High-weather-resistance wide-temperature-range bottom filling adhesive for semiconductor packaging and preparation method of high-weather-resistance wide-temperature-range bottom filling adhesive

Abstract

The invention discloses a high-weather-resistance wide-temperature-range bottom filling adhesive for semiconductor packaging and a preparation method thereof, and relates to the technical field of filling adhesives for semiconductor packaging, and the preparation method comprises the following steps: synthesizing glycidyl sulfonate by taking bio-based glycidyl and sulfonyl chloride as raw materials, and synthesizing halogen-free DGEBA resin by taking bisphenol and glycidyl sulfonate as raw materials; the preparation method comprises the following steps: synthesizing phosphorylated modified resin by taking halogen-free DGEBA resin and phosphoryl chloride as raw materials; the preparation method comprises the following steps: uniformly stirring and melting halogen-free DGEBA resin and phosphorylated modified resin, adding a cross-linking agent, and uniformly stirring to obtain a resin matrix; the preparation method comprises the following steps: sequentially adding the siloxane latent accelerator and the composite filler into the resin matrix, stirring in vacuum, defoaming, adding the initiator, uniformly stirring, injecting into a mold, heating, curing, and cooling to room temperature to obtain the filling adhesive for semiconductor packaging, the composite filler is prepared from KH550 modified FeNi alloy particles.

Description

A high weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive and its preparation method Technical Field

[0001] This invention relates to the field of semiconductor packaging filler technology, specifically a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive and its preparation method. Background Technology

[0002] As semiconductor technology advances towards higher density, higher integration, and extreme service environments, the performance requirements for underfill adhesives, as a core material ensuring the integrity and reliability of the packaging structure, are becoming increasingly stringent. During semiconductor packaging, underfill adhesives must possess excellent weather resistance, wide temperature range stability, process adaptability, and compatibility with the substrate to cope with multiple challenges such as high-temperature aging, temperature cycling, and circuit corrosion.

[0003] Current underfill adhesives for semiconductor packaging still face several technical bottlenecks: First, traditional epoxy resins are often synthesized using halogen-containing raw materials, which can easily leave residual halogen elements in the finished product. Under long-term service or in environments with changing temperature and humidity, these residual halogen elements can migrate and release, causing corrosion of semiconductor circuits and severely affecting device lifespan. Second, to improve flame retardancy, existing technologies often add additional flame retardants. However, this method often leads to poor compatibility between the flame retardant and the resin matrix, and it is difficult to form a highly efficient flame retardant system. It also suffers from insufficient high-temperature aging resistance, easily resulting in performance degradation and structural failure under high-temperature environments. Third, wide temperature... In application scenarios, the thermal expansion characteristics of existing fillers are poorly matched with those of semiconductor substrates (such as silicon wafers and substrates). In addition, the bonding between the filler and the resin interface is not tight, which easily generates significant internal stress, leading to defects such as cracking and warping in the packaging structure. Fourth, the latency control of existing curing accelerators is not good. Either the gelation time is too short to meet the process window requirements of narrow gap packaging, or the curing efficiency is insufficient, affecting production efficiency. Fifth, some fillers tend to sacrifice insulation performance in pursuit of interfacial bonding or thermal conductivity, which increases the risk of signal interference and cannot meet the insulation requirements of high-density packaging.

[0004] In summary, existing underfill adhesives cannot simultaneously meet the comprehensive requirements of semiconductor packaging for high weather resistance, wide temperature range stability, non-corrosive and environmentally friendly properties, excellent process compatibility, and high insulation. Developing an underfill adhesive with balanced performance and compatibility with advanced packaging technologies has significant practical significance and application value. Summary of the Invention

