TGV electroplating solution and application thereof

Abstract

The invention relates to a TGV electroplating solution and application thereof, the TGV electroplating solution comprises a copper source, an inorganic acid, a chlorine source and additives, and the additives comprise a wetting agent, a brightening agent and a leveling agent. By limiting the structure of the leveling agent, the filling capacity of the through glass vias (TGV) is improved, and for a TGV plate with a high aspect ratio, efficient filling of the TGV can be achieved, and the problem of defects or cavities caused by the high aspect ratio can be solved. Meanwhile, the production efficiency of the TGV plate can be greatly improved. The method is wide in raw material source, low in price, low in manufacturing cost and free of pollution in the production process, and therefore the method has wide application prospects in the field of high-aspect-ratio TGV filling.

Description

Technical Field

[0001] The present invention relates to the technical field of electroplating solution, and in particular to a TGV electroplating solution and application thereof. Background Art

[0002] At present, the method of filling through holes by electroplating has been widely used in the production of electronic devices, such as printed circuit boards used in mobile phones or tablets. The electroplating copper solution needs to add many organic additives, such as wetting agents, brighteners and leveling agents. By preparing additives of different types or different proportions, it can be ensured that copper is deposited on the surface of the circuit board or the surface of certain special structures during the electroplating process.

[0003] As Moore's Law approaches its limit, 2.5D / 3D packaging beyond Moore's Law has come onto the historical stage. Through glass via (TGV) is a key technology to achieve vertical interconnection of multi-dimensional packaging, and is also one of the important representative technologies in the current high-end electronic manufacturing field. Compared with through silicon via (TSV) interconnection, through glass via (TGV) interposer has attracted extensive attention in the field of 2.5D / 3D advanced packaging due to its advantages such as excellent high-frequency electrical properties, simple process, low cost and adjustable coefficient of thermal expansion (CTE). Glass interposer has serious heat dissipation problems. In order to obtain high-quality TGV interposer, not only an efficient and low-cost through-hole preparation process is required, but also a defect-free filling process. The challenges currently faced by glass interposer are mainly concentrated in these two aspects.

[0004] As the aspect ratio of TGV continues to increase, its electroplating becomes increasingly difficult. Excessive hole depth will make it difficult to exchange the solution in the hole. After electroplating, defects or voids are likely to exist in the TGV hole. These defects or voids will greatly reduce the reliability of electronic devices and thus affect the life of the device. In addition, the increase in dielectric thickness and hole diameter will greatly extend the hole filling time, resulting in a decrease in industrial production efficiency.

[0005] CN113066758A discloses a TGV deep hole filling method, which makes the surface of the glass substrate and the glass through hole rough by corroding the glass substrate and the glass through hole, increases the friction coefficient between the seed layer and the glass substrate and the glass through hole, and enhances the adhesion strength of the seed layer. In the subsequent activation and electroplating process, the seed layer can be prevented from falling off to a certain extent, thereby ensuring the effect of electroplating. The method disclosed in the invention requires pretreatment of the glass substrate to ensure the effect of deep hole filling, and the process is complicated, which is not conducive to large-scale production.

[0006] CN115537885A discloses a hole-filling conductive liquid, which ensures the filling effect of blind holes by adding fillers into the conductive liquid. However, the invention has a good filling effect when applied to tiny blind holes, but is not suitable for filling through holes with high aspect ratios.

[0007] There are defects in the process or application field in the existing technology. Therefore, how to achieve the filling of high aspect ratio TGV plates efficiently and at low cost has become a problem that needs to be solved urgently. Summary of the invention

[0008] In order to solve the above technical problems, the present invention provides a TGV electroplating solution and its application. The present invention improves the filling capacity of through glass vias (TGVs) by limiting the structure of the leveling agent. For TGV boards with high aspect ratios, it can not only achieve efficient filling of TGVs, but also solve the defects or voids caused by the high aspect ratio. At the same time, the present invention can also greatly improve the production efficiency of TGV boards. The raw materials of the present invention are widely available, low in price, low in manufacturing cost, and pollution-free in the production process. Therefore, it has broad application prospects in the field of high aspect ratio TGV filling.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a TGV electroplating solution, the TGV electroplating solution comprising a copper source, an inorganic acid, a chlorine source and an additive, the additive comprising a wetting agent, a brightener and a leveling agent, the structural formula of the leveling agent being Among them, R1 includes Any one or a combination of at least two of

