CN111484335A - Sintering aid composite additive for silicon nitride ceramic slurry, silicon nitride ceramic slurry and preparation method and application thereof - Google Patents
Sintering aid composite additive for silicon nitride ceramic slurry, silicon nitride ceramic slurry and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of composite materials, in particular to a sintering aid composite additive for silicon nitride ceramic slurry, the silicon nitride ceramic slurry, a preparation method and application thereof, wherein an inorganic sintering aid is added to realize accurate mixing of an organic system and an inorganic system, so that after the silicon nitride ceramic substrate material is prepared into the silicon nitride ceramic substrate material, the substrate material has high strength and high thermal conductivity, and the thermal conductivity can reach 70-160W/m.K. Nitride whiskers and/or carbide whiskers are added, so that the strength and the toughness of the silicon nitride ceramic substrate material are effectively improved, the mechanical property of the silicon nitride ceramic substrate material is effectively improved, the bending strength reaches 600-900MPa, and the fracture toughness reaches 6-9.5 MPa-m1/2。
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a sintering aid composite additive for silicon nitride ceramic slurry, silicon nitride ceramic slurry and a preparation method and application thereof.
Background
With the continuous development of integrated circuits and functional devices, higher requirements are put on the heat dissipation problem of circuit operation, so that a new material substrate (base plate) must be adopted for heat dissipation. Ceramic materials are currently used in a wide variety of applications in electronic and circuit substrates, such as Al2O3、BeO、AlN、Si3N4And the like. And wherein silicon nitride (Si)3N4) The ceramic is a structural material with excellent comprehensive performance, the theoretical thermal conductivity can reach more than 400W/m.K, and the silicon nitride ceramic material has higher bending strength and fracture toughness, and excellent thermal radiation performance and thermal cycle resistance, so that the silicon nitride ceramic material is used as a raw material for preparing circuit substrates and electronic substrates, and is wider than other ceramic materials. However, when the silicon nitride ceramic material is prepared, different sintering aids and different additives affect the thermal conductivity and strength of the silicon nitride ceramic material, so that the comprehensive performance of the silicon nitride ceramic material is poor, and therefore, the proper sintering aids and additives are selected and added into the preparation of the silicon nitride ceramic material, which is beneficial to improving the thermal conductivity, strength and toughness of the silicon nitride ceramic material, improving the comprehensive performance of the silicon nitride ceramic material and ensuring the application effect of the silicon nitride ceramic material in the preparation of the substrate product for circuit components.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a sintering aid composite additive for silicon nitride ceramic slurry, and a preparation method and application thereof.
The method is realized by the following technical scheme:
the invention provides a preparation method of silicon nitride ceramic slurry, which is prepared by taking silicon nitride powder, a mixed solvent, a binder, a plasticizer, a dispersant, a functional assistant, a sintering assistant and an additive as raw materials through slurry ball milling and slurry defoaming; wherein, the mass of the mixed solvent is 45-80%, the mass of the binder is 5-45%, the mass of the plasticizer is 5-38%, the mass of the dispersant is 0.5-3%, the mass of the sintering aid is 0.5-10%, and the mass of the additive is less than 16%.
Preferably, the additive is added in an amount different from zero. Is beneficial to improving the comprehensive performance of the silicon nitride ceramic material, leads the heat conductivity to reach 70-160W/m.K, leads the bending strength to reach 600-900MPa and the fracture toughness to reach 6-9.5 MPa-m.K after being prepared into the substrate1/2。
The additive adopted by the invention is one or more of aluminum nitride whisker, silicon nitride whisker and silicon carbide whisker, and the sum of the addition amount of the three is less than 16%.
The sintering aid adopted by the invention is one or more of magnesium fluoride, aluminum fluoride, yttrium fluoride and silicon magnesium nitride.
Preferably, the mixed solvent is at least two of butanone, absolute ethyl alcohol, isopropanol, n-butanol, ethyl acetate, propyl acetate and butyl acetate; the binder is polyvinyl butyral; the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate and polyethylene glycol; the dispersant is one or more of castor oil, phosphate ester, fish oil, oleic acid and triolein.
The slurry ball milling is carried out by taking silicon nitride powder, sintering aid, additive, dispersant and mixed solvent as raw materials and silicon nitride balls as ball milling medium for 12-48h, and adopting NH3·H2Adjusting the pH value to be between 9 and 11 by O; and adding the binder and the plasticizer, and performing secondary ball milling for 12-48h to obtain the material.
