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CN-122011631-A - Fluororubber compound, preparation method thereof and semiconductor sealing assembly

CN122011631ACN 122011631 ACN122011631 ACN 122011631ACN-122011631-A

Abstract

The invention relates to the technical field of rubber sealing materials, in particular to fluororubber compound, a preparation method thereof and a semiconductor sealing assembly. The preparation method comprises the steps of providing SiC@SiO 2 composite filler and modified boron carbide, mixing the SiC@SiO 2 and the modified boron carbide according to a first preset proportion to form plasma-resistant composite filler, providing fluororubber raw rubber, a vulcanizing agent, a fluorine-based low-temperature-resistant plasticizer and an additive, mixing the fluororubber raw rubber and the additive after plasticating, carrying out first-stage mixing, continuing to add the plasma-resistant composite filler after the first-stage mixing is finished, carrying out second-stage mixing, continuing to add the fluorine-based low-temperature-resistant plasticizer after the second-stage mixing is finished, carrying out third-stage mixing, carrying out rolling treatment after the third-stage mixing is finished to obtain master batch, and mixing the vulcanizing agent and the master batch to obtain the fluororubber compound. Solves the problems of insufficient bonding strength of interfaces, and easy interfacial peeling under the impact of plasma bombardment and temperature cycle in the prior art.

Inventors

  • HU XIAORAN
  • HU YUPING
  • LI SHIHAO
  • LUO YONGQUAN

Assignees

  • 电子科技大学

Dates

Publication Date
20260512
Application Date
20260324

Claims (10)

