CN112638062A - Active brazing filler metal for ceramic circuit board - Google Patents
Active brazing filler metal for ceramic circuit board Download PDFInfo
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- CN112638062A CN112638062A CN202110257634.5A CN202110257634A CN112638062A CN 112638062 A CN112638062 A CN 112638062A CN 202110257634 A CN202110257634 A CN 202110257634A CN 112638062 A CN112638062 A CN 112638062A
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- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
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Abstract
The invention provides an active brazing filler metal for a ceramic circuit board, which relates to the technical field of ceramic circuit board manufacturing and comprises the following raw materials: 95.0-99.5 wt% of silver-based active brazing alloy and 5.0-5 wt% of complex phase material X0.5wt%; the silver-based active brazing alloy comprises Ag, Cu and an active metal material, wherein the weight percentage of the Ag-based active brazing alloy is as follows: 20-40wt%, active metal material: 1-10wt% and the balance of Ag. The invention adds TiC, diamond C, BN and Al into the active metal brazing slurry2O3The complex phase material is dispersed in the active metal brazing slurry in a mode of controlling the particle shape and equivalent particle size of the complex phase material, and can reduce stress concentration, thereby reducing residual stress, improving the heat cycle resistance, bending strength, flexibility and other properties of the ceramic circuit board prepared by brazing, and improving the reliability of the ceramic circuit board.
Description
Technical Field
The invention relates to the technical field of ceramic circuit board manufacturing, in particular to an active solder for a ceramic circuit board.
Background
Through years of development, the copper-clad ceramic substrate connection technology mainly comprises soldering, diffusion welding, fusion welding, oxide glass solder connection methods and the like, wherein the soldering has unique advantages and is economically feasible for materials with large connection performance difference and sensitive melting, and the soldering is also one of the main methods for obtaining high-strength ceramic circuit board joints. The Brazing process is further classified into a metallization process and an Active Metal Brazing (AMB). Both brazing methods require the use of brazing materials, with the difference that the metallization process is mainly using conventional brazing filler metals, whereas the active metal brazing method is mainly using active brazing materials containing active metals.
Currently, in the prior art, active brazing filler metal is mostly prepared by adding active metal into brazing materials, and then brazing is carried out. The method is to add a small amount of active metals Ti, Hf or Zr into the eutectic solder, and the active metals have high affinity to substances such as oxides, silicates and the like due to high chemical activity.
However, the active solders used in the prior art have a problem: because of the difference in thermal expansion coefficient among the ceramic base material, the metal base material, the brazing filler metal layer or the intermediate layer, in the brazing cooling process, the ceramic undergoes small volume shrinkage and the metal undergoes large volume shrinkage, so that residual tensile stress is generated on the outer surface of the ceramic in the position close to the bonding interface. The larger residual tensile stress can obviously reduce the fracture toughness and the joint fracture strength of the ceramic base material at the position close to the interface, so that the ceramic or the area near the interface can generate cracks or generate cracks under smaller external load, the bonding strength and the reliability of the copper-clad ceramic substrate are influenced, and the reliability of the ceramic circuit board is further influenced.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides an active solder for a ceramic circuit board, wherein a complex phase material is added in the active metal solder, so that the complex phase material is dispersed in the solder material, and the stress concentration effect is further reduced.
According to one aspect of the invention, the active solder for the ceramic circuit board is composed of the following raw materials: 95.0-99.5 wt% of silver-based active brazing alloy and 5.0-5 wt% of complex phase material X0.5wt%; the silver-based active brazing alloy comprises Ag, Cu and an active metal material, wherein the weight percentage of the Ag-based active brazing alloy is as follows: 20-40wt%, active metal material: 1-10wt%, and the balance of Ag.
Further optionally, the complex phase material X is made of TiC, diamond C, BN and Al2O3And one or more of the materials.
Further optionally, the compoundThe phase material X is TiC, diamond C, BN, Al2O3When at least two materials are combined, the selection rule of the complex phase material X is as follows: the thermal expansion coefficient of the complex phase material mixture should satisfy alphaCeramic < (R) >αSilver-based active brazing alloy metal + complex phase material X <αSilver-based active brazing alloy<αCopper (Cu)Condition (a) whereinSilver-based active brazing alloy metal + complex phase material X=∑Wiαi;WiIs the weight percentage of the mixed material formed by adding the complex phase material X in the silver-based active brazing alloy, alphaiIs the thermal expansion coefficient of silver-based active brazing alloy and the complex phase material X.
Further optionally, the weight percentage of the multiphase material in the active solder is 0.5wt% -5.0 wt%.
Further optionally, the shape of the particles of the complex phase material is selected from one or more of needle shape, rod shape, prism shape, column shape, sheet shape, tumor shape and sphere shape with the shape coefficient more than 1; the equivalent grain diameter of the complex phase material is 1-10 μm.
