CN109648221A - A kind of soldering electric slurry and its preparation method and application - Google Patents
A kind of soldering electric slurry and its preparation method and application Download PDFInfo
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- CN109648221A CN109648221A CN201811443407.6A CN201811443407A CN109648221A CN 109648221 A CN109648221 A CN 109648221A CN 201811443407 A CN201811443407 A CN 201811443407A CN 109648221 A CN109648221 A CN 109648221A
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- Mechanical Engineering (AREA)
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Abstract
The present invention provides a kind of soldering electric slurries and its preparation method and application, belong to ceramic circuit board technical field, soldering electric slurry provided by the invention is by including that the raw material of following mass fraction is prepared: 50~70 parts of brazing alloy powder, 18~32 parts of silver powder, 2~6 parts of metal hydride powder, 0.01~1 part of surface modifier；7~15 parts of organic carrier.Above-mentioned slurry is used for the preparation of ceramic copper-clad plate, it is using soldering alloyed metal powder substitution copper powder soldering electric slurry and by it that copper foil is directly laminating on ceramic wafer, copper powder technical problem easy to oxidize in air is avoided, and the obtained resistance to temperature impact capacity of ceramic copper-clad plate is high, highly reliable.
Description
Technical field
The present invention relates to ceramic circuit board technical field, in particular to a kind of soldering electric slurry and preparation method thereof and answer
With.
Background technique
High power power electronic devices and module are widely used in electric car, renewable energy, electric locomotive and intelligence
The field of conversion of electrical energy such as power grid.Ceramic copper-clad plate is that highly conductive oxygen-free copper is passed through to Direct Bonding under high temperature or is soldered to ceramic watch
On face or direct copper electroplating layer to ceramics and formed a kind of composite cermet substrate, it both had ceramics high-termal conductivity,
The characteristics such as high electrical insulating properties, high mechanical strength, low thermal coefficient of expansion, and high conductivity and excellent weldering with anaerobic copper metal
Performance is connect, and various circuitous patterns can be etched as PCB wiring board, is that field of power electronics power module package can not
Or scarce key basic material.
Currently, be high temperature Direct Bonding (DBC) technology respectively there are four types of the technology of production ceramic copper-clad plate substrate is total, it is high
(DPC) technology and laser activation (LAM) technology is electroplated in warm active metal brazing (AMB) technology.Wherein made from AMB technology
Ceramic copper-clad plate can be relieved between ceramics and metal because its bond strength is high, intermediate there are one layer of active soldering buffer layers because of heat
The coefficient of expansion mismatches bring thermal stress and there is higher high-low temperature resistant thermal shock resistance properties and high/low temperature to recycle reliability,
Using commonplace in the encapsulation of the high power module of high voltage and high power electric locomotive and power grid application.And requiring higher
There are very big potentiality in the application of three generations's high power high temperature SiC module.Wherein, Chinese patent CN102365733A discloses one
The method of kind manufacture metallized substrate, the mixture of powders compounded by a certain percentage using copper powder, silver powder and hydride powder
Metal paste is formed as packing material and organic carrier formula, is formed through silk-screen printing and vacuum-sintering, the disadvantage is that copper powder
Formation copper oxide easy to oxidize in air is unfavorable for liquid phase Kufil in the wetting of ceramic surface.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of soldering electric slurry and its preparation method and application, the present invention
The soldering electric slurry of offer is used for the preparation of ceramic copper-clad plate, and copper foil is directly laminating in ceramic wafer by soldering electric slurry
On, copper powder technical problem easy to oxidize in air is avoided using electric slurry formula of the invention.
The present invention provides a kind of soldering electric slurries, are prepared by the raw material for including following mass fraction:
The brazing alloy powder is the alloyed powder containing silver and copper；The quality percentage of silver and copper contains in the brazing alloy powder
Amount is respectively (50~80) %, (20~50) %；The partial size of the brazing alloy powder is 1~20 μm；
The partial size of the silver powder is 0.1~2 μm；
The metal hydride powder is TiH2Powder, ZrH2Powder or HfH2Powder, the partial size of the metal hydride powder are 1~10 μ
m。
Preferably, the brazing alloy powder is that cu-ag alloy powders, copper silver Titanium Powder, copper silver zircaloy powder or copper silver hafnium close
Bronze it is one or more.