  1. 1. A method of preparing a fluororubber compound, said method comprising; Providing SiC@SiO 2 composite filler and modified boron carbide, and mixing the SiC@SiO 2 and the modified boron carbide to form a plasma-resistant composite filler; providing fluororubber raw rubber, a vulcanizing agent, a fluorine-based low-temperature-resistant plasticizer and an additive, plasticating the fluororubber raw rubber, mixing the fluororubber raw rubber with the additive, and carrying out first-stage mixing; after the first-stage mixing is finished, continuously adding a plasma-resistant composite filler to carry out the second-stage mixing; after finishing the second-stage mixing, continuously adding a fluorine-based low-temperature-resistant plasticizer for the third-stage mixing; And (3) rolling the mixture after the third-stage mixing to obtain a master batch, mixing the vulcanizing agent and the master batch, and mixing to obtain a fluororubber compound, wherein the SiC@SiO 2 composite filler and the modified boron carbide in the fluororubber compound respectively form hydrogen bonds with fluororubber, and the modified boron carbide forms covalent bonds with fluororubber.
  2. 2. The method of preparing a fluororubber compound of claim 1, wherein providing a sic@sio 2 composite filler and modified boron carbide, and mixing the sic@sio 2 and modified boron carbide to form a plasma resistant composite filler comprises: Providing silicon carbide, a solvent and ethyl orthosilicate, dispersing the silicon carbide in the solvent for ultrasonic treatment for 20-30 min, adding ammonia water at a stirring rate of 100-200 r/min to obtain a mixed solution, wherein the pH value of the mixed solution is 9.2-9.5, adding the ethyl orthosilicate into the mixed solution, reacting for 5-7 h at a constant temperature of 50-55 ℃, centrifuging after the reaction is completed, and drying to obtain SiC@SiO 2 composite filler; Providing boron nitride, a solvent and a titanate coupling agent, dispersing the boron nitride in the solvent, adding the titanate coupling agent, and refluxing and stirring at 70-80 ℃ for 3-4 hours to react; and mixing the SiC@SiO 2 and modified boron carbide in a mass ratio of 1:0.8-1.2 to form the plasma-resistant composite filler.
  3. 3. The method for preparing a fluororubber compound according to claim 1, wherein providing the fluororubber raw rubber, the vulcanizing agent, the fluorine-based low-temperature-resistant plasticizer and the additive comprises: providing fluororubber and perfluororubber, and mixing the fluororubber and the perfluororubber according to the mass ratio of 70-80:20-30 to obtain fluororubber raw rubber, wherein the difference of Mooney viscosities of the fluororubber and the perfluororubber is less than or equal to 20; Providing perfluoropolyether ester and fluoroalkyl phosphonate, and mixing the perfluoropolyether ester and the fluoroalkyl phosphonate according to the mass ratio of 6-8:1 to obtain a fluorine-based low-temperature-resistant plasticizer; Providing 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and triallyl isocyanurate, and mixing the 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and the triallyl isocyanurate according to the mass ratio of 1:1.2-1.5 to obtain a vulcanizing agent; The additive comprises an acid absorbent, a processing aid and an antioxidant, wherein the acid absorbent comprises magnesium oxide and calcium hydroxide, and the mass ratio of the magnesium oxide to the calcium hydroxide is 2:1.
  4. 4. A process for preparing a fluororubber compound as claimed in claim 1, wherein the mixing of the fluororubber raw rubber after plasticating with the additives and the first-stage mixing comprises: plasticating the fluororubber raw rubber at 35-40 rpm for 2-4 min; And mixing the plasticated fluororubber raw rubber with the additive after plastication, and mixing for 2-4 min at the temperature of 45-50 ℃ and the stirring speed of 30-35 rpm to complete the first-stage mixing.
  5. 5. The method for preparing a fluororubber compound according to claim 1, wherein the step of continuing to add the plasma-resistant composite filler for the second-stage mixing after the first-stage mixing is completed comprises the steps of: The method comprises the steps of dividing a plasma-resistant composite filler into two parts according to the components, adding one part of the plasma-resistant composite filler after finishing the first-stage mixing, mixing for 3-6 min at the temperature of 55-60 ℃ and the stirring speed of 45-50 rpm, continuously adding the other part of the plasma-resistant composite filler, mixing for 3-6 min at the temperature of 55-60 ℃ and the stirring speed of 45-50 rpm, and heating the temperature from 55-60 ℃ to 85-90 ℃ to finish the second-stage mixing.
  6. 6. The method for preparing a fluororubber compound according to claim 1, wherein the step of continuing the addition of the fluorine-based low-temperature-resistant plasticizer for the third-stage kneading after the completion of the second-stage kneading comprises: And adding the fluorine-based low-temperature-resistant plasticizer after finishing the second-stage mixing, and mixing for 2-4 min at the stirring speed of 35-40 rpm to finish the third-stage mixing.
  7. 7. The method for preparing a fluororubber compound according to claim 1, wherein the step of subjecting the mixture after completion of the third-stage kneading to a roll-press treatment to obtain a master batch, and the step of mixing a vulcanizing agent and the master batch and then kneading to obtain the fluororubber compound comprises the steps of: Providing a rolling assembly, discharging rubber at 85-90 ℃ after the third-stage mixing is completed to obtain initial rubber, rolling the rubber in the rolling assembly for 4-5 times at a roller spacing of less than 1mm and a roller temperature of less than or equal to 50 ℃ to form initial rolling sheets, and standing the rolling sheets at room temperature for 10-12 hours to obtain master batch; Adding a vulcanizing agent into the masterbatch at the temperature of 40-45 ℃, mixing for 2-4 min at the stirring speed of 35-40 rpm, and continuously heating the masterbatch from the temperature of 40-45 ℃ to 75-80 ℃ to discharge the masterbatch to form colloid to be treated; And rolling the colloid to be treated in a rolling assembly for 2-3 times at a roller spacing of less than 2-3 mm and a roller temperature of less than or equal to 50 ℃ to form a rolling sheet to be treated, and standing the rolling sheet to be treated at room temperature for 10-12 hours to obtain the fluororubber compound.
  8. 8. The fluororubber compound is characterized by comprising 100 parts of fluororubber raw rubber, 20-30 parts of plasma-resistant composite filler, 4-6 parts of fluorine-based low-temperature-resistant plasticizer, 4-5 parts of vulcanizing agent and 4-6 parts of additive, wherein the raw materials of the plasma-resistant composite filler comprise SiC@SiO 2 composite filler and modified boron carbide, and the mass ratio of the SiC@SiO 2 composite filler to the modified boron carbide is 1:0.8-1.2.
  9. 9. The fluororubber compound of claim 8, wherein: the fluororubber raw rubber comprises fluororubber and perfluororubber, wherein the mass ratio of the fluororubber to the perfluororubber is 70-80:20-30, and the difference of the Mooney viscosities of the fluororubber and the perfluororubber is less than or equal to 20; The fluorine-based low-temperature-resistant plasticizer comprises perfluoropolyether ester and fluoroalkyl phosphonate, and the mass ratio of the perfluoropolyether ester to the fluoroalkyl phosphonate is 6-8:1; the vulcanizing agent comprises 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and triallyl isocyanurate, and the mass ratio of the 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane to the triallyl isocyanurate is 1:1.2-1.5; The additive comprises an acid absorber, a processing aid and an antioxidant, wherein the acid absorber comprises magnesium oxide and calcium hydroxide, and the mass ratio of the magnesium oxide to the calcium hydroxide is 2:1.
  10. 10. A semiconductor sealing assembly characterized in that at least part of the semiconductor sealing assembly is made of the fluororubber compound as claimed in claim 8 or 9.

