CN115404533A - Copper-based diamond radiating fin and preparation method thereof - Google Patents

Copper-based diamond radiating fin and preparation method thereof Download PDF

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CN115404533A
CN115404533A CN202211166517.9A CN202211166517A CN115404533A CN 115404533 A CN115404533 A CN 115404533A CN 202211166517 A CN202211166517 A CN 202211166517A CN 115404533 A CN115404533 A CN 115404533A
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copper
diamond
electroplating
plating
solution
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陈明
李建生
鹿宪珂
赵禹
刘桐
桂凯旋
王秒
王刚
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Anhui Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

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Abstract

The invention discloses a copper-based diamond radiating fin and a preparation method thereof, wherein the preparation method comprises the following steps: 1) Carrying out surface copper plating treatment on the diamond powder by adopting chemical plating to obtain copper plated diamond powder; 2) Dispersing the copper-plated diamond powder in an electroplating solution to form an electroplating solution colloid; 3) Connecting a copper substrate with a negative electrode of a direct current power supply as an electroplating cathode, connecting a lead plate with a positive electrode of the direct current power supply as an electroplating anode, and placing the electroplating anode and the copper substrate in an electroplating solution colloid to form an electroplating loop; 4) And (5) starting a power supply, and preparing the copper-based diamond cooling fin in a deposition manner. The preparation method has the characteristics of simple raw material preparation, simple manufacturing process path, easiness in realizing batch production, high density of the diamond and good combination of the diamond and copper, so that the copper-based diamond radiating fin has excellent heat conducting property.

Description

Copper-based diamond radiating fin and preparation method thereof
Technical Field
The invention relates to a copper-based composite material, in particular to a copper-based diamond cooling fin and a preparation method thereof.
Background
The diamond has the excellent performances of large forbidden band width, extremely high hardness and thermal conductivity, high electron saturation drift velocity, high temperature resistance, corrosion resistance, irradiation resistance and the like, and has extremely important application prospects in the fields of high-voltage and high-efficiency power electronics, high-frequency and high-power microelectronics, deep ultraviolet light electronics and the like. Diamond is a natural substance with the highest thermal conductivity (2200W/(m · K)) known at present, is 4 times greater than silicon carbide (SiC), 13 times greater than silicon (Si), 43 times greater than gallium arsenide (GaAs), and 4-5 times greater than copper and silver. Therefore, diamond is the preferred material for the heat conductive member. However, since it cannot be processed and deformed, it is only possible to combine it with a metal having good heat conductivity to prepare a metal-based diamond composite material for industrial production.
Diamond is a cubic crystal formed by carbon atoms bonded by covalent bonds. Many of the very attributes of diamond are the formation of sp rigid structures 3 The strength of the covalent bond and the direct result of the small number of carbon atoms. Metal conducts heat through free electrons, which high thermal conductivity is associated with high electrical conductivity, in contrast to heat conduction in diamond which is accomplished only by lattice vibrations (i.e., phonons). The strong covalent bonds between the diamond atoms give a rigid lattice with a high vibration frequency and therefore a debye characteristic temperature as high as 2220K. Since most applications are well below debye, phonon scattering is small and therefore phonon mediated resistance to thermal conduction is minimal. However, any lattice defect (grain boundaries, interfaces, dislocations, etc.) produces phonon scattering, thereby reducing electrical and thermal conductivity, which is an inherent characteristic of all crystalline materials.
Once the matrix material and the diamond particle reinforcing phase are selected, the design and optimization of the interface is a key factor in determining whether the composite material achieves good thermal properties. The diamond and the copper are not wetted and do not react, the good interface combination of the diamond and the copper is difficult to realize by direct compounding, except a high-temperature and high-pressure method, the actual heat-conducting performance of diamond/copper compounding is seriously influenced by the problems of non-wetting, poor interface combination and the like of the direct compounding of the diamond and the metal matrix. In addition to the poor wetting ability of both, diamond (2.3X 10) -6 K) and copper (16.5X 10) -6 and/K) the great difference of the thermal expansion coefficients can introduce thermal stress at the interface of the composite material, the stress is expressed as tensile stress in the cooling process, and if the interface bonding strength is insufficient, the risk of interface debonding in the preparation and service processes of the composite material can be increased, and the performance reliability of the composite material is directly threatened. Therefore, it is necessary to design the composite interface.
