CN112277406A - High-reliability aluminum-based copper-clad plate and preparation method thereof - Google Patents
High-reliability aluminum-based copper-clad plate and preparation method thereof Download PDFInfo
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- CN112277406A CN112277406A CN202011180587.0A CN202011180587A CN112277406A CN 112277406 A CN112277406 A CN 112277406A CN 202011180587 A CN202011180587 A CN 202011180587A CN 112277406 A CN112277406 A CN 112277406A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 88
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000010410 layer Substances 0.000 claims abstract description 63
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000012790 adhesive layer Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011889 copper foil Substances 0.000 claims abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 3
- 230000006798 recombination Effects 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 238000009413 insulation Methods 0.000 abstract description 2
- 230000008646 thermal stress Effects 0.000 abstract description 2
- 239000003292 glue Substances 0.000 description 21
- 239000004033 plastic Substances 0.000 description 13
- 238000004806 packaging method and process Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- -1 usually Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
- B32B37/1018—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using only vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
- H05K1/0204—Cooling of mounted components using means for thermal conduction connection in the thickness direction of the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an aluminum-based copper-clad plate which comprises an aluminum plate and a copper foil compounded on the surface of the aluminum plate, wherein one surface of the aluminum plate is provided with an aluminum oxide layer, the other surface of the aluminum plate is provided with a porous aluminum oxide structure layer, an insulating heat-conducting adhesive layer is compounded on the surface of the copper foil, and the insulating heat-conducting adhesive layer is partially overlapped with the porous aluminum oxide structure layer. The aluminum-based copper-clad plate insulation heat-conducting adhesive layer and the porous alumina structure improve the adhesive force of the interface, regulate and control the thermal stress generated by thermal mismatch, and further improve the application reliability of the aluminum-based copper-clad plate.
Description
Technical Field
The invention relates to the technical field of electronic packaging materials, in particular to a high-reliability aluminum-based copper-clad plate and a preparation method thereof.
Background
With the development of electronic technology, power devices with high integration level such as LEDs have higher requirements on electrical conductivity, thermal conductivity and reliability of packaging structure materials. The aluminum-based copper clad laminate has good electric conduction and heat conduction performance and is more and more widely applied to the packaging of power devices such as LEDs and the like.
The aluminum-based copper clad laminate is generally composed of an aluminum plate, an insulating layer and a copper foil, in order to improve the heat conduction capability of the insulating layer, usually, fillers with strong heat conductivity, such as silicon powder and the like, are added into an epoxy resin insulating adhesive according to a certain proportion, an insulating heat conduction adhesive layer is formed through the technological processes of dispersion, curing and the like, and the aluminum-based copper clad laminate bonded by the aluminum plate, the insulating layer and the copper foil is realized through high-temperature pressing. However, in practical packaging applications, the thermal mismatch damage of the packaging substrate material occurs at the interface due to the high and low temperature processes, and the material gradually expands and delaminates until the device fails; the important factor influencing the interface stability is the bonding force of the metal and the cured insulating adhesive interface, the filler at the interface can reduce the bonding force, and the reduction of the filler can reduce the thermal conductivity. Therefore, the method can improve the interface bonding force while ensuring the filler content, and is the key for improving the reliability of the aluminum-based copper-clad plate.
Disclosure of Invention
The invention aims to provide an aluminum-based copper-clad plate, which enhances the effective contact area and the bonding force between an insulating adhesive and an aluminum substrate and can improve the heat conduction capability of the aluminum-based copper-clad plate.
In view of this, the application provides an aluminum-based copper-clad plate, including aluminum plate and the copper foil of compounding in aluminum plate surface, aluminum plate's a surface has the aluminium oxide layer, and another surface has porous aluminium oxide structural layer, copper foil surface complex has insulating heat-conducting glue layer, and insulating heat-conducting glue layer with porous aluminium oxide structural layer part coincidence.
Preferably, the porous alumina structure layer has a pore density of more than 100 pores per square centimeter, a pore depth of 3-15 μm and a pore diameter of 100-300 nm.
Preferably, the heat conducting filler in the insulating heat conducting adhesive layer is selected from one or more of alumina, silica, aluminum nitride, silicon carbide, silicon nitride and boron nitride, and the heat conducting filler comprises 0.02-0.10 wt% of linear filler and sheet filler; the particle size of the heat-conducting filler is larger than the pore diameter of the porous alumina structure layer.
Preferably, the thickness of the insulating and heat-conducting adhesive layer is more than 10 times of the depth of the porous alumina pores of the porous alumina structure layer.
