Glass adapter plate, filling method of glass through hole of glass adapter plate and chip

Abstract

The invention discloses a glass adapter plate, a filling method of a glass through hole of the glass adapter plate and a chip. The filling method comprises the following steps: carrying out ultrasonic cleaning on a glass substrate with a processed glass through hole; manufacturing a seed layer by adopting a chemical copper plating method; carrying out vacuumizing treatment on the glass substrate; the glass substrate is placed in the electroplating solution to be subjected to infiltration pretreatment; a double-anode electroplating system is adopted; the glass substrate is arranged between the two anodes and serves as a cathode, and the cathode is parallel to the anodes; according to the electroplating system, bidirectional asymmetric pulse current is adopted, copper ions in the middle of the glass through hole are supplemented through forward pulse current, and a protruding structure generated in the glass through hole in the deposition process is dissolved through reverse pulse current; and when the forward pulse current and the reverse pulse current are both in a closed state, copper ions in the glass through hole are supplemented. The scheme has the advantages of high efficiency, wide process adjustable range, high electroplating quality, simplicity in operation and the like, and solves the problem of defects such as gaps and holes during TGV electroplating.

Description

Technical Field

[0001] The invention relates to the field of glass transfer plates, and in particular to a glass transfer plate and a filling method and chip of a glass through hole thereof. 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 put forward higher requirements for advanced packaging. 3D packaging technology represented by silicon-based adapter plates (TSV) achieves high integration of multifunctional electronic devices by stacking chips with different functions in the vertical direction. It also has the characteristics of small size, light weight, short interconnection distance, and low transmission loss, and greatly improves the efficiency of signal transmission. However, since silicon is a semiconductor, there is an obvious electromagnetic coupling effect when high-frequency electrical signals are transmitted in silicon-based adapter plates, which easily leads to problems such as signal crosstalk. Glass is an insulator, and there will be no problems such as crosstalk in signal transmission. In addition, glass has the advantages of a thermal expansion coefficient similar to that of silicon and low manufacturing cost, which makes it have broad application prospects in high-frequency communications and other fields.

[0003] The metallization of the glass adapter is one of the key processes for achieving vertical interconnection of 3D packaging. The most commonly used TGV metallization method is the electroplating deposition process. When using a conventional DC electroplating scheme for electroplating filling, ideally, the current density amplitude decreases from the middle of the through-hole to the two end openings. Since the electroplating deposition rate is directly proportional to the current amplitude, the deposition rate in the middle of the through-hole is the highest. In this way, the middle of the through-hole is closed first, forming two blind holes with a small aspect ratio. Therefore, in the subsequent electroplating process, it will be transformed into a super-filling mode, thereby achieving complete filling of the TGV.

[0004] However, due to the large current density gradient in the geometrically sharp areas such as the corners of the TGV orifice and the internal protrusions, the deposition rate in this area is also increased synchronously, so that these areas are usually closed first, resulting in defects such as gaps and holes. In addition, under DC plating conditions, the copper ions in the TGV are constantly consumed, especially for TGVs with a high aspect ratio, and it is difficult for the copper ions to be replenished in a timely and sufficient amount by natural diffusion based on the concentration difference alone, causing the maximum deposition rate area of ​​the glass through hole to shift to both ends of the orifice and close 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 achieve 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 present invention also provides a glass adapter plate, the surface of which is processed by the above filling method.

[0007] The present invention also provides a chip which uses one of the above glass adapter plates.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] A method for filling a glass through-hole of a glass adapter plate includes the following steps:

[0010] S1: Ultrasonically clean the glass substrate with the processed glass through-holes.

[0011] S2: Fabricate a seed layer by electroless copper plating.

[0012] S3: Perform a vacuum pumping treatment on the glass substrate.

[0013] S4: Place the glass substrate in an electroplating solution for infiltration pretreatment.

