CN113421866B - Graphene cooling fin with three-dimensional structure and ultrahigh vertical heat conduction coefficient for semiconductor component and manufacturing method thereof - Google Patents
Graphene cooling fin with three-dimensional structure and ultrahigh vertical heat conduction coefficient for semiconductor component and manufacturing method thereof Download PDFInfo
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- CN113421866B CN113421866B CN202110652501.8A CN202110652501A CN113421866B CN 113421866 B CN113421866 B CN 113421866B CN 202110652501 A CN202110652501 A CN 202110652501A CN 113421866 B CN113421866 B CN 113421866B
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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 vertical heat conduction coefficient in a semiconductor component and a manufacturing method thereof. The technical key points are as follows: the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient in the semiconductor component consists of a polyimide framework and a graphene body, wherein the polyimide framework and the graphene body form a three-dimensional bridged micro-chain lock-shaped structure. The graphene cooling fin prepared by the method has the vertical heat conductivity reaching more than 100W/mK, 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 vertical heat conduction coefficient in a semiconductor assembly and a manufacturing method thereof.
Background
The popularity of 5G communication, except for mobile phones, is a great trend in new times of industries such as cloud end and data center construction, automatic driving, electric vehicles and the like, along with the increase of power and the thinner products, electronic instruments and equipment develop towards the directions of light, thin, short, small, compound and the like, and under the high-frequency working frequency, the heat generated by electronic components in the semiconductor field is rapidly accumulated and increased, and the problem of how to spread the heat is increasingly displayed, so that the stability of the products is directly improved.
Thermal management materials are widely used to cool high power electronic devices and to ensure that the devices operate in a high speed and efficient manner and with long-term reliability. However, the development of high-power and highly-developed integrated devices has long faced technical engineering problems, and in addition, the development of intelligent devices and flexible electronic devices has driven new challenges, namely, requirements of high heat dissipation and design requirements of flexible substrates are met. It has become critical to develop materials with excellent thermal conductivity, efficient heat release, and easy workability that enable use in next generation integrated circuits and flexible devices.
In high power electronics, metallic materials have been mostly used as thermal management components in the last decades because of their high thermal conductivity. However, high density, high stiffness, high corrosiveness, and limited heat dissipation coefficient (≡400W/mK) severely hamper their viable use in high power, flexible devices.
Alternatively, graphite, graphene and their composite heat sinks have many very excellent heat dissipation properties, such as artificial graphite films, which are xy-direction thermally conductiveThe rate is up to 1600W/mK, and the density is about 1.6-1.9g/cm 3 Meanwhile, the heat dissipation device has the effects of softness, flexibility and electromagnetic wave shielding (EMI), and can meet the heat dissipation requirements of thin and high-functional action intelligence. However, the heat conduction value in the z-axis is very important, and the greatest disadvantage of the heat conduction value in the x-and y-plane is that the heat conduction value in the z-axis is only 3-5W/mK, besides the advantage that the heat conduction in the xy-direction can be rapidly dissipated. In addition, the highly ordered and dense graphene structure provides a solid basis for thermal conductivity, but therefore sacrifices some flexibility.
With respect to the related art among the above, the inventors consider that the graphene film in the related art is currently still to be improved in terms of thermal conductivity and flexibility in the vertical direction.
Disclosure of Invention
In order to develop a low-cost and easy-to-mass-produce high z-axis heat conduction value radiating fin technology, and simultaneously has high vertical heat conduction and high flexibility, the application provides a graphene radiating fin with a three-dimensional structure and an ultrahigh vertical heat conduction coefficient and a manufacturing method thereof.