The application also provides a preparation method of the aluminum-based copper-clad plate, which comprises the following steps:
cleaning an aluminum plate, preparing an aluminum oxide layer on one surface of the aluminum plate, and preparing a porous aluminum oxide structure layer on the other surface of the aluminum plate;
coating an insulating heat-conducting adhesive layer on the surface of the copper foil, and then curing at high temperature;
and contacting and pressing the insulating heat-conducting adhesive layer with the porous alumina structural layer to obtain the aluminum-based copper-clad plate.
Preferably, the aluminum oxide layer is prepared by a micro-arc oxidation method.
Preferably, the preparation of the porous alumina structure layer specifically comprises:
sealing one surface of the cleaned aluminum plate, performing constant-current electrochemical polishing on the other surface, performing primary anodic oxidation in oxalic acid electrolyte, corroding in a mixed solution of phosphoric acid and chromium oxide, and finally performing secondary anodic oxidation.
Preferably, the insulating heat-conducting adhesive layer is prepared from epoxy resin, a toughening agent, a coupling agent, a curing agent and a heat-conducting filler, and the content of the heat-conducting filler is 40-80 wt%.
Preferably, the pressing is vacuum pre-pressing and then vacuum pressing.
Preferably, the temperature of the vacuum pressing is 200-300 ℃, and the pressure is 200-300 psi.
The application provides an aluminium base copper-clad plate, it includes aluminum plate and compound in aluminum surface's copper foil, aluminum plate's a surface has the alumina layer, and another surface has porous alumina structural layer, copper foil surface recombination has insulating heat-conducting adhesive layer, just insulating heat-conducting adhesive layer with the coincidence of porous alumina structural layer part. The invention utilizes the porous alumina structure to enable the insulating heat-conducting adhesive layer to infiltrate into the holes, shields most of fillers outside the holes, and effectively increases the effective contact area and the bonding force of the insulating heat-conducting adhesive and the aluminum plate.
Drawings
FIG. 1 is a schematic structural diagram of an aluminum-based copper-clad plate prepared by the embodiment of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the existence of insulating layer and heat conduction filler between aluminium base copper-clad plate's the metal substrate and the copper foil and then influence aluminium base copper-clad plate adhesion and heat conductivility, this application provides an aluminium base copper-clad plate, and it is through constructing porous alumina structure between insulating heat conduction glue and aluminium base board, has effectively increased the effective area of contact and the cohesive force of insulating glue with the metal substrate, has reduced the contact of filler with the base plate, has promoted product reliability. Specifically, the application provides an aluminium base copper-clad plate, include aluminum plate and compound in aluminum surface's copper foil, aluminum plate's a surface has the alumina layer, and another surface has the porous alumina structural layer, copper foil surface recombination has insulating heat-conducting glue layer, just insulating heat-conducting glue layer with the coincidence of porous alumina structural layer part.
In the application, the pore density of the porous alumina structure layer on the surface of the aluminum plate is more than 100 pores per square centimeter, the pore depth is 3-15 mu m, and the pore diameter is 100-300 nm; more specifically, the depth of the holes is 3-10 μm, and the diameter of the holes is 150-250 nm.
In this application, copper foil surface complex has insulating heat conduction glue film, and it has the effect of performance heat conduction insulation, the particle diameter of the heat conduction filler in the insulating heat conduction glue film is greater than the aperture of porous alumina structure layer to make it can not get into in the hole of above-mentioned porous alumina structure layer, make interface department insulating heat conduction glue film bigger with the effective area of contact of base plate, make peel strength resistance and resistant soaking effect better. The thickness of the insulating heat-conducting adhesive layer is more than 10 times of the depth of the porous alumina pores of the porous alumina structure layer.
The application also provides a preparation method of the aluminum-based copper-clad plate, which comprises the following steps:
cleaning an aluminum plate, preparing an aluminum oxide layer on one surface of the aluminum plate, and preparing a porous aluminum oxide structure layer on the other surface of the aluminum plate;
coating an insulating heat-conducting adhesive layer on the surface of the copper foil, and then curing at high temperature;
and contacting and pressing the insulating heat-conducting adhesive layer with the porous alumina structural layer to obtain the aluminum-based copper-clad plate.
