Diamond-copper composite heat dissipation material and preparation method and application thereof

Abstract

The application discloses a diamond-copper composite heat dissipation material and a preparation method and application thereof, and belongs to the technical field of electronic packaging heat dissipation substrate materials. The preparation method of the diamond-copper composite heat dissipation material comprises the following steps: mixing diamond, metal powder and active substances to obtain a mixture one, and sintering the mixture one to obtain surface metallization modified diamond; mixing the surface metallization modified diamond with copper powder to obtain a mixture two, and sintering the mixture two by using a discharge plasma to obtain the diamond-copper composite heat dissipation material. A new surface modification technology is adopted to modify a titanium carbide layer on the surface of the diamond, then the diamond with the modified titanium carbide layer is mixed with copper powder, and the discharge plasma sintering technology is adopted to prepare the diamond-copper composite heat dissipation material. The diamond-copper composite heat dissipation material prepared by the application has excellent heat conduction performance, and the highest thermal conductivity is 633.3 W·m ‑1 ·K ‑1 .

Description

Technical Field

[0001] This invention belongs to the field of electronic packaging heat dissipation substrate material technology, specifically relating to a diamond-copper composite heat dissipation material and its preparation method and application. Background Technology

[0002] With the rapid development of electronic technology and power devices, the integration density of devices is constantly increasing, and the heat flux density per unit area is increasing day by day. Traditional packaging heat dissipation materials can no longer meet the requirements of high-performance electronic devices for high thermal conductivity and good thermal matching performance. Diamond has high thermal conductivity, but diamond itself is difficult to process and shape. Therefore, diamond-reinforced metal matrix composites have become a research hotspot in the field of electronic packaging. Copper has good thermal conductivity, processability, and price advantages, and is a commonly used metal matrix material in electronic packaging. Therefore, diamond-copper composites are expected to become a new generation of heat dissipation materials. However, the poor interfacial wettability and high interfacial thermal resistance between diamond and copper seriously affect the overall thermal conductivity of diamond-copper composites. Summary of the Invention

[0003] The first objective of this invention is to provide a method for preparing a diamond-copper composite heat dissipation material to solve the technical problem that poor wettability at the diamond-copper interface affects the thermal conductivity of diamond-copper composite materials.

[0004] The second objective of this invention is to provide a diamond-copper composite heat dissipation material.

[0005] The third objective of this invention is to provide an application of a diamond-copper composite heat dissipation material.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows: A method for preparing a diamond-copper composite heat dissipation material includes the following steps: S1: Mix diamond, metal powder and active material to obtain mixture one, and sinter mixture one to obtain diamond with surface metallization modification; S2: Mixing surface-metallized diamond with copper powder yields mixture two, which is then sintered by spark plasma to obtain the final product.

[0007] Furthermore, the metal powder mentioned in S1 is titanium powder, and the active substance is aluminum powder.

[0008] Furthermore, the particle size of the metal powder described in S1 is 10-20 μm.

[0009] Furthermore, the mass ratio of diamond to metal powder in S1 is 1:0.8-1.4, and the mass ratio of diamond to active material is 1:0.1-0.3.

[0010] Furthermore, the sintering described in S1 is sintering under vacuum conditions, with a sintering temperature of 730-980 ℃ and a sintering time of 30-80 min.

[0011] Furthermore, the mass ratio of the surface-metallized diamond to copper powder described in S2 is 1:0.5-2.

[0012] Furthermore, the discharge plasma sintering temperature described in S2 is 700-950 ℃, the time is 0-20 min, the heating rate is 50-100 ℃ / min, and the pressure is 5-50 MPa.

[0013] Furthermore, the diamond described in S1 needs to undergo pretreatment before being mixed with metal powder and active substances. The pretreatment steps include degreasing, alkaline washing, and acid washing.

[0014] A diamond-copper composite heat dissipation material is prepared using the above-mentioned method for preparing diamond-copper composite heat dissipation materials.

[0015] Application of a diamond-copper composite heat dissipation material as a heat dissipation material in electronic packaging.

