CN114853497B - Active metal brazing copper-clad ceramic substrate and preparation method thereof - Google Patents

Active metal brazing copper-clad ceramic substrate and preparation method thereof Download PDF

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CN114853497B
CN114853497B CN202210475489.2A CN202210475489A CN114853497B CN 114853497 B CN114853497 B CN 114853497B CN 202210475489 A CN202210475489 A CN 202210475489A CN 114853497 B CN114853497 B CN 114853497B
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ceramic substrate
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CN114853497A (en
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赵建光
黄礼侃
赵尉宁
林晓光
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Nanjing Zhongjiang New Material Technology Co ltd
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Abstract

The invention discloses an active metal brazing copper-clad ceramic substrate and a preparation method thereof. The preparation method of the copper-clad ceramic substrate comprises the following steps: step 1: arranging a positioning reference hole on the ceramic substrate; placing the ceramic substrate in a cleaning agent for ultrasonic washing and drying to obtain a ceramic substrate A; and 2, step: pre-pattern coating active metal solder on the ceramic substrate A, and drying to obtain an active metal solder layer; fixing a copper sheet on the active metal solder layer, and carrying out vacuum brazing to obtain a ceramic substrate C; and step 3: and (4) carrying out graphical processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate. In the scheme, the problem of cracking in the thermal cycle process is solved by introducing the graphene compound and increasing stress buffering; the inorganic powder is respectively treated by using organic auxiliary agents, so that the dispersibility is improved; meanwhile, the material proportion is comprehensively regulated and controlled, so that the paste has good thixotropic property, the screen printing property is improved, the porosity is reduced, and the compactness is increased.

Description

Active metal brazing copper-clad ceramic substrate and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to an active metal brazing copper-clad ceramic substrate and a preparation method thereof.
Background
The copper-clad ceramic substrate is an electronic material formed by compounding a copper foil on the surface of a ceramic material, and is widely applied to the multidirectional electronic fields of automobile electronics, aerospace navigation, solar cells and the like. The composite process comprises electroplating technology, high-temperature bonding technology, laser activation technology and active metal brazing technology. The active metal brazing technology is the most common processing technology due to better performance and more convenience.
The active metal brazing technology is to weld metal solder on a ceramic substrate and then bond copper foil through vacuum brazing by taking the metal solder as a medium, so that the copper-clad ceramic substrate prepared in the mode has good reliability and heat dissipation. However, conventionally, active metal solders are generally obtained by combining silver powder, copper powder, an active metal, and an organic auxiliary agent. In the brazing process, as the difference between the thermal property and the mechanical property of the ceramic material and the metal is large, residual stress exists in an interface in the preparation process, the bonding strength is influenced, and meanwhile, the problems of cracking and the like exist in the thermal cycle process; meanwhile, in the screen printing process, the dispersibility and thixotropy of the active metal solder can influence the printing quality, so that the problems that the active metal layer after brazing has more and larger pores and the like are influenced, and the compactness and the flatness are influenced.
In conclusion, the preparation of the active metal brazing copper-clad ceramic substrate has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide an active metal brazing copper-clad ceramic substrate and a preparation method thereof, and aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of an active metal brazing copper-clad ceramic substrate comprises the following steps:
step 1: arranging a positioning reference hole on the ceramic substrate; placing the ceramic substrate in a cleaning agent for ultrasonic washing and drying to obtain a ceramic substrate A;
step 2: pre-pattern coating active metal solder on the ceramic substrate A, and drying to obtain an active metal solder layer; fixing a copper sheet on the active metal solder layer, and carrying out vacuum brazing to obtain a ceramic substrate C;
and step 3: and (4) carrying out graphical processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
Preferably, in step 1, the raw material of the ceramic substrate includes one or more of aluminum nitride, aluminum oxide, and silicon nitride; the diameter of the positioning reference hole is 1.0-2.0 mm; the temperature of the ultrasonic washing is 70-80 ℃, and the ultrasonic time is 3-8 minutes.