Preferably, the preparation method of the brazing alloy powder is the following steps are included: carry out vacuum after alloy raw material is melted
Atomization.
Preferably, the surface modifier includes one in organosilan, organic titanate and organic aluminates coupling agent
Kind is a variety of.
Preferably, the organic carrier includes the raw material composition of following mass percentage:
The auxiliary agent is one of defoaming agent, wetting agent and levelling agent or a variety of.
Preferably, the organic solvent is one of terpinol, propylene glycol phenylate and butyl carbitol acetate or several
Kind；Described adhesive is one or more of vinyl cellulose, polyvinyl alcohol, polyacrylic acid and polyvinyl butyral；
The plasticizer is one or more of dibutyl phthalate (DBP), citrate and epoxidized soybean oil；The dispersing agent is
Polyethylene glycol, lecithin, oleic acid, linoleic acid, linolenic acid, zinc naphthenate, alkyl phenol polyoxyethylene ether, erucyl amide and three
One or more of olein, organo silane coupling agent, organic titanate and organic aluminates coupling agent；The thixotroping
Agent is the one or more of rilanit special, organobentonite, triethyl citrate.
The present invention also provides the preparation methods of above-mentioned soldering electric slurry, comprising the following steps:
Brazing alloy powder, silver powder, metal hydride powder, surface modifier and organic carrier are mixed by the mass fraction
It closes, obtains soldering electric slurry.
The present invention also provides the methods that soldering electric slurry prepares ceramic copper-clad plate, comprising the following steps:
Soldering electric slurry is painted on ceramic substrate one or both sides surface, the pottery for being covered with slurry dry film is obtained after drying
Porcelain substrate；
Copper metal film is placed in the slurry dry film one or both sides of the ceramic substrate for being covered with slurry dry film, vacuum high-temperature
Welding obtains ceramic copper-clad plate.
Preferably, the ceramic substrate with a thickness of 0.2~1mm；It is described soldering electric slurry brushing with a thickness of 0.005
~0.2mm；The copper metal film with a thickness of 0.2~1.0mm.
Preferably, the temperature of the vacuum high-temperature welding is 800~900 DEG C, and vacuum degree is 3.5 × 10-3~1.0 × 10-5Pa。
The present invention also provides the ceramic copper-clad plates being prepared using the above method, from bottom to top successively include ceramic base
Plate, active interface layer, solder layer, alloy transition layer and copper metal film；It or from top to bottom successively include copper metal film, alloy mistake
Cross layer, solder layer, active interface layer, ceramic substrate, active interface layer, solder layer and alloy transition layer.
The present invention also provides application of the above-mentioned ceramic copper-clad plate in ceramic circuit board.
Advantageous effects: the present invention provides a kind of soldering electric slurries and its preparation method and application, and the present invention mentions
The soldering electric slurry of confession is used for the preparation of ceramic copper-clad plate, and copper sheet is directly laminating in ceramic wafer by soldering electric slurry
On, copper powder technical problem easy to oxidize in air is avoided using electric slurry formula of the invention.And obtained ceramics
The resistance to temperature impact capacity of copper-clad plate is high, highly reliable, and embodiment experimental data shows thermal shock reliability number > 500 time, heat
Recycle reliable number > 3000 time.
