High-dispersion pulse copper electroplating additive and use method thereof

Abstract

The invention discloses a high-dispersion pulse electro-coppering additive and a use method thereof, belongs to the technical field of electro-coppering, and aims to solve the technical problem that the adsorption rate and the stability of pulse electro-coppering need to be further improved in the prior art. The zwitter-ion modified polyol dispersant prepared by the preparation method provides a stable dispersion environment and a good wetting basis, so that an electroplating solution keeps uniform entering and continuous covering in a complex structure; the boron-containing imine dynamic complexing agent reversibly adjusts copper ions under a pulse condition, so that the nucleation and deposition processes are continuously kept in a proper interval; a selective adsorption layer is constructed near an interface by a mercaptotriazine leveling agent, so that the deposition morphology gradually develops in a regular direction, and after the three components are introduced according to a set proportion, multiple indexes such as solution stability, adsorption rate, grain refinement, thickness distribution and filling in holes are kept in excellent intervals, peak current and frequency are also kept stable in a pulse process, and the performance of the device is improved. Therefore, the electro-deposition copper layer which is complete in structure and uniform in morphology is obtained.

Description

Technical Field

[0001] This invention relates to the field of copper electroplating technology, specifically to a highly dispersed pulse copper electroplating additive and its application method. Background Technology

[0002] In the study of adsorption kinetics, pulsed copper plating technology has gradually shifted from overall control to the analysis of transient interfacial behavior. With the increasing application of high aspect ratio structures, the adsorption rate has become a key parameter determining the nucleation density and deposition uniformity. Studies generally adjust the structure of dispersants, leveling agents, and inhibitors to enable them to be rapidly adsorbed onto the cathode surface during the peak pulse current phase, thereby affecting the local deposition rate distribution. The adsorption rate Ra is therefore used to characterize the interface's response to pulsed current. At the same time, the stability of the pulsed electroplating system is affected by periodic current fluctuations. The concentration of copper ions and additives changes continuously in the high and low current ranges, making dispersion stability, complexation regulation ability, and waveform retention important considerations. Existing studies usually characterize the stability of the electroplating solution using indicators such as sedimentation ratio, transmittance change, peak current change rate, and frequency change rate to ensure that the deposition process maintains uniformity and structural integrity under pulsed conditions.

[0003] Existing pulsed copper plating technology is often affected by the uneven interfacial adsorption behavior when processing high aspect ratio structures. Due to the limited response speed of additive molecules during the peak current phase of the pulse, interfacial adsorption often exhibits a lag characteristic, leading to a widening difference in deposition rates between the orifice and the bottom of the orifice. In complex structures, this mismatch in adsorption kinetics can easily cause problems such as insufficient local nucleation, uneven deposition thickness distribution, and incomplete filling. In addition, the structural stability of the adsorbent in some systems is limited, and there are issues such as adsorption efficiency decay and decreased interfacial coverage during long-term electroplating, which further affect the deposition quality. On the other hand, pulsed electroplating solutions are prone to compositional fluctuations under the action of periodic current. Copper ions and organic additives exhibit differences in migration rates between high and low current ranges, leading to a decrease in system stability. Common problems include: sedimentation or micro-flocculation of the dispersed system after standing or repeated pulses, aggravated changes in transmittance, and peak drift and frequency fluctuations in the current waveform during deposition. These factors reduce the controllability of the deposition process, making it more likely for phenomena such as grain coarsening, surface morphology fluctuations, and internal filling asymmetry to occur, thus limiting the stability of its application in the field of fine-structure electroplating.

[0004] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a highly dispersed pulse electroplating copper additive and its application method, which solves the technical problem that the adsorption rate and stability of pulse electroplating copper need to be further improved in the prior art.

[0006] The objective of this invention can be achieved through the following technical solutions: A highly dispersed pulse electroplating copper additive comprises the following raw materials in parts by weight: 12-15 parts zwitterionic modified polyol dispersant, 1-2 parts mercaptotriazine leveling agent, 10-15 parts boron-containing imine dynamic complexing agent, and 200 parts dispersant, wherein the dispersant is deionized water. The preparation method of the zwitterionic modified polyol dispersant includes the following steps: A1. Add the micro-acetalized polyvinyl alcohol solution to the reaction vessel and stir. Heat the reaction vessel to 60-70℃ and add p-toluenesulfonic acid. Then add glycidyl methacrylate and keep it warm and stir for 2-3 hours. After the reaction is completed, let the reaction vessel cool to room temperature to obtain the epoxy side-group polyol modified solution. A2. Add the epoxy-side-chain polyol modified liquid to the reaction vessel, and adjust the pH of the reaction system to 8-9 using 10wt% sodium hydroxide aqueous solution. Then add taurine, heat the reaction vessel to 50-60℃, keep it warm and stir for 2-3 hours, and then process to obtain zwitterionic modified polyol dispersant.

[0007] The reaction principle for preparing zwitterionic modified polyol dispersants is as follows: Amphoteric modified polyol dispersants were prepared by introducing epoxy functional groups into polyvinyl alcohol (PVA) molecular chains stepwise and further constructing zwitterionic side chains. First, the hydroxyl groups in microacetalized PVA molecules underwent a ring-opening esterification reaction with glycidyl methacrylate under acidic catalysis. The epoxy acrylate groups formed stable ester bonds with the polyol segments, giving the polyol a further functionalizable epoxy side group structure. Subsequently, under weakly alkaline conditions, the thiol or amine groups in taurine molecules nucleophilically opened the epoxy side groups, adding to generate a zwitterionic structure containing both quaternary ammonium and sulfonic acid groups. This gave the polyol segments both positive and negative charge distribution and good water-phase affinity. This two-step reaction, through the mode of "introducing active sites first and then undergoing nucleophilic ring opening," gave the polyol molecular chains a stable, compliant structure with zwitterionic side groups, thereby endowing the material with excellent interfacial wettability, dispersibility, and synergistic adsorption capacity for metal ions.

[0008] Furthermore, in step A1, the ratio of the amount of the microacetalized polyvinyl alcohol solution, p-toluenesulfonic acid, and glycidyl methacrylate is 100mL:0.05-0.08g:5-8g. Furthermore, in step A2, the ratio of the epoxy side-group polyol modified liquid to taurine is 100mL:3-5g. The post-treatment includes: after the reaction is completed, the reaction vessel is cooled to room temperature, the reaction liquid is filtered to collect the filter cake, and the filter cake is transferred to a drying oven at 80°C and vacuum dried to constant weight to obtain zwitterionic modified polyol dispersant.

[0009] Furthermore, the preparation method of the micro-acetalized polyvinyl alcohol solution is as follows: polyvinyl alcohol and deionized water are added to a reaction vessel and stirred. The reaction temperature is raised to 50-60℃ and stirred until the polyvinyl alcohol is completely dissolved. Then, the reaction vessel is cooled to 35-40℃, nitrogen gas is introduced for protection, and 25-30wt% glutaraldehyde aqueous solution is added. After the addition is complete, acetic acid is used to adjust the pH of the reaction system to 4-5. The mixture is kept warm and stirred for 1-2 hours. After the reaction is completed, the reaction vessel is allowed to cool naturally to room temperature to obtain the micro-acetalized polyvinyl alcohol solution.