[0005] The purpose of this invention is to provide a high weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: synthesizing glycidyl sulfonate using bio-based glycidyl and sulfonyl chloride as raw materials; adding bisphenol A and glycidyl sulfonate to a dioxane solvent; adding 40wt% sodium hydroxide solution; heating to 80-85℃ and stirring for 1-2 hours; quenching with hydrochloric acid; extraction with ethyl acetate; and purification by vacuum distillation to obtain halogen-free DGEBA resin; furthermore, in the preparation process of the halogen-free DGEBA resin, the molar ratio of bisphenol A to glycidyl sulfonate is 1:(2-2). 5); The amount of sodium hydroxide solution added is 1.5-2 times the molar amount of bisphenol A; Further, the preparation method of the glycidyl sulfonate includes the following steps: adding bio-based glycidyl and sulfonyl chloride to anhydrous dichloromethane, adding triethylamine under nitrogen atmosphere and ice bath conditions, stirring for 2-3 hours, washing successively with 1 mol / L hydrochloric acid and saturated sodium bicarbonate solution, purifying the organic phase by vacuum distillation after drying with anhydrous magnesium sulfate to obtain glycidyl sulfonate; Further, in the preparation process of the glycidyl sulfonate, the molar ratio of bio-based glycidyl:sulfonyl chloride is 1:(1.0-1.1); the amount of triethylamine added is... 1.5-2 times the molar amount of bio-based glycidyl; S2: Mix 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane evenly, add tetramethylammonium hydroxide, and polymerize to obtain vinyl-terminated polymethylphenylsiloxane; Add vinyl-terminated polymethylphenylsiloxane and trimethoxysilane propanethiol to toluene solvent, react under nitrogen atmosphere at 64-66℃ for 9-10 h, and vacuum distill to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; Add trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxy... Naphthalene and sodium methoxide are added to anhydrous ethanol and reacted at room temperature for 4-6 hours to obtain a sodium intermediate. The sodium intermediate and tetraphenylphosphine bromide are added to anhydrous ethanol and reacted at room temperature for 2-4 hours. The precipitate is collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain a siloxane latent promoter. Further, in the preparation of the vinyl-terminated polymethylphenylsiloxane, the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is (5-15):1; the amount of tetramethylammonium hydroxide added is 0% of the total mass of the mixed monomers.5-1 wt%; Further, the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is adjusted by the number of repeating units n of polymethylphenylsiloxane, where n=6 and the mass ratio is 5:1; n=24 and the mass ratio is 10:1; n=35 and the mass ratio is 15:1; Further, in the preparation of the trimethoxysilyl-terminated polymethylphenylsiloxane, the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilane propanethiol is 1:(2-2.2); Further, in the preparation of the sodium-type intermediate, the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane to 2,3-divinyl-1,1,3,3-tetramethyldisiloxane is 1:(2-2.2); The molar ratio of hydroxynaphthalene to sodium methoxide is 1:(2-2.5):(2-2.5); further, in the preparation process of the siloxane latent promoter, the molar ratio of sodium intermediate to tetraphenylphosphine bromide is 1:(1-1.2); further, the number of repeating polymethylphenylsiloxane units n in the siloxane latent promoter is 6-35; S3: The FeNi alloy particles are ultrasonically cleaned with anhydrous ethanol, dried and dispersed in an ethanol aqueous solution, KH550 is added, activated at 50-55℃ for 30-35 min, the pH of the system is adjusted to 9-10, tetraethyl orthosilicate solution is added, stirred at 50-55℃ for 4-4.5 h, the product is collected by centrifugation, washed with anhydrous ethanol, and vacuum dried to obtain the composite filler; Further, the volume ratio of the ethanol to the aqueous solution is 20:1; further, the concentration of KH550 added is 0.01 mol / L; further, the concentration of the tetraethyl orthosilicate solution is 0.01-0.05 mol / L; S4: Halogen-free DGEBA resin and phosphoryl chloride are added to toluene solvent, reacted under nitrogen atmosphere at 60-65℃ for 8-9 h, acetonitrile is added to precipitate, the product is collected by filtration and vacuum drying to obtain phosphorylated modified resin; further, in the preparation process of the phosphorylated modified resin, the mass ratio of halogen-free DGEBA resin to phosphoryl chloride is 1:(0.05-0.1); S5: Halogen-free DGEBA resin and phosphorylated modified resin are mixed and stirred to melt at 120-125℃. The mixture is cooled to 80-85℃, and a crosslinking agent is added and stirred until homogeneous to obtain a resin matrix. Further, in the preparation of the resin matrix, the mass ratio of halogen-free DGEBA resin to phosphorylated modified resin is 1:(0.1-0.3); the amount of crosslinking agent added is 1-3wt% of the total resin mass. Further, the crosslinking agent is a compound of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of (1-2):1. S6: The siloxane latent accelerator and composite filler are added sequentially to the resin matrix, vacuum stirred, degassed, and an initiator is added. After stirring until homogeneous, the mixture is poured into a mold and cured at 140-142℃ for 1-1.5 hours, then heated to 150-152℃ for 4-4 hours of curing.After 5 hours, the mixture is cooled to room temperature to obtain a semiconductor encapsulating filler. Further, in the preparation of the semiconductor encapsulating filler, the mass ratio of resin matrix: siloxane latent promoter: composite filler: initiator is 1:(0.5-2):(10-30):(0.1-0.5). Further, the initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of (5-8):1. Further, the preparation method of the FeNi alloy particles includes the following steps: mixing ferrous sulfate and nickel sulfate according to Fe... 2+ :Ni 2+ An aqueous solution was prepared at a molar ratio of 64:36. Sodium hydroxide solution was added to adjust the pH to 10-11. The reduction reaction was carried out at 80-85℃ and 0.1 MPa for 4-4.5 hours under a hydrogen atmosphere. The product was then filtered, washed, dried, and ball-milled to obtain FeNi alloy particles. Further, the FeNi alloy particles were of specification D... 50 =18-20μm.