Preferably, in the step 2, the process of pre-pattern coating is a screen printing process, and the mesh number of the screen printing plate is 250-300 meshes; the temperature of the vacuum brazing process is 500-900 ℃, the brazing time is 40-60 minutes, and the vacuum degree is 4.5 multiplied by 10 -4 ～5×10 -4 Pa; in step S4, the patterning process is one of laser etching, mechanical processing, and chemical etching.
Preferably, the raw materials of the cleaning agent comprise the following components: 10-12 parts of phytic acid, 4-5 parts of sodium dodecyl benzene sulfonate, 5-6 parts of ethanol and 78-80 parts of deionized water.
5. The method for preparing an active metal brazing copper clad ceramic substrate according to claim 1, wherein: the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 64 to 66 portions of silver powder, 19 to 21 portions of copper powder, 2.5 to 3.5 portions of titanium hydride and 4.5 to 5.5 portions of graphene compound.
Preferably, the preparation method of the graphene composite comprises the following steps: ultrasonically dispersing graphene oxide in ethanol, adding tetrabutyl titanate, tetraethyl silicate and deionized water, uniformly stirring, refluxing for 5-7 hours at the set temperature of 79-82 ℃, and freeze-drying; placing the mixture in a high-temperature furnace, and carrying out heat treatment for 3 to 4 hours at the temperature of 400 to 450 ℃ under the atmosphere of nitrogen; heating to 800-850 deg.c, replacing nitrogen with ammonia in the flow rate of 80-100 cm 3 And/min, carrying out heat treatment for 3-4 hours, and cooling in a nitrogen atmosphere to obtain the graphene composite.
Preferably, the ratio of the graphene oxide to the ethanol to the tetrabutyl titanate to the tetraethyl silicate to the deionized water is 1g.
Preferably, the preparation method of the active metal solder comprises the following steps: putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 60-70 ℃, and stirring for 1-2 hours; adding sodium phytate, caprylic acid and silica sol, and stirring for 1-2 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; and (3) uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing batch ball milling for 1-2 hours at a material ratio of 10.
Preferably, the organic auxiliary agent comprises the following materials: 0.05 to 0.1 portion of silica sol, 0.15 to 0.3 portion of ethyl cellulose, 0.15 to 0.26 portion of methyl trichloro siloxane, 0.25 to 0.4 portion of sodium phytate, 0.35 to 0.5 portion of caprylic acid, 0.15 to 0.24 portion of lauryl sodium sulfate, 0.8 to 1.2 portions of triethanolamine, 0.1 to 0.2 portion of hydrogenated castor oil, 7 to 10 portions of propylene glycol phenyl ether and 1 to 2 portions of deionized water.
Preferably, the copper-clad ceramic substrate is prepared by the preparation method of the active metal brazing copper-clad ceramic substrate.
In the technical scheme, the graphene compound is introduced into the active slurry, so that stress buffering is increased, and the problem of cracking in the thermal cycle process is solved; the inorganic powder is respectively treated by using the organic auxiliary agent, so that the dispersibility is increased, and meanwhile, the material proportion is comprehensively regulated and controlled, so that the paste has good thixotropic property, the screen printing property is improved, the porosity is reduced, and the compactness is increased; and preparing the high-performance copper-clad ceramic substrate.
(1) In the scheme, titanium carbide and silicon carbide are prepared and loaded on graphene to obtain a graphene compound; the graphene/titanium carbide/silicon carbide composite material is added into a metal solder, and due to stress transfer of graphene, titanium carbide and silicon carbide, deformation and cracks of a metal layer are effectively inhibited. In general, the metal solder layer has a larger stress shrinkage than the ceramic substrate, and a residual stress is present at the interface between the metal solder layer and the ceramic substrate, which causes generation of voids and cracks, and affects the bonding strength. When the graphene composite is added, the graphene composite is filled in metal, and is softer than the metal, so that stress transfer is generated in a solder layer, and the bonding strength is increased. Meanwhile, in the scheme, in order to increase compactness and dispersity, silicon carbide and titanium carbide are used for modifying graphene, so that the cohesiveness and the dispersity of the graphene in a solder layer are effectively increased. Meanwhile, since the graphene composite contains titanium, in order to balance the content of titanium, the content of titanium hydride needs to be appropriately reduced to reach a balance. Meanwhile, the addition amount of the metal solder is not excessive, but the excessive addition amount can reduce the plasticity of the metal solder and the bonding strength.
