Modified epoxy resin and preparation method thereof

Abstract

The invention relates to modified epoxy resin and a preparation method thereof.The preparation method comprises the steps that S1, nano aluminum nitride and mesoporous silica are subjected to an ultrasonic reaction in an organic solvent, then a reaction product is sequentially subjected to centrifugal separation, filtering, washing and drying, and a precursor AlN-coated SiO2 is obtained; s2, the precursor AlN-coated SiO2 and epoxy resin are mixed and then heated to a molten state, heat preservation is conducted in the molten state, modified epoxy resin is obtained, and the modified epoxy resin is used as a heat conduction epoxy plastic packaging material for semiconductor structure packaging. Nanometer aluminum nitride and mesoporous silica are subjected to an ultrasonic reaction to obtain a precursor AlN-coated SiO2, and the precursor AlN-coated SiO2 is doped with epoxy resin, so that the heat-conducting property of the modified epoxy resin is remarkably enhanced, the modified epoxy resin can provide an additional heat dissipation way when being applied to semiconductor structure packaging, the requirement of electronic packaging for a high-heat-conducting packaging material is met, and the service life of the high-heat-conducting packaging material is prolonged. Meanwhile, the modified epoxy resin has good thermal property and mechanical property.

Description

Technical Field

[0001] The invention belongs to the field of electronic packaging plastic packaging materials, and specifically relates to a modified epoxy resin and a preparation method thereof. Background Art

[0002] At present, integrated circuit products tend to develop towards high performance, high integration and high reliability. Correspondingly, semiconductor electronic devices are gradually developing towards integration, high efficiency and safety. With the continuous improvement of packaging technology, electronic products have gradually become light, thin, short and small. Correspondingly, the form of electronic packaging has changed to high-density packaging such as BGA, SIP, and 3D stacking. High integration and high density make electronic devices generate a large amount of concentrated heat under high power, thus putting forward higher requirements for product heat dissipation. Therefore, thermal management methods play an increasingly important role in integrated circuit packaging.

[0003] Currently, a feasible thermal management method is to use thermally conductive epoxy molding materials to encapsulate semiconductor structures, and transfer the heat generated by semiconductor electronic devices to the external environment through the packaging materials, thereby providing an additional heat dissipation path and further meeting the urgent need for high thermal conductivity packaging in electronic packaging. Summary of the invention

[0004] In order to solve the above problems existing in the prior art, the present invention provides a modified epoxy resin and a preparation method thereof. The technical problem to be solved by the present invention is achieved by the following technical solution:

[0005] The embodiment of the present invention provides a method for preparing a modified epoxy resin, comprising the steps of:

[0006] S1, subjecting nano-aluminum nitride and mesoporous silica to ultrasonic reaction in an organic solvent, and then centrifugally separating, filtering, washing and drying the reaction products in sequence to obtain a precursor AlN@SiO2;

[0007] S2. Mix the precursor AlN@SiO2 and epoxy resin, raise the temperature to a molten state, and keep the mixture in the molten state to obtain a modified epoxy resin, which is used as a thermally conductive epoxy molding material for semiconductor structure packaging.

[0008] In one embodiment of the present invention, in step S1, the molar ratio of the nano-aluminum nitride to the mesoporous silica is 3:1 to 10:1.

[0009] In one embodiment of the present invention, in step S1, the organic solvent includes any one of N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, carbon tetrachloride, ethanol or a mixed solvent in any proportion thereof.

[0010] In one embodiment of the present invention, in step S1, the temperature of the ultrasonic reaction is 45-80° C. and the time is 6-12 hours.

[0011] In one embodiment of the present invention, in step S1, the washing solvent includes any one of methanol, ethanol, ethylene glycol, water, acetonitrile, chloroform or a mixture thereof in any proportion.

[0012] In one embodiment of the present invention, in step S1, the drying temperature is 35-75°C.

[0013] In one embodiment of the present invention, in step S2, the epoxy resin has the structural formula:

[0014]

[0015] In one embodiment of the present invention, in step S2, the mass percentage of the precursor AlN@SiO2 is 5% to 10%, and the mass percentage of the epoxy resin is 90% to 95%.

[0016] In one embodiment of the present invention, in step S2, the temperature of the temperature increased to reach the molten state is 200-300°C, and the time of keeping the temperature in the molten state is 1.5-3h.

[0017] Another embodiment of the present invention provides a modified epoxy resin prepared by the preparation method described in the above embodiment.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The present invention ultrasonically reacts nano-aluminum nitride with mesoporous silica to obtain a precursor AlN@SiO2. Nano-aluminum nitride has good insulation and thermal conductivity, and mesoporous silica has good chemical and thermal stability. The two have good interface compatibility. The formed precursor AlN@SiO2 has good thermal conductivity. When doped with epoxy resin, the thermal conductivity of the modified epoxy resin is significantly enhanced, so that the modified epoxy resin can provide an additional heat dissipation path when used in semiconductor structure packaging, meeting the demand for high thermal conductivity packaging materials in electronic packaging. At the same time, the modified epoxy resin has good thermal and mechanical properties, which is conducive to the high integration, high density and green development of electronic packaging materials.

