CN114150311A - Ceramic/copper composite substrate and preparation method thereof - Google Patents
Ceramic/copper composite substrate and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 111
- 239000000919 ceramic Substances 0.000 title claims abstract description 95
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 76
- 239000000758 substrate Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 230000008021 deposition Effects 0.000 claims abstract description 55
- 238000005507 spraying Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 26
- 238000010285 flame spraying Methods 0.000 claims abstract description 14
- 239000007921 spray Substances 0.000 claims abstract description 14
- 238000007750 plasma spraying Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005488 sandblasting Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000003746 surface roughness Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001788 irregular Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000010288 cold spraying Methods 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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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
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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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
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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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
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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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
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
Abstract
The invention belongs to the technical field of functional coating preparation, and particularly relates to a ceramic/copper composite substrate and a preparation method thereof. The method comprises the following steps: (1) using plasma spraying or flame spraying equipment to spray ceramic powder (which may be Al)2O3、AlN、Si3N4Etc.) is sprayed on a pure Cu plate under certain conditions to form a ceramic deposition layer. (2) Spraying high-purity Cu powder on the surface of the prepared ceramic deposition layer by adopting cold gas dynamic spraying equipment to obtain a pure Cu deposition layer. The ceramic deposition layer prepared by the method is thin, has low thermal resistance and good mechanical property; prepared byThe Cu deposition layer has low oxygen content and can meet the requirements of the packaging material of the power module in the power electronic device.
Description
Technical Field
The invention belongs to the technical field of functional coating preparation, and particularly relates to a ceramic/copper composite substrate and a preparation method thereof.
Background
The ceramic copper-clad substrate has the characteristics of high thermal conductivity coefficient, high heat resistance, high electrical insulation, high mechanical strength, thermal expansion coefficient similar to that of a silicon chip, low dielectric loss and the like of ceramic, and also has high electrical conductivity and excellent welding performance of oxygen-free copper, so that the ceramic copper-clad substrate is an excellent packaging material for a power module. A conventional power module heat sink includes a ceramic copper-clad substrate. On top of the substrate, the electronic devices are connected by a Cu layer. High power modules can handle currents of several hundred amperes. The ceramic copper-clad substrate needs to bear thousands of times of thermal cycles at-50-200 ℃ without failure so as to ensure the reliability of the power module.
The traditional direct copper-clad process DBC (direct Bonded copper) is to coat one or two surfaces of a ceramic substrate with Cu foil and then generate Cu-Cu on the surface of the ceramic substrate under the conditions of high temperature and micro-oxidation2The O eutectic phase and the ceramic generate good wetting, and then the ceramic copper-clad substrate is formed. The control requirements of DBC on the process temperature and the oxygen content are very strict, and the temperature and the oxygen content range shown in a phase diagram are required to be within the range to enable the surface of the copper layer to form an eutectic phase and realize the tight combination with the ceramic substrate. The method has high manufacturing cost, and the Cu has large thermal expansion coefficient difference with the ceramic, so the thermal stress is large after cooling, and the strength and the stability (the heat cycle resistance) of the product are influenced. Meanwhile, the method has higher reaction temperature, and the equipment and process conditions are difficult to control, thereby influencing the service performance of the prepared product. Therefore, a novel, simple and reliable ceramic substrate copper-clad material and a manufacturing method thereof are developed to solve the problems in the prior art, and have great application value.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a ceramic/copper composite substrate and a preparation method thereof, wherein a ceramic deposition layer (which can be Al) is prepared on the surface of a pure Cu plate by plasma spraying or flame spraying2O3、AlN、Si3N4And the like), and preparing a high-purity Cu deposition layer on the surface of the ceramic deposition layer by using a cold air power spraying technology.
The technical scheme of the invention is as follows:
a ceramic/copper composite substrate, the ceramic/copper composite substrate comprising: pure copper sheet material, spraying in the ceramic deposit layer on pure copper sheet material surface, spraying in the pure copper deposit layer on ceramic deposit layer surface, wherein: the ceramic deposition layer is prepared by a hot spraying process, and the component of the ceramic deposition layer is Al2O3AlN or Si3N4The pure copper deposit is prepared by a cold gas dynamic spray process.
The ceramic/copper composite substrate is characterized in that the thickness of a pure copper plate is 1000-1500 mu m, the thickness of a ceramic deposition layer is 100-400 mu m, and the thickness of a pure copper deposition layer is 50-2000 mu m.
The ceramic/copper composite substrate is subjected to thermal spraying by plasma spraying or flame spraying.