(2) In the scheme, ethyl cellulose and silica sol are used as a binder, hydrogenated castor oil is used as a catalyst, and methyl trichlorosiloxane, sodium phytate, caprylic acid and triethanolamine are used as modifiers. Hydrolyzing and polymerizing copper powder on the surface of the copper powder by using methyl trichlorosiloxane, generating anionic groups by using sodium phytate and caprylic acid, performing nucleophilic substitution with the hydrolyzed siloxane, and synergistically increasing the dispersibility of the copper powder by using the hydrophobic effect of octyl on methyl, wherein the sodium phytate has an antioxidation effect and can protect the copper powder; on the other hand, the silver powder is mixed by sodium dodecyl sulfate, triethanolamine and ethyl cellulose, so that the dispersibility of the silver powder is effectively improved; after being dispersed independently, the titanium hydride-graphene composite is mixed with the titanium hydride-graphene composite, so that the uniformity of elements in a brazing layer is effectively improved. In addition, a pseudo-plastic fluid is generated between the caprylic acid in the mixed material A and the triethanolamine in the mixed material B, so that the screen printing property can be improved; the silica sol added into the mixed material A is used as an adhesive, and silicon oxide or silicon carbide nano particles are generated at high temperature and are embedded into the solder, so that the compactness and stress buffering of a brazing layer can be increased, and the adhesive strength is increased. It should be noted that the ratio of each substance needs to be balanced, otherwise, thixotropy is affected, so that printing quality is reduced, and leveling and uniformity are affected; thereby affecting bond strength and densification.
(3) The cleaning agent is arranged for removing an oxide layer on the surface of the ceramic substrate, so that the surface of the ceramic substrate has certain roughness, the polarity of the surface is similar to that of the metal slurry, and the anchorage of the active metal brazing solder is increased; is beneficial to screen printing.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a front view of a copper-clad ceramic substrate produced in example 1;
FIG. 2 is a back view of the copper-clad ceramic substrate produced in example 1;
FIG. 3 is a front view of the copper-clad ceramic substrate produced in example 1 after thermal cycling;
FIG. 4 is a reverse view of the copper-clad ceramic substrate prepared in example 1 after thermal cycling.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, graphene oxide and silica sol were purchased as they are.
Example 1:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at the temperature of 420 ℃ under the atmosphere of nitrogen; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 part of silica sol, 0.2 part of ethyl cellulose, 0.2 part of methyl trichloro siloxane, 0.35 part of sodium phytate, 0.45 part of caprylic acid, 0.2 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 part of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Example 2:
step 1: (1) Putting 10 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 5 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.0mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 70 ℃, ultrasonically washing for 8 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing at 79 ℃ for 7 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and carrying out heat treatment for 4 hours at the temperature of 400 ℃ under the atmosphere of nitrogen; heating to 800 deg.C, and replacing nitrogen with ammonia gas at flow rate of 80cm 3 Performing heat treatment for 4 hours at a temperature of min, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane in a one-third mixed solvent of propylene glycol phenyl ether and deionized water, performing ultrasonic dispersion uniformly, heating to 60 ℃, and stirring for 2 hours; adding sodium phytate, caprylic acid and silica sol, and stirring for 2 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; mixing the mixture A, the mixture B, titanium hydride and graphene compoundMixing uniformly, and performing intermittent ball milling for 2 hours at a material ratio of 10, wherein the milling speed is 200rmp, and the milling is stopped for 20 minutes every 15 minutes; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying for 1 hour at the set temperature of 100 ℃ to obtain an active metal solder layer; fixing copper sheet on the active metal solder layer at 500 deg.C and vacuum degree of 5 × 10 -4 Pa, carrying out vacuum brazing for 60 minutes to obtain a ceramic substrate C;
and 3, step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 64 parts of silver powder, 19 parts of copper powder, 2.5 parts of titanium hydride and 4.5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.05 part of silica sol, 0.15 part of ethyl cellulose, 0.15 part of methyl trichloro siloxane, 0.25 part of sodium phytate, 0.35 part of caprylic acid, 0.15 part of sodium dodecyl sulfate, 0.8 part of triethanolamine, 0.1 part of hydrogenated castor oil, 7 parts of propylene glycol phenyl ether and 1 part of deionized water.