[0016] The beneficial effects of this invention are: This invention employs a novel surface modification technique to modify the surface of diamond with a titanium carbide layer. Then, the titanium carbide-modified diamond is mixed with copper powder, and a diamond-copper composite heat dissipation material is prepared using spark plasma sintering technology. Figure 17 It can be seen that the diamond-copper composite heat dissipation material prepared by this invention has excellent thermal conductivity, with the highest thermal conductivity being 633.3 W·m. -1 ·K -1 . Attached Figure Description

[0017] Figure 1 Image of a real diamond; Figure 2 This is a photograph of the diamond with surface metallization modification as shown in Example 1. Figure 3 This is a scanning electron microscope image of the surface-metallized diamond in Example 1; Figure 4 The X-ray photoelectron spectroscopy (XPS) characteristics of the surface-metallized diamond in Example 1 are shown in (a) for Ti 2p, (b) for C 1s, and (c) for Al 2p. Figure 5 Comparison of X-ray diffraction patterns of surface-metallized diamonds in Examples 1, 2 and 3; Figure 6 This is a photograph of the diamond with surface metallization modification as shown in Example 2. Figure 7 This is a scanning electron microscope image of the surface-metallized diamond in Example 2; Figure 8 The energy dispersive spectroscopy (EDS) characteristic image of the diamond surface with surface metallization modification in Example 2; Figure 9 The following are the X-ray photoelectron spectroscopy (XPS) characteristics of the diamond with surface metallization modification in Example 2, where (a) is the Ti 2p spectrum, (b) is the C 1s spectrum, and (c) is the Al 2p spectrum. Figure 10 This is a photograph of the diamond with surface metallization modification in Example 3; Figure 11 This is a scanning electron microscope image of the surface-metallized diamond in Example 3; Figure 12 The energy dispersive spectroscopy (EDS) instrument characterization of the diamond surface with surface metallization modification in Example 3; Figure 13 The X-ray photoelectron spectroscopy (XPS) spectra of the diamond with surface metallization modification in Example 3 are shown in (a) for Ti 2p, (b) for C 1s, and (c) for Al 2p. Figure 14 This is a scanning electron microscope image of the surface-metallized diamond in Example 4; Figure 15 The energy dispersive spectroscopy (EDS) instrument characterization of the diamond surface with surface metallization modification in Example 4; Figure 16 The image shows a scanning electron microscope (SEM) image of the surface-metallized diamond in Comparative Example 1. Figure 17 The thermal conductivity diagrams are for the diamond-copper composite heat dissipation materials in Examples 1-3 and Comparative Example 1. Detailed Implementation

[0018] The following will provide further details with reference to embodiments of the present invention.

[0019] Example 1 The preparation method of the diamond-copper composite heat dissipation material in Example 1 includes the following steps: S1: 1 kg of diamond was sequentially ultrasonically cleaned with acetone for 15 min, cleaned with deionized water until neutral, cleaned with anhydrous ethanol for 15 min, cleaned with deionized water until neutral, boiled with 10% sodium hydroxide for 20 min, cleaned with deionized water until neutral, boiled with dilute nitric acid for 20 min, cleaned with deionized water until neutral, and dried to obtain pretreated diamond. The pretreated diamond was mixed with 1.2 kg of titanium powder and 0.2 kg of aluminum powder to obtain mixture one. Mixture one was kept at 750 ℃ ​​in a tube furnace under vacuum for 60 min, cooled to room temperature with the furnace, and then cleaned and dried to obtain surface metallized diamond. The particle size of the titanium powder was 10-20 μm. S2: 1 kg of surface-metallized diamond was mixed with 0.8 kg of copper powder to obtain mixture two. Mixture two was then subjected to spark plasma sintering and cooled in the furnace to obtain the final product. The spark plasma sintering temperature was 800 ℃, the time was 10 min, the heating rate was 80 ℃ / min, and the pressure was 30 MPa.