Further optionally, the equivalent grain size of the multiphase material in the active solder is 4.0-6.0 μm.
Further optionally, the active metal material comprises at least one of Ti, Zr, Hf, Cr, Nd, V.
The invention has the beneficial effects that:
the invention adds TiC, diamond C, BN and Al into the active metal brazing slurry2O3The complex phase material is dispersed in the active metal brazing slurry in a mode of controlling the particle shape and equivalent particle size of the complex phase material, and can reduce stress concentration, thereby reducing residual stress, improving the heat cycle resistance, bending strength, flexibility and other properties of the ceramic circuit board prepared by brazing, and improving the reliability of the ceramic circuit board.
Drawings
FIG. 1 shows a schematic cross-sectional view of a ceramic wiring board of the present invention;
FIG. 2 shows an electron microscope photograph of a brazing layer of the ceramic wiring board of the present invention;
FIG. 3 shows a peel strength test and sample of the ceramic circuit board of the present invention;
FIG. 4 shows a first photomicrograph of a ceramic circuit board of the present invention taken with an ultrasonic scan to observe void fraction;
FIG. 5 shows a second photomicrograph of the ceramic circuit board of the present invention taken with an ultrasonic scan to observe void ratio;
fig. 6 shows a graph of a test of the resistance to thermal cycling of the ceramic wiring board of the present invention.
Detailed Description
The content of the invention will now be discussed with reference to a number of exemplary embodiments. It is to be understood that these examples are discussed only to enable those of ordinary skill in the art to better understand and thus implement the teachings of the present invention, and are not meant to imply any limitations on the scope of the invention.
As used herein, the term "include" and its variants are to be read as open-ended terms meaning "including, but not limited to. The term "based on" is to be read as "based, at least in part, on". The terms "one embodiment" and "an embodiment" are to be read as "at least one embodiment". The term "another embodiment" is to be read as "at least one other embodiment".
Any feature disclosed in this specification, or a step in any method or process so disclosed, may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise, in addition to the mutually exclusive features and/or steps. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
The specific formulation of the active solder for ceramic wiring board of the present invention will be described in detail according to the present example, and in example 1 below, a ceramic wiring board shown in fig. 1 was prepared.
The preparation steps are as follows:
100g of active brazing material AgCuTi powder of 325 meshes, wherein the components of the active brazing material AgCuTi powder are 66wt% of Ag, 30wt% of Cu and 4wt% of Ti, the mass of Ag is 66g, the mass of Cu is 30g and the mass of Ti is 4 g; taking BN powder (5 g) with the purity of 99.9 percent and the particle size of 5um, and carrying out ball milling and powder mixing under the protection of inert gas to prepare an active brazing material AgCuTi-BN; the active brazing material is preferably prepared using a spherical heterogeneous material having a shape factor greater than 1 in this embodiment.
Stirring and mixing the active brazing material AgCuTi-BN powder, adding an organic solvent, fully stirring and uniformly mixing to prepare AgCuTi-BN active brazing paste;
coating AgCuTi-BN active brazing paste on the upper surface and the lower surface of the ceramic substrate, and correspondingly placing an oxygen-free copper foil;
clamping the ceramic substrate coated with the AgCuTi-BN active brazing paste and an oxygen-free copper foil, and then brazing in a vacuum brazing furnace to realize brazing of the ceramic substrate and the oxygen-free copper foil;
and etching the circuit on the oxygen-free copper foil by adopting a wet etching process to prepare the ceramic circuit board shown in the figure 1.
The embodiment has the beneficial effects that TiC, diamond C, BN and Al are added into the active metal brazing slurry2O3The complex phase material is dispersed in the active metal brazing slurry in a mode of controlling the particle shape and equivalent particle size of the complex phase material, and can reduce stress concentration, thereby reducing residual stress, improving the heat cycle resistance, bending strength, flexibility and other properties of the ceramic circuit board prepared by brazing, and improving the reliability of the ceramic circuit board.
Example 2
The specific formulation of the active solder for ceramic wiring board of the present invention will be described in detail according to the present example, and in example 1 below, a ceramic wiring board shown in fig. 1 was prepared.
The preparation steps are as follows:
100g of active brazing material AgCuTi powder of 325 meshes, wherein the components of the active brazing material AgCuTi powder are 66wt% of Ag, 30wt% of Cu and 4wt% of Ti, the mass of Ag is 66g, the mass of Cu is 30g and the mass of Ti is 4 g; taking 5g of diamond C powder with the purity of 99.95% and the particle size of 10um, and carrying out ball milling and powder mixing under the protection of inert gas to prepare AgCuTi-diamond C containing an active brazing material; the active brazing material is preferably prepared using a spherical heterogeneous material having a shape factor greater than 1 in this embodiment.
