CN113645765B - Copper-clad substrate for high-end printed circuit board and preparation method thereof - Google Patents
Copper-clad substrate for high-end printed circuit board and preparation method thereof Download PDFInfo
- Publication number
- CN113645765B CN113645765B CN202111058388.7A CN202111058388A CN113645765B CN 113645765 B CN113645765 B CN 113645765B CN 202111058388 A CN202111058388 A CN 202111058388A CN 113645765 B CN113645765 B CN 113645765B
- Authority
- CN
- China
- Prior art keywords
- copper
- layer
- silicon nitride
- conductive film
- ceramic substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- H05K1/0207—Cooling of mounted components using internal conductor planes parallel to the surface for thermal conduction, e.g. power planes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a copper-clad substrate for a high-end printed circuit board, and particularly relates to the technical field of copper-clad substrates. The conductive film layer can effectively improve the heat dissipation efficiency of the copper-clad substrate, has a certain buffering effect on the thermal stress generated by the copper-clad substrate under the condition of cold and hot circulation, and can effectively improve the service life of the copper-clad substrate.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a copper-clad substrate for a high-end printed circuit board and a preparation method thereof.
Background
The ceramic copper-clad substrate is an electronic base material prepared by directly sintering copper foil on the surface of ceramic by using DBC (direct copper) technology. 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 a key material for packaging power modules, connecting chips and radiating substrates in the field of power electronics at present, and is widely applied to various electrical equipment and electronic products. In two of the most important processes for ceramic metallization, direct copper clad ceramic substrates (DCB) are produced by directly bonding copper to ceramic using an oxygen-containing eutectic liquid of copper, and active metal brazing copper clad ceramic substrates (AMB) are produced by sintering ceramic plates and metal copper foils together using a brazing material. Compared with a direct copper-clad ceramic substrate, the active metal brazing copper-clad ceramic substrate has higher reliability.
During active soldering, the ceramic and the metal can form a compact interface through the wettability and the interface reaction of the solder, but the large residual thermal stress is a common problem in ceramic metallization. In addition, the obvious difference of the thermal expansion coefficients of the copper ceramics causes that when the AMB copper-clad ceramic substrate is in a cold-hot circulation condition, microcracks are easily generated on the ceramic side of a solder bonding layer, and warping is easily generated on the metal side, so that the substrate fails.
Disclosure of Invention
The present invention is directed to a copper-clad substrate for high-end printed circuit board and a method for manufacturing the same, which solves the above-mentioned problems of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: the copper-clad substrate for the high-end printed circuit board comprises a silicon nitride ceramic substrate and a copper foil layer covering at least one surface of the silicon nitride ceramic substrate, wherein an interface bonding layer is arranged between the silicon nitride ceramic substrate and the copper foil layer, and the interface bonding layer comprises a conductive film layer, a metal stress layer and a welding layer.
In a preferred embodiment, the silicon nitride ceramic substrate has a thickness of 0.3 to 0.8mm, a surface roughness of 0.3 to 0.6 μm, the copper foil layer is oxygen-free copper, a purity of the oxygen-free copper is 99.99% or more, the copper foil layer has a thickness of 0.1 to 0.6mm, the interface bonding layer has a thickness of 2 to 6um, and a thickness ratio of the conductive film layer, the metal stress layer, and the solder layer is 1: (1.5-2): (2.2-2.6).
In a preferred embodiment, the conductive film layer comprises the following raw materials in parts by weight: 40-60 parts of polyimide resin, 10-18 parts of nano heat conduction material, 1-3 parts of lubricant, 5-10 parts of filler and 50-80 parts of dispersant, wherein the metal stress layer is one of copper, aluminum and silver.
In a preferred embodiment, the nano heat conduction material comprises nano aluminum nitride, magnesium oxide and aluminum oxide, the filler comprises talcum powder, silicon dioxide, polyaniline and polypyrrole, and the dispersing agent is N-methylpyrrolidone or N, N-dimethylacetamide.
In a preferred embodiment, the weight ratio of the nano aluminum nitride, the magnesium oxide and the aluminum oxide in the nano heat conduction material is 1: (1-1.5): (1-1.5), wherein the weight ratio of the talcum powder, the silicon dioxide, the polyaniline and the polypyrrole in the filler is 1: (1-1.2): (0.6-0.8): (0.6-0.8).