[0007] Compared with the prior art, the beneficial effects of the present invention are: 1. The present invention synthesizes glycidyl sulfonate by γ-SN2 nucleophilic substitution of bio-based glycidyl chloride with sulfonyl chloride. When reacting with bisphenol A, it inhibits the generation of epoxy ring-opening byproducts and chlorine-containing oligomers. Combined with purification process, it obtains high-purity halogen-free DGEBA resin, avoids circuit corrosion and reduces environmental impact.

[0008] 2. The phosphosilicate structure of the siloxane latent accelerator remains stable at room temperature. During high-temperature curing, it dissociates and releases catalytic sites to accelerate the cross-linking reaction. Its polymethylphenylsiloxane flexible segments work synergistically with the low expansion characteristics of the composite filler to both delay gelation to broaden the process window and disperse internal stress to avoid brittle cracking of the material.

[0009] 3. FeNi alloy particles achieve near-zero thermal expansion through the Invar effect. After modification with KH550 and SiO2 coating, they form a strong interfacial bond with the resin matrix. Simultaneously, the SiO2 coating blocks electron transport to ensure insulation, synergistically reducing thermal stress and thermal expansion mismatch issues across a wide temperature range with the halogen-free resin. A crosslinking agent complex constructs a rigid-flexible balanced crosslinking network, synergistically lowering the curing activation energy with the initiator system, enabling rapid and complete curing of the material and ensuring the filler neither cracks nor softens across a wide temperature range.

[0010] 4. This invention achieves a multi-dimensional synergistic effect among its components, enabling the filler to possess non-corrosive and environmentally friendly properties, high flame retardancy, low thermal expansion, high insulation, and excellent process compatibility. This meets the core requirements of semiconductor packaging for high weather resistance, wide temperature range stability, and narrow gap filling, effectively extending the service life of devices. Detailed Implementation

[0011] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0012] In the following examples, the preparation method of glycidyl sulfonate includes the following steps: adding bio-based glycidyl and sulfonyl chloride to anhydrous dichloromethane, adding triethylamine under a nitrogen atmosphere and ice bath conditions, stirring for 2 hours, washing successively with 1 mol / L hydrochloric acid and saturated sodium bicarbonate solution, purifying the organic phase by vacuum distillation after drying with anhydrous magnesium sulfate, and obtaining glycidyl sulfonate; the molar ratio of bio-based glycidyl to sulfonyl chloride is 1:1; the amount of triethylamine added is twice the molar amount of bio-based glycidyl.

[0013] The preparation method of FeNi alloy particles includes the following steps: ferrous sulfate and nickel sulfate are mixed according to Fe... 2+ :Ni 2+ An aqueous solution was prepared with a molar ratio of 64:36. Sodium hydroxide solution was added to adjust the pH to 10. The reduction reaction was carried out at 80°C and 0.1 MPa for 4 hours under a hydrogen atmosphere. The mixture was then filtered, washed, dried, and ball-milled to obtain FeNi alloy particles.

[0014] The preparation method of the composite filler includes the following steps: FeNi alloy particles are ultrasonically cleaned with anhydrous ethanol, dried and dispersed in an ethanol-water solution, KH550 is added, activated at 50℃ for 30 min, the pH of the system is adjusted to 9, tetraethyl orthosilicate solution is added, stirred at 50℃ for 4 h, the product is collected by centrifugation, washed with anhydrous ethanol, and vacuum dried to obtain the composite filler; the volume ratio of ethanol to water solution is 20:1; the concentration of KH550 added is 0.01 mol / L; the concentration of tetraethyl orthosilicate solution is 0.03 mol / L.