In a first aspect, the present application provides a graphene heat sink with a three-dimensional structure and an ultra-high vertical heat conduction coefficient for use in a semiconductor assembly, which adopts the following technical scheme:
a graphene cooling fin with a three-dimensional structure and an ultrahigh vertical heat conduction coefficient used in a semiconductor component is composed of 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 folding shrinkage is prepared by utilizing the combination of the graphene nano-corrugations and the three-dimensional microstructure formed by winding the two-dimensional graphene nano-sheets and polyimide fibers. And (3) by adjusting the content of graphene oxide, a framework-like structure sheet which is vertically inclined and graphitized on polyimide fibers is established, so that a three-dimensional bridged micro-chain lock-like structure is formed. The graphene cooling fin prepared by the method has the vertical heat conductivity reaching more than 100W/mK, is about 10 times of that of a common heat conducting film, has the heat transfer and heat transfer functions of super metal, becomes a proper Thermal Interface Material (TIM), and provides a novel and effective strategy for next-generation heat management equipment in design.
More preferably, the mass ratio of the polyimide skeleton to the graphene matrix is 1 (0.6-1).
By adopting the technical scheme, the mass ratio of the polyimide framework to the graphene matrix is controlled to be 1 (0.6-1), and the obtained graphene cooling fin has the best performance within a certain thickness range.
Further preferably, the horizontal heat conductivity of the graphene radiating fin is more than or equal to 1400W/mK, and the vertical heat conductivity is more than or equal to 100W/mK; the folding endurance test shows that the folding times are more than 1000 times when the bearing radius is 100 mu m and the folding angle is 180 degrees.
Further preferably, the preparation method of the polyimide skeleton comprises the following steps: mixing polyimide fiber, adhesive, dispersing agent and deionized water, dispersing for 15-30Min at 800-1200rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of PET film material, and drying at 60-80 ℃ to obtain the polyimide skeleton.
By adopting the technical scheme, polyimide is adopted as a framework, and because polyimide fibers have well-defined molecular structures, good graphitization characteristics and high-quality carbon products are provided, and the one-dimensional structure of the fiber form of the polyimide fibers can provide a heat conduction effect in a fixed direction; in addition, the graphene oxide structure contains rich oxygen-containing and nitrogen-containing functional groups, so that the polyimide fiber slurry has good wettability with the polyimide fiber slurry, and the interaction with the graphene oxide is enhanced.
It is further preferred that the mass ratio of the polyimide fiber, the binder, the dispersant and the deionized water is 20:3:25:50000.
By adopting the technical scheme, the polyimide skeleton prepared from the raw materials in the proportion has a good one-dimensional structure and uniform oxygen supply graphene embedded pores.
Further preferably, the binder is polyvinyl alcohol, and the dispersant is polyacrylamide.
By adopting the technical scheme, the polyvinyl alcohol has higher solubility in water and has good binding power with hydrophilic fibers, and the polyimide skeleton obtained by taking the polyvinyl alcohol as an adhesive has higher strength; the polyacrylamide has good thermal stability, can be dissolved in water in any proportion, and has extremely large flocculation effect due to extremely small dosage.
Further preferably, the graphene matrix is 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 sulfuric acid with the mass fraction of 98% under the condition that the ice bath temperature is less than 2 ℃, heating to 0-5 ℃, then gradually adding 6 parts by weight of potassium permanganate in 4 hours, and continuing to react for 20 hours;
s2, pouring the reactant 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=7 of the supernatant liquid is obtained, performing 400W ultrasonic treatment to obtain a dispersion liquid, and continuing centrifuging to remove residual sediment to obtain the graphene oxide dispersion liquid.
In a second aspect, the present application provides a method for preparing a graphene heat sink with a three-dimensional structure and an ultra-high vertical heat conduction coefficient in a semiconductor component, which adopts the following technical scheme:
a preparation method of a graphene radiating fin with a three-dimensional structure and an ultrahigh vertical heat conduction coefficient in a semiconductor assembly comprises the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film;
(2) Carbonizing the composite film at 1200 ℃ for 2 hours, then introducing inert gas, heating to 2300 ℃, graphitizing for 1 hour, cooling to room temperature, and compacting for 30 minutes under 30MPa to obtain the graphene radiating fin.