At present, the preparation method of the diamond/copper composite material mainly comprises a high-temperature high-pressure method, a hot-pressing sintering method (powder metallurgy method), a discharge plasma sintering method and an extrusion casting method. The preparation methods of the diamond/copper composite materials generally face the problems of low density and poor interface bonding property.
Disclosure of Invention
The invention aims to improve the density and the bonding interface and overcome the crystal defect of a base material, and provides the copper-based diamond radiating fin and the preparation method thereof.
In order to achieve the above object, the present invention provides a method for manufacturing a copper-based diamond heat sink, the method comprising:
1) Carrying out surface copper plating treatment on the diamond powder by adopting chemical plating to obtain copper plated diamond powder;
2) Dispersing the copper-plated diamond powder in an electroplating solution to form an electroplating solution colloid;
3) Connecting a copper substrate with a negative electrode of a direct current power supply as an electroplating cathode, connecting a lead plate with a positive electrode of the direct current power supply as an electroplating anode, and placing the electroplating anode and the copper substrate in an electroplating solution colloid to form an electroplating loop;
4) And (5) starting a power supply, and preparing the copper-based diamond cooling fin in a deposition manner.
The invention also provides a preparation method of the copper-based diamond cooling fin, and the copper-based diamond cooling fin is prepared by the method.
In the above technical solution, the improvement points of the present invention are as follows:
1) Firstly, the surface of the diamond powder is plated with copper, and the formation of the copper plating layer has the following advantages: can improve the affinity and wettability of diamond and copper matrix and enhance the bonding strength of the bonding interface.
2) In the steps 4) -5), the diamond powder and the copper are combined by electroplating, and the electroplating process is mainly divided into two parts: firstly, copper atoms are continuously deposited, a freely-grown copper matrix is carried out towards a low-energy state, and the defect density of a grown copper crystal is very low; secondly, because the surface of the diamond is plated with copper, the diamond has good affinity and wettability with the copper substrate, and can form colloid suspension in plating solution, under the action of stirring, the diamond is easy to deposit on the copper substrate along with the interaction of water flow and the copper substrate, and is gradually immersed in the copper substrate along with the continuous accumulation of copper atoms, and the interface can be seamlessly and seamlessly combined, so that the prepared copper-based diamond radiating fin has good heat-conducting property.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a diagram of an apparatus in a preferred embodiment of a method for manufacturing a copper-based diamond heat sink according to the present invention;
fig. 2 is a microscopic view of a cross section of a copper-based diamond heat sink manufactured according to the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a copper-based diamond cooling fin, which comprises the following steps:
1) Carrying out surface copper plating treatment on the diamond powder by adopting chemical plating to obtain copper plated diamond powder;
2) Dispersing the copper-plated diamond powder in electroplating solution to form electroplating solution colloid;
3) Connecting a copper substrate with a negative electrode of a direct current power supply as an electroplating cathode, connecting a lead plate with a positive electrode of the direct current power supply as an electroplating anode, and placing the electroplating anode and the copper substrate in an electroplating solution colloid to form an electroplating loop;
4) And (5) starting a power supply, and preparing the copper-based diamond cooling fin in a deposition manner.
In the present invention, the conditions of the diamond powder may be selected within a wide range, but in order to further improve the heat conductive property of the copper-based diamond heat sink, it is preferable that, in step 1), the diamond powder satisfies at least the following conditions: the average particle size is 1-10 μm. When the granularity is small, the diamond particles can be agglomerated; when the particle size is larger, the diamond particles can be settled and are not easy to deposit on the surface of the cathode in the electroplating process
In the present invention, the thickness of the surface-deposited copper plating layer of the copper-coated diamond powder may be selected within a wide range, but in order to further improve the heat conductive performance of the copper-based diamond heat sink, it is preferable that the thickness of the surface-deposited copper plating layer of the copper-coated diamond powder is 20 to 40nm.