[0011] Any one of halogen ion or sulfonic acid group or a combination of at least two, n = 2-6; R3 includes and / or

[0012] The present invention improves the filling capacity of through glass vias (TGVs) by limiting the structure of the leveling agent. For TGV boards with high aspect ratios, not only can the TGVs be efficiently filled, but also the defects or voids caused by the high aspect ratios can be solved. At the same time, the present invention can also greatly improve the production efficiency of TGV boards. The present invention has a wide source of raw materials, low prices, low manufacturing costs, and a pollution-free production process. Therefore, it has broad application prospects in the field of high aspect ratio TGV filling.

[0013] Specifically, typical but non-limiting combinations of R1 include A combination of Typical but non-limiting combinations of R2 include and a sulfonic acid group, or A combination of a halide ion and a sulfonic acid group.

[0014] Preferably, the halogen ion includes any one of chloride ion, bromide ion or iodide ion or a combination of at least two thereof, and a typical but non-limiting combination includes a combination of chloride ion and bromide ion, or a combination of chloride ion, bromide ion and iodide ion.

[0015] Specifically, the leveling agent may be n can be 2, 3, 4, 5 or 6,

[0016]

[0017] Leveling agents have an inhibitory effect during the electroplating process. Azo bonds provide adsorption sites, and quaternary ammonium cations can increase the electrostatic potential value. The positively charged leveling agent is adsorbed on the cathode surface, especially in high current density areas such as the tip protrusion, and has little effect on low current density areas, ultimately playing a leveling role.

[0018] Preferably, the volume concentration of the leveler solution in the TGV plating solution is 5 mL / L-15 mL / L, for example, 5 mL / L, 7 mL / L, 9 mL / L, 11 mL / L, 13 mL / L or 15 mL / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0019] Preferably, the concentration of the leveler solution is 6wt%-10wt%, for example, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0020] The present invention can improve the inhibition of the electroplating solution by further regulating the concentration of the leveling agent, thereby preventing the copper layer from growing too fast and causing hole sealing, and can also improve the electroplating effect and the brightness and flatness of the electroplated board surface.

[0021] Preferably, the wetting agent comprises a solution containing any one of polyethylene glycol, polyoxyethylene polyoxypropylene triblock copolymer or polypropylene glycol, or a combination of at least two thereof. Typical but non-limiting combinations include a solution containing a combination of polyethylene glycol and polyoxyethylene polyoxypropylene triblock copolymer, or a solution containing a combination of polyethylene glycol, polyoxyethylene polyoxypropylene triblock copolymer and polypropylene glycol.

[0022] Preferably, the wetting agent comprises a solution containing any one of PEG4000, PEG20000, EPE3000 or PPG8000 or a combination of at least two of them. Typical but non-limiting combinations include a solution containing a combination of PEG4000 and PEG20000, or a solution containing a combination of PEG20000, EPE3000 and PPG8000.

[0023] The wetting agent has an inhibitory effect in the electroplating process. The present invention helps to improve the inhibitory effect by further regulating the type of the wetting agent. By further selecting an appropriate wetting agent combination, it helps to further improve the inhibitory effect of the wetting agent.

[0024] Preferably, the volume concentration of the wetting agent solution in the TGV plating solution is 8 mL / L-20 mL / L, for example, it can be 8 mL / L, 12 mL / L, 15 mL / L, 18 mL / L or 20 mL / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] Preferably, the concentration of the wetting agent solution is 12wt%-15wt%, for example, 12wt%, 13wt%, 14wt%, 14.5wt% or 15wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0026] Preferably, the brightener comprises a solution containing any one of sodium 3-mercaptopropane sulfonate, sodium polydisulfide propane sulfonate, sodium N,N-dimethyldithioamide propane sulfonate, sodium 3-(benzothiazole-2-mercapto)-propane sulfonate or sodium thiazolinyl disulfide propane sulfonate, or a combination of at least two thereof. Typical but non-limiting combinations include a solution containing a combination of sodium polydisulfide propane sulfonate and sodium N,N-dimethyldithioamide propane sulfonate, or a solution containing a combination of sodium 3-mercaptopropane sulfonate, sodium 3-(benzothiazole-2-mercapto)-propane sulfonate and sodium thiazolinyl disulfide propane sulfonate.