[0010] The reaction principle for preparing microacetalized polyvinyl alcohol solution is as follows: Microacetalized polyvinyl alcohol (PVA) solutions were prepared by acetalization of the hydroxyl groups on the polyvinyl alcohol (PVA) molecular chain with the aldehyde groups in the glutaraldehyde molecule under acidic conditions. Glutaraldehyde, acting as a dialdehyde crosslinking agent, allows its two aldehyde groups to undergo nucleophilic addition with the ortho- or near-ortho-hydroxyl groups of PVA, followed by dehydration to form an acetal structure. This results in stable acetal bonds forming part of the PVA molecular chain, leading to microacetalized PVA with a certain degree of crosslinking, a denser structure, and a more stable molecular conformation. This acetalization process does not cause complete crosslinking and gelation of the PVA macromolecules, but rather forms a uniform, soluble, partially acetalized structure. This allows the material to maintain both good solubility and moderate structural stability, providing more suitable reaction sites and molecular environments for subsequent functionalization reactions. By controlling the participation of the aldehyde groups, the flexibility, reactivity, and spatial configuration of the PVA chain segments can be adjusted, thereby achieving controllable regulation of its chemical properties.

[0011] Furthermore, in the process of preparing the microacetalized polyvinyl alcohol solution, the ratio of polyvinyl alcohol, deionized water and glutaraldehyde aqueous solution is 10g:200mL:4-6g.

[0012] Furthermore, the preparation method of the mercaptotriazine leveling agent includes the following steps: B1. Add 2,4,6-trichloro-1,3,5-triazine and deionized water to a reaction vessel. After purging with nitrogen, cool the reaction vessel to 3-5°C. Then add cysteine ​​hydrochloride to adjust the pH of the reaction system to 8-9. After maintaining the temperature for 40-60 min, heat the reaction vessel to 30-40°C, add taurine and maintain the temperature for 40-60 min. Then heat the reaction vessel to 70-80°C and add ethanolamine. Maintain the temperature for 60-90 min. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain a triazine mercaptosulfonate intermediate solution. B2. Add the intermediate solution of mercaptosulfonic acid triazine to the reaction vessel, adjust the pH of the reaction system to 8-9 using 10wt% sodium hydroxide aqueous solution, add hydrogen peroxide and stir for 40-60 min, and then perform post-treatment to obtain mercaptotriazine leveling agent.

[0013] The reaction principle for preparing mercaptotriazine leveling agents is as follows: Mercaptotriazine leveling agents were prepared through a reaction involving the stepwise nucleophilic substitution of the triazine ring followed by oxidation to construct structures containing thiol functional groups. Among these, 2,4,6-trichloro-1,3,5-triazine, as an active halotriazine with three sequentially substituted nucleophiles, had its chlorine atom selectively substituted by nucleophiles containing thiol, amino, or sulfonic acid groups, such as cysteine, taurine, and ethanolamine, under different temperature conditions, forming triazine derivatives simultaneously possessing thiol, sulfonic acid, and hydroxyl side groups. With increasing substitution amount, the electronic structure of the triazine ring gradually... The reaction stabilizes the triazine skeleton and acquires multifunctional characteristics, placing the thiol groups in an active state that is easily regulated. Furthermore, under alkaline conditions, the addition of hydrogen peroxide causes a mild oxidative transformation of the thiol groups, forming an oxidized thiol structure with higher chemical stability and interface regulation capabilities. This results in the construction of a triazine-type organic modifier with good hydrophilicity, adsorption, and metal surface leveling properties. The combination of controlled substitution and directional oxidation enables the triazine skeleton to acquire synergistic coordination and surface regulation capabilities, providing a structural basis for its use as a leveling agent.

[0014] Furthermore, in step B1, the ratio of the amount of 2,4,6-trichloro-1,3,5-triazine, deionized water, taurine and ethanolamine is 5g:150mL:3-5g:2-3g. Furthermore, in step B2, the ratio of the mercaptosulfonic acid triazine intermediate solution to hydrogen peroxide is 100mL:0.3-0.5g. The post-treatment includes: after the reaction is completed, the reaction vessel is allowed to cool naturally to room temperature, the reaction solution is filtered to collect the filter cake, and the filter cake is washed 3-5 times with anhydrous ethanol and deionized water. The filter cake is then placed in an 80℃ drying oven and vacuum dried to constant weight to obtain mercaptotriazine leveling agent.

[0015] Furthermore, the preparation method of the boron-containing imine dynamic complexing agent includes the following steps: C1. Add 3-aminophenylboronic acid, diethylenetriamine and deionized water to the reactor, purge with nitrogen and heat the reactor to 40-50℃, add glyoxal and keep it heated and stirred for 2-3 hours. After the reaction is completed, let the reactor cool naturally to room temperature to obtain boron-containing imine prepolymer liquid. C2. Add the boron-containing imine prepolymer to the reactor, adjust the pH of the reaction system to 8-9 using a 10wt% sodium hydroxide aqueous solution, add catechol and stir at room temperature for 1-2 hours, and then perform post-treatment to obtain the boron-containing imine dynamic complexing agent.

[0016] The reaction principle for preparing boron-containing imine dynamic complexing agents is as follows: A boron-containing imine dynamic complexing agent was prepared by condensation reaction between an aromatic boric acid skeleton, an aliphatic polyamine, and a dialdehyde to form an imine, and by using catechol to coordinate and stabilize the boric acid sites to form a reversible dynamic complex structure. First, 3-aminophenylboronic acid and diethylenetriamine undergo multi-site condensation with glyoxal under mild conditions. The amino group forms an imine bond with the carbonyl group of the dialdehyde, enabling the boric acid group and the polyamine segment to synergistically construct a boron-containing imine network structure. This type of imine bond is reversible, giving the system a certain dynamic regulation capability. Furthermore, after adding catechol under a weakly alkaline environment, its ortho-phenolic hydroxyl group can form a stable chelated boronate ester structure with aromatic boric acid, further balancing the electronic environment of the boron center and endowing the molecule with the ability to form reversible and responsive complexes with metal ions. This multiple condensation and chelation process together constructs a boron-containing imine complex system with dynamic bond characteristics, strong coordination ability, and flexible structure, providing a chemical basis for ion control and deposition kinetic regulation of materials during electroplating.

[0017] Furthermore, in step C1, the ratio of 3-aminophenylboronic acid, diethylenetriamine, deionized water and glyoxal is 3g:2g:150mL:3-4g. Further, in step C2, the ratio of the boron-containing imine prepolymer to catechol is 100mL:2-3g. The post-treatment includes: after the reaction is completed, the reaction vessel is allowed to cool naturally to room temperature, the reaction solution is filtered to collect the filter cake, and the filter cake is washed 3-5 times with anhydrous ethanol and deionized water. The filter cake is then placed in an 80℃ drying oven and vacuum dried to constant weight to obtain the boron-containing imine dynamic complexing agent.

[0018] Furthermore, the present invention also discloses a method for using a highly dispersed pulse electroplating copper additive, comprising the following steps: S1. Add the dispersant to the mixing tank and stir. Then add the zwitterionic modified polyol dispersant, boron-containing imine dynamic complexing agent and mercaptotriazine leveling agent in sequence. Stir at room temperature for 40-60 minutes and then pass through a 100-mesh filter to obtain the composite electroplating copper additive. S2. Add deionized water and copper sulfate pentahydrate to the tank and stir. After the copper sulfate pentahydrate is completely dissolved, add 98% concentrated sulfuric acid, then add sodium chloride, followed by composite copper plating additives, and then add deionized water to obtain pulse copper plating solution. Add the workpiece to be plated and perform pulse copper plating operation.

[0019] The application principle of composite electroplating copper additives is as follows: In the process of pulse electroplating copper, zwitterionic modified polyol dispersants form a stable hydrophilic spatial network in the solution, promoting the uniform distribution of copper ions in micropores or through-holes through dispersion, wetting, and interfacial tension regulation. Boron-containing imine dynamic complexing agents control the effective concentration of free copper ions through reversible complexation, slowing down surface supersaturation deposition and optimizing copper layer growth kinetics, making it easier to maintain a balanced current density at the bottom and walls of the holes. Mercaptotriazine leveling agents, with their multifunctional groups selectively adsorbing onto the metal surface, form an inhibitory layer in high current density areas, thereby reducing rapid growth at the top and promoting gradient filling from the bottom up. Under the condition of periodic reversal of the pulse current, the three agents work synergistically to simultaneously achieve dispersion, leveling, selective adsorption, and dynamic complexation regulation, resulting in a dense and smooth coating morphology and significantly improved hole filling effect, ensuring a high-quality copper deposition structure during pulse electroplating.