Detailed description of the invention:
Fig. 1 is the structural schematic diagram of ceramic copper-clad plate to be welded；10- ceramic substrate, 40- slurry dry film, 30- metallic copper
Film；
Fig. 2 is the structural schematic diagram of ceramic copper-clad plate；10- ceramic substrate, 201- active layer, 202- solder alloy layer,
203- alloy transition layer, 30- copper metal film；
Fig. 3 is the scanning electron microscope (SEM) photograph of the cross section of ceramic copper-clad plate to be welded obtained in embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the cross section of ceramic copper-clad plate obtained in embodiment 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of solid powder after the volatilization of electric slurry solvent；
Fig. 6 is ceramic copper-clad plate obtained in embodiment 1 and is swept using the ultrasound of ceramic copper-clad plate made from Copper powder
Retouch schematic diagram；Left figure is ceramic copper-clad plate obtained in embodiment 1, and right figure is ceramic copper-clad plate made from Copper powder；
Fig. 7 is the side view of the schematic diagram of ceramic circuit board obtained in embodiment 1；10- ceramic substrate, 201- activity
Layer, 202- solder alloy layer, 203- alloy transition layer, 30- copper metal film；
Fig. 8 is the top view of the schematic diagram of ceramic circuit board obtained in embodiment 1.
Specific embodiment
The present invention provides a kind of soldering electric slurries, are prepared by the raw material for including following mass fraction:
The brazing alloy powder is the alloyed powder containing silver and copper；The quality percentage of silver and copper contains in the brazing alloy powder
Amount is respectively (50~80) %, (20~50) %；The partial size of the brazing alloy powder is 1~20 μm；
The partial size of the silver is 0.1~2 μm；
The metal hydride powder is TiH2Powder, ZrH2Powder or HfH2Powder, the partial size of the metal hydride powder are 1~10 μ
m。
In the present invention, the brazing alloy powder be preferably cu-ag alloy powders, copper silver Titanium Powder, copper silver zircaloy powder or
Copper silver hafnium alloy powder.
In the present invention, the mass ratio of copper and silver is preferably 50~80:20~50 in the Kufil, and more preferably 69
~73:27~31.
In the present invention, in the copper silver titanium alloy mass ratio of copper, silver and titanium be preferably 10~25:60~90:2~
6, more preferably 15~20:70~80:4~5.
In the present invention, the mass ratio of copper, silver and zirconium is preferably 5~50:60~90:2~6 in the copper silver zircaloy,
More preferably 10~25:70~80:4~5.
In the present invention, the mass ratio of copper, silver and hafnium is preferably 5~50:60~90:2~6 in the copper silver zircaloy,
More preferably 10~25:70~80:4~5.
In the present invention, the preparation method of the brazing alloy powder preferably includes following steps: after alloy raw material is melted
Carry out vacuum atomizing.
The present invention is not particularly limited the temperature of high-temperature fusion, can melt alloy raw material.
The present invention is not particularly limited the method for vacuum atomizing, selects the arbitrarily well known vacuum atomizing side of art technology
Method.
Specifically, the present invention is by successively high-temperature fusion and vacuum atomizing after the copper of the mass percentage and silver mixing,
Obtain Kufil；Successively high-temperature fusion and vacuum atomizing after the copper, silver and titanium of the mass percentage are mixed, obtain copper
Silver-colored titanium alloy；Successively high-temperature fusion and vacuum atomizing after the copper, silver and zirconium of the mass percentage are mixed, obtain copper silver zirconium
Alloy；Successively high-temperature fusion and vacuum atomizing after the copper, silver and hafnium of the mass percentage are mixed, obtain the conjunction of copper silver hafnium
Gold.
In the present invention, the partial size of the brazing alloy powder is preferably 5~15 μm, and more preferably 10~13 μm.
In the present invention, the surface modifier preferably includes organo silane coupling agent, organic titanate and organic aluminic acid
One or more, the more preferably organo silane coupling agent of ester.
In the present invention, the organo silane coupling agent preferably with active group silane coupling agent, more preferably
KH550 or KH560.
In the present invention, when surface modifier is two or more mixture, the present invention is to the mixture
In the amount ratio of each raw material be not particularly limited, mixed with arbitrary proportion.
In the present invention, the organic carrier preferably includes the raw material composition of following mass percentage:
The auxiliary agent is one of defoaming agent, wetting agent and levelling agent or a variety of.
