CN113421866A - Graphene radiating fin with three-dimensional structure and ultrahigh heat conduction coefficient in vertical direction for semiconductor assembly and manufacturing method thereof - Google Patents
Graphene radiating fin with three-dimensional structure and ultrahigh heat conduction coefficient in vertical direction for semiconductor assembly and manufacturing method thereof Download PDFInfo
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- CN113421866A CN113421866A CN202110652501.8A CN202110652501A CN113421866A CN 113421866 A CN113421866 A CN 113421866A CN 202110652501 A CN202110652501 A CN 202110652501A CN 113421866 A CN113421866 A CN 113421866A
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- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
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Abstract
The application relates to the field of 5G heat dissipation materials, and particularly discloses a graphene heat dissipation sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction and a manufacturing method of the graphene heat dissipation sheet. The technical key points are as follows: the graphene radiating fin with the three-dimensional structure and the ultrahigh heat conduction coefficient in the vertical direction is used in a semiconductor assembly and consists of a polyimide framework and a graphene basal body, wherein the polyimide framework and the graphene basal body form a three-dimensional bridged micro-chain lock-shaped structure. The graphene radiating fin prepared by the application has the vertical thermal conductivity of more than 100W/mK, which is about 10 times of that of a common heat conducting film, can bear larger extension and folding deformation external bending, and has excellent flexibility.
Description
Technical Field
The application relates to the technical field of 5G heat dissipation materials, in particular to a graphene heat dissipation sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction and a manufacturing method thereof.
Background
The prevalence of 5G communication, in addition to mobile phones, cloud and data center building, autonomous driving, electric vehicles, and other new-age industries, has been a big trend, with the increase in power and the thinner products, electronic instruments and devices are developed in the directions of light, thin, short, small, composite, and so on, and under high frequency operating frequencies, in the semiconductor field, heat generated by electronic components is rapidly accumulated and increased, and the problem of how to dissipate heat is increasingly manifested, which is the stability of direct products.
Thermal management materials are widely used to cool high power electronic devices and ensure that the devices operate at high speed and in an efficient manner, and have long term reliability. However, high-power and highly developed integrated devices have long faced technical engineering problems, and in addition, the development of smart devices and flexible electronic devices has driven new challenges, i.e., the design requirements of flexible substrates need to be met in addition to high heat dissipation requirements. It has become critical to develop materials with excellent thermal conductivity, efficient heat release, and easy workability to enable use in next-generation integrated circuits and flexible devices.
In high power electronic devices, metal materials have been used mostly as thermal management components in the past decades because of the high thermal conductivity of metals. However, high density, high stiffness, high corrosiveness, and limited heat dissipation factor (≈ 400W/mK) severely hamper their viable applications in high power, flexible devices.
Alternatively, graphite, graphene and composite material heat sinks have many very excellent heat dissipation characteristics, such as artificial graphite films with xy-direction thermal conductivities as high as 1600W/mK and densities of about 1.6-1.9g/cm3Meanwhile, it has the effects of flexibility, flexibility and electromagnetic wave shielding (EMI), and can satisfy the heat dissipation requirements of thin and high-functional mobile intelligence. However, in addition to the advantage that the excellent xy-direction thermal conductivity can rapidly dissipate heat in the x and y plane directions, the greatest disadvantage is that the z-direction thermal conductivity is only 3-5W/mK, and optimizing the z-axis thermal conductivity value is one of the very important issues. In addition, the structure of highly ordered and dense graphene provides a solid foundation for thermal conductivity, but some flexibility is sacrificed as a result.
In view of the above-mentioned related art, the inventors consider that the graphene film in the related art still needs to be improved in terms of thermal conductivity and flexibility in the vertical direction.
Disclosure of Invention
In order to develop a high-z-axis heat conduction value heat dissipation sheet technology which is low in cost and easy to produce in mass, and simultaneously has high vertical direction heat conduction and high flexibility, the application provides a graphene heat dissipation sheet which is used for a semiconductor assembly and has a three-dimensional structure and an ultrahigh vertical direction heat conduction coefficient, and a manufacturing method of the graphene heat dissipation sheet.
