CN110218973B - Preparation method of Cu-Diamond composite layer on CuCr0.5 surface - Google Patents

Preparation method of Cu-Diamond composite layer on CuCr0.5 surface Download PDF

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CN110218973B
CN110218973B CN201910535225.XA CN201910535225A CN110218973B CN 110218973 B CN110218973 B CN 110218973B CN 201910535225 A CN201910535225 A CN 201910535225A CN 110218973 B CN110218973 B CN 110218973B
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diamond
hexadecanoic acid
die
composite layer
cooling
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CN110218973A (en
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邱万奇
赵满圆
陈思婷
门德玛娜
李雨茵
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/12—Organic material
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Abstract

The invention belongs to the field of heat dissipation materials of electronic devices, and discloses a preparation method of a Cu-Diamond composite layer on the surface of CuCr0.5. Evaporating a layer of hexadecanoic acid hexadecane film on the surface of a CuCr0.5 matrix, then settling diamond powder on the surface of the hexadecanoic acid hexadecane film, pressing the diamond particles into the matrix in a half way through room-temperature die pressing, and finally pressing all the diamond particles on the surface of the CuCr0.5 matrix into the matrix through a hot die pressing method. The invention effectively combines the hot die pressing and the CuCr0.5 solid solution and aging process, reduces the heat loss, simplifies the preparation process, effectively coats the diamond particles, effectively reduces the interface thermal resistance and simultaneously reduces the surface thermal expansion coefficient.

Description

Preparation method of Cu-Diamond composite layer on CuCr0.5 surface
Technical Field
The invention belongs to the field of heat dissipation materials of electronic devices, and particularly relates to a preparation method of a Cu-Diamond composite layer on the surface of CuCr0.5.
Background
With the rapid development of microelectronic integration technology and high-density packaging technology of hollow printed boards, semiconductor integrated circuits have higher density and higher power density, joule heat generated in unit area is also higher and higher, and how to quickly and fully radiate the heat to the external environment is a key for ensuring stable and reliable operation of devices. One effective measure for thermal management control in the production of microelectronic devices is to incorporate a heat sink of high thermal conductivity at the bottom of the device to absorb heat emitted from the components and quickly transfer the heat to the environment. The heat sink should not only have high thermal conductivity, but also have a thermal expansion coefficient matched with that of the semiconductor material to prevent the device from being damaged due to thermal fatigue during service. Although the common good conductors such as copper, silver, aluminum and the like have higher thermal conductivity, the good conductors cannot be directly used as heat dissipation bodies due to too large thermal expansion coefficients; most of the heat dissipation body materials widely applied at present are composite materials sintered by copper and granular diamond, and the diamond not only has high heat conductivity, but also has low thermal expansion coefficient, but is difficult to form and process and expensive; the diamond powder and the copper are sintered into the composite material, so that the thermal expansion coefficient is reduced, and simultaneously, high thermal conductivity is kept. The method has the defects that the Cu-Diamond composite material containing a large amount of granular Diamond has poor forming and processing performances and low strength, a certain thickness is required to ensure the strength, but the thermal diffusion distance along the thickness direction is increased, and the thermal resistance is increased. In addition, an excessively thick heat sink does not utilize miniaturization of microelectronic devices. The Cu-Diamond layer with the thickness of single Diamond particles is prepared on the surface of Cu, so that the problem can be solved well. The currently published method of producing Cu-Diamond layers on copper is in powdering, cold stamping and diffusion annealing. The main reason is that the cold die pressing can not form high-strength metallurgical bonding on a Cu/Diamond interface, the thermal expansion coefficient is difficult to effectively reduce to the utmost extent, and the thermal resistance of the interface is large, so that the thermal resistance of the whole radiator is large.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a Cu-Diamond composite layer on the surface of CuCr0.5.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a Cu-Diamond composite layer on the surface of CuCr0.5 comprises the following preparation steps:
(1) evaporating an oil film: evaporating a layer of hexadecanoic acid hexadecane film on the surface of a CuCr0.5 matrix;
(2) settling and sanding of the diamond suspension: ultrasonically dispersing diamond powder in a hot water container to obtain a diamond-water suspension, then placing a CuCr0.5 matrix evaporated with hexadecanoic acid palmitate at the bottom of the diamond-water suspension to enable the surface evaporated with the hexadecanoic acid palmitate to be upward, settling the diamond to the surface of the hexadecanoic acid palmitate and adhering a layer of diamond powder, and taking out after cooling;
(3) semi-cold die pressing: pressing the diamond powder adhered to the surface of the CuCr0.5 into a CuCr0.5 substrate by using a mould press under the pressure of 300-350 MPa, so that the diamond particles can be firmly adhered to the surface of the substrate;
(4) degreasing and cleaning: ultrasonically cleaning the sample subjected to semi-cold die pressing in the step (3) by using an alkaline degreasing agent to remove hexadecanoic acid palmitate, then ultrasonically cleaning by using distilled water to remove residual degreasing agent, and drying;
(5) hot die pressing: putting the degreased and cleaned sample obtained in the step (4) into a hot-molding die, enabling the surface containing the diamond to be attached to a lower die, and placing the lower die in a position N2+H2And heating the furnace to 900-950 ℃ in a protective atmosphere furnace, performing mould pressing for 20-30 min under the pressure of 500-600 MPa, cooling, releasing pressure and discharging to obtain the CuCr0.5 surface Cu-Diamond composite layer.