Example 3:
step 1: (1) Placing 12 parts of phytic acid and 5 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 80 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 2.0mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 80 ℃, ultrasonically washing for 3 minutes, and drying by nitrogen to obtain a ceramic substrate A;
and 2, step: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing for 5 hours at the set temperature of 82 ℃, and freeze-drying; placing the mixture in a high-temperature furnace, and carrying out heat treatment for 3 hours at the temperature of 450 ℃ under the atmosphere of nitrogen; heating to 850 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 4 hours at a temperature of min, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Mixing copper powder and methyl trichloro silicaPlacing the alkane in one third of mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1 hour; adding sodium phytate, caprylic acid and silica sol, and stirring for 1 hour; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Pre-pattern coating active metal solder on a ceramic substrate A by using a 300-mesh silk screen; drying for 1 hour at the set temperature of 100 ℃ to obtain an active metal solder layer; fixing copper sheet on the active metal solder layer at 900 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 40 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 66 parts of silver powder, 21 parts of copper powder, 3.5 parts of titanium hydride and 5.5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.1 part of silica sol, 0.3 part of ethyl cellulose, 0.26 part of methyl trichloro siloxane, 0.4 part of sodium phytate, 0.5 part of caprylic acid, 0.24 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.2 part of hydrogenated castor oil, 10 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Example 4:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the silicon nitride ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
and 2, step: (1) Ultrasonically dispersing 1g of graphene oxide in 25 gAdding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water into 0mL of ethanol, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at a temperature of 420 ℃ under nitrogen atmosphere; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane in a one-third mixed solvent of propylene glycol phenyl ether and deionized water, performing ultrasonic dispersion uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 part of silica sol, 0.2 part of ethyl cellulose, 0.2 part of methyl trichloro siloxane, 0.35 part of sodium phytate, 0.45 part of caprylic acid, 0.2 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 part of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 1:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B and titanium hydride, and performing intermittent ball milling for 2 hours at a material ratio of 10, wherein the milling speed is 200rmp, and the milling is stopped for 20 minutes every 15 minutes; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying for 1 hour at the set temperature of 100 ℃ to obtain an active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder and 6 parts of titanium hydride by weight. The organic auxiliary agent comprises the following materials: by weight, 0.08 parts of silica sol, 0.2 parts of ethyl cellulose, 0.2 parts of methyl trichlorosiloxane, 0.35 parts of sodium phytate, 0.45 parts of octanoic acid, 0.2 parts of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 parts of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 2:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
and 2, step: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at a temperature of 420 ℃ under nitrogen atmosphere; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 9 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 parts of silica sol, 0.2 parts of ethyl cellulose, 0.2 parts of methyl trichlorosiloxane, 0.35 parts of sodium phytate, 0.45 parts of octanoic acid, 0.2 parts of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 parts of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 3:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
and 2, step: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate and 5mL of deionized water, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at the temperature of 420 ℃ under the atmosphere of nitrogen; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min manner, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and 3, step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 part of silica sol, 0.2 part of ethyl cellulose, 0.2 part of methyl trichloro siloxane, 0.35 part of sodium phytate, 0.45 part of caprylic acid, 0.2 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 part of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 4:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (2) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and graphene oxide, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, vacuumBrazing for 50 minutes to obtain a ceramic substrate C;
