CN111534016B - Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof - Google Patents
Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electronic packaging material with heat conduction and electromagnetic shielding performances and a preparation method thereof, and belongs to the technical field of electronic packaging materials. The microstructure of the electronic packaging material is in a continuous network shape, the microstructure consists of polymer-based composite microspheres with the particle size range of 100nm-20 mu m and heat-conducting insulating fillers coated on the polymer-based composite microspheres, and the polymer-based composite microspheres consist of polymer resin and modified heat-conducting and electric-conducting fillers. The preparation method of the material uses organic solution as solvent, prepares the polymer-based composite microspheres with the modified heat-conducting and electric-conducting fillers uniformly distributed by a phase separation method, then uniformly mixes the heat-conducting and electric-conducting fillers with the microspheres, and obtains the electronic packaging material with a continuous network structure by a hot-press molding method. The novel electronic packaging material designed by the invention synchronously realizes excellent heat conduction and electromagnetic shielding performance on the basis of keeping electric insulation, and has the advantages of simple process route, low cost and easy mass production.
Description
Technical Field
The invention belongs to the technical field of electronic packaging materials, and particularly relates to a heat-conducting and anti-electromagnetic interference composite material and a preparation method thereof.
Background
With the development of transistor technology, electronic devices are required to be smaller, lighter and faster, and therefore, the packaging of electronic chips tends to have higher power density. The high integration level of the electronic chip inevitably generates a large amount of heat during operation, and if the heat is not removed in time, the stability and even the service life of the device are reduced. Meanwhile, dense electronic chips are also components generating electromagnetic radiation, which can cause signal interference and information leakage among the components. Particularly, with the rapid development of the 5G information technology, the processing efficiency of the electronic device is further improved, the chip size is further reduced, the internal device is more compact, the heat dissipation capability of the device needs to be further improved, and the antenna and the radio frequency front end of the device obviously improve the speed and the frequency band and provide higher requirements for electromagnetic shielding. Therefore, it is a trend of developing electronic packaging materials in the future to have good thermal conductivity and electromagnetic shielding performance.
Polymers are widely used in electronic packaging materials due to their low cost, light weight, excellent chemical resistance and good electrical insulation, but the bulk of the polymer is thermally insulating and cannot be applied directly. Ceramic materials or carbon materials are typically added to polymers, and the continuous thermal conduction path formed in the polymer matrix can increase the thermal conductivity of the composite. Constructing a continuous heat conducting path generally requires a large amount of filler, which makes processing of the compound difficult and the mechanical properties of the product decrease. On one hand, the high thermal conductivity ceramic material is insulating and cannot meet the requirement of the device on the electromagnetic shielding performance. On the other hand, the electrical conductivity of carbon materials does not meet the insulation requirements of devices. Therefore, how to combine the heat conduction, insulation and electromagnetic shielding performance is one of the challenging technologies in this field.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a polymer-based electronic packaging material with heat conduction and electromagnetic shielding properties.
The invention provides a preparation method of the polymer-based electronic packaging material with heat conduction and electromagnetic shielding performances.
In order to solve the technical problem, the technical scheme is that the electronic packaging material with heat conduction and electromagnetic shielding performance is characterized in that the microstructure of the electronic packaging material is in a continuous network shape and is formed by compounding polymer-based composite microspheres with the particle size range of 100nm-20 mu m and heat conduction insulating fillers coated on the polymer-based composite microspheres, the polymer-based composite microspheres are composed of polymer resin and modified heat conduction and electric conduction fillers, and the mass ratio of the polymer resin to the modified heat conduction and electric conduction fillers to the heat conduction and electric insulation fillers is (1-20) to (2-40).
The electronic packaging material with heat conduction and electromagnetic shielding performance is further improved:
preferably, the polymer resin is any one of epoxy resin, polyimide and polystyrene.
Preferably, the heat and electricity conducting filler is any one or two of single-layer graphene, few-layer graphene, graphene nanosheets, carbon fibers, metal powder and low-melting-point metal alloy.
Preferably, the heat-conducting insulating filler is one or two of boron nitride, silicon nitride, aluminum oxide and ferroferric oxide.