[0027] Preferably, the volume concentration of the brightener solution in the TGV plating solution is 1 mL / L-5 mL / L, for example, 1 mL / L, 2 mL / L, 3 mL / L, 4 mL / L, 4.5 mL / L or 5 mL / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] Preferably, the concentration of the brightener solution is 3wt%-10wt%, for example, 3wt%, 5wt%, 7wt%, 9wt% or 10wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] The present invention can further improve the hole filling ability of the electroplating solution and avoid the formation of core during the electroplating stage by further adjusting the concentration of the brightener. On the other hand, it can also improve the hole filling efficiency, refine the copper crystals, make the copper crystals grow densely, and improve the brightness of the electroplated board surface.

[0030] Preferably, the copper source comprises copper sulfate.

[0031] Preferably, the mass concentration of the copper source in the TGV electroplating solution is 230 g / L-290 g / L, for example, 230 g / L, 240 g / L, 260 g / L, 280 g / L or 290 g / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0032] The copper source of the present invention is used to supplement copper ions in the electroplating process, and by further adjusting the concentration of the copper source, a sufficient supply of copper ions can be guaranteed during the electroplating hole filling process, thereby further improving the hole filling capacity of the electroplating solution and avoiding the formation of a core structure during the electroplating stage.

[0033] Preferably, the inorganic acid comprises concentrated sulfuric acid.

[0034] Preferably, the mass concentration of the inorganic acid in the TGV plating solution is 20 g / L-50 g / L, for example, it can be 20 g / L, 30 g / L, 40 g / L, 45 g / L or 50 g / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] Preferably, the chlorine source comprises chloride and / or hydrochloric acid.

[0036] Preferably, the chloride comprises potassium chloride and / or sodium chloride.

[0037] Preferably, the mass concentration of chloride ions in the chlorine source in the TGV plating solution is 30 mg / L-70 mg / L, for example, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L or 70 mg / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] The chlorine source of the present invention can act as an ion bridge for the conversion reaction between divalent copper ions and monovalent copper ions, and by further regulating the concentration of chloride ions, the reduction rate of divalent copper ions can be increased, and the filling quality of TGV can also be improved.

[0039] In a second aspect, the present invention provides an application of the TGV electroplating solution as described in the first aspect, wherein the TGV electroplating solution is applied to TGV filling.

[0040] Preferably, the TGV filling method comprises the following steps: immersing the TGV in the TGV electroplating solution described in the first aspect, and sequentially performing pulse electroplating and direct current electroplating to obtain a copper-filled TGV board.

[0041] The present invention forms a copper bridge in the middle of the TGV board by pulse electroplating, divides the TGV board into two parts, and then fills the double-sided blind hole structure by direct current electroplating. The electroplating method provided by the present invention can improve the electroplating efficiency and greatly shorten the electroplating time.

[0042] Preferably, the current density of the pulse plating is 0.8A / dm 2 -4A / dm 2 , for example, it can be 0.8A / dm 2 , 1A / dm 2 , 2A / dm 2 、3A / dm 2 or 4A / dm 2 , but not limited to the listed values, other unlisted values ​​within the numerical range are also applicable.

[0043] Preferably, the forward and reverse ratio of the pulse plating is 1:(2-5), for example, it can be 1:2, 1:2.5, 1:3, 1:4 or 1:5, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0044] Preferably, the pulse width ratio of the pulse plating is 20:1-1000:50, for example, it can be 20:1, 200:10, 600:30, 800:40 or 1000:50, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 40:2-100:5.