Preferably, the method for evaporating a layer of hexadecanoic acid film in the step (1) comprises the following steps: adding hexadecanoic acid palmitate into an open container, then placing a CuCr0.5 matrix at an upper opening of the container, heating the hexadecanoic acid palmitate to 200-220 ℃, controlling the temperature of the CuCr0.5 matrix to be 60-65 ℃, evaporating for 5-10 min, and cooling to obtain the hexadecanoic acid film.
Preferably, the thickness of the hexadecanoic acid lipid film in the step (1) is 15-35 μm, and the particle size of the diamond powder in the step (2) is W20-40. More preferably, the thickness of the hexadecanoic acid film is 60% of the diamond powder particle size.
Preferably, the temperature of the hot water in the step (2) is 60-70 ℃, and the taking out after cooling means that the temperature is reduced to below 40 ℃ and the hot water is taken out.
Preferably, the concentration of the diamond-water suspension in the step (2) is determined by: according to the area S (cm) of the bottom of the container2) Calculating the mass m (mg) of the diamond powder to be added by using a formula m which is 0.35 eta Sh; the coverage rate eta ranges from 0.6 to 0.7. The hexadecanoic acid cetyl esters are melted at the temperature of more than 56 ℃, are insoluble in water, have strong adsorption force on diamond powder, and after the diamond powder suspended in water at the temperature of 60-70 ℃ is uniformly precipitated on the hexadecanoic acid cetyl esters film, the diamond particles are partially immersed in the hexadecanoic acid cetyl esters, and when the temperature is reduced to be lower than 40 ℃, the liquid hexadecanoic acid cetyl esters film is solidified and fixed to be uniformly distributedThe scattered diamond particles prevent the surface diamond from agglomerating when the surface diamond is air-dried.
Preferably, said N in step (5)2+H2H in a protective atmosphere2Is 10% by volume.
Preferably, the die in the step (5) is a limited backward extrusion die, and the gap between an upper die and a limited ring is 0.3-0.4 mm, so as to prevent the extruded copper from turning over; the limiting ring is made of high-temperature alloy materials with the heat intensity temperature exceeding 700 ℃, such as GH4169, Inconel718 and the like, and the upper die and the lower die are made of corundum ceramics.
Preferably, the step of cooling, releasing pressure and discharging in the step (5) is as follows: keeping pressure and blowing cold N2+H2Quickly cooling the mixed gas to 430-450 ℃, releasing the pressure, keeping the temperature for 120min, cooling the furnace to below 60 ℃, and discharging.
The preparation method of the invention has the following advantages and beneficial effects:
the invention adopts hexadecanoic acid cetyl ester to replace stearic acid to adhere the diamond particles, obviously reduces the adhesive strength of the diamond particles, replaces middle-temperature and long-time die pressing with short-time and high-temperature die pressing, obviously improves the productivity, and effectively reduces the work hardening of CuCr0.5 during die pressing. The invention effectively combines hot die pressing and CuCr0.5 solid solution and aging processes together, reduces heat loss and simplifies the preparation process, the diamond particles are more effectively coated, and the high-temperature pressure maintaining enables Cr in the CuCr0.5 to be fully diffused to a copper/diamond interface to form interface carbide, thereby obviously improving the interface adhesion, effectively reducing the surface thermal expansion coefficient and simultaneously reducing the interface thermal resistance.