In the present invention, the organic solvent is preferably in terpinol, propylene glycol phenylate and butyl carbitol acetate
One or more, more preferably terpinol and/or propylene glycol phenylate.When the organic solvent is two or more mixing
When object, the present invention is not particularly limited the amount ratio of each raw material of mixture, is mixed with arbitrary proportion.
In the present invention, described adhesive is preferably vinyl cellulose, polyvinyl alcohol, polyacrylic acid and polyvinyl alcohol contracting
One or more of butyraldehyde, more preferably polyvinyl alcohol and/or polyacrylic acid.When described adhesive is two or more
Mixture when, the present invention is not particularly limited the amount ratio of each raw material of mixture, is mixed with arbitrary proportion.
In the present invention, the plasticizer is preferably in dibutyl phthalate (DBP), citrate and epoxidized soybean oil
One or more, more preferably dibutyl phthalate (DBP) and/or citrate.When the plasticizer is two or more
Mixture when, the present invention is not particularly limited the amount ratio of each raw material of mixture, is mixed with arbitrary proportion.
In the present invention, the dispersing agent is preferably polyethylene glycol, lecithin, oleic acid, linoleic acid, linolenic acid, ring
One or more of alkanoic acid zinc, alkyl phenol polyoxyethylene ether, erucyl amide and olein, more preferably polyethylene second
One or more of glycol, linoleic acid and zinc naphthenate.When the dispersing agent is two or more mixture, this
Invention is not particularly limited the amount ratio of each raw material of mixture, is mixed with arbitrary proportion.
In the present invention, the thixotropic agent is preferably one kind of rilanit special, organobentonite and triethyl citrate
Or several, more preferably rilanit special and/or organobentonite.When the thixotropic agent is two or more mixture
When, the present invention is not particularly limited the amount ratio of each raw material of mixture, is mixed with arbitrary proportion.
The present invention also provides the preparation methods of above-mentioned soldering electric slurry, comprising the following steps:
The brazing alloy powder, silver powder, metal hydride, surface modifier and organic carrier are mixed by the mass fraction
It closes, obtains soldering electric slurry.
The present invention is not particularly limited mixed method, selects mixed method well known to those skilled in the art.
Specifically, after the present invention preferably mixes brazing alloy powder, silver powder, metal hydride, solder mixed powder is obtained, then
It is ground after solder mixed powder is successively mixed with surfactant and organic carrier, obtains soldering electric slurry.
The present invention is not particularly limited the method for grinding, selects those skilled in the art known ground grinding method.
In the present invention, it is preferred to for the ground and mixed in three-roll grinder.The present invention keeps each raw material mixing more uniform by grinding.
The present invention also provides the methods that soldering electric slurry prepares ceramic copper-clad, comprising the following steps:
Soldering electric slurry obtained above is painted on ceramic substrate one or both sides surface, obtains being covered with slurry after drying
Expect the ceramic substrate of dry film；
Copper metal film is placed in the slurry dry film one or both sides of the ceramic substrate for being covered with slurry dry film, vacuum high-temperature
Welding obtains ceramic copper-clad plate.
Above-mentioned soldering electric slurry is painted on ceramic substrate single side surface by the present invention, and it is dry to obtain being covered with slurry after drying
The ceramic substrate of film.In the present invention, the ceramic substrate is preferably that aluminium oxide, aluminium nitride or silicon nitride tape casting obtain
Ceramic substrate；The thickness of the ceramic substrate is preferably 0.2~1.0mm, more preferably 0.3~0.5mm.
In the present invention, the thickness of the soldering electric slurry brushing is preferably 0.01~0.05mm, more preferably 0.1~
0.03mm。
In the present invention, the temperature of the drying is preferably 200~400 DEG C, and more preferably 250~300 DEG C.
It obtains after being covered with the ceramic substrate of slurry dry film, copper metal film is placed in the pottery for being covered with slurry dry film by the present invention
The slurry dry film one or both sides of porcelain substrate, vacuum high-temperature weld to obtain ceramic copper-clad plate.
Copper metal film is placed in the slurry dry film one or both sides of the ceramic substrate for being covered with slurry dry film by the present invention, is obtained
To ceramic copper-clad plate to be welded.