Through adopting above-mentioned technical scheme, earlier making the polyimide fiber slurry dry into the skeleton, the polyimide skeleton that obtains has great interlaminar interval and micropore, is immersed in the graphene oxide dispersion with it, and graphene oxide can be fully embedded, and in the heat treatment process, the skeleton form of polyimide allows a part of graphene sheet to stand perpendicularly, and adjacent graphene layer plane is in order to form 3D structure micropore, and this kind of holistic nanometer wrinkle structure is crooked and densification in succession, makes the film have the ability of maintaining, and has improved pliability by a wide margin.
The composite membrane is subjected to induced graphitization, the porosity and pore volume of the composite membrane can be increased, the pore diameter of the composite membrane is also enlarged by high-temperature treatment, then the radiating fins can be converted into silver gray from the bright black of the raw material by pressure treatment, and the adjacent graphene 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 heat sink with a three-dimensional structure and an ultra-high vertical thermal conductivity in a semiconductor assembly, which adopts the following technical scheme:
a preparation method of a graphene radiating fin with a three-dimensional structure and an ultrahigh vertical heat conduction coefficient in a semiconductor assembly comprises the following steps:
(1) Uniformly mixing polyimide fiber slurry and graphene oxide dispersion liquid to obtain mixed liquid, continuously coating the mixed liquid on the surface of a PET film material in a roll-to-roll mode, and continuously drying at 40-80 ℃ for 24 hours to obtain a composite film;
(2) Carbonizing the composite film at 1200 ℃ for 2 hours, then introducing inert gas, heating to 2300 ℃, graphitizing for 1 hour, cooling to room temperature, and compacting for 30 minutes under 30MPa to obtain the graphene radiating fin.
Through adopting above-mentioned technical scheme, adopt reel-to-reel mode continuous coating to replace polyimide skeleton dip-coating graphene oxide dispersion, need not to make polyimide skeleton with polyimide fiber slurry, can directly mix fiber slurry and graphene oxide dispersion, then carry out the coating drying, its preparation is efficient, and preparation is simple, is fit for industrial scale production.
It is further preferable that 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 range, the coating effect is good, and the heat conduction performance and the mechanical performance are excellent.
In summary, the present application has the following beneficial effects:
(1) According to the preparation method, the graphene nano-corrugation and the three-dimensional microstructure formed by winding the two-dimensional graphene nano-sheets and the polyimide fibers are combined to prepare the carbon fiber structure with super flexibility and folding shrinkage, and the graphene oxide content is adjusted to establish a skeleton-like structure sheet vertically inclined in the graphitization of the polyimide fibers, so that a three-dimensional bridged micro-chain lock-like structure is formed, and the obtained graphene radiating fin not only has high flexibility, but also has the thermal conductivity in the vertical direction reaching more than 100W/mK;
(2) The application provides a preparation method of a graphene radiating fin, which comprises the steps of firstly preparing polyimide frameworks and graphene oxide dispersion liquid, immersing the polyimide frameworks 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, wherein the graphene radiating fin is obtained by directly mixing polyimide fiber slurry and graphene oxide dispersion liquid and then continuously coating the polyimide fiber slurry and the graphene oxide dispersion liquid on a PET sheet in a roll-to-roll manner.
Drawings
FIG. 1 is a schematic structural diagram of a polyimide skeleton in example 1 of the present application;
fig. 2 is a schematic structural diagram of a graphene heat sink obtained by dip-coating a graphene oxide dispersion with a polyimide skeleton in embodiment 1 of the present application, wherein PI is the polyimide skeleton and GO is the graphene dispersion;
fig. 3 is a schematic structural diagram of a graphene heat sink obtained after coating in a roll-to-roll manner in embodiment 2 of the present application.
Detailed Description
The present application is described in further detail below with reference to the drawings and examples.
Preparation example
Preparation example 1
A polyimide backbone prepared by the steps of: mixing 0.02kg of polyimide fiber, 0.003kg of adhesive, 0.025kg of dispersing agent and 50kg of deionized water, dispersing for 30Min at a rotating speed of 1000rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of a PET film material, and drying at 75 ℃ to obtain the polyimide framework.
Wherein the adhesive is polyvinyl alcohol, and the dispersing agent is polyacrylamide.
