CN115926224A - High-thermal-conductivity prepreg for packaging carrier plate and manufacture of copper-clad plate using prepreg - Google Patents
High-thermal-conductivity prepreg for packaging carrier plate and manufacture of copper-clad plate using prepreg Download PDFInfo
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- CN115926224A CN115926224A CN202211287466.5A CN202211287466A CN115926224A CN 115926224 A CN115926224 A CN 115926224A CN 202211287466 A CN202211287466 A CN 202211287466A CN 115926224 A CN115926224 A CN 115926224A
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- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a prepreg for a high-thermal-conductivity packaging carrier plate and a manufacturing method of a copper-clad plate using the prepreg, and belongs to the technical field of electronic materials. The prepreg comprises a reinforced fiber cloth core and a resin layer coated outside the reinforced cloth core; the reinforced cloth core is silicon carbide fiber cloth, and the silicon carbide fiber cloth is modified silicon carbide fiber cloth subjected to surface reinforcing modification treatment; according to the invention, the silicon carbide fiber cloth is modified, so that adverse effects caused by high dielectric constant of silicon carbide are reduced, the bonding force between the silicon carbide fiber and matrix resin, and the compatibility and the cohesiveness between the heat-conducting filler and the matrix resin and between the heat-conducting filler and the silicon carbide fiber are increased, the peeling strength of the prepreg and the copper foil can be improved, and the heat conductivity coefficient of the copper-clad plate can be further improved.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a prepreg for a high-thermal-conductivity packaging carrier plate and a manufacturing method of a copper-clad plate using the prepreg.
Background
With the continuous development of microelectronic technology, the variety of electronic devices is diversified, the integration density is increased, and heat dissipation becomes one of important influencing factors in the design and manufacture of high-density devices, particularly high-power devices such as LEDs, power modules, cameras and the like, and the requirements on heat dissipation are higher than those of common devices. The thermal conductivity of the package carrier is improved, which is one of the main approaches for high power applications.
The prepreg and the copper-clad plate are basic materials for manufacturing the packaging carrier plate, and the prepreg and the copper-clad plate are prepared by taking glass fiber cloth as a reinforcing framework material at present, but the glass fiber cloth has low thermal conductivity which is usually 0.2-2.2W/m.K, and is difficult to meet the heat dissipation requirement. Wong C P, bollamparyr S, journal of Applied Polymer Science,2015,74 (14): 3396-3403 describes a method for improving the thermal conductivity of a resin substrate by changing the molecular chain structure of the Polymer itself to improve the order of the physical structure, reduce the phonon scattering and reduce the thermal resistance of the Polymer itself, but this method is not easy to implement, and has high cost and is not suitable for industrial production. Documents Chen H, ginzburg V, progress in Polymer Science,2016,59, and Gao J S, shiu S C, journal of Composite Materials,2013,47 (4): 449-458: the common heat-conducting fillers such as silicon carbide and boron nitride are added, the heat-conducting performance of the composite material can be improved by utilizing the interaction of the resin base material and the heat-conducting fillers, but the method needs to be filled with a large amount of heat-conducting filler powder, the heat-conducting filler powder is poor in dispersion uniformity, physical properties such as resin dielectric, hardness and thermal expansion and contraction rate can be changed, and processes such as drilling, pressing and hole metallization in carrier plate manufacturing are influenced.
In recent years, various composite materials with an isolation structure show excellent heat conduction and electric conductivity, such as silicon carbide fiber materials, which have the advantages of strong high-temperature bearing capacity, high hardness, oxidation resistance, wear resistance, large heat conductivity, small thermal expansion coefficient, chemical corrosion resistance and the like, and the heat conductivity of the materials can reach 16.7W/m.K, and specific values are shown in Table 1. The composite material has a larger length-diameter ratio, can effectively contact with each other to form a heat-conducting network, and the compounding of the silicon carbide fiber and the heat-conducting filler can not only increase the contact area of the silicon carbide fiber and the matrix resin, but also effectively promote the directional distribution of the heat-conducting particles so as to improve the heat-conducting property of the composite material.