[0020] Furthermore, in step S2, the ratio of deionized water, copper sulfate pentahydrate, 98% concentrated sulfuric acid, sodium chloride, and composite electroplating copper additive to replenish deionized water is 6000mL:750g:2300g:0.6g:20-30g:4000mL. The operating conditions for the pulse electroplating copper are: a temperature of 25-30℃, a pulse frequency of 400-500Hz, and 3-5A / dm². 2 Peak current density and 40-60% duty cycle.

[0021] The present invention has the following beneficial effects: 1. The zwitterionic modified polyol dispersant prepared in this invention constructs a stable and highly hydrophilic dispersion network in the aqueous phase through the internal salt structure formed by the quaternary ammonium groups and sulfonic acid groups on its molecular chain. This ensures that the additive is uniformly distributed in the plating solution, avoiding macromolecular aggregation or sedimentation, and fundamentally ensuring that the system maintains good steric stability under long-term cyclic electroplating conditions. Simultaneously, the boron-containing imine dynamic complexing agent, based on the dynamic coordination of reversible borate ester bonds, adaptively adjusts the effective concentration of copper ions, enabling the system to quickly respond to instantaneous polarization changes under pulsed current, maintaining the current peak value and frequency. Stability is ensured to prevent pulse waveform drift due to local ion concentration fluctuations. In addition, the mercaptotriazine leveling agent, with its multifunctional groups, can form a stable interface conditioning layer during the rapid switching of the pulse potential cycle, effectively suppressing local sudden deposition and interface instability. The synergistic effect of the above materials ensures that the solution dispersion stability, current response stability and interface adsorption stability are maintained simultaneously during the pulse electroplating process, thereby significantly improving the chemical and electrochemical stability of the system under high-frequency pulse conditions. This provides a key guarantee for obtaining a uniform, dense, and waveform-drift-free high-quality copper deposition layer.

[0022] 2. The boron-containing imine dynamic complexing agent prepared in this invention can self-regulate the local concentration of copper ions through its reversible borate complexing structure, so that metal ions are continuously replenished near the interface at a suitable mass transfer rate, avoiding uneven grain growth caused by instantaneous enrichment or depletion of ions. The zwitterionic modified polyol dispersant, due to the zwitterionic structure containing both quaternary ammonium and sulfonic acid groups on its molecular chain, can rapidly migrate to the cathode interface in the initial stage of electroplating and form a uniform adsorption layer, effectively covering the high current density area, inhibiting local over-reduction and instantaneous coarse crystal nucleus generation, thereby creating a stable interface environment for uniform nucleation. At the same time, the mercaptotriazine leveling agent, with its multi-point adsorption characteristics of mercapto, amine, and sulfonic acid groups, can selectively attach to high-energy crystal faces during crystal growth, inhibiting preferential grain growth and promoting synchronous nucleation of multi-cells. The synergistic effect of the three enables the rapid formation of a dense and stable micro-adsorption control layer on the cathode surface, achieving both rapid adsorption and controlled nucleation and grain refinement, thereby significantly improving the density, smoothness, and mechanical stability of the coating.

[0023] 3. The mercaptotriazine leveling agent prepared in this invention, due to its multi-point selective adsorption characteristics of mercapto, hydroxyl, and sulfonic acid groups, can preferentially adsorb in high current density regions, forming an inhibitory interface layer. This effectively slows down the excessively rapid growth on the top surface, making the deposition rate more consistent across different current density ranges, thereby significantly improving the macroscopic leveling of the coating. Simultaneously, the boron-containing imine dynamic complexing agent, through reversible complexation, regulates the effective concentration and mass transfer rate of copper ions in the solution, making the supply of metal ions inside deep pores and micropores more balanced, avoiding "bottleneck" blockage at the pore opening due to ion enrichment. The process promotes continuous growth from the bottom of the hole upwards. Furthermore, the zwitterionic modified polyol dispersant reduces interfacial tension and improves solution wettability, making it easier for the electroplating solution to enter the high aspect ratio through-hole and form a uniform adsorption environment on the hole wall. This provides a stable micro-interface for metal deposition within the hole. The three mechanisms work together to achieve complementary synergy between the inhibition layer controlling surface growth, the complexing agent regulating ion supply, and the dispersant improving wetting within the hole. This enhances the leveling effect macroscopically and improves the filling efficiency in the three-dimensional structure, ultimately resulting in a copper deposition structure with high flatness, full filling, and no void defects. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 The image shows the infrared absorption spectrum of the zwitterionic modified polyol dispersant prepared in Example 3 of this invention. Figure 2 The infrared absorption spectrum image of the mercaptotriazine leveling agent prepared in Example 6 of this invention; Figure 3 The image shows the infrared absorption spectrum of the boron-containing imine dynamic complexing agent prepared in Example 9 of this invention. Figure 4 This is a SEM image of the copper foil surface after pulse electroplating of the copper foil substrate using a pulse electroplating copper solution during performance testing.

[0026] like Figure 4 As shown, the copper foil obtained by pulse electroplating of copper foil substrate with pulse electroplating solution has a continuous and dense surface with relatively uniform grain distribution. No obvious dendritic protrusions, pores, island discontinuous deposition, or other defects are observed. The surface undulation is small, demonstrating good deposition stability and surface smoothness. This morphological result shows that under pulse current conditions, the system of the present invention can effectively regulate the deposition process at the cathode interface, making copper deposition tend to be uniformly nucleated and inhibiting local overgrowth, thereby obtaining an electrodeposited copper layer with complete structure and uniform morphology. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] In this application, the polyvinyl alcohol used was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with the product number P434370.

[0029] Example 1 This embodiment provides a method for preparing an amphoteric modified polyol dispersant, comprising the following steps: Step ①: Prepare microacetalized polyvinyl alcohol solution Weigh 10.0g of polyvinyl alcohol and 200.0mL of deionized water and add them to the reaction vessel. Stir the mixture and heat the reaction vessel to 50℃. Stir until the polyvinyl alcohol is completely dissolved. Then, cool the reaction vessel to 35℃, purge with nitrogen for protection, and add 4.0g of 25wt% glutaraldehyde aqueous solution. After the addition is complete, adjust the pH of the reaction system to 5 with acetic acid. Keep the mixture warm and stir for 1 hour. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain a micro-aldehyde polyvinyl alcohol solution.

[0030] Step 2: Preparation of epoxy-side-group polyol modified solution Weigh 100.0 mL of microacetalized polyvinyl alcohol solution and add it to the reaction vessel. Stir the reaction vessel, heat it to 60°C, add 0.05 g of p-toluenesulfonic acid, and then add 5.0 g of glycidyl methacrylate. Keep the mixture warm and stir for 2 hours. After the reaction is complete, let the reaction vessel cool to room temperature to obtain epoxy side-group polyol modified solution.

[0031] Step ③: Preparation of zwitterionic modified polyol dispersant Weigh 100.0 mL of epoxy-side-chain polyol modified solution and add it to the reaction vessel. Adjust the pH of the reaction system to 8 using 10 wt% sodium hydroxide aqueous solution, then add 3.0 g of taurine. Heat the reaction vessel to 50 °C and stir for 2 h. After the reaction is complete, let the reaction vessel cool to room temperature, filter the reaction solution to collect the filter cake, and transfer the filter cake to a drying oven at 80 °C to vacuum dry to constant weight to obtain zwitterionic modified polyol dispersant.