Preparation example 2
A graphene oxide dispersion prepared by the steps of:
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% under the condition that the ice bath temperature is less than 2 ℃, heating to 0 ℃, then gradually adding 0.06kg of potassium permanganate within 4 hours, and continuing to react for 20 hours;
s2, pouring the reactant 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=7 of the supernatant liquid is reached, performing 400W ultrasonic treatment to obtain a dispersion liquid, and continuously centrifuging to remove residual sediment to obtain the graphene oxide dispersion liquid.
Examples
Example 1
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film, wherein the mass ratio of the polyimide framework to the graphene oxide in the composite film is 1:0.5;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at a speed of 5 ℃/min, continuously carbonizing for 2 hours at a temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at a speed of 5 ℃/min, graphitizing for 1 hour, and cooling to room temperature of 25 ℃;
(3) And (3) sandwiching the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the composite film for 30min under the pressure of 30MPa to obtain the composite film.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component prepared by the embodiment is composed of a polyimide framework and a graphene matrix, and the polyimide framework and the graphene matrix form a three-dimensional bridged micro-chain lock-shaped structure, wherein the polyimide framework is shown in fig. 1, and the graphene cooling fin structure is shown in fig. 2.
Example 2
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film, wherein the mass ratio of the polyimide framework to the graphene oxide in the composite film is 1:0.6;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at a speed of 5 ℃/min, continuously carbonizing for 2 hours at a temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at a speed of 5 ℃/min, graphitizing for 1 hour, and cooling to room temperature of 25 ℃;
(3) And (3) sandwiching the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the composite film for 30min under the pressure of 30MPa to obtain the composite film.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component prepared by the embodiment is composed of a polyimide framework and a graphene matrix, and the polyimide framework and the graphene matrix form a three-dimensional bridged micro-chain lock-shaped structure, wherein the polyimide framework is shown in fig. 1, and the graphene cooling fin structure is shown in fig. 2.
Example 3
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film, wherein the mass ratio of the polyimide framework to the graphene oxide in the composite film is 1:0.8;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at the speed of 8 ℃/min, continuously carbonizing for 2 hours at the temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at the speed of 8 ℃/min, graphitizing for 1 hour, and cooling to the room temperature of 25 ℃;
(3) And (3) sandwiching the graphitized composite film between two smooth tungsten sheets, and keeping the composite film for 30min under the pressure of 30 MPa.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component prepared by the embodiment is composed of a polyimide framework and a graphene matrix, and the polyimide framework and the graphene matrix form a three-dimensional bridged micro-chain lock-shaped structure, wherein the polyimide framework is shown in fig. 1, and the graphene cooling fin structure is shown in fig. 2.
Example 4
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film, wherein the mass ratio of the polyimide framework to the graphene oxide in the composite film is 1:1;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at the speed of 10 ℃/min, continuously carbonizing for 2 hours at the temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at the speed of 10 ℃/min, graphitizing for 1 hour, and cooling to the room temperature of 25 ℃;
(3) And (3) sandwiching the graphitized composite film between two smooth tungsten sheets, and keeping the composite film for 30min under the pressure of 30 MPa.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component prepared by the embodiment is composed of a polyimide framework and a graphene matrix, and the polyimide framework and the graphene matrix form a three-dimensional bridged micro-chain lock-shaped structure, wherein the polyimide framework is shown in fig. 1, and the graphene cooling fin structure is shown in fig. 2.
Example 5
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Uniformly mixing polyimide fiber slurry and graphene oxide dispersion liquid according to a mass ratio of 1:0.6 to obtain mixed liquid, continuously coating the mixed liquid on the surface of a PET film material in a roll-to-roll mode at a speed of 3m/min, and continuously drying at a temperature of 40 ℃ for 24 hours to obtain a composite film;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at a speed of 5 ℃/min, continuously carbonizing for 2 hours at a temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at a speed of 5 ℃/min, graphitizing for 1 hour, and cooling to room temperature;
(3) And (3) sandwiching the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the composite film for 30min under the pressure of 30MPa to obtain the composite film.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component, which is prepared by mixing polyimide fiber slurry and graphene dispersion liquid, is shown in fig. 3.