In the present invention, the conditions of the surface electroless copper plating treatment may be selected within a wide range, but in order to further improve the heat conductive property of the copper-based diamond heat sink, it is preferable that the surface electroless copper plating treatment in step 1) includes: sequentially comprises the following steps: chemical plating, cleaning with pure water for 2-5min, passivating, cleaning with pure water for 2-5min, and vacuum drying; more preferably, the plating solution for chemical plating contains 3-8g/L of copper sulfate, 22-28g/L of sodium methyl tartrate, 5-10g/L of sodium hydroxide, 8-12g/L of formaldehyde, 0.05-0.15g/L of stabilizer and solvent water, and the deposition time of chemical plating is 10-20min; further preferably, the passivation solution in passivation contains 14-16g/L of citric acid, 1.5-2.5g/L of amino trimethylene phosphonic acid, 3.0-5.0g/L of ammonium acrylate, 2.0-4.0g/L of triazene metallocene, 20-24ml/L of hydrogen peroxide, 6-8g/L of phytic acid, 5-8g/L of monocalcium phosphate, 18-20ml/L of polyethylene glycol, 0.3-0.5g/L of cerium chloride, 0.3-0.5g/L of lanthanum chloride and solvent water, wherein the pH of the passivation solution is 3.5-4.5; the soaking time for passivation is 10-20min.
In the above embodiment, the kind of the stabilizer may be selected from a wide range in order to obtain more excellent electroless plating effect, and preferably, the stabilizer is selected from at least one of bipyridine, phenanthroline, and dimethylphenanthroline.
In the present invention, the manner and conditions of the dispersion may be selected within a wide range, but in order to further improve the heat conductivity of the copper-based diamond heat sink, it is preferable that, in step 2), the dispersion is applied by an ultrasonic method, the ultrasonic frequency is 20 to 50kHZ, and the ultrasonic time is 20 to 40min.
In step 2) of the present invention, the amount of each material may be selected within a wide range, but in order to further improve the thermal conductivity of the copper-based diamond heat sink, it is preferable that the amount of the copper-plated diamond powder in step 2) is 0.8 to 16mg based on 1000mL of the plating solution.
In step 2) of the present invention, the composition of the plating solution may be selected within a wide range, but in order to further improve the heat conductive property of the copper-based diamond heat sink, it is preferable that in step 2), the following components are contained in the plating solution, and the concentrations of the components are as follows: 80-150g/L of copper sulfate, 50-90g/L of copper chloride, 40-70g/L of sodium sulfate, 60-120g/L of potassium sulfate, 5-30g/L of brightening agent, 5-20g/L of wetting agent and 25-55g/L of buffering agent; more preferably, the brightening agent is selected from at least one of sodium polydithio-dipropyl sulfonate, dimercapto benzimidazole, ethylene thiourea, sodium dodecyl sulfate and polyethylene glycol, the wetting agent is selected from at least one of propylene glycol, polyoxyethylene fatty acid ester and sodium butyl naphthalene sulfonate, and the buffering agent is selected from at least one of benzotriazole, methyl benzotriazole and sodium mercaptobenzothiazole.
In step 2) of the present invention, the specification of the copper substrate may be selected within a wide range, but in order to further improve the heat conductive property of the copper-based diamond heat sink, it is preferable that, in step 2), the thickness of the copper substrate is 150 to 300 μm; more preferably, the copper substrate is rectangular, and the specific size is 15-25cm in length and 5-15cm in width.
In step 4) of the present invention, the condition of plating may be selected within a wide range, but in order to further improve the heat conductive property of the copper-based diamond heat sink, it is preferable that in step 4), plating satisfies at least the following condition: stirring the electroplating liquid colloid in the electroplating process, wherein the electroplating temperature is 45-65 ℃, and the electroplating current density is 2-5A/dm 2 The plating voltage is controlled by the current density (driven amount), and the plating time is 4-20h.
In the present invention, in order to obtain a complete copper-based diamond heat sink, preferably, after step 4), the manufacturing method further comprises: taking down the copper-based diamond composite material obtained by the cathode, removing redundant copper, and finishing the shape; specifically, the excessive copper is removed, the mechanical polishing is carried out, and then the numerical control machine tool is used for processing and producing the required radiating fin size
In the present invention, in order to further improve the heat conductivity of the copper-based diamond heat sink, preferably, before step 1), the preparation method further comprises a pretreatment of the diamond powder, specifically: sequentially carrying out oil removal, activation, sensitization, pure water soaking for 5min and vacuum drying on the diamond powder; wherein the oil removal at least meets the following conditions: soaking in 100-150 deg.C alkali solution for 10-20min; the activation at least satisfies the following conditions: soaking the deoiled diamond particles in AgNO with the concentration of 5-10g/L at the temperature of 30-35 DEG C 3 Stirring the solution for 5 to 10min at the speed of 500 to 1000 r/min; the sensitization at least satisfies the following conditions: placing the activated diamond particles in SnCl 2 ·2H 2 In O + HCl solution, vibrating for 5-10min at 20-25 deg.C with 50-70W power ultrasonic wave; in the SnCl 2 ·2H 2 In O + HCl solution, snCl 2 ·2H 2 The concentration of O is 8-12g/L, and the concentration of HCl is 15-25ml/L; wherein the alkali solution can be sodium hydroxide solution or potassium hydroxide solution.