In a first aspect, the present application provides a graphene heat sink with a three-dimensional structure and an ultrahigh heat conduction coefficient in a vertical direction, which adopts the following technical scheme:
the graphene radiating fin with the three-dimensional structure and the ultrahigh heat conduction coefficient in the vertical direction is used in a semiconductor assembly and comprises a polyimide framework and a graphene base body, wherein the polyimide framework and the graphene base body form a three-dimensional bridged micro-chain lock-shaped structure.
By adopting the technical scheme, the carbon fiber structure with super-flexibility and foldability shrinkage is prepared by combining the graphene nano corrugation and the three-dimensional microstructure formed by winding the two-dimensional graphene nano sheet and the polyimide fiber. By adjusting the content of graphene oxide, a skeleton-structured sheet vertically inclined on the polyimide fiber for graphitization is established, so that a three-dimensional bridged micro-chain lock-like structure is formed. The graphene radiating fin prepared by the application has the vertical thermal conductivity of more than 100W/mK, which is about 10 times of that of a common heat conducting film, has the heat transfer and heat transfer functions of the super-metal, so that the graphene radiating fin becomes a proper Thermal Interface Material (TIM), provides a novel and effective strategy during design, and is used by next-generation thermal management equipment.
More preferably, the mass ratio of the polyimide skeleton to the graphene substrate is 1 (0.6-1).
By adopting the technical scheme, the mass ratio of the polyimide framework to the graphene substrate is controlled to be 1 (0.6-1), and the obtained graphene radiating fin has the best performance within a certain thickness range.
More preferably, the horizontal thermal conductivity of the graphene radiating fin is more than or equal to 1400W/mK, and the vertical thermal conductivity of the graphene radiating fin is more than or equal to 100W/mK; the folding times are more than 1000 times when the bearing radius is 100 mu m and the folding angle is 180 degrees through a folding resistance test.
More preferably, the preparation method of the polyimide skeleton comprises the following steps: mixing the polyimide fiber, the adhesive, the dispersant and the deionized water, dispersing for 15-30Min at the rotation speed of 800 plus 1200rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of the PET film material, and drying at the temperature of 60-80 ℃ to obtain the polyimide framework.
By adopting the technical scheme, the polyimide is used as the framework, and the polyimide fiber has a well-defined molecular structure, so that good graphitization characteristics and high-quality carbon products are provided, and the one-dimensional structure of the fiber form can provide a heat conduction effect in a fixed direction; in addition, abundant oxygen-containing and nitrogen-containing functional groups in the graphene oxide structure can have good wettability with polyimide fiber slurry, and interaction with graphene oxide is enhanced.
More preferably, the mass ratio of the polyimide fibers, the binder, the dispersant and the deionized water is 20:3:25: 50000.
By adopting the technical scheme, the polyimide skeleton prepared by adopting the raw materials according to the proportion has a good one-dimensional structure and uniform pores for embedding the graphene oxide.
More preferably, the binder is polyvinyl alcohol, and the dispersant is polyacrylamide.
By adopting the technical scheme, the polyvinyl alcohol has higher solubility in water, has good bonding force with hydrophilic fibers, and is used as an adhesive, so that the obtained polyimide framework has higher strength; the polyacrylamide has good thermal stability, can be dissolved in water in any proportion, and can have great flocculation effect with little dosage of polyacrylamide.
More preferably, the graphene substrate is a graphene oxide dispersion liquid, and the preparation method comprises the following steps:
s1, dispersing 1 part by weight of graphite powder and 3 parts by weight of sodium nitrate in 50 parts by weight of 98% sulfuric acid at an ice bath temperature of less than 2 ℃, heating to 0-5 ℃, then gradually adding 6 parts by weight of potassium permanganate within 4 hours, and continuing to react for 20 hours;
s2, pouring the reactants into 1000 parts by weight of ice water, and gradually adding 30 parts by weight of 3% hydrogen peroxide until no gas is generated;
s3, adding 500 parts by weight of deionized water, centrifuging at 1000-1200rpm until the pH of the supernatant is =7, performing 400W ultrasonic treatment to obtain a dispersion, and continuing centrifuging to remove residual precipitate to obtain the graphene oxide dispersion.
In a second aspect, the present application provides a method for preparing a graphene heat sink with a three-dimensional structure and an ultrahigh heat conduction coefficient in a vertical direction, which adopts the following technical scheme:
a preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly comprises the following steps:
(1) immersing the polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane;
(2) carbonizing the composite film at 1200 ℃ for 2h, introducing inert gas, heating to 2300 ℃, graphitizing for 1h, cooling to room temperature, and compacting for 30min under 30MPa to obtain the graphene radiating fin.
