:20:100, and the electroplating time is 60 min;

[0136] The pulse current setting of the second stage: the forward current density amplitude is 0.2 ASD, the forward and reverse current density amplitude ratio is 1:2, and the duty cycle t on 2: t rev 2: t off 2 = 100:10:100, and the electroplating time is 60 min;

[0137] The pulse current setting of the third stage: the forward current density amplitude is 0.3 ASD, the forward and reverse current density amplitude ratio is 1:1, and the duty cycle t on 3: t rev 3: t off3 = 100:10:100, electroplating time is 30 minutes;

[0138] The pulse current setting of the fourth stage is: forward current density amplitude 0.4ASD, forward and reverse current density amplitude ratio 1:1, duty cycle t on 4:t rev 4:t off 4=100:5:100, electroplating time is 30min.

[0139] After the electroplating is completed, the glass substrate is cleaned with deionized water and dried. The electroplated morphology of the glass substrate surface is observed under a metallographic microscope. The surface results are shown in Figure 7 The glass substrate was cut into 10mm×10mm pieces and cured with epoxy resin. A metallographic grinding and polishing machine was used to make the through-hole cross section. A metallographic microscope was used to observe whether there were any electroplating defects in the through-hole cross section. The results are shown in Fig. Figure 8 , the coating is uniform and has no defects.

[0140] At the same time, it can be seen from the comparison between Example 2 and Example 1 that Figure 5 and Figure 7 Since Example 2 performs the electroplating process in four stages, the through-glass hole of Example 2 will have a more uniform deposition effect.

[0141] It explains how to gradually improve the filling efficiency by adjusting the pulse current amplitude and duty cycle, ultimately achieving efficient and defect-free filling.

[0142] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to the embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the claims and their equivalents.

Claims

1. A method for filling a through-glass hole of a glass transition plate, characterized in that: The steps include: S1: Ultrasonic cleaning of the glass substrate with through-glass holes processed; S2: A seed layer is prepared by electroless copper plating; S3: vacuuming the glass substrate; S4: placing the glass substrate in the electroplating solution for immersion pretreatment; S5: A dual-anode electroplating system is used. The glass substrate is placed between two anodes and serves as a cathode, with the cathode and anode maintained parallel to each other. The electroplating system uses a bidirectional asymmetric pulse current. The forward pulse current replenishes the copper ions in the middle of the glass hole, and the reverse pulse current dissolves the protrusions inside the glass hole generated during the deposition process. The copper ions inside the glass hole are replenished when both the forward and reverse pulse currents are in the off state. In step S5, electroplating filling is performed in stages according to the filling rate F(t) and filling rate f(t) of the through-glass via. The pulse current amplitude and duty cycle in different electroplating filling stages are different. The filling rate f(t) is the first-order derivative of the filling rate F(t). The filling rate F(t) in different electroplating filling stages is a function of time t: Phase 1: ; The forward current amplitude is I on 1 , the reverse current amplitude is I rev 1 t1 is the time for the first stage of deposition, which is the time required for the central area of ​​the glass through hole to form a seal during the electroplating process, and is determined based on the aperture, aspect ratio, and filling rate; The duty cycle is t on 1 :t rev 1 :t off 1 ;t on 1 is the forward current duration of the first stage, t rev 1 is the reverse current duration, t on 1 It is the shutdown time; and is the coefficient related to current in the first stage; Phase 2: ; The forward current amplitude is I on 2 , the reverse current amplitudes are I rev 2 ; The duty cycle is t on 2 :t rev 2 :t off 2 ;t on 2 is the forward current duration of the second stage, t rev 2 is the reverse current duration, t off 2 It is the shutdown time; and is the coefficient related to current in stage 2; t2 refers to the second stage deposition time, which is determined based on the filling ratio and filling rate; Stage n: ； The forward current amplitude is I on n , the reverse current amplitude is I rev n ; The duty cycle is t on n :t rev n :t off n ;t on n is the forward current duration of the nth stage, t rev n is the reverse current duration, t on n It is the shutdown time; and is the coefficient related to the current in the nth stage; t n refers to the deposition time of stage n, t n-1 refers to the deposition time of stage n-1; Perform polynomial curve fitting on the filling rate F(t) and electroplating time t of the first stage to obtain the quadratic polynomial function of F(t) with respect to t, and determine the coefficients a1 and b1; perform polynomial curve fitting on the filling rate F(t) and electroplating time t of the second stage to obtain the quadratic polynomial function of F(t) with respect to t, and determine the coefficients a2 and b2; perform polynomial curve fitting on the filling rate F(t) and electroplating time t of the nth stage to obtain the quadratic polynomial function of F(t) with respect to t, and determine a n 、b n coefficient.

2. The method for filling a through-glass hole of a glass transition plate according to claim 1, characterized in that: The step S2 comprises: S21: placing the glass substrate in a solution containing stannous ions for sensitization treatment; S22: placing the glass substrate in a solution containing palladium ions for activation treatment, so that the stannous ions attached to the glass surface and inside the through-hole react with the palladium ions to form an activation layer; S23: placing the glass substrate in a chemical copper plating solution to perform chemical copper plating to form a seed layer.

3. The method for filling a through-glass hole of a glass transition plate according to claim 1, characterized in that: Execute step S20 before executing step S21; Step S20: placing the glass substrate in a bath containing a roughening solution for roughening treatment; Roughening solutions include: hydrofluoric acid and sulfuric acid.

4. The method for filling a through-glass hole of a glass transition plate according to claim 3, characterized in that: In steps S20 to S22 , ultrasonic assistance with a frequency of 40 to 100 kHz and a power of 70 to 100 W is applied.

5. The method for filling a through-glass hole of a glass transition plate according to claim 3, characterized in that: In step S20, the roughening solution includes: 5-15 wt% hydrofluoric acid, 50-70 wt% sulfuric acid and the balance deionized water; In step S21, the concentration of stannous ions is 0.2 to 0.5 mol / L; In step S22, the palladium ion concentration is 0.2 to 0.5 mol / L.

6. The method for filling a through-glass hole of a glass transition plate according to claim 3, characterized in that: During the execution of steps S20 to S23 , the glass substrate is cleaned with deionized water after each step is completed.

7. The method for filling a through-glass hole of a glass transition plate according to claim 1, characterized in that: The glass substrate is placed between the two anodes, the cathode and the anode are kept parallel, and the distance between the cathode and the anode is 15 to 30 mm.

8. A glass transfer plate, characterized in that: The surface is processed by the filling method of the glass through hole of the glass transition plate according to any one of claims 1 to 7.

9. A chip, characterized in that: Use the glass transition plate described in claim 8.

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