[0020] 2. The preparation method of the present invention is simple, the solvent is easily available, the reaction temperature is relatively mild, the synthesis time is short, no by-products are produced, and the post-processing is simple. The obtained product has excellent thermal conductivity, is environmentally friendly and pollution-free, and is in line with the development direction of green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1A schematic flow chart of a method for preparing a modified epoxy resin provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0022] The present invention is further described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.

[0023] See also Figure 1 , Figure 1 The present invention provides a schematic flow diagram of a method for preparing a modified epoxy resin. The method for preparing the modified epoxy resin comprises the following steps:

[0024] S1. Ultrasonic reaction is performed on nano-aluminum nitride and mesoporous silica in an organic solvent, and then the reaction product is centrifuged, filtered, washed and dried in sequence to obtain a precursor AlN@SiO2.

[0025] Specifically, nano-aluminum nitride and mesoporous silica are dispersed in an organic solvent at a molar ratio of 3:1 to 10:1 and subjected to ultrasonic reaction at a temperature of 45 to 80°C for 6 to 12 hours, and a mixture containing AlN@SiO2 is formed after sufficient reaction. The organic solvent includes any one of N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, carbon tetrachloride, and ethanol, or a mixed solvent in any proportion thereof.

[0026] The mixture is then centrifuged, and the centrifugal separation product is filtered, washed, and dried to obtain a white powder solid, which is the precursor AlN@SiO2. The washing solvent includes any one of methanol, ethanol, ethylene glycol, water, acetonitrile, and chloroform, or a mixture thereof in any proportion; the drying temperature is 35 to 75°C.

[0027] S2. Mix the precursor AlN@SiO2 and epoxy resin, raise the temperature to a molten state, and keep the mixture in the molten state to obtain a modified epoxy resin, which is used as a thermally conductive epoxy molding material for semiconductor structure packaging.

[0028] Specifically, the raw material precursor AlN@SiO2 and the epoxy resin are weighed, the mass percentage of the precursor AlN@SiO2 is 5% to 10%, and the mass percentage of the epoxy resin is 90% to 95%. The weighed epoxy resin is ground into powder and mixed with the powdered precursor AlN@SiO2, and then the mixed powder is heated to 200 to 300° C. so that the mixed powder reaches a molten state, and the mixed powder is kept warm for 1.5 to 3 hours in the molten state, and then cooled to obtain a modified epoxy resin doped with AlN@SiO2.

[0029] Specifically, the raw epoxy resin contains epoxy groups that can participate in the curing reaction and can be cured together with the matrix. Its structural formula is:

[0030]

[0031] Furthermore, the prepared modified epoxy resin not only contains epoxy groups that can participate in the curing reaction, but is also doped with AlN@SiO2 composite materials, which can significantly enhance the thermal conductivity of the resin. The modified epoxy resin is a high thermal conductivity epoxy resin and can be used as a thermal conductive epoxy molding material for semiconductor structure packaging.

[0032] Based on the above preparation method of modified epoxy resin, this embodiment further provides a modified epoxy resin, which includes raw materials: 5% to 10% by mass of AlN@SiO2 and 90% to 95% by mass of AlN@SiO2.

[0033] The preparation method of this embodiment is simple, the solvent is easily available, the reaction temperature is relatively mild, the synthesis time is short, no by-products are generated, and the post-processing is simple. The obtained product has excellent thermal conductivity, is environmentally friendly and pollution-free, and is in line with the development direction of green chemistry.

[0034] Aluminum nitride (AlN) is a new type of inorganic non-metallic material with high thermal conductivity, high resistivity, good electrical insulation, high strength, wear resistance and high temperature resistance. Due to its unique physical and chemical properties, it has shown broad application prospects in many fields. The modified aluminum nitride material - nano aluminum nitride has a small particle size, large specific surface area, high surface activity, and very obvious insulation and thermal conductivity. It also has good interfacial compatibility with silicon. Mesoporous silica nanoparticles have a highly ordered mesoporous structure and good chemical and thermal stability, making them ideal materials for preparing composite materials. In this embodiment, nano-aluminum nitride and mesoporous silica are subjected to ultrasonic reaction to obtain a precursor AlN@SiO2. Nano-aluminum nitride has good insulating thermal conductivity, and mesoporous silica has good chemical and thermal stability. The two have good interface compatibility. The formed precursor AlN@SiO2 has good thermal conductivity. When doped with epoxy resin, the thermal conductivity of the modified epoxy resin is significantly enhanced, so that the modified epoxy resin can provide an additional heat dissipation path when used in semiconductor structure packaging, meeting the demand for high thermal conductivity packaging materials in electronic packaging. At the same time, the modified epoxy resin has good thermal and mechanical properties, which is conducive to the high integration, high density and green development of electronic packaging materials.

[0035] Furthermore, the preparation method of the modified epoxy resin is further illustrated by the following examples.