TABLE 1 physical properties such as thermal conductivity of each material
Patent CN202210170426 discloses a high-frequency copper-clad plate of high heat conduction hydrocarbon resin base prepreg and preparation thereof, adopts carborundum fiber cloth to simply replace glass fiber cloth, obtains the high-frequency copper-clad plate through impregnating hydrocarbon resin glue solution, and this high-frequency copper-clad plate has advantages such as low dielectric constant, low dielectric loss, high heat conductivility, high peel strength. However, since silicon carbide has a dielectric constant of 9.66 to 10.03 (300K, table 1), it is a high dielectric material and is not suitable for high-frequency and high-speed signal transmission. Secondly, the prepreg and the copper-clad plate thereof have high chemical stability, so that the catalyst is difficult to adsorb during the metallization of through holes and blind holes which are interconnected among layers, copper deposition is not facilitated, and the silicon carbide fiber cloth has the problems of poor bonding force with resin and the like, so that the application of the silicon carbide prepreg and the copper-clad plate in a packaging carrier plate is limited.
Disclosure of Invention
The invention aims to: the prepreg for the high-heat-conduction packaging carrier plate is characterized in that surface enhancement modification treatment is carried out on the silicon carbide fiber cloth, adverse effects caused by high dielectric constant and high chemical stability of silicon carbide are reduced, the binding force between the silicon carbide fiber and matrix resin, the compatibility and the cohesiveness between the heat-conduction filler and the matrix resin and between the heat-conduction filler and the silicon carbide fiber are increased, and the peel strength, the tensile strength and the heat-conduction performance of a copper-clad plate of the silicon carbide fiber cloth and a copper foil are improved.
Another object of the invention is: the prepared silicon carbide fiber copper-clad plate has high heat-conducting property, low dielectric constant and dielectric loss and better through hole metallization characteristic, and is particularly suitable for manufacturing the carrier plate for packaging high-power devices such as LEDs, PICs and the like. .
In order to realize the purpose, the invention adopts the following technical scheme:
a prepreg for a high-thermal-conductivity packaging carrier plate comprises a reinforced fiber cloth core and a resin layer coated outside the reinforced cloth core;
the reinforced cloth core is silicon carbide fiber cloth, and the silicon carbide fiber cloth is modified silicon carbide fiber cloth subjected to surface reinforcing modification treatment;
the resin layer is obtained by curing and drying a resin glue solution, and the resin glue solution comprises the following components in parts by weight: cyanate ester: 15-30 parts by weight of hydrocarbon resin: 30-60 parts by weight of heat-conducting powder: 5-10 parts by weight of curing agent: 5-15 parts by weight, solvent: 30 to 50 parts by weight.
Further, the preparation method of the modified silicon carbide fiber cloth comprises the following steps:
s1, soaking silicon carbide fiber pulp in 0.1-3 mg/mL polyphenol water solution A for 20-30 min, adding a solution containing a water-based adhesive, papermaking and forming, and performing vacuum drying to obtain a silicon carbide fiber cloth core;
s2, putting the reinforced cloth core into dipping slurry C, dipping for 30-60 min, taking out, and vacuum drying to obtain the modified silicon carbide fiber cloth core, wherein the dipping slurry C is 20-30 parts by mass of silicate solution and 30-60K 2 Ti 6 O 13 The pH value of the dipping slurry C is controlled within the range of 7 to 9 by using silicic acid.
Furthermore, the polyphenol solution A is one or a mixture of more of tannic acid, gentisic acid, ferulic acid, gallic acid and protocatechuic acid.
Further, the curing agent is one or more of triallyl isocyanurate, dicumyl peroxide and trimethylolpropane triacrylate.
Further, the heat-conducting powder is one or more of hexagonal boron nitride, alumina, spherical aluminum nitride and boron aluminate whiskers, and the particle size of the heat-conducting filler is 0.5-5 um.