A preparation method of a copper-clad substrate for a high-end printed circuit board comprises the following specific preparation steps:
the method comprises the following steps: weighing polyimide resin, nano heat conducting material, lubricant, filler and dispersant according to the weight parts of the raw materials of the conductive film layer, putting the weighed polyimide resin, nano heat conducting material and lubricant into the dispersant for stirring and ultrasonic dispersion, adding the filler into the dispersion liquid after the dispersion is finished, and mixing to obtain a conductive film layer feed liquid for later use;
step two: selecting a silicon nitride ceramic substrate, cleaning the selected silicon nitride ceramic substrate, performing thermal oxidation treatment on the surface of the silicon nitride ceramic substrate after cleaning is completed, coating the conductive film layer feed liquid in the step one on the surface of the silicon nitride ceramic substrate, and cyclizing at high temperature to form a conductive film layer on the surface of the silicon nitride ceramic substrate;
step three: carrying out corona treatment on the conductive film layer obtained in the second step, carrying out surface pretreatment after the corona treatment is finished, uniformly depositing raw materials in the metal stress layer on the surface of the pretreated conductive film layer by using a magnetron sputtering method after the surface pretreatment is finished, carrying out electrochemical polishing treatment on the deposited metal layer, and putting the metal stress layer into electrolyte for anodic oxidation after the treatment is finished to obtain the metal stress layer with a rough surface;
step four: and cleaning the selected solder sheets and the copper foil layer, sequentially laying the solder sheets and the copper foil layer on the surface of the metal stress layer, clamping and fixing by using a clamp, then sending into a vacuum brazing furnace for high-temperature welding, and obtaining the copper-clad substrate for the high-end printed circuit board after welding.
In a preferred embodiment, the frequency of the ultrasonic dispersion in the first step is 100-140Hz, the stirring speed is 400-600 rpm, and the stirring ultrasonic dispersion time is 30-60 min.
In a preferred embodiment, when cleaning the silicon nitride ceramic substrate in the second step, firstly, absolute ethyl alcohol is used to clean the silicon nitride ceramic substrate for 10-15min by an ultrasonic cleaning instrument, and then deionized water is used to rinse the substrate for 3-6min, the temperature during thermal oxidation treatment in the second step is 110-.
In a preferred embodiment, the power of the corona treatment in the third step is 3-4kw, the conductive film layer is soaked in concentrated sulfuric acid, concentrated nitric acid or aqua regia in the surface pretreatment in the third step, the soaking time is 5-10min, and the roughness of the rough surface of the metal stress layer in the third step is 0.5-2.5.
In a preferred embodiment, when cleaning the solder sheet and the copper foil layer in the fourth step, absolute ethyl alcohol, deionized water, an alkaline solution, an acidic solution and deionized water are sequentially used for washing, and the welding temperature of vacuum high-temperature welding in the fourth step is 800-950 ℃, and the vacuum degree is less than 0.01 Pa.
The invention has the technical effects and advantages that:
1. the invention relates to a copper-clad substrate for a high-end printed circuit board, wherein an interface bonding layer is arranged between a silicon nitride ceramic substrate and a copper foil layer, the interface bonding layer comprises a conductive film layer, a metal stress layer and a welding layer, the conductive film layer adopts polyimide resin as a raw material and is filled with nano aluminum nitride, magnesium oxide, aluminum oxide, talcum powder, silicon dioxide, polyaniline and polypyrrole, the conductive film layer has higher heat conductivity while ensuring that the conductive film layer does not influence signal transmission, the outer side of the conductive film layer is subjected to corona treatment and surface pretreatment, so that the specific surface area of the conductive film layer is increased, then the metal stress layer is sputtered on the surface of the conductive film layer, the metal stress layer is subjected to electrochemical polishing and anodic oxidation treatment to form a rough surface structure with micropores, the rough surface structure can effectively release the thermal stress generated by the copper-clad substrate under the condition of cold and heat circulation, and the heat dissipation efficiency of the copper-clad substrate can be effectively improved by the conductive film layer, the buffer effect on the thermal stress generated by the copper-clad substrate under the condition of cold and hot circulation is certain, and the service life of the copper-clad substrate can be effectively prolonged;
2. the filler in the conductive film layer can be filled into polyimide resin, so that the conductive film layer can form a compact conductive and heat-conducting net, the buffer effect on the thermal stress generated by the copper-clad substrate under the condition of cold and hot circulation is good, the processing technology is simple, and the yield is high.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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.