The slurry defoaming is carried out for 10-60min under the vacuum condition of-0.95 MPa, and the viscosity of the slurry is adjusted to 5000-30000 mPa.s. In the defoaming process, a proper functional auxiliary agent is added, the functional auxiliary agent consists of a defoaming agent and a leveling agent, and the defoaming agent and the leveling agent are purchased from the market.
The invention also provides the silicon nitride ceramic slurry prepared by the preparation method.
The invention also aims to provide the application of the silicon nitride ceramic slurry in the preparation of circuit substrates. When in application, a casting machine is adopted to cast and form the silicon nitride ceramic slurry, the silicon nitride ceramic slurry is dried for 0.5 to 5 hours at the temperature of between 50 and 120 ℃ to obtain a blank sheet, and the blank sheet is prepared by a degreasing-sintering process; wherein the degreasing is carried out at the temperature of 550-650 ℃, the heating rate of 40-80 ℃/h and the degreasing time of 2-6h to obtain a green body; sintering, namely placing the green body into a high-temperature tungsten vacuum resistance furnace, sintering under no pressure at the temperature of 1650-1950 ℃, and adopting mixed gas of hydrogen and nitrogen for protection when sintering, wherein the flow ratio of the hydrogen to the nitrogen is 1: 1-2; or sintering, namely putting the green body into an air pressure furnace, wherein the atmosphere is nitrogen, the sintering pressure is 0.8-8MPa, and the sintering temperature is 1650-.
The invention can refer to Si in the casting forming process3N4The ceramic substrate is produced by a casting production method or a casting production method of ceramic substrates such as AlN, glass ceramics and the like.
The invention provides a composite additive of sintering aid for silicon nitride ceramic slurry, which is characterized in that nitride whiskers and/or carbide whiskers are compounded with one or more of magnesium fluoride, aluminum fluoride, yttrium fluoride and silicon magnesium nitride, wherein the mass percentage of the nitride whiskers and/or the carbide whiskers is 2-100%.
Compared with the prior art, the invention has the technical effects that:
the silicon nitride ceramic material created by the invention realizes the accurate mixing of an organic system and an inorganic system by adding the inorganic sintering aid, so that after the silicon nitride ceramic material is prepared into the silicon nitride ceramic substrate material, the substrate material has high strength and high thermal conductivity, and the thermal conductivity can reach 70-160W/m.K. By adding nitride whiskers and/or carbide whiskers, the strength and toughness of the silicon nitride ceramic substrate material are effectively improved, the mechanical property of the silicon nitride ceramic substrate material is effectively improved, the bending strength reaches 600-900MPa, and the fracture toughness reaches 6-9.5 MPa.m1/2。
The silicon nitride ceramic material created by the invention can be used for preparing a blank sheet with the thickness of 20 mu m-2.0mm after tape casting and drying so as to meet the requirements of different sizes and specifications in a circuit substrate.
Detailed Description
The technical solution of the present invention is further defined below with reference to the specific embodiments, but the scope of the claims is not limited to the description.
Examples
The preparation method of the silicon nitride ceramic slurry comprises the following steps of 45-80% of mixed solvent, 5-45% of binder, 5-38% of plasticizer, 0.5-3% of dispersant, 0.5-10% of sintering aid, less than 16% of additive and ingredients, wherein the silicon nitride ceramic slurry accounts for silicon nitride powder.
After the ingredients are weighed: silicon nitride powder, sintering aid, additive, dispersant and mixed solvent are used as raw materials, silicon nitride balls are used as ball milling medium, ball milling is carried out for 12-48h, and NH is adopted3·H2Adjusting the pH value to be between 9 and 11 by O; adding a binder and a plasticizer, and performing secondary ball milling for 12-48h to obtain ball milling slurry; then bubble is removed for 10-60min under the vacuum condition of-0.95 MPa, the viscosity of the ball milling slurry is adjusted to 5000-.
Preparation of a substrate sample:
casting and molding the silicon nitride ceramic slurry by using a casting machine, and drying at 50-120 ℃ for 0.5-5h to obtain a blank sheet;
degreasing for 2-6h at the temperature of 550-650 ℃ and the heating rate of 40-80 ℃/h to obtain a green body;
placing the green body into a high-temperature tungsten vacuum resistance furnace, sintering under no pressure at the temperature of 1650-1950 ℃, and adopting mixed gas of hydrogen and nitrogen for protection during sintering, wherein the flow ratio of the hydrogen to the nitrogen is 1: 1-2;
the adopted additive is one or more of aluminum nitride whisker, silicon nitride whisker and silicon carbide whisker. The adopted sintering aid is one or more of magnesium fluoride, aluminum fluoride, yttrium fluoride and silicon magnesium nitride. The adopted mixed solvent is at least two of butanone, absolute ethyl alcohol, isopropanol, n-butanol, ethyl acetate, propyl acetate and butyl acetate; the adopted binder is polyvinyl butyral; the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate and polyethylene glycol; the adopted dispersant is one or more of castor oil, phosphate, fish oil, oleic acid and triolein.
