CN108147832B - Copper-clad ceramic and preparation method thereof - Google Patents

Copper-clad ceramic and preparation method thereof Download PDF

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CN108147832B
CN108147832B CN201611095518.3A CN201611095518A CN108147832B CN 108147832 B CN108147832 B CN 108147832B CN 201611095518 A CN201611095518 A CN 201611095518A CN 108147832 B CN108147832 B CN 108147832B
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copper
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oxide film
aluminum nitride
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CN108147832A (en
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邵长健
林信平
徐强
刘成臣
宋山青
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BYD Co Ltd
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Abstract

In order to solve the problems that a ceramic layer and a copper layer are not tightly combined, small bubbles exist at an interface, the copper layer is easy to bulge, and the bonding strength is low in the conventional aluminum nitride ceramic copper-clad technology, the invention provides a copper-clad ceramic and a preparation method thereof, and the preparation method of the copper-clad ceramic comprises the following operation steps: forming an aluminum oxide film on the surface of the aluminum nitride ceramic; forming a modified layer on the surface of the aluminum oxide film; wherein the modified layer comprises modified particles, and the modified particles comprise glass powder; and forming a copper layer on the surface of the modified layer, and combining the copper layer, the modified layer and the aluminum nitride ceramic into a whole through heat treatment. The invention also provides the copper-clad ceramic prepared by the method. According to the invention, a surface modification layer containing glass powder is formed on the surface of the aluminum nitride ceramic, so that the generation of phenomena such as small bubbles, bulges and the like is inhibited in the DBC process, and the interface bonding force between the copper layer and the aluminum nitride ceramic is increased.

Description

Copper-clad ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of ceramic copper-clad, and particularly relates to copper-clad ceramic and a preparation method thereof.
Background
The aluminum nitride ceramic is a non-oxygen compound with strong covalent bonds, the A L-N has strong directionality of the covalent bonds, and is ceramic with good chemical stability, and an aluminum nitride ceramic copper clad laminate formed by coating copper on the surface of the aluminum nitride ceramic is a basic key material in the manufacture of high-power electronic device high-integration modules.
The existing aluminum nitride ceramic copper-clad plate realizes the direct covering and connection of a rolled copper sheet and an aluminum nitride ceramic substrate by utilizing a DBC (direct copper-clad) technology, and the aluminum nitride substrate is not wetted with copper-oxygen eutectic, so that the aluminum nitride ceramic substrate needs to be subjected to surface modification treatment to improve the wettability of the aluminum nitride ceramic substrate and the copper-oxygen eutectic, and the direct copper-clad of the aluminum nitride ceramic substrate is realized. In the prior art, an aluminum nitride ceramic substrate is mainly subjected to oxidation treatment, an aluminum oxide film is formed on the surface, and direct copper coating of the aluminum nitride ceramic substrate is realized by utilizing the wettability of aluminum oxide and copper-oxygen eutectic crystal.
The aluminum nitride ceramic copper-clad plate manufactured by the prior art has the defects of non-compact combination of a ceramic layer and a copper layer, small bubbles at an interface, easy bulging, low bonding strength and the like.
The above disadvantages are mainly due to: the surface alumina film formed by the oxidation of the aluminum nitride ceramic substrate is not compact, and the copper foil used in the DBC (direct copper clad) technological process is subjected to surface oxidation treatment, a cuprous oxide film is arranged on the surface, a contact layer copper and cuprous oxide can form a liquid phase in the copper clad technological process, the copper foil is contacted with the aluminum nitride through the permeation of the loose oxide film, nitrogen is reacted and released, gas cannot be discharged, small bubbles and a bulge phenomenon are generated between the ceramic layer and the copper layer, the contact area between the copper layer and the ceramic layer is further reduced, and therefore the bonding strength of the copper layer and the ceramic layer is reduced.
Disclosure of Invention
Aiming at the problems that a ceramic layer and a copper layer are not tightly combined, small bubbles exist at an interface, the ceramic layer and the copper layer are easy to bulge, and the bonding strength is low in the existing aluminum nitride ceramic copper-clad technology, the invention provides copper-clad ceramic and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
providing a copper-clad ceramic, which comprises an aluminum nitride ceramic, a modified layer and a copper layer;
an aluminum oxide film is formed on the surface of the aluminum nitride ceramic;
the modified layer comprises modified particles, the modified particles comprise glass powder, and the modified layer is located between the aluminum oxide film and the copper layer;
and the modified layer penetrates into the aluminum oxide film partially to form a mullite phase.