Further, the prepreg for the high-thermal-conductivity packaging carrier plate is prepared by the following steps:
s1, adding 15-30 parts by weight of cyanate ester and 30-60 parts by weight of hydrocarbon resin into a solvent at the temperature of 70-110 ℃ for full dissolution, heating the solvent to 100-130 ℃, adding 5-10 parts by weight of heat-conducting powder, 1-5 parts by weight of curing agent and the rest solvent, keeping the temperature at 100-130 ℃, and stirring until the mixture is uniform to obtain a resin glue solution;
and S2, placing the reinforced cloth core into the resin glue solution obtained in the step S1, soaking for 10-30 min, curing at 120-200 ℃ for 1-10 h, and cooling to room temperature after curing to obtain the high-thermal-conductivity resin-based prepreg.
Furthermore, the heat-conducting powder is hexagonal boron nitride, and is added into the resin glue solution after ball milling, drying and silane surface treatment in sequence.
The invention also provides a copper-clad plate prepared by using the prepreg for the high-thermal-conductivity packaging carrier plate, and the copper-clad plate is prepared by the following steps: the high-thermal-conductivity resin-based prepreg and the copper foil are symmetrically overlapped, then the prepreg and the copper foil are placed into a hot press, and the copper-clad plate is obtained by hot pressing after vacuumizing, wherein the conditions of the hot pressing process are as follows: the temperature is 150-350 ℃, the pressing time is 2-8 h, and the pressure is 1-50 MPa.
Due to the adoption of the technical scheme, the invention has the following advantages:
1. the prepreg for the high-thermal-conductivity packaging carrier plate comprises a reinforcing cloth core and a resin layer, wherein the reinforcing cloth core is a silicon carbide fiber cloth core, and the silicon carbide fiber has excellent performances of high thermal conductivity coefficient, high strength, high modulus, high temperature resistance, oxidation resistance, low thermal expansion coefficient and the like, and is beneficial to design and manufacture of high-power and high-density devices.
2. The treatment liquid used in the modification treatment process of the reinforced cloth core comprises silicate solution, composite glass powder and acetone solution. Silicates are the most widely used materials in inorganic adhesives, havingRegular tetrahedronThe structure improves the porosity of a matrix and reduces the density of the material by introducing air pores, so that the number of polarized molecules in unit volume is reduced, and the dielectric constant of the material is reduced. Meanwhile, the adhesive has good adhesion, and can meet the adhesion requirements of silicon carbide and common materials such as ceramics, glass, packaging materials, metals and the like. However, with a single silicate adhesive, the bond strength tends to decrease over time, and K is 2 Ti 6 O 13 The whisker modified silicate solution can improve the stability of the silicate adhesive to a certain extent. The glass powder also has good affinity and good compatibility with resin, and is a good adhesive. Silicon carbide fibers have the advantage of high thermal conductivity, while also having the disadvantages of high dielectric constant and poor bonding to resins. The solution such as silicate is utilized to carry out surface enhancement coating modification treatment, thus reducing the adverse effect caused by the high dielectric constant of the silicon carbide, increasing the bonding force between the silicon carbide fiber and matrix resin, the compatibility and the cohesiveness between the heat-conducting filler and the matrix resin and between the heat-conducting filler and the silicon carbide fiber, and further improving the heat conductivity coefficient of the copper-clad plate.
3. According to the invention, the reinforcing cloth core is preferably prepared by taking polyphenol as a modified solution, after impregnation, the polyphenol is attached to the surface of the composite fiber, and when a prepreg is prepared, the polyphenol on the surface of the composite fiber can participate in the cross-linking curing reaction of hydrocarbon resin and cyanate ester, so that the bonding force between the silicon carbide fiber and the resin can be further enhanced.
Drawings
FIG. 1 is a comparison of samples of silicon carbide fiber substrate subjected to reinforcing modification treatment and samples of silicon carbide fiber substrate not subjected to reinforcing modification treatment, wherein A is cracking of the silicon carbide fiber substrate after tin floating of the samples which are not subjected to reinforcing modification treatment; b is that the sample is not cracked after tin floating of the sample is treated by the silicon carbide fiber for enhancing and modifying;
FIG. 2 is a diagram of an actual product prepared by using the copper-clad plate obtained by the method of the present invention, wherein A is a diagram of an actual product of a power management chip carrier plate prepared by using the copper-clad plate obtained by the method; b is a real object diagram of the packaging carrier plate prepared by the copper-clad plate obtained by the method.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention as claimed.