In the present invention, in order to remove surface oxides and oil stains and facilitate the bonding performance of the bonding surface, preferably, before step 3), the preparation method further comprises sequentially polishing the surface of the copper substrate (polishing the surface to be plated using # 2000 abrasive paper, increasing the surface roughness to increase the interfacial bonding capability), cleaning (washing the surface to be plated with pure water to remove dust), removing oil (NaOH solution, 100-150 ℃, soaking for 10-20 min), and vacuum drying.
The invention provides a preparation method of a copper-based diamond radiating fin, and the copper-based diamond radiating fin is prepared by the method.
In the above copper-based diamond heat sink, in order to further improve the heat conductive performance, the heat conductivity of the copper-based diamond heat sink is preferably 400 to 700W/(m · K).
The present invention will be described in detail below by way of examples. In the following examples, the copper substrate meets the following specifications: rectangular, 20cm long, 10cm wide, 99.95wt% copper, and is commercially available under the trade name of Touling nonferrous metals group Limited T1. The diamond powder is a commercial product of single crystal diamond fine particle diamond powder of type W1-W60 from Zhonghuan Zhongyuan original super-hard abrasive grinding tool GmbH.
The diamond powder is pretreated before use, and specifically comprises the following steps: sequentially deoiling diamond powder (NaOH solution, soaking at 130 deg.C for 15 min), and activating (soaking deoiled diamond particles in 7.8 mol/LAgNO) 3 Stirring at 33 deg.C and 700r/min for 8min, and sensitizing (placing the activated diamond particles in SnCl) 2 ·2H 2 O + HCl solution (SnCl) 2 ·2H 2 O concentration of 10g/L and HCl concentration of 20 ml/L), ultrasonic vibration at 60W for 8min at normal temperature, water washing (soaking in pure water for 5 min), and drying,Vacuum drying;
the copper substrate is pretreated before use, and specifically comprises the following steps: the upper copper substrate and the lower copper substrate were sequentially subjected to polishing (polishing the surface to be plated with # 2000 abrasive paper to increase surface roughness to increase interfacial bonding ability), cleaning (washing the surface to be plated with pure water to remove dust), degreasing (NaOH solution, soaking at 130 ℃, for 15 min), and vacuum drying.
Example 1
1) Carrying out surface copper plating treatment on diamond powder with the average particle size of 5 mu m by adopting chemical plating to obtain copper plated diamond powder, wherein the thickness of a copper plating layer deposited on the surface is controlled to be 30nm;
the specific process of electroless plating is as follows: chemical plating (plating solution formula: 5g/L copper sulfate, 25g/L sodium methyl tartrate, 7g/L sodium hydroxide, 10g/L formaldehyde, 0.1g/L stabilizer (bipyridine) and solvent water, the deposition time is 10 min), washing with pure water (3 min), passivating (passivation solution formula: 15g/L citric acid, 2.0g/L amino trimethylene phosphonic acid, 4.0g/L ammonium acrylate, 3.0g/L triazene, 22ml/L hydrogen peroxide, 7g/L phytic acid, 7g/L calcium dihydrogen phosphate, 19ml/L polyethylene glycol, 0.4g/L cerium chloride, 0.4g/L lanthanum chloride and solvent water, the pH is adjusted to 4, the soaking time is 15 min), passing through pure water (3 min), and vacuum drying. 2) Dispersing 16g of copper-plated diamond powder in 2L of electroplating solution by adopting an ultrasonic method (the ultrasonic frequency is 40KHZ, and the ultrasonic time is 40 min) to form electroplating solution colloid;
the electroplating solution contains the following components in concentration: 100g/L of copper sulfate, 70g/L of copper chloride, 50g/L of sodium sulfate, 100g/L of potassium sulfate, 15g/L of brightener (sodium polydithio-dipropyl sulfonate), 15g/L of wetting agent (sodium butylnaphthalene sulfonate) and 35g/L of buffering agent (benzotriazole);
3) As shown in fig. 1, a copper substrate with a thickness of 200 μm is connected with a negative electrode of a direct current power supply to serve as a plating cathode, a lead plate is connected with a positive electrode of the direct current power supply to serve as a plating anode, and the copper substrate and the lead plate are placed in a plating solution colloid to form a plating loop;
4) Stirring the colloid of the electroplating solution, turning on the power supply, controlling the electroplating temperature to be 60 ℃ and the electroplating current density to be 4A/dm 2 The electroplating voltage is driven, the electroplating time is 4 hours, and the copper-based diamond radiating fin is prepared by deposition;
5) And taking down the copper-based diamond composite material obtained by the cathode, removing redundant copper, finishing the shape and finishing the processing production of the radiating fin.