In the present invention, the copper metal film preferably rolls copper book or cathode copper book.
In the present invention, the thickness of the copper metal film is preferably 0.2~1.0mm, more preferably 0.25~0.50mm.
In the present invention, when the soldering electric slurry is painted on ceramic substrate side, the ceramic copper-clad to be welded
The structural schematic diagram of plate is as shown in Figure 1；In Fig. 1, ceramic substrate, 40- slurry dry film, 30- copper metal film.
After obtaining ceramic copper-clad plate to be welded, ceramic copper-clad plate to be welded is carried out vacuum high-temperature welding by the present invention, is obtained
Ceramic copper-clad plate.In the present invention, the temperature of the vacuum high-temperature welding is preferably 800~900 DEG C, and vacuum degree is preferably 3.5
×10-3~1.0 × 10-5Pa.In the present invention, the vacuum high-temperature welding carries out preferably in vacuum brazing furnace.
The present invention makes to make pottery by vacuum high-temperature welding forms the activity of titanium nitride, zirconium or hafnium close to the side of ceramic layer
Layer, centre are solder alloy layer, form Kufil layer gold transition zone close to the side of metallic copper layers of foil.
In the present invention, when soldering electric slurry is painted on ceramic substrate side, the structure of the ceramic copper-clad plate is shown
It is intended to as shown in Figure 2；In Fig. 2: 10- ceramic substrate, 201- active layer, 202- solder alloy layer, 203- alloy transition layer, 30-
Copper metal film.
The present invention also provides the ceramic copper-clad plates that above-mentioned application is prepared, from bottom to top successively include ceramic substrate,
Active layer, solder alloy layer, alloy transition layer and copper metal film；Alternatively, from bottom to top successively including copper metal film, alloy transition
Layer, solder layer, active interface layer, ceramic substrate, active interface layer, solder layer and alloy transition layer.
The present invention also provides application of the above-mentioned ceramic copper-clad plate in ceramic circuit board.
In the present invention, the application is specially to prepare ceramic circuit board using ceramic copper-clad plate.
In the present invention, the utilization ceramic copper-clad plate prepares ceramic circuit board method and preferably includes following steps:
The ceramic copper-clad plate is successively subjected to photoresistance film lamination joint, exposure, development and etching, obtains ceramic circuit
Plate.
The present invention is not particularly limited photoresistance film lamination joint, the method for exposure and imaging, selects those skilled in the art
Member known ground method.
In the present invention, the etching liquid is preferably commercial copper and active metal nitrides etching solution.
In the present invention, a small amount of residual metal titanium whisker can be removed or be aoxidized by laser ablation technology after the etching,
Smooth etched edge is ultimately formed, tip partial discharge phenomenon is advantageously reduced.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) by 43.2g metallic silver and 16.8g metallic copper high-temperature fusion, after vacuum atomizing, obtaining partial size is 2~50um's
Kufil powder, preferably 5~15 μm of powder after sieving；
2) the 22g metallic silver powder that Kufil powder, 2.4g titantium hydride and the partial size obtained step 1) is 0.05 μm
Mixing, obtains solder mixed powder；
3) the solder mixed powder that step 2) obtains is mixed with 0.5g silane coupling agent and 5g organic solvent terpinol is stirring
It mixes in mixing machine and uniformly mixes, obtain the solder mixed powder mud of Ti-Ag-Cu；
4) the solder mixed powder mud for obtaining step 3) successively exists with the 6.5g organic carrier solution for including following proportion
It is uniformly mixed in stirring mixer and three-roll grinder, the soldering electric slurry containing Ti-Ag-Cu is prepared；
The organic carrier solution is made of the raw material of following mass percentage:
Surface needed for obtaining with a thickness of a side surface grinding and polishing of the sheet-type alumimium nitride ceramic sheet of 0.32mm processing is thick
Rugosity is about 0.4 μm；It is brazed electric slurry obtained in the side coating embodiment 1 on surface after treatment, coating thickness is
0.02mm is coated with the ceramic substrate of the active metal electric slurry dry out solvent in vacuum drying oven, obtains dry with slurry
The ceramic substrate of film；
It will be placed in the slurry dry film side with the ceramic substrate of slurry dry film with a thickness of the anaerobic copper sheet of 0.25mm, obtains
Ceramic copper-clad plate to be welded is welded in vacuum brazing furnace high temperature, is obtained by ceramic copper-clad plate (its structure is as shown in Figure 3) to be welded
To ceramic copper-clad plate.
