CN117326886A - Slurry for ceramic copper-clad part, and preparation method and application thereof - Google Patents

Abstract

This application provides a slurry for ceramic copper-clad parts, including in parts by mass: 75-88 parts of copper powder, 5-18 parts of solvent, 0.05-1 part of adhesive, and 5-15 parts of sintering aids , 0.05-1 part of complexing agent; the complexing agent includes hydrogenated castor oil and/or polyamide wax. This application uses a specific complexing agent configured in the slurry to form a three-dimensional network structure in the slurry, thereby improving the three-dimensional sense of the slurry, enabling high-thickness screen printing of the slurry on the ceramic substrate, and controlling various The proportion of materials can be improved to improve the bonding force between the copper layer and the ceramic substrate, thereby obtaining ceramic copper-clad parts with high peel strength and low resistance.

Description

Slurry for ceramic copper-clad parts, ceramic copper-clad parts and preparation methods and applications thereof

Technical field

The present application relates to the technical field of substrate technology, and specifically relates to a slurry for ceramic copper-clad parts, ceramic copper-clad parts and preparation methods and applications thereof.

Background technique

Currently, DBC and copper plating are the mainstream methods for copper coating on ceramic substrates. DBC (Direct Bonding Copper) ceramic copper clad laminate refers to a composite board in which copper foil is directly bonded to the surface of a ceramic substrate at high temperature. Its preparation process is usually to first oxidize the copper foil to form a copper oxide layer, and then oxidize the copper foil to form a copper oxide layer. The copper oxide layer is bonded to the ceramic substrate, and the copper foil and ceramic substrate are sintered at high temperature to achieve the overlay. The copper plating method refers to depositing a uniform conductive layer on the hole wall through a redox reaction, and then thickening the copper plating through electroplating to achieve the required plating layer. The DBC method has many processes, troublesome operations, high equipment requirements and relatively high cost.

Contents of the invention

The purpose of this application is to overcome the problems existing in the above-mentioned prior art and provide a slurry for ceramic copper-clad parts, ceramic copper-clad parts and preparation methods and applications thereof.

The first aspect of this application is to provide a slurry for ceramic copper-clad parts, including in parts by mass: 75-88 parts of copper powder, 5-18 parts of solvent, 0.05-1 part of adhesive, and sintering aid. 5-15 parts of agent, 0.05-1 part of complexing agent; the complexing agent includes hydrogenated castor oil and/or polyamide wax.

Preferably, the slurry for ceramic copper-clad parts includes, in parts by mass: 80-85 parts of copper powder, 8-15 parts of solvent, 0.3-0.8 parts of adhesive, and 8-12 parts of sintering aid. part, complexing agent 0.05-1 part.

Preferably, the mass ratio of the copper powder to the sintering aid is 8-12.

Preferably, the sintering aid includes one or more of silica, calcium carbonate, aluminum oxide, sodium oxide, cobalt oxide and barium sulfate.

Preferably, the solvent includes one or more of ethylene glycol, ethanol, xylene, terpineol and glycerol.

Preferably, the binder includes one or more of polyvinyl butyral, cellulose and dioctyl phthalate.

The second aspect of the present application is to provide a method for preparing ceramic copper-clad parts, which includes: coating the aforementioned slurry for ceramic copper-clad parts on the surface of a ceramic substrate; and then drying and sintering to obtain a ceramic copper-clad part.

Preferably, the sintering is performed in a vacuum environment or an inert atmosphere, and the sintering temperature is 600-1200°C.

Preferably, the ceramic substrate is made of one or more of zirconium oxide, aluminum oxide, aluminum nitride, silicon carbide, silicon oxide, zirconium nitride and zirconium carbide.

The third aspect of the present application is to provide a ceramic copper-clad part, which is prepared by the aforementioned preparation method of a ceramic copper-clad part.

This application uses a specific complexing agent configured in the slurry to form a three-dimensional network structure in the slurry, thereby improving the three-dimensional sense of the slurry. The fourth aspect of this application is to provide an application of ceramic copper-clad parts. The application includes: using the aforementioned ceramic copper-clad parts to prepare refrigeration chips or current-carrying plates.