Drawings
FIG. 1 is a schematic diagram of a process for settling diamond powder in an example of the present invention; the labels in the figures illustrate the following: 1-dispersion vessel, 2-diamond-water suspension, 3-monolayer diamond particles settled on the surface of the sample, 4-hexadecanoic acid hexadecimal film, 5-cucr0.5 matrix.
FIG. 2 is an SEM topography of the surface of a sample adhered with diamond powder after settling and sanding in example 1 of the present invention.
FIG. 3 is a schematic view of a hot embossing process in an embodiment of the present invention; the labels in the figures illustrate the following: 3-half pressing single-layer diamond particles on the surface of a sample, 5-CuCr0.5 matrix, 6-upper die, 7-limiting ring and 8-lower die.
FIG. 4 is an SEM topography of a Cu-Diamond layer on the surface of CuCr0.5 prepared in example 1 of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Cutting the CuCr0.5 alloy (matrix) into a sample with the size of phi 20 multiplied by 3mm, grinding and polishing two end faces of the sample, washing with distilled water and air-drying.
(2) Weighing 10g hexadecanoic acid ester, placing in a 100ml beaker, heating stearic acid to 200 ℃ by using a temperature-controllable electric furnace, placing a polished sample (with the front surface facing downwards) at the opening of the beaker (about 65mm away from the evaporation surface of the hexadecanoic acid ester), heating the sample to 60 ℃ by using an infrared baking lamp, evaporating for 5min to obtain an oily hexadecanoic acid ester film, and cooling to room temperature to form a solid film with the thickness of about 17 mu m.
(3) MBD4 grade W26 diamond powder was used as the insert particles. A100 ml flat-bottomed beaker having an inner diameter of 5.0 cm was used as a dispersion vessel. The coverage rate of the diamond powder on the bottom surface of the container is 65%, the addition amount of the W26 diamond powder is calculated to be 111mg according to a formula of 65% multiplied by 0.35 multiplied by Sh (mg), 111mg MBD4 grade W26 diamond powder is accurately weighed by an electronic balance into a 100ml beaker, 60ml distilled water is added, the diamond powder is fully dispersed and mixed in water bath ultrasonic waves, and after uniform diamond suspension is formed, the ultrasonic is stopped, and the diamond powder is slowly settled.
(4) Heating the diamond suspension liquid in a beaker to 65 ℃ in water bath, suspending the diamond powder by using ultrasound again to be turbid, immediately placing a sample at the bottom of the container, evaporating a hexadecanoic acid film upwards, and fully standing to ensure that the diamond micro powder is uniformly settled at the bottom of the container and on the surface of the sample. The schematic diagram of the diamond powder settling process is shown in fig. 1.
(5) And after the diamond micro powder in the suspension is fully settled, reducing the temperature of the water bath to reduce the temperature of the beaker with the sample to below 40 ℃, taking out the sample, and drying the sample in the air to obtain the SEM appearance of the surface of the sample as shown in figure 2.
(6) And placing the sample adhered with the diamond powder on a lower die of a half die pressing die, enabling the surface adhered with the diamond powder to face upwards, slowly lowering the upper die to contact the surface of the sample, pressurizing to 320MPa, and not allowing the upper die and the lower die to move horizontally during die pressing, otherwise, changing the distribution of diamonds on the surface of the sample. After cold pressing, part of W26 diamond particles are pressed into the matrix to fully fix the diamond particles, and meanwhile, hexadecanoic acid cetyl ester is extruded in gaps of the diamond particles to have partial fixing effect.
(7) And (3) placing the semi-molded sample in an alkaline degreasing agent at 75 ℃ for ultrasonic cleaning for 30min to remove residual hexadecanoic acid membranes, then carrying out ultrasonic cleaning for 3 times in distilled water to remove residual degreasing agent, and finally drying.
(8) Putting the degreased and cleaned sample into a hot-pressing mould (the mould is a limited backward extrusion mould, the gap between an upper mould and a limited ring is 0.3-0.4 mm to prevent the extruded copper from peeling, the limited ring is made of high-temperature alloy materials with the heat intensity temperature exceeding 700 ℃, such as GH4169, Inconel718 and the like, an oxide separating agent is sprayed on the working surface of a mould cavity to prevent the copper from being bonded with the wall of a hot-pressing film, the upper mould and the lower mould are made of corundum ceramics), a diamond-containing surface is attached to a lower mould, and the lower mould is pressed on an N-shaped die2+H2Heating the furnace to 920 ℃ in a 10 vol.% protective atmosphere furnace, molding for 25min under the pressure of 550MPa, volatilizing trace degreasing agent residue at the moment, and cooling by blowing N2+H2Quickly cooling 10 vol.% gas to 440 ℃, unloading, preserving heat and aging for 120min, and then cooling the furnace to below 60 ℃ and discharging. The schematic diagram of the hot embossing process of this step is shown in fig. 3.