Furthermore, the aluminum nitride ceramic is a sheet material, and the thickness of the aluminum nitride ceramic is 0.3-2 mm.
Further, the glass frit includes one or more of silicon oxide and silicate.
Further, the modified particles also comprise alumina, and the weight component ratio of the glass powder to the alumina is as follows: 30-70: 1 to 60.
Further, the modified particles further comprise cuprous oxide and copper powder, and the weight component ratio of the glass powder to the cuprous oxide to the copper powder is as follows: 30-70: 1-30: 1 to 30.
Further, the modified particles also comprise zirconium oxide and manganese dioxide, and the weight component ratio of the glass powder to the zirconium oxide to the manganese dioxide is as follows: 30-70: 1-20: 1 to 20.
Further, the thickness of the copper layer is 0.1 mm-1 mm.
Furthermore, a cuprous oxide film is formed on one surface of the copper layer, which is in contact with the modified layer, and the modified layer is partially penetrated into the cuprous oxide film.
The preparation method of the copper-clad ceramic comprises the following operation steps:
forming an aluminum oxide film on the surface of the aluminum nitride ceramic;
forming a modified layer on the surface of the aluminum oxide film; wherein the modified layer comprises modified particles, and the modified particles comprise glass powder;
and forming a copper layer on the surface of the modified layer, and combining the copper layer, the modified layer and the aluminum nitride ceramic into a whole through heat treatment.
Further, an aluminum oxide film is formed on the surface of the aluminum nitride ceramic through a thermal oxidation process.
Further, the thermal oxidation process specifically includes: placing the aluminum nitride ceramic in a flowing atmosphere with the oxygen partial pressure of 0.01 atm-0.5 atm, heating to 800-1300 ℃ at the heating rate of 2-20 ℃/min, preserving the heat for 10-300 min, and then cooling to the room temperature.
Further, the "forming a modified layer on the surface of the aluminum oxide film" includes:
covering the modified slurry containing the modified particles on the aluminum oxide film, baking to dry the modified slurry, and forming a modified layer on the surface of the aluminum oxide film.
Further, the "forming a modified layer on the surface of the aluminum oxide film" includes:
covering the modified slurry containing the modified particles on the aluminum oxide film, and baking to dry the modified slurry;
placing the treated aluminum nitride ceramic in a flowing atmosphere environment with the oxygen partial pressure of 0.001-0.5 atm, heating to 1000-1500 ℃ at the heating rate of 2-20 ℃/min, and then preserving the temperature for 10-300 min, thereby forming a modified layer on the surface of the aluminum oxide film.
Further, the modified slurry comprises the following components in parts by weight: 40-60 parts of modified particles, terpineol: 40-60 parts of ethyl cellulose: 1-4 parts of dibutyl phthalate: 3-6 parts of a leveling agent: 0.2 to 0.5 portion.
Further, the modified slurry is printed on the surface of the aluminum oxide film of the aluminum nitride ceramic through silk screen printing, and the printing thickness of the modified slurry is 0.5-50 microns.
Further, "forming a copper layer on the surface of the modified layer" includes:
pre-oxidizing the copper sheet to form a cuprous oxide film on the surface of the copper sheet in contact with the modified layer;
covering the pre-oxidized copper sheet on the modified layer;
and (3) placing the treated aluminum nitride ceramic in a protective atmosphere with the oxygen partial pressure of 0-100 ppm, heating to 1065-1083 ℃, and then preserving the temperature for 10-180 min to integrate the copper layer, the modified layer and the aluminum nitride ceramic.