[0020] Example 2 The preparation method of the diamond-copper composite heat dissipation material in Example 2 includes the following steps: S1: 1 kg of diamond was sequentially ultrasonically cleaned with acetone for 15 min, cleaned with deionized water until neutral, cleaned with anhydrous ethanol for 15 min, cleaned with deionized water until neutral, boiled with 10% sodium hydroxide for 20 min, cleaned with deionized water until neutral, boiled with dilute nitric acid for 20 min, cleaned with deionized water until neutral, and dried to obtain pretreated diamond. The pretreated diamond was mixed with 1.2 kg of titanium powder and 0.2 kg of aluminum powder to obtain mixture one. Mixture one was kept at 850 ℃ in a tube furnace under vacuum for 60 min, cooled to room temperature with the furnace, and then cleaned and dried to obtain surface metallized diamond. The particle size of the titanium powder was 10-20 μm. S2: 1 kg of surface-metallized diamond was mixed with 0.8 kg of copper powder to obtain mixture two. Mixture two was then subjected to spark plasma sintering and cooled in the furnace to obtain the final product. The spark plasma sintering temperature was 800 ℃, the time was 10 min, the heating rate was 80 ℃ / min, and the pressure was 30 MPa.

[0021] Example 3 The preparation method of the diamond-copper composite heat dissipation material in Example 3 includes the following steps: S1: 1 kg of diamond was sequentially ultrasonically cleaned with acetone for 15 min, cleaned with deionized water until neutral, cleaned with anhydrous ethanol for 15 min, cleaned with deionized water until neutral, boiled with 10% sodium hydroxide for 20 min, cleaned with deionized water until neutral, boiled with dilute nitric acid for 20 min, cleaned with deionized water until neutral, and dried to obtain pretreated diamond. The pretreated diamond was mixed with 1.2 kg of titanium powder and 0.2 kg of aluminum powder to obtain mixture one. Mixture one was kept at 950 ℃ in a tube furnace under vacuum for 60 min, cooled to room temperature with the furnace, and then cleaned and dried to obtain surface metallized diamond. The particle size of the titanium powder was 10-20 μm. S2: 1 kg of surface-metallized diamond was mixed with 0.8 kg of copper powder to obtain mixture two. Mixture two was then subjected to spark plasma sintering and cooled in the furnace to obtain the final product. The spark plasma sintering temperature was 800 ℃, the time was 10 min, the heating rate was 80 ℃ / min, and the pressure was 30 MPa.

[0022] Example 4 The preparation method of the diamond-copper composite heat dissipation material in Example 4 includes the following steps: S1: 1 kg of diamond was sequentially ultrasonically cleaned with acetone for 15 min, cleaned with deionized water until neutral, cleaned with anhydrous ethanol for 15 min, cleaned with deionized water until neutral, boiled with 10% sodium hydroxide for 20 min, cleaned with deionized water until neutral, boiled with dilute nitric acid for 20 min, cleaned with deionized water until neutral, and dried to obtain pretreated diamond. The pretreated diamond was mixed with 1.2 kg of titanium powder and 0.3 kg of aluminum powder, and then heated in a tube furnace at 950 ℃ under vacuum for 60 min. After cooling to room temperature in the furnace, the mixture was removed, cleaned, and dried to obtain surface metallized diamond. The particle size of the titanium powder was 10-20 μm. S2: 1 kg of surface-metallized diamond was mixed with 0.8 kg of copper powder to obtain a mixture. The mixture was then subjected to spark plasma sintering and cooled in the furnace. The spark plasma sintering temperature was 850 ℃, the time was 10 min, the heating rate was 70 ℃ / min, and the pressure was 40 MPa.

[0023] Comparative Example 1 The preparation method of the diamond-copper composite heat dissipation material of Comparative Example 1 includes the following steps: S1: 1 kg of diamond was sequentially ultrasonically cleaned with acetone for 15 min, cleaned with deionized water until neutral, cleaned with anhydrous ethanol for 15 min, cleaned with deionized water until neutral, boiled with 10% sodium hydroxide for 20 min, cleaned with deionized water until neutral, boiled with dilute nitric acid for 20 min, cleaned with deionized water until neutral, and dried to obtain pretreated diamond; the pretreated diamond was mixed with 1.2 kg of titanium powder and held in a tube furnace at 950 ℃ under vacuum for 60 min, cooled to room temperature with the furnace, removed, cleaned and dried to obtain surface metallized modified diamond; the particle size of the titanium powder was 10-20 μm; S2: 1 kg of surface-metallized diamond was mixed with 0.8 kg of copper powder to obtain a mixture. The mixture was then subjected to spark plasma sintering and cooled in the furnace. The spark plasma sintering temperature was 800 ℃, the time was 10 min, the heating rate was 80 ℃ / min, and the pressure was 30 MPa.

