CN114717441A - Method for preparing diamond/copper composite material with low density and high thermal conductivity at low cost - Google Patents
Method for preparing diamond/copper composite material with low density and high thermal conductivity at low cost Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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Abstract
The invention provides a method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost, which comprises the following steps: preprocessing a diamond crushing material; plating tungsten on the surface of the diamond by a direct-current magnetron sputtering method to prepare a coating simple substance tungsten film; annealing in a vacuum tube furnace to convert the tungsten simple substance on the surface of the diamond into tungsten carbide; and (3) coating the diamond and the copper powder wrapped with the tungsten carbide according to the weight ratio of 3: 1-4: 1, fully mixing and pressing into a cylinder; and then, carrying out a high-temperature high-pressure process by using a cubic press to obtain the diamond/copper composite material. According to the invention, the diamond crushing material is selected as the raw material, so that the cost is greatly reduced; the diamond composite material is synthesized by adopting a high-temperature high-pressure process, so that the compactness is high, the preparation time is short, and the efficiency is high; the prepared sample has low density and high thermal conductivity, and the method has simple operation and low manufacturing cost, can be used for large-scale batch production, and has wide industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost, belonging to the field of composite materials.
Background
Along with the rapid development of artificial intelligence technology and 5G communication technology, the integration level of an electronic circuit and the performance of an electronic component are continuously improved, the speed of processing data by a cpu is faster and faster, the working power of a high-power device is improved, more and more heat is generated, and how to quickly and efficiently transmit the heat is the key for ensuring the normal work of the high-power device. The packaging materials commonly used for heat dissipation in the current market comprise a metal-based packaging material, a polymer-based composite material and a ceramic-based packaging material, wherein the ceramic packaging material needs to be subjected to powder high-temperature sintering during preparation, secondary processing is difficult to perform due to the brittleness of the ceramic, and the large-scale application of the ceramic is difficult to limit due to high cost and processing; the polymer-based composite material has low thermal conductivity, and the poor thermal stability at high temperature absorbs moisture in the air to cause failure.
Metal-based materials are one of the most widely used packaging materials at the beginning, and their large-scale application is limited due to the high density and high thermal expansion coefficient of metals such as Al, Cu, W, etc. of the conventional metal-based packaging materials. The diamond has high thermal conductivity of 1000-2200W/(m.K) and low expansion rate of 7.6-9.6X 10-7K-1And the industrial production is realized, the copper has the highest neutral cost ratio in all base materials, and the metal copper and the diamond are compounded to be an ideal heat dissipation material. The diamond/copper composite material has excellent heat-conducting property, the thermal expansion coefficient of the diamond/copper composite material is matched with semiconductor materials such as Si, GaAs, GaN, SiC and the like, and the diamond composite material also has the advantages of excellent mechanical property, low density and the like, and is a representative of a new generation of heat management materials in the field of electronic packaging and heat dissipation.
Diamond has the characteristics of high hardness, high chemical stability and the like, does not react with copper, and is difficult to be wetted by alloy or metal generally, so that the bonding condition of a contact interface between the diamond and the copper is poor, and the high heat-conducting property of the diamond cannot be fully exerted. The interface of the diamond/Cu composite material is improved by optimizing the preparation process. The commonly used preparation methods of the diamond/Cu composite material include a high-temperature high-pressure sintering method, a discharge plasma sintering method, a hot-pressing sintering method, an infiltration method and the like. The diamond/Cu composite material prepared by the high-temperature high-pressure sintering method has high density, short time consumption and high efficiency, so that the diamond/Cu composite material is quite wide in application. The heat-conducting property of the diamond/Cu composite material is improved by means of long-time continuous sintering, metal matrix alloying, diamond surface metallization and the like. The cost of the single crystal diamond particles is high, and the prepared diamond composite material has high density and low thermal conductivity. Therefore, in order to reduce the cost, reduce the density of the composite material and increase the thermal conductivity of the composite material, a new method needs to be further researched to improve the thermal conductivity.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost comprises the following steps:
(1) pretreatment of diamond crushing material
Recovering defective products generated in the industrial production of diamond crystals, and crushing to obtain a diamond crushed material with the granularity of 100-120 meshes for later use;
soaking the diamond crushed material in aqua regia for 2.5-3.5 h to remove metal pollutants on the surface of the diamond; then, respectively using acetone, alcohol and deionized water to carry out ultrasonic treatment for 8-12 min, and removing organic pollutants; drying the diamond for later use;
(2) preparing a film wrapping elemental tungsten
Plating tungsten on the surface of the diamond by a direct-current magnetron sputtering method, wherein the thickness of a plating layer is 80-120 nm;
(3) forming tungsten carbide on the surface of diamond
Annealing the diamond coated with the metal tungsten in a vacuum tube furnace under the condition of Ar2Annealing for 0.5-1.5 h at 900-1000 ℃ in the atmosphere to convert the tungsten simple substance on the surface of the diamond into tungsten carbide;
(4) preparation of diamond/copper composite Material
And (3) coating the diamond and the copper powder coated with the tungsten carbide in the step (3) according to the weight ratio of 3: 1-4: 1, uniformly mixing, and pressing into a cylinder with the diameter of 10mm multiplied by the thickness of 2 mm; and then, carrying out a high-temperature high-pressure process by using a cubic press, wherein the sintering temperature is 950-1350 ℃, the pressure is 5-7 Gpa, and the heat preservation time is 8-12 min, so as to obtain the diamond/copper composite material.