According to the copper-clad ceramic and the preparation method thereof provided by the invention, the glass powder can form a liquid phase in the heat treatment process and can be combined with the alumina film at high temperature to form a mullite phase, so that the liquid glass phase can form wetting with loose alumina on the surface of the aluminum nitride ceramic substrate and permeate into pores through capillary action to densify a surface oxide layer, and cuprous oxide-copper liquid phase permeation and aluminum nitride reaction deflation are inhibited in the DBC (direct copper-clad) process, so that the generation of bubbles and bulges is reduced; meanwhile, the liquid glass phase and the copper layer have good bonding capacity, and the liquid glass phase can form physical bonding in the middle to play a role of a solder. In conclusion, the technical scheme reduces bubbles and bulges and increases the bonding strength between the aluminum nitride ceramic and the copper layer.
Drawings
FIG. 1 is an electron micrograph of the surface topography of a copper layer after delamination in example 1 of the present invention;
FIG. 2 is an electron micrograph of the surface topography of a copper layer after delamination in example 2 of the present invention;
FIG. 3 is an electron micrograph of the surface topography of a copper layer after delamination in example 3 of the present invention;
FIG. 4 is an electron micrograph of the surface topography of a copper layer after delamination in example 4 of the present invention;
FIG. 5 is an electron micrograph of the surface topography of a copper layer after delamination in example 5 of the present invention;
FIG. 6 is an electron micrograph of the surface morphology after peeling off the copper layer in comparative example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the preferred embodiment of the invention, the copper-clad ceramic comprises aluminum nitride ceramic, a modified layer and a copper layer;
an aluminum oxide film is formed on the surface of the aluminum nitride ceramic;
the modified layer comprises modified particles, the modified particles comprise glass powder, and the modified layer is located between the aluminum oxide film and the copper layer;
and the modified layer penetrates into the aluminum oxide film partially to form a mullite phase.
In this embodiment, the aluminum nitride ceramic is a sheet material with a thickness of 0.3-2 mm.
The glass powder comprises one or more of silicon oxide and silicate, wherein the silicon oxide can be silicon dioxide or silicon monoxide, and is preferably silicon dioxide; the silicate can be selected from one or more of sodium silicate, aluminum silicate, calcium silicate, potassium silicate, asbestos and feldspar; the main principle is that the alumina film on the surface of the aluminum nitride ceramic is densified through the reaction between silicon dioxide and alumina at high temperature to prevent the copper layer from reacting with the aluminum nitride to generate gas, so the glass powder can select a substance which contains silicon dioxide or generates the silicon dioxide under certain conditions (such as high temperature).
As a preferred embodiment of the present invention, the modified particle further comprises alumina, and the weight ratio of the glass powder to the alumina is: glass powder: 30-70% of alumina: 1 to 60.
The effect of adding alumina into the modified layer is mainly to supplement alumina on the surface of the aluminum nitride ceramic, so that the reaction rate between the glass powder and the alumina is improved, and the reaction effect is improved.
In order to further improve the bonding strength between the copper layer and the modified layer, the modified particles further comprise cuprous oxide and copper powder, and the weight ratio of the glass powder to the cuprous oxide to the copper powder is as follows: glass powder: cuprous oxide: and (3) copper powder is 30-70: 1-30: 1 to 30.
Cuprous oxide and copper powder are added into the modified layer, the copper layer is mainly supplemented, the melting point of the copper-cuprous oxide eutectic is 1064 ℃, the melting point of the copper is 1083 ℃, and a copper-cuprous oxide liquid phase is formed on the surface of the copper sheet due to the cuprous oxide film in a certain temperature range and is used for interface connection, so that the mutual eutectic permeation effect between the copper layer and the modified layer is improved, and the bonding strength between the copper layer and the modified layer is enhanced.
As a preferred embodiment of the present invention, the modified particle further comprises zirconia and manganese dioxide, and the weight ratio of the glass powder to the zirconia to the manganese dioxide is: glass powder: zirconium oxide: 30-70% of manganese dioxide: 1-20: 1 to 20.
Similar to the effect of adding the aluminum oxide, cuprous oxide and copper powder, the aluminum oxide film on the surface of the zirconium oxide and aluminum nitride ceramic has better wettability, and the manganese dioxide and the copper layer have better eutectic effect.
In this embodiment, the thickness of the copper layer is 0.1mm to 1 mm.
In this embodiment, a cuprous oxide film is formed on a surface of the copper layer in contact with the modified layer, and the modified layer partially penetrates into the cuprous oxide film.
