CN111356329A - Thin high-conductivity heat-dissipation composite material with low interface thermal resistance - Google Patents
Thin high-conductivity heat-dissipation composite material with low interface thermal resistance Download PDFInfo
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- CN111356329A CN111356329A CN201811574415.4A CN201811574415A CN111356329A CN 111356329 A CN111356329 A CN 111356329A CN 201811574415 A CN201811574415 A CN 201811574415A CN 111356329 A CN111356329 A CN 111356329A
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- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
Abstract
The invention discloses a thin type high-conductivity heat-dissipation composite material with low interface thermal resistance, which comprises a copper foil substrate and an epitaxial graphene layer, and is characterized in that: the invention adopts the combination of copper metal with heat conduction isotropy and graphite material with extremely high horizontal heat conductivity and high heat radiation characteristic, and adopts the thin film technology of low-temperature high-density plasma sputtering to grow the graphene coating epitaxy on the surface of the metal copper foil so as to form the novel thin heat conduction and dissipation material. Because the graphene layer is a composite structure of the graphene layer epitaxy on the metal copper foil, the interface thermal resistance of the composite structure is extremely low. When the composite structure is contacted with a heat source, the metal copper foil can transfer heat to the graphene layer, and the graphene layer can enable the heat to rapidly and planarly bloom and radiate to the atmosphere, so that high heat conduction and high heat dissipation are realized. The defects of the prior art are overcome.
Description
Technical Field
The invention relates to the technical field of high-conductivity heat-dissipation composite materials with low interface thermal resistance, in particular to a thin high-conductivity heat-dissipation composite material with low interface thermal resistance.
Background
With the rapid development of modern electronic technologies, no devices such as tablet computers, thin notebooks, smart phones, and pico-projectors, which are light, thin, short, and portable, have a structure with more specifications and operation performance integrated in a very limited space under the design concept that the current 3C device emphasizes being light, thin, short, and easy to carry. While the integration degree and the packing density of electronic components are continuously increased to provide strong functions, the operating power consumption and the heat generation amount thereof are also sharply increased. It is known that high temperatures will have a detrimental effect on the stability, reliability and lifetime of electronic components. When the average operating temperature of an electronic component is increased by 10 ℃, the component lifetime is reduced by 50%. Therefore, how to provide a heat dissipation design with high efficiency and without causing extra power consumption under the conditions of unlimited functions and limited space/cost to ensure that the heat generated by the electronic components can be discharged in time, so that the electronic components have long-term operation stability and the product life is prolonged, which is a problem that needs to be overcome in the 3C industry field nowadays.
The heat dissipation method mainly comprises three main directions: conduction, radiation and convection, designers can choose different heat dissipation solutions according to the required heat dissipation density, space limitation and cost consideration. However, in the design concept of ultra-thin and thin 3C products, the space with a thickness of only 0.1mm can be used as the load of the heat dissipation device, so copper guide plates, heat pipes, heat dissipation fins, air cooling, water cooling, and heat dissipation fans cannot be used. Therefore, there is a strong demand for a thin heat dissipating material with high thermal conductivity. In addition to the requirement of high thermal conductivity, low density and low expansion coefficient are also the requirements of thin high thermal conductivity heat dissipation material. Therefore, among the material systems satisfying the above three conditions, the commercially available thin heat conductive and dissipating material is most widely used as a graphite sheet. Mainly because the planar thermal conductivity of the ideal graphite crystal can be as high as 1600-2000W/mK, which is much higher than that of copper 401W/mK and aluminum 237W/mK. Furthermore, the density of graphite is only 2.09g/cm3And is also much lower than 8.96g/cm of copper3And 2.70g/cm of aluminum3The planar thermal expansion coefficient of graphite is only 6.5 × 10-6K is also much lower than 16.5 × 10 for copper-623.2 × 10 of/K and aluminium-6and/K. In addition, as in consideration of emissivity, graphite desirably has emissivity as high as 0.98, and copper and aluminum are only 0.023 to 0.052 and 0.04 to 0.09. The graphite product can be further divided