Example 1
The prepreg for the high-thermal-conductivity packaging carrier plate provided by the embodiment comprises a reinforced fiber cloth core and a resin layer coated outside the reinforced cloth core; the reinforced cloth core is silicon carbide fiber cloth, and the silicon carbide fiber cloth is modified silicon carbide fiber cloth with the surface subjected to surface reinforcing modification treatment; the resin layer is obtained by drying resin glue solution, and the resin glue solution comprises the following components in parts by weight: cyanate ester: 25 parts by weight, hydrocarbon resin: 30 parts by weight, heat conductive powder: 5 parts by weight, curing agent: 5 parts by weight, solvent: 30 parts by weight.
The preparation method of the modified silicon carbide fiber cloth comprises the following steps:
s1, soaking silicon carbide fiber pulp in 0.1mg/mL polyphenol water solution for 20min, adding a water-based adhesive, making paper, forming, and drying in vacuum to obtain a silicon carbide fiber cloth core;
s2, placing the reinforced cloth core into the dipping slurry for dipping for 30min, and drying in vacuum to obtain the modified silicon carbide fiber cloth core, wherein the dipping solution is 40 parts by mass of K 2 Ti 6 O 13 Whisker modified silicate solution and 20 parts by mass of composite glass powder. . The pH of the impregnation solution was 8.
The prepreg for the high-thermal-conductivity packaging carrier plate is prepared by the following steps:
s1, adding 15 parts by mass of cyanate ester and 30 parts by mass of hydrocarbon resin into a 100-DEG C solvent for sufficient dissolution, heating the solvent to 110 ℃, adding 8 parts by mass of hexagonal boron nitride, 3 parts by weight of a curing agent and the rest of the solvent, keeping the temperature at 110 ℃, and stirring until the mixture is uniform to obtain a resin glue solution;
and S2, placing the reinforced cloth core into the resin glue solution obtained in the step S1, soaking for 30min, curing at 185 ℃ for 3h, and cooling to room temperature after curing to obtain the high-thermal-conductivity resin-based prepreg.
The invention also provides a copper-clad plate prepared by using the prepreg for the high-thermal-conductivity packaging carrier plate, and the copper-clad plate is prepared by the following steps: the high-thermal-conductivity resin-based prepreg and the copper foil are symmetrically overlapped, then the prepreg and the copper foil are placed into a hot press, and the copper-clad plate is obtained by hot pressing after vacuumizing, wherein the conditions of the hot pressing process are as follows: the temperature is 210 ℃, the pressing time is 3.5h, and the pressure is 25MPa.
Comparative example 1
The prepreg for the package carrier provided by the embodiment comprises a reinforced fiber cloth core and a resin layer coated outside the reinforced fiber cloth core; the reinforced cloth core is made of silicon carbide fiber cloth, the resin layer is obtained by drying resin glue liquid, and the resin glue liquid comprises the following components in parts by weight: cyanate ester: 25 parts by weight, hydrocarbon resin: 30 parts by weight, heat conductive powder: 5 parts by weight, curing agent: 5 parts by weight, solvent: 30 parts by weight.
The preparation method of the silicon carbide fiber cloth comprises the following steps:
s1, soaking silicon carbide fiber pulp in 0.1mg/mL polyphenol water solution for 20min, adding a water-based adhesive, making paper, molding, and drying in vacuum to obtain a silicon carbide fiber cloth core;
the prepreg for the high-thermal-conductivity packaging carrier plate is prepared by the following steps:
s1, adding 15 parts by mass of cyanate ester and 30 parts by mass of hydrocarbon resin into a 100-DEG C solvent for full dissolution, heating the solvent to 110 ℃, adding 8 parts by mass of hexagonal boron nitride, 3 parts by mass of a curing agent and the rest of the solvent, keeping the temperature at 110 ℃, and stirring until the mixture is uniform to obtain a resin glue solution;
and S2, placing the reinforced cloth core into the resin glue solution obtained in the step S1, soaking for 30min, curing at 185 ℃ for 3h, and cooling to room temperature after curing to obtain the high-thermal-conductivity resin-based prepreg.