and 3, step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene oxide by weight. The organic auxiliary agent comprises the following materials: by weight, 0.08 part of silica sol, 0.2 part of ethyl cellulose, 0.2 part of methyl trichloro siloxane, 0.35 part of sodium phytate, 0.45 part of caprylic acid, 0.2 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 part of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 5:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at the temperature of 420 ℃ under the atmosphere of nitrogen; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane in a one-third mixed solvent of propylene glycol phenyl ether and deionized water, performing ultrasonic dispersion uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate and caprylic acid, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound according to the material ratio ofPerforming batch ball milling for 2 hours under the condition of 1, wherein the milling speed is 200rmp, and the milling is stopped for 20 minutes every 15 minutes; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.3 part of ethyl cellulose, 0.2 part of methyl trichlorosiloxane, 0.35 part of sodium phytate, 0.45 part of octanoic acid, 0.2 part of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 part of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 6:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water, uniformly stirring, refluxing at 80 ℃ for 6 hours, and freeze-drying; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at the temperature of 420 ℃ under the atmosphere of nitrogen; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Copper powder and methyl trichloro siloxane are put in one third of propylene glycol phenyl ether andin the deionized water mixed solvent, uniformly dispersing by ultrasonic, heating to 70 ℃, and stirring for 1.5 hours; adding octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Pre-pattern coating active metal solder on a ceramic substrate A by using a 250-mesh silk screen; drying for 1 hour at the set temperature of 100 ℃ to obtain an active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and 3, step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 parts of silica sol, 0.2 parts of ethyl cellulose, 0.2 parts of methyl trichlorosiloxane, 0.45 parts of octanoic acid, 0.2 parts of sodium dodecyl sulfate, 1.2 parts of triethanolamine, 0.15 parts of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Comparative example 7:
step 1: (1) Placing 12 parts of phytic acid and 4 parts of sodium dodecyl benzene sulfonate into a mixed solvent of 6 parts of ethanol and 78 parts of deionized water to obtain a cleaning agent; (2) Arranging a positioning reference hole with the aperture of 1.5mm on the AIN ceramic substrate; placing the ceramic substrate in a cleaning agent, setting the temperature to be 75 ℃, ultrasonically washing for 5 minutes, and drying by nitrogen to obtain a ceramic substrate A;
step 2: (1) Ultrasonically dispersing 1g of graphene oxide in 250mL of ethanol, adding 5mL of tetrabutyl titanate, 2mL of tetraethyl silicate and 5mL of deionized water,stirring, refluxing at 80 deg.C for 6 hr, and lyophilizing; placing the mixture in a high-temperature furnace, and performing heat treatment for 3.5 hours at the temperature of 420 ℃ under the atmosphere of nitrogen; heating to 820 deg.C, replacing nitrogen with ammonia gas at 100cm flow 3 Performing heat treatment for 3.5 hours in a min mode, and cooling in a nitrogen atmosphere to obtain a graphene compound; can be amplified in equal proportion. (2) Putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 70 ℃, and stirring for 1.5 hours; adding sodium phytate, octanoic acid and silica sol, and stirring for 1.5 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into two thirds of propylene glycol phenyl ether, and uniformly dispersing by ultrasonic to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing intermittent ball milling for 2 hours at a material ratio of 10; obtaining the active metal solder.
(3) Coating active metal solder on a ceramic substrate A in a pre-pattern mode by using a 250-mesh silk screen; drying at 100 deg.C for 1 hr to obtain active metal solder layer; fixing copper sheet on the active metal solder layer at 800 deg.C and 4.5 × 10 vacuum degree -4 Pa, carrying out vacuum brazing for 50 minutes to obtain a ceramic substrate C;
and 3, step 3: and carrying out laser etching patterning processing on the ceramic substrate C, and removing the redundant copper layer to obtain the copper-clad ceramic substrate.