In another embodiment of the invention, a copper-clad ceramic preparation method is disclosed, which comprises the following operation steps:
forming an aluminum oxide film on the surface of the aluminum nitride ceramic;
forming a modified layer on the surface of the aluminum oxide film; wherein the modified layer comprises modified particles, and the modified particles comprise glass powder;
and forming a copper layer on the surface of the modified layer, and combining the copper layer, the modified layer and the aluminum nitride ceramic into a whole through heat treatment.
It should be noted that the present embodiment does not limit the specific shape of the aluminum nitride ceramic, and the aluminum nitride ceramic may be a flat sheet material, a regular solid shape, or an irregular curved material, and those skilled in the art can select the shape as needed.
In this embodiment, an aluminum oxide film is formed on the surface of the aluminum nitride ceramic, the surface of the aluminum nitride film is modified by glass powder, the glass powder forms a liquid phase during the heat treatment process, and the glass powder and the aluminum oxide film are combined at a high temperature to form a mullite phase (3 Al)2O3·2SiO2) Therefore, the liquid glass phase can form wetting with loose alumina on the surface of the aluminum nitride ceramic substrate, and the liquid glass phase permeates into pores through capillary action to densify a surface oxide layer, so that the cuprous oxide-copper liquid phase is inhibited from permeating into the pores to react with the aluminum nitride to release gas in the DBC (direct copper coating) process, and the generation of bubbles and bulges is reduced; meanwhile, the liquid glass phase and the copper layer have good bonding capacity, and the liquid glass phase can form physical bonding in the middle to play a role of a solder. In conclusion, the technical scheme reduces bubbles and bulges and increases the bonding strength between the aluminum nitride ceramic and the copper layer.
In this embodiment, an aluminum oxide film is formed on the surface of the aluminum nitride ceramic by a thermal oxidation process.
The thermal oxidation process specifically comprises: placing the aluminum nitride ceramic in a flowing atmosphere with the oxygen partial pressure of 0.01-0.5 atm, heating to 800-1300 ℃ at the heating rate of 2-20 ℃/min, preserving the heat for 10-300 min, and then cooling to the room temperature
The reactivity of the aluminium nitride is increased by heating in a flowing atmosphere with a certain partial pressure of oxygen, since Al2O3The heat of formation of (A) is-1669.75 kJ/mol, which is much lower than that of AlN (-241.42kJ/mol), aluminum element is more easily bonded with oxygen, and oxygen enters AlN lattice to replace nitrogen atom to produce Al2O3In the above thermal oxidation process, the oxygen partial pressure of the flowing atmosphere has a certain influence on the interfacial voids and porosity of the formed aluminum oxide film, and the thickness of the formed aluminum oxide film can be controlled by controlling the heat preservation time in the thermal oxidation process, it should be noted that the selection of the ranges of the oxygen partial pressure, the treatment temperature, the heat preservation time and the temperature rise rate in the flowing atmosphere in the thermal oxidation process is a preferred range obtained by a lot of experiments, and simple parameter replacement under the guidance of the technical scheme of the present application should also be included in the protection scope of the present invention.
In one embodiment, "forming a modified layer on a surface of the aluminum oxide film" includes:
covering the modified slurry containing the modified particles on the aluminum oxide film, baking to dry the modified slurry, and forming a modified layer on the surface of the aluminum oxide film.
In another embodiment, the "forming a modified layer on the surface of the aluminum oxide film" includes:
covering the modified slurry containing the modified particles on the aluminum oxide film, and baking to dry the modified slurry;
placing the treated aluminum nitride ceramic in a flowing atmosphere environment with the oxygen partial pressure of 0.001-0.5 atm, heating to 1000-1500 ℃ at the heating rate of 2-20 ℃/min, and then preserving the temperature for 10-300 min, thereby forming a modified layer on the surface of the aluminum oxide film.
It should be noted that the selection of the ranges of oxygen partial pressure, treatment temperature, holding time and heating rate in the above operation for forming the modified layer on the aluminum oxide film are preferable ranges obtained by the inventors through a large number of experiments, and simple parameter replacement under the guidance of the technical scheme of the present application should be included in the protection scope of the present invention.