[0015] Example 1: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: Glycidyl sulfonate is synthesized from bio-based glycidyl and sulfonyl chloride. Bisphenol A and glycidyl sulfonate are added to a dioxane solvent, and 40 wt% sodium hydroxide solution is added. The mixture is heated to 80°C and stirred for 1 h. After quenching with hydrochloric acid, extraction with ethyl acetate, and purification by vacuum distillation, halogen-free DGEBA resin is obtained. The molar ratio of bisphenol A to glycidyl sulfonate is 1:2. The amount of sodium hydroxide solution added is twice the molar amount of bisphenol A. S2: 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed evenly, and then added to... Tetramethylammonium hydroxide was polymerized to yield vinyl-terminated polymethylphenylsiloxane; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was 10:1; the amount of tetramethylammonium hydroxide added was 0.5 wt% of the total mass of the mixed monomers; vinyl-terminated polymethylphenylsiloxane and trimethoxysilane propanethiol were added to toluene solvent, reacted at 64°C for 9 h under a nitrogen atmosphere, and vacuum distilled to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilane propanethiol was 1:2; trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene and sodium methoxide were added to a solvent without... In aqueous ethanol, the reaction was carried out at room temperature for 4-6 h to obtain a sodium intermediate; the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane: 2,3-dihydroxynaphthalene: sodium methoxide was 1:2:2. The sodium intermediate and tetraphenylphosphine bromide were added to anhydrous ethanol and reacted at room temperature for 2-4 h. The precipitate was collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain a siloxane latent promoter; the molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1; S3: Halogen-free DGEBA resin and phosphoryl chloride were added to toluene solvent and reacted at 60 °C for 8-9 h under a nitrogen atmosphere. Acetonitrile was added to precipitate, the product was collected by filtration, and dried under vacuum to obtain a phosphorylated modified resin; the mass ratio of halogen-free DGEBA resin to phosphoryl chloride was 1:0.05; S4: Halogen-free DG EBA resin and phosphorylated modified resin are mixed and stirred at 120°C until uniformly melted. After cooling to 80°C, a crosslinking agent is added and stirred until uniform to obtain the resin matrix. The mass ratio of halogen-free DGEBA resin to phosphorylated modified resin is 1:0.2. The amount of crosslinking agent added is 1 wt% of the total resin mass. The crosslinking agent is a compound of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1. S5: Siloxane latent accelerator and composite filler are added to the resin matrix in sequence, vacuum stirred, degassed, initiator added, stirred until uniform, injected into a mold, heated and cured, and cooled to room temperature to obtain a semiconductor encapsulating filler. The mass ratio of resin matrix:siloxane latent accelerator:composite filler:initiator is 1:1.2:20:0.3; The initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of 6:1.

[0016] Example 2: A method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S4: Mixing halogen-free DGEBA resin with phosphoric acid modified resin, stirring and melting uniformly at 120°C, cooling to 80°C, adding a crosslinking agent, stirring uniformly to obtain a resin matrix; the mass ratio of halogen-free DGEBA resin to phosphoric acid modified resin is 1:0.2; the amount of crosslinking agent added is 1wt% of the total resin mass; the crosslinking agent is a compound of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1; the remaining steps are the same as in Example 1.

[0017] Example 3: A method for preparing a high weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S5: adding siloxane latent accelerator and composite filler sequentially to a resin matrix, vacuum stirring, degassing, adding an initiator, stirring evenly, injecting into a mold, heating to cure, and cooling to room temperature to obtain a semiconductor packaging underfill adhesive; the mass ratio of resin matrix: siloxane latent accelerator: composite filler: initiator is 1:1.2:25:0.3; the remaining steps are the same as in Example 1.

[0018] Example 4: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S2: 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed evenly, tetramethylammonium hydroxide is added, and a polymerization reaction is carried out to obtain vinyl-terminated polymethylphenylsiloxane; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is 5:1; the amount of tetramethylammonium hydroxide added is 0.5 wt% of the total mass of the mixed monomers; vinyl-terminated polymethylphenylsiloxane and trimethoxysilanepropanethiol are added to toluene solvent under a nitrogen atmosphere. The reaction was carried out at 64℃ for 9 hours, followed by vacuum distillation to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilanethiol was 1:2; trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide were added to anhydrous ethanol and reacted at room temperature for 4-6 hours to obtain a sodium intermediate; the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane to 2,3-dihydroxynaphthalene to sodium methoxide was 1:2:2; the sodium intermediate and tetraphenylphosphine bromide were added to anhydrous ethanol and reacted at room temperature for 2-4 hours, the precipitate was collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain a siloxane latent promoter; the molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1; the remaining steps were the same as in Example 1.

[0019] Example 5: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S2: 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed evenly, tetramethylammonium hydroxide is added, and a polymerization reaction is carried out to obtain vinyl-terminated polymethylphenylsiloxane; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is 15:1; the amount of tetramethylammonium hydroxide added is 0.5 wt% of the total mass of the mixed monomers; vinyl-terminated polymethylphenylsiloxane and trimethoxysilanepropanethiol are added to toluene solvent under a nitrogen atmosphere. The reaction was carried out at 64℃ for 9 hours, followed by vacuum distillation to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilanethiol was 1:2; trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide were added to anhydrous ethanol and reacted at room temperature for 4-6 hours to obtain a sodium intermediate; the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane to 2,3-dihydroxynaphthalene to sodium methoxide was 1:2:2; the sodium intermediate and tetraphenylphosphine bromide were added to anhydrous ethanol and reacted at room temperature for 2-4 hours, the precipitate was collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain a siloxane latent promoter; the molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1; the remaining steps were the same as in Example 1.