In the technical scheme, the active metal solder comprises composite powder and an organic auxiliary agent; the composite powder comprises the following components: 65 parts of silver powder, 20 parts of copper powder, 3 parts of titanium hydride and 5 parts of graphene compound. The organic auxiliary agent comprises the following materials: by weight, 0.08 parts of silica sol, 0.2 parts of ethyl cellulose, 0.2 parts of methyl trichloro siloxane, 0.35 parts of sodium phytate, 0.45 parts of caprylic acid, 0.2 parts of sodium dodecyl sulfate, 0.15 parts of hydrogenated castor oil, 8.5 parts of propylene glycol phenyl ether and 2 parts of deionized water.
Experiment: the copper-clad ceramic substrates prepared in examples and comparative examples (1 to 3 in examples 1 to 7, 1mmAlN @0.2mmCu in comparative examples, and active gold)The thickness of the brazing layer is 40 mu m; 0.32mmSi in example 4 3 N 4 @0.3mmCu, thickness of active metal brazing layer 20 μm), and performing peel strength test (adopting 90-degree tensile test), cyclic thermal shock performance test (temperature is 150 ℃/-55 ℃; the high temperature and the low temperature are respectively kept for 15min in each circulation, the conversion time is less than or equal to 5 min), and the void ratio is increased; the data obtained are shown in the following table:
examples Peel strength A Number of cycles Void fraction
Example 1 24.6N/mm 1521 ＜0.02％
Example 2 24.1N/mm 1516 ＜0.02％
Example 3 24.3N/mm 1519 ＜0.02％
Example 4 33.7N/mm 5086 ＜0.02％
Comparative example 1 20.6N/mm 1216 ＜0.02％
Comparative example 2 22.7N/mm 1326 ＜0.02％
Comparative example 3 23.6N/mm 1459 ＜0.02％
Comparative example 4 21.5N/mm 1398 ＞0.02％
Comparative example 5 24.1N/mm 1491 ＜0.02％
Comparative example 6 23.8N/mm 1457 ＞0.02％
Comparative example 7 23.7N/mm 1406 ＞0.02％
And (4) conclusion: from the data in the table above, it can be seen that: the copper-clad ceramic substrates prepared in the embodiments 1 to 4 have higher bonding strength and excellent reliability by using the active brazing material in the scheme; meanwhile, the method has small void ratio and higher compactness. Comparing comparative examples 1 to 7 with example 1, it can be found that: in comparative example 1, since the graphene composite is not added, the thermal stress buffering performance is reduced because the graphene composite is softer than a metal and can effectively buffer thermal stress. In comparative example 2, the performance was degraded due to the addition of excessive graphene composite, because the addition thereof reduced the plasticity of the metal brazing layer. In comparative example 3, since tetraethyl silicate was not introduced in the graphene composite preparation process, the thermal buffer performance was reduced; in comparative example 4, since it was not modified, the compatibility of graphene was reduced, so that the performance was degraded; in comparative example 5, no silica sol was introduced into the organic auxiliary agent, so that the properties such as bonding strength were reduced; in comparative example 6, the compactness is reduced because sodium phytate is not introduced, and the thixotropic property is reduced because sodium phytate is not introduced, so that the void ratio is increased; in comparative example 7, since triethanolamine was not introduced, the properties of the paste were changed, so that the printability was lowered and the properties such as void ratio were lowered.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The preparation method of the active metal brazing copper-clad ceramic substrate is characterized by comprising the following steps: the method comprises the following steps:
step 1: arranging a positioning reference hole with the diameter of 1.0-2.0 mm on the ceramic substrate; placing the ceramic substrate in a cleaning agent, ultrasonically washing the ceramic substrate for 3 to 8 minutes at the temperature of between 70 and 80 ℃, and drying the ceramic substrate to obtain a ceramic substrate A;