into natural graphite flakes and artificial graphite flakes. Generally, the thermal conductivity of commercially available natural graphite flake products is about 100-600W/mK depending on the process conditions and purity. The artificial graphite sheet is prepared by using a polymer (such as polyimide) as a precursor and performing high-temperature thermal cracking and graphitization. Due to its graphiteThe crystal structure is complete and the carbon content and purity are high, so the thermal conductivity of the current commercial artificial graphite sheet can be more than 1000W/mK. Although the graphite flake has the conditions of high thermal conductivity, low density, low thermal expansion coefficient, high thermal radiation coefficient and the like, so that the graphite flake can be used as a thin high-thermal conductivity heat dissipation material, the processing temperature is more than 2000 ℃ at most, the processing time is long, and a chemical cleaning process is required, so that the energy consumption is extremely high, the production speed is slow, and the problems of air pollution and environmental protection are difficult to overcome. In addition, graphite dust of graphite flakes has a risk of falling off, which may cause short-circuiting of electric wires. More importantly, the thermal conductivity anisotropy of graphite is very large, the high thermal conductivity is only limited to XY plane (i.e. the direction of crystalline carbon layer), the thermal conductivity of Z axis is less than 10W/mK, and the flexibility of graphite sheet is limited, so that it is difficult to completely attach the heat source, and the heat generated by electronic device is difficult to be conducted to the graphite sheet for heat conduction and dissipation. On the other hand, graphene is a perfect single-layer graphite crystal structure, and the horizontal heat conduction coefficient of the graphene is better than that of graphite and is as high as 5300W/mK.
Based on the above problems, the present invention employs a thin film technology combining the characteristics of copper metal with heat conduction isotropy and graphite material with extremely high horizontal heat conductivity and high heat radiation to epitaxially grow the graphene coating on the surface of the metal copper foil by low temperature high density plasma sputtering, so as to form a novel thin heat conduction and dissipation material. Because the graphene layer is a composite structure of the graphene layer epitaxy on the metal copper foil, the interface thermal resistance of the composite structure is extremely low. When the composite structure is contacted with a heat source, the metal copper foil can transfer heat to the graphene layer, and the graphene layer can enable the heat to rapidly and planarly bloom and radiate to the atmosphere, so that high heat conduction and high heat dissipation are realized. The defects of the prior art are overcome.
Disclosure of Invention
The invention aims to provide a thin high-heat-conduction and heat-dissipation composite material with low interface thermal resistance, which reasonably and effectively solves the problems of large thickness and volume, high interface thermal resistance and poor heat-conduction and heat-dissipation function of the heat-conduction and heat-dissipation material in the prior art.
Principle of the technology
When the metal copper foil of the copper foil substrate-epitaxial graphene layer composite structure arranged on the high-conductivity heat-dissipation composite material with low interface thermal resistance is contacted with a heat source, the metal copper foil can transfer heat to the graphene layer in an equidirectional mode, the graphene layer rapidly and planarly blunts the heat and radiates or transfers the heat to a heat-dissipation mechanism medium or air in a heat-dissipation space of the epitaxial graphene layer, and the functions of high heat conductivity and high heat dissipation are achieved.
The invention adopts the following technical scheme:
the utility model provides a high heat dissipation combined material that leads of thin low interfacial thermal resistance, includes copper foil substrate, epitaxy graphite alkene layer, its characterized in that:
the high-conductivity heat-dissipation composite material with low interface thermal resistance is prepared by adopting a copper foil substrate and a graphite target material to prepare an epitaxial graphene layer on the surface of the copper foil substrate through a low-temperature high-density plasma sputtering process, wherein the temperature parameter of the low-temperature high-density plasma sputtering process is less than 1000 ℃, the epitaxial growth layer number, the thickness and the epitaxial growth direction of the epitaxial graphene layer are controlled through plasma power supply frequency, plasma power supply pulse duration, plasma power supply power, substrate negative bias and plating time, the copper foil substrate has heat conduction isotropy, and the epitaxial graphene layer has the performances of high plane thermal conductivity and high heat radiation performance.