In order to solve another technical problem of the invention, the technical scheme is a preparation method of the electronic packaging material with heat conduction and electromagnetic shielding performance, which comprises the following steps:
s1, preparing a modified heat-conducting and electric-conducting filler: weighing the same mass parts of 1-butyl-3-methylimidazole hexafluorophosphate and the heat and electricity conducting filler in a mortar, and fully mixing at room temperature to prepare the modified heat and electricity conducting filler;
s2, preparing the polymer-based composite microspheres: weighing 1-20 parts by mass of the modified heat-conducting and electric-conducting filler, ultrasonically dispersing in an organic solvent, adding 100 parts by mass of polymer resin to obtain a mixed solution, wherein the mass ratio of the organic solvent to the polymer resin is (3-6) to 1, stirring the mixed solution in a water bath kettle at 60-90 ℃ for 8-12h, transferring the mixed solution into a constant-temperature and constant-humidity box with the humidity of 80-98% and the temperature of 25-65 ℃ for 14-36h, collecting a product, washing with deionized water, and drying to obtain the polymer-based composite microsphere;
s3, preparing an electronic packaging material: weighing 2-40 parts by mass of heat-conducting insulating filler, uniformly mixing the heat-conducting insulating filler with the polymer-based composite microspheres prepared in the step S2, placing the mixture in a model, and performing hot press molding at the temperature of 155-230 ℃ and under the pressure of 10-20MPa for 10-20min to obtain the electronic packaging material with heat-conducting and electromagnetic shielding properties.
The preparation method of the electronic packaging material with heat conduction and electromagnetic shielding performance is further improved as follows:
preferably, the organic solvent in step S2 is one of N, N-dimethylformamide, N-dimethylacetamide, acetone, cyclohexane and chloroform.
Preferably, the mixing method of the heat conductive and insulating filler and the polymer-based composite microspheres in step S3 includes one or both of mechanical stirring and manual grinding.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the traditional method, a network structure is constructed in a polymer by using a single-function filler, and the application of the compound is limited by the heat conduction and electric conduction or heat conduction and electric insulation performance of the single-function filler. According to the invention, the electronic packaging composite material with a continuous network structure is designed and constructed by adding two fillers with different functions, so that the electronic packaging material can meet the requirement of electrical insulation on the basis of good heat conduction electromagnetic shielding performance.
(2) The method for preparing the electronic packaging material with good heat-conducting electromagnetic shielding performance adopts the following principle: under the condition of certain temperature and humidity, the composite solution formed by the modified heat-conducting and electric-conducting filler and the polymer resin is subjected to phase separation under the action of water vapor, so that the precipitation of the polymer composite microspheres is induced to separate out, uniform regular spherical particles are formed, and the polymer composite microspheres have certain heat-conducting and shielding properties; the continuous network structure formed by the polymer composite microspheres and the heat-conducting insulating filler in the hot-pressing process can further improve the heat-conducting property of the composite material, so that the good electrical insulating property of the electronic packaging material is maintained while the heat-conducting and shielding properties are realized.
(3) The thermal conductivity of the electronic packaging material is increased along with the increase of the contents of the heat-conducting and electric-conducting filler and the heat-conducting insulating filler, and the composite materials with different heat-conducting and electromagnetic shielding performances can be prepared by adjusting the contents of the heat-conducting and electric-conducting filler and the heat-conducting insulating filler, so that different requirements are met, and the electromagnetic shielding performance of the electronic packaging material can be improved by increasing the content of the heat-conducting and electric-conducting filler.
(4) The preparation method of the electronic packaging material is simple and easy to implement, low in cost and suitable for large-scale production and processing.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the electronic packaging material 4 prepared in example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
A preparation method of a polymer composite material with heat conduction and electromagnetic shielding performance comprises the following steps:
(1) Preparing the modified heat-conducting and electric-conducting filler: weighing 1-butyl-3-methylimidazolium hexafluorophosphate and graphene with the same mass in a mortar, and fully mixing for 15min at 25 ℃.
(2) Preparation of polymer-based composite microspheres: weighing 0.5g of modified graphene in 50ml of N, N-dimethylformamide, carrying out ultrasonic dispersion for 30min, then adding 10g of polystyrene, stirring for 9h in a 75 ℃ water bath kettle, transferring the mixed solution into a constant temperature and humidity box with the humidity of 85% and the temperature of 25 ℃ for 18h, collecting a product, washing with deionized water for 5 times, and drying.
(3) Preparing an electronic packaging material: 0g of alumina (with the size of 1 mu m) is weighed and evenly mixed with the composite microspheres obtained in the step 1 through mechanical stirring of 2000 (r/min) for 30min, the mixture is placed in a model with the size of 30mm multiplied by 2mm, and hot pressing is carried out for 15min under the conditions of 175 ℃ and 15MPa, so as to obtain the electronic packaging material 1 with the continuous network structure.