[0014] S5: Adopt a dual-anode electroplating system; the glass substrate is placed between two anodes and serves as the cathode, and the cathode and the anodes are kept parallel; the electroplating system adopts a bidirectional asymmetric pulsed current, the copper ions in the middle of the glass through-hole are supplemented by the forward pulsed current, and the convex structure generated during the deposition inside the glass through-hole is dissolved by the reverse pulsed current; when both the forward pulsed current and the reverse pulsed current are in the off state, the copper ions inside the glass through-hole are supplemented.

[0015] Optimally, in step S5, staged electroplating filling is performed according to the filling rate F(t) and the filling rate f(t) of the glass through-hole, and 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:

[0016] First stage: F(t) = a1t - b1t 2 , 0 ≤ t < t1; the forward current amplitude is I on 1, 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 shutdown time; a1 and b1 are coefficients related to the current in the first stage;

[0018] The second stage: t1 ≤ t < t2; the forward current amplitude is I on 2, and the reverse current amplitudes are I rev 2;

[0019] 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 coefficients related to the current in the second stage;

[0020] The nth stage: t n-1 ≤ t < t n ; the forward current amplitude is I on n , and the reverse current amplitude is I rev n ;

[0021] 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 is the shutdown time; a n and b n are coefficients related to the current in the nth stage.

[0022] Optimally, the step S2 includes:

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

[0024] S22: Place 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 holes react with the palladium ions to form an activation layer;

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

[0026] Optimally, step S20 is executed before executing step S21;

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

[0028] Optimally, 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.

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

[0030] In step S21, the concentration of stannous ions 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 to S23 , the glass substrate is cleaned with deionized water after each step is completed.

[0033] 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.

[0034] A glass transfer plate, the surface of which is processed by the above-mentioned method for filling a glass through hole of a glass transfer plate.

[0035] A chip uses the above-mentioned glass transfer plate.

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

[0037] The present invention provides a method for filling glass through holes of a glass transfer plate, which adopts asymmetric bidirectional pulse current electroplating, divides the electroplating filling into different stages according to the electroplating filling rate, adopts different pulse currents and duty cycles in different stages, realizes the regulation of the electroplating filling morphology of high aspect ratio and large aperture glass through holes, and finally realizes the purpose of efficient and 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 that are easy to appear during TGV electroplating. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a flow chart of a method for filling a through-glass hole of a glass transfer plate;

[0039] Figure 2 It is a schematic structural diagram of one embodiment of a dual-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] Fig. 9 It is the fitting curve diagram of comparative example 1, embodiment 1 and embodiment 2;

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

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

[0049] Fig.12 Schematic diagram of pulse current in 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] Embodiments of the present invention are described in detail below, examples of which 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 only used to explain the present invention, and cannot be understood as limiting the present invention.

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

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

[0055] Ultrasonic cleaning can effectively remove impurities on the surface of the glass substrate and avoid the influence of impurities on subsequent electroplating. For example, it can clean and remove oil stains on the glass substrate, 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: using chemical copper plating to make a seed layer;

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

[0058] S3: vacuumizing the glass substrate;

[0059] The gas inside the through hole is discharged to avoid the bubbles in the hole causing defects in the electroplating process; vacuum treatment is a well-known method, for example, a glass substrate clamped by an electrode clamp is placed in a container filled with a copper sulfate solution (the concentration is the same 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 in the initial stage, and the vacuum treatment is started to discharge the air in the glass through hole. When the vacuum degree reaches 0.1MPa, the vacuum box is restored to an upright state 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 the small beaker is taken out of the electroplating tank (in the process of taking out the small beaker, the glass substrate is always 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 according to the needs. In the 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. According to this ratio, the diffusion speed of the plating solution under the concentration difference is moderate, and the concentration gradient is evenly distributed, which can meet the requirement of only 30 minutes of infiltration to make the plating solution distributed in the glass through hole; in the best 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 two anodes and serves as a cathode, and the cathode and anode are kept parallel; the electroplating system uses a bidirectional asymmetric pulse current, and the copper ions in the middle of the glass through hole are replenished by a forward pulse current, and the raised structure inside the glass through hole generated during the deposition process is dissolved by a 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 through hole are replenished.