The diamond crushing material has nitrogen content (wt%) of 0.015-0.020% and heat conductivity of 1500-2000W/(m.K).
HCl in the aqua regia: HNO3(v/v) ═ 3: 1; the volume fraction of the alcohol is 97%.
The drying temperature is 80 ℃, and the drying time is 10 min.
The sputtering current of the direct current magnetron sputtering method is 1A, the sputtering vacuum degree is 3 multiplied by 10-3Pa, sputtering rate of 0.02 nm/min-0.08 nm/min.
The purity of the copper powder is 99.9%; the granularity of the copper powder is 120-200 meshes.
The sintering temperature is 1050 ℃, the pressure is 6GPa, and the heat preservation time is 10 min.
The density of the diamond/copper composite material obtained by the method is 3.70g/cm3～4.0g/cm3。
The invention has the beneficial effects that:
according to the invention, the diamond crushing material is selected as a raw material, so that the cost is greatly reduced; the diamond composite material is synthesized by adopting a high-temperature high-pressure process, so that the compactness is high, the preparation time is short, and the efficiency is high; and the prepared sample has low density and high thermal conductivity, and the method has simple operation and low manufacturing cost, can be used for large-scale batch production, and has wide industrial application prospect. The specific analysis is as follows:
(1) the diamond crushing material used in the invention is obtained by crushing defective diamond products with poor crystal forms generated in the industrial production of diamond. The method has three advantages of adopting the diamond crushing material, and the first cost is low and is easy to obtain; secondly, because the gap between the broken materials is small, the broken diamond materials are combined with the copper matrix more tightly than the diamond with the complete crystal form; the third crushed material has smaller gaps, so that more diamond can be contained in the same volume, and the density of the composite material can be reduced and the thermal conductivity of the composite material can be improved by increasing the content of the diamond. When the volume content of the diamond exceeds 90 percent, the diamond can fall off because the diamond and the copper are not firmly combined due to overhigh content, gaps among the broken diamond materials are small, and when the volume content of the broken diamond materials exceeds 90 percent, the combination is still firm and is not easy to fall off.
(2) The raw materials used in the invention are as follows: the diamond broken material, copper powder and tungsten are all low-cost raw materials. The granularity of the diamond crushing material is 100-120 meshes, and when the diamond particles are too large, gaps between the diamonds are large, so that the thermal conductivity is low; when the diamond particles are too small, the diamond-copper interface is too large, resulting in low thermal conductivity. Therefore, the diamond particles are 100-120 meshes, and the interface bonding is good and the thermal conductivity is high. The broken diamond material has larger specific surface area than the diamond with a complete crystal form, and the broken material can generate a plurality of unstable crystal faces in the process of breaking the diamond, so that the crystal faces are easy to react with a substrate, and the holding force of the substrate to the diamond is increased; secondly, the matrix is selected from copper, and compared with a matrix such as silver, aluminum and the like, the copper-based composite material has higher thermal conductivity and lower cost. Diamond and copper in the diamond/copper composite material are not wetted, the interface combination is not firm, metal carbide is introduced to improve the interface state, and the heat conductivity of W and WC is relatively higher than that of other carbides through comparing the solubility, wetting angle and heat conductivity of different carbides in copper, and W is insoluble in Cu, so that the W plating is more advantageous for improving the heat conductivity of the composite material.