Furthermore, the epitaxial graphene layer is epitaxially grown on the surface of the copper foil substrate.
Furthermore, the epitaxial growth layer number of the epitaxial graphene layer is 1-100, and the thickness is 0.3nm-30 nm.
Furthermore, the epitaxial growth direction of the epitaxial graphene layer is horizontal, vertical, or a combination of horizontal and vertical to the surface of the copper foil substrate.
Further, the epitaxial graphene layer has characteristic peaks of a D band, a G band and a 2D band in a Raman spectrometer.
Furthermore, the epitaxial graphene layer has a layered structure in a transmission electron microscope image, and the interlayer distance is 0.30nm-0.36 nm.
Further, the purity of the copper foil substrate is not particularly limited, preferably the purity is > 99%, the thickness is not particularly limited, preferably the thickness is 10 to 100 μm, the surface roughness is not particularly limited, preferably the average surface roughness is < 1 nm.
Furthermore, the metal copper foil side of the copper foil substrate is used for being attached to a heating source of an electronic product. The beneficial technical effects of the invention are as follows:
the invention discloses a thin high-heat-conduction and heat-dissipation composite material with low interface thermal resistance, which reasonably and effectively solves the problems of large thickness and volume, high interface thermal resistance and poor heat-conduction and heat-dissipation function of a heat-conduction and heat-dissipation material in the prior art.
The invention adopts the combination of copper metal with heat conduction isotropy and graphite material with extremely high horizontal heat conductivity and high heat radiation characteristic, and adopts the thin film technology of low-temperature high-density plasma sputtering to grow the graphene coating epitaxy on the surface of the metal copper foil so as to form the novel thin heat conduction and dissipation material. Because the graphene layer is a composite structure of the graphene layer epitaxy on the metal copper foil, the interface thermal resistance of the composite structure is extremely low. When the composite structure is contacted with a heat source, the metal copper foil can transfer heat to the graphene layer, and the graphene layer can enable the heat to rapidly and planarly bloom and radiate to the atmosphere, so that high heat conduction and high heat dissipation are realized. The defects of the prior art are overcome.
Drawings
FIG. 1 is a pattern of the composite material of the present invention.
Fig. 2 is a raman spectrum of an epitaxial graphene layer obtained in an example of the present invention.
Fig. 3 is a schematic structural view of an epitaxial graphene layer with a 10-layer structure obtained in an embodiment of the invention under a transmission electron microscope.
Shown in the figure: 1-copper foil substrate, 2-epitaxial graphene layer, 3-layer gap and 4-0.358nm layer gap.
Detailed Description
The invention will be better understood by the following description of embodiments thereof, but the applicant's specific embodiments are not intended to limit the invention to the particular embodiments shown, and any changes in the definition of parts or features and/or in the overall structure, not essential changes, are intended to define the scope of the invention.
Examples
As shown in fig. 1, a thin composite material with low interface thermal resistance and high thermal conductivity and dissipation performance includes a copper foil substrate 1 and an epitaxial graphene layer 2.
In the embodiment, a copper foil substrate 1 is used as a substrate, and an epitaxial graphene layer 2 is prepared on the surface of the copper foil substrate 1 by a low-temperature high-density plasma sputtering process using a graphite target, so as to form a composite structure of the copper foil substrate 1 and the epitaxial graphene layer 2. The purity of the copper foil substrate 1 is 99.8%, and the thickness is 25 μm.
The method comprises the steps of firstly, soaking the copper foil substrate 1 in an acetic acid aqueous solution, removing an oxide layer of the copper foil substrate, respectively washing the copper foil substrate with deionized water and alcohol, and wiping residual alcohol with dust-free paper to finish cleaning the copper foil substrate 1.
And step two, performing electrochemical polishing on the copper foil substrate 1 to improve the surface smoothness of the copper foil substrate 1. The electrolyte is a mixed solution of phosphoric acid, glycerol and acetic acid, the copper foil substrate 1 is used as an anode, the other copper sheet is used as a cathode, and voltage is applied. And then, respectively washing with deionized water and alcohol, and wiping the residual alcohol with dust-free paper to finish the electrochemical polishing of the copper foil substrate 1.