[0063] This solution uses pulse current to supply power, which can generate asymmetric bidirectional pulse 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; and when the reverse pulse current is turned on, the tip and protrusion generated in the deposition process inside the glass through hole will be dissolved, avoiding defects caused by abnormal protrusions in the local morphology during the electroplating process; when both the forward pulse current and the reverse pulse current are in the off state, the copper ions inside the glass through hole can be further well replenished;

[0064] This scheme 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 achieve the regulation of the electroplating filling morphology of high aspect ratio and large aperture glass through holes, and finally achieve the purpose of efficient and defect-free electroplating filling; this 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 that are prone to occur during TGV electroplating.

[0065] Compared with DC electroplating, the pulse electroplating of this scheme can not only adjust the forward current size, but also adjust 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 other parameters. In addition, pulse plating allows larger current for electroplating.

[0066] It can be optimized that in step S5, electroplating filling is performed in stages according to the filling rate F(t) and filling rate f(t) of the glass through hole, and the pulse current amplitude and duty cycle in different electroplating filling stages are different; the filling rate F(t) is determined according to the change of the actual measurement data over time t. Adjusting the amplitude of the forward pulse current is conducive to improving the transportation efficiency of copper ions inside the TGV and thus improving the filling efficiency; adjusting the reverse pulse current is conducive to dissolving the protrusions and tip parts during the filling process, making the coating more dense and uniform, and eliminating defects during the filling process; adjusting the duty cycle allows the copper ions inside the TGV to be replenished in time, which is conducive to improving the quality of electroplating.

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

[0068] Stage 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 hole diameter, 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 the case of multi-step electroplating, firstly, the filling rate F(t) of the first step and the electroplating time t are fitted with a polynomial curve to obtain the quadratic polynomial function of F(t) with respect to t, and the coefficients a1 and b1 are determined, such as Fig. 9 is the fitting curve of comparative example 1, embodiment 1 and embodiment 2; then the filling rate F(t) and the 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 the 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, and the pulse current amplitude and duty cycle are different in different stages; first, electroplating deposition is carried out under a small-amplitude pulse current to achieve defect-free filling and closure 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, and finally efficient defect-free filling is achieved.

[0079] Preferably, step S2 includes:

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

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

[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;

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

[0087] The roughening solution can roughen the glass substrate, forming a hydrophilic microstructure on the sidewall of the through-glass hole, which can increase the adhesion between the subsequent seed layer and the sidewall and surface of the through-glass hole, thereby ensuring that the structure of the subsequent deposited layer remains the most stable.

[0088] Optimally, 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.

[0089] Ultrasonic treatment is used in each sub-step of making the seed layer. Through high-speed convection, low-concentration components in the liquid are concentrated to high-concentration areas, and their precipitation, coagulation and precipitation are accelerated, thereby achieving concentration and purification of the plating solution 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 concentration of stannous ions 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 5-15wt% hydrofluoric acid and 50-70wt% sulfuric acid to shorten the roughening treatment time to 2 minutes, with the highest roughening efficiency. When the sensitization treatment is performed at a stannous ion solution concentration of 0.2mol / L, the sensitization treatment time can be shortened to 5 minutes, with the highest sensitization treatment efficiency. At a palladium ion concentration of 0.2mol / L, the activation treatment time can be shortened to 5 minutes, with the highest activation treatment efficiency.

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

[0095] Deionized water can remove the residual processing liquid, and the processing liquid is dissolved in the deionized water to prevent the residual processing liquid from affecting the subsequent steps.

[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 the two anodes. The electroplating system based on the double anode is conducive to the symmetrical distribution of the electric field on both sides centered on the middle of the glass through hole, which improves the efficiency of copper ion transportation to the inside of the glass through hole. The advantage of the distance between the cathode and the anode being 15 to 30 mm is that the current density is evenly distributed on the glass substrate, which improves the efficiency of copper ion transportation from the anode to the inside of the glass through hole.