[0020] Comparative Example 1: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: synthesizing glycidyl sulfonate from bio-based glycidyl and sulfonyl chloride; adding bisphenol A and glycidyl sulfonate to dioxane solvent; adding 40wt% sodium hydroxide solution; heating to 80℃ and stirring for 1h; quenching with hydrochloric acid; extraction with ethyl acetate; and purification by vacuum distillation to obtain halogen-free DGEBA resin; the molar ratio of bisphenol A to glycidyl sulfonate is 1:2; the amount of sodium hydroxide solution added is twice the molar amount of bisphenol A; S2: reacting 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane with 1,3-diethylene Divinyl-1,1,3,3-tetramethyldisiloxane was mixed evenly, and tetramethylammonium hydroxide was added. Polymerization was then carried out to obtain vinyl-terminated polymethylphenylsiloxane. The mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was 10:1. The amount of tetramethylammonium hydroxide added was 0.5 wt% of the total mass of the mixed monomers. Vinyl-terminated polymethylphenylsiloxane and trimethoxysilane propanethiol were added to toluene solvent, reacted at 64°C for 9 h under a nitrogen atmosphere, and vacuum distilled to obtain trimethoxysilyl-terminated polymethylphenylsiloxane. The ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilane propanethiol was 0.5 wt%. The molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide was 1:2. Trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide were added to anhydrous ethanol and reacted at room temperature for 4-6 hours to obtain a sodium intermediate. The molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane:2,3-dihydroxynaphthalene:sodium methoxide was 1:2:2. The sodium intermediate and tetraphenylphosphine bromide were added to anhydrous ethanol and reacted at room temperature for 2-4 hours. The precipitate was collected by filtration, washed with anhydrous ethanol, and vacuum dried to obtain a siloxane latent promoter. The molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1. S3: Halogen-free DGEBA resin was heated to 120°C and stirred until uniformly melted, then cooled to... At 80℃, add the crosslinking agent and stir evenly to obtain the resin matrix; the amount of crosslinking agent added is 1wt% of the total mass of the halogen-free DGEBA resin; the crosslinking agent is a mixture of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1; S4: Add the siloxane latent accelerator and composite filler to the resin matrix in sequence, stir under vacuum, degas, add the initiator, stir evenly, pour into the mold, heat to cure, and cool to room temperature to obtain the semiconductor encapsulating filler; the mass ratio of resin matrix: siloxane latent accelerator: composite filler: initiator is 1:1.2:20:0.3; the initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of 6:1.

[0021] Comparative Example 2: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: Glycidyl sulfonate is synthesized from bio-based glycidyl and sulfonyl chloride. Bisphenol A and glycidyl sulfonate are added to a dioxane solvent, and 40 wt% sodium hydroxide solution is added. The mixture is heated to 80°C and stirred for 1 h. After quenching with hydrochloric acid, extraction with ethyl acetate, and purification by vacuum distillation, halogen-free DGEBA resin is obtained. The molar ratio of bisphenol A to glycidyl sulfonate is 1:2. The amount of sodium hydroxide solution added is twice the molar amount of bisphenol A. S2: Halogen-free DGEBA resin and phosphoryl chloride are added to toluene solvent. The mixture is reacted at 60°C for 8-9 h under a nitrogen atmosphere. Acetonitrile is added to precipitate the product. The product is collected by filtration and vacuum drying to obtain a phosphorylated modified resin. The mass ratio of halogen-free DGEBA resin to phosphoryl chloride is... S3: Mix halogen-free DGEBA resin and phosphoric acid modified resin, stir and melt evenly at 120℃, cool to 80℃, add crosslinking agent, stir evenly to obtain resin matrix; the mass ratio of halogen-free DGEBA resin to phosphoric acid modified resin is 1:0.2; the amount of crosslinking agent added is 1wt% of the total resin mass; the crosslinking agent is a compound of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1; S4: Add composite filler to resin matrix in sequence, vacuum stir, degas, add initiator, stir evenly, pour into mold, heat to cure, cool to room temperature to obtain semiconductor encapsulation filler; the mass ratio of resin matrix: composite filler: initiator is 1:20:0.3; the initiator is a compound of ammonium persulfate and ferrous sulfate in a molar ratio of 6:1.