In the process of preparing the aluminum-based copper-clad plate, the aluminum substrate is firstly cleaned according to a method well known to those skilled in the art, and the method is not particularly limited in the application. After cleaning, preparing an alumina layer on one surface of the cleaned aluminum plate, and preparing a porous alumina structure layer on the other surface; the preparation of the alumina layer and the porous alumina structure layer is not in sequence; but when any one surface is prepared, the other surface is subjected to plastic sealing. The aluminum oxide layer is prepared by a micro-arc oxidation method, namely micro-arc oxidation is carried out under certain voltage, frequency, duty ratio and time, and the electrolyte of the micro-arc oxidation is a mixed solution of sodium silicate and sodium hexametaphosphate; and after the micro-arc oxidation method is completed, annealing treatment is carried out to obtain an aluminum oxide layer, wherein the annealing treatment is carried out at 500-600 ℃ under the protection of nitrogen.
The porous alumina structure layer is prepared on the other surface of the aluminum plate, and the preparation of the porous alumina structure layer specifically comprises the following steps: firstly, carrying out electrochemical polishing on an aluminum substrate, then carrying out primary anodic oxidation in oxalic acid electrolyte, then corroding in a mixed solution of phosphoric acid and chromium oxide, and finally carrying out secondary anodic oxidation. The electrochemical polishing is specifically carried out according to the volume ratio of (3-5): 1, performing constant current electrochemical polishing in a mixed solution of perchloric acid and ethanol, wherein the current of the constant current polishing is 1-5A, and the time is 5-20 min; the primary anodic oxidation is carried out in oxalic acid electrolyte, the oxidation voltage is 30-50V, the temperature is 5-20 ℃, and the time is 1-5 h; the corrosive liquid is a mixed liquid of phosphoric acid and chromium sesquioxide, and the time is 3-5 hours to remove the primary oxide film layer; the relevant conditions of the secondary anodization are the same as those of the primary anodization.
The application simultaneously or then compound insulating heat-conducting glue layer on the copper foil surface, high temperature curing again. The insulating heat-conducting adhesive layer is prepared from 40-80 parts by weight of epoxy resin, 1-5 parts by weight of toughening agent, 1-5 parts by weight of coupling agent and 1-5 parts by weight of curing agent, the total mass of the insulating heat-conducting adhesive layer is taken as a basis, the content of the heat-conducting filler is 40-80 wt%, the heat-conducting filler is selected from one or more of aluminum oxide, aluminum nitride, silicon dioxide, silicon carbide, silicon nitride and boron nitride, and more specifically, the heat-conducting filler is selected from aluminum oxide, aluminum nitride, silicon dioxide, silicon carbide and boron nitride. The high-temperature curing is specifically baking curing at 50-100 ℃.
Finally, contacting and pressing the insulating heat-conducting adhesive layer with the porous alumina structural layer to obtain the aluminum-based copper-clad plate; the pressing is specifically performed in vacuum, rolling and pre-pressing are performed, and then pressing is performed in a vacuum environment with the temperature of 200-300 ℃ and the pressure of 200-300 psi.
The porous alumina structure is prepared on the aluminum plate, the insulating property of the interface is improved, and meanwhile, epoxy resin insulating cement can seep into the hole under the action of pressure in the pressing process, most of filler is shielded outside the hole, so that the interface is in contact with the substrate-insulating cement in a larger area, the bearing capacity of the contact structure to thermal stress can be effectively improved, and the reliability of the aluminum-based copper-clad plate is improved.
The invention aims to provide a high-reliability aluminum-based copper-clad plate and a preparation method thereof, wherein a porous alumina structure at a pressing interface is utilized, so that epoxy resin insulating glue permeates into holes under the action of pressure in the pressing process, most of fillers are shielded outside the holes, the effective contact area and the bonding force of the insulating glue and a metal substrate are effectively increased, meanwhile, the larger hole diameter not only can effectively eliminate natural hole sealing caused by moisture, but also is more beneficial to the permeation of the insulating glue, the product reliability is increased, and meanwhile, the content of the fillers is increased in the insulating glue under the condition for improving the heat conductivity. The method has simple process, can effectively improve the product quality, and has wide application prospect in power device packaging.
