CN109137035B - Preparation method of aluminum-based copper-clad plate - Google Patents

Preparation method of aluminum-based copper-clad plate Download PDF

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CN109137035B
CN109137035B CN201810995016.9A CN201810995016A CN109137035B CN 109137035 B CN109137035 B CN 109137035B CN 201810995016 A CN201810995016 A CN 201810995016A CN 109137035 B CN109137035 B CN 109137035B
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copper
aluminum
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arc oxidation
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CN109137035A (en
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谢新林
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Abstract

The invention relates to a preparation method of an aluminum-based copper-clad plate, which comprises the following steps: deoiling and cleaning an aluminum plate; one surface of the composite material is subjected to micro-arc oxidation, and a layer of micro-arc oxidation film formed on the surface of the composite material is used as an insulating heat conducting layer; then putting the micro-arc oxidation film into a vacuum chamber, and sequentially carrying out the treatment of cleaning and activating double-sided plasma beams, depositing double-sided diamond-like films, injecting metal ions into single-sided ions, depositing metal by single-sided plasma, and depositing copper by single-sided plasma on the micro-arc oxidation film to form a conductor; finally, electroplating copper in the electroplating bath to ensure that the thickness of the electroplated copper layer meets the preset requirement. The invention has the advantages that the aluminum-based copper-clad plate has good thermal conductivity, low thermal resistance, thin insulating layer and high breakdown voltage resistance, and the electroplated copper foil has good bonding force with the insulating layer.