[0022] Comparative Example 3: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: synthesizing glycidyl sulfonate using bio-based glycidyl and sulfonyl chloride as raw materials; adding bisphenol A and glycidyl sulfonate to dioxane solvent, adding 40wt% sodium hydroxide solution, heating to 80℃ and stirring for 1h; quenching with hydrochloric acid, extraction with ethyl acetate, and purification by vacuum distillation to obtain halogen-free DGEBA resin; the molar ratio of bisphenol A to glycidyl sulfonate is 1:2; the amount of sodium hydroxide solution added is twice the molar amount of bisphenol A; S2: mixing 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane evenly, adding... Tetramethylammonium hydroxide was polymerized to yield vinyl-terminated polymethylphenylsiloxane; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was 10:1; the amount of tetramethylammonium hydroxide added was 0.5 wt% of the total mass of the mixed monomers; vinyl-terminated polymethylphenylsiloxane and trimethoxysilane propanethiol were added to toluene solvent, reacted at 64°C for 9 h under a nitrogen atmosphere, and vacuum distilled to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilane propanethiol was 1:2; trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene and sodium methoxide were added to a solvent without... In aqueous ethanol, the reaction was carried out at room temperature for 4-6 h to obtain a sodium intermediate; the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane: 2,3-dihydroxynaphthalene: sodium methoxide was 1:2:2. The sodium intermediate and tetraphenylphosphine bromide were added to anhydrous ethanol and reacted at room temperature for 2-4 h. The precipitate was collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain a siloxane latent promoter; the molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1; S3: Halogen-free DGEBA resin and phosphoryl chloride were added to toluene solvent and reacted at 60 °C for 8-9 h under a nitrogen atmosphere. Acetonitrile was added to precipitate, the product was collected by filtration, and dried under vacuum to obtain a phosphorylated modified resin; the mass ratio of halogen-free DGEBA resin to phosphoryl chloride was 1:0.05; S4: Halogen-free DGEBA resin and phosphoryl chloride were reacted to halogen-free DGEBA resin and phosphoryl chloride in anhydrous ethanol. BA resin and phosphorylated modified resin are mixed and stirred at 120°C until homogeneous. After cooling to 80°C, a crosslinking agent is added and stirred until homogeneous to obtain a resin matrix. The mass ratio of halogen-free DGEBA resin to phosphorylated modified resin is 1:0.2. The amount of crosslinking agent added is 1 wt% of the total resin mass. The crosslinking agent is a compound of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1. S5: Siloxane latent accelerator and FeNi alloy particles are added to the resin matrix in sequence, vacuum stirred, degassed, and initiator is added. After stirring until homogeneous, the mixture is poured into a mold, heated to cure, and cooled to room temperature to obtain a semiconductor encapsulating filler. The mass ratio of resin matrix:siloxane latent accelerator:FeNi alloy particles:initiator is 1:1.The ratio of ammonium persulfate to ferrous sulfate is 2:20:0.3; the initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of 6:1.

[0023] Comparative Example 4: A method for preparing a high-weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, comprising the following steps: S1: 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed evenly, tetramethylammonium hydroxide is added, and a polymerization reaction is carried out to obtain vinyl-terminated polymethylphenylsiloxane; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is 10:1; the amount of tetramethylammonium hydroxide added is 0.5 wt% of the total mass of the mixed monomers; the vinyl-terminated polymethylphenylsiloxane... A trimethoxysilane-terminated polymethylphenylsiloxane was obtained by reacting a vinyl-terminated polymethylphenylsiloxane with trimethoxysilane in toluene under a nitrogen atmosphere at 64°C for 9 hours, followed by vacuum distillation. The molar ratio of the vinyl-terminated polymethylphenylsiloxane to trimethoxysilane was 1:2. The trimethoxysilane-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide were then added to anhydrous ethanol and reacted at room temperature for 4-6 hours to obtain a sodium intermediate. The molar ratio of the trimethoxysilane-terminated polymethylphenylsiloxane to 2,3-dihydroxynaphthalene to sodium methoxide was 1:2:2. The sodium intermediate was then added to anhydrous ethanol and subjected to a metathesis reaction at room temperature for 2-4 hours. The precipitate was collected by filtration and washed with anhydrous ethanol. S1: The siloxane latent promoter was obtained by vacuum drying; the molar ratio of sodium intermediate to tetraphenylphosphine bromide was 1:1; S2: Traditional halogenated DGEBA resin and phosphoryl chloride were added to toluene solvent, reacted at 60℃ for 8-9 hours under nitrogen atmosphere, acetonitrile was added to precipitate, the product was collected by filtration and vacuum drying to obtain phosphorylated modified resin; the mass ratio of traditional halogenated DGEBA resin to phosphoryl chloride was 1:0.05; S3: Traditional halogenated DGEBA resin and phosphorylated modified resin were mixed, stirred and melted uniformly at 120℃, cooled to 80℃, crosslinking agent was added, and stirred uniformly to obtain resin matrix; the mass ratio of traditional halogenated DGEBA resin to phosphorylated modified resin was 1:0.2; The crosslinking agent is added at 1 wt% of the total resin mass; the crosslinking agent is a mixture of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of 1:1; S4: the siloxane latent accelerator and composite filler are added to the resin matrix in sequence, vacuum stirred, degassed, initiator added, stirred evenly, poured into a mold, heated and cured, and cooled to room temperature to obtain a semiconductor encapsulating filler; the mass ratio of resin matrix: siloxane latent accelerator: composite filler: initiator is 1:1.2:20:0.3; the initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of 6:1; the traditional halogenated DGEBA resin is synthesized from epichlorohydrin, with chlorine residue >500 ppm.

