A radiation-resistant epoxy plastic packaging material and its application

Abstract

The present application relates to the technical field of packaging materials, and specifically discloses a radiation-resistant epoxy molding compound and its application. The radiation-resistant epoxy molding compound includes the following components in parts by weight: 5-10 parts of epoxy resin, 2-35 parts of nano-tantalum, 0.1-0.5 parts of black phosphorene, 0.1-0.7 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-10 parts of curing agent and 0.3-0.5 parts of stress release agent; further, in the radiation-resistant epoxy molding compound, the addition amount of nano-tantalum, black phosphorene and carbon nanotubes is: 10-25 parts of nano-tantalum, 0.2-0.4 parts of black phosphorene, and 0.2-0.6 parts of carbon nanotubes. The radiation-resistant epoxy molding compound provided by the present application has good thermal conductivity, excellent mechanical properties, and strong radiation resistance, and can be used to package integrated circuits to improve the radiation resistance of integrated circuits.

Description

Technical Field

[0001] The present application relates to the technical field of packaging materials, and in particular to a radiation-resistant epoxy molding compound and its application. Background Art

[0002] With the rapid development of aerospace industry, the demand for radiation-resistant integrated circuits is increasing. Especially in extreme environments such as outer space and nuclear tests, the irradiation of high-energy particles has a serious impact on the stability of microelectronic devices. In order to ensure the reliable operation of electronic systems, especially in core integrated circuits, effective radiation hardening measures must be taken.

[0003] Although the traditional anti-radiation method can improve the radiation resistance of integrated circuits to a certain extent, it still has some limitations; for example, in ultra-large-scale digital-analog hybrid integrated circuits, the traditional reinforcement method has the following disadvantages: First, due to the inability to accurately estimate the area of ​​each anti-radiation unit, it is necessary to leave enough "space margin" between each module during design, which is easy to cause a large amount of area waste, increase the difficulty and time cost of design; second, the radiation reinforcement method requires manual labor to complete the design optimization and replacement placement of all module layouts, as well as the connection between modules, so the manpower and time cost are high; third, the reinforced integrated circuit is not conducive to optimization and revision design; fourth, at this stage, there are few manufacturers of production process lines and the production volume of processing lines is small, resulting in high costs. In addition, in the fields of aerospace, nuclear industry, etc., the reliability requirements for integrated circuits are very high, so it is still very important to further improve the radiation resistance of integrated circuits.

[0004] Therefore, continuously exploring new radiation-resistant technologies and packaging materials has important practical significance for improving the radiation resistance and performance of integrated circuits. Summary of the invention

[0005] In order to improve the radiation resistance of integrated circuits without significantly increasing costs, the present application provides a radiation-resistant epoxy molding compound and its application.

[0006] In a first aspect, the present application provides a radiation-resistant epoxy molding compound, which adopts the following technical solution:

[0007] A radiation-resistant epoxy molding compound comprises the following components in parts by weight: 5-10 parts of epoxy resin, 2-35 parts of nano-tantalum, 0.1-0.5 parts of black phosphorene, 0.1-0.7 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-8 parts of curing agent and 0.3-0.5 parts of stress release agent.