(3) The invention adopts the magnetron sputtering technology to complete the coating of the diamond crushing material, and the thickness of the magnetron sputtering coating metal can be relatively accurately controlled by a film thickness meter. And the metal thickness of magnetron sputtering is level and even, does not have the area of leaking plating, can accomplish the parcel to a large amount of diamonds once. The preparation of the diamond/copper composite material adopts a high-temperature high-pressure process, and a composite material sample prepared at high temperature and high pressure has high compactness, high thermal conductivity, short preparation time and high efficiency. Wherein, the too long sintering time can cause the metal tungsten on the surface of the diamond to be precipitated into the copper matrix, thereby causing the heat conductivity of the copper matrix to be reduced, and the too short sintering time can not cause the copper to fully flow into the gap between the diamond and the diamond, therefore, the sintering time of the method of the invention is 10min, and the highest heat conductivity is found when the sintering temperature is 1050 ℃.
(4) Meter based on thermal conductivity of composite materialCalculating a formula: γ ═ ρ · C ρ · α where γ is the thermal conductivity; rho is the sample density; crho is the constant pressure specific heat capacity of the sample; α is a thermal diffusivity. It can be seen that the higher the thermal conductivity of the prepared composite material, the better, and the lower the density of the composite material, the better. The density of the composite material is generally reduced by increasing the diamond content, but a reduction in density also results in a reduction in thermal conductivity. Therefore, the thermal conductivity is generally improved by lowering the thermal interface resistance between diamond and copper to increase the thermal diffusion coefficient. The invention adopts the diamond crushing material to plate tungsten to improve the interface and reduce the interface thermal resistance. Wherein the diamond crushing material is still firmly combined when the volume content reaches 90 percent, and the diamond content of 90 percent leads the sample density to be lower than 4g/cm3The strong bonding of the diamond and copper interface results in a high thermal diffusivity (331 mm)-2·s-1) And high thermal conductivity (655.2002 W.m)-1·k-1)。
(5) The density of the diamond/copper composite material sample obtained by the invention is calculated by measurement and is 3.7-4.0 g/cm3The constant pressure specific heat capacity is 0.50-0.51 kJ/(kg. DEG C.), and the thermal diffusion coefficient is 188-331 mm-2·s-1The thermal conductivity is 360-656 W.m-1·k-1。
Drawings
FIG. 1 shows a crushed diamond material before magnetron sputtering in example 1;
FIG. 2 shows a crushed material of tungsten-plated diamond after magnetron sputtering and before annealing in example 1;
FIG. 3 shows a crushed tungsten-plated diamond material annealed in example 1;
FIG. 4 is a scanning electron microscope photograph of the tungsten-plated diamond before annealing in example 1;
FIG. 5 is a scanning electron microscope photograph of the tungsten-plated diamond after annealing in example 1;
FIG. 6 is an X-ray diffraction chart of tungsten-plated diamond before annealing in example 1;
FIG. 7 is an X-ray diffraction chart of tungsten-plated diamond after annealing in example 1;
fig. 8, scanning electron microscope image of diamond/copper composite prepared in example 1;
fig. 9, scanning electron microscope image of diamond/copper composite prepared in example 2;
fig. 10, scanning electron microscope image of diamond/copper composite prepared in example 3;
fig. 11, scanning electron microscope image of diamond/copper composite prepared in example 4;
fig. 12, scanning electron microscope image of diamond/copper composite prepared in example 5;
FIG. 13, thermal diffusivity of diamond/copper composite prepared in examples 1-5;
figure 14, thermal conductivity of diamond/copper composites prepared in examples 1-5.
Detailed Description
The following examples further illustrate the embodiments of the present invention in detail. Unless otherwise stated, the instruments and equipment referred to in the examples are conventional instruments and equipment; the related reagents are all conventional reagents sold in the market; the related test methods are all conventional methods.