For further understanding of the present invention, the aluminum-based copper-clad plate and the preparation method thereof provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
As shown in figure 1, the high-reliability aluminum-based copper-clad plate and the preparation method thereof comprise the following steps:
(1) the aluminum substrate oxidation treatment specifically comprises the following steps: one surface of the cleaned pure aluminum plate 4 is subjected to plastic packaging sealing by using plastic packaging equipment (the material of a plastic packaging film is PET), the other surface is subjected to oxidation on micro-arc oxidation equipment to form an oxidation layer 5, the voltage is 500V, the frequency is 500Hz, the duty ratio is 10%, the micro-arc oxidation time is 10-20 minutes, and the micro-arc oxidation electrolyte is a mixed solution of 15g/L sodium silicate and 8g/L sodium hexametaphosphate;
(2) multiple purposePreparing a porous alumina structure: removing the plastic package seal in the steps, cleaning, annealing for 4 hours at 500 ℃ under the protection of nitrogen, cooling to room temperature along with the furnace, and ultrasonically cleaning the annealed sample in acetone and deionized water for 30min respectively; then, carrying out plastic packaging sealing treatment on the surface of the oxide layer 5, and preparing the porous alumina structure 3 on the surface of the pure aluminum by using a secondary anodic oxidation method, wherein the specific method comprises the following steps: in a volume ratio of 4: 1 perchloric acid and absolute ethyl alcohol mixed solution is subjected to constant-current electrochemical polishing, the current is 1A, the time is 10min, then the mixture is subjected to primary anodic oxidation in 0.3mol/L oxalic acid electrolyte, the oxidation voltage is 40V, the temperature is 6 ℃, the oxidation time is 2h, and then the mixture is placed in 60 ℃, 6 percent phosphoric acid and 1.6 percent Cr2O3Etching for 4h in the mixed solution to remove the primary oxide film layer, carrying out secondary anodic oxidation under the same conditions, wherein the oxidation time is 2h, more than 100 pores per square centimeter, the average pore depth is 5 micrometers, and the average pore diameter is 150 nanometers, and finally removing the plastic package and carrying out cleaning and annealing treatment;
(2) preparing insulating heat-conducting glue: the insulating heat-conducting glue 2 comprises the following components: 50 parts of epoxy resin, 2 parts of toughening agent, 2 parts of coupling agent, 3 parts of curing agent, 43 parts of heat-conducting filler (aluminum oxide accounts for 90 wt%, silicon dioxide accounts for 5 wt%, silicon carbide accounts for 4.95 wt%, and 0.05 wt% of flaky boron nitride), wherein the sizes of filler particles are randomly distributed, and more than 99% of the particle sizes are larger than 500 nanometers;
(3) preparing a copper-clad aluminum substrate: after the insulating heat-conducting glue is prepared according to the components, the insulating heat-conducting glue is uniformly coated on the copper foil 1 through a coating machine, and is baked and cured at 70 ℃, wherein the thickness of the heat-conducting glue is 60 micrometers; and then, laminating and combining one side of the insulating heat-conducting adhesive 2 and one side of the porous alumina structure 3 of the aluminum plate, firstly carrying out rolling prepressing in vacuum, and then carrying out pressing in a vacuum environment with the pressure of 200 ℃ and 300psi to prepare the aluminum-based copper-clad plate.
Example 2
As shown in figure 1, the high-reliability aluminum-based copper-clad plate and the preparation method thereof comprise the following steps:
(1) the aluminum substrate oxidation treatment specifically comprises the following steps: one surface of the cleaned pure aluminum plate 4 is subjected to plastic packaging sealing by using plastic packaging equipment (the material of a plastic packaging film is PET), the other surface is subjected to oxidation on micro-arc oxidation equipment to form an oxidation layer 5, the voltage is 500V, the frequency is 500Hz, the duty ratio is 10%, the micro-arc oxidation time is 10-20 minutes, and the micro-arc oxidation electrolyte is a mixed solution of 15g/L sodium silicate and 8g/L sodium hexametaphosphate;
(2) preparing a porous alumina structure: removing the plastic package seal in the steps, cleaning, annealing for 4 hours at 500 ℃ under the protection of nitrogen, cooling to room temperature along with the furnace, and ultrasonically cleaning the annealed sample in acetone and deionized water for 30min respectively; then, carrying out plastic packaging sealing treatment on the surface of the oxide layer 5, and preparing the porous alumina structure 3 on the surface of the pure aluminum by using a secondary anodic oxidation method, wherein the specific method comprises the following steps: in a volume ratio of 4: 1 perchloric acid and absolute ethyl alcohol mixed solution is subjected to constant-current electrochemical polishing, the current is 1A, the time is 10min, then the mixture is subjected to primary anodic oxidation in 0.3mol/L oxalic acid electrolyte, the oxidation voltage is 40V, the temperature is 6 ℃, the oxidation time is 2h, and then the mixture is placed in 60 ℃, 6 percent phosphoric acid and 1.6 percent Cr2O3Etching for 4h in the mixed solution to remove the primary oxide film layer, carrying out secondary anodic oxidation under the same condition, wherein the oxidation time is 4h, more than 100 holes per square centimeter, the average hole depth is 10 micrometers, and the average pore diameter is 250 nanometers, and finally removing the plastic package and carrying out cleaning and annealing treatment;
(2) preparing insulating heat-conducting glue: the insulating heat-conducting glue 2 comprises the following components: 45 parts of epoxy resin, 2 parts of toughening agent, 2 parts of coupling agent, 3 parts of curing agent, 48 parts of heat-conducting filler (aluminum oxide accounts for 85 wt%, silicon nitride 5 wt%, silicon dioxide 5 wt%, silicon carbide 4.95 wt% and 0.05 wt% of flaky boron nitride), wherein the sizes of filler particles are randomly distributed, and more than 99% of the particle sizes are larger than 500 nanometers;
(3) preparing a copper-clad aluminum substrate: after the insulating heat-conducting adhesive is prepared according to the components, the insulating heat-conducting adhesive is uniformly coated on the copper foil 1 through a coating machine, and is baked and cured at 70 ℃, wherein the thickness of the heat-conducting adhesive is 100 micrometers; and then, laminating and combining one side of the insulating heat-conducting adhesive 2 and one side of the porous alumina structure 3 of the aluminum plate, firstly carrying out rolling prepressing in vacuum, and then carrying out pressing in a vacuum environment with the pressure of 200 ℃ and 300psi to prepare the aluminum-based copper-clad plate.