The modified particles may be dispersed to form the modified slurry using a dispersant, an organic polymer binder, which are commonly used by those skilled in the art, and the modified particles may be coated on the surface of the aluminum nitride ceramic in the form of a slurry.
Specifically, the modified slurry comprises the following components in parts by weight: 40-60 parts of modified particles, terpineol: 40-60 parts of ethyl cellulose: 1-4 parts of dibutyl phthalate: 3-6 parts of a leveling agent: 0.2 to 0.5 portion.
The modified slurry is printed on the surface of the aluminum oxide film of the aluminum nitride ceramic through silk screen printing, and the printing thickness of the modified slurry is 0.5-50 mu m.
In other embodiments, the modified slurry may be applied to the surface of the aluminum oxide film of the aluminum nitride ceramic by other methods, such as spraying, curtain coating, etc., and those skilled in the art may select the application method of the modified slurry and the corresponding components of the modified slurry according to the needs.
In the present embodiment, "forming a copper layer on the surface of the modified layer" includes:
pre-oxidizing the copper sheet to form a cuprous oxide film on the surface of the copper sheet in contact with the modified layer;
covering the pre-oxidized copper sheet on the modified layer;
and (3) placing the treated aluminum nitride ceramic in a protective atmosphere with the oxygen partial pressure of 0-100 ppm, heating to 1065-1083 ℃, and then preserving the temperature for 10-180 min to integrate the copper layer, the modified layer and the aluminum nitride ceramic.
The protective atmosphere refers to an atmosphere that prevents the copper layer from reacting with oxygen at high temperature, and nitrogen or other inert gases can be used as the protective atmosphere.
The present invention will be further described with reference to specific examples.
Example 1
The embodiment is used for explaining the copper-clad ceramic and the preparation method thereof, and the copper-clad ceramic comprises the following process steps:
① placing the aluminum nitride ceramic substrate in a flowing atmosphere, heating to 1200 deg.C at a heating rate of 10 deg.C/min, maintaining the temperature for 90min, forming an aluminum oxide film on the surface of the aluminum nitride ceramic substrate at an oxygen partial pressure of 0.21atm in the flowing atmosphere, and naturally cooling to room temperature;
② dispersing the modified particles in disperser and organic binder to obtain modified slurry, wherein the modified particles comprise (by weight) glass powder (silicate and silicon dioxide as main components) 50%, and alumina powder (Al as molecular formula)2O3): 45 percent; copper powder: 5 percent;
③, printing the prepared modified slurry on the surface of an alumina film of the aluminum nitride ceramic substrate by screen printing, and baking the aluminum oxide film in a baking oven at 90 ℃ for 120min to dry and form the modified slurry on the aluminum nitride ceramic substrate;
④ placing the aluminum nitride ceramic substrate in flowing atmosphere for high temperature treatment (oxygen partial pressure in flowing atmosphere is 0.21atm), heating to 1300 deg.C at a heating rate of 10 deg.C/min, and maintaining for 60min to make the glass powder and aluminum oxide film fully react;
⑤ placing the copper sheet in a micro-oxygen environment with oxygen partial pressure of 100ppm for thermal oxidation, heating to 750 deg.C and maintaining the temperature for 60min to form a layer of cuprous oxide film on the surface;
⑥, the treated aluminum nitride ceramic substrate and the pre-oxidized copper sheet are bonded together, and the copper sheet and the aluminum nitride ceramic substrate are connected in a covering way under the conditions of nitrogen atmosphere with 10ppm of oxygen partial pressure and 60min of heat preservation at 1070 ℃, so as to obtain the copper-clad ceramic substrate.
The resulting copper-clad ceramic substrate is labeled S1.