[0045] Preferably, the plating time of the pulse plating is 25 min-80 min, for example, 25 min, 40 min, 50 min, 70 min or 80 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] Preferably, the pulse electroplating spray flow rate is 0.5L / min-1.75L / min, for example, it can be 0.5L / min, 1L / min, 1.25L / min, 1.5L / min or 1.75L / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] Preferably, the current density of the DC electroplating is 0.1A / dm 2 -1A / dm 2 , for example, it can be 0.1A / dm 2 , 0.2A / dm 2 , 0.4A / dm 2 , 0.6A / dm 2 or 1A / dm 2 , but not limited to the listed values, other unlisted values ​​within the numerical range are also applicable.

[0048] Preferably, the electroplating time of the direct current electroplating is 4h-7h, for example, 4h, 5h, 6h, 6.5h or 7h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] Compared with the prior art, the present invention has at least the following beneficial effects:

[0050] (1) The present invention improves the filling capacity of through glass vias (TGVs) by limiting the structure of the leveler. For TGV boards with high aspect ratios, not only can efficient filling of the TGVs be achieved, but also defects or voids caused by the high aspect ratios can be solved.

[0051] (2) The use of the TGV electroplating solution of the present invention can greatly improve the production efficiency of TGV boards.

[0052] (3) The raw materials of the present invention are widely available and inexpensive, the manufacturing cost is low, and the production process is pollution-free. Therefore, the present invention has broad application prospects in the field of high aspect ratio TGV filling. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 is a slice diagram of the copper-filled TGV board obtained in Application Example 1-1 of the present invention;

[0054] Figure 2 is a slice diagram of the copper-filled TGV board obtained in Application Example 8 of the present invention;

[0055] Figure 3 is a slice diagram of the copper-filled TGV board obtained in Comparative Application Example 1 of the present invention;

[0056] Figure 4 This is a slice diagram of the copper-filled TGV board obtained in Comparative Application Example 2 of the present invention. DETAILED DESCRIPTION

[0057] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0058] The manufacturer of PEG20000 used in the following examples is Guangdong Tiancheng Technology, with a batch number of SC240914C, the manufacturer of PPG8000 is Guangdong Tiancheng Technology, with a batch number of SD240803B, the manufacturer of EPE3000 is Guangdong Tiancheng Technology, with a batch number of SN240817D, and the manufacturer of sodium polydisulfide propane sulfonate is Guangdong Tiancheng Technology, with a batch number of SY240913O.

[0059] Example 1

[0060] This embodiment provides a TGV plating solution, wherein the TGV plating solution includes the following components:

[0061] 260g / L copper sulfate pentahydrate, 30g / L concentrated sulfuric acid, and hydrochloric acid with a chloride ion concentration of 40mg / L;

[0062] Also included are additives, including wetting agents, brighteners, and leveling agents;

[0063] The wetting agent is a mixed solution of 5wt% EPE3000 and 7wt% PEG20000, the solvent is deionized water, and the volume concentration in the TGV plating solution is 10mL / L;

[0064] The brightener is a solution of sodium polydisulfide propane sulfonate, the solvent is deionized water, the mass concentration is 5wt%, and the volume concentration in the TGV electroplating solution is 3mL / L;

[0065] The mass concentration of the leveling agent solution is 6wt%, the solvent is deionized water, the volume concentration in the TGV plating solution is 15mL / L, and the leveling agent is

[0066] Example 2

[0067] This embodiment provides a TGV plating solution, wherein the TGV plating solution includes the following components:

[0068] 230g / L copper sulfate pentahydrate, 20g / L concentrated sulfuric acid, sodium chloride with a chloride ion concentration of 70mg / L;

[0069] Also included are additives, including wetting agents, brighteners, and leveling agents;

[0070] The wetting agent is a mixed solution of 6wt% PEG20000 and 7wt% PPG8000, the solvent is deionized water, and the volume concentration in the TGV plating solution is 20mL / L;

[0071] The brightener is a sodium N,N-dimethyldithiocarboxamide propane sulfonate solution, the solvent is deionized water, the mass concentration is 3wt%, and the volume concentration in the TGV electroplating solution is 5mL / L;

[0072] The mass concentration of the leveling agent solution is 10wt%, the solvent is deionized water, the volume concentration in the TGV plating solution is 15mL / L, and the leveling agent is n=5.