[0032] Example 2 This embodiment provides a method for preparing an amphoteric modified polyol dispersant, comprising the following steps: Step ①: Prepare microacetalized polyvinyl alcohol solution Weigh 10.0g of polyvinyl alcohol and 200.0mL of deionized water and add them to the reaction vessel. Stir the mixture and heat the reaction vessel to 60℃. Stir until the polyvinyl alcohol is completely dissolved. Then, cool the reaction vessel to 40℃, purge with nitrogen for protection, and add 6.0g of 30wt% glutaraldehyde aqueous solution. After the addition is complete, adjust the pH of the reaction system to 4 with acetic acid. Keep the mixture warm and stir for 2 hours. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain a micro-aldehyde polyvinyl alcohol solution.

[0033] Step 2: Preparation of epoxy-side-group polyol modified solution Weigh 100.0 mL of microacetalized polyvinyl alcohol solution and add it to the reaction vessel. Stir the reaction vessel, heat it to 70°C, add 0.08 g of p-toluenesulfonic acid, and then add 8.0 g of glycidyl methacrylate. Keep the mixture warm and stir for 3 hours. After the reaction is complete, let the reaction vessel cool to room temperature to obtain epoxy side-group polyol modified solution.

[0034] Step ③: Preparation of zwitterionic modified polyol dispersant Weigh 100.0 mL of epoxy-side-chain polyol modified solution and add it to the reaction vessel. Adjust the pH of the reaction system to 9 using 10 wt% sodium hydroxide aqueous solution, then add 5.0 g of taurine. Heat the reaction vessel to 60 °C and stir for 3 h. After the reaction is complete, let the reaction vessel cool to room temperature, filter the reaction solution to collect the filter cake, and transfer the filter cake to a drying oven at 80 °C to vacuum dry to constant weight to obtain zwitterionic modified polyol dispersant.

[0035] Example 3 This embodiment provides a method for preparing an amphoteric modified polyol dispersant, comprising the following steps: Step ①: Prepare microacetalized polyvinyl alcohol solution Weigh 10.0g of polyvinyl alcohol and 200.0mL of deionized water and add them to the reaction vessel. Stir the mixture and heat the reaction vessel to 55℃. Stir until the polyvinyl alcohol is completely dissolved. Then, cool the reaction vessel to 40℃, purge with nitrogen for protection, and add 5.0g of 28wt% glutaraldehyde aqueous solution. After the addition is complete, adjust the pH of the reaction system to 4 with acetic acid. Keep the mixture warm and stir for 2 hours. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain a micro-aldehyde polyvinyl alcohol solution.

[0036] Step 2: Preparation of epoxy-side-group polyol modified solution Weigh 100.0 mL of microacetalized polyvinyl alcohol solution and add it to the reaction vessel. Stir the reaction vessel, heat it to 65°C, add 0.06 g of p-toluenesulfonic acid, and then add 7.0 g of glycidyl methacrylate. Keep the mixture warm and stir for 3 hours. After the reaction is complete, let the reaction vessel cool to room temperature to obtain epoxy side-group polyol modified solution.

[0037] Step ③: Preparation of zwitterionic modified polyol dispersant Weigh 100.0 mL of epoxy-side-chain polyol modified solution and add it to the reaction vessel. Adjust the pH of the reaction system to 9 using 10 wt% sodium hydroxide aqueous solution, then add 4.0 g of taurine. Heat the reaction vessel to 55 °C and stir for 3 h. After the reaction is complete, let the reaction vessel cool to room temperature, filter the reaction solution and collect the filter cake. Transfer the filter cake to a drying oven at 80 °C and vacuum dry it to constant weight to obtain zwitterionic modified polyol dispersant.

[0038] right Figure 1 Analysis reveals that: The infrared absorption spectrum of zwitterionic modified polyol dispersants is at 3380 cm⁻¹ -1 A broad and strong absorption band appears nearby, attributed to the OH / NH stretching vibrations of numerous hydroxyl groups and introduced amino groups, indicating that the polyvinyl alcohol backbone still maintains a high content of hydrophilic groups; 2940 cm⁻¹ -1 With 2870cm -1 The presence of a moderate absorption peak corresponds to the CH stretching vibration of the polyvinyl alcohol segment and the residual hydrocarbon chain of glycidyl methacrylate, indicating that the organic framework structure is intact. At 1730cm -1 A distinct strong absorption band was observed nearby, which can be attributed to the C=O stretching vibration of the ester group. This band is newly observed and significantly enhanced compared to the original polyvinyl alcohol sample, directly confirming that an esterification reaction occurred between the microacetalized polyvinyl alcohol and glycidyl methacrylate, with the epoxy side group stably grafted onto the polyol backbone via ester bonds; 1450 cm⁻¹ -1The absorption in the vicinity mainly comes from the bending vibration of -CH2-, further confirming that the polyvinyl alcohol backbone is still the main component of the material; At 1210cm -1 A strong and sharp absorption peak appears at this point, which can be attributed to the sulfonic acid group (-SO3). - Asymmetric S=O stretching vibration; 1080-1040 cm -1 The region exhibits a set of overlapping strong absorption bands, which can be attributed to the symmetric S=O stretching of the sulfonic acid group and the COC and CO stretching vibrations. This indicates that the sulfonic acid group in taurine has been effectively introduced into the polyol chain segment, and the epoxy characteristic absorption (approximately 910 cm⁻¹) is observed. -1 The presence of taurine in the sample was significantly reduced or even almost disappeared, indicating that the epoxy ring underwent ring-opening and was consumed by the nucleophilic addition of taurine in subsequent reactions. In 1140-950cm -1 A series of moderate-intensity absorption peaks are visible in the range, which can be attributed to quaternary ammonium CN. + The stretching vibrations and the coupled vibrations of the adjacent COC structure, combined with the aforementioned S=O characteristic signal, indicate that both cationic ammonium salt structures and anionic sulfonate structures exist on the molecular chain, which is consistent with the design of zwitterionic side chains. Combining the characteristic absorptions of the hydroxyl / amino, ester, sulfonic acid, and quaternary ammonium structures, it can be confirmed that a polyol skeleton with sulfonic acid-quaternary ammonium zwitterionic side chains has been successfully constructed in the sample, and the target structure of the zwitterionic modified polyol dispersant has been verified at the infrared spectroscopy level.

[0039] Example 4 This embodiment provides a method for preparing a mercaptotriazine leveling agent, comprising the following steps: Step I: Preparation of triazine mercaptosulfonate intermediate solution Weigh 5.0 g of 2,4,6-trichloro-1,3,5-triazine and 150.0 mL of deionized water and add them to the reaction vessel. After purging with nitrogen, cool the reaction vessel to 5°C. Then add cysteine ​​hydrochloride to adjust the pH of the reaction system to 8. After maintaining the temperature for 40 min, heat the reaction vessel to 30°C, add 3.0 g of taurine and maintain the temperature for 40 min. Then heat the reaction vessel to 70°C and add 2.0 g of ethanolamine. Maintain the temperature for 60 min. After the reaction is completed, allow the reaction vessel to cool naturally to room temperature to obtain the triazine mercaptosulfonate intermediate solution.

[0040] Step II: Preparation of mercaptotriazine leveling agent Weigh 100.0 mL of the mercaptosulfonic acid triazine intermediate solution and add it to the reaction vessel. After adjusting the pH of the reaction system to 8 with 10 wt% sodium hydroxide aqueous solution, add 0.3 g of hydrogen peroxide and stir for 40 min. After the reaction is completed, let the reaction vessel cool naturally to room temperature, filter the reaction solution to collect the filter cake, and wash the filter cake three times with anhydrous ethanol and deionized water. Then, place the filter cake in an 80℃ drying oven and vacuum dry it to constant weight to obtain mercaptotriazine leveling agent.