[0008] The present application provides a radiation-resistant epoxy molding compound, which can be used as a packaging material for integrated circuits, significantly improving the radiation resistance of integrated circuits. Specifically, the large atomic number and nanosheet structure of nano-tantalum can effectively absorb and shield radiation energy, reduce the direct effect of radiation on the epoxy resin matrix, and thus improve the radiation resistance of epoxy resin; black phosphorene, as a new type of two-dimensional semiconductor material composed of ordered phosphorus atoms peeled from black phosphorus, a single atomic layer, and a direct band gap, is composed of ordered phosphorus atoms, which are arranged in a wrinkled honeycomb lattice. The wrinkled honeycomb lattice structure can give black phosphorene a certain radiation resistance; and the high carrier mobility of black phosphorene helps to quickly transfer and disperse the charge generated by radiation, reducing the damage caused by charge accumulation; in addition, the high melting point and chemical stability of nano-tantalum complement the stability of black phosphorene, thereby forming a more stable composite material under irradiation; the excellent mechanical properties of nano-tantalum can provide a physical protective layer, and the electrical properties of black phosphorene can provide chemical protection or electronic protection, thereby jointly resisting radiation damage. Carbon nanotubes undergo a series of structural changes under electron beam irradiation, such as the closure of the central hole and the appearance of a carbon onion structure on the surface. These structural changes can improve their stability against radiation. In addition, in radiation-resistant epoxy molding compounds, carbon nanotubes can also form a three-dimensional network structure with black phosphorene, which can improve the thermal conductivity and mechanical properties of the molding compound. On the other hand, it can also improve the dispersibility of nano-tantalum, so that the nano-tantalum is evenly loaded on the network structure, further improving the radiation resistance of the molding compound. The use of stress release agents can reduce the internal stress of the molding compound and prevent the material from cracking during irradiation. In summary, the radiation-resistant epoxy molding compound provided in this application has good radiation resistance, thermal conductivity and mechanical properties, and is suitable for electronic device packaging in the fields of aerospace and nuclear industry.

[0009] In some embodiments, the weight proportion of the nano tantalum may be 2-10 parts, 2-20 parts, 2-25 parts, 2-35 parts, 10-20 parts, 10-25 parts, 10-35 parts, 20-25 parts, 20-30 parts or 25-35 parts.

[0010] In a specific embodiment, the weight proportion of the nano-tantalum can also be 2 parts, 10 parts, 20 parts, 25 parts or 35 parts.

[0011] In some embodiments, the weight proportion of the black phosphorene may be 0.1-0.2, 0.1-0.3, 0.1-0.4, 0.1-0.5, 0.2-0.3, 0.2-0.4, 0.2-0.5, 0.3-0.4, 0.3-0.5 or 0.4-0.5.

[0012] In a specific embodiment, the weight portion of the black phosphorene can also be 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part.

[0013] In some embodiments, the weight portion of the carbon nanotubes may be 0.1-0.2 parts, 0.1-0.4 parts, 0.1-0.6 parts, 0.1-0.7 parts, 0.2-0.4 parts, 0.2-0.6 parts, 0.2-0.7 parts, 0.4-0.6 parts, 0.4-0.7 parts or 0.6-0.7 parts.

[0014] In a specific embodiment, the weight portion of the carbon nanotubes can also be 0.1 part, 0.2 part, 0.4 part, 0.6 part or 0.7 part.

[0015] Optionally, the radiation-resistant epoxy molding compound comprises the following components in parts by weight: 5-10 parts of epoxy resin, 10-25 parts of nano-tantalum, 0.2-0.4 parts of black phosphorene, 0.2-0.6 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-8 parts of curing agent and 0.3-0.5 parts of stress release agent.

[0016] In this application, the combined effect of nano-tantalum, black phosphorene and carbon nanotubes will affect the radiation resistance of the radiation-resistant epoxy molding compound. Through experimental research, it was found that by further controlling the addition amount of nano-tantalum, black phosphorene and carbon nanotubes within the above range, the radiation resistance of the radiation-resistant epoxy molding compound is better. Compared with pure epoxy molding compound, its protection efficiency against electron radiation can be increased by more than 70%.

[0017] Optionally, the epoxy resin is selected from one or more of o-cresol epoxy resin, aliphatic glycidyl ether epoxy resin, polyphenol glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, resorcinol formaldehyde epoxy resin and trishydroxyphenylmethane epoxy resin.

[0018] Optionally, the curing agent is selected from one or more of phenol linear phenolic resin and its derivatives, cresol linear phenolic resin and its derivatives, monohydroxy or dihydroxy naphthol phenolic resin, biphenyl phenolic resin, aralkyl phenol type epoxy resin and its derivatives, methyl hexahydrophthalic anhydride, 4,4'-diaminodiphenylmethane; the stress release agent is selected from one or more of liquid silicone oil, polysiloxane rubber powder, and silicone-modified epoxy resin.