[0073] Example 3

[0074] This embodiment provides a TGV plating solution, wherein the TGV plating solution includes the following components:

[0075] 290g / L copper sulfate pentahydrate, 50g / L concentrated sulfuric acid, and potassium chloride with a chloride ion concentration of 30mg / L;

[0076] Also included are additives, including wetting agents, brighteners, and leveling agents;

[0077] The wetting agent is a mixed solution of 6wt% PEG20000, 5wt% PPG8000 and 4wt% EPE3000, the solvent is deionized water, and the volume concentration in the TGV plating solution is 8mL / L;

[0078] The brightener is a sodium 3-(benzothiazole-2-mercapto)-propane sulfonate solution, the solvent is deionized water, the mass concentration is 10wt%, and the volume concentration in the TGV electroplating solution is 1mL / L;

[0079] The mass concentration of the leveling agent solution is 8wt%, the solvent is deionized water, and the volume concentration in the TGV plating solution is 5mL / L; the leveling agent is

[0080] Example 4

[0081] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the leveler in the TGV electroplating solution is 4.5 mL / L, the rest is the same as embodiment 1.

[0082] Example 5

[0083] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the leveler in the TGV electroplating solution is 15.5 mL / L, the rest is the same as embodiment 1.

[0084] Example 6

[0085] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the wetting agent in the TGV electroplating solution is 7.5 mL / L, the rest is the same as embodiment 1.

[0086] Example 7

[0087] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the wetting agent in the TGV electroplating solution is 20.5 mL / L, the rest is the same as embodiment 1.

[0088] Example 8

[0089] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the brightener in the TGV electroplating solution is 0.5 mL / L, the rest is the same as embodiment 1.

[0090] Example 9

[0091] The only difference between this embodiment and embodiment 1 is that, except that the volume concentration of the brightener in the TGV electroplating solution is 5.5 mL / L, the rest is the same as embodiment 1.

[0092] Example 10

[0093] The only difference between this embodiment and embodiment 1 is that, except that the wetting agent is replaced with 12 wt % EPE3000 solution, the rest is the same as embodiment 1.

[0094] Comparative Example 1

[0095] The difference between this comparative example and Example 1 is that the leveling agent is replaced by 2,2-dithiodipyridine, and the rest is the same as Example 1.

[0096] Comparative Example 2

[0097] The difference between this comparative example and Example 1 is that the leveling agent is replaced by diketopyrrole, and the rest is the same as Example 1.

[0098] Application Example 1-1

[0099] This application example provides a TGV filling method, the method comprising the following steps:

[0100] A TGV with a thickness of 500 μm and a pore size of 50 μm was dipped in acid (10% sulfuric acid) for 10 seconds. In the TGV electroplating solution described in Example 1, an insoluble anode was used at 23°C and the current was 2A / dm 2 The current density of pulse plating was 30min, the forward pulse width: reverse pulse width = 200:10, the forward and reverse ratio was 1:4, the pulse plating jet flow rate was 1.25L / min, the DC plating was 6h, and the current density was 0.5A / dm 2 , and a copper-filled TGV structure is obtained.

[0101] Figure 1 This is a slice diagram of the copper-filled TGV board obtained in Application Example 1-1 of the present invention. It can be seen from the figure that the copper-filled TGV board has a bright surface without defects or voids.

[0102] Application Example 1-2

[0103] This application example provides a TGV filling method, the method comprising the following steps:

[0104] A TGV with a thickness of 500 μm and a pore size of 50 μm was dipped in acid (10% sulfuric acid) for 10 seconds. In the TGV electroplating solution described in Example 1, an insoluble anode was used at 20°C and the current was 0.8 A / dm 2The current density of pulse plating is 80min, the forward pulse width: reverse pulse width = 20:1, the forward and reverse ratio is 1:2, the pulse plating jet flow rate is 0.5L / min, the DC plating is 7h, and the current density is 0.1A / dm 2 , a copper-filled TGV board was obtained.