The Cu-Diamond layer prepared in this example was integrated with a CuCr0.5 substrate, the thickness of the Cu-Diamond composite layer was about 26 μm, and the surface thermal expansion coefficient measured with a resistance strain gage was 7.2X 10-6and/DEG C, the requirement of matching with the thermal expansion coefficient of the chip is met. The surface SEM topography of the Cu-Diamond layer on the surface of the obtained CuCr0.5 is shown in FIG. 4. As can be seen from fig. 4, the W26 diamond particles were tightly coated with cucr0.5 extruded from the diamond particle gap, and the surface was flat.
Example 2
(1) Cutting the CuCr0.5 alloy (matrix) into a sample with the size of phi 20 multiplied by 3mm, grinding and polishing two end faces of the sample, washing with distilled water and air-drying.
(2) Weighing 10g of hexadecanoic acid cetyl ester, placing the hexadecanoic acid cetyl ester in a 100ml beaker, heating stearic acid to 220 ℃ by using an electric furnace with controllable temperature, placing a polished sample (with the front surface facing downwards) at the opening of the beaker (about 65mm away from the evaporation surface of the hexadecanoic acid cetyl ester), heating the sample to 65 ℃ by using an infrared baking lamp, evaporating for 7min to obtain an oily hexadecanoic acid cetyl ester film, and cooling to room temperature to form a solid film with the thickness of about 28 mu m.
(3) MBD4 grade W40 diamond powder was used as the insert particles. A100 ml flat-bottomed beaker having an inner diameter of 5.0 cm was used as a dispersion vessel. The coverage rate of the diamond powder on the bottom surface of the container is 55%, the addition amount of the W40 diamond powder is calculated to be 151mg according to the formula 55% multiplied by 0.35 multiplied by Sh (mg), 151mg MBD4 grade W40 diamond powder is accurately weighed by an electronic balance into a 100ml beaker, 60ml of distilled water is added, the diamond powder is fully dispersed and mixed in water bath ultrasonic waves, and after uniform diamond suspension is formed, the ultrasonic is stopped, and the diamond powder is slowly settled.
(4) Heating the diamond suspension liquid in a beaker to 65 ℃ in water bath, suspending the diamond powder by using ultrasound again to be turbid, immediately placing a sample at the bottom of the container, evaporating a hexadecanoic acid film upwards, and fully standing to ensure that the diamond micro powder is uniformly settled at the bottom of the container and on the surface of the sample.
(5) And after the diamond micro powder in the suspension is fully settled, reducing the temperature of the water bath, and taking out the sample to air dry when the temperature of the beaker filled with the sample is reduced to below 40 ℃.
(6) And placing the sample adhered with the diamond powder on a lower die of a half die pressing die, enabling the surface adhered with the diamond powder to face upwards, slowly lowering the upper die to be in contact with the surface of the sample, pressurizing to 350MPa, and not allowing the upper die and the lower die to move horizontally during die pressing, otherwise, changing the distribution of diamonds on the surface of the sample. After cold pressing, part of W40 diamond particles are pressed into the matrix to fully fix the diamond particles, and meanwhile, hexadecanoic acid cetyl ester is extruded in gaps of the diamond particles to have partial fixing effect.
(7) And (3) placing the semi-molded sample in an alkaline degreasing agent at 75 ℃ for ultrasonic cleaning for 30min to remove residual hexadecanoic acid membranes, then carrying out ultrasonic cleaning for 3 times in distilled water to remove residual degreasing agent, and finally drying.
(8) Putting the degreased and cleaned sample into a hot-pressing mould (the mould is a limited backward extrusion mould, the gap between an upper mould and a limited ring is 0.3-0.4 mm to prevent the extruded copper from peeling, the limited ring is made of high-temperature alloy materials with the heat intensity temperature exceeding 700 ℃, such as GH4169, Inconel718 and the like, an oxide separating agent is sprayed on the working surface of a mould cavity to prevent the copper from being bonded with the wall of a hot-pressing film, the upper mould and the lower mould are made of corundum ceramics), a diamond-containing surface is attached to a lower mould, and the lower mould is pressed on an N-shaped die2+H2Heating the furnace to 950 ℃ in a 10 vol.% protective atmosphere furnace, molding the die for 20min under the pressure of 500MPa, volatilizing trace degreasing agent residue at the time, and cooling by blowing N2+H2Quickly cooling 10 vol.% gas to 450 ℃, unloading, preserving heat and aging for 120min, and then cooling the furnace to below 60 ℃ and discharging.