step 2: pre-pattern coating active metal solder on the ceramic substrate A, and drying to obtain an active metal solder layer; fixing a copper sheet on the active metal solder layer, and carrying out vacuum brazing to obtain a ceramic substrate C;
and step 3: carrying out graphical processing on the ceramic substrate C, and removing the redundant copper layer to obtain a copper-clad ceramic substrate;
the raw material of the ceramic substrate is aluminum nitride, aluminum oxide or silicon nitride;
the cleaning agent comprises the following raw materials: 10-12 parts of phytic acid, 4-5 parts of sodium dodecyl benzene sulfonate, 5-6 parts of ethanol and 78-80 parts of deionized water by weight;
the active metal solder consists of composite powder and organic auxiliary agent; the composite powder consists of the following components: 64-66 parts of silver powder, 19-21 parts of copper powder, 2.5-3.5 parts of titanium hydride and 4.5-5.5 parts of graphene compound by weight;
the organic auxiliary agent consists of the following materials: 0.05 to 0.1 portion of silica sol, 0.15 to 0.3 portion of ethyl cellulose, 0.15 to 0.26 portion of methyl trichloro siloxane, 0.25 to 0.4 portion of sodium phytate, 0.35 to 0.5 portion of caprylic acid, 0.15 to 0.24 portion of lauryl sodium sulfate, 0.8 to 1.2 portions of triethanolamine, 0.1 to 0.2 portion of hydrogenated castor oil, 7 to 10 portions of propylene glycol phenyl ether and 1 to 2 portions of deionized water;
the preparation method of the graphene composite comprises the following steps: ultrasonically dispersing graphene oxide in ethanol, adding tetrabutyl titanate, tetraethyl silicate and deionized water, uniformly stirring, refluxing for 5-7 hours at the set temperature of 79-82 ℃, and freeze-drying; placing the mixture in a high-temperature furnace, and carrying out heat treatment for 3 to 4 hours at the temperature of 400 to 450 ℃ under the atmosphere of nitrogen; heating to 800-850 deg.C, replacing nitrogen with ammonia gas at flow rate of 80-100 cm 3 Performing heat treatment for 3-4 hours in min, and cooling in a nitrogen atmosphere to obtain a graphene compound;
the preparation method of the active metal solder comprises the following steps: putting copper powder and methyl trichlorosiloxane into a one-third mixed solvent of propylene glycol phenyl ether and deionized water, ultrasonically dispersing uniformly, heating to 60-70 ℃, and stirring for 1-2 hours; adding sodium phytate, caprylic acid and silica sol, and stirring for 1-2 hours; obtaining a mixed material A; putting silver powder, lauryl sodium sulfate, hydrogenated castor oil and ethyl cellulose into triethanolamine and two thirds of propylene glycol phenyl ether, and performing ultrasonic dispersion uniformly to obtain a mixed material B; uniformly mixing the mixed material A, the mixed material B, titanium hydride and the graphene compound, and performing batch ball milling for 1-2 hours at a material ratio of 10; obtaining the active metal solder.
2. The method for preparing an active metal brazing copper-clad ceramic substrate according to claim 1, wherein the method comprises the following steps: in the step 2, the pre-pattern coating process is a screen printing process, and the mesh number of a screen printing plate is 250-300 meshes; the temperature of the vacuum brazing process is 500-900 ℃, the brazing time is 40-60 minutes, and the vacuum degree is 4.5 multiplied by 10 -4 ～5×10 -4 Pa; in step 3, the graphical processing is one of laser etching, mechanical processing and chemical etching.
3. The method for preparing an active metal brazing copper-clad ceramic substrate according to claim 1, wherein the method comprises the following steps: the ratio of the graphene oxide to the ethanol to the tetrabutyl titanate to the tetraethyl silicate to the deionized water is 1g.
4. The copper-clad ceramic substrate prepared by the method for preparing the active metal brazing copper-clad ceramic substrate according to any one of claims 1 to 3.
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