Example 1:
the invention provides a copper-clad substrate for a high-end printed circuit board, which comprises a silicon nitride ceramic substrate and a copper foil layer covered and connected on at least one surface of the silicon nitride ceramic substrate, wherein an interface bonding layer is arranged between the silicon nitride ceramic substrate and the copper foil layer, and the interface bonding layer comprises a conductive film layer, a metal stress layer and a welding layer.
In a preferred embodiment, the thickness of the silicon nitride ceramic substrate is 0.6mm, the surface roughness is 0.5 μm, the copper foil layer is oxygen-free copper, the purity of the oxygen-free copper is 99.99% or more, the thickness of the copper foil layer is 0.3mm, the thickness of the interface bonding layer is 5 μm, and the thickness ratio of the conductive film layer, the metal stress layer and the welding layer is 1: 1.6: 2.4.
in a preferred embodiment, the conductive film layer comprises the following raw materials in parts by weight: 40 parts of polyimide resin, 10 parts of nano heat conduction material, 1 part of lubricant, 5 parts of filler and 50 parts of dispersant, wherein the metal stress layer is copper.
In a preferred embodiment, the nano heat conducting material comprises nano aluminum nitride, magnesium oxide and aluminum oxide, the filler comprises talcum powder, silicon dioxide, polyaniline and polypyrrole, and the dispersing agent is N-methylpyrrolidone or N, N-dimethylacetamide.
In a preferred embodiment, the weight ratio of the nano aluminum nitride, the magnesium oxide and the aluminum oxide in the nano heat conduction material is 1: 1.2: 1.2, the weight ratio of the talcum powder, the silicon dioxide, the polyaniline and the polypyrrole in the filler is 1: 1: 0.6: 0.7.
a preparation method of a copper-clad substrate for a high-end printed circuit board comprises the following specific preparation steps:
the method comprises the following steps: weighing polyimide resin, nano heat conducting material, lubricant, filler and dispersant according to the weight parts of the raw materials of the conductive film layer, putting the weighed polyimide resin, nano heat conducting material and lubricant into the dispersant for stirring and ultrasonic dispersion, adding the filler into the dispersion liquid after the dispersion is finished, and mixing to obtain a conductive film layer feed liquid for later use;
step two: selecting a silicon nitride ceramic substrate, cleaning the selected silicon nitride ceramic substrate, performing thermal oxidation treatment on the surface of the silicon nitride ceramic substrate after cleaning is completed, coating the conductive film layer feed liquid in the step one on the surface of the silicon nitride ceramic substrate, and cyclizing at high temperature to form a conductive film layer on the surface of the silicon nitride ceramic substrate;
step three: performing corona treatment on the conductive film layer obtained in the step two, performing surface pretreatment after the corona treatment is finished, uniformly depositing raw materials in the metal stress layer on the surface of the pretreated conductive film layer by using a magnetron sputtering method after the surface pretreatment is finished, performing electrochemical polishing treatment on the deposited metal layer, and putting the metal stress layer into electrolyte for anodic oxidation after the treatment is finished to obtain the metal stress layer with a rough surface;
step four: and cleaning the selected solder sheets and the copper foil layer, sequentially laying the solder sheets and the copper foil layer on the surface of the metal stress layer, clamping and fixing by using a clamp, then sending into a vacuum brazing furnace for high-temperature welding, and obtaining the copper-clad substrate for the high-end printed circuit board after welding.
In a preferred embodiment, the frequency of ultrasonic dispersion in the first step is 120Hz, the stirring rate is 500 rpm, and the stirring ultrasonic dispersion time is 40 min.