The preparation method of the ceramic/copper composite substrate comprises the following steps:
(1) spraying powder used by the ceramic deposition layer on the surface of the pure copper plate by adopting a plasma spraying or flame spraying process to form the ceramic deposition layer;
(2) and spraying high-purity copper powder on the surface of the prepared ceramic deposition layer by adopting cold air power spraying equipment to form a pure copper deposition layer, thereby obtaining the ceramic/copper composite substrate.
In the preparation method of the ceramic/copper composite substrate, in the step (1), the shape of powder used for the ceramic deposition layer is spherical or irregular, and the particle size range is 20-100 mu m.
In the preparation method of the ceramic/copper composite substrate, in the step (1), the pure copper plate needs to be subjected to sand blasting treatment before being sprayed to enable the pure copper plate to have surface roughness, and acetone, absolute ethyl alcohol and deionized water are sequentially used for cleaning.
In the preparation method of the ceramic/copper composite substrate, in the step (1), the plasma spraying process parameters are as follows: the current is 500-700A, the voltage is 50-80V, the spraying distance is 80-300 mm, the Ar flow is 30-50L/min, and H2The flow rate is 5-20L/min, and the powder feeding rate is 20-50 g/min.
In the preparation method of the ceramic/copper composite substrate, in the step (1), the flame spraying process parameters are as follows: the flow rate of oxygen is 20-40L/min, the flow rate of propane is 30-40L/min, the flow rate of air is 30-50L/min, the spraying distance is 100-400 mm, and the powder feeding rate is 30-60 g/min.
In the preparation method of the ceramic/copper composite substrate, in the step (2), compressed air or nitrogen is used as a propelling gas for cold air dynamic spraying, the gas heating temperature is 180-600 ℃, the gas working pressure is 0.5-3.5 MPa, and the spraying distance is 10-40 mm.
In the preparation method of the ceramic/copper composite substrate, in the step (2), the purity of the high-purity copper powder is greater than or equal to 99.99 wt%, the morphology of the high-purity copper powder is similar to spherical or dendritic, and the particle size range of the high-purity copper powder is 3-50 mu m.
The design idea of the invention is as follows: on one hand, the ceramic deposition layer is prepared by utilizing the high-temperature melting of plasma spraying or flame spraying, so that not only can different types of ceramic deposition layers be conveniently prepared, but also the thickness of the ceramic deposition layer can be conveniently controlled, and therefore different types of ceramic/copper composite substrates can be prepared; on the other hand, the pure copper deposition layer is prepared by cold spraying, the steps of chemical etching and the like are avoided, the patterned ceramic copper-clad plate can be directly prepared, and the preparation process is simple and controllable.
The invention has the advantages and beneficial effects that:
1. compared with DBC and other processes, the method provided by the invention is simple to operate, easy to control process conditions, free of specific high-temperature and micro-oxygen conditions, low in preparation cost and high in yield.
2. The copper-clad layer with the graphic circuit can be directly prepared by a method of adding a mask in the process of cold spraying the pure Cu deposition layer without processes such as chemical etching and the like.
3. In the process of preparing the ceramic/copper composite substrate by cold gas dynamic spraying, the cold spraying temperature is lower, the introduction of thermal stress is effectively avoided, a thicker copper-clad layer can be prepared, and the bonding strength with a ceramic deposition layer is high and the thermal shock resistance is good.
4. The process can directly prepare the ceramic/copper composite substrate on the surface of the Cu radiator, thereby saving the welding structure between the traditional substrate and the radiator and effectively improving the reliability of the ceramic/copper composite substrate.
Drawings
FIG. 1 is a schematic structural view of a ceramic/copper composite substrate prepared according to the present invention;
in the figure: 1-pure copper deposition layer, 2-ceramic deposition layer and 3-pure copper plate.
Detailed Description
In the specific implementation process, the method for preparing the ceramic/copper composite substrate by adopting the spraying method firstly prepares a ceramic deposition layer (can be Al) on the surface of a pure Cu plate by plasma spraying or flame spraying2O3、AlN、Si3N4And the like), and then preparing a high-purity Cu deposition layer on the surface of the ceramic deposition layer by using a cold pneumatic spraying technology, thereby realizing the preparation of the ceramic/copper composite substrate. The method comprises the following specific steps:
step 1, sand blasting and cleaning: the pure Cu plate needs to be subjected to sand blasting treatment before spraying to enable the pure Cu plate to have certain surface roughness, and acetone, absolute ethyl alcohol and deionized water are sequentially used for ultrasonic cleaning.
Step 2, spraying of a ceramic deposition layer: the ceramic powder (may be Al) is sprayed by plasma spraying or flame spraying2O3、AlN、Si3N4Etc.) is sprayed on the surface of the pure Cu plate under certain conditions to form a ceramic deposition layer.