By adopting the technical scheme, the polyimide fiber slurry is dried to form the framework, the obtained polyimide framework has larger interlayer spacing and micropores, the polyimide framework is immersed into the graphene oxide dispersion liquid, the graphene oxide can be completely embedded, in the heat treatment process, the skeleton shape of the polyimide allows a part of graphene sheets to stand vertically, the planes of adjacent graphene layers form micropores with a 3D structure, the whole nano wrinkle structure is continuously bent and densified, so that the film has the capability of maintaining, and the flexibility is greatly improved.
The composite film is subjected to induced graphitization, so that the porosity and pore volume of the composite film can be increased, the pore diameter of the composite film is also enlarged through high-temperature treatment, then the heat radiating fins can be changed from bright black of the raw material to silver gray through pressure treatment, and the adjacent graphene heat radiating fins are bonded together and pressed to form a complete continuous surface with rich nano wrinkles.
In a third aspect, the present application provides another method for preparing a graphene thermal fin with a three-dimensional structure and an ultrahigh heat conduction coefficient in a vertical direction, which is used in a semiconductor assembly, and adopts the following technical scheme:
a preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly comprises the following steps:
(1) uniformly mixing the polyimide fiber slurry with the graphene oxide dispersion liquid to obtain a mixed liquid, continuously coating the mixed liquid on the surface of a PET (polyethylene terephthalate) membrane material in a roll-to-roll mode, and continuously drying for 24 hours at the temperature of 40-80 ℃ to obtain a composite membrane;
(2) carbonizing the composite film at 1200 ℃ for 2h, introducing inert gas, heating to 2300 ℃, graphitizing for 1h, cooling to room temperature, and compacting for 30min under 30MPa to obtain the graphene radiating fin.
Through adopting above-mentioned technical scheme, adopt roll-to-roll mode continuous type coating to replace polyimide skeleton dip-coating to oxidize graphite alkene dispersion, need not to make polyimide fiber slurry into polyimide skeleton, can directly mix fiber slurry and oxidation graphite alkene dispersion, then carry out the coating drying, its preparation efficiency is high, and preparation is simple, is fit for industrial large-scale production.
More preferably, the coating thickness of the mixed solution on the surface of the PET film material is 5-50 μm.
By adopting the technical scheme, the thickness of the radiating fin is controlled within the thickness interval, the coating effect is good, and the heat conducting performance and the mechanical performance are excellent.
In summary, the present application has the following beneficial effects:
(1) according to the method, a carbon fiber structure with super-flexibility and foldability shrinkage is prepared by combining graphene nano corrugation and a three-dimensional microstructure formed by winding two-dimensional graphene nano sheets and polyimide fibers, and a skeleton-shaped structure sheet vertically inclined on the polyimide fibers is established by adjusting the content of graphene oxide, so that a three-dimensional bridging micro-chain lock-shaped structure is formed, the obtained graphene radiating fin has high flexibility, and the heat conductivity in the vertical direction reaches more than 100W/mK;
(2) the application provides a preparation method of a graphene radiating fin, which comprises the steps of firstly preparing a polyimide framework and graphene oxide dispersion liquid, then soaking the polyimide framework with larger interlayer spacing and micropores into the graphene oxide dispersion liquid, and carrying out post-treatment such as graphitization to obtain the graphene radiating fin with high flexibility;
(3) the application also provides another preparation method of the graphene radiating fin, which is characterized in that the polyimide fiber slurry and the graphene oxide dispersion liquid are directly mixed and then are continuously coated on a PET sheet in a roll-to-roll mode to obtain the graphene radiating fin.
Drawings
FIG. 1 is a schematic structural view of a polyimide skeleton in example 1 of the present application;
fig. 2 is a schematic structural diagram of a graphene heat sink sheet obtained by dip-coating a polyimide skeleton with a graphene oxide dispersion liquid in embodiment 1 of the present application, where PI is the polyimide skeleton, and GO is the graphene dispersion liquid;
fig. 3 is a schematic structural view of a graphene heat sink sheet obtained by roll-to-roll coating in example 2 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
Preparation example
Preparation example 1
A polyimide skeleton, which is prepared by the following steps: mixing 0.02kg of polyimide fiber, 0.003kg of adhesive, 0.025kg of dispersant and 50kg of deionized water, dispersing for 30Min at the rotating speed of 1000rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of a PET (polyethylene terephthalate) film material, and drying at 75 ℃ to obtain the polyimide framework.