Example 2
The embodiment is used for explaining the copper-clad ceramic and the preparation method thereof, and the copper-clad ceramic comprises the following process steps:
① placing the aluminum nitride ceramic substrate in a flowing atmosphere, heating to 1200 deg.C at a heating rate of 10 deg.C/min, maintaining the temperature for 90min, forming an aluminum oxide film on the surface of the aluminum nitride ceramic substrate at an oxygen partial pressure of 0.21atm in the flowing atmosphere, and naturally cooling to room temperature;
② dispersing the modified particles in disperser and organic binder to obtain modified slurry, wherein the modified particles comprise (by weight) glass powder (silicate and silicon dioxide as main components) 50%, and alumina powder (Al as molecular formula)2O3): 40 percent; cuprous oxide: 5 percent; copper powder: 5 percent;
③, printing the prepared modified slurry on the surface of an alumina film of the aluminum nitride ceramic substrate by screen printing, and baking the aluminum oxide film in a baking oven at 90 ℃ for 120min to dry and form the modified slurry on the aluminum nitride ceramic substrate;
④ placing the aluminum nitride ceramic substrate in flowing atmosphere for high temperature treatment (oxygen partial pressure in flowing atmosphere is 0.21atm), heating to 1300 deg.C at a heating rate of 10 deg.C/min, and maintaining for 60min to make the glass powder and aluminum oxide film fully react;
⑤ placing the copper sheet in a micro-oxygen environment with oxygen partial pressure of 100ppm for thermal oxidation, heating to 750 deg.C and maintaining the temperature for 60min to form a layer of cuprous oxide film on the surface;
⑥, the treated aluminum nitride ceramic substrate and the pre-oxidized copper sheet are bonded together, and the copper sheet and the aluminum nitride ceramic substrate are connected in a covering way under the conditions of nitrogen atmosphere with 10ppm of oxygen partial pressure and 60min of heat preservation at 1070 ℃, so as to obtain the copper-clad ceramic substrate.
The resulting copper-clad ceramic substrate is labeled S2.
Example 3
The embodiment is used for explaining the copper-clad ceramic and the preparation method thereof, and the copper-clad ceramic comprises most of the process steps in the embodiment 1, and the difference is that:
in step ②, modified particles are dispersed in a dispersant and an organic binder to prepare a modified slurry, wherein the modified particles comprise 100 wt% of glass powder (silicate and silicon dioxide as main components).
The resulting copper-clad ceramic substrate is labeled S3.
Example 4
The embodiment is used for explaining the copper-clad ceramic and the preparation method thereof, and the copper-clad ceramic comprises most of the process steps in the embodiment 1, and the difference is that:
in step ②, modified particles are dispersed in dispersant and organic binder to obtain modified slurry, wherein the modified particles comprise (by weight) glass powder (silicate and silicon dioxide as main ingredients) 50%, and alumina powder (Al as molecular formula)2O3): 30 percent; copper powder: 5 percent; cuprous oxide: 5 percent; zirconium oxide: 5 percent; manganese dioxide: 5 percent.
The resulting copper-clad ceramic substrate is labeled S4.
Example 5
The embodiment is used for explaining the copper-clad ceramic and the preparation method thereof, and the copper-clad ceramic comprises most of the process steps in the embodiment 1, and the difference is that:
in step ②, modified particles are dispersed in a dispersant and an organic binder to prepare modified slurry, wherein the modified particles comprise, by weight, 70% of glass powder (silicate and silicon dioxide as main components), 15% of copper powder and 15% of cuprous oxide.
The resulting copper-clad ceramic substrate is labeled S5.
Comparative example 1
The comparative example is used for comparatively explaining the copper-clad ceramic and the preparation method thereof disclosed by the invention, and comprises the following process steps:
① placing the aluminum nitride ceramic substrate in a flowing atmosphere, heating to 1200 deg.C at a heating rate of 10 deg.C/min, maintaining the temperature for 90min, forming an aluminum oxide film on the surface of the aluminum nitride ceramic substrate at an oxygen partial pressure of 0.21atm in the flowing atmosphere, and naturally cooling to room temperature;
② placing the copper sheet in a micro-oxygen environment with oxygen partial pressure of 100ppm for thermal oxidation, heating to 750 deg.C and maintaining the temperature for 60min to form a layer of cuprous oxide film on the surface;
③, the treated aluminum nitride ceramic substrate and the pre-oxidized copper sheet are bonded together, and the copper sheet and the aluminum nitride ceramic substrate are connected in a covering way under the conditions of nitrogen atmosphere with 10ppm of oxygen partial pressure and 60min of heat preservation at 1070 ℃, so as to obtain the copper-clad ceramic substrate.
The resulting copper-clad ceramic substrate was labeled D1.