[0041] Example 5 This embodiment provides a method for preparing a mercaptotriazine leveling agent, comprising the following steps: Step I: Preparation of triazine mercaptosulfonate intermediate solution Weigh 5.0 g of 2,4,6-trichloro-1,3,5-triazine and 150.0 mL of deionized water and add them to the reaction vessel. After purging with nitrogen, cool the reaction vessel to 3°C. Then add cysteine ​​hydrochloride to adjust the pH of the reaction system to 9. After maintaining the temperature for 60 min, heat the reaction vessel to 40°C, add 5.0 g of taurine and maintain the temperature for 60 min. Then heat the reaction vessel to 80°C and add 3.0 g of ethanolamine. Maintain the temperature for 90 min. After the reaction is completed, allow the reaction vessel to cool naturally to room temperature to obtain the triazine mercaptosulfonate intermediate solution.

[0042] Step II: Preparation of mercaptotriazine leveling agent Weigh 100.0 mL of the mercaptosulfonic acid triazine intermediate solution and add it to the reaction vessel. After adjusting the pH of the reaction system to 9 with 10 wt% sodium hydroxide aqueous solution, add 0.5 g of hydrogen peroxide and stir for 60 min. After the reaction is completed, let the reaction vessel cool naturally to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water, and then place the filter cake in an 80℃ drying oven and vacuum dry it to constant weight to obtain mercaptotriazine leveling agent.

[0043] Example 6 This embodiment provides a method for preparing a mercaptotriazine leveling agent, comprising the following steps: Step I: Preparation of triazine mercaptosulfonate intermediate solution Weigh 5.0 g of 2,4,6-trichloro-1,3,5-triazine and 150.0 mL of deionized water and add them to the reaction vessel. After purging with nitrogen, cool the reaction vessel to 4°C. Then add cysteine ​​hydrochloride to adjust the pH of the reaction system to 9. After holding the temperature for 50 min, heat the reaction vessel to 35°C, add 4.0 g of taurine and hold the temperature for 50 min. Then heat the reaction vessel to 75°C and add 2.5 g of ethanolamine. Hold the temperature for 75 min. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain the triazine mercaptosulfonate intermediate solution.

[0044] Step II: Preparation of mercaptotriazine leveling agent Weigh 100.0 mL of mercaptosulfonic acid triazine intermediate solution and add it to the reaction vessel. Adjust the pH of the reaction system to 9 using 10 wt% sodium hydroxide aqueous solution, add 0.4 g of hydrogen peroxide and stir for 50 min. After the reaction is completed, allow the reaction vessel to cool naturally to room temperature, filter the reaction solution to collect the filter cake, and wash the filter cake 4 times with anhydrous ethanol and deionized water. Place the filter cake in an 80℃ drying oven and vacuum dry it to constant weight to obtain mercaptotriazine leveling agent.

[0045] right Figure 2 Analysis reveals that: The infrared spectrum of mercaptotriazine leveling agent is at 3380 cm⁻¹ -1 The presence of a broad and strong absorption band nearby, attributed to the OH / NH stretching vibrations of hydroxyl and polyamine groups, indicates the presence of numerous hydrophilic groups in the external branches of the triazine skeleton. (2950 cm⁻¹) -1 With 2870cm -1 The nearby medium-intensity absorption peaks correspond to the CH stretching vibrations of -CH2- and -CH3, which originate from the hydrocarbon chain structure of organic substituents such as cysteine, taurine, and ethanolamine, providing evidence for the existence of multi-substituted organic side chains around the triazine ring. At 1640cm -1 and 1570cm -1 A set of relatively distinct absorption bands can be observed in the region, which can be attributed to the characteristic peaks of the C=N stretching vibration of the triazine ring coupled with the NH bending vibration, indicating that the triazine skeleton remains intact after the substitution reaction. (1450 cm⁻¹) -1 The absorption peaks appearing on the left and right sides mainly correspond to the -CH2- bending vibration, which is also consistent with the introduced chain-like organic substituents, 1330-1280 cm⁻¹. -1 The moderate-intensity absorption in the range can be attributed to C–N stretching and triazine ring vibration modes, further confirming the formation of polyamine and multi-substituted triazine structures; At 1210cm -1 A strong and sharp absorption peak appears at 1120, 1070, and 1030 cm⁻¹, which is due to the asymmetric S=O stretching vibration of the sulfonic acid group / sulfonate, a typical characteristic of taurine after the introduction of the triazine skeleton; -1 A series of overlapping strong absorption bands are attributed to the coupled signals of the symmetric S=O stretching, CO stretching, and CN vibrations of the sulfonic acid group, indicating the simultaneous presence of sulfonic acid groups and oxygen-containing hydrophilic groups in the system. Notably, the characteristic stretching vibration of the thiol group (≈2550 cm⁻¹) is also present. -1 No obvious absorption was observed in the spectrum of this sample (region), and combined with the strong S=O characteristic peak, it can be inferred that the original thiol group has been mainly converted into the oxidized sulfur-containing structure under the action of hydrogen peroxide. At 800cm -1 With 760cm -1Nearby, triazine ring respiration and out-of-plane vibration characteristic signals were also observed, further confirming the existence of the triazine skeleton. Considering the broad OH / NH peak, triazine C=N / CN vibration, strong S=O characteristic absorption, and the disappearance of the thiol signal, it can be determined that a thiol triazine leveling agent structure has been successfully constructed in the sample, with triazine as the skeleton, cysteine, taurine and ethanolamine substituents introduced, and oxidatively regulated.

[0046] Example 7 This embodiment provides a method for preparing a boron-containing imine dynamic complexing agent, comprising the following steps: Step (1): Preparation of boron-containing imine prepolymer solution Weigh out 3.0g of 3-aminophenylboronic acid, 2.0g of diethylenetriamine and 150.0mL of deionized water and add them to the reaction vessel. After purging with nitrogen, heat the reaction vessel to 40℃, add 3.0g of glyoxal and keep it warm and stirred for 2h. After the reaction is completed, let the reaction vessel cool naturally to room temperature to obtain boron-containing imine prepolymer.

[0047] Step 2: Preparation of boron-containing imine dynamic complexing agent Weigh 100.0 mL of boron-containing imine prepolymer solution and add it to the reactor. Adjust the pH of the reaction system to 8 using 10 wt% sodium hydroxide aqueous solution, add 2.0 g of catechol and stir at room temperature for 1 h. After the reaction is completed, allow the reactor to cool naturally to room temperature, filter the reaction solution to collect the filter cake, and wash the filter cake three times with anhydrous ethanol and deionized water. Place the filter cake in an 80 ℃ drying oven and vacuum dry it to constant weight to obtain the boron-containing imine dynamic complexing agent.

[0048] Example 8 This embodiment provides a method for preparing a boron-containing imine dynamic complexing agent, comprising the following steps: Step (1): Preparation of boron-containing imine prepolymer solution Weigh out 3.0g of 3-aminophenylboronic acid, 2.0g of diethylenetriamine and 150.0mL of deionized water and add them to the reaction vessel. After purging with nitrogen, heat the reaction vessel to 50℃, add 4.0g of glyoxal and keep it warm and stirred for 3h. After the reaction is completed, let the reaction vessel cool naturally to room temperature to obtain boron-containing imine prepolymer.