In a preferred embodiment, when cleaning the silicon nitride ceramic substrate in the second step, firstly, the silicon nitride ceramic substrate is cleaned by an ultrasonic cleaning instrument for 12min by using absolute ethyl alcohol, and then is rinsed by deionized water for 4min, wherein the temperature during thermal oxidation treatment in the second step is 140 ℃, the thermal oxidation treatment is performed in a mixed nitrogen-oxygen gas atmosphere, the flow rate of the mixed nitrogen-oxygen gas is 1.2L/min, and the temperature during high-temperature cyclization in the second step is 360 ℃.
In a preferred embodiment, the power of the corona treatment in the third step is 3.5kw, the conductive film layer is soaked in concentrated sulfuric acid, concentrated nitric acid or aqua regia during the surface pretreatment in the third step, the soaking time is 8min, and the roughness of the rough surface of the metal stress layer in the third step is 1.5.
In a preferred embodiment, the solder sheet and the copper foil layer in the fourth step are cleaned by sequentially washing with absolute ethyl alcohol, deionized water, an alkaline solution, an acidic solution and deionized water, and the welding temperature of the vacuum high-temperature welding in the fourth step is 860 ℃ and the vacuum degree is less than 0.01 Pa.
Example 2:
the invention provides a copper-clad substrate for a high-end printed circuit board, wherein a conductive film layer comprises the following raw materials in parts by weight: 50 parts of polyimide resin, 14 parts of nano heat conduction material, 2 parts of lubricant, 8 parts of filler and 65 parts of dispersant.
Example 3:
different from the embodiments 1 and 2, the invention provides a copper-clad substrate for a high-end printed circuit board, wherein the conductive film layer comprises the following raw materials in parts by weight: 60 parts of polyimide resin, 18 parts of nano heat conduction material, 3 parts of lubricant, 10 parts of filler and 80 parts of dispersant.
Example 4:
the invention provides a copper-clad substrate for a high-end printed circuit board, which comprises a silicon nitride ceramic substrate and a copper foil layer covered and connected on at least one surface of the silicon nitride ceramic substrate, wherein an interface bonding layer is arranged between the silicon nitride ceramic substrate and the copper foil layer, and the interface bonding layer comprises a metal stress layer and a welding layer.
In a preferred embodiment, the thickness of the silicon nitride ceramic substrate is 0.6mm, the surface roughness is 0.5 μm, the copper foil layer is oxygen-free copper, the purity of the oxygen-free copper is 99.99% or more, the thickness of the copper foil layer is 0.3mm, the thickness of the interface bonding layer is 5 μm, and the thickness ratio of the metal stress layer to the welding layer is 1.6: 2.4, the metal stress layer is made of copper.
A preparation method of a copper-clad substrate for a high-end printed circuit board comprises the following specific preparation steps:
the method comprises the following steps: selecting a silicon nitride ceramic substrate, cleaning the selected silicon nitride ceramic substrate, performing thermal oxidation treatment on the surface of the silicon nitride ceramic substrate after cleaning, uniformly depositing raw materials in a metal stress layer on the surface of the silicon nitride ceramic substrate subjected to thermal oxidation treatment by using a magnetron sputtering method, performing electrochemical polishing treatment on a deposited metal layer, and putting the metal stress layer into electrolyte for anodic oxidation after treatment to obtain the metal stress layer with a rough surface;
step two: and cleaning the selected solder sheets and the copper foil layer, sequentially laying the solder sheets and the copper foil layer on the surface of the metal stress layer, clamping and fixing by using a clamp, then sending into a vacuum brazing furnace for high-temperature welding, and obtaining the copper-clad substrate for the high-end printed circuit board after welding.
In a preferred embodiment, when the silicon nitride ceramic substrate is cleaned in the first step, the silicon nitride ceramic substrate is cleaned by an ultrasonic cleaner for 12min by using absolute ethyl alcohol, and then is rinsed for 4min by using deionized water, and the temperature of the thermal oxidation treatment in the second step is 140 ℃.
In a preferred embodiment, the roughness of the rough surface of the metal stress layer in the first step is 1.5.