Example 2
1) Carrying out surface copper plating treatment on diamond powder with the average particle size of 1 mu m by adopting chemical plating to obtain copper plated diamond powder, wherein the thickness of a copper plating layer deposited on the surface is controlled to be 20nm;
the specific process of electroless plating is as follows: chemical plating (plating solution formula: 5g/L copper sulfate, 25g/L sodium methyl tartrate, 7g/L sodium hydroxide, 10g/L formaldehyde, 0.1g/L stabilizer (bipyridine) and solvent water, deposition time is 7 min), washing with pure water (3 min), passivating (passivation solution formula: 14g/L citric acid, 1.5g/L amino trimethylene phosphonic acid, 3.0g/L ammonium acrylate, 2.0g/L triazene, 20-24ml/L hydrogen peroxide, 6g/L phytic acid, 5g/L calcium dihydrogen phosphate, 18ml/L polyethylene glycol, 0.3g/L cerium chloride, 0.3g/L lanthanum chloride and solvent water, pH is adjusted to 3.5, soaking time is 15 min), passing through pure water (3 min), and vacuum drying.
2) Dispersing 16g of copper-plated diamond powder in 2L of electroplating solution by adopting an ultrasonic method (the ultrasonic frequency is 50kHZ, and the ultrasonic time is 30 min) to form electroplating solution colloid;
the electroplating solution contains the following components in concentration: 80g/L of copper sulfate, 50g/L of copper chloride, 40g/L of sodium sulfate, 60g/L of potassium sulfate, 5g/L of brightening agent (ethylene thiourea), 5g/L of wetting agent (propylene glycol) and 25g/L of buffering agent (mercapto benzothiazole sodium salt);
3) As shown in fig. 1, a copper substrate with a thickness of 200 μm is connected with a negative electrode of a direct current power supply to serve as a plating cathode, a lead plate is connected with a positive electrode of the direct current power supply to serve as a plating anode, and the copper substrate and the lead plate are placed in a plating solution colloid to form a plating loop;
4) Stirring the electroplating solution colloid, turning on the power supply, and controlling the electroplating temperature at 55 ℃ and the electroplating current at 2.5A/dm 2 The electroplating voltage is driven, the electroplating time is 10 hours, and the copper-based diamond radiating fin is prepared by deposition;
5) And taking down the copper-based diamond composite material obtained by the cathode, removing redundant copper, finishing the shape and finishing the processing production of the radiating fin.
Example 3
1) Carrying out surface copper plating treatment on the diamond powder with the average particle size of 10 mu m by adopting chemical plating to obtain copper plated diamond powder, wherein the thickness of a copper plating layer deposited on the surface is controlled to be 40nm;
the specific process of the electroless plating is as follows: chemical plating (plating solution formula: 5g/L copper sulfate, 25g/L sodium methyl tartrate, 7g/L sodium hydroxide, 10g/L formaldehyde, 0.1g/L stabilizer (bipyridine) and solvent water, the deposition time is 20 min), washing with pure water (3 min), passivating (passivation solution formula: 16g/L citric acid, 2.5g/L amino trimethylene phosphonic acid, 5.0g/L ammonium acrylate, 4.0g/L triazene, 24ml/L hydrogen peroxide, 8g/L phytic acid, 8g/L calcium dihydrogen phosphate, 20ml/L polyethylene glycol, 0.5g/L cerium chloride, 0.5g/L lanthanum chloride and solvent water, the pH is adjusted to 4.5, the soaking time is 15 min), passing through pure water (3 min), and vacuum drying.