Fig. 3 is the scanning electron microscope (SEM) photograph of the cross section of welding ceramics copper-clad plate before being sintered obtained in embodiment 1；It can by Fig. 3
Know the slurry dry film flawless after solidifying before being sintered, nano-silver powder particle and brazing filler metal alloy powder even particle distribution.
Fig. 4 is the scanning electron microscope (SEM) photograph of the cross section of sintered ceramic copper-clad plate obtained in embodiment 1；As shown in Figure 4
Brazing layer is tightly combined with copper metal film and ceramic substrate, without obvious macroscopic-void.
Fig. 5 is the scanning electron microscope (SEM) photograph of solid powder after the volatilization of electric slurry solvent.It is wrapped in slurry solids powder as shown in Figure 5
Containing spherical brazing filler metal alloy powder, nano silver powder and metal hydride powder, it is uniformly mixed.
Fig. 6 is ceramic copper-clad plate obtained in embodiment 1 and is swept using the ultrasound of ceramic copper-clad plate made from Copper powder
Retouch schematic diagram.Left figure is ceramic copper-clad plate obtained in embodiment 1, and right figure is ceramic copper-clad plate made from Copper powder.In Fig. 6
White point be welding defect caused by cavity.It can be seen that using the pottery after the welding of electric slurry made from alloy brazed powder of the invention
Porcelain metal copper-clad plate cavity is smaller.
By one layer of photoresistance film of dry-pressing on above-mentioned resulting ceramic copper-clad plate copper sheet side, pass through uv-exposure, development and two
Ceramic circuit board shown in Fig. 3 is formed after step etching and laser post-treatment.The wherein preferably commercial copper of etching step and active metal nitrogen
The etching solution of compound.
In the present invention, the side view of the schematic diagram for covering copper ceramic circuit board after the etching and top view are respectively as schemed
Shown in 7 and Fig. 8.Wherein the black portions of Fig. 7 indicate copper surface, and white indicates ceramic wafer.
Embodiment 2
1) by 43.2g metallic silver, 16.8g metallic copper and 1.2g Titanium high-temperature fusion, after vacuum atomizing, obtaining partial size is
2~50 μm of titanium copper silver alloy powder, preferably 5~15 μm of powder after sieving；
2) the 22g silver powder that titanium copper silver alloy powder, 1.8g titantium hydride and the partial size for obtaining step 1) are 0.05 μm
End mixing, obtains solder mixed powder；
Remaining step is identical with embodiment 1.
Embodiment 3
Above-mentioned raw materials substrate is changed to sheet-type Si3N4Potsherd, remaining is same as Example 1.
Embodiment 4
Above-mentioned raw materials substrate is changed to sheet-type Si3N4Potsherd, remaining is same as Example 1.
Performance parameter of above-described embodiment typical metallization ceramic substrate before circuit etching is as shown in table 1.
The performance for the metallized substrate that the different case study on implementation of table 1 obtain
| Performance parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Thermal coefficient | 170 | 170 | 85 | 85 |
| Dielectric strength KV/mm | >15 | >15 | >15 | >15 |
| Bending strength MPa | 400 | 400 | 700 | 700 |
| Fracture toughness MPam1/2 | 3.5 | 3.5 | 7 | 7 |
| Peel strength N/mm | >10 | >10 | >10 | >10 |
| Thermal shock reliability number | > 100 times | > 100 times | > 500 times | > 500 times |
| Cycle reliability number | > 500 times | > 500 times | > 3000 times | > 3000 times |
The superior performances such as the peel strength of metallized ceramic substrate and thermal shock and cycle reliability as shown in Table 1.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (12)
1. a kind of soldering electric slurry is prepared by the raw material for including following mass fraction:
The brazing alloy powder is the alloyed powder containing silver and copper；In the brazing alloy powder silver-colored mass percentage be 50~
80%, the mass percentage of copper is 20~50%, and the partial size of the brazing alloy powder is 1~20 μm；
The partial size of the silver powder is 0.1~2 μm；
The metal hydride powder is TiH2Powder, ZrH2Powder or HfH2Powder, the partial size of the metal hydride powder are 1~10 μm.
