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CN-122013163-A - Uniform compact bright compound additive for electroless copper plating and preparation method thereof

CN122013163ACN 122013163 ACN122013163 ACN 122013163ACN-122013163-A

Abstract

The invention provides a uniform, compact and bright compound additive for electroless copper plating and a preparation method thereof, wherein the compound additive comprises, by weight, 2-3% of organic acid, 70-85% of ethanol, 0.1-0.3% of benzimidazole derivative, 1-3% of benzotriazole derivative salt, 2-4% of Na 2 SO 4 , 0.5-1% of sodium hypophosphite, 5-10% of potassium sodium tartrate, 2-3% of imidazoline quaternary ammonium salt, 2-3% of polyethylene glycol, 0.8-1.5% of silane modified cerium-chitosan graft and 0.5-1.2% of amino mesoporous silicon-supported copper-tin nanocrystalline. The invention can make the plating layer deposited uniformly and compact in structure, is suitable for the chemical copper plating process of precise electronic components such as semiconductor wafers and the like, and ensures the comprehensive performance of the copper plating layer so as to meet the requirement of precise electronic manufacturing.

Inventors

  • ZHOU LIANG
  • Jie Lehao

Assignees

  • 杭州金昇粉体新材料有限公司

Dates

Publication Date
20260512
Application Date
20260224

Claims (10)