Description

Preparation method of aluminum-based copper-clad plate
Technical Field
The invention belongs to the field of preparation methods of heat conduction materials, and particularly relates to a preparation method of a novel aluminum-based copper-clad plate with high heat conduction and low heat resistance.
Background
The existing aluminum-based copper-clad plates on the market are all formed by adopting an aluminum plate, an epoxy resin adhesive (filled with insulating heat-conducting particles such as aluminum oxide and silicon carbide) and a copper foil, the heat-conducting effect depends on the shape, size and number of the insulating heat-conducting particles filled in the epoxy resin adhesive, and the insulating effect depends on the epoxy resin adhesive. Because epoxy has poor thermal conductivity and to achieve a certain insulation resistance, the thickness of the layer of glue is typically greater than 100 microns.
Therefore, aluminum-based copper clad plates on the market at present have the defects of poor thermal conductivity, high thermal resistance and thick insulating layer.
Disclosure of Invention
In order to overcome the defects of the method, the invention adopts the scheme that the micro-arc oxidation film and the diamond-like film (aluminum nitride film) replace the existing epoxy resin and filler, and the prepared aluminum-based copper-clad plate has the advantages of good heat conductivity, low thermal resistance, thin insulating layer, breakdown resistance and high voltage resistance, and the bonding force between the electroplated copper foil and the insulating layer is good, and the method is realized by the following technical scheme.
A preparation method of an aluminum-based copper-clad plate comprises the following steps:
step 1, assembling an aluminum plate into a clamp, performing oil removal cleaning, performing micro-arc oxidation on one surface of the aluminum plate, and forming a layer of micro-arc oxidation film with a certain thickness on the surface of the aluminum plate to serve as an insulating heat-conducting layer;
step 2, after cleaning and drying, putting the film into a vacuum chamber, and sequentially carrying out treatment of double-sided plasma beam cleaning and activation, double-sided diamond-like carbon film (DLC film) deposition, ion implantation of metal ions, plasma deposition of metal and plasma deposition of metal copper on the micro-arc oxidation film;
and 3, putting the processed aluminum plate into a clamp, and electroplating copper in an electroplating bath to ensure that the thickness of the electroplated copper foil meets the set requirement to form the single-sided aluminum-based copper-clad plate.
Further, in the step 2, the diamond-like film is replaced by an aluminum nitride film (AlN film), and then the single-side aluminum-based copper-clad plate is formed through the step 3.
Further, in the step 1, an aluminum plate is assembled into a clamp, after oil removal and cleaning, micro-arc oxidation is carried out on one surface or two surfaces of the aluminum plate, and then the single-sided or double-sided aluminum-based copper-clad plate is formed according to the steps 2 and 3.
In step 2, the ion-implanted metal ions include titanium ions, cobalt ions, nickel ions, chromium ions, and copper ions, the plasma-deposited metal includes Ti, Co, Ni, Cr, Cu, or an alloy thereof, and the ion-implanted metal ions and the plasma-deposited metal are the same metal or different metals.
Further, the micro-arc oxidation film is crystal Al2O3Film, mainly of crystalline alpha-Al2O3、γ-Al2O3And (4) forming.
Furthermore, the thickness of the micro-arc oxide film is 5-75 microns, and the working temperature is as follows: 20 to 50 ℃.
Further, the plasma beam cleaning and activating is to perform plasma beam cleaning and activating on two surfaces of the aluminum plate by using a gas ion source, and the working gas can be argon (Ar) or nitrogen (N)2) And other inert gases or the mixed gas thereof, the vacuum degree is 0.01-20 Pa, the voltage is 500-1500V, the duty ratio is 60-90%, and the process temperature of cleaning and activating is normal temperature-400 ℃.
Further, diamond-like carbon film (DLC film) deposition was performed on both surfaces of the aluminum plate by: with acetylene (C)2H2) Or methane (CH)4) As working gas, voltage: 1500-3500V, vacuum degree: 0.1-100 Pa, time: 1-10 minutes, temperature: 20 to 150 ℃.
Further, ion implantation is carried out on one surface with the micro-arc oxidation film, metal vapor vacuum arc ion source (MEVVA source) is adopted for ion implantation, metal Ti, Co, Ni, Cr, Cu or binary alloy thereof is used as a cathode, and the vacuum degree during implantation is superior to 5 multiplied by 10-2Pa, acceleration voltage of 5-500 KV, and implantation dose of 1.0 × 1012～5.0×1016ion/cm2The injection depth is 1-100 nm, and the process temperature is normal temperature-250 ℃.
Further, on the surface of the aluminum plate with ion implantation, a magnetic filtration cathode vacuum arc plasma deposition (FCVAD deposition) technology is adopted, the same material with metal ion implantation is adopted for the first deposition, namely, the same metal (alloy) with the ion implantation is deposited, the deposition thickness is 5-500 nm, the vacuum degree is better than 5 multiplied by 10-2Pa, and the process temperature is 25-250 ℃.
Further, on the basis of the same material, a magnetic filtration cathode vacuum arc plasma deposition (FCVAD deposition) technology is adopted, metal copper is used as a cathode to carry out copper deposition, the deposition thickness is 5-500 nm, and the vacuum degree is superior to 5 multiplied by 10-2Pa, and the process temperature is 25-250 ℃.
Drawings
FIG. 1 is a flow chart of a method for preparing an aluminum-based copper-clad plate according to a specific embodiment of the invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in figure 1, the preparation method of the novel aluminum-based copper-clad plate with high thermal conductivity and low thermal resistance provided by the invention has the advantages of thin insulating layer, good thermal conductivity, low thermal resistance, high breakdown voltage resistance and good bonding force between the electroplated copper foil and the insulating layer, and comprises the following steps:
step 1, assembling an aluminum plate into a clamp, performing micro-arc oxidation on one surface of the aluminum plate after oil removal and cleaning, and forming a layer of micro-arc oxidation film with a certain thickness on the surface of the aluminum plate;
step 2, after cleaning and drying, putting the micro-arc oxidation film into a vacuum chamber, and sequentially carrying out the treatment of plasma beam cleaning and activation, diamond-like carbon film (DLC film) deposition, ion implantation of metal ions, plasma deposition of metal and plasma deposition of metal copper on the micro-arc oxidation film;
and 3, placing the aluminum plate subjected to the treatment into a clamp, and carrying out electro-coppering in an electroplating bath to enable the copper layer after electroplating to reach a set thickness.
The following examples are specifically described below.
The first embodiment is as follows:
firstly, carrying out micro-arc oxidation on an aluminum plate to form a micro-arc oxidation layer, and implementing the following steps:
preparing a micro-arc oxidation electrolyte: sodium silicate: 30g/L, potassium hydroxide: 4g/L, disodium ethylene diamine tetraacetate: 5g/L, additive: 5 g/L;
mounting an aluminum plate on a hanger, removing oil, cleaning, using the aluminum plate as an anode for micro-arc oxidation, using a stainless steel plate as a cathode, and adjusting the distance between the anode and the cathode to be 200 mm; the output voltage is controlled to be 650V under the constant voltage mode, the frequency is 1000 Hz, and the duty ratio is 15%;
placing an aluminum plate in the electrolyte, and controlling the temperature: oxidizing for 30min at 25 ℃, turning off the power supply, taking out, cleaning with deionized water and blow-drying. The main component of the formed micro-arc oxidation film is crystalline aluminum oxide which is composed of crystalline alpha-Al2O3、γ-Al2O3The thickness of the micro-arc oxide film is 45 microns.
Then, the aluminum plate which is subjected to micro-arc oxidation is placed in a vacuum chamber, and the steps of cleaning and activating by double-sided plasma beams, depositing a double-sided diamond-like carbon film (DLC film), injecting nickel ions into single-sided ions, depositing nickel by single-sided plasma, depositing copper by single-sided plasma are sequentially carried out in sequence, so that a layer of diamond-like carbon film (DLC film) with very good insulating and heat conducting properties is added on the micro-arc oxidation film, and meanwhile, the surface of the micro-arc oxidation film is made to be conductive, and the preparation is made for next electroplating.
The process comprises the following steps:
1) the plasma beam cleaning and activating process is to perform plasma beam cleaning and activating on two surfaces of the aluminum plate by adopting a gas ion source, wherein the working gas is Ar, the vacuum degree is 10Pa, the voltage is 1000V, the duty ratio is 80%, the cleaning and activating process temperature is normal temperature, and the time is 2 minutes.
2) Deposition of DLC film: the working gas being acetylene (C)2H2) The vacuum degree is 5Pa, the voltage is 1800V, the process temperature is 100 ℃, and the time is 5 minutes.
3) Nickel ion implantation: the degree of vacuum was 2.0X 10-3Pa, voltage 20KV, beam current 2.5mA, time 3 minutes.
4) Nickel deposition: the degree of vacuum was 3.5X 10-2Pa, arc flow 50A, time 5 minutes.
5) Copper deposition: the degree of vacuum was 3.0X 10-2Pa, arc flow 55A, time 5 minutes.
And finally, taking out the aluminum plate which finishes the procedures, mounting a hanger, and carrying out sulfate acid bright copper plating:
copper sulfate pentahydrate: 180 g/l;
sulfuric acid: 70 g/L;
chloride ion: 60 mg/l;
additive: according to the requirements
At 3.5A/dm2Electroplating at normal temperature to make the thickness of the copper layer reach 72 microns.
Wherein, the diamond-like carbon film (DLC film) is replaced by an aluminum nitride (AlN) film, and the other type of single-side aluminum-based copper-clad plate can be manufactured by the same process. The double-sided aluminum-based copper-clad plate can also be manufactured by a similar process by a method of double-sided injection, double-sided deposition and double-sided electroplating.
The single-sided aluminum-based copper-clad plate prepared by the method is tested by Shenzhen Hua detection company, and the data is shown in the following table:
Figure BDA0001781663590000051
although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (3)