[0019] Optionally, the radiation-resistant epoxy molding compound further comprises 0.1-0.3 parts of a curing accelerator, 0.1-0.5 parts of a coupling agent, 0.1-1 parts of a colorant, 3-7 parts of a flame retardant and 0.3-0.6 parts of a release agent.

[0020] Optionally, the curing agent accelerator is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol and imidazole accelerators; the coupling agent is selected from one or more of epoxy silane coupling agents, amino silane coupling agents, and mercapto silane coupling agents; the colorant is selected from one or more of carbon black, titanium dioxide, and oil-soluble aniline black; the flame retardant is selected from one or more of organic flame retardants or inorganic flame retardants; the release agent is selected from one or more of stearic acid, oxidized or non-oxidized polyethylene wax, montan wax, and Fischer-Tropsch wax.

[0021] The preparation method of the radiation-resistant epoxy molding compound provided in the present application comprises the following steps: uniformly mixing the components, then heating and kneading the mixture, cooling, crushing, mixing, and making cakes to obtain the radiation-resistant epoxy molding compound.

[0022] In a second aspect, the present application provides an application of a radiation-resistant epoxy molding compound in electronic device packaging.

[0023] In summary, this application has the following beneficial effects:

[0024] 1. This application uses epoxy resin, nano-tantalum, black phosphorene and carbon nanotubes to prepare a radiation-resistant epoxy molding compound with good mechanical properties, thermal conductivity and radiation resistance. The flexural strength is 167-177MPa, the thermal conductivity is 3.0-4.1W / m.℃, and the protection efficiency against electron radiation is 58.5-77.8%. It can be used as a packaging material for integrated circuits to improve the radiation resistance of integrated circuits.

[0025] 2. This application further controls the addition amount of nano tantalum, black phosphorene and carbon nanotubes within the following range: 10-25 parts of nano tantalum, 0.2-0.4 parts of black phosphorene, and 0.2-0.6 parts of carbon nanotubes. The obtained radiation-resistant epoxy molding compound has better radiation resistance. Compared with pure epoxy molding compound, its protection efficiency against electron radiation can be improved by more than 70%. DETAILED DESCRIPTION

[0026] The present application provides a plastic encapsulation material composition, comprising the following components in parts by weight: 5-10 parts of epoxy resin, 2-35 parts of nano-tantalum, 0.1-0.5 parts of black phosphorene, 0.1-0.7 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-10 parts of curing agent, 0.3-0.5 parts of stress release agent, 0.1-0.3 parts of curing accelerator, 0.1-0.5 parts of coupling agent, 0.1-1 parts of colorant, 3-7 parts of flame retardant and 0.3-0.6 parts of release agent; Furthermore, the radiation-resistant epoxy molding compound includes the following components in parts by weight: 5-10 parts of epoxy resin, 10-25 parts of nano-tantalum, 0.2-0.4 parts of black phosphorene, 0.2-0.6 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-8 parts of curing agent, 0.3-0.5 parts of stress release agent, 0.1-0.3 parts of curing accelerator, 0.1-0.5 parts of coupling agent, 0.1-1 parts of colorant, 3-7 parts of flame retardant and 0.3-0.6 parts of release agent.