And step three, placing the copper foil substrate 1 subjected to the electrochemical polishing process in a low-temperature high-density plasma sputtering cavity, exhausting air to a vacuum environment, heating the copper foil substrate 1 to 600 ℃, introducing argon, using graphite as a target material and a pulse power supply as a power supply, and applying a negative bias to a substrate to perform graphene low-temperature high-density plasma sputtering to obtain the epitaxial graphene layer 2 on the surface of the copper foil substrate 1. In the low-temperature high-density plasma sputtering process, the power frequency, the power pulse time, the power, the substrate negative bias voltage, the plating time and the like are regulated and controlled, so that the number and the thickness of the epitaxial growth layers of the graphene layers of the epitaxial graphene layers 2 and the epitaxial growth direction are controlled.
Further, the raman spectrum of the epitaxial graphene layer 2 epitaxially grown on the surface of the copper foil substrate 1 has a characteristic peak of graphene: the D band, G band and 2D band signals can confirm that the low temperature plasma charging process has been successful in epitaxially forming a graphene layer on the copper foil substrate 1.
Further, the epitaxial graphene layer 2 epitaxially grown on the surface of the copper foil substrate 1 shows a layered structure of the graphene layer under a transmission electron microscope, the layer-to-layer distance is 0.358nm, and the number of layers of the epitaxial graphene layer 2 is 10. The implementation of the thin high heat conduction and dissipation composite material with low interface thermal resistance is completed.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (7)
1. The utility model provides a high heat dissipation combined material that leads of thin low interfacial thermal resistance, includes copper foil substrate, epitaxy graphite alkene layer, its characterized in that:
the high-conductivity heat-dissipation composite material with low interface thermal resistance is prepared by adopting a copper foil substrate and a graphite target material to prepare an epitaxial graphene layer on the surface of the copper foil substrate through a low-temperature high-density plasma sputtering process, wherein the temperature parameter of the low-temperature high-density plasma sputtering process is less than 1000 ℃, the epitaxial growth layer number, the thickness and the epitaxial growth direction of the epitaxial graphene layer are controlled through plasma power supply frequency, plasma power supply pulse duration, plasma power supply power, substrate negative bias and plating time, the copper foil substrate has heat conduction isotropy, and the epitaxial graphene layer has the performances of high plane thermal conductivity and high heat radiation performance.
2. The thin low-interfacial-thermal-resistance high-thermal-conductivity and heat-dissipation composite material as claimed in claim 1, wherein the epitaxial graphene layer is epitaxially grown on the surface of the copper foil substrate.
3. The thin low-interface-thermal-resistance high-thermal-conductivity and heat-dissipation composite material as claimed in claim 1, wherein the number of epitaxially grown layers of the epitaxial graphene layer is 1-100, and the thickness is 0.3nm-30 nm.
4. The thin low-interfacial-thermal-resistance high-thermal-conductivity and heat-dissipation composite material as claimed in claim 1, wherein the epitaxial growth direction of the epitaxial graphene layer is horizontal, or vertical, or a combination of horizontal and vertical to the surface of the copper foil substrate.
5. The thin low-interface-thermal-resistance high-thermal-conductivity composite material as claimed in claim 1 or 3, wherein the epitaxial graphene layer has characteristic peaks of D band, G band and 2D band in a Raman spectrometer.
6. The thin high thermal conductivity and dissipation composite material with low interfacial thermal resistance as claimed in claim 1, wherein the epitaxial graphene layer has a layered structure in transmission electron microscopy, and the interlayer distance is 0.30nm-0.36 nm.
7. The thin high thermal conductivity and dissipation composite material with low interfacial thermal resistance as claimed in claim 1, wherein the metal copper foil side of the copper foil substrate is used for bonding a heat source of an electronic product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113853099A (en) * | 2021-09-08 | 2021-12-28 | 深圳热声智能科技有限公司 | Heat-conducting composite substrate, preparation method, electronic equipment, application, heat dissipation device and method |
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