Example 6
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Uniformly mixing polyimide fiber slurry and graphene oxide dispersion liquid according to a mass ratio of 1:0.8 to obtain mixed liquid, continuously coating the mixed liquid on the surface of a PET film material in a roll-to-roll mode at a speed of 8m/min, and continuously drying at 80 ℃ for 24 hours to obtain a composite film;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at the speed of 8 ℃/min, continuously carbonizing for 2 hours at the temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at the speed of 8 ℃/min, graphitizing for 1 hour, and cooling to room temperature;
(3) And (3) sandwiching the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the composite film for 30min under the pressure of 30MPa to obtain the composite film.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component, which is prepared by mixing polyimide fiber slurry and graphene dispersion liquid, is shown in fig. 3.
Example 7
The preparation method of the graphene radiating fin with the three-dimensional structure and the ultrahigh vertical heat conduction coefficient for the semiconductor component specifically comprises the following steps:
(1) Uniformly mixing polyimide fiber slurry and graphene oxide dispersion liquid according to a mass ratio of 1:1 to obtain mixed liquid, continuously coating the mixed liquid on the surface of a PET film material in a roll-to-roll mode at a speed of 8m/min, and continuously drying at 80 ℃ for 24 hours to obtain a composite film;
(2) Placing the composite film into a high-temperature furnace, heating to 1200 ℃ at the speed of 10 ℃/min, continuously carbonizing for 2 hours at the temperature of 1200 ℃, then introducing nitrogen, heating to 2300 ℃ at the speed of 10 ℃/min, graphitizing for 1 hour, and cooling to room temperature;
(3) And (3) sandwiching the graphitized composite film between two smooth copper sheets/graphite plates, and keeping the composite film for 30min under the pressure of 30MPa to obtain the composite film.
The polyimide skeleton described in this example was prepared in preparation example 1, and the graphene oxide dispersion was prepared in preparation example 2.
The graphene cooling fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient for the semiconductor component, which is prepared by mixing polyimide fiber slurry and graphene dispersion liquid, is shown in fig. 3.
Performance test
Performance tests were performed on the graphene heat sinks prepared in examples 1 to 7, respectively.
Wherein the vertical thermal conductivity is measured according to the measurement of the thermal conductivity coefficient of graphene powder (established by the society standard of special equipment industry in Guangdong province). The test results are shown in Table 1 below.
TABLE 1 Performance test results
| Test item | 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 |
| 100 μm, 180 degree folding times (times) | 1019 | 1200 | 1257 | 1104 | 1043 | 1027 | 1010 |
| Resistivity after 1000 folds | 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, 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 forming the polyimide fiber slurry and the graphene dispersion liquid are described, and the performance of the radiating fin prepared by the polyimide framework is better than that of the radiating fin prepared by the polyimide framework.
Wherein, example 3 is the best example, the vertical heat conductivity can reach 163W/mK, the radius is 100 μm, the bending angle is 180 DEG, the folding reaches 1257 times of cyclic bending, and the resistance after 1000 times of cyclic bending is increased by 7.1 percent.
In conclusion, the graphene radiating fin prepared by the method has excellent heat conduction performance, excellent flexibility and mechanical property, and is suitable for radiating related equipment in a semiconductor component.
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 examples, and all technical solutions belonging to the concept of the present application belong to the protection scope of the present application. It should be noted that modifications and adaptations to those skilled in the art without departing from the principles of the present application are intended to be comprehended within the scope of the present application.