Stirring and mixing the active brazing material AgCuTi-BN powder, adding an organic solvent, fully stirring and uniformly mixing to prepare AgCuTi-BN active brazing paste;
coating AgCuTi-BN active brazing paste on the upper surface and the lower surface of the ceramic substrate, and correspondingly placing an oxygen-free copper foil;
clamping the ceramic substrate coated with the AgCuTi-BN active brazing paste and an oxygen-free copper foil, and then brazing in a vacuum brazing furnace to realize brazing of the ceramic substrate and the oxygen-free copper foil;
and etching the circuit on the oxygen-free copper foil by adopting a wet etching process to prepare the ceramic circuit board shown in the figure 1.
The embodiment has the beneficial effects that TiC, diamond C, BN and Al are added into the active metal brazing slurry2O3The complex phase material is dispersed in the active metal brazing slurry in a mode of controlling the particle shape and equivalent particle size of the complex phase material, and can reduce stress concentration, thereby reducing residual stress, improving the heat cycle resistance, bending strength, flexibility and other properties of the ceramic circuit board prepared by brazing, and improving the reliability of the ceramic circuit board.
Example 3
The specific formulation of the active solder for ceramic wiring board of the present invention will be described in detail according to the present example, and in example 1 below, a ceramic wiring board shown in fig. 1 was prepared.
The preparation steps are as follows:
100g of active brazing material AgCuTi powder of 325 meshes, wherein the components of the active brazing material AgCuTi powder are 66wt% of Ag, 30wt% of Cu and 4wt% of Ti, the mass of Ag is 66g, the mass of Cu is 30g and the mass of Ti is 4 g; selecting 1.65g of diamond C powder with the purity of 99.96% and the particle size of 10um and 3.35g of TiC powder with the purity of 99.9% and the particle size of 10um, and performing ball milling and powder mixing under the protection of inert gas to prepare an active brazing material AgCuTi-C & TiC; the active brazing material is preferably prepared using a spherical heterogeneous material having a shape factor greater than 1 in this embodiment.
In this embodiment, the ceramic circuit board is made of a combination of aluminum nitride ceramic and copper foil, wherein the linear expansion coefficient of the aluminum nitride ceramic is 4.7ppm/k, and the linear expansion coefficient of the copper foil is 18.6 ppm/k.
AgCuTi-C&The TiC active solder is 100g of active solder material AgCuTi (linear expansion coefficient of 17.4 ppm/k), and 1.65g of diamond (linear expansion coefficient of 3.1 ppm/k) and 3.35g of titanium nitride (linear expansion coefficient of 7.74 ppm/k) are added into the active solder. Calculated to obtain AgCuTi-C&TiC active brazing filler metal to linear expansion coefficient alphaAgCuTi-C&TiCComprises the following steps:
100/(100+1.65+3.35)*17.4+1.65/(100+1.65+3.35)*3.1+3.35/(100+1.65+3.35)*7.74=16.87
can see alphaAgCuTi-C&TiC＜αAgCuTiThus AgCuTi-C&Compared with the original active brazing material AgCuTi, the TiC active brazing filler metal can reduce the thermal expansion difference between aluminum nitride ceramic (the linear expansion coefficient is 4.7 ppm/k) and copper foil (the linear expansion coefficient is 18.6 ppm/k) to a greater extent, can play a role in buffering an intermediate layer between the aluminum nitride ceramic and the copper foil, and improves the reliability of a ceramic circuit board.
Stirring and mixing the active brazing material AgCuTi-BN powder, adding an organic solvent, fully stirring and uniformly mixing to prepare AgCuTi-BN active brazing paste;
coating AgCuTi-BN active brazing paste on the upper surface and the lower surface of the ceramic substrate, and correspondingly placing an oxygen-free copper foil;
clamping the ceramic substrate coated with the AgCuTi-BN active brazing paste and an oxygen-free copper foil, and then brazing in a vacuum brazing furnace to realize brazing of the ceramic substrate and the oxygen-free copper foil;
and etching the circuit on the oxygen-free copper foil by adopting a wet etching process to prepare the ceramic circuit board shown in the figure 1.
FIG. 2 shows an electron microscope photograph of a solder layer of the ceramic wiring board prepared in the example;
FIG. 3 shows a peel strength test and a sample of a ceramic wiring board in an example;
FIG. 4 shows a first photomicrograph of the ceramic wiring board in an example of the voidage observed by ultrasonic scanning;
FIG. 5 shows a second photomicrograph of the ceramic wiring board in the example of the voidage observed by ultrasonic scanning;
the ceramic wiring boards prepared in the above examples were tested for peel strength, void ratio, thermal cycle resistance, etc., and the test data are shown in table 1. Wherein the peel strength of the ceramic wiring board was obtained by testing the ceramic wiring board prepared in each example using a peel strength tester; the voidage of the ceramic circuit board is obtained by observing and calculating through an ultrasonic scanning electron microscope; the thermal cycle resistance of the ceramic circuit board was obtained by testing the parameters of the curve shown in fig. 6.