[0027] The epoxy resin is selected from one or more of o-cresol epoxy resin, aliphatic glycidyl ether epoxy resin, polyphenol glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, resorcinol formaldehyde epoxy resin and trishydroxyphenylmethane epoxy resin; the curing agent is selected from phenol linear phenolic resin and its derivatives, cresol linear phenolic resin and its derivatives, monohydroxy or dihydroxy naphthyl phenolic resin, biphenyl phenolic resin, aralkyl phenolic epoxy resin and its derivatives, methyl hexahydrophthalic anhydride, 4,4 '-diaminodiphenylmethane; the stress release agent is selected from one or more of liquid silicone oil, polysiloxane rubber powder, and silicone-modified epoxy resin; the curing agent accelerator is selected from one or more of 2,4,6-tris (dimethylaminomethyl) phenol and imidazole accelerators; the coupling agent is selected from one or more of epoxy silane coupling agent, amino silane coupling agent, and mercapto silane coupling agent; the colorant is selected from one or more of carbon black, titanium dioxide, and oil-soluble aniline black; the flame retardant is selected from one or more of organic flame retardants or inorganic flame retardants; the release agent is selected from one or more of stearic acid, oxidized or non-oxidized polyethylene wax, montan wax, and Fischer-Tropsch wax.

[0028] The present application provides a method for preparing a radiation-resistant epoxy molding compound, comprising the following steps: uniformly mixing the components, then heating and kneading the mixture, cooling, crushing, mixing, and making cakes to obtain the radiation-resistant epoxy molding compound.

[0029] In the embodiments of the present application, the epoxy resin is o-cresol epoxy resin; the curing agent is phenol linear phenolic resin and benzocresol linear phenolic resin; nano tantalum is purchased from Beijing Dekedaojin Technology Co., Ltd.; black phosphorene is purchased from Shenzhen Liutan Technology Co., Ltd.; carbon nanotubes are purchased from Bailingwei Technology; the CAS number of aluminum oxide is 13344-28-1; the CAS number of silicon dioxide is 7631-86-9; the stress release agent is liquid silicone oil; the curing accelerator is 2,4,6-tris(dimethylaminomethyl)phenol; the coupling agent is epoxy silane coupling agent; the colorant is carbon black; the flame retardant is a phosphorus silicon flame retardant; the release agent is Fischer-Tropsch wax; the raw materials, reagents, solvents, etc. used in this application can all be obtained commercially.

[0030] The present application is further described in detail below in conjunction with embodiments and performance testing experiments.

[0031] Examples 1-13

[0032] Embodiments 1-13 respectively provide a radiation-resistant epoxy molding compound.

[0033] The difference between the above embodiments is that the amount of nano-tantalum, black phosphorene or carbon nanotube added to the radiation-resistant epoxy molding compound is specifically shown in Table 1 below.

[0034] The preparation method of the radiation-resistant epoxy molding compound provided in Examples 1-13 comprises the following steps: firstly weigh 8 g of epoxy resin, nano-tantalum, black phosphorene, carbon nanotubes, 20 g of boron nitride, 40 g of aluminum oxide, 50 g of silicon dioxide, 0.5 g of colorant, 5 g of flame retardant, 0.4 g of stress release agent, 2 g of phenol linear phenolic resin, 2 g of benzocresol linear phenolic resin, 0.2 g of 2,4,6-tris(dimethylaminomethyl)phenol, 0.3 g of epoxy silane coupling agent and 0.4 g of Fischer-Tropsch wax, mix the above raw materials evenly, then heat and knead the mixture, cool, crush, mix and make cakes to obtain the radiation-resistant epoxy molding compound.

[0035] Table 1 Addition amount of nano-tantalum, black phosphorene or carbon nanotube in Examples 1-13

[0036] Comparative Example 1

[0037] Comparative Example 1 provides a radiation-resistant epoxy molding compound.

[0038] The difference between the above comparative example and Example 3 is that the amount of nano-tantalum added in the radiation-resistant epoxy molding compound is 0. Comparative Example 2

[0039] Comparative Example 2 provides a radiation-resistant epoxy molding compound.

[0040] The difference between the comparative example and Example 3 is that the amount of black phosphorene added to the radiation-resistant epoxy molding compound is 0. Comparative Example 3

[0041] Comparative Example 3 provides a radiation-resistant epoxy molding compound.