Claims (2)
1. The graphene radiating fin with the three-dimensional structure and the ultra-high vertical heat conduction coefficient is used in a semiconductor component 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;
the mass ratio of the polyimide framework to the graphene matrix is 1 (0.6-1);
the horizontal heat conductivity of the graphene radiating fin is more than or equal to 1400W/mK, and the vertical heat conductivity is more than or equal to 100W/mK; through the folding endurance test, when the bearing radius is 100 mu m and the folding angle is 180 DEG, the folding times are more than 1000 times;
the preparation method of the polyimide framework comprises the following steps: mixing polyimide fiber, adhesive, dispersing agent and deionized water, dispersing for 15-30Min at 800-1200rpm to obtain polyimide fiber slurry, coating the polyimide fiber slurry on the surface of PET film material, and drying at 60-80 ℃ to obtain polyimide skeleton;
the mass ratio of the polyimide fiber to the adhesive to the dispersing agent to the deionized water is 20:3:25:50000;
the adhesive is polyvinyl alcohol, and the dispersing agent is polyacrylamide;
the graphene matrix is 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 sulfuric acid with the mass fraction of 98% under the condition that the ice bath temperature is less than 2 ℃, heating to 0-5 ℃, then gradually adding 6 parts by weight of potassium permanganate in 4 hours, and continuing to react for 20 hours;
s2, pouring the reactant obtained in the step S1 into 1000 parts by weight of ice water, and gradually adding 30 parts by weight of hydrogen peroxide with the mass fraction of 3% until no gas is generated;
s3, adding 500 parts by weight of deionized water, centrifuging at 1000-1200rpm until the pH=7 of the supernatant liquid is obtained, performing 400W ultrasonic treatment to obtain a dispersion liquid, and continuing centrifuging to remove residual sediment to obtain the graphene oxide dispersion liquid.
2. A method for preparing the graphene heat sink with three-dimensional structure and ultra-high vertical heat conduction coefficient for semiconductor assembly according to claim 1, comprising the following steps:
(1) Immersing a polyimide framework into graphene oxide dispersion liquid, and keeping for 15min to form a composite film;
(2) Carbonizing the composite film at 1200 ℃ for 2 hours, then introducing inert gas, heating to 2300 ℃, graphitizing for 1 hour, cooling to room temperature, and compacting for 30 minutes under 30MPa to obtain the graphene radiating fin.
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|---|---|---|---|---|
| CN103122075A (en) * | 2013-03-19 | 2013-05-29 | 苏州格瑞丰纳米科技有限公司 | High heat-conducting thin graphene-based composite material, as well as preparation method and application thereof |
| CN105694427B (en) * | 2014-11-26 | 2019-05-28 | 中国科学院金属研究所 | A kind of application of graphene composite material as electromagnetic shielding material |
| CN106853966B (en) * | 2015-12-07 | 2019-08-16 | 株洲时代新材料科技股份有限公司 | Utilize the method for graphene doping polyamic acid resin preparation high thermal conductivity graphite film |
| CN106243379B (en) * | 2016-07-23 | 2019-10-18 | 天津大学 | A kind of electromagnetic shielding foamed composite and preparation method based on graphene oxide and polymer |
| CN107871541B (en) * | 2016-09-23 | 2019-12-06 | 北京化工大学 | Light-weight high-temperature-resistant high-specific-surface-area polyimide conductive pulp and preparation method thereof |
| CN106930100A (en) * | 2017-03-20 | 2017-07-07 | 上海大学 | A kind of preparation method of polyimides/graphene oxide complex fiber material |
| CN106750296B (en) * | 2017-03-20 | 2019-03-22 | 西北工业大学 | A kind of modified graphene/polyimides heat-conductive composite material and preparation method thereof |
| CN106968128B (en) * | 2017-04-12 | 2018-04-03 | 株洲时代新材料科技股份有限公司 | A kind of soft graphite alkenyl extrusion coating paper and preparation method thereof |
| CN110776657B (en) * | 2019-11-05 | 2022-02-11 | 株洲时代华鑫新材料技术有限公司 | High-thermal-conductivity polyimide film and preparation method thereof |
| CN111218112A (en) * | 2020-03-11 | 2020-06-02 | 南京航空航天大学 | rGO/polyimide composite aerogel and preparation method and application thereof |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378191A (en) * | 2020-04-22 | 2020-07-07 | 宁波石墨烯创新中心有限公司 | Graphene/polyimide heat conduction film and preparation method thereof |
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