Example 1
A method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost comprises the following steps:
(1) pretreatment of diamond crushing material
Recovering defective products generated in the industrial production of diamond crystals, and crushing to obtain a diamond crushed material with the granularity of 100-120 meshes, wherein the nitrogen content (wt%) of the diamond crushed material is 0.015-0.020%, and the thermal conductivity of the diamond crushed material is 1500-2000W/(m.K) for later use;
crushing diamond in aqua regia (HCl: HNO)3(v/v) ═ 3: 1) soaking for 3h to remove metal pollutants on the surface of the diamond; then, respectively carrying out ultrasonic treatment for 10min by using acetone, 97% (v/v) alcohol and deionized water to remove organic pollutants; finally, drying the processed diamond at 80 ℃ for 10min for later use (as shown in figure 1, the diamond is yellow powder);
(2) preparing a film wrapping elemental tungsten
Placing the diamond treated in the step (1) in a furnace withPlating tungsten on the surface of the diamond by a direct current magnetron sputtering method on a magnetron sputtering sample table with the functions of ultrasound, vibration and rolling; the sputtering current was 1A, and the sputtering vacuum degree was 3X 10-3Pa, sputtering rate of 0.02-0.08 nm/min; the final diamond surface was deposited with 100nm thick metal tungsten (as shown in figure 2).
(3) Forming tungsten carbide on the surface of diamond
Annealing the diamond coated with the metal tungsten in a vacuum tube furnace under the condition of Ar2Annealing at 950 ℃ for 1h in the atmosphere to convert the tungsten simple substance on the surface of the diamond into tungsten carbide (the conversion rate is more than 80%), and changing the original silvery white color of the obtained diamond sample into grey black color (as shown in figure 3).
Evaluation of phase analysis: scanning electron microscope analysis (as shown in fig. 4 and 5) is carried out on the tungsten-plated diamond before and after annealing, SEM test results show that the tungsten carbide on the surface of the diamond is good in wrapping uniformity and compactness, and metal is hardly dropped off after annealing treatment, which shows that the magnetron sputtering technology can enable the material to be tightly bonded to the deposited material, and has a better bonding effect compared with thermal evaporation. The microstructure of the diamond surface is changed before and after annealing, for example, metal on the surface of a sample is changed from flat to gully after annealing, so that the sample is more easily and tightly combined with copper, and the interface thermal resistance is reduced, and the thermal conductivity is improved.
X-ray diffraction analysis (as shown in fig. 6 and 7) was performed on the tungsten-plated diamond before and after annealing, and XRD test results showed that the metal tungsten on the diamond surface was converted into tungsten carbide by annealing.
(4) Preparation of diamond/copper composite Material
And (3) coating the diamond coated with the tungsten carbide in the step (2) and pure copper powder (the purity is 99.9%, and the granularity of the copper powder is 120-200 meshes) according to the weight ratio of 3.54: 1, pressing the mixture into a cylinder with the diameter of 10mm multiplied by 2mm by using a full-automatic cutter head press after uniform mixing, and finally placing a sample in a hot high-pressure assembly cavity of a domestic hinge type cubic press (UDS 650);
the high-temperature high-pressure process adopts a domestic hinge type cubic press as high-pressure equipment, and the experiment is carried out by heating a graphite tube to reach the temperature required by the experiment, wherein the sintering temperature is 950 ℃, the pressure is 6Gpa, and the heat preservation time is 10min, so as to obtain the diamond/copper composite material.
Evaluation of thermoelectric properties: the results of SEM tests showed that diamond and copper were tightly bonded through the tungsten carbide interface (fig. 8). The density of the diamond/copper composite sample was calculated by the measurement to be 3.787682g/cm3The specific heat capacity at constant pressure is 0.505522kJ/(kg DEG C), and the thermal diffusion coefficient is 188mm-2·s-1Thermal conductivity of 360.5966 W.m-1·k-1。
Example 2
The sintering temperature in the high-temperature high-pressure process of the step (3) in the example 1 is changed to 1050 ℃, and other method steps are the same as the example 1, so that the diamond/copper composite material is obtained.
Evaluation of thermoelectric properties: the results of SEM tests showed that diamond and copper were tightly bonded through the tungsten carbide interface (fig. 9). The density of the diamond/copper composite sample was calculated by measurement to be 3.941599g/cm3The specific heat capacity at constant pressure is 0.502196 kJ/(kg. DEG C.), and the thermal diffusion coefficient is 331mm-2·s-1Thermal conductivity of 655.2002 W.m-1·k-1。
Example 3
The sintering temperature in the high-temperature high-pressure process of the step (3) in the example 1 is changed to 1150 ℃, and other steps of the method are the same as the example 1, so that the diamond/copper composite material is obtained.