[0024] Performance Testing: High weather resistance testing includes: High temperature aging performance: aging in a 150℃ oven for 1000h, testing the retention rate of tensile strength after aging; Corrosion resistance performance: accelerated corrosion test of copper foil at 80℃ and 60% humidity for 1500h, observing the surface corrosion morphology and testing the corrosion rate; Wide temperature range performance testing includes: Wide temperature range thermal expansion performance: -55℃ to 150℃, heating rate 5℃ / min, testing CTE; Wide temperature range mechanical properties: 25℃ to 125℃, frequency 1Hz, testing the storage modulus; -55℃ tensile test; Insulation performance testing: at 25℃, volume resistivity is tested using a high-resistivity meter.

[0025] The performance test results are shown in Table 1 below.

[0026] Table 1. Performance Test Data of Filler Adhesive for Semiconductor Packaging Table 1. Tensile Strength Retention Rate at 150℃ / % Copper Foil Corrosion Rate / mm / a α1-CTE / ppm / ℃ α2-CTE / ppm / ℃ Tensile Elongation at Break at -55℃ / % Storage Modulus at 25℃ / GPa Storage Modulus at 125℃ / GPa Volume Resistivity / Ω·cm Example 1 92.5 0.00 83 0.4 105.5 5.8 6.8 2.2 2.1 × 10 13 Example 294.30.00731.1106.76.17.02.31.8×10 13 Example 393.10.00930.6107.15.96.92.42.3×10 13 Example 491.80.00830.5106.55.56.62.11.9×10 13 Example 592.90.00730.4106.45.76.72.22.0×10 13 Comparative Example 178.60.001075.4263.73.24.21.52.5×10 13 Comparative Example 289.20.00936.1125.44.95.82.01.7×10 13 Comparative Example 387.50.01250.3165.64.55.41.88.6×10 10 Conclusion: The semiconductor packaging filler prepared by the multi-component synergistic design of this invention achieves low thermal expansion, high insulation and wide temperature range stability on the basis of halogen-free and environmentally friendly, meeting the stringent requirements of semiconductor packaging for high weather resistance and narrow gap filling, and has significant industrial application value.

[0027] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing a high weather-resistant, wide-temperature-range semiconductor packaging underfill adhesive, characterized in that: Includes the following steps: S1: Glycidyl sulfonate was synthesized from bio-based glycidyl and sulfonyl chloride. Bisphenol A and glycidyl sulfonate were added to dioxane solvent, sodium hydroxide solution was added, and the mixture was heated to 80-85℃ and stirred for 1-2 hours. After purification, halogen-free DGEBA resin was obtained. S2: Halogen-free DGEBA resin and phosphoryl chloride were added to toluene solvent and reacted at 60-65℃ for 8-9 hours under nitrogen atmosphere. Acetonitrile was added to precipitate the product, which was then filtered and collected. The product was dried under vacuum to obtain phosphorylated modified resin. S3: Halogen-free DGEBA resin and phosphorylated modified resin were mixed, stirred and melted evenly, cooled, and crosslinking agent was added. The mixture was stirred evenly to obtain resin matrix. S4: Siloxane latent accelerator and composite filler were added to the resin matrix in sequence. The mixture was stirred under vacuum to remove bubbles, and an initiator was added. After stirring evenly, the mixture was injected into a mold, heated and cured, and cooled to room temperature to obtain semiconductor encapsulation filler. The composite filler was prepared from KH550 modified FeNi alloy particles.

2. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 1, characterized in that: In the preparation of halogen-free DGEBA resin, the molar ratio of bisphenol A to glycidyl sulfonate is 1:(2-2.5); the amount of sodium hydroxide solution added is 1.5-2 times the molar amount of bisphenol A; in the preparation of phosphorylated modified resin, the mass ratio of halogen-free DGEBA resin to phosphoryl chloride is 1:(0.05-0.1); in the preparation of resin matrix, the mass ratio of halogen-free DGEBA resin to phosphorylated modified resin is 1:(0.1-0.3); the amount of crosslinking agent added... The crosslinking agent is 1-3 wt% of the total resin mass; the crosslinking agent is a mixture of 4,4'-methylenebis(2-ethyl)aniline and isophorone diamine in a mass ratio of (1-2):1; in the preparation process of the semiconductor encapsulation filler, the mass ratio of resin matrix: siloxane latent promoter: composite filler: initiator is 1:(0.5-2):(10-30):(0.1-0.5); the initiator is a mixture of ammonium persulfate and ferrous sulfate in a molar ratio of (5-8):

1.

3. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 1, characterized in that: The preparation method of the glycidyl sulfonate includes the following steps: adding bio-based glycidyl sulfonate and sulfonyl chloride into anhydrous dichloromethane, adding triethylamine under a nitrogen atmosphere and ice bath conditions, stirring and reacting for 2-3 hours, washing successively with 1 mol / L hydrochloric acid and saturated sodium bicarbonate solution, and purifying the organic phase by vacuum distillation after drying with anhydrous magnesium sulfate to obtain glycidyl sulfonate.

4. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 3, characterized in that: In the preparation of glycidyl sulfonate, the molar ratio of bio-based glycidyl sulfonyl chloride is 1:(1.0-1.1); the amount of triethylamine added is 1.5-2 times the molar amount of bio-based glycidyl sulfonyl chloride.

5. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 1, characterized in that: The preparation method of the siloxane latency promoter includes the following steps: 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed evenly, tetramethylammonium hydroxide is added, and a polymerization reaction is carried out to obtain vinyl-terminated polymethylphenylsiloxane; vinyl-terminated polymethylphenylsiloxane and trimethoxysilanethiol are added to toluene solvent, and the reaction is carried out at 64-66℃ for 9-10 h under a nitrogen atmosphere, followed by vacuum distillation to obtain trimethoxysilyl-terminated polymethylphenylsiloxane; trimethoxysilyl-terminated polymethylphenylsiloxane, 2,3-dihydroxynaphthalene, and sodium methoxide are added to anhydrous ethanol, and the reaction is carried out at room temperature for 4-6 h to obtain a sodium intermediate; the sodium intermediate and tetraphenylphosphine bromide are added to anhydrous ethanol, and the reaction is carried out at room temperature for 2-4 h, the precipitate is collected by filtration, washed with anhydrous ethanol, and dried under vacuum to obtain the siloxane latency promoter.

6. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 5, characterized in that: In the preparation of vinyl-terminated polymethylphenylsiloxane, the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is (5-15):1; the amount of tetramethylammonium hydroxide added is 0.5-1 wt% of the total mass of the mixed monomers; the mass ratio of 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is adjusted by the number of repeating units n of polymethylphenylsiloxane, where the mass ratio is 5:1 when n=6 and 1:1 when n=24. The mass ratio is 15:1 when n=35; in the preparation of trimethoxysilyl-terminated polymethylphenylsiloxane, the molar ratio of vinyl-terminated polymethylphenylsiloxane to trimethoxysilanethiol is 1:(2-2.2); in the preparation of sodium-type intermediate, the molar ratio of trimethoxysilyl-terminated polymethylphenylsiloxane to 2,3-dihydroxynaphthalene to sodium methoxide is 1:(2-2.5):(2-2.5); in the preparation of siloxane latent promoter, the molar ratio of sodium-type intermediate to tetraphenylphosphine bromide is 1:(1-1.2); the number of repeating polymethylphenylsiloxane units in the siloxane latent promoter is n=6-35.

7. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 1, characterized in that: The preparation method of the composite filler includes the following steps: FeNi alloy particles are ultrasonically cleaned with anhydrous ethanol, dried and dispersed in an ethanol aqueous solution, KH550 is added, activated at 50-55℃ for 30-35 min, the pH of the system is adjusted to 9-10, tetraethyl orthosilicate solution is added, stirred at 50-55℃ for 4-4.5 h, the product is collected by centrifugation, washed with anhydrous ethanol, and vacuum dried to obtain the composite filler.

8. The method for preparing a high weather-resistant wide-temperature-range semiconductor packaging underfill adhesive according to claim 7, characterized in that: The preparation method of the FeNi alloy particles includes the following steps: mixing ferrous sulfate and nickel sulfate according to Fe... 2+ :Ni 2 + An aqueous solution was prepared with a molar ratio of 64:

36. Sodium hydroxide solution was added to adjust the pH to 10-11. The reduction reaction was carried out at 80-85℃ and 0.1MPa for 4-4.5 hours under a hydrogen atmosphere. The product was then filtered, washed, dried, and ball-milled to obtain FeNi alloy particles.

9. The semiconductor packaging filler prepared by the method for preparing a high weather-resistant wide-temperature-range semiconductor packaging filler according to any one of claims 1-8.