[0105] Application Examples 1-3

[0106] This application example provides a TGV filling method, the method comprising the following steps:

[0107] A TGV with a thickness of 500 μm and a pore size of 40 μm was dipped in acid (10% sulfuric acid) for 10 seconds. In the TGV electroplating solution described in Example 1, an insoluble anode was used at 25°C and the current was 4 A / dm 2 The current density pulse plating was 25min, the forward pulse width: reverse pulse width = 1000:50, the forward and reverse ratio was 1:5, the pulse plating jet flow rate was 1.75L / min, the DC plating was 4h, and the current density was 1A / dm 2 , a copper-filled TGV board was obtained.

[0108] Application Example 2

[0109] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 2 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0110] Application Example 3

[0111] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 3 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0112] Application Example 4

[0113] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 4 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0114] Application Example 5

[0115] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 5 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0116] Application Example 6

[0117] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 6 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0118] Application Example 7

[0119] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 7 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0120] Application Example 8

[0121] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 8 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0122] Figure 2 This is a slice diagram of the copper-filled TGV board obtained in Application Example 8 of the present invention. It can be seen from the figure that the copper-filled TGV board has a matte and bright surface without defects or voids.

[0123] Application Example 9

[0124] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 9 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0125] Application Example 10

[0126] The only difference between this application example and application example 1-1 is that the plating solution used is replaced by the TGV plating solution described in Example 10 instead of the TGV plating solution described in Example 1, and the rest is the same as application example 1-1.

[0127] Comparative application example 1

[0128] The only difference between this application example and application example 1-1 is that the electroplating solution used is replaced by the TGV electroplating solution described in Example 1 with the TGV electroplating solution described in Comparative Example 1, and the rest is the same as application example 1-1.

[0129] Figure 3 This is a slice diagram of the copper-filled TGV board obtained in Comparative Application Example 1 of the present invention. It can be seen from the figure that there are voids on the surface of the copper-filled TGV board.

[0130] Comparative Application Example 2

[0131] The only difference between this application example and application example 1-1 is that the electroplating solution used is replaced by the TGV electroplating solution described in Example 1 with the TGV electroplating solution described in Comparative Example 2, and the rest is the same as application example 1-1.

[0132] Figure 4 This is a slice diagram of the copper-filled TGV board obtained in comparative application example 2 of the present invention. It can be seen from the figure that there are voids on the surface of the copper-filled TGV board.

[0133] Test Method

[0134] The copper-filled TGV boards obtained in Application Example 1 to Application Example 10 and Comparative Application Example 1 to Comparative Example 2 were tested for core coverage, depression, copper thickness and board surface condition, and the test results were recorded in Table 1, wherein the core coverage test method is to observe the experimental board with X-Ray, count the number of cored holes and the total number of holes observed, and the core coverage ratio = number of cored holes / total number of holes observed.

[0135] Table 1

[0136] Core rate (%) Depression (μm) Copper thickness (μm) Board situation Application Example 1-1 0 Less than 5 23 bright Application Example 1-2 0 Less than 5 26 bright Application Examples 1-3 0 Less than 5 26 bright Application Example 2 0 Less than 5 28 bright Application Example 3 0 Less than 5 25 bright Application Example 4 12 12-19 31 bright Application Example 5 5 Less than 10 24 Matte Application Example 6 7 15-20 35 Fog Application Example 7 3 13-15 24 Matte Application Example 8 0 Less than 10 23 Matte Application Example 9 6 Less than 10 25 Redness Application Example 10 2 6-13 26 bright Comparative application example 1 46 35-56 40 Matte Comparative Application Example 2 40 34-46 38 Fog

[0137] The test results show that:

[0138] (1) It can be seen from Application Examples 1 to 10 and Comparative Application Examples 1 to Comparative Example 2 that the present invention improves the filling capacity of through glass vias (TGVs) by limiting the structure of the leveling agent. For TGVs with high aspect ratios, not only can the TGVs be filled efficiently, but also the defects or voids caused by the high aspect ratios can be solved. At the same time, the present invention can also greatly improve the production efficiency of TGV boards. The raw materials of the present invention are widely available, inexpensive, low in manufacturing cost, and pollution-free in the production process. Therefore, the present invention has broad application prospects in the field of high aspect ratio TGV filling.