Evaluation of thermoelectric properties: the results of SEM tests showed that diamond and copper were tightly bonded through the tungsten carbide interface (fig. 10). The density of the diamond/copper composite sample was calculated by measurement to be 3.988798g/cm3The specific heat capacity at constant pressure is 0.50103 kJ/(kg. DEG C), and the thermal diffusion coefficient is 262.53mm-2·s-1Thermal conductivity of 524.6684 W.m-1·k-1。
Example 4
The sintering temperature in the high-temperature high-pressure process of the step (3) in the example 1 is changed to 1250 ℃, and other method steps are the same as the example 1, so that the diamond/copper composite material is obtained.
Evaluation of thermoelectric properties: test results by SEMIt was shown that diamond and copper were tightly bonded through the tungsten carbide interface (fig. 11). The density of the diamond/copper composite sample was calculated by measurement to be 3.997079g/cm3The specific heat capacity at constant pressure is 0.500918 kJ/(kg. DEG C.), and the thermal diffusion coefficient is 233.999mm-2·s-1Thermal conductivity of 468.5152 W.m-1·k-1。
Example 5
The sintering temperature in the high-temperature high-pressure process of the step (3) in the example 1 is changed to 1350 ℃, and other method steps are the same as the example 1, so that the diamond/copper composite material is obtained.
Evaluation of thermoelectric properties: the results of SEM tests showed that diamond and copper were tightly bonded through the tungsten carbide interface (fig. 12). The density of the diamond/copper composite sample was calculated by measurement to be 3.9905g/cm3The specific heat capacity at constant pressure is 0.500678 kJ/(kg. DEG C.), and the thermal diffusion coefficient is 227.401mm-2·s-1Thermal conductivity of 456.133 W.m-1·k-1。
Claims (8)
1. A method for preparing a diamond/copper composite material with low density and high thermal conductivity at low cost is characterized by comprising the following steps:
(1) pretreatment of diamond crushing material
Recovering defective products generated in the industrial production of diamond crystals, and crushing to obtain a diamond crushed material with the granularity of 100-120 meshes for later use;
soaking the diamond crushed material in aqua regia for 2.5-3.5 h to remove metal pollutants on the surface of the diamond; then, respectively using acetone, alcohol and deionized water to carry out ultrasonic treatment for 8-12 min, and removing organic pollutants; drying the diamond for later use;
(2) preparing a film wrapping elemental tungsten
Plating tungsten on the surface of the diamond by a direct-current magnetron sputtering method, wherein the thickness of a plating layer is 80-120 nm;
(3) forming tungsten carbide on the surface of diamond
Annealing the diamond coated with the metal tungsten in a vacuum tube furnace under the condition of Ar2900-10 ℃ in atmosphereAnnealing at 00 ℃ for 0.5-1.5 h to convert the tungsten simple substance on the surface of the diamond into tungsten carbide;
(4) preparation of diamond/copper composite Material
And (3) coating the diamond and the copper powder coated with the tungsten carbide in the step (3) according to the weight ratio of 3: 1-4: 1, uniformly mixing, and pressing into a cylinder with the diameter of 10mm multiplied by the thickness of 2 mm; and then, carrying out a high-temperature high-pressure process by using a cubic press, wherein the sintering temperature is 950-1350 ℃, the pressure is 5-7 Gpa, and the heat preservation time is 8-12 min, so as to obtain the diamond/copper composite material.
2. The method of claim 1, wherein the diamond compact has a nitrogen content (wt%) of 0.015% to 0.020% and a thermal conductivity of 1500W/(m-K) to 2000W/(m-K).
3. The method of claim 1, wherein the aqua regia is HCl: HNO3(v/v) ═ 3: 1; the volume fraction of the alcohol is 97%.
4. The method according to claim 1, wherein the drying process is carried out at a temperature of 80 ℃ for a drying time of 10 min.
5. The method of claim 1, wherein the sputtering current of the DC magnetron sputtering method is 1A, and the sputtering vacuum degree is 3 x 10-3Pa, sputtering rate of 0.02 nm/min-0.08 nm/min.
6. The method of claim 1 wherein said copper powder has a purity of 99.9%; the granularity of the copper powder is 120-200 meshes.
7. The method of claim 1, wherein the sintering temperature is 1050 ℃, the pressure is 6Gpa, and the holding time is 10 min.
8. The method of claim 1, wherein the method produces a diamond/copper compositeThe density of the composite material is 3.7g/cm3～4.0g/cm3。
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| CN117020209B (en) * | 2023-10-09 | 2024-01-26 | 赣州金顺科技有限公司 | Heat dissipation substrate and preparation method thereof |
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| CN114717441B (en) | 2023-01-13 |
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