Step 3, preparing a pure Cu deposition layer: and (3) spraying and depositing pure copper powder on the surface of the ceramic deposition layer under a certain condition by adopting cold air power spraying equipment to form a pure copper deposition layer.
Wherein, the shape of the ceramic powder in the step 2 is spherical or irregular, and the particle size range is 20-100 μm; the plasma spraying process parameters are as follows: electric current 500E700A, 50-80V of voltage, 80-150 mm of spraying distance, 30-50L/min of Ar flow and H2The flow rate is 5-20L/min, and the powder feeding speed is 20-50 g/min; the technological parameters of flame spraying are as follows: the flow rate of oxygen is 20-40L/min, the flow rate of propane is 30-40L/min, the flow rate of air is 30-50/min, the spraying distance is 100-300 mm, and the powder feeding rate is 30-60 g/min.
In the step 3, the purity of the Cu powder is more than or equal to 99.99 wt%, the Cu powder is in a shape of a quasi-sphere or a dendritic crystal, and the granularity range is 25-50 mu m; compressed air or nitrogen is used as propelling gas for cold air power spraying, the gas heating temperature is 180-500 ℃, the gas working pressure is 0.5-3.5 MPa, and the spraying distance is 10-30 mm;
for cold spray equipment, refer to a cold air dynamic spray device or other commercial cold spray, dynamic spray or low pressure cold spray equipment mentioned in the Chinese patent application (patent No. 01128130.8, grant No. CN 1161188C). The spray gun is a Laval (De Laval) spray gun made of metal, and the spray gun can smoothly discharge powder for a long time in the deposition process and is not blocked.
As shown in fig. 1, the ceramic/copper composite substrate prepared by the present invention includes: the ceramic plate comprises a pure copper plate 3, a ceramic deposition layer 2 sprayed on the surface of the pure copper plate 3 and a pure copper deposition layer 1 sprayed on the surface of the ceramic deposition layer 2. Wherein the thickness of the pure copper plate is 1000-1500 μm, the thickness of the ceramic deposition layer is 100-400 μm, and the thickness of the pure copper deposition layer is 200-2000 μm.
The following examples are given for the detailed description of the embodiments of the present invention, and the detailed implementation and specific operation procedures are given on the premise of the technical scheme of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
In this example, Al2O3The preparation method of the ceramic/copper composite substrate comprises the following steps:
(1) firstly, carrying out sand blasting treatment on a pure Cu plate with the thickness of 1200 mu m to ensure that the pure Cu plate has a certain surface roughness Ra of 18 mu m, and sequentially carrying out ultrasonic cleaning by using acetone, absolute ethyl alcohol and deionized water;
(2) spherical Al with the granularity of 30-50 mu m2O3Powder is deposited on the surface of the pure Cu plate through plasma spraying, and the technological parameters are as follows: current 620A, voltage 72V, spraying distance 110mm, Ar flow 45L/min, H2The flow rate is 10L/min, the powder feeding rate is 35g/min, and Al with the thickness of 300 mu m is formed2O3Depositing a layer;
(3) depositing electrolytic dendrite Cu powder with the particle size of 25-40 mu m on the Al through cold gas dynamic spraying2O3On the surface of the deposition layer, the purity of Cu powder is 99.996 wt%, and the cold spray accelerating gas is N2The heating temperature of the accelerating gas is 600 ℃, the working pressure of the accelerating gas is 2.2MPa, the spraying distance is 20mm, and the thickness of the pure copper deposition layer is 1000 mu m, thus obtaining the Al2O3A ceramic/copper composite substrate.
Example 2
In this embodiment, the method for preparing the AlN ceramic/copper composite substrate includes the following steps:
(1) firstly, carrying out sand blasting treatment on a pure Cu plate with the thickness of 1000 microns to ensure that the pure Cu plate has a certain surface roughness Ra of 18 microns, and carrying out ultrasonic cleaning by sequentially using acetone, absolute ethyl alcohol and deionized water;
(2) depositing irregular AlN powder with the granularity of 30-60 mu m on the surface of a pure Cu plate by supersonic flame spraying, wherein the process parameters are as follows: 30L/min of oxygen flow, 35L/min of propane flow, 40L/min of air flow, 230mm of spraying distance and 45g/min of powder feeding rate to form an AlN deposition layer with the thickness of 350 mu m;
(3) depositing the atomized spherical Cu powder with the granularity of 30-50 mu m on the Al through cold gas dynamic spraying2O3On the surface of the deposition layer, the purity of Cu powder is 99.996 wt%, and the cold spray accelerating gas is N2The heating temperature of the accelerating gas is 600 ℃, the working pressure of the accelerating gas is 2.2MPa, the spraying distance is 30mm, and the thickness of the pure copper deposition layer is 1000 mu m, thus obtaining the AlN ceramic/copper composite substrate.