The invention also provides a copper-clad plate prepared by using the prepreg for the high-thermal-conductivity packaging carrier plate, and the copper-clad plate is prepared by the following steps: the high-thermal-conductivity resin-based prepreg and the copper foil are symmetrically overlapped, then the prepreg and the copper foil are placed into a hot press, and the copper-clad plate is obtained by hot pressing after vacuumizing, wherein the conditions of the hot pressing process are as follows: the temperature is 210 ℃, the pressing time is 3.5h, and the pressure is 25MPa.
Comparative example 2
The prepreg for the package carrier board provided by the embodiment comprises a reinforced fiber cloth core and a resin layer coated outside the reinforced cloth core; the reinforced cloth core is glass fiber cloth, the resin layer is obtained by drying resin glue solution, and the resin glue solution comprises the following components in parts by weight: cyanate ester: 25 parts by weight of a hydrocarbon resin: 30 parts by weight, heat conductive powder: 5 parts by weight, curing agent: 5 parts by weight, solvent: 30 parts by weight.
The preparation method of the glass fiber cloth comprises the following steps:
s1, soaking glass fiber pulp in 0.1mg/mL polyphenol water solution for 20min, adding a water-based adhesive, making and molding, and performing vacuum drying to obtain a glass fiber cloth core;
the prepreg for the high-thermal-conductivity packaging carrier plate is prepared by the following steps:
s1, adding 15 parts by mass of cyanate ester and 30 parts by mass of hydrocarbon resin into a 100-DEG C solvent for sufficient dissolution, heating the solvent to 110 ℃, adding 8 parts by mass of hexagonal boron nitride, 3 parts by weight of a curing agent and the rest of the solvent, keeping the temperature at 110 ℃, and stirring until the mixture is uniform to obtain a resin glue solution;
and S2, placing the reinforced cloth core into the resin glue solution obtained in the step S1, soaking for 30min, curing at 185 ℃ for 3h, and cooling to room temperature after curing to obtain the high-thermal-conductivity resin-based prepreg.
And symmetrically superposing the resin-based prepregs prepared in the comparative example 1 and the resin-based prepregs prepared in the comparative example 2 with the copper foil, putting the prepregs into a hot press, vacuumizing and carrying out hot pressing to obtain the copper-clad plate. The hot pressing process meets the following conditions: the temperature is 210 ℃, the pressing time is 3.5h, and the pressure is 25Mpa.
The test methods of comparative examples 1 and 2 were performed according to the IPC-TM 650 related requirements.
And comparing the performance of the copper-clad plates in the example 1, the comparative example 1 and the comparative example 2. The comparative results are shown in Table 2.
Table 2 shows a comparison of the properties of the three examples
Therefore, it is easy to find that the silicon carbide fiber copper-clad plate subjected to surface enhancement modification treatment provided by the embodiment has good comprehensive performance, has high heat conductivity, can achieve a heat conductivity coefficient of 12.8W/m.K, and also has low dielectric constant and dielectric loss, and better through hole metallization characteristics (the highest copper rear backlight index). In addition, the silicon carbide fiber copper-clad plate subjected to the surface enhancement modification treatment provided by the embodiment is not easy to crack, and the copper-clad plate not subjected to the surface enhancement modification treatment is easy to crack inside, as shown in fig. 1, which illustrates that the silicon carbide fiber surface enhancement modification treatment enhances the bonding capability of the silicon carbide fiber and the resin. Therefore, the improved copper-clad plate provided by the embodiment is particularly suitable for manufacturing the carrier plate for packaging high-power devices such as an LED, a PIC and the like, as shown in fig. 2.