1. The preparation method of the aluminum-based copper-clad plate is characterized by comprising the following steps:
step 1, assembling an aluminum plate into a clamp, performing micro-arc oxidation on one surface or two surfaces of the aluminum plate after oil removal and cleaning to form a layer of micro-arc oxidation film on one surface or two surfaces of the aluminum plate as an insulating heat conducting layer, wherein the micro-arc oxidation film is a crystal aluminum sesquioxide film or a micro-arc oxidation filmThe thickness is 5-75 μm, and the crystal alpha-Al is mainly used2O3、γ-Al2O3The working temperature in the micro-arc oxidation process is as follows: 20-50 ℃;
step 2, after cleaning and drying, putting the micro-arc oxidation film into a vacuum chamber, and sequentially carrying out the processes of plasma beam cleaning and activation, diamond-like carbon film deposition, ion implantation of first metal ions, plasma deposition of first metal and plasma deposition of metal copper on the micro-arc oxidation film;
wherein:
the plasma beam cleaning and activating step is to perform plasma beam cleaning and activating on two surfaces of the aluminum plate by adopting a gas ion source, wherein the working gas is argon, nitrogen, other inert gases or a mixed gas of the argon, the nitrogen, the other inert gases or the mixed gas of the argon, the nitrogen, the other inert gases, the vacuum degree of 0.01-20 Pa, the voltage of 500-1500V, the duty ratio of 60-90 percent, and the cleaning and activating process temperature of normal temperature-400 ℃;
and (2) performing diamond-like carbon film deposition on two surfaces of the aluminum plate, wherein the diamond-like carbon film deposition adopts the following steps: acetylene or methane is used as working gas, and the voltage: 1500-3500V, vacuum degree: 0.1-100 Pa, time: 1-10 minutes, temperature: 20-150 ℃;
performing ion implantation on the surface of the diamond-like film deposited on the micro-arc oxidation film, wherein the ion implantation adopts a metal vapor vacuum arc ion source, takes a first metal as a cathode, the first metal is titanium, cobalt, nickel, chromium or an alloy thereof, and the vacuum degree is lower than 5 x 10 during the implantation-2Pa, acceleration voltage of 5-500 KV, and implantation dose of 1.0 × 1012～5.0×1016Ion/cm2The injection depth is 1-100 nanometers, and the temperature is normal temperature-250 ℃;
on the surface of the diamond-like film implanted with the first metal ions, adopting a magnetic filtration cathode vacuum arc plasma deposition technology, and adopting the same metal as the ion-implanted first metal to carry out first metal deposition, wherein the deposition thickness is 5-500 nm, and the vacuum degree is less than 5 multiplied by 10-2Pa, the temperature is 25-250 ℃;
and 3, putting the processed aluminum plate into a clamp, electroplating copper on the surface of the deposited copper in an electroplating bath and passivating, so that the thickness of the electroplated copper layer reaches a preset thickness and has certain corrosion resistance, and preparing the aluminum-based copper-clad plate.
2. A method of manufacturing according to claim 1, wherein in step 2, the diamond-like film deposition is replaced by an aluminum nitride film deposition.
3. The method according to claim 1, wherein the conditions for plasma deposition of metallic copper comprise: then, a magnetic filtration cathode vacuum arc plasma deposition technology is adopted, metal copper is taken as a cathode, copper deposition is carried out, the deposition thickness is 5-500 nm, and the vacuum degree is lower than 5 multiplied by 10-2Pa, at a temperature of between 25 and 250 ℃.
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