Example 3
In this example, Si3N4The preparation method of the ceramic/copper composite substrate comprises the following steps:
(1) firstly, carrying out sand blasting treatment on a pure Cu plate with the thickness of 1500 mu m to ensure that the pure Cu plate has certain surface roughness Ra of 16 mu m, and sequentially carrying out ultrasonic cleaning by using acetone, absolute ethyl alcohol and deionized water;
(2) irregular Si with the granularity of 30-60 mu m3N4Powder is deposited on the surface of the pure Cu plate by supersonic flame spraying, and the technological parameters are as follows: the flow rate of oxygen is 30L/min, the flow rate of propane is 35L/min, the air flow rate is 40L/min, the spraying distance is 230mm, the powder feeding rate is 45g/min, and Si with the thickness of 350 mu m is formed3N4Depositing a layer;
(3) depositing the atomized spherical Cu powder with the granularity of 30-50 mu m on the Al through cold gas dynamic spraying2O3On the surface of the deposition layer, the purity of Cu powder is 99.996 wt%, and the cold spray accelerating gas is N2Heating with accelerated gas at 600 deg.C, working pressure of accelerated gas at 2.2MPa, spraying distance at 10mm, and pure copper deposit thickness at 1200 μm to obtain Si3N4A ceramic/copper composite substrate.
The results of the examples show that the ceramic deposition layer prepared by the method is thin, has low thermal resistance and good mechanical property; the prepared pure Cu deposition layer has low oxygen content and can meet the requirements of packaging materials of power modules in power electronic devices.
Claims (10)
1. A ceramic/copper composite substrate, comprising: pure copper sheet material, spraying in the ceramic deposit layer on pure copper sheet material surface, spraying in the pure copper deposit layer on ceramic deposit layer surface, wherein: the ceramic deposition layer is prepared by a hot spraying process, and the component of the ceramic deposition layer is Al2O3AlN or Si3N4The pure copper deposit is prepared by a cold gas dynamic spray process.
2. The ceramic/copper composite substrate according to claim 1, wherein the thickness of the pure copper plate is 1000 to 1500 μm, the thickness of the ceramic deposition layer is 100 to 400 μm, and the thickness of the pure copper deposition layer is 50 to 2000 μm.
3. The ceramic/copper composite substrate according to claim 1, wherein the thermal spraying is plasma spraying or flame spraying.
4. The method of manufacturing a ceramic/copper composite substrate according to any one of claims 1 to 3, comprising the steps of:
(1) spraying powder used by the ceramic deposition layer on the surface of the pure copper plate by adopting a plasma spraying or flame spraying process to form the ceramic deposition layer;
(2) and spraying high-purity copper powder on the surface of the prepared ceramic deposition layer by adopting cold air power spraying equipment to form a pure copper deposition layer, thereby obtaining the ceramic/copper composite substrate.
5. The method of claim 4, wherein in the step (1), the ceramic deposition layer is formed by a powder having a spherical or irregular shape and a particle size of 20-100 μm.
6. The method for preparing a ceramic/copper composite substrate according to claim 4, wherein in the step (1), the pure copper plate is subjected to sand blasting treatment to make the pure copper plate have surface roughness before spraying, and is sequentially cleaned by acetone, absolute ethyl alcohol and deionized water.
7. The method for preparing a ceramic/copper composite substrate according to claim 4, wherein in the step (1), the plasma spraying process parameters are as follows: the current is 500-700A, the voltage is 50-80V, the spraying distance is 80-300 mm, the Ar flow is 30-50L/min, and H2The flow rate is 5-20L/min, and the powder feeding rate is 20-50 g/min.
8. The method for preparing a ceramic/copper composite substrate according to claim 4, wherein in the step (1), the process parameters of the flame spraying are as follows: the flow rate of oxygen is 20-40L/min, the flow rate of propane is 30-40L/min, the flow rate of air is 30-50L/min, the spraying distance is 100-400 mm, and the powder feeding rate is 30-60 g/min.
9. The method for preparing a ceramic/copper composite substrate according to claim 4, wherein in the step (2), compressed air or nitrogen is used as a propelling gas for cold gas dynamic spraying, the gas heating temperature is 180-600 ℃, the gas working pressure is 0.5-3.5 MPa, and the spraying distance is 10-40 mm.
10. The method for preparing the ceramic/copper composite substrate according to claim 4, wherein in the step (2), the purity of the high-purity copper powder is greater than or equal to 99.99 wt%, the morphology of the high-purity copper powder is similar to spherical or dendritic, and the particle size of the high-purity copper powder is 3-50 μm.
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