The foregoing embodiments are provided merely to illustrate the principles and efficacy of the invention, and not to limit the invention, but rather to facilitate an understanding of the principles of the invention, and the scope of the invention is not limited to the configurations and embodiments described above, and those skilled in the art can make various other specific modifications and combinations without departing from the spirit of the invention, and still be within the scope of the invention.
Claims (8)
1. The utility model provides a high thermally conductive encapsulation prepreg for carrier plate, includes reinforcing fiber cloth core and the cladding at the outside resin layer of reinforcing cloth core, its characterized in that:
the reinforced cloth core is silicon carbide fiber cloth, and the silicon carbide fiber cloth is modified silicon carbide fiber cloth subjected to surface reinforcing modification treatment;
the resin layer is obtained by curing and drying resin glue solution, and the resin glue solution comprises the following components in parts by weight: cyanate ester: 15-30 parts by weight of hydrocarbon resin: 30-60 parts by weight of heat-conducting powder: 5-10 parts by weight of curing agent: 5-15 parts by weight, solvent: 30 to 50 portions.
2. The prepreg for the packaging carrier plate with high thermal conductivity according to claim 1, wherein the modified silicon carbide fiber cloth is prepared by the following steps:
s1, soaking silicon carbide fiber pulp in 0.1-3 mg/mL polyphenol water solution A for 20-30 min, adding a solution containing a water-based adhesive, papermaking, forming and vacuum drying to obtain a silicon carbide fiber cloth core;
s2, placing the reinforced cloth core into a dipping slurry C, dipping for 30-60 min, taking out, and drying in vacuum to obtain the modified silicon carbide fiber cloth core, wherein the dipping slurry C is 20-30 parts by mass of silicate solution and 30-60K 2 Ti 6 O 13 The pH value of the dipping slurry C is controlled within the range of 7 to 9 by using silicic acid.
3. The prepreg according to claim 2, wherein: the polyphenol solution A is one or more of tannic acid, gentisic acid, ferulic acid, gallic acid and protocatechuic acid.
4. The prepreg according to claim 1, wherein: the curing agent is one or more of triallyl isocyanurate, dicumyl peroxide and trimethylolpropane triacrylate.
5. The prepreg according to claim 1, wherein: the heat-conducting powder is one or more of hexagonal boron nitride, alumina, spherical aluminum nitride and boron aluminate whiskers, and the particle size of the heat-conducting filler is 0.5-5 um.
6. The prepreg according to claim 1, wherein: the prepreg for the high-thermal-conductivity packaging carrier plate is prepared by the following steps:
s1, adding 15-30 parts by weight of cyanate ester and 30-60 parts by weight of hydrocarbon resin into a solvent at the temperature of 70-110 ℃ for full dissolution, heating the solvent to 100-130 ℃, adding 5-10 parts by weight of heat-conducting powder, 1-5 parts by weight of curing agent and the rest solvent, keeping the temperature at 100-130 ℃, and stirring until the mixture is uniform to obtain a resin glue solution;
and S2, placing the reinforced cloth core into the resin glue solution obtained in the step S1, soaking for 10-30 min, curing at 120-200 ℃ for 1-10 h, and cooling to room temperature after curing to obtain the high-thermal-conductivity resin-based prepreg.
7. The prepreg according to claim 6, wherein: the heat conducting powder is hexagonal boron nitride, and the hexagonal boron nitride is added into resin glue solution after ball milling, drying and silane surface treatment in sequence.
8. The copper-clad plate prepared by using the prepreg for the high-thermal-conductivity packaging carrier plate according to claim 1 is characterized by being prepared by the following steps: the high-thermal-conductivity resin-based prepreg and the copper foil are symmetrically overlapped, then the prepreg and the copper foil are placed into a hot press, and the copper-clad plate is obtained by hot pressing after vacuumizing, wherein the conditions of the hot pressing process are as follows: the temperature is 150-350 ℃, the pressing time is 2-8 h, and the pressure is 1-50 MPa.
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