In a preferred embodiment, when cleaning the solder sheet and the copper foil layer in the second step, absolute ethyl alcohol, deionized water, an alkaline solution, an acidic solution and deionized water are sequentially used for washing, and the welding temperature of the vacuum high-temperature welding in the fourth step is 860 ℃ and the vacuum degree is less than 0.01 Pa.
Example 5:
the invention provides a copper-clad substrate for a high-end printed circuit board, which comprises a silicon nitride ceramic substrate and a copper foil layer covered and connected on at least one surface of the silicon nitride ceramic substrate, wherein an interface bonding layer is arranged between the silicon nitride ceramic substrate and the copper foil layer, and the interface bonding layer comprises a conductive film layer, a metal stress layer and a welding layer.
In a preferred embodiment, the thickness of the silicon nitride ceramic substrate is 0.6mm, the surface roughness is 0.5 μm, the copper foil layer is oxygen-free copper, the purity of the oxygen-free copper is 99.99% or more, the thickness of the copper foil layer is 0.3mm, the thickness of the interface bonding layer is 5um, and the thickness ratio of the conductive film layer, the metal stress layer and the welding layer is 1: 1.6: 2.4.
in a preferred embodiment, the conductive film layer comprises the following raw materials in parts by weight: 40 parts of polyimide resin, 10 parts of nano heat conduction material, 1 part of lubricant, 5 parts of filler and 50 parts of dispersant, wherein the metal stress layer is copper.
In a preferred embodiment, the nano heat conducting material comprises nano aluminum nitride, magnesium oxide and aluminum oxide, the filler comprises talcum powder, silicon dioxide, polyaniline and polypyrrole, and the dispersing agent is N-methylpyrrolidone or N, N-dimethylacetamide.
In a preferred embodiment, the weight ratio of the nano aluminum nitride, the magnesium oxide and the aluminum oxide in the nano heat conduction material is 1: 1.2: 1.2, the weight ratio of the talcum powder, the silicon dioxide, the polyaniline and the polypyrrole in the filler is 1: 1: 0.6: 0.7.
a preparation method of a copper-clad substrate for a high-end printed circuit board comprises the following specific preparation steps:
the method comprises the following steps: weighing polyimide resin, nano heat conducting material, lubricant, filler and dispersant according to the weight parts of the raw materials of the conductive film layer, putting the weighed polyimide resin, nano heat conducting material and lubricant into the dispersant for stirring and ultrasonic dispersion, adding the filler into the dispersion liquid after the dispersion is finished, and mixing to obtain a conductive film layer feed liquid for later use;
step two: selecting a silicon nitride ceramic substrate, cleaning the selected silicon nitride ceramic substrate, performing thermal oxidation treatment on the surface of the silicon nitride ceramic substrate after cleaning is completed, coating the conductive film layer feed liquid in the step one on the surface of the silicon nitride ceramic substrate, and cyclizing at high temperature to form a conductive film layer on the surface of the silicon nitride ceramic substrate;
step three: performing corona treatment on the conductive film layer obtained in the step two, performing surface pretreatment after the corona treatment is completed, and uniformly depositing raw materials in the metal stress layer on the surface of the pretreated conductive film layer by using a magnetron sputtering method after the surface pretreatment is completed to obtain a metal stress layer;
step four: and cleaning the selected solder sheets and the copper foil layer, sequentially laying the solder sheets and the copper foil layer on the surface of the metal stress layer, clamping and fixing by using a clamp, then sending into a vacuum brazing furnace for high-temperature welding, and obtaining the copper-clad substrate for the high-end printed circuit board after welding.
In a preferred embodiment, the frequency of ultrasonic dispersion in the first step is 120Hz, the stirring rate is 500 rpm, and the stirring ultrasonic dispersion time is 40 min.
In a preferred embodiment, when cleaning the silicon nitride ceramic substrate in the second step, firstly, the silicon nitride ceramic substrate is cleaned by an ultrasonic cleaning instrument for 12min by using absolute ethyl alcohol, and then is rinsed by deionized water for 4min, wherein the temperature during thermal oxidation treatment in the second step is 140 ℃, the thermal oxidation treatment is performed in a mixed nitrogen-oxygen gas atmosphere, the flow rate of the mixed nitrogen-oxygen gas is 1.2L/min, and the temperature during high-temperature cyclization in the second step is 360 ℃.