Performance testing
The properties of the copper-clad ceramic substrates S1 to S5 and D1 prepared in examples 1 to 5 and comparative example 1 were evaluated by the following methods.
Peel Strength test
①, etching the copper layer of the copper-clad ceramic substrate into a strip with the size of 80mm × 5mm by using a chemical etching method, ② fixing the etched test sample on a test fixture, peeling the copper strip from the surface of the ceramic along the vertical direction by using a universal tester, reading the measured minimum peeling force F1 and the average peeling force F2 on a computer, ③ measuring the width d of the peeled copper strip by using a caliper, ④ calculating the corresponding peeling strength according to the following formula:
peel strength (N/mm) is peel force (N)/width (mm) of the sample bar.
And (3) testing conditions are as follows: the temperature is 15-25 ℃, and the humidity is 50-60%.
The test results are shown in table 1:
TABLE 1
Experimental sample Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1
Minimum peel strength 7.30N/mm 7.11N/mm 6.91N/mm 7.53N/mm 7.37N/mm 5.63N/mm
Average peel strength 8.06N/mm 7.97N/mm 7.56N/mm 8.23N/mm 8.09N/mm 6.32N/mm
From the peel strength test results, it can be seen that the minimum peel strength values and the average peel strength values of the samples S1-S5 are both greater than those of the comparative samples, which indicates that the bonding strength between the copper layer and the aluminum nitride ceramic substrate is better for the samples prepared by the technical scheme of the present invention.
Porosity test
The testing steps are as follows: and (3) stripping the copper sheet from the sample, observing the surface morphology of the stripped copper by using a scanning electron microscope, and counting the number of the comparative holes.
And (3) testing conditions are as follows: the temperature is 15-25 ℃, and the humidity is 50-60%.
The test results are shown in the attached figures 1 to 6 and table 2:
TABLE 2
Figure BDA0001169300320000101
It can be seen from the electron microscope photographs shown in fig. 1 to 6 that the copper surfaces of the samples S1 to S5 according to the present invention are smooth, the number of voids and bubbles between the copper layer and the aluminum nitride ceramic substrate is less, and a large number of bubbles appear on the copper surface of the comparative sample D1, which indicates that the copper layer and the aluminum nitride ceramic substrate in the samples S1 to S5 have a large contact area and a high bonding strength.
Cold and heat shock test
And testing the cold and heat shock resistance of the aluminum nitride ceramic copper-clad plate by using GB/T2423.22-2012.
And (3) testing conditions are as follows: 40 ℃/30min, 150 ℃/30min, conversion time < 5min, 100 cyecles;
and (4) judging the result: and (5) after the test, the appearance detection meets the composite requirements.
The test results are shown in table 3:
TABLE 3
Experimental sample Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1
Test results By passing By passing By passing By passing By passing Failed through
Remarking: in the cold and hot impact process of the sample, the copper layer and the aluminum nitride ceramic layer have no adverse phenomena of copper layer stripping, separation, ceramic chip cracking and the like, and the sample is regarded as passing the cold and hot impact.
As shown in table 3, samples S1 to S5 according to the present invention all passed the thermal shock test, while comparative sample D1 failed the thermal shock test due to the occurrence of poor phenomena such as copper layer peeling, and ceramic chip cracking.
It is to be understood that while the invention has been described in detail in connection with specific aluminum nitride ceramic substrates, modified particle compositions, copper layers and operating parameters in various embodiments of the invention, the foregoing is merely for the purpose of satisfying legal requirements and the invention is not limited to the specific embodiments disclosed. One skilled in the art can select the appropriate aluminum nitride ceramic substrate, modified particle composition, copper layer, and operating parameters based on the teachings and teachings of the present specification. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (16)

1. The copper-clad ceramic is characterized by comprising aluminum nitride ceramic, a modified layer and a copper layer;
an aluminum oxide film is formed on the surface of the aluminum nitride ceramic;
the modified layer comprises modified particles, the modified particles comprise glass powder, and the modified layer is located between the aluminum oxide film and the copper layer;
and the modified layer penetrates into the aluminum oxide film partially to form a mullite phase.
2. The copper-clad ceramic according to claim 1, wherein the aluminum nitride ceramic is a sheet material having a thickness of 0.3 to 2 mm.