2) Dispersing 20mg of copper-plated diamond powder in 2mL of electroplating solution by adopting an ultrasonic method (the ultrasonic frequency is 40kHZ, and the ultrasonic time is 30 min) to form electroplating solution colloid;
the electroplating solution contains the following components in concentration: 150g/L of copper sulfate, 90g/L of copper chloride, 70g/L of sodium sulfate, 120g/L of potassium sulfate, 30g/L of brightener (ethylene thiourea), 20g/L of wetting agent (sodium butylnaphthalene sulfonate), and 55g/L of buffering agent (benzotriazole and mercapto benzothiazole sodium salt)
3) As shown in figure 1, a copper substrate with the thickness of 150 μm is connected with a direct current power supply cathode to be used as an electroplating cathode, a lead plate is connected with a direct current power supply anode to be used as an electroplating anode, and the copper substrate and the lead plate are placed in an electroplating solution colloid to form an electroplating loop;
4) Stirring the electroplating solution colloid, turning on the power supply, and controlling the electroplating temperature to 65 ℃ and the electroplating current density to 3A/dm 2 The electroplating voltage is driven, the electroplating time is 6 hours, and the copper-based diamond radiating fin is prepared by deposition;
5) And taking down the copper-based diamond composite material obtained by the cathode, removing redundant copper, finishing the shape and finishing the processing production of the radiating fin.
Example 4
Copper-based diamond heat sinks were produced by following the procedure of example 1, except that the average particle size of the diamond powder was 0.8. Mu.m.
Example 5
Copper-based diamond fins were produced by the method of example 1, except that the average particle size of the diamond powder was 12 μm.
Comparative example 1
A copper-based diamond heat sink was produced in the same manner as in example 1, except that in step 1), the surface of the diamond powder was not subjected to a copper plating treatment.
Detection example 1
1) The cross section of the copper-based diamond cooling fin prepared in example 1 is observed by using a Quanta250 type scanning electron microscope (FEI), and the specific result is shown in fig. 2, and as can be seen from fig. 2: the diamond particles are uniformly embedded in the copper matrix, the bonding property of the diamond surface and the copper matrix is good, and obvious pores and cracks are not found under a scanning electron microscope; in addition, electroplating is a process of atomic continuous deposition, a free-growing copper matrix is carried out towards a low-energy state, and crystal defects in the matrix are very low, which is the root cause of good heat-conducting property of the copper-based diamond composite heat sink prepared by the invention.
The test was carried out in the same manner as in example 1 and example 3, wherein the test results substantially agreed with those of example 2; however, the detection results of the embodiments 4 to 5 are slightly poor, which is specifically shown in that when the diamond particle size is smaller than 1 μm, part of the diamond particles are easily agglomerated in the plating solution, and the agglomerated particles introduce cavities into the matrix, so that the density is reduced, and when the diamond particle size is larger than 10 μm, the diamond particles are easily settled, so that the probability of diamond deposition on the copper substrate is reduced; the test result of comparative example 1 was the worst, and it was shown that after the electroplating formation, the copper matrix and diamond were poorly bonded, and there were many cracks and gaps at the interface between the two, and the thermal conductivity was the lowest.
2) The heat conductivity of the copper-based diamond heat sink prepared above was measured using an a-1000 type thermal conductivity tester (Lin Saisi scientific instruments ltd.), and the results are shown in table 1.
TABLE 1
Figure BDA0003861629350000111
Figure BDA0003861629350000121
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of a copper-based diamond cooling fin is characterized by comprising the following steps:
1) Carrying out surface copper plating treatment on the diamond powder by adopting chemical plating to obtain copper plated diamond powder;
2) Dispersing the copper-plated diamond powder in an electroplating solution to form an electroplating solution colloid;
3) Connecting a copper substrate with a negative electrode of a direct current power supply as an electroplating cathode, connecting a lead plate with a positive electrode of the direct current power supply as an electroplating anode, and placing the electroplating anode and the copper substrate in an electroplating solution colloid to form an electroplating loop;
4) And (5) starting a power supply, and preparing the copper-based diamond cooling fin in a deposition manner.
2. The production method according to claim 1, wherein in step 1), the diamond powder satisfies at least the following condition: the average particle size is 1-10 μm;
preferably, the thickness of the copper plating layer deposited on the surface of the copper-plated diamond powder is 20-40nm.