Wherein the adhesive is polyvinyl alcohol, and the dispersant is polyacrylamide.
Preparation example 2
A graphene oxide dispersion liquid is prepared by the following steps:
s1, dispersing 0.01kg of graphite powder and 0.03kg of sodium nitrate in 0.5kg of sulfuric acid with the mass fraction of 98% at the ice bath temperature of less than 2 ℃, heating to 0 ℃, then gradually adding 0.06kg of potassium permanganate in 4 hours, and continuing to react for 20 hours;
s2, pouring the reactants into 1000mL of ice water, and gradually adding 0.3kg of hydrogen peroxide with the mass fraction of 3% until no gas is generated;
and S3, adding 5kg of deionized water, centrifuging at 1100rpm until the pH of the supernatant is =7, performing 400W ultrasonic treatment to obtain a dispersion, and continuously centrifuging to remove residual precipitates to obtain the graphene oxide dispersion.
Examples
Example 1
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) immersing a polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane, wherein the mass ratio of the polyimide framework to the graphene oxide in the obtained composite membrane is 1: 0.5;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 5 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 5 ℃/min, graphitizing for 1h, and cooling to the room temperature of 25 ℃;
(3) and clamping the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the pressure of 30MPa for 30min to obtain the composite film.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is composed of a polyimide skeleton and a graphene substrate, and the polyimide skeleton and the graphene substrate form a three-dimensional bridged micro-chain-locked structure, where the polyimide skeleton is shown in fig. 1, and the graphene heat sink sheet structure is shown in fig. 2.
Example 2
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) immersing a polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane, wherein the mass ratio of the polyimide framework to the graphene oxide in the obtained composite membrane is 1: 0.6;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 5 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 5 ℃/min, graphitizing for 1h, and cooling to the room temperature of 25 ℃;
(3) and clamping the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the pressure of 30MPa for 30min to obtain the composite film.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is composed of a polyimide skeleton and a graphene substrate, and the polyimide skeleton and the graphene substrate form a three-dimensional bridged micro-chain-locked structure, where the polyimide skeleton is shown in fig. 1, and the graphene heat sink sheet structure is shown in fig. 2.
Example 3
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) immersing a polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane, wherein the mass ratio of the polyimide framework to the graphene oxide in the obtained composite membrane is 1: 0.8;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 8 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 8 ℃/min, graphitizing for 1h, and cooling to the room temperature of 25 ℃;
(3) and (3) clamping the graphitized composite membrane between two smooth tungsten sheets, and keeping the tungsten sheets under the pressure of 30MPa for 30min to obtain the composite membrane.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is composed of a polyimide skeleton and a graphene substrate, and the polyimide skeleton and the graphene substrate form a three-dimensional bridged micro-chain-locked structure, where the polyimide skeleton is shown in fig. 1, and the graphene heat sink sheet structure is shown in fig. 2.
Example 4
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) immersing a polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane, wherein the mass ratio of the polyimide framework to the graphene oxide in the obtained composite membrane is 1: 1;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 10 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, then introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 10 ℃/min, graphitizing for 1h, and cooling to the room temperature of 25 ℃;
(3) and (3) clamping the graphitized composite membrane between two smooth tungsten sheets, and keeping the tungsten sheets under the pressure of 30MPa for 30min to obtain the composite membrane.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink sheet with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is composed of a polyimide skeleton and a graphene substrate, and the polyimide skeleton and the graphene substrate form a three-dimensional bridged micro-chain-locked structure, where the polyimide skeleton is shown in fig. 1, and the graphene heat sink sheet structure is shown in fig. 2.
Example 5
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) uniformly mixing the polyimide fiber slurry and the graphene oxide dispersion liquid according to the mass ratio of 1:0.6 to obtain a mixed solution, continuously coating the mixed solution on the surface of a PET (polyethylene terephthalate) film material in a roll-to-roll mode at the speed of 3m/min, and continuously drying for 24 hours at the temperature of 40 ℃ to obtain a composite film;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 5 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 5 ℃/min, graphitizing for 1h, and cooling to room temperature;
(3) and clamping the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the pressure of 30MPa for 30min to obtain the composite film.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is prepared by mixing a polyimide fiber slurry and a graphene dispersion liquid, and the structure of the graphene heat sink is shown in fig. 3.