[0042] The difference between the comparative example and Example 3 is that the amount of carbon nanotubes added to the radiation-resistant epoxy molding compound is 0. Comparative Example 4

[0043] Comparative Example 4 provides a radiation-resistant epoxy molding compound.

[0044] The difference between the comparative example and Example 3 is that black phosphorene is replaced by graphene (CAS No. 1043-98-0).

[0045] Performance testing

[0046] Various performance tests were performed on the radiation-resistant epoxy molding compounds prepared in Examples 1-13 and Comparative Examples 1-4. The results are shown in Table 2 below.

[0047] 1. Bending strength: The radiation-resistant epoxy molding compound was made into a bending specimen with a size of 80 mm × 10 mm × 4 mm, and then the bending strength was tested according to GB / T9341-2008; the test speed was 1 mm / min, and the bending span was 64 mm;

[0048] 2. Thermal conductivity: The radiation-resistant epoxy molding compound is made into a sample with a size of 30*30*10mm, and then the thermal conductivity is tested according to GB / T40564-2021.

[0049] 3. Protection efficiency of electron irradiation: The radiation-resistant epoxy plastic packaging material and pure aluminum were placed in 1MeV electrons (model is a high-frequency high-voltage electron accelerator with a flux of 1×10 10 e / cm 2 ·s, irradiation time is 4000s) and the absorbed dose detector, the incident electron energy is fixed, and the absorbed dose after the electron passes through the radiation-resistant epoxy molding compound or the pure epoxy molding compound is collected by the dose detector. The mass thickness of the radiation-resistant epoxy molding compound and the pure epoxy molding compound is 0.1g / cm 2 ; And calculate the protection efficiency of radiation-resistant epoxy plastic packaging materials against electron radiation. The calculation formula is as follows:

[0050] Protection efficiency = (absorbed dose after electrons pass through pure epoxy molding compound - absorbed dose after electrons pass through radiation-resistant epoxy molding compound) / absorbed dose after electrons pass through pure epoxy molding compound × 100%;

[0051] Note: The preparation method of pure epoxy molding compound is as follows: first weigh 8g of epoxy resin, 20g of boron nitride, 40g of aluminum oxide, 50g of silicon dioxide, 0.5g of colorant, 5g of flame retardant, 0.4g of stress release agent, 2g of phenol linear phenolic resin, 2g of cresol linear phenolic resin, 0.2g of 2,4,6-tris(dimethylaminomethyl)phenol, 0.3g of epoxy silane coupling agent and 0.4g of Fischer-Tropsch wax, mix the above raw materials evenly, then heat and knead the mixture, cool and crush it to obtain pure epoxy molding compound.

[0052] Table 2 Performance test results of radiation-resistant epoxy molding materials obtained in Examples 1-13 and Comparative Examples 1-4

[0053]

[0054] According to the test results in Table 2, the radiation-resistant epoxy molding compound obtained by using epoxy resin, nano-tantalum, black phosphorene and carbon nanotubes in Examples 1-13 of the present application has a bending strength of 167-177MPa, a thermal conductivity of 3.0-4.1W / m.℃, and a protection efficiency of 58.5-77.8% against electron irradiation. However, the protection efficiency of the radiation-resistant epoxy molding compound obtained by Example 1 without adding nano-tantalum against electron irradiation is only 10.5%; the protection efficiency of the radiation-resistant epoxy molding compound obtained by Example 2 without adding black phosphorene against electron irradiation is only 31.9%; the protection efficiency of the radiation-resistant epoxy molding compound obtained by Example 3 without adding carbon nanotubes against electron irradiation is only 36.3%; the protection efficiency of the radiation-resistant epoxy molding compound obtained by Example 4 using epoxy resin, nano-tantalum, graphene and carbon nanotubes against electron irradiation is only 41.7%. Therefore, it is shown that the radiation-resistant epoxy molding compound prepared by epoxy resin, nano-tantalum, black phosphorene and carbon nanotubes in the present application has excellent mechanical properties, thermal conductivity and radiation resistance, and can be used as a packaging material for integrated circuits to improve the radiation resistance of integrated circuits.