The slurry can be screen-printed on the ceramic substrate to achieve high-thickness screen printing, and the ratio of each substance can be controlled, thereby improving the bonding force between the copper layer and the ceramic substrate, and obtaining ceramic copper-clad parts with high peel strength and low resistance.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.

This application provides a slurry for ceramic copper-clad parts, including in parts by mass: 75-88 parts of copper powder, 5-18 parts of solvent, 0.05-1 part of adhesive, and 5-15 parts of sintering aid. part, 0.05-1 part of complexing agent; the complexing agent includes hydrogenated castor oil and/or polyamide wax.

This application uses a specific complexing agent configured in the slurry to form a three-dimensional network structure in the slurry, thereby improving the three-dimensional sense of the slurry, enabling high-thickness screen printing of the slurry on the ceramic substrate, and controlling various The proportion of materials can be improved to improve the bonding force between the copper layer and the ceramic substrate, thereby obtaining ceramic copper-clad parts with high peel strength and low resistivity.

Specifically, the mass fraction of copper powder in the embodiments of the present application ranges from 75 to 88 parts. The mass fraction of copper powder within this range can play a role in low resistivity conductivity and better improve the bonding force between the copper layer and the ceramic substrate. If the mass fraction of copper powder is less than 75 parts, the resistance of the ceramic copper-clad parts will be too high, affecting the conduction effect; if the mass fraction of copper powder is greater than 88 parts, the strength of the copper layer will be low and the bonding with the ceramic substrate will be poor. Weak strength. Preferably, the mass fraction of copper powder ranges from 80 to 85 parts.

In some embodiments, the copper powder can be pure copper powder, copper alloy powder, or a mixture of pure copper and copper alloy. The particle size range of copper powder can be 0.5-100μm, which can play a good dispersion role and help sintering molding.

The mass parts of the sintering aid in the embodiments of this application range from 5 to 15 parts. The mass fraction of the sintering aid is within this range, which can enhance the physical strength of the copper layer and the bonding force between the copper layer and the ceramic substrate. If the mass fraction of the sintering aid is less than 5 parts, the copper layer will have poor physical strength and poor bonding force with the ceramic substrate; if the mass fraction of the sintering aid is greater than 15 parts, the copper layer will have excessive resistance. Preferably, the mass parts of the sintering aid range from 8 to 12 parts.

In some embodiments, in order to further improve the bonding force between the copper layer and the ceramic substrate, the mass ratio of the copper powder and the sintering aid can be adjusted to be in the range of 8-12.

In some embodiments, the sintering aid includes one or more of silica, calcium carbonate, aluminum oxide, sodium oxide, cobalt oxide, and barium sulfate. It can better enhance the bonding force between the copper layer and the ceramic substrate.

The mass parts of the solvent in the embodiments of this application range from 5 to 18 parts. When the mass fraction of the solvent is within this range, the slurry can be well mixed and formed well. If the mass fraction of the solvent is less than 5 parts, the slurry will be mixed unevenly and the moldability will be poor; if the mass fraction of the solvent is greater than 18 parts, the slurry will have poor moldability. Preferably, the mass parts of the solvent range from 8 to 15 parts.

In some embodiments, the solvent includes one or more of ethylene glycol, ethanol, xylene, terpineol, and glycerol.

The mass parts of the adhesive in the embodiments of this application range from 0.05 to 1 part. The mass fraction of the adhesive within this range promotes the molding strength of the copper layer screen printing and the shape retention of the sintering process. If the mass fraction of the adhesive is less than 0.05 parts, the effect will not be obvious and the copper layer will be easily lost in strength after screen printing; if the mass fraction of the adhesive is greater than 1 part, the sintering effect of the copper layer will be affected. Preferably, the mass parts of the adhesive range from 0.3 to 0.8 parts.

In some embodiments, the binder includes one or more of polyvinyl butyral (PVB), cellulose, and dioctyl phthalate (DOP).