[0098] A glass transfer plate, the surface of which is processed by a filling method for a glass through hole of a glass transfer 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, embodiment 1 and embodiment 2 for further explanation.

[0101] Comparative Example:

[0102] S1: The glass substrate with 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 40kHz and the power was 70w.

[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, wherein the activation treatment time is 5 min, and ultrasonic assistance at 40 kHz and a power of 70 W is applied simultaneously; and the activated glass substrate is rinsed 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 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 plating solution for immersion pretreatment, so that the plating solution diffuses into the hole driven by the concentration difference to form a concentration gradient. The immersion pretreatment time is 30 minutes. At this time, the plating 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; a glass substrate is placed between two anodes and serves as a cathode, and the cathode and the anode are 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 two stages, such as Fig.10 ; The filling rate f(t) is directly obtained through the derivative of the filling rate F(t); The pulse current setting of the first stage: the forward current density amplitude is 0.1ASD, the forward and reverse current density amplitude ratio is 1:2, and the duty cycle is t on 1:t rev 1:t off 1; = 100:20:100, electroplating time is 120min; the pulse current setting of the second stage: 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 undesirable phenomena 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 section was made using a metallographic grinding and polishing machine. The through-hole section was observed using a metallographic microscope to see if there were any electroplating defects. The results are shown in Figure 1. Figure 4 , the coating is uniform and without defects.

[0111] Embodiment 1:

[0112] S1: The glass substrate with 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 40kHz and the power was 70w.

[0113] S2 includes:

[0114] S20: placing the cleaned glass substrate in a roughening solution containing 50wt% sulfuric acid, 10wt% hydrofluoric acid and the remainder deionized water for roughening treatment, while applying ultrasonic assistance at 100kHz and a power of 100W, the roughening temperature is 60°C, and the roughening treatment time is 3min; using a large amount of deionized water to clean the roughened glass substrate;

[0115] S21: transferring the glass substrate to a solution containing 0.2 mol / L stannous ions for sensitization treatment, the sensitization treatment time is 5 min, and ultrasonic assistance of 40 kHz and 70 W power is applied simultaneously; and the sensitized glass substrate is rinsed 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, wherein the activation treatment time is 5 min, and ultrasonic assistance at 40 kHz and a power of 70 W is applied simultaneously; and the activated glass substrate is rinsed 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 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 plating solution for immersion pretreatment, so that the plating solution diffuses into the hole driven by the concentration difference to form a concentration gradient. The immersion pretreatment time is 30 minutes. At this time, the plating 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, and the cathode and anode are 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, and specifically, electroplating is performed in three stages, such as Fig.11 ; The filling rate f(t) is directly obtained through the derivative of the 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 120 minutes;

[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 minutes;

[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 small pieces of 10 mm × 10 mm and cured with epoxy resin. A metallographic polishing machine was used to make the through-hole cross section. A metallographic microscope was used to observe whether there were electroplating defects in the through-hole cross section. The results are shown in Figure 6 The coating is uniform and has no defects. This shows that the first embodiment solves the problem that defects such as gaps and holes are prone to occur during TGV electroplating.

[0125] Embodiment 2:

[0126] S1: The glass substrate with 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, an ultrasonic frequency of 40kHz and a power of 70W.

[0127] S2 includes:

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

[0129] S21: transferring the glass substrate to a solution containing 0.2 mol / L stannous ions for sensitization treatment, the sensitization treatment time is 5 min, and ultrasonic assistance of 40 kHz and 70 W power is applied simultaneously; and the sensitized glass substrate is rinsed with a large amount of deionized water;

[0130] S22: transferring the glass substrate to a solution containing 0.2 mol / L palladium ions for activation treatment, wherein the activation treatment time is 5 min, and ultrasonic assistance at 40 kHz and a power of 70 W is applied simultaneously; and the activated glass substrate is rinsed with a large amount of deionized water;

[0131] 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 chemical copper plating with a large amount of deionized water.