[0024] from Figure 2 As can be seen, the surface-metallized diamond in Example 1 changed from its original golden yellow color to black, and there was a clear coating deposition on the diamond surface. From Figure 3 It can be seen that the morphological changes of surface-metallized diamond are relatively small, with only a smooth thin film covering the surface, indicating that the diamond crystal structure is relatively intact at a lower temperature of 750 ℃. Figure 4 and Figure 5 It can be seen that the titanium element in the coating exists in the form of titanium carbide. From Figure 6 It can be seen that the surface of the diamond with surface metallization modification in Example 2 changes from yellow to silver-black, has good brightness and obvious glaze color. From Figure 7 It can be seen that air bubbles are present inside the diamond, and the surface morphology of the diamond particles has changed significantly, exhibiting clearer and more regular structural features with a uniform coating distribution. The surface roughness of the diamond particles has increased, and there are almost no exposed diamond areas. From Figure 8 It can be seen that titanium diffuses sufficiently and adheres evenly to the diamond surface, with good coating coverage in both edge and planar areas, indicating that raising the temperature to 850 ℃ is beneficial for forming a continuous and stable coating. Figure 9 It can be seen that the titanium element in the coating mainly exists in the form of titanium carbide. From Figure 10 and 11 It can be seen that when the calcination temperature rises to 950 ℃, a coating forms on the diamond surface, but there are small areas of incomplete coating. From Figure 13 It can be seen that the titanium element in the coating exists in the form of titanium carbide. From Figure 14 It can be seen that when the mass of the active material aluminum powder is increased, a coating still exists on the diamond surface, but there are large areas of uncoated areas. FromFigure 16 It can be seen that without the addition of the active substance aluminum powder, the diamond surface in Comparative Example 1 has no coating. From... Figure 17 It can be seen that, in Comparative Example 1, the diamond-copper composite heat dissipation material prepared from diamond and copper powder without the addition of aluminum powder and without metallization modification has the lowest thermal conductivity. From Examples 1-3, it can be seen that the diamond-copper composite heat dissipation material prepared by performing diamond surface metallization modification at 850 °C has the highest thermal conductivity, reaching 633.3 W·m. -1 ·K -1 .

Claims

1. A method for preparing a diamond-copper composite heat dissipation material, characterized in that, Includes the following steps: S1: Mix diamond, metal powder and active material to obtain mixture one, and sinter mixture one to obtain diamond with surface metallization modification; S2: Mixing surface-metallized diamond with copper powder yields mixture two, which is then sintered by spark plasma to obtain the final product.

2. The preparation method of the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The metal powder mentioned in S1 is titanium powder, and the active substance is aluminum powder.

3. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The metal powder described in S1 has a particle size of 10-20 μm.

4. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The mass ratio of diamond to metal powder in S1 is 1:0.8-1.4, and the mass ratio of diamond to active material is 1:0.1-0.

3.

5. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The sintering described in S1 is sintering under vacuum conditions, with a sintering temperature of 730-980 ℃ and a sintering time of 30-80 min.

6. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The mass ratio of surface-metallized diamond to copper powder described in S2 is 1:0.5-2.

7. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, The discharge plasma sintering temperature described in S2 is 700-950 ℃, the time is 0-20 min, the heating rate is 50-100 ℃ / min, and the pressure is 5-50 MPa.

8. The method for preparing the diamond-copper composite heat dissipation material according to claim 1, characterized in that, Before mixing the diamond with metal powder and active material as described in S1, a pretreatment process is required, which includes degreasing, alkaline washing and acid washing.

9. A diamond-copper composite heat dissipation material, characterized in that, It is prepared by the method of any one of claims 1-8 for the preparation of diamond-copper composite heat dissipation material.

10. The application of the diamond-copper composite heat dissipation material as described in claim 9 as a heat dissipation material in electronic packaging.

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