  1. 1. A uniform, compact and bright compound additive for electroless copper plating is characterized by comprising, by weight, 2-3% of organic acid, 70-85% of ethanol, 0.1-0.3% of benzimidazole derivative, 1-3% of benzotriazole derivative salt, 2-4% of Na 2 SO 4 , 0.5-1% of sodium hypophosphite, 5-10% of potassium sodium tartrate, 2-3% of imidazoline quaternary ammonium salt, 2-3% of polyethylene glycol, 0.8-1.5% of silane modified cerium-chitosan graft and 0.5-1.2% of amino mesoporous silicon copper-tin nanocrystalline.
  2. 2. The uniform and compact brightening compound additive for electroless copper plating according to claim 1, wherein the organic acid is at least one of citric acid and tartaric acid, the benzimidazole derivative is at least one of 2-mercaptobenzimidazole and 5-chlorobenzoimidazole, and the benzotriazole derivative salt is at least one of benzotriazole sodium salt and carboxyl benzotriazole potassium salt.
  3. 3. The uniform, compact and bright compound additive for electroless copper plating according to claim 1, wherein the imidazoline quaternary ammonium salt is at least one of 1-hydroxyethyl-2-undecylenic imidazoline quaternary ammonium salt and 1-aminoethyl-2-heptadecenyl imidazoline quaternary ammonium salt, and the polyethylene glycol is at least one of polyethylene glycol 4000 and polyethylene glycol 6000.
  4. 4. The uniform, dense and bright compound additive for electroless copper plating according to claim 1, wherein the preparation raw materials of the silane modified cerium-chitosan graft comprise 15-20g of ammonium cerium nitrate, 8-12g of chitosan, 5-8g of acrylic acid, 0.3-0.5g of AIBN, 100-150mL of 1-2wt% acetic acid solution, 80-120mL of absolute ethyl alcohol, and 3-5mL of 5wt% gamma-glycidol ether oxypropyl trimethoxy silane ethanol solution.
  5. 5. The uniform, dense and bright compound additive for electroless copper plating according to claim 4, wherein the preparation method of the silane modified cerium-chitosan graft comprises the following steps: 1) Dissolving ceric ammonium nitrate in 100-150mL of deionized water, keeping stirring at the rotation speed of 200-300r/min at the temperature of 30-40 ℃, dropwise adding 20-25wt% of ammonia water to adjust the pH value to 8.5-9.5, continuously stirring at the same rotation speed for reacting for 1.5-2.5 hours, centrifuging and collecting precipitate, washing with deionized water for 3-5 times, vacuum drying for 4-6 hours at the temperature of 80-90 ℃ and the vacuum degree of less than or equal to 30Pa, and sieving with a 200-300 mesh sieve after crushing to obtain nano cerium oxide powder; 2) Adding nano cerium oxide powder into absolute ethyl alcohol, performing ultrasonic dispersion for 20-30min at the power of 200-250W and the frequency of 40kHz, slowly adding gamma-glycidoxypropyl trimethoxy silane ethanol solution, stirring at the rotating speed of 300-400r/min at the temperature of 50-60 ℃ for reacting for 2-3h, centrifuging and collecting the product, and performing vacuum drying for 3-5h at the temperature of 80-90 ℃ and the vacuum degree of less than or equal to 30Pa to obtain silane modified nano cerium oxide; 3) Dissolving chitosan in acetic acid solution, adding acrylic acid and AIBN, heating to 60-70 ℃ under the protection of nitrogen, adding silane modified nano cerium oxide, stirring at a rotating speed of 300-400r/min for reaction for 4-6 hours, slowly dripping the reaction solution into 200-300mL of absolute ethyl alcohol, centrifuging and collecting precipitate, and vacuum drying for 5-7 hours under the conditions of 70-80 ℃ and vacuum degree of less than or equal to 30Pa to obtain the silane modified cerium-chitosan graft.
  6. 6. The uniform, compact and bright compound additive for electroless copper plating according to claim 1, wherein the preparation raw materials of the amino mesoporous silicon-loaded copper-tin nanocrystalline comprise 10-15g of TEOS, 5-8g of CTAB, 2-3g of CuSO 4 5-8g、SnCl 2 , 3-5mL of KH-550, 2-3mL of 5wt% sodium citrate solution and 5-8mL of 10wt% sodium borohydride solution.
  7. 7. The uniform, compact and bright compound additive for electroless copper plating according to claim 6, wherein the preparation method of the amino mesoporous silicon-loaded copper-tin nanocrystalline comprises the following steps: (1) Adding TEOS and CTAB into 100-150mL of deionized water, keeping stirring at a rotating speed of 200-300r/min at 40-50 ℃, dropwise adding 25-30wt% of ammonia water to adjust the pH to 9.0-10.0, stirring and reacting for 2-3h, then adding KH-550, continuing stirring and reacting for 1.5-2.5h at the temperature and the rotating speed, centrifuging and collecting precipitate, washing 3-5 times with absolute ethyl alcohol, and roasting for 3-4h under the conditions of air atmosphere and 550-600 ℃ to obtain amino-functionalized mesoporous silica; (2) Dissolving CuSO 4 and SnCl 2 in 80-100mL of deionized water, adding sodium citrate solution to adjust the pH to 5.0-6.0, and stirring until the solution is completely dissolved to obtain a precursor solution; (3) Adding amino-functionalized mesoporous silica into a precursor solution, stirring and adsorbing for 1-2 hours at the temperature of 30-40 ℃ at the rotating speed of 200-300r/min, slowly dripping sodium borohydride solution, continuously stirring and reacting for 1.5-2.5 hours at the temperature and the rotating speed, centrifuging and collecting precipitate, washing 3-5 times with deionized water, and vacuum drying for 3-5 hours at the temperature of 70-80 ℃ and the vacuum degree of less than or equal to 30Pa to obtain the amino-mesoporous silicon-loaded copper-tin nanocrystalline.
  8. 8. A method for preparing a uniform, dense and bright compound additive for electroless copper plating according to any one of claims 1 to 7, comprising the steps of: S1, adding ethanol into a reaction kettle at room temperature, keeping stirring at a rotating speed of 200-300r/min, sequentially adding organic acid, potassium sodium tartrate, benzotriazole derivative salt, sodium hypophosphite and Na 2 SO 4 , and continuing stirring for 10-15min after the addition is completed to obtain a base solution; s2, adding benzimidazole derivatives and imidazoline quaternary ammonium salt into the base solution, and stirring for 20-30min at the rotating speed of 300-400r/min to form a corrosion inhibition-brightness composite system; S3, adding polyethylene glycol into the corrosion inhibition-brightness composite system, stirring for 10-15min at a rotating speed of 300-400r/min, then sequentially adding the silane modified cerium-chitosan graft and the amino mesoporous silicon-supported copper-tin nanocrystalline, starting ultrasonic dispersion, and simultaneously keeping stirring at a rotating speed of 200-300r/min for 30-40min; S4, stirring the system obtained in the step S3 for 15-20min at the temperature of 35-45 ℃ at the rotating speed of 200-300r/min, cooling to room temperature, and filtering by using a microporous filter membrane to obtain the uniform, compact and bright compound additive for electroless copper plating.
  9. 9. The method for preparing a uniform, dense and bright compound additive for electroless copper plating according to claim 8, wherein in step S3, the power of ultrasonic dispersion is 200-250W and the frequency is 40kHz.
  10. 10. The method for preparing a uniform, dense and bright compound additive for electroless copper plating according to claim 8, wherein in step S4, the pore size of the microporous filter membrane is 0.22-0.45 μm.