Table 1 example sample test data summary table
Several embodiments of the present invention have been described, but these examples are provided as examples and are not intended to limit the scope of the present invention. These new embodiments can be implemented in other various forms, and various omissions, substitutions, changes, and improvements can be made without departing from the overall spirit of the invention. These embodiments and modifications are intended to be included within the scope and overall spirit of the present invention, and are intended to be included within the scope of the invention as set forth in the claims and the equivalents thereof.
Claims (7)
1. The active brazing filler metal for the ceramic circuit board is characterized by comprising the following raw materials:
95.0-99.5 wt% of silver-based active brazing alloy and 5.0-5 wt% of complex phase material X0.5wt%; the silver-based active brazing alloy comprises Ag, Cu and an active metal material, wherein the weight percentage of the Ag-based active brazing alloy is as follows: 20-40wt%, active metal material: 1-10wt%, and the balance of Ag.
2. The active solder for ceramic circuit board as claimed in claim 1, wherein the complex phase material X is selected from TiC, diamond C, BN and Al2O3And one or more of the materials.
3. According to claimThe active solder for the ceramic circuit board, according to the claim 2, is characterized in that the complex phase material X is TiC, diamond C, BN, Al2O3When at least two materials are combined, the selection rule of the complex phase material X is as follows:
the thermal expansion coefficient of the complex phase material mixture should satisfy alphaCeramic < (R) >αSilver-based active brazing alloy metal + complex phase material X <αSilver-based active brazing alloy<αCopper (Cu)The conditions under which, among others,
αsilver-based active brazing alloy metal + complex phase material X=∑Wiαi;
WiIs the weight percentage of the mixed material formed by adding the complex phase material X in the silver-based active brazing alloy, alphaiIs the thermal expansion coefficient of silver-based active brazing alloy and the complex phase material X.
4. The active solder for the ceramic circuit board as claimed in claim 1, wherein the weight percentage of the multiphase material in the active solder is 0.5wt% -5.0 wt%.
5. The active solder for the ceramic circuit board as claimed in claim 1, wherein the shape of the particles of the complex phase material is selected from one or more of needle shape, rod shape, prism shape, column shape, sheet shape, nodular shape and spherical shape with shape factor greater than 1; the equivalent grain diameter of the complex phase material is 1-10 μm.
6. The active filler metal for the ceramic circuit board according to claim 5, wherein the equivalent grain size of the complex phase material in the active filler metal is 4.0 μm-6.0 μm.
7. An active filler metal for ceramic circuit boards according to claim 1, wherein the active metal material comprises at least one of Ti, Zr, Hf, Cr, Nd, V.
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Citations (4)
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| CN104588863A (en) * | 2014-12-05 | 2015-05-06 | 南昌大学 | Ultrasonic welding preparation method of Ag-Cu-Ti layer-shaped composite solder |
| CN105195846A (en) * | 2015-10-26 | 2015-12-30 | 哈尔滨工业大学 | Multi-scale combined method for improving strength of soldered joint made of conductive ceramic base materials |
| CN110734297A (en) * | 2019-11-14 | 2020-01-31 | 上海富驰高科技股份有限公司 | Method for connecting ceramic and metal and joint structure |
| CN111168588A (en) * | 2020-01-06 | 2020-05-19 | 四川涂展科技有限公司 | Brazing grinding wheel based on hard alloy-diamond film particles as abrasive and manufacturing method thereof |
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2021
- 2021-03-10 CN CN202110257634.5A patent/CN112638062A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588863A (en) * | 2014-12-05 | 2015-05-06 | 南昌大学 | Ultrasonic welding preparation method of Ag-Cu-Ti layer-shaped composite solder |
| CN105195846A (en) * | 2015-10-26 | 2015-12-30 | 哈尔滨工业大学 | Multi-scale combined method for improving strength of soldered joint made of conductive ceramic base materials |
| CN110734297A (en) * | 2019-11-14 | 2020-01-31 | 上海富驰高科技股份有限公司 | Method for connecting ceramic and metal and joint structure |
| CN111168588A (en) * | 2020-01-06 | 2020-05-19 | 四川涂展科技有限公司 | Brazing grinding wheel based on hard alloy-diamond film particles as abrasive and manufacturing method thereof |
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Application publication date: 20210409 |