The Cu-Diamond layer prepared in this example was integrated with a CuCr0.5 substrate, the thickness of the Cu-Diamond composite layer was about 40 μm, and the surface thermal expansion coefficient measured by a resistance strain gage was 7.8X 10-6and/DEG C, the requirement of matching with the thermal expansion coefficient of the chip is met.
Example 3
(1) Cutting the CuCr0.5 alloy (matrix) into a sample with the size of phi 20 multiplied by 3mm, grinding and polishing two end faces of the sample, washing with distilled water and air-drying.
(2) Weighing 10g hexadecanoic acid ester, placing in a 100ml beaker, heating stearic acid to 200 ℃ by using a temperature-controllable electric furnace, placing a polished sample (with the front surface facing downwards) at the opening of the beaker (about 65mm away from the evaporation surface of the hexadecanoic acid ester), heating the sample to 60 ℃ by using an infrared baking lamp, evaporating for 5min to obtain an oily hexadecanoic acid ester film, and cooling to room temperature to form a solid film with the thickness of about 12 mu m.
(3) MBD4 grade W20 diamond powder was used as the insert particles. A100 ml flat-bottomed beaker having an inner diameter of 5.0 cm was used as a dispersion vessel. Taking 70% of the coverage rate of the diamond powder on the bottom surface of the container, calculating the addition amount of the W20 diamond powder to be 96mg according to a formula of 70% multiplied by 0.35 multiplied by Sh (mg), accurately weighing 96mg MBD4 grade W20 diamond powder into a 100ml beaker by using an electronic balance, adding 60ml distilled water, fully dispersing and mixing in water bath ultrasonic waves to form uniform diamond suspension, stopping ultrasonic treatment, and slowly settling the diamond powder.
(4) Heating the diamond suspension in a beaker to 70 ℃ in water bath, suspending the diamond powder by using ultrasound again to be turbid, immediately placing a sample at the bottom of the container, evaporating a hexadecanoic acid film upwards, and fully standing to ensure that the diamond micro powder is uniformly settled at the bottom of the container and on the surface of the sample.
(5) And after the diamond micro powder in the suspension is fully settled, reducing the temperature of the water bath, and taking out the sample to air dry when the temperature of the beaker filled with the sample is reduced to below 40 ℃.
(6) And placing the sample adhered with the diamond powder on a lower die of a half die pressing die, enabling the surface adhered with the diamond powder to face upwards, slowly lowering the upper die to be in contact with the surface of the sample, pressurizing to 300MPa, and not allowing the upper die and the lower die to move horizontally during die pressing, otherwise, changing the distribution of diamonds on the surface of the sample. After cold pressing, part of W20 diamond particles are pressed into the matrix to fully fix the diamond particles, and meanwhile, hexadecanoic acid cetyl ester is extruded in gaps of the diamond particles to have partial fixing effect.
(7) And (3) placing the semi-molded sample in an alkaline degreasing agent at 80 ℃ for ultrasonic cleaning for 30min to remove residual hexadecanoic acid membranes, then carrying out ultrasonic cleaning for 3 times in distilled water to remove residual degreasing agent, and finally drying.
(8) Putting the degreased and cleaned sample into a hot-pressing mould (the mould is a limited backward extrusion mould, the gap between an upper mould and a limited ring is 0.3-0.4 mm to prevent the extruded copper from peeling, the limited ring is made of high-temperature alloy materials with the heat intensity temperature exceeding 700 ℃, such as GH4169, Inconel718 and the like, an oxide separating agent is sprayed on the working surface of a mould cavity to prevent the copper from being bonded with the wall of a hot-pressing film, the upper mould and the lower mould are made of corundum ceramics), a diamond-containing surface is attached to a lower mould, and the lower mould is pressed on an N-shaped die2+H2Heating to 900 ℃ in a 10 vol.% protective atmosphere furnace, molding for 30min under the pressure of 600MPa, volatilizing trace degreasing agent residue at the moment, and cooling by blowing N2+H210 vol.% gas quick cooling to 450 ℃ dischargeCarrying, keeping the temperature and aging for 120min, cooling the furnace to below 60 ℃, and discharging.