According to the above-mentioned working examples, the present investigators prepared the raw materials in the following ratio as shown in table 1 during the preparation of the specific test samples.
TABLE 1(1-1)
TABLE 1 continuation (1-2)
TABLE 1 continuation (1-3)
According to the preparation method of the embodiment, silicon nitride ceramic slurry is obtained after primary ball milling, secondary ball milling and defoaming treatment; and controlling each technological parameter in the processes of primary ball milling, secondary ball milling and bubble removal by adopting interval values, and stabilizing the technological parameters in corresponding intervals to realize the ball milling.
The obtained silicon nitride ceramic slurry is prepared according to a substrate sample preparation method, in the preparation process, the preparation of the substrate sample can be completed by controlling the corresponding parameter values to be within the corresponding interval values, the prepared substrate sample is used for measuring the bending strength, the fracture toughness and the thermal conductivity, and the test results are recorded in the following table 2.
TABLE 2
| Thermal conductivity (W/m. K) | Flexural Strength (MPa) | Fracture toughness (MPa. m)1/2) | |
| Example 1 | 85.62 | 520.6 | 4.62 |
| Example 2 | 92.41 | 487.6 | 4.03 |
| Example 3 | 81.36 | 562.4 | 5.02 |
| Example 4 | 87.38 | 601.5 | 5.60 |
| Example 5 | 98.87 | 623.7 | 5.61 |
| Example 6 | 122.74 | 751.2 | 6.08 |
| Example 7 | 135.58 | 801.2 | 6.31 |
| Example 8 | 127.19 | 698.5 | 6.76 |
| Example 9 | 135.67 | 724.5 | 6.95 |
| Example 10 | 139.83 | 785.2 | 7.24 |
| Example 11 | 146.52 | 766.3 | 7.97 |
| Example 12 | 132.33 | 878.2 | 7.72 |
| Example 13 | 148.52 | 852.3 | 8.41 |
| Example 14 | 148.41 | 828.5 | 7.32 |
| Example 15 | 152.35 | 900.2 | 8.65 |
As shown in the data of the tables 1(1-1), 1 continuous (1-2), 1 continuous (1-3) and 2, the sintering aid is added, so that the thermal conductivity of the substrate prepared from the ceramic slurry can reach more than 80W/m.K, the bending strength reaches more than 480MPa, and the fracture toughness reaches more than 4.00. By the composite addition of the additive and the sintering aid, the thermal conductivity is greatly improved, so that the thermal conductivity reaches more than 120W/m.K, the bending strength reaches more than 698MPa, and the fracture toughness reaches more than 6.5.
In addition, during the research process, the present investigators performed experimental research on the addition of conventional sintering aids according to the operation manner of example 1, wherein the changes of the addition amounts of the sintering aids and silicon nitride powders are shown in table 3 below, and the thermal conductivity of the obtained substrate was detected and recorded in table 3 below.
TABLE 3
| Silicon nitride powder | Magnesium oxide | Aluminum oxide | Yttria | CeO2 | Thermal conductivity (W/m. K) | |
| Group 1 | 97 | 1 | 2 | 0 | 0 | 13.50 |
| Group 2 | 97 | 1.5 | 0 | 1.5 | 0 | 11.46 |
| Group 3 | 95.5 | 1.5 | 1 | 2 | 0 | 25.90 |
| Group 4 | 98 | 1 | 0 | 0 | 1 | 13.61 |
| Group 5 | 93 | 0 | 2 | 3 | 2 | 15.21 |
The data in tables 1(1-1), 1 (1-2), 1 (1-3), 2 and 3 show that when different sintering aids are added in the preparation of the silicon nitride ceramic material, the properties of the ceramic material such as thermal conductivity and the like after the ceramic material is prepared into a substrate can be influenced, and the selection of the proper sintering aid is helpful for improving the comprehensive properties of the substrate.
In addition to the sintering processes in the above examples and experimental procedures, the ceramic material created by the present invention is also suitable for the following sintering processes: the sintering is to place the green body into an air pressure furnace, the atmosphere is nitrogen, the sintering pressure is 0.8-8MPa, the sintering temperature is 1650-.