[0049] Step 2: Preparation of boron-containing imine dynamic complexing agent Weigh 100.0 mL of boron-containing imine prepolymer solution and add it to the reactor. Adjust the pH of the reaction system to 9 using 10 wt% sodium hydroxide aqueous solution, add 3.0 g of catechol and stir at room temperature for 2 h. After the reaction is completed, allow the reactor to cool naturally to room temperature, filter the reaction solution to collect the filter cake, and wash the filter cake 5 times with anhydrous ethanol and deionized water. Place the filter cake in an 80 ℃ drying oven and vacuum dry it to constant weight to obtain the boron-containing imine dynamic complexing agent.

[0050] Example 9 This embodiment provides a method for preparing a boron-containing imine dynamic complexing agent, comprising the following steps: Step (1): Preparation of boron-containing imine prepolymer solution Weigh out 3.0g of 3-aminophenylboronic acid, 2.0g of diethylenetriamine and 150.0mL of deionized water and add them to the reactor. After purging with nitrogen, heat the reactor to 45℃, add 3.5g of glyoxal and keep it heated and stirred for 3h. After the reaction is completed, let the reactor cool naturally to room temperature to obtain boron-containing imine prepolymer.

[0051] Step 2: Preparation of boron-containing imine dynamic complexing agent Weigh 100.0 mL of boron-containing imine prepolymer solution and add it to the reactor. Adjust the pH of the reaction system to 9 using 10 wt% sodium hydroxide aqueous solution, add 2.5 g of catechol and stir at room temperature for 2 h. After the reaction is completed, allow the reactor to cool naturally to room temperature, filter the reaction solution to collect the filter cake, and wash the filter cake 4 times with anhydrous ethanol and deionized water. Place the filter cake in an 80 ℃ drying oven and vacuum dry it to constant weight to obtain the boron-containing imine dynamic complexing agent.

[0052] right Figure 3 After analysis, it can be found that: Infrared spectrum at 3360 cm⁻¹ -1 A broad and distinct absorption band is observed nearby, attributed to the OH / NH stretching vibrations of the polyamine segment and the residual hydroxyl groups of catechol, indicating that the material still retains some polar groups capable of forming hydrogen bonds, at 2920 cm⁻¹. -1 With 2850cm -1 The position shows a moderate intensity CH stretching vibration absorption, which originates from the hydrocarbon chain segment of the diethylenetriamine and arylboronic acid structure; At 1630cm -1 The strong and sharp absorption peak at 1580 cm⁻¹ clearly belongs to the stretching vibration of the imine bond (C=N), which is important evidence for the formation of the imine skeleton in the condensation reaction; in addition, the peak at 1580 cm⁻¹... -1 and 1500cm -1 The absorption band corresponds to the C=C vibration of the aromatic ring, confirming the retention of the main structure of arylboronic acid, 1450 cm⁻¹. -1 The nearby intermediate intensity peaks are due to the bending vibration of -CH2-, which is consistent with the introduced aliphatic polyamine segment; 1350-1280cm -1 A distinct set of absorptions can be observed in the region, which can be attributed to the stretching vibrations of the B–N and B–O bonds, a typical spectral feature of stable interactions between the boron center and the imine network; the presence of this region indicates that the boric acid groups have been effectively embedded in the condensation network, at 1190, 1120, and 1070 cm⁻¹. -1The three overlapping strong absorption bands correspond to the stretching vibration of the borate ester BOC bond formed by catechol and aromatic boric acid, providing direct spectroscopic evidence for the catechol chelation at the boric acid position, while also demonstrating the strong characteristic absorption brought about by the chelation structure. At 760cm -1 With 720cm -1 The presence of out-of-plane bending vibration peaks of the aromatic ring CH in the region further confirms the integrity of the arylboronic acid structure in the reaction. Combined with the broad OH / NH peak, strong C=N peak, key absorption bands of BN and BO, and strong characteristic signals in the boronic acid ester region, it can be verified that a boron-containing imine complex system with an imine bond as the main chain and a boric acid-catechol chelate structure as the dynamic regulation center has been successfully constructed in the material.

[0053] Example 10 This embodiment provides a highly dispersed pulse electroplating copper additive and its application method, including the following steps: Step 1: Preparation of composite copper plating additives Weigh out 200 parts by weight of deionized water and add it to a stirring vessel. Then add 12 parts of the zwitterionic modified polyol dispersant prepared in Example 1, 10 parts of the boron-containing imine dynamic complexing agent prepared in Example 7, and 1 part of the mercaptotriazine leveling agent prepared in Example 4 in sequence. Stir at room temperature for 40 minutes and then filter through a 100-mesh screen to obtain the composite electroplating copper additive.

[0054] Step 2: Preparation of composite copper plating additives Weigh out 6000.0 mL of deionized water and 750.0 g of copper sulfate pentahydrate and add them to the tank. Stir until the copper sulfate pentahydrate is completely dissolved. Then add 2300.0 g of 98% concentrated sulfuric acid, followed by 0.6 g of sodium chloride. Next, add 20.0 g of composite copper plating additive, and then add 4000.0 mL of deionized water to make up the difference, thus obtaining the pulse copper plating solution. Add the workpiece to be plated at a temperature of 25°C, a pulse frequency of 400 Hz, and a pulse rate of 3 A / dm². 2 The peak current density and 40% duty cycle are used for pulsed copper plating.

[0055] Example 11 This embodiment provides a highly dispersed pulse electroplating copper additive and its application method, including the following steps: Step 1: Preparation of composite copper plating additives Weigh out 200 parts by weight of deionized water and add it to a stirring vessel. Then add 15 parts of the zwitterionic modified polyol dispersant prepared in Example 2, 15 parts of the boron-containing imine dynamic complexing agent prepared in Example 8, and 2 parts of the mercaptotriazine leveling agent prepared in Example 5 in sequence. Stir at room temperature for 60 minutes and then filter through a 100-mesh screen to obtain the composite electroplating copper additive.

[0056] Step 2: Preparation of composite copper plating additives Weigh out 6000.0 mL of deionized water and 750.0 g of copper sulfate pentahydrate and add them to the tank. Stir until the copper sulfate pentahydrate is completely dissolved. Then add 2300.0 g of 98% concentrated sulfuric acid, followed by 0.6 g of sodium chloride. Next, add 30.0 g of composite copper plating additive, and then add 4000.0 mL of deionized water to make up the difference, thus obtaining the pulse copper plating solution. Add the workpiece to be plated at a temperature of 30°C, a pulse frequency of 500 Hz, and a pulse rate of 5 A / dm. 2 The peak current density and 60% duty cycle are used for pulsed copper plating.

[0057] Example 12 This embodiment provides a highly dispersed pulse electroplating copper additive and its application method, including the following steps: Step 1: Preparation of composite copper plating additives Weigh out 200 parts by weight of deionized water and add it to a stirring vessel. Then add 13 parts of the zwitterionic modified polyol dispersant prepared in Example 3, 12 parts of the boron-containing imine dynamic complexing agent prepared in Example 9, and 2 parts of the mercaptotriazine leveling agent prepared in Example 6 in sequence. Stir at room temperature for 50 minutes and then filter through a 100-mesh screen to obtain the composite electroplating copper additive.

[0058] Step 2: Preparation of composite copper plating additives Weigh out 6000.0 mL of deionized water and 750.0 g of copper sulfate pentahydrate and add them to the tank. Stir until the copper sulfate pentahydrate is completely dissolved. Then add 2300.0 g of 98% concentrated sulfuric acid, followed by 0.6 g of sodium chloride. Next, add 25.0 g of composite copper plating additive, and then add 4000.0 mL of deionized water to make up the difference, thus obtaining the pulse copper plating solution. Add the workpiece to be plated at a temperature of 28℃, a pulse frequency of 450 Hz, and a pulse rate of 4 A / dm. 2 The peak current density and 50% duty cycle are used for pulsed copper plating.

[0059] Comparative Example 1 The difference between this comparative example and Example 12 is that the zwitterionic modified polyol dispersant was omitted in step one.