[0036] Example 1

[0037] After setting up the device, add 2.46g of nano-aluminum nitride (AlN) and 0.64g of mesoporous silica (SiO2) to a 500ml glass bottle, and then add 50ml of anhydrous ethanol as a solvent. Place the glass bottle in an ultrasonic machine, heat it to 50°C to start the reaction, end the reaction after 8 hours, cool it to room temperature, transfer it to a centrifuge, centrifuge it at 10,000rpm for 45 minutes, and obtain a milky white solution. After filtering, washing, and drying the solution, a white powder solid AlN@SiO2 is obtained.

[0038] Weigh 5% by mass of AlN@SiO2 and 95% by mass of epoxy resin, grind the weighed epoxy resin into powder, and mix it with powdered AlN@SiO2, heat the mixed powder to 200°C to make the mixed powder reach a molten state, keep it warm in the molten state for 1.5 hours, and cool it to obtain a modified epoxy resin doped with AlN@SiO2.

[0039] Example 2

[0040] After setting up the device, add 1.85g of nano aluminum nitride (AlN) and 1.28g of mesoporous silica (SiO2) into a 500ml glass bottle, then add 50ml of ethylene glycol as a solvent, place the glass bottle in an ultrasonic machine, heat it to 75°C to start the reaction, end the reaction after 6 hours, cool it to room temperature, transfer it to a centrifuge, and centrifuge it at 10,000rpm for 45 minutes to obtain a milky white solution. After filtering, washing, and drying the solution, a white powdery solid AlN@SiO2 was obtained.

[0041] Weigh 8% by mass of AlN@SiO2 and 92% by mass of epoxy resin, grind the weighed epoxy resin into powder, and mix it with powdered AlN@SiO2, heat the mixed powder to 260°C to make the mixed powder reach a molten state, keep it in the molten state for 2 hours, and cool it to obtain a modified epoxy resin doped with AlN@SiO2.

[0042] Example 3

[0043] After setting up the device, add 4.93g of nano aluminum nitride (AlN) and 0.96g of mesoporous silica (SiO2) into a 500ml glass bottle, then add 60ml of carbon tetrachloride as solvent, place the glass bottle in an ultrasonic machine, heat it to 65°C to start the reaction, end the reaction after 6h, cool it to room temperature, transfer it to a centrifuge, and centrifuge it at 10000rpm for 30min to obtain a milky white solution. After filtering, washing and drying the solution, a white powdery solid AlN@SiO2 was obtained.

[0044] Weigh 10% by mass of AlN@SiO2 and 90% by mass of epoxy resin, grind the weighed epoxy resin into powder, and mix it with powdered AlN@SiO2, heat the mixed powder to 300°C to make the mixed powder reach a molten state, keep the mixture in a molten state for 3 hours, and cool it to obtain a modified epoxy resin doped with AlN@SiO2.

[0045] The modified epoxy resin prepared in this embodiment has excellent thermal conductivity, so that the modified epoxy resin can provide an additional heat dissipation path when used in semiconductor structure packaging, meeting the demand of electronic packaging for high thermal conductivity packaging materials. At the same time, the modified epoxy resin has good thermal and mechanical properties, which is conducive to the high integration, high density and green development of electronic packaging materials.

[0046] The preparation method of this embodiment has a simple route, a mild reaction temperature, a short synthesis time, no by-products are generated, and the post-processing is simple. The obtained product has excellent thermal conductivity.

[0047] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as falling within the protection scope of the present invention.

Claims

1. A method for preparing a modified epoxy resin, characterized in that: Includes steps: S1, subjecting nano-aluminum nitride and mesoporous silica to ultrasonic reaction in an organic solvent, and then centrifugally separating, filtering, washing and drying the reaction products in sequence to obtain a precursor AlN@SiO2; S2. Mix the precursor AlN@SiO2 and epoxy resin, raise the temperature to a molten state, and keep the mixture in the molten state to obtain a modified epoxy resin, which is used as a thermally conductive epoxy molding material for semiconductor structure packaging.

2. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S1, the molar ratio of the nano-aluminum nitride to the mesoporous silica is 3:1 to 10:

1.

3. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S1, the organic solvent includes any one of N,N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, ethylene glycol, anhydrous acetonitrile, dichloromethane, carbon tetrachloride, and ethanol, or a mixed solvent in any proportion thereof.

4. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S1, the temperature of the ultrasonic reaction is 45-80° C. and the time is 6-12 hours.

5. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S1, the washing solvent includes any one of methanol, ethanol, ethylene glycol, water, acetonitrile, chloroform or a mixture thereof in any proportion.

6. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S1, the drying temperature is 35-75°C.

7. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S2, the structural formula of the epoxy resin is:

8. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S2, the mass percentage of the precursor AlN@SiO2 is 5% to 10%, and the mass percentage of the epoxy resin is 90% to 95%.

9. The method for preparing the modified epoxy resin according to claim 1, characterized in that: In step S2, the temperature of the heating to reach the molten state is 200-300°C, and the time of keeping the temperature in the molten state is 1.5-3h.

10. A modified epoxy resin, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 9.

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