Example 2
(1) Preparing the modified heat-conducting and electric-conducting filler: weighing the same mass of 1-butyl-3-methylimidazolium hexafluorophosphate and graphene in a mortar, and fully mixing for 15min at 25 ℃.
(2) Preparation of polymer-based composite microspheres: weighing 0g of modified graphene in 50ml of N, N-dimethylformamide, carrying out ultrasonic dispersion for 30min, adding 10g of polystyrene, stirring for 9h in a 75 ℃ water bath, transferring the mixed solution to a constant temperature and humidity box with the humidity of 85% and the temperature of 25 ℃ for 18h, collecting a product, washing with deionized water for 5 times, and drying.
(3) Preparing an electronic packaging material: weighing 2g of aluminum nitride (with the size of 5 mu m) and the composite microspheres obtained in the step 1, uniformly mixing the aluminum nitride and the composite microspheres through mechanical stirring at 2000 (r/min) for 30min, placing the mixture in a model with the size of 30mm multiplied by 2mm, and carrying out hot pressing at 175 ℃ and 15MPa for 15min to obtain the electronic packaging material 2 with the continuous network structure.
Example 3
The preparation method is the same as example 1, except that 1g of alumina (1 μm in size) is weighed in step (3) to prepare an electronic packaging material 3 of a continuous network structure as a comparative example of example 1.
Example 4
The preparation method is the same as example 1, except that 2g of alumina (1 μm in size) is weighed in step (3) as a comparative example between example 1 and example 3, and an electronic packaging material 4 of a continuous network structure is prepared.
Scanning the prepared electronic packaging material 4 by an electron microscope, wherein the scanning picture is shown in fig. 1, and as can be seen from fig. 1, the polymer-based composite microspheres and the heat-conducting insulating filler in the electronic packaging material form a continuous micro-network structure.
Example 5
The preparation method was the same as example 1, except that 4g of alumina (size 1 μm) was weighed in step (3) as comparative examples of example 2, example 3 and example 4, to prepare an electronic packaging material 5 of a continuous network structure.
Example 6
The preparation method is the same as example 2, except that 0.1g of modified graphene is weighed in the step (2) to be used as a comparative example of example 2 and example 4, and the electronic packaging material 6 with a continuous network structure is prepared.
Example 7
The preparation method is the same as example 2, except that 1g of modified graphene is weighed in the step (2) to be used as comparative examples of example 2, example 4 and example 6, and the electronic packaging material 7 with a continuous network structure is prepared.
Samples of the electronic packaging materials prepared in examples 1, 3, 4 and 5 were subjected to measurements of electrical conductivity, thermal conductivity and shielding effectiveness parameters, and the results are shown in table 1 below:
table 1 comparison of electrical conductivity, thermal conductivity and shielding effectiveness for examples 1, 3, 4 and 5
As can be seen from the data in table 1, on the one hand, the electrical conductivity of the composite material is greatly reduced with the increase of the alumina content of the heat-conducting insulating filler, so that the electrical insulating property of the composite material can be controlled by controlling the addition amount of alumina. On the other hand, as the alumina content increases, the thermal conductivity of the composite material gradually increases. The electromagnetic shielding effectiveness of the composite material is mainly contributed by the absorption of electromagnetic waves by the internal modified heat-conducting and electric-conducting graphene, and the electromagnetic shielding effectiveness of the composite material is basically kept unchanged under the condition that the composite material is insulating.
Samples of the electronic packaging materials prepared in examples 2, 6, 4 and 7 were subjected to measurements of electrical conductivity, thermal conductivity and shielding effectiveness parameters, and the results are shown in table 2 below:
table 2 shows a comparison of the electrical conductivity, thermal conductivity and shielding effectiveness of examples 2, 6, 4 and 7.