[0060] Comparative Example 2 The difference between this comparative example and Example 12 is that the boron-containing imine dynamic complexing agent is omitted in step one.

[0061] Comparative Example 3 The difference between this comparative example and Example 12 is that the use of mercaptotriazine leveling agent is omitted in step one.

[0062] Performance testing: The composite copper plating additives prepared in Examples 10-12 and Comparative Examples 1-3 were adjusted to a concentration of 1.0 g / L. After stirring magnetically for 30 min, the solution was filtered through a 0.45 μm filter membrane and then placed into a 50 mL transparent colorimetric tube. The initial liquid level height H0 and the initial transmittance T0 were recorded (using a spectrophotometer, wavelength 600 nm). The colorimetric tube was then placed in a constant temperature environment of 25 °C for 72 h. After the settling period, the sedimentation layer height H was recorded. S and the transmittance T of the supernatant 72 The settlement ratio S=H was determined. S / H0×100% and transmittance change ΔT=|T 72- T0|; Adsorption tests were conducted using a 250 mL Hull bath. Pulse electroplating copper solutions prepared in Examples 10-12 and Comparative Examples 1-3 were added. A 75 mm × 100 mm copper sheet was used as the cathode, cleaned, and installed in the Hull bath. The electroplating solution was heated to 25°C, and electroplating was performed at a constant current of 2 A for 60 seconds. After electroplating, the sample was immediately rinsed and dried. The length L of the bright band in the high-current region was measured using a microscope. b and the length L of the charred zone s Record the values ​​and calculate the adsorption rate R. a =L b / L s ; On a copper foil substrate, copper was electroplated in the pulsed copper plating solution prepared in Examples 10-12 and Comparative Examples 1-3 at a constant current density of 2.0 A / dm³. 2 Electroplating for 15 min yielded a coating approximately 6 μm thick. The sample was cut into 10 mm × 10 mm pieces, cleaned with deionized water, dried, and then subjected to X-ray diffraction testing. The XRD scanning range was fixed at 2θ = 40°-50°, the step interval was 0.02°, and the scanning rate was 2° / min. The Cu(111) diffraction peak was selected, and the full width at half maximum (FWHM) β was fitted using software. The grain size D was calculated using the Scherrer formula D = 0.9λ / (βcosθ), where λ = 0.154 nm. Using a 250 mL Hull bath, pulsed copper plating solutions prepared in Examples 10-12 and Comparative Examples 1-3 were used to electroplate standard copper sheets at a current of 2 A, a plating time of 10 min, and a temperature of 25 °C. After plating, the thickness was measured at three points in the high current, medium current, and low current regions using a micro-thickness gauge, and the average value was recorded as t. h t m and t l With a thickness ratio U=t l / t h ×100% is used as an indicator of leveling capability; A PCB through-hole board with a hole diameter of 0.25 mm, a board thickness of 2.5 mm, and a depth-to-width ratio of 10:1 was selected. Electroplating was performed for 40 min in the pulsed copper plating solution prepared in Examples 10-12 and Comparative Examples 1-3 using a pulsed current (frequency 400 Hz, duty cycle 50%). After electroplating, the board was cut along the hole axis and a metallographic section was prepared. The copper plating thickness inside the hole and the copper plating thickness on the board surface were measured under a microscope, and the deep plating capability F was calculated as: F = (copper plating thickness inside the hole / copper plating thickness on the board surface) × 100%. The pulsed copper plating solution electroplating system prepared in Examples 10-12 and Comparative Examples 1-3 was connected to a pulse power supply, with a fixed pulse frequency of 500Hz, duty cycle of 50%, and peak current density of 4A / dm³. 2 The electroplating solution temperature was maintained at 25℃, and I was recorded. p0 For electroplating at f0, continuous electroplating was performed for 4 hours. During each of the 4 hours of electroplating, the current waveform was acquired using a digital oscilloscope, and the peak current I was recorded. p4h and frequency f 4h Calculate the peak current change rate ΔI p =|I p0- I p4h | / I p0 ×100% and the rate of change of frequency Δf=|f 0- f 4h | / I p0 ×100%, see Table 1 for specific data; Table 1 - Performance Test Data for Each Sample

[0063] Data Analysis: Comparing the data in Table 1, it can be found that the composite electroplating copper additive prepared in this invention has a 72-hour sedimentation ratio S of 3.4%, a 72-hour transmittance change ΔT of 1.7, and an adsorption rate R of the pulse electroplating copper solution prepared using the composite electroplating copper additive prepared in this invention. a The parameters are 3.6, the coating grain size D is 72nm, the coating thickness ratio U is 90%, the in-hole copper filling rate F is 97%, and the peak current change rate ΔI during pulse electroplating is also 3.6. p The percentages are 2.3% and the rate of change of frequency Δf is 1.7%, all of which are better than the comparative example. This indicates that: In Comparative Example 1, since the system no longer contains zwitterionic modified polyol dispersant, the original uniform dispersion state in the plating solution cannot be maintained, and its intermolecular electrostatic equilibrium structure is destroyed, resulting in a decrease in the distribution stability of the additive components in the solution. After losing the dispersant's regulation of the solution's interfacial tension and wettability within the pores, the degree of wetting of the electroplating solution in high aspect ratio micropores or through holes is significantly reduced, making it easy for the liquid to fail to fully penetrate to the bottom of the hole, causing local mass transfer imbalance of metal ions during the hole filling process. On the other hand, the solution microenvironment near the interface is no longer stable, and the migration rate of metal ions during the pulse current cycle is more easily disturbed, resulting in a deposition rate at the hole opening that is much higher than that at the bottom of the hole. The above-mentioned uneven interfacial dynamic behavior ultimately leads to defects such as thin hole bottom, hole opening blockage, or cross-sectional asymmetry, which are manifested as deterioration of the electroplated structure morphology and a decrease in filling capacity. In Comparative Example 2, due to the lack of a boron-containing imine dynamic complexing agent, the electroplating system lost its dynamic regulation mechanism for the effective concentration of copper ions. This made it difficult for metal ions to maintain a stable supply balance under the action of pulsed current, causing a significant enhancement of local polarization in the peak range of the pulsed current. Without reversible complexation regulation, copper ions are prone to instantaneous enrichment or depletion at the electrode interface, resulting in periodic fluctuations in the nucleation and growth process. At the same time, without the buffer regulation of the complexing agent, the local deposition rate during the coating formation process is directly driven by the current pulse, leading to uneven crystal orientation, rapid grain growth, and increased fluctuations in the interface deposition thickness. In addition, the mass transfer difference between the inside and outside regions of the hole is amplified, resulting in a significant lack of metal supply at high aspect ratio structures, causing deposition interruption or insufficient nucleation at the bottom of the hole. Ultimately, this manifests as structural instability phenomena such as rough surface, bulging hole opening, and coarse internal grains. In Comparative Example 3, due to the lack of multi-point adsorption regulation by the mercaptotriazine leveling agent, the electrochemical reaction at the electrode interface is no longer subject to selective adsorption control. This results in the metal deposition rate in the high current density region being unrestricted, leaving the interface in a free growth state. Consequently, the deposition behavior becomes more dependent on the local current distribution, significantly accelerating deposition at the electrode surface edges and protrusions. Simultaneously, without the leveling agent covering the high-energy crystal planes and active sites, the crystal growth direction is no longer inhibited, and the local crystal nucleus growth rate is significantly increased, causing the coating to gradually form an uneven macroscopic morphology. At the same time, the orifice region is more prone to overgrowth under the action of the pulse peak current, hindering the entry of deep metal ions, resulting in insufficient deposition at the bottom of the orifice and premature closure of the orifice. Overall, this manifests as increased surface fluctuations, decreased coating smoothness, and incomplete filling of the orifice, ultimately forming typical surface roughness and orifice blockage defects. In conclusion, this invention constructs a unified system by integrating amphoteric modified polyol dispersant, boron-containing imine dynamic complexing agent, and mercaptotriazine leveling agent. This system creates a continuous and unified chain of action in multiple key aspects of the electroplating solution, including dispersion stability, interfacial adsorption behavior, ion dynamic regulation, and crystal growth control. The amphoteric modified polyol dispersant provides a stable dispersion environment and a good wetting foundation, ensuring uniform entry and continuous coverage of the electroplating solution in complex structures. The boron-containing imine dynamic complexing agent reversibly regulates copper ions under pulsed conditions, keeping the nucleation and deposition processes within an appropriate range. The mercaptotriazine leveling agent constructs a selective adsorption layer near the interface, gradually developing the deposition morphology towards a more regular shape. When these three agents are introduced in a set ratio, multiple indicators such as solution stability, adsorption rate, grain refinement, thickness distribution, and pore filling remain within excellent ranges. The peak current and frequency also remain stable during the pulsed process, resulting in a structurally complete and uniformly morphologically uniform electrodeposited copper layer. The overall system forms a continuous connection across multiple dimensions of action, leading to a significant overall performance improvement in the final electroplating process.