The mass fraction of the complexing agent in the embodiments of this application ranges from 0.05 to 1 part. The mass fraction of the complexing agent is within this range. A specific complexing agent is configured in the slurry to form a three-dimensional network structure in the slurry, thereby improving the three-dimensional sense of the slurry and allowing the slurry to be screen-printed on the ceramic substrate. Able to achieve high thickness screen printing. If the mass fraction of the complexing agent is less than 0.05 parts, the slurry will have poor three-dimensional effect and low thickness; if the mass fraction of the complexing agent is greater than 1 part, the viscosity of the slurry will be too high, affecting screen printing. The complexing agent includes hydrogenated castor oil and/or polyamide wax.

This application also provides a method for preparing ceramic copper-clad parts, which includes: coating the aforementioned slurry for ceramic copper-clad parts on the surface of a ceramic substrate; and then drying and sintering to obtain a ceramic copper-clad part.

In some embodiments, the slurry used for ceramic copper-clad parts can be coated on the surface of the ceramic substrate in the following manner: the prepared slurry is passed through a screen to screen-print a preset pattern or line on the surface of the ceramic substrate. It is then dried to shape the slurry. Specifically, it can be dried in a drying oven at 50-200°C to allow the organic solvent to evaporate and preform.

In some embodiments, the sintering is performed in a vacuum environment or an inert atmosphere, which can effectively protect copper and its alloys from oxidation. The inert atmosphere may be a nitrogen atmosphere. Preferably, the sintering temperature is 600-1200°C and the sintering time is 1-10 h.

In some embodiments, the ceramic substrate is made of one or more of zirconium oxide, aluminum oxide, aluminum nitride, silicon carbide, silicon oxide, zirconium nitride and zirconium carbide.

This application also provides a ceramic copper-clad part, which is prepared by the aforementioned preparation method of a ceramic copper-clad part. Ceramic copper-clad parts have high peel strength and low resistance characteristics.

This application also provides an application of ceramic copper-clad parts, which application includes: using the aforementioned ceramic copper-clad parts to prepare refrigeration chips or current-carrying plates. Refrigeration sheets or current-carrying plates can be used in automobiles, medical care, daily appliances and other fields. The present application will be described in detail through examples below, but the present application is not limited to the following examples.

Example 1

(1) Mix the slurry according to the following components, disperse at 500r/min and disperse for 2h:

Copper and copper alloy powder: 80 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: hydrogenated castor oil, 0.5 parts.

(2) Use the prepared slurry to screen-print the preset lines on the zirconia ceramic substrate through the screen.

(3) Dry the ceramic substrate with silk-printed circuits at 100°C, and then sinter it in a vacuum at a sintering temperature of 800°C and a sintering time of 4 hours to obtain a ceramic copper-clad part.

Example 2

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 85 parts;

Solvent: terpineol, 5 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: hydrogenated castor oil, 0.5 parts.

Example 3

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 84 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aid: silica: sodium carbonate = 1:1, a total of 5 parts

Complexing agent: hydrogenated castor oil, 0.5 part

Example 4

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 88 parts;

Solvent: terpineol, 15 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 11 parts;

Complexing agent: polyamide wax, 0.5 parts.

Example 5

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 80 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: hydrogenated castor oil and polyamide wax, 0.8 parts.

Comparative example 1

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 65 parts;

Solvent: terpineol, 3 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: hydrogenated castor oil, 0.5 parts.

Comparative example 2

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 84 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 4 parts;

Complexing agent: hydrogenated castor oil, 0.5 parts.

Comparative example 3

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 80 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: sodium hexametaphosphate, 0.5 parts.

Comparative example 4

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 80 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aids: silica: sodium carbonate = 1:1, a total of 9 parts;

Complexing agent: hydrogenated castor oil, 2 parts.

Comparative example 5

The same as Example 1, except that the components of the slurry are:

Copper and copper alloy powder: 80 parts;

Solvent: terpineol, 10 parts;

Adhesive: PVB, 0.5 parts;

Sintering aid: silica: sodium carbonate = 1:1, 9 parts in total.