[0139] (2) It can be seen from Application Examples 1 and 4 to 9 that the present invention can prepare a defect-free TGV board by further regulating the volume concentration of the leveler, wetting agent and brightener in the TGV plating solution. The core coverage rate, concavity and copper thickness of the TGV board are further reduced, and the board surface is bright.

[0140] (3) It can be seen from Application Example 1-1 and Application Example 10 that the present invention further improves the inhibitory effect of the wetting agent by using a variety of wetting agents with different molecular weights, and can prepare a defect-free TGV board. The core coverage rate, concavity and copper thickness of the TGV board are further reduced, and the board surface is bright.

[0141] In summary, the present invention improves the filling capacity of through glass vias (TGVs) by limiting the structure of the leveling agent. For TGV boards with high aspect ratios, not only can the efficient filling of TGVs be achieved, but also the defects or voids caused by the high aspect ratios can be solved. At the same time, the present invention can also greatly improve the production efficiency of TGV boards. The present invention has a wide source of raw materials, low prices, low manufacturing costs, and a pollution-free production process. Therefore, it has broad application prospects in the field of high aspect ratio TGV filling.

[0142] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A TGV electroplating solution, characterized in that: The TGV electroplating solution includes a copper source, an inorganic acid, a chlorine source and an additive, wherein the additive includes a wetting agent, a brightener and a leveling agent, and the structural formula of the leveling agent is Among them, R1 includes Any one or a combination of at least two of Any one of halogen ion or sulfonic acid group or a combination of at least two, n = 2-6; R3 includes 2. The TGV plating solution according to claim 1, characterized in that: The volume concentration of the leveler solution in the TGV electroplating solution is 5 mL / L-15 mL / L.

3. The TGV plating solution according to claim 1 or 2, characterized in that: The wetting agent includes a solution containing any one of polyethylene glycol, polyoxyethylene polyoxypropylene triblock copolymer or polypropylene glycol or a combination of at least two thereof; Preferably, the volume concentration of the wetting agent solution in the TGV electroplating solution is 8 mL / L-20 mL / L.

4. The TGV plating solution according to any one of claims 1 to 3, characterized in that: The brightener comprises a solution containing any one or a combination of at least two of sodium 3-mercaptopropane sulfonate, sodium polydisulfide propane sulfonate, sodium N,N-dimethyldithiocarboxamide propane sulfonate, sodium 3-(benzothiazole-2-mercapto)-propane sulfonate or sodium thiazoline disulfide propane sulfonate; Preferably, the volume concentration of the brightener solution in the TGV electroplating solution is 1 mL / L-5 mL / L.

5. The TGV plating solution according to any one of claims 1 to 4, characterized in that: The copper source includes copper sulfate; Preferably, the mass concentration of the copper source in the TGV electroplating solution is 230 g / L-290 g / L.

6. The TGV plating solution according to any one of claims 1 to 5, characterized in that: The inorganic acid includes concentrated sulfuric acid; Preferably, the mass concentration of the inorganic acid in the TGV electroplating solution is 20 g / L-50 g / L.

7. The TGV plating solution according to any one of claims 1 to 6, characterized in that: The chlorine source includes chloride and / or hydrochloric acid; Preferably, the mass concentration of chloride ions in the chlorine source in the TGV electroplating solution is 30 mg / L-70 mg / L.

8. An application of the TGV electroplating solution according to any one of claims 1 to 7, characterized in that: The TGV plating solution is used for TGV filling.

9. The use according to claim 8, characterized in that: The TGV filling method comprises the following steps: The TGV board is immersed in the TGV electroplating solution according to any one of claims 1 to 7, and pulse electroplating and direct current electroplating are performed in sequence to obtain a copper-filled TGV board.

10. The use according to claim 8 or 9, characterized in that: The current density of the pulse plating is 0.8A / dm 2 -4A / dm 2 ; Preferably, the positive and negative ratio of the pulse plating is 1:(2-5); Preferably, the electroplating time of the pulse electroplating is 25min-80min; Preferably, the current density of the DC electroplating is 0.1A / dm 2 -1A / dm 2 .

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