[0055] The test results of Examples 1-13 show that the bending strength of the radiation-resistant epoxy molding compound obtained in Examples 2-4, 7-8, and 11-12 is 172-177MPa (≥172MPa), the thermal conductivity is 3.5-4.2W / m.℃ (≥3.5W / m.℃), and the protection efficiency against electron irradiation is 71.4-77.8% (≥70.0%); while the protection efficiency against electron irradiation of the radiation-resistant epoxy molding compound obtained in Examples 1, 5-6, 9-10, and 13 is only 58.5-68.9%. Therefore, it is explained that the application further controls the addition amount of nano-tantalum, black phosphorene, and carbon nanotubes within the following range: 10-25 parts of nano-tantalum, 0.2-0.4 parts of black phosphorene, and 0.2-0.6 parts of carbon nanotubes, and the radiation-resistant epoxy molding compound obtained has better radiation resistance.

[0056] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A radiation-resistant epoxy molding compound, characterized in that: The invention comprises the following components in parts by weight: 5-10 parts of epoxy resin, 10-25 parts of nano tantalum, 0.2-0.4 parts of black phosphorene, 0.2-0.6 parts of carbon nanotubes, 10-35 parts of boron nitride, 30-50 parts of aluminum oxide, 45-60 parts of silicon dioxide, 2-8 parts of curing agent, 0.3-0.5 parts of stress release agent, 0.1-0.3 parts of curing accelerator, 0.1-0.5 parts of coupling agent, 0.1-1 parts of colorant, 3-7 parts of flame retardant and 0.3-0.6 parts of release agent.

2. The radiation-resistant epoxy molding compound according to claim 1, characterized in that: The radiation-resistant epoxy molding compound comprises the following components in parts by weight: 8 parts of epoxy resin, 20 parts of nano-tantalum, 0.3 parts of black phosphorene, 0.4 parts of carbon nanotubes, 20 parts of boron nitride, 40 parts of aluminum oxide, 50 parts of silicon dioxide, 4 parts of curing agent, 0.4 parts of stress release agent, 0.1-0.3 parts of curing accelerator, 0.1-0.5 parts of coupling agent, 0.1-1 parts of colorant, 3-7 parts of flame retardant and 0.3-0.6 parts of release agent.

3. The radiation-resistant epoxy molding compound according to claim 1, characterized in that: The epoxy resin is selected from one or more of o-cresol epoxy resin, aliphatic glycidyl ether epoxy resin, polyphenol glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, resorcinol formaldehyde epoxy resin and trishydroxyphenylmethane epoxy resin.

4. The radiation-resistant epoxy molding compound according to claim 1, characterized in that: The curing agent is selected from one or more of phenol linear phenolic resin and its derivatives, cresol linear phenolic resin and its derivatives, monohydroxy or dihydroxy naphthol phenolic resin, biphenyl phenolic resin, aralkyl phenol epoxy resin and its derivatives, methyl hexahydrophthalic anhydride, 4,4'-diaminodiphenylmethane; the stress release agent is selected from one or more of liquid silicone oil, polysiloxane rubber powder, and silicone-modified epoxy resin.

5. The radiation-resistant epoxy molding compound according to claim 1, characterized in that: The curing accelerator is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol and imidazole accelerators; the coupling agent is selected from one or more of epoxy silane coupling agent, amino silane coupling agent and mercapto silane coupling agent; the colorant is selected from one or more of carbon black, titanium dioxide and oil-soluble aniline black; the flame retardant is selected from one or more of organic flame retardants or inorganic flame retardants; the release agent is selected from one or more of stearic acid, oxidized or non-oxidized polyethylene wax, montan wax and Fischer-Tropsch wax.

6. Use of the radiation-resistant epoxy molding compound according to any one of claims 1 to 5 in electronic device packaging.

Images