[0132] S24: The glass substrate is clamped and fixed with an electrode clamp, and placed in a wetting tank for vacuum treatment, with a vacuum degree of 0.1 kPa and a pressure holding time of 30 min.

[0133] S4: The glass substrate is quickly transferred to the plating solution for immersion pretreatment, so that the plating solution diffuses into the hole driven by the concentration difference to form a concentration gradient. The immersion pretreatment time is 30 minutes. At this time, the plating 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.

[0134] S5: A dual-anode electroplating system is used; a glass substrate is placed between two anodes and serves as a cathode, and the cathode and anode are 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, and specifically, electroplating is performed in four stages, such as Fig.12 ;

[0135] The pulse current settings for the first stage are: 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 60 minutes;

[0136] The pulse current settings for the second stage are: 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 minutes;

[0137] The pulse current setting of the third stage: forward current density amplitude 0.3ASD, forward and reverse current density amplitude ratio 1:1; 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 small pieces of 10 mm × 10 mm and cured with epoxy resin. A metallographic polishing machine was used to make the through-hole cross section. A metallographic microscope was used to observe whether there were electroplating defects in the through-hole cross section. The results are shown in Figure 8 , the coating is uniform and without 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 electroplating in four stages, the deposition effect of the through glass hole in Example 2 will be more uniform.

[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] Although the 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 present invention, and that the scope of the present invention is defined by the claims and their equivalents.

Claims

1. A method for filling a glass through hole of a glass transition plate, characterized in that: The steps include: S1: Ultrasonic cleaning of a glass substrate with a through-glass hole processed; S2: using chemical copper plating to make a seed layer; S3: vacuumizing 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, and the cathode and anode are kept parallel; the electroplating system uses a bidirectional asymmetric pulse current, and the copper ions in the middle of the glass through hole are replenished by a forward pulse current, and the raised structure inside the glass through hole generated during the deposition process is dissolved by a 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 through hole are replenished.

2. The method for filling a glass through hole of a glass transition plate according to claim 1, characterized in that: 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 hole, and 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), and the function of the filling rate F(t) in different electroplating filling stages with respect to time t is: First stage: F(t) = a1t - b1t 2 , 0 ≤ t < t1; the forward current amplitude is I on1 , the reverse current amplitude is I rev1 ; The duty cycle is t on1 :t rev1 :t off1 ;t on1 is the forward current duration of the first stage, t rev1 is the reverse current duration, t on1 is the shutdown time; a1 and b1 are the coefficients related to the current in the first stage; Second stage: t1 ≤ t < t2; the forward current amplitude is I on2 , and the reverse current amplitudes are respectively I rev2 ; The duty cycle is t on2 :t rev2 :t off2 ;t on2 is the forward current duration of the second stage, t rev2 is the reverse current duration, t off2 is the shutdown time; a2 and b2 are the coefficients related to the current in the second stage; Stage n: t n-1 ≤t <t n ; The forward current amplitude is I onn , the reverse current amplitude is I revn ; The duty cycle is t onn :t revn :t offn ;t onn is the forward current duration of the nth stage, t revn is the reverse current duration, t onn is the shutdown time; n and b n is the coefficient related to the current in the nth stage.

3. The method for filling a glass through 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.

4. The method for filling a glass through 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.

5. The method for filling a glass through hole of a glass transition plate according to claim 4, 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.

6. The method for filling a glass through hole of a glass transition plate according to claim 4, characterized in that: In step S20, the roughening solution includes: 5-15wt% hydrofluoric acid, 50-70wt% sulfuric acid and the balance deionized water; In step S21, the concentration of stannous ions is 0.2-0.5 mol / L; In step S22, the palladium ion concentration is 0.2-0.5 mol / L.

7. The method for filling a glass through hole of a glass transition plate according to claim 4, characterized in that: During the execution of steps S20 to S23 , the glass substrate is cleaned with deionized water after each step is completed.

8. The method for filling a glass through 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.

9. A glass transfer plate, characterized in that: The surface is processed by the filling method of the glass through hole of a glass transition plate as described in any one of claims 1-8.

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

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