In a preferred embodiment, the power of the corona treatment in the third step is 3.5kw, the conductive film layer is soaked in concentrated sulfuric acid, concentrated nitric acid or aqua regia during the surface pretreatment in the third step, the soaking time is 8min, and the roughness of the rough surface of the metal stress layer in the third step is 0.4.
In a preferred embodiment, the solder sheet and the copper foil layer in the fourth step are cleaned by sequentially washing with absolute ethyl alcohol, deionized water, an alkaline solution, an acidic solution and deionized water, and the welding temperature of the vacuum high-temperature welding in the fourth step is 860 ℃ and the vacuum degree is less than 0.01 Pa.
The copper-clad substrates prepared in the above examples 1 to 5 were respectively used as an experimental group 1, an experimental group 2, an experimental group 3, an experimental group 4, and an experimental group 5, and a commercially available copper-clad substrate for a circuit board was selected as a control group, and the selected copper-clad substrate was subjected to thermal conductivity, peel strength, and the number of cold and hot impacts/times when warpage and cracking failed. The test results are shown in the first table:
watch 1
As can be seen from table one, the copper-clad substrate produced by the invention has better thermal conductivity and peel strength compared with the conventional copper-clad substrate for a circuit board, and the copper-clad substrate has better thermal stress release effect under the condition of cold and hot circulation, example 4 lacks a conductive film layer compared with example 1, the thermal conductivity of the copper-clad plate of example 4 is obviously reduced, and example 5 does not treat a metal stress layer compared with example 1, the impact frequency of the copper-clad plate of example 5 is reduced, an interface bonding layer comprises the conductive film layer, the metal stress layer and a welding layer, the conductive film layer adopts polyimide resin as a raw material and is filled with nano aluminum nitride, magnesium oxide, aluminum oxide, talcum powder, silicon dioxide, polyaniline and polypyrrole, the conductive film layer has higher thermal conductivity while ensuring that the conductive film layer does not influence signal transmission, and the corona treatment and the surface pretreatment are carried out on the outer side of the conductive film layer, the conductive film layer can effectively improve the heat dissipation efficiency of the copper-clad substrate, has a certain buffering effect on the thermal stress generated by the copper-clad substrate under the cold and heat circulation conditions, and can effectively prolong the service life of the copper-clad substrate.
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. The utility model provides a copper clad substrate for high-end printed wiring board, includes silicon nitride ceramic substrate and covers and connect in the copper foil layer of at least one surface of silicon nitride ceramic substrate which characterized in that: an interface bonding layer is arranged between the silicon nitride ceramic substrate and the copper foil layer, and the interface bonding layer comprises a conductive film layer, a metal stress layer and a welding layer;
the preparation method of the copper-clad substrate for the high-end printed circuit board comprises the following specific preparation steps:
the method comprises the following steps: weighing polyimide resin, nano heat conducting material, lubricant, filler and dispersant according to the weight parts of the raw materials of the conductive film layer, putting the weighed polyimide resin, nano heat conducting material and lubricant into the dispersant for stirring and ultrasonic dispersion, adding the filler into the dispersion liquid after the dispersion is finished, and mixing to obtain a conductive film layer feed liquid for later use;
step two: selecting a silicon nitride ceramic substrate, cleaning the selected silicon nitride ceramic substrate, performing thermal oxidation treatment on the surface of the silicon nitride ceramic substrate after cleaning is completed, coating the conductive film layer feed liquid in the step one on the surface of the silicon nitride ceramic substrate, and cyclizing at high temperature to form a conductive film layer on the surface of the silicon nitride ceramic substrate;
step three: performing corona treatment on the conductive film layer obtained in the step two, performing surface pretreatment after the corona treatment is finished, uniformly depositing raw materials in the metal stress layer on the surface of the pretreated conductive film layer by using a magnetron sputtering method after the surface pretreatment is finished, performing electrochemical polishing treatment on the deposited metal layer, and putting the metal stress layer into electrolyte for anodic oxidation after the treatment is finished to obtain the metal stress layer with a rough surface;
step four: and cleaning the selected solder sheets and the copper foil layer, sequentially laying the solder sheets and the copper foil layer on the surface of the metal stress layer, clamping and fixing by using a clamp, then sending into a vacuum brazing furnace for high-temperature welding, and obtaining the copper-clad substrate for the high-end printed circuit board after welding.
2. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: the thickness of silicon nitride ceramic substrate is 0.3-0.8mm, and surface roughness is 0.3-0.6 mu m, the copper foil layer is oxygen-free copper, just oxygen-free copper's purity is more than 99.99%, the thickness of copper foil layer is 0.1-0.6mm, the thickness of interface anchor coat is 2-6um, the thickness ratio of electrically conductive rete, metal stress layer and welded layer is 1: (1.5-2): (2.2-2.6).
3. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: the conductive film layer comprises the following raw materials in parts by weight: 40-60 parts of polyimide resin, 10-18 parts of nano heat conduction material, 1-3 parts of lubricant, 5-10 parts of filler and 50-80 parts of dispersant, wherein the metal stress layer is one of copper, aluminum and silver.
4. A copper-clad substrate for a high-end printed wiring board according to claim 3, wherein: the nano heat conduction material comprises nano aluminum nitride, magnesium oxide and aluminum oxide, the filler comprises talcum powder, silicon dioxide, polyaniline and polypyrrole, and the dispersing agent is N-methylpyrrolidone or N, N-dimethylacetamide.
5. The copper-clad substrate for a high-end printed wiring board according to claim 4, wherein: the weight ratio of the nano aluminum nitride, the magnesium oxide and the aluminum oxide in the nano heat conduction material is 1: (1-1.5): (1-1.5), wherein the weight ratio of the talcum powder, the silicon dioxide, the polyaniline and the polypyrrole in the filler is 1: (1-1.2): (0.6-0.8): (0.6-0.8).
6. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: the frequency of ultrasonic dispersion in the first step is 100-140Hz, the stirring speed is 400-600 r/min, and the stirring ultrasonic dispersion time is 30-60 min.
7. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: and cleaning the silicon nitride ceramic substrate by using absolute ethyl alcohol through an ultrasonic cleaning instrument for 10-15min during cleaning in the second step, and then washing the silicon nitride ceramic substrate by using deionized water for 3-6min, wherein the temperature during thermal oxidation treatment in the second step is 110-160 ℃, the thermal oxidation treatment is carried out in the atmosphere of mixed nitrogen-oxygen gas, the flow of the mixed nitrogen-oxygen gas is 0.2-3L/min, and the temperature during high-temperature cyclization in the second step is 320-400 ℃.
8. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: the power of the corona treatment in the third step is 3-4kw, the conductive film layer is soaked in concentrated sulfuric acid, concentrated nitric acid or aqua regia during the surface pretreatment in the third step, the soaking time is 5-10min, and the roughness of the rough surface of the metal stress layer in the third step is 0.5-2.5.
9. The copper-clad substrate for a high-end printed wiring board according to claim 1, wherein: and when cleaning the solder sheet and the copper foil layer in the fourth step, sequentially washing by using absolute ethyl alcohol, deionized water, an alkaline solution, an acidic solution and deionized water, wherein the welding temperature of the vacuum high-temperature welding in the fourth step is 800-950 ℃, and the vacuum degree is less than 0.01 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111058388.7A CN113645765B (en) | 2021-09-09 | 2021-09-09 | Copper-clad substrate for high-end printed circuit board and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111058388.7A CN113645765B (en) | 2021-09-09 | 2021-09-09 | Copper-clad substrate for high-end printed circuit board and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113645765A CN113645765A (en) | 2021-11-12 |
| CN113645765B true CN113645765B (en) | 2022-08-23 |
Family
ID=78425512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111058388.7A Active CN113645765B (en) | 2021-09-09 | 2021-09-09 | Copper-clad substrate for high-end printed circuit board and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113645765B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230361B (en) * | 2022-01-10 | 2022-12-02 | 江苏耀鸿电子有限公司 | Silicon nitride ceramic copper-clad substrate and preparation method thereof |