The aluminum-based copper-clad plates prepared in the embodiments 1 and 2 were tested, and the test results are shown in table 1:
table 1 table of performance data of aluminum-based copper-clad plate prepared in example
| Main performance index | Example 1 | Example 2 |
| Coefficient of thermal conductivity (W/m.k) | 2.4 | 2.6 |
| Peel strength (N/mm) | 1.7 | 2.8 |
| Withstand voltage (kV) | >5.5 | >5.5 |
| Dip soldering resistance (s,300 ℃ C.) | >350 | >350 |
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The utility model provides an aluminium base copper-clad plate, includes aluminum plate and the copper foil of compound in aluminum plate surface, aluminum plate's a surface has the aluminium oxide layer, and another surface has porous alumina structural layer, copper foil surface recombination has insulating heat-conducting adhesive layer, just insulating heat-conducting adhesive layer with the coincidence of porous alumina structural layer part.
2. The aluminum-based copper-clad plate according to claim 1, wherein the porous alumina structure layer has a pore density of more than 100 pores per square centimeter, a pore depth of 3 to 15 μm, and a pore diameter of 100 to 300 nm.
3. The aluminum-based copper-clad plate according to claim 1 or 2, wherein the heat conducting filler in the insulating heat conducting adhesive layer is selected from one or more of aluminum oxide, silicon dioxide, aluminum nitride, silicon carbide, silicon nitride and boron nitride, and the heat conducting filler comprises 0.02-0.10 wt% of linear filler and sheet filler; the particle size of the heat-conducting filler is larger than the pore diameter of the porous alumina structure layer.
4. The aluminum-based copper-clad plate according to claim 1, wherein the thickness of the insulating and heat-conducting adhesive layer is more than 10 times the depth of the porous alumina pores of the porous alumina structure layer.
5. The preparation method of the aluminum-based copper-clad plate of claim 1, comprising the following steps:
cleaning an aluminum plate, preparing an aluminum oxide layer on one surface of the aluminum plate, and preparing a porous aluminum oxide structure layer on the other surface of the aluminum plate;
coating an insulating heat-conducting adhesive layer on the surface of the copper foil, and then curing at high temperature;
and contacting and pressing the insulating heat-conducting adhesive layer with the porous alumina structural layer to obtain the aluminum-based copper-clad plate.
6. The method according to claim 5, wherein the aluminum oxide layer is prepared by micro-arc oxidation.
7. The preparation method according to claim 5, wherein the porous alumina structural layer is prepared by:
sealing one surface of the cleaned aluminum plate, performing constant-current electrochemical polishing on the other surface, performing primary anodic oxidation in oxalic acid electrolyte, corroding in a mixed solution of phosphoric acid and chromium oxide, and finally performing secondary anodic oxidation.
8. The preparation method according to claim 5, wherein the insulating heat-conducting adhesive layer is prepared from epoxy resin, a toughening agent, a coupling agent, a curing agent and a heat-conducting filler, and the content of the heat-conducting filler is 40-80 wt%.
9. The method according to claim 5, wherein the pressing is vacuum pre-pressing followed by vacuum press-pressing.
10. The method according to claim 9, wherein the temperature of the vacuum press is 200 to 300 ℃ and the pressure is 200 to 300 psi.
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