Description

Fluororubber compound, preparation method thereof and semiconductor sealing assembly Technical Field The invention relates to the technical field of rubber sealing materials, in particular to fluororubber compound, a preparation method thereof and a semiconductor sealing assembly. Background Semiconductor manufacturing processes are typically performed in high temperature, high vacuum, and highly corrosive plasma environments, where gas-formed plasmas place extremely high demands on the sealing materials. Fluororubbers (FKM) and perfluororubbers (FFKM) are core materials for semiconductor seals due to their excellent chemical resistance and thermal stability. To ensure that the wafer is not contaminated, the sealing material must have very low particle release rates, excellent plasma etch resistance, and broad temperature range sealing capability. In the prior art, the main means for solving the problems is to adopt single perfluoro rubber (FFKM) as a matrix, add traditional reinforcing fillers such as carbon black and the like, and improve the compactness and corrosion resistance through high-temperature secondary vulcanization. The heat resistance and chemical inertness of the material are improved to a certain extent. However, the traditional filler and fluororubber are only physically adsorbed, the interface bonding strength is insufficient, interface stripping is easy to occur under the impact of plasma bombardment and temperature cycle, particles are caused to fall off and pollute the wafer, and meanwhile, the stripped interface becomes a channel for plasma erosion, so that material degradation is accelerated. Disclosure of Invention The invention provides fluororubber compound, a preparation method thereof and a semiconductor sealing component in order to solve the problem that the prior art is insufficient in interface bonding strength and is easy to generate interface stripping under the impact of plasma bombardment and temperature cycle. The invention provides a preparation method of fluororubber compound, which comprises the following steps of providing SiC@SiO 2 composite filler and modified boron carbide, mixing SiC@SiO 2 and modified boron carbide to form plasma-resistant composite filler, providing fluororubber raw rubber, a vulcanizing agent, a fluorine-based low-temperature-resistant plasticizer and an additive, mixing the fluororubber raw rubber and the additive, carrying out first-stage mixing, continuing to add the plasma-resistant composite filler after the first-stage mixing is finished, carrying out second-stage mixing, continuing to add the fluorine-based low-temperature-resistant plasticizer after the second-stage mixing is finished, carrying out third-stage mixing, carrying out rolling treatment on the mixture after the third-stage mixing to obtain master batch, mixing a vulcanizing agent and the master batch, and carrying out mixing to obtain fluororubber compound, wherein the SiC@SiO 2 composite filler and the modified boron carbide in the fluororubber compound respectively form hydrogen bonds with fluororubber, and the modified boron carbide and the fluororubber form covalent bonds. The preparation method comprises the steps of providing silicon carbide, a solvent and ethyl orthosilicate, dispersing the silicon carbide in the solvent, conducting ultrasonic treatment for 20-30 min, adding ammonia water at a stirring rate of 100-200 r/min to obtain a mixed solution, adding the ethyl orthosilicate into the mixed solution, conducting constant temperature reaction for 5-7 h at 50-55 ℃, conducting centrifugal separation and drying after the reaction is finished to obtain the SiC@SiO 2 composite filler, providing boron nitride, the solvent and a titanate coupling agent, dispersing the boron nitride in the solvent, adding the titanate coupling agent, conducting reflux stirring for 3-4 h at 70-80 ℃ to react, conducting filtration and washing drying treatment after the reaction is finished to obtain the modified boron nitride, wherein the mass fraction of the titanate coupling agent is 3-4 wt%, and mixing the SiC@SiO 2 and the modified boron carbide at a mass ratio of 1:0.8-1.2 to form the composite filler. The fluororubber raw rubber, the vulcanizing agent, the fluorine-based low-temperature-resistant plasticizer and the additive are provided, wherein the fluororubber raw rubber is obtained by mixing the fluororubber and the perfluororubber according to the mass ratio of 70-80:20-30, the Mooney viscosity difference of the fluororubber and the perfluororubber is less than or equal to 20, the perfluoro polyether ester and the fluoroalkyl phosphonate are provided, the fluorine-based low-temperature-resistant plasticizer is obtained by mixing the perfluoro polyether ester and the fluoroalkyl phosphonate according to the mass ratio of 6-8:1, the 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and the triallyl isocyanurate are provided, the vulcanizing agent is obtained by mixing the 2, 5-dime