Performance Testing:

Test the resistance of the sample. The size of the copper foil of the resistance test sample is: 3mm*1.2mm*0.3mm (the size of the copper layer of Comparative Example 5 is 3mm*1.2mm*0.01mm); use a DC resistance tester model YP2512.

Pullout force test: Use the universal material testing machine model TS2000M for testing.

Bonding force test: First use a hundred-square knife to mark the test surface, then use 3M tape to stick the test surface and roll it with a rubber roller. Then pull the tape in a 90° vertical direction at a constant speed. Test results, good: no peeling or warping of the copper layer; average: slight warping or partial peeling of the copper layer; poor: all or most of the copper layer peeling off and warping.

Table 1

It can be seen from the results in Table 1 that using the slurry for ceramic copper-clad parts of the present application can achieve high thickness silk screen printing of the slurry. The copper layer thickness of the prepared ceramic copper-clad parts is greater than 100 μm; and the resistance is low, less than 7mΩ. , Ceramic copper-clad parts have good thermal conductivity; and the bonding force between the copper layer and the ceramic substrate is high. However, the ceramic copper-clad parts prepared in Comparative Examples 1-5 cannot meet the above requirements at the same time.

The preferred embodiments of the present application have been described in detail above. However, the present application is not limited to the specific details in the above-mentioned embodiments. Within the scope of the technical concept of the present application, a variety of simple modifications can be made to the technical solutions of the present application. These simple modifications All fall within the protection scope of this application.

In addition, it should be noted that each of the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner without conflict. In order to avoid unnecessary repetition, this application describes various possible combinations. The combination method will not be further explained.

In addition, any combination of various embodiments of the present application can also be carried out. As long as they do not violate the idea of the present application, they should also be regarded as the contents disclosed in the present application.

Claims (11)

1. A slurry for ceramic copper-clad parts, characterized in that, in parts by mass, it includes: 75-88 parts of copper powder, 5-18 parts of solvent, 0.05-1 part of binder, 5-15 parts of sintering aids, and 0.05-1 part of complexing agent; the complexing agent includes hydrogenated castor oil and/or polymer Amide wax. 2. The slurry for ceramic copper-clad parts according to claim 1, characterized in that, in terms of parts by mass, it includes: 80-85 parts of copper powder, 8-15 parts of solvent, and 0.3-0.8 parts of adhesive. , 8-12 parts of sintering aids, 0.05-1 parts of complexing agent. 3. The slurry for ceramic copper-clad parts according to claim 1, characterized in that the mass ratio of the copper powder to the sintering aid is 8-12. 4. The slurry for ceramic copper-clad parts according to claim 1, wherein the sintering aid includes one of silicon dioxide, calcium carbonate, alumina, sodium oxide, cobalt oxide and barium sulfate. or more. 5. The slurry for ceramic copper-clad parts according to claim 1, wherein the solvent includes one or more of ethylene glycol, ethanol, xylene, terpineol and glycerol. 6. The slurry for ceramic copper-clad parts according to claim 1, characterized in that the adhesive includes one of polyvinyl butyral, cellulose and dioctyl phthalate or Various. 7. A method for preparing ceramic copper-clad parts, which is characterized by comprising: The slurry for ceramic copper-clad parts according to any one of claims 1 to 6 is coated on the surface of the ceramic substrate; and then dried and sintered to obtain a ceramic copper-clad part. 8. The method for preparing ceramic copper-clad parts according to claim 7, characterized in that the sintering is performed in a vacuum environment or an inert atmosphere, and the sintering temperature is 600-1200°C. 9. The preparation method of ceramic copper-clad parts according to claim 7, characterized in that the material of the ceramic substrate includes zirconium oxide, aluminum oxide, aluminum nitride, silicon carbide, silicon oxide, zirconium nitride and zirconium carbide. one or more of them. 10. A ceramic copper-clad part, characterized in that it is prepared by the preparation method of a ceramic copper-clad part according to any one of claims 7-9. 11. An application of ceramic copper-clad parts, the application includes: using the ceramic copper-clad parts according to claim 10 to prepare a cooling chip or a current carrying plate.