3. The production method according to claim 1, wherein in step 1), the electroless plating includes: chemical plating, cleaning with pure water for 2-5min, passivating, cleaning with pure water for 2-5min, and vacuum drying;
preferably, the plating solution for chemical plating contains 3-8g/L of copper sulfate, 22-28g/L of sodium methyl tartrate, 5-10g/L of sodium hydroxide, 8-12g/L of formaldehyde, 0.05-0.15g/L of stabilizer and solvent water, and the deposition time of chemical plating is 10-20min;
preferably, the passivation solution in passivation contains 14-16g/L of citric acid, 1.5-2.5g/L of amino trimethylene phosphonic acid, 3.0-5.0g/L of ammonium acrylate, 2.0-4.0g/L of triazene, 20-24ml/L of hydrogen peroxide, 6-8g/L of phytic acid, 5-8g/L of calcium dihydrogen phosphate, 18-20ml/L of polyethylene glycol, 0.3-0.5g/L of cerium chloride, 0.3-0.5g/L of lanthanum chloride and solvent water, and the pH of the passivation solution is 3.5-4.5; the soaking time for passivation is 10-20min.
4. The production method according to claim 1, wherein in step 2), the dispersion is carried out by an ultrasonic method, the ultrasonic frequency is 20 to 50kHZ, and the ultrasonic time is 20 to 40min.
5. The production method according to claim 1, wherein in step 2), the amount of the copper-plated diamond powder is 0.8 to 16g based on 1000mL of the plating solution;
preferably, in step 2), the concentrations of the components in the electroplating solution are as follows: 80-150g/L of copper sulfate, 50-90g/L of copper chloride, 40-70g/L of sodium sulfate, 60-120g/L of potassium sulfate, 5-30g/L of brightening agent, 5-20g/L of wetting agent and 25-55g/L of buffering agent;
more preferably, the brightening agent is at least one selected from sodium polydithio-dipropyl sulfonate, dimercapto benzimidazole, ethylene thiourea, sodium dodecyl sulfate and polyethylene glycol, the wetting agent is at least one selected from propylene glycol, polyoxyethylene fatty acid ester and sodium butyl naphthalene sulfonate, and the buffering agent is at least one selected from benzotriazole, methyl benzotriazole and sodium mercaptobenzothiazole.
6. The production method according to claim 1, wherein in step 2), the thickness of the copper substrate is 150 to 300 μm;
preferably, the copper substrate is rectangular, and the specific size is 15-25cm in length and 5-15cm in width.
7. The production method according to claim 1, wherein in step 4), the plating satisfies at least the following condition: stirring the electroplating liquid colloid in the electroplating process, wherein the electroplating temperature is 45-65 ℃, and the electroplating current density is 2-5A/dm 2 The plating voltage is controlled by current density, and the plating time is 4-20h.
8. The method of claim 1, further comprising, after step 4): and taking down the copper-based diamond composite material obtained by the cathode, removing redundant copper, and finishing the shape.
9. The preparation method according to the claim, wherein before the step 1), the preparation method further comprises a pretreatment of the diamond powder, specifically: sequentially carrying out oil removal, activation, sensitization, pure water soaking for 5min and vacuum drying on the diamond powder;
wherein the oil removal at least meets the following conditions: soaking in 100-150 deg.C alkali solution for 10-20min; the activation at least satisfies the following conditions: soaking the deoiled diamond particles in AgNO with the concentration of 5-10g/L at the temperature of 30-35 DEG C 3 Stirring the solution for 5 to 10min at the speed of 500 to 1000 r/min; the sensitization at least satisfies the following conditions: placing the activated diamond particles in SnCl 2 ·2H 2 In O + HCl solution, vibrating for 5-10min at 20-25 deg.C with 50-70W power ultrasonic wave; in the SnCl 2 ·2H 2 In O + HCl solution, snCl 2 ·2H 2 The concentration of O is 8-12g/L, the concentration of HCl is15-25ml/L；
Preferably, before the step 3), the preparation method further comprises the steps of sequentially polishing, cleaning, degreasing and vacuum drying the surface of the copper substrate;
wherein, the grinding is carried out at the speed of 1000-1500r/min by adopting an angle grinder, and the oil removal at least meets the following conditions: soaking in 100-150 deg.C alkali solution for 10-20min.
10. A method for producing a copper-based diamond heat sink, characterized in that the copper-based diamond heat sink is produced by the method according to any one of claims 1 to 9;
preferably, the thermal conductivity of the copper-based diamond heat sink is 400-700W/(m.K).
CN202211166517.9A 2022-09-23 2022-09-23 Copper-based diamond radiating fin and preparation method thereof Pending CN115404533A (en)

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