The Cu-Diamond layer prepared in this example was integrated with a CuCr0.5 substrate, the thickness of the Cu-Diamond composite layer was about 40 μm, and the surface thermal expansion coefficient measured by a resistance strain gage was 7.0X 10-6and/DEG C, the requirement of matching with the thermal expansion coefficient of the chip is met.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A preparation method of a Cu-Diamond composite layer on the surface of CuCr0.5 is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
(1) evaporating an oil film: evaporating a layer of hexadecanoic acid hexadecane film on the surface of a CuCr0.5 matrix;
(2) settling and sanding of the diamond suspension: ultrasonically dispersing diamond powder in a hot water container to obtain a diamond-water suspension, then placing a CuCr0.5 matrix evaporated with hexadecanoic acid palmitate at the bottom of the diamond-water suspension to enable the surface evaporated with the hexadecanoic acid palmitate to be upward, settling the diamond to the surface of the hexadecanoic acid palmitate and adhering a layer of diamond powder, and taking out after cooling;
(3) semi-cold die pressing: pressing the diamond powder adhered to the surface of the CuCr0.5 into a CuCr0.5 substrate by using a mould press under the pressure of 300-350 MPa, so that the diamond particles can be firmly adhered to the surface of the substrate;
(4) degreasing and cleaning: ultrasonically cleaning the sample subjected to semi-cold die pressing in the step (3) by using an alkaline degreasing agent to remove hexadecanoic acid palmitate, then ultrasonically cleaning by using distilled water to remove residual degreasing agent, and drying;
(5) hot die pressing: putting the degreased and cleaned sample obtained in the step (4) into a hot-molding die, enabling the surface containing the diamond to be attached to a lower die, and placing the lower die in a position N2+H2Heating the furnace to 900-950 ℃ in a protective atmosphere furnace, molding the die for 20-30 min under the pressure of 500-600 MPa, cooling and dischargingPressing out the alloy from the furnace to obtain a Cu-Diamond composite layer on the surface of the CuCr0.5;
the thickness of the hexadecanoic acid lipid film in the step (1) is 15-35 mu m, and the particle size of the diamond powder in the step (2) is W20-40.
2. The method for preparing a Cu-Diamond composite layer on the surface of CuCr0.5 according to claim 1, wherein: the method for evaporating the hexadecanoic acid film in the step (1) comprises the following steps: adding hexadecanoic acid palmitate into an open container, then placing a CuCr0.5 matrix at an upper opening of the container, heating the hexadecanoic acid palmitate to 200-220 ℃, controlling the temperature of the CuCr0.5 matrix to be 60-65 ℃, evaporating for 5-10 min, and cooling to obtain the hexadecanoic acid film.
3. The method for preparing a Cu-Diamond composite layer on the surface of CuCr0.5 according to claim 1, wherein: the thickness of the hexadecanoic acid film was 60% of the diamond powder particle size.
4. The method for preparing a Cu-Diamond composite layer on the surface of CuCr0.5 according to claim 1, wherein: in the step (2), the temperature of the hot water is 60-70 ℃, and the taking out after cooling means that the temperature is reduced to below 40 ℃ and the hot water is taken out.
5. The method for preparing a CuCr0.5 surface Cu-Diamond composite layer according to claim 1, wherein the concentration of the Diamond-water suspension in step (2) is determined by: calculating the mass m of the diamond powder to be added according to the area S of the bottom of the container, the granularity h of the diamond powder and the area coverage rate eta of the diamond powder by using a formula m which is 0.35 eta Sh; the coverage rate eta ranges from 0.6 to 0.7.
6. The method for preparing a Cu-Diamond composite layer on the surface of CuCr0.5 according to claim 1, wherein: said N in step (5)2+H2H in a protective atmosphere2Is 10% by volume.
7. The method for preparing a Cu-Diamond composite layer on the surface of CuCr0.5 according to claim 1, wherein: in the step (5), the die is a limited backward extrusion die, and the gap between an upper die and a limited ring is 0.3-0.4 mm; the limiting ring is made of high-temperature alloy material with heat intensity temperature over 700 ℃, and the upper die and the lower die are made of corundum porcelain.
8. The method for preparing the CuCr0.5 surface Cu-Diamond composite layer according to claim 1, wherein the step of cooling, pressure relief and tapping in step (5) comprises the steps of: keeping pressure and blowing cold N2+H2Quickly cooling the mixed gas to 430-450 ℃, releasing the pressure, keeping the temperature for 120min, cooling the furnace to below 60 ℃, and discharging.
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