[0064] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0065] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0066] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A highly dispersed pulse electroplating copper additive, characterized in that, The raw material composition includes the following parts by weight: 12-15 parts zwitterionic modified polyol dispersant, 1-2 parts mercaptotriazine leveling agent, 10-15 parts boron-containing imine dynamic complexing agent and 200 parts dispersant, wherein the dispersant is deionized water; The preparation method of the zwitterionic modified polyol dispersant includes the following steps: A1. Add the micro-acetalized polyvinyl alcohol solution to the reaction vessel and stir. Heat the reaction vessel to 60-70℃ and add p-toluenesulfonic acid. Then add glycidyl methacrylate and keep it warm and stir for 2-3 hours. After the reaction is completed, let the reaction vessel cool to room temperature to obtain the epoxy side-group polyol modified solution. A2. Add the epoxy-side-chain polyol modified liquid to the reaction vessel, and adjust the pH of the reaction system to 8-9 using 10wt% sodium hydroxide aqueous solution. Then add taurine, heat the reaction vessel to 50-60℃, keep it warm and stir for 2-3 hours, and then process to obtain zwitterionic modified polyol dispersant.

2. The highly dispersed pulse electroplating copper additive according to claim 1, characterized in that, In step A1, the ratio of the amount of the microacetalized polyvinyl alcohol solution, p-toluenesulfonic acid, and glycidyl methacrylate is 100mL:0.05-0.08g:5-8g; in step A2, the ratio of the amount of the epoxy side-group polyol modified solution to taurine is 100mL:3-5g.

3. The highly dispersed pulse electroplating copper additive according to claim 1, characterized in that, The preparation method of the micro-aldehyde polyvinyl alcohol solution is as follows: polyvinyl alcohol and deionized water are added to a reaction vessel and stirred. The reaction temperature is raised to 50-60℃ and stirred until the polyvinyl alcohol is completely dissolved. Then the reaction vessel is cooled to 35-40℃, nitrogen gas is introduced for protection, and 25-30wt% glutaraldehyde aqueous solution is added. After the addition is complete, acetic acid is used to adjust the pH of the reaction system to 4-5. The mixture is kept warm and stirred for 1-2 hours. After the reaction is completed, the reaction vessel is allowed to cool naturally to room temperature to obtain the micro-aldehyde polyvinyl alcohol solution.

4. The highly dispersed pulse electroplating copper additive according to claim 3, characterized in that, In the preparation of the microacetalized polyvinyl alcohol solution, the ratio of polyvinyl alcohol, deionized water and glutaraldehyde aqueous solution is 10g:200mL:4-6g.

5. The highly dispersed pulse electroplating copper additive according to claim 1, characterized in that, The preparation method of the mercaptotriazine leveling agent includes the following steps: B1. Add 2,4,6-trichloro-1,3,5-triazine and deionized water to a reaction vessel. After purging with nitrogen, cool the reaction vessel to 3-5°C. Then add cysteine ​​hydrochloride to adjust the pH of the reaction system to 8-9. After maintaining the temperature for 40-60 min, heat the reaction vessel to 30-40°C, add taurine and maintain the temperature for 40-60 min. Then heat the reaction vessel to 70-80°C and add ethanolamine. Maintain the temperature for 60-90 min. After the reaction is complete, allow the reaction vessel to cool naturally to room temperature to obtain a triazine mercaptosulfonate intermediate solution. B2. Add the intermediate solution of mercaptosulfonic acid triazine to the reaction vessel, adjust the pH of the reaction system to 8-9 using 10wt% sodium hydroxide aqueous solution, add hydrogen peroxide and stir for 40-60 min, and then perform post-treatment to obtain mercaptotriazine leveling agent.

6. The highly dispersed pulse electroplating copper additive according to claim 5, characterized in that, In step B1, the ratio of 2,4,6-trichloro-1,3,5-triazine, deionized water, taurine, and ethanolamine is 5g:150mL:3-5g:2-3g; in step B2, the ratio of the triazine mercaptosulfonate intermediate solution to hydrogen peroxide is 100mL:0.3-0.5g.

7. The highly dispersed pulse electroplating copper additive according to claim 1, characterized in that, The preparation method of the boron-containing imine dynamic complexing agent includes the following steps: C1. Add 3-aminophenylboronic acid, diethylenetriamine and deionized water to the reactor, purge with nitrogen and heat the reactor to 40-50℃, add glyoxal and keep it heated and stirred for 2-3 hours. After the reaction is completed, let the reactor cool naturally to room temperature to obtain boron-containing imine prepolymer liquid. C2. Add the boron-containing imine prepolymer to the reactor, adjust the pH of the reaction system to 8-9 using a 10wt% sodium hydroxide aqueous solution, add catechol and stir at room temperature for 1-2 hours, and then perform post-treatment to obtain the boron-containing imine dynamic complexing agent.

8. The highly dispersed pulse electroplating copper additive according to claim 7, characterized in that, In step C1, the ratio of 3-aminophenylboronic acid, diethylenetriamine, deionized water, and glyoxal is 3g:2g:150mL:3-4g; in step C2, the ratio of boron-containing imine prepolymer to catechol is 100mL:2-3g.

9. The method of using a highly dispersed pulse electroplating copper additive as described in any one of claims 1-8, characterized in that, The method of using the highly dispersed pulse electroplating copper additive includes the following steps: S1. Add the dispersant to the mixing tank and stir. Then add the zwitterionic modified polyol dispersant, boron-containing imine dynamic complexing agent and mercaptotriazine leveling agent in sequence. Stir at room temperature for 40-60 minutes and then pass through a 100-mesh filter to obtain the composite electroplating copper additive. S2. Add deionized water and copper sulfate pentahydrate to the tank and stir. After the copper sulfate pentahydrate is completely dissolved, add 98% concentrated sulfuric acid, then add sodium chloride, followed by composite copper plating additives, and then add deionized water to obtain pulse copper plating solution. Add the workpiece to be plated and perform pulse copper plating operation.

10. The method of using a highly dispersed pulse electroplating copper additive according to claim 9, characterized in that, In step S2, the ratio of deionized water, copper sulfate pentahydrate, 98% concentrated sulfuric acid, sodium chloride, and composite copper plating additive to replenish deionized water is 6000mL:750g:2300g:0.6g:20-30g:4000mL. The operating conditions for pulse copper plating are: temperature 25-30℃, pulse frequency 400-500Hz, and A / dm³. 2 Peak current density and 40-60% duty cycle.

Images