| CN114874030B (en) * | 2022-07-08 | 2023-03-31 | 江苏富乐华功率半导体研究院有限公司 | Preparation method for improving insulation reliability of copper-clad ceramic substrate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07288296A (en) * | 1994-04-18 | 1995-10-31 | Matsushita Electric Works Ltd | Ceramic circuit substrate |
| CN108033810A (en) * | 2017-12-12 | 2018-05-15 | 北京科技大学 | A kind of preparation method of aluminium nitride ceramics copper-clad plate |
| CN110484877A (en) * | 2019-10-09 | 2019-11-22 | 安徽鸿海新材料股份有限公司 | A kind of preparation method of ceramic base copper-clad plate |
| CN111933610A (en) * | 2020-07-17 | 2020-11-13 | 江苏富乐德半导体科技有限公司 | Metal ceramic substrate with buffer layer and preparation method thereof |
| CN112164687A (en) * | 2020-09-07 | 2021-01-01 | 江苏富乐德半导体科技有限公司 | Copper-clad ceramic substrate and preparation method thereof |
-
2021
- 2021-09-09 CN CN202111058388.7A patent/CN113645765B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07288296A (en) * | 1994-04-18 | 1995-10-31 | Matsushita Electric Works Ltd | Ceramic circuit substrate |
| CN108033810A (en) * | 2017-12-12 | 2018-05-15 | 北京科技大学 | A kind of preparation method of aluminium nitride ceramics copper-clad plate |
| CN110484877A (en) * | 2019-10-09 | 2019-11-22 | 安徽鸿海新材料股份有限公司 | A kind of preparation method of ceramic base copper-clad plate |
| CN111933610A (en) * | 2020-07-17 | 2020-11-13 | 江苏富乐德半导体科技有限公司 | Metal ceramic substrate with buffer layer and preparation method thereof |
| CN112164687A (en) * | 2020-09-07 | 2021-01-01 | 江苏富乐德半导体科技有限公司 | Copper-clad ceramic substrate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113645765A (en) | 2021-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113645765B (en) | Copper-clad substrate for high-end printed circuit board and preparation method thereof | |
| JP5705506B2 (en) | Clad material for insulating substrate | |
| WO2002067324A1 (en) | Member for electronic circuit, method for manufacturing the member, and electronic part | |
| CN111403347A (en) | Copper-ceramic interface structure of high-reliability silicon nitride copper-clad ceramic substrate and preparation method thereof | |
| JP2002043482A (en) | Member for electronic circuit, its manufacturing method and electronic component | |
| US6197435B1 (en) | Substrate | |
| CN106888551A (en) | A kind of ceramic base copper-clad plate and its preparation technology | |
| JP4674983B2 (en) | Manufacturing method of joined body | |
| CN110843272B (en) | Ceramic copper-clad plate and preparation process and application thereof | |
| JP4104429B2 (en) | Module structure and module using it | |
| CN113698213A (en) | High-thermal-conductivity general copper-clad ceramic substrate and preparation method thereof | |
| JP2008147307A (en) | Circuit board and semiconductor module having same | |
| JP4323706B2 (en) | Method of joining ceramic body and copper plate | |
| JPH08102570A (en) | Ceramic circuit board | |
| CN111885852A (en) | Preparation method of ceramic copper-clad plate | |
| JP7298988B2 (en) | Ceramic circuit board and its manufacturing method | |
| CN216528873U (en) | Circuit substrate and insulated gate bipolar transistor module | |
| JP4111253B2 (en) | Circuit board | |
| JPH0518477B2 (en) | ||
| JP2001024296A (en) | Ceramic circuit board | |
| US20240304516A1 (en) | Ceramic circuit substrate, semiconductor device, method for manufacturing ceramic circuit substrate, and method for manufacturing semiconductor device | |
| CN214797405U (en) | High-bonding-force aluminum nitride copper-clad ceramic substrate | |
| JPH01301866A (en) | Formation of metallic layer on aluminum nitride surface | |
| CN114171663A (en) | Heat dissipation substrate and preparation method thereof | |
| CN206790778U (en) | A kind of ceramic base copper-clad plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Liming Inventor after: Wu Haibing Inventor after: Chen Yingfeng Inventor before: Wu Haibing Inventor before: Chen Yingfeng |