3. The copper-clad ceramic of claim 1, wherein the glass frit comprises one or more of silicon oxide and silicate.
4. The copper-clad ceramic according to claim 1 or 3, wherein the modified particles further comprise alumina, and the weight component ratio of the glass powder to the alumina is as follows: 30-70: 1 to 60.
5. The copper-clad ceramic according to claim 1 or 3, wherein the modified particles further comprise cuprous oxide and copper powder, and the weight component ratio of the glass powder to the cuprous oxide to the copper powder is as follows: 30-70: 1-30: 1 to 30.
6. The copper-clad ceramic according to claim 1 or 3, wherein the modified particles further comprise zirconia and manganese dioxide, and the glass powder, the zirconia and the manganese dioxide are in the following weight ratio: 30-70: 1-20: 1 to 20.
7. The copper-clad ceramic according to claim 1, wherein the copper layer has a thickness of 0.1mm to 1 mm.
8. The copper-clad ceramic according to claim 1, wherein a cuprous oxide film is formed on a surface of the copper layer in contact with the modified layer, and the modified layer partially penetrates into the cuprous oxide film.
9. The method for preparing the copper-clad ceramic according to any one of claims 1 to 8, comprising the following steps:
forming an aluminum oxide film on the surface of the aluminum nitride ceramic;
forming a modified layer on the surface of the aluminum oxide film; wherein the modified layer comprises modified particles, and the modified particles comprise glass powder;
and forming a copper layer on the surface of the modified layer, and combining the copper layer, the modified layer and the aluminum nitride ceramic into a whole through heat treatment.
10. The copper-clad ceramic preparation method according to claim 9, wherein an aluminum oxide film is formed on the surface of the aluminum nitride ceramic by a thermal oxidation process.
11. The copper-clad ceramic preparation method according to claim 10, wherein the thermal oxidation process specifically comprises: placing the aluminum nitride ceramic in a flowing atmosphere with the oxygen partial pressure of 0.01 atm-0.5 atm, heating to 800-1300 ℃ at the heating rate of 2-20 ℃/min, preserving the heat for 10-300 min, and then cooling to the room temperature.
12. The method of manufacturing a copper-clad ceramic according to claim 9, wherein forming a modified layer on the surface of the aluminum oxide film comprises:
covering the modified slurry containing the modified particles on the aluminum oxide film, baking to dry the modified slurry, and forming a modified layer on the surface of the aluminum oxide film.
13. The method of manufacturing a copper-clad ceramic according to claim 9, wherein forming a modified layer on the surface of the aluminum oxide film comprises:
covering the modified slurry containing the modified particles on the aluminum oxide film, and baking to dry the modified slurry;
placing the treated aluminum nitride ceramic in a flowing atmosphere environment with the oxygen partial pressure of 0.001-0.5 atm, heating to 1000-1500 ℃ at the heating rate of 2-20 ℃/min, and then preserving the temperature for 10-300 min, thereby forming a modified layer on the surface of the aluminum oxide film.
14. The copper-clad ceramic preparation method according to claim 12 or 13, wherein the modified slurry comprises the following components by weight: 40-60 parts of modified particles, terpineol: 40-60 parts of ethyl cellulose: 1-4 parts of dibutyl phthalate: 3-6 parts of a leveling agent: 0.2 to 0.5 portion.
15. The copper-clad ceramic preparation method according to claim 12 or 13, wherein the modified paste is printed on the surface of the aluminum oxide film of the aluminum nitride ceramic by screen printing, and the printing thickness of the modified paste is 0.5 μm to 50 μm.
16. The method of manufacturing a copper-clad ceramic according to claim 9, wherein forming a copper layer on the surface of the modified layer comprises:
pre-oxidizing the copper sheet to form a cuprous oxide film on the surface of the copper sheet in contact with the modified layer;
covering the pre-oxidized copper sheet on the modified layer;
and (3) placing the treated aluminum nitride ceramic in a protective atmosphere with the oxygen partial pressure of 0-100 ppm, heating to 1065-1083 ℃, and then preserving the temperature for 10-180 min to integrate the copper layer, the modified layer and the aluminum nitride ceramic.
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