2. soldering electric slurry according to claim 1, which is characterized in that the brazing alloy powder be cu-ag alloy powders,
One of copper silver Titanium Powder, copper silver zircaloy powder and copper silver hafnium alloy powder are a variety of.
3. soldering electric slurry according to claim 2, which is characterized in that the preparation method of the brazing alloy powder includes
Following steps: vacuum atomizing is carried out after alloy raw material is melted.
4. soldering electric slurry according to claim 1, which is characterized in that the surface modifier includes organosilan idol
Join one of agent, organic titanate and organic aluminates coupling agent or a variety of.
5. soldering electric slurry according to claim 1, which is characterized in that the organic carrier includes following quality percentage
The raw material of content forms:
Surplus is auxiliary agent；
The auxiliary agent is one of defoaming agent, wetting agent and levelling agent or a variety of.
6. soldering electric slurry according to claim 5, which is characterized in that the organic solvent is terpinol, propylene glycol
One or more of phenylate and butyl carbitol acetate；Described adhesive is vinyl cellulose, polyvinyl alcohol, polypropylene
One or more of acid and polyvinyl butyral；The plasticizer is dibutyl phthalate (DBP), citrate and epoxy
One or more of soybean oil；The dispersing agent is polyethylene glycol, lecithin, oleic acid, linoleic acid, linolenic acid, cycloalkanes
One or more of sour zinc, alkyl phenol polyoxyethylene ether, erucyl amide and olein；The thixotropic agent is hydrogenation castor
The one or more of sesame oil, organobentonite and triethyl citrate.
7. being brazed the preparation method of electric slurry described in claim 1~6 any one, comprising the following steps:
Brazing alloy powder, silver powder, metal hydride powder, surface modifier and organic carrier are mixed by the mass fraction, obtained
To soldering electric slurry.
8. a kind of utilize preparation method system described in soldering electric slurry described in claim 1~6 any one or claim 7
The method that standby soldering electric slurry prepares ceramic copper-clad plate, comprising the following steps:
Soldering electric slurry is painted on ceramic substrate one or both sides surface, the ceramic base for being covered with slurry dry film is obtained after drying
Plate；The soldering electric slurry is to make described in soldering electric slurry described in claim 1~6 any one or claim 7
The soldering electric slurry of Preparation Method preparation；Copper metal film is placed in the slurry dry film one of the ceramic substrate for being covered with slurry dry film
Side or two sides, vacuum high-temperature weld to obtain ceramic copper-clad plate.
9. according to the method described in claim 8, it is characterized in that, the ceramic substrate with a thickness of 0.2~1mm；The pricker
Weld electric slurry brushing with a thickness of 0.005~0.2mm；The copper metal film with a thickness of 0.2~1.0mm.
10. according to the method described in claim 8, it is characterized in that, the vacuum high-temperature welding temperature be 800~900 DEG C,
Vacuum degree is 3.5 × 10-3~1.0 × 10-5Pa。
11. the ceramic copper-clad plate that method described in claim 8~10 any one is prepared, which is characterized in that the pottery
Porcelain copper-clad plate successively includes ceramic substrate, active interface layer, solder layer, alloy transition layer and copper metal film from bottom to top；Or
It from top to bottom successively include copper metal film, alloy transition layer, solder layer, active interface layer, ceramic substrate, active interface layer, pricker
The bed of material and alloy transition layer.
12. application of the ceramic copper-clad plate described in claim 11 in ceramic circuit board.
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