Example 6
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) uniformly mixing the polyimide fiber slurry and the graphene oxide dispersion liquid according to the mass ratio of 1:0.8 to obtain a mixed solution, continuously coating the mixed solution on the surface of a PET (polyethylene terephthalate) film material in a roll-to-roll mode at the speed of 8m/min, and continuously drying for 24 hours at the temperature of 80 ℃ to obtain a composite film;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 8 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 8 ℃/min, graphitizing for 1h, and cooling to room temperature;
(3) and clamping the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the pressure of 30MPa for 30min to obtain the composite film.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is prepared by mixing a polyimide fiber slurry and a graphene dispersion liquid, and the structure of the graphene heat sink is shown in fig. 3.
Example 7
A preparation method of a graphene heat sink with a three-dimensional structure and ultrahigh heat conduction coefficient in the vertical direction for a semiconductor assembly specifically comprises the following steps:
(1) uniformly mixing the polyimide fiber slurry and the graphene oxide dispersion liquid according to the mass ratio of 1:1 to obtain a mixed solution, continuously coating the mixed solution on the surface of a PET (polyethylene terephthalate) film material in a roll-to-roll mode at the speed of 8m/min, and continuously drying for 24 hours at the temperature of 80 ℃ to obtain a composite film;
(2) placing the composite membrane in a high-temperature furnace, raising the temperature to 1200 ℃ at the speed of 10 ℃/min, continuing carbonizing for 2h at the temperature of 1200 ℃, introducing nitrogen, raising the temperature to 2300 ℃ at the speed of 10 ℃/min, graphitizing for 1h, and cooling to room temperature;
(3) and clamping the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the pressure of 30MPa for 30min to obtain the composite film.
The polyimide skeleton described above in this example was prepared from preparation example 1, and the graphene oxide dispersion was prepared from preparation example 2.
The graphene heat sink with a three-dimensional structure and an ultrahigh heat conduction coefficient in the vertical direction, which is prepared in this embodiment, is prepared by mixing a polyimide fiber slurry and a graphene dispersion liquid, and the structure of the graphene heat sink is shown in fig. 3.
Performance test
The performance tests were performed on the graphene heat sinks prepared in examples 1 to 7, respectively.
The vertical thermal conductivity was measured according to "measurement of thermal conductivity of graphene powder" (established by standards of the society for the Special Equipment and industry, Guangdong province). The test results are reported in table 1 below.
Table 1 results of performance testing
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Vertical thermal conductivity (W/mK) | 150 | 162 | 163 | 160 | 154 | 152 | 148 |
| Folding times (times) of 100 μm and 180 ° | 1019 | 1200 | 1257 | 1104 | 1043 | 1027 | 1010 |
| Resistance increase rate after 1000 times of folding | 11.0% | 7.5% | 7.1% | 8.2% | 9.6% | 10.5% | 11.3% |
As can be seen from the test results in table 1 above, the graphene heat sinks prepared in examples 1 to 4 have slightly better vertical thermal conductivity and flexibility than those of examples 5 to 7; the method for immersing the polyimide framework into the graphene dispersion liquid and the method for mixing and molding the polyimide fiber slurry and the graphene dispersion liquid are explained, and the performance of the radiating fin prepared by the polyimide fiber slurry is superior to that of the radiating fin prepared by the graphene dispersion liquid.
Among them, the best example of example 3 is that the vertical thermal conductivity can reach 163W/mK, the radius is 100 μm, the bending angle is 180 degrees, the folding reaches 1257 times of cyclic bending, and the resistance after 1000 times of cyclic bending is increased by only 7.1%.
In conclusion, the graphene heat dissipation sheet prepared by the method has excellent heat conduction performance, excellent flexibility and mechanical property, and is suitable for heat dissipation of related equipment in a semiconductor assembly.
The above description is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above embodiments, and all technical solutions belonging to the idea of the present application belong to the protection scope of the present application. It should be noted that several improvements and modifications to the present application without departing from the principles of the present application will occur to those skilled in the art, and such improvements and modifications should also be considered within the scope of the present application.