As can be seen from the data in table 2, as the content of the modified graphene serving as the thermal and electrical conductive filler increases, the electrical conductivity of the composite material gradually increases, so that the composite materials with different electrical conductivity can be prepared by adjusting and controlling the content of the modified graphene. In addition, as the content of the modified graphene increases, the thermal conductivity of the composite material also gradually increases. The addition of the modified graphene and the alumina filler is beneficial to increasing the thermal conductivity of the composite material. The modified graphene can effectively absorb electromagnetic waves due to dielectric polarization, and the electromagnetic shielding performance of the composite is gradually increased along with the increase of the content of the modified graphene.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (7)
1. The electronic packaging material with the heat conduction and electromagnetic shielding performance is characterized in that the microstructure of the electronic packaging material is in a continuous network shape and is formed by compounding polymer-based composite microspheres with the particle size range of 100nm-20 mu m and heat conduction insulating fillers coated on the polymer-based composite microspheres, the polymer-based composite microspheres are composed of polymer resin and modified heat conduction and electric conduction fillers, and the mass ratio of the polymer resin to the modified heat conduction and electric conduction fillers to the heat conduction and electric insulation fillers is 100 (1-20): 2-40.
2. The electronic packaging material with heat conducting and electromagnetic shielding properties as claimed in claim 1, wherein the polymer resin is any one of epoxy resin, polyimide, and polystyrene.
3. The electronic packaging material with heat conduction and electromagnetic shielding properties as claimed in claim 1, wherein the heat conduction and electric conduction filler is one or two of single-layer graphene, few-layer graphene, graphene nanosheet, carbon fiber, metal powder and low-melting-point metal alloy.
4. The electronic packaging material with heat conducting and electromagnetic shielding properties as claimed in claim 1, wherein the heat conducting insulating filler is one or two of boron nitride, silicon nitride, aluminum oxide and ferroferric oxide.
5. A method for preparing the electronic packaging material with heat conduction and electromagnetic shielding performance as claimed in any one of claims 1 to 4, comprising the following steps:
s1, preparing a modified heat-conducting and electric-conducting filler: weighing 1-butyl-3-methylimidazole hexafluorophosphate and heat and electricity conducting filler in the same mass part, and placing the mixture in a mortar for fully mixing at room temperature to prepare the modified heat and electricity conducting filler;
s2, preparing the polymer-based composite microspheres: weighing 1-20 parts by mass of the modified heat-conducting and electric-conducting filler, ultrasonically dispersing the modified heat-conducting and electric-conducting filler in an organic solvent, adding 100 parts by mass of polymer resin to obtain a mixed solution, wherein the mass ratio of the organic solvent to the polymer resin is (3-6) to 1, placing the mixed solution in a water bath kettle at 60-90 ℃, stirring for 8-12h, then transferring the mixed solution into a constant-temperature and constant-humidity box with the humidity of 80-98% and the temperature of 25-65 ℃, placing for 14-36h, collecting a product, washing with deionized water, and drying to obtain polymer-based composite microspheres;
s3, preparing an electronic packaging material: weighing 2-40 parts by mass of heat-conducting insulating filler, uniformly mixing with the polymer-based composite microspheres prepared in the step S2, placing the mixture in a model, and performing hot press molding at the temperature of 155-230 ℃ and under the pressure of 10-20MPa for 10-20min to obtain the electronic packaging material with heat-conducting and electromagnetic shielding properties.
6. The method according to claim 5, wherein the organic solvent in step S2 is one of N, N-dimethylformamide, N-dimethylacetamide, acetone, cyclohexane, and chloroform.
7. The method for preparing an electronic packaging material with heat conductivity and electromagnetic shielding property according to claim 5, wherein the mixing method of the heat conductive insulating filler and the polymer-based composite microspheres in step S3 is one or both of mechanical stirring and manual grinding.
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| CN113337231B (en) * | 2021-06-01 | 2022-10-04 | 中国科学院合肥物质科学研究院 | Epoxy composite material with heterostructure and preparation method thereof |
| CN113652059A (en) * | 2021-08-25 | 2021-11-16 | 北京超材信息科技有限公司 | Encapsulating resin composition for surface acoustic wave device, laminate, and method for producing the same |
| CN114094001B (en) * | 2021-09-29 | 2023-12-01 | 华灿光电（浙江）有限公司 | Substrate, light-emitting diode epitaxial wafer and manufacturing method thereof |
| CN115025439B (en) * | 2022-05-12 | 2023-05-02 | 深圳联众安消防科技有限公司 | Composite environment-friendly aerosol fire extinguishing agent and preparation method thereof |
| CN115403928B (en) * | 2022-08-01 | 2023-05-30 | 中国科学院合肥物质科学研究院 | Electronic packaging material with heat conduction electromagnetic shielding performance and preparation method thereof |
| CN115678499B (en) * | 2022-10-28 | 2023-05-16 | 北京理工大学 | Flexible attachable thermal management/electromagnetic shielding composite material and preparation method thereof |
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