Other matters in the invention are not to be considered as being obvious and may be achieved by those skilled in the art by referring to the relevant technical means disclosed in the prior art documents and the common general knowledge and the conventional technical means which are familiar to those skilled in the art.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (13)
1. A silicon nitride ceramic slurry preparation method is characterized in that silicon nitride powder, mixed solvent, binder, plasticizer, dispersant, sintering aid and additive are used as raw materials, and the silicon nitride ceramic slurry is prepared by slurry ball milling and slurry defoaming; wherein, the mass of the mixed solvent is 45-80%, the mass of the binder is 5-45%, the mass of the plasticizer is 5-38%, the mass of the dispersant is 0.5-3%, the mass of the sintering aid is 0.5-10%, and the mass of the additive is less than 16%.
2. The method of preparing a silicon nitride ceramic slurry according to claim 1, wherein the additive is added in an amount different from zero.
3. The method for preparing silicon nitride ceramic slurry according to claim 1 or 2, wherein the additive is one or more of aluminum nitride whisker, silicon nitride whisker and silicon carbide whisker, and the sum of the addition amount of the three is less than 16%.
4. The method for preparing silicon nitride ceramic slurry according to claim 1, wherein the sintering aid is one or more of magnesium fluoride, aluminum fluoride, yttrium fluoride and magnesium silicon nitride.
5. The method for preparing silicon nitride ceramic slurry according to claim 1, wherein the mixed solvent is at least two of butanone, absolute ethyl alcohol, isopropyl alcohol, n-butanol, ethyl acetate, propyl acetate, and butyl acetate; the binder is polyvinyl butyral; the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate and polyethylene glycol; the dispersant is one or more of castor oil, phosphate ester, fish oil, oleic acid and triolein.
6. The preparation method of silicon nitride ceramic slurry according to claim 1, wherein the slurry ball milling is performed for 12-48h by using silicon nitride powder, sintering aid, additive, dispersant and mixed solvent as raw materials and silicon nitride balls as ball milling medium and adopting NH3·H2Adjusting the pH value to be between 9 and 11 by O; and adding the binder and the plasticizer, and performing secondary ball milling for 12-48h to obtain the material.
7. The method for preparing silicon nitride ceramic slurry according to claim 1, wherein the defoaming of the slurry is carried out under a vacuum condition of-0.95 MPa for 10-60min, and the viscosity of the slurry is adjusted to 5000-30000 mPa-s.
8. A silicon nitride ceramic slurry prepared by the preparation process as claimed in claims 1 to 7.
9. Use of the silicon nitride ceramic slurry prepared by the preparation method according to claims 1 to 7 for the preparation of a circuit substrate.
10. The composite additive is characterized in that nitride whiskers and/or carbide whiskers are compounded with one or more of magnesium fluoride, aluminum fluoride, yttrium fluoride and silicon magnesium nitride, wherein the mass percentage of the nitride whiskers and/or the carbide whiskers is 2-100%.
11. The composite additive for sintering aid of silicon nitride ceramic slurry according to claim 10, wherein the nitride whisker is one or two of aluminum nitride whisker and silicon nitride whisker; the carbide whisker is silicon carbide whisker.
12. The application of nitride whisker and/or carbide whisker in improving the comprehensive performance of silicon nitride ceramic slurry.
13. The use of claim 12, wherein the nitride whiskers are one or both of aluminum nitride whiskers and silicon nitride whiskers; the carbide whisker is silicon carbide whisker.
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| CN112745126A (en) * | 2020-12-21 | 2021-05-04 | 南京工程学院 | Si3N4Whisker toughened high-thermal-conductivity AlN ceramic substrate and preparation method thereof |
| CN113061039A (en) * | 2021-02-24 | 2021-07-02 | 福建华清电子材料科技有限公司 | Preparation method of aluminum nitride ceramic heating body |
| CN113149662A (en) * | 2021-04-20 | 2021-07-23 | 中材高新氮化物陶瓷有限公司 | Preparation method and application of high-thermal-conductivity silicon nitride ceramic casting film |
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| CN112209722A (en) * | 2020-09-08 | 2021-01-12 | 衡阳凯新特种材料科技有限公司 | Silicon nitride composite material, preparation method thereof and heating element |
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| CN114538935A (en) * | 2022-03-17 | 2022-05-27 | 天津硕科科技有限公司 | Forming method of high-thermal-conductivity silicon nitride substrate |
| CN115611639A (en) * | 2022-12-19 | 2023-01-17 | 江苏富乐华功率半导体研究院有限公司 | Silicon wafer casting slurry and silicon wafer forming method |
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