Claims (10)
1. The graphene radiating fin with the three-dimensional structure and the ultrahigh heat conduction coefficient in the vertical direction is used in a semiconductor assembly and is characterized by comprising a polyimide framework and a graphene base body, wherein the polyimide framework and the graphene base body form a three-dimensional bridged micro-chain lock-shaped structure.
2. The graphene heat sink with the ultra-high vertical thermal conductivity coefficient for the semiconductor assembly as claimed in claim 1, wherein the mass ratio of the polyimide skeleton to the graphene substrate is 1 (0.6-1).
3. The graphene heat sink with the ultrahigh vertical thermal conductivity coefficient for the semiconductor assembly as claimed in claim 1, wherein the horizontal thermal conductivity of the graphene heat sink is more than or equal to 1400W/mK, and the vertical thermal conductivity of the graphene heat sink is more than or equal to 100W/mK; the folding times are more than 1000 times when the bearing radius is 100 mu m and the folding angle is 180 degrees through a folding resistance test.
4. The graphene heat sink sheet with a three-dimensional structure and an ultrahigh vertical thermal conductivity coefficient for use in a semiconductor assembly according to claim 1, wherein the polyimide skeleton is prepared by a method comprising: mixing the polyimide fiber, the adhesive, the dispersant and the deionized water, dispersing for 15-30Min at the rotation speed of 800 plus 1200rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of the PET film material, and drying at the temperature of 60-80 ℃ to obtain the polyimide framework.
5. The graphene heat sink with the ultra-high vertical thermal conductivity coefficient for the semiconductor assembly as claimed in claim 4, wherein the mass ratio of the polyimide fibers, the binder, the dispersant and the deionized water is 20:3:25: 50000.
6. The graphene heat sink with a three-dimensional structure and an ultrahigh vertical thermal conductivity coefficient for use in a semiconductor assembly according to claim 4, wherein the binder is polyvinyl alcohol and the dispersant is polyacrylamide.
7. The graphene heat sink sheet with a three-dimensional structure and an ultrahigh vertical thermal conductivity coefficient for use in a semiconductor assembly according to claim 1, wherein the graphene matrix is a graphene oxide dispersion liquid, and the preparation method comprises:
s1, dispersing 1 part by weight of graphite powder and 3 parts by weight of sodium nitrate in 50 parts by weight of 98% sulfuric acid at an ice bath temperature of less than 2 ℃, heating to 0-5 ℃, then gradually adding 6 parts by weight of potassium permanganate within 4 hours, and continuing to react for 20 hours;
s2, pouring the reactants into 1000 parts by weight of ice water, and gradually adding 30 parts by weight of 3% hydrogen peroxide until no gas is generated;
s3, adding 500 parts by weight of deionized water, centrifuging at 1000-1200rpm until the pH of the supernatant is =7, performing 400W ultrasonic treatment to obtain a dispersion, and continuing centrifuging to remove residual precipitate to obtain the graphene oxide dispersion.
8. The method of fabricating a graphene thermal fin for a semiconductor package having a three-dimensional structure with an ultra-high vertical thermal conductivity as recited in any one of claims 1 to 7, comprising the steps of:
(1) immersing the polyimide framework into the graphene oxide dispersion liquid, and keeping for 15min to form a composite membrane;
(2) carbonizing the composite film at 1200 ℃ for 2h, introducing inert gas, heating to 2300 ℃, graphitizing for 1h, cooling to room temperature, and compacting for 30min under 30MPa to obtain the graphene radiating fin.
9. The method of fabricating a graphene thermal fin for a semiconductor package having a three-dimensional structure with an ultra-high vertical thermal conductivity as recited in any one of claims 1 to 7, comprising the steps of:
(1) uniformly mixing the polyimide fiber slurry with the graphene oxide dispersion liquid to obtain a mixed liquid, continuously coating the mixed liquid on the surface of a PET (polyethylene terephthalate) membrane material in a roll-to-roll mode, and continuously drying for 24 hours at the temperature of 40-80 ℃ to obtain a composite membrane;
(2) carbonizing the composite film at 1200 ℃ for 2h, introducing inert gas, heating to 2300 ℃, graphitizing for 1h, cooling to room temperature, and compacting for 30min under 30MPa to obtain the graphene radiating fin.
10. The method of claim 9, wherein the mixed solution is coated on the surface of the PET film to a thickness of 5 to 50 μm.
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