Description

Uniform compact bright compound additive for electroless copper plating and preparation method thereof Technical Field The invention relates to the technical field of copper coating additives, in particular to a uniform, compact and bright compound additive for electroless copper plating and a preparation method thereof. Background The electroless copper plating technology is widely applied to the fields of electronic manufacture, alloy powder preparation and the like because of the advantages of no need of an external power supply, good plating uniformity and the like, and is a key process for guaranteeing the product performance especially in the scenes of precise copper plating of semiconductor wafers and the like. The performance of the compound additive serving as a core composition of the electroless copper plating system directly determines key indexes such as uniformity, compactness, brightness and the like of a copper plating layer, and simultaneously influences the stability and application suitability of a plating solution. The existing compound additive for electroless copper plating mostly adopts the design thought of simple superposition of conventional components, and mainly improves the plating performance by introducing components such as a general corrosion inhibitor, a brightening agent, a dispersing agent and the like, but lacks deep collaborative design among the components. The existing products are difficult to meet the strict requirements of precise processes such as semiconductor wafer and bronze-coated iron alloy powder preparation on a copper plating layer, the technical problems of insufficient plating uniformity and poor compactness generally exist, the defects such as pores and thickness fluctuation of the plating are easily caused, the conductivity, corrosion resistance and bonding strength of subsequent products are further affected, and the comprehensive quality of precise electronic elements and alloy powder products cannot be guaranteed. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a uniform, compact and bright compound additive for electroless copper plating and a preparation method thereof. In order to achieve the above purpose, the invention is realized by the following technical scheme: The application discloses a uniform, compact and bright compound additive for electroless copper plating, which comprises, by weight, 2-3% of organic acid, 70-85% of ethanol, 0.1-0.3% of benzimidazole derivative, 1-3% of benzotriazole derivative salt, 2-4% of Na 2SO4, 0.5-1% of sodium hypophosphite, 5-10% of potassium sodium tartrate, 2-3% of imidazoline quaternary ammonium salt, 2-3% of polyethylene glycol, 0.8-1.5% of silane modified cerium-chitosan graft and 0.5-1.2% of amino mesoporous silicon copper-tin-carrying nanocrystalline. According to the technical scheme, the organic acid and the potassium sodium tartrate can form a complexing system to stabilize copper ions, sodium hypophosphite is used as a reducing agent to realize reduction deposition of the copper ions, benzimidazole derivative, benzotriazole derivative salt and imidazoline quaternary ammonium salt cooperatively play roles of corrosion inhibition, grain refinement and leveling, a bright coating is facilitated, polyethylene glycol ensures uniform dispersion of components by means of a steric hindrance effect, particle aggregation is avoided, the silane modified cerium-chitosan graft can promote corrosion resistance and component compatibility of the coating, the amino mesoporous silicon-loaded copper-tin nanocrystalline can serve as a secondary nucleation center to promote uniform nucleation of copper ions, and the two are cooperatively matched with components such as the organic acid, na 2SO4 and the like, so that the coating is uniformly deposited and compact in structure, is suitable for chemical copper plating processes of precise electronic components such as semiconductor wafers, ensures comprehensive performance of a copper plating layer and meets precise electronic manufacturing requirements. Preferably, the organic acid is at least one of citric acid and tartaric acid, the benzimidazole derivative is at least one of 2-mercaptobenzimidazole and 5-chlorobenzoimidazole, and the benzotriazole derivative salt is at least one of benzotriazole sodium salt and carboxyl benzotriazole potassium salt. By adopting the technical scheme, the organic acid is at least one of citric acid and tartaric acid, the organic acid can form a stable complex with copper ions so as to regulate the reduction rate of the copper ions, the benzimidazole derivative is at least one of 2-mercaptobenzimidazole and 5-chlorobenzoimidazole, and can be adsorbed on a high active site of a matrix to inhibit excessive corrosion, the benzotriazole derivative salt is at least one of benzotriazole sodium salt and carboxyl benzotriazole potassium salt, and can refine plating grains to reduce pores, and the synergis