Silica-based composite multilayer ceramic substrate and method of manufacturing the same

Abstract

The application relates to the technical field of ceramic substrate, and discloses a silicon dioxide-based composite multilayer ceramic substrate and a preparation method thereof.The silicon dioxide-based composite multilayer ceramic substrate comprises the following components by weight: boron-zinc composite coated silicon dioxide 90-100 parts, aluminum nitride 8-10 parts, sintering aid 3-5 parts, toughening aid 2-4 parts, dispersant 2-3 parts, binder 5-9 parts, plasticizer 1-2 parts and solvent 100-150 parts; the boron-zinc composite coated silicon dioxide comprises the following components by weight: silicon dioxide 100 parts, zinc nitrate hexahydrate 6-10 parts and boron trioxide 8-12 parts.Through the technical scheme, the problem of low bending strength of the silicon dioxide-based composite multilayer ceramic substrate in the related art is solved.

Description

Technical Field

[0001] This invention relates to the field of ceramic substrate technology, specifically to a silicon dioxide-based composite multilayer ceramic substrate and its preparation method. Background Technology

[0002] With the rapid iteration of high-frequency electronic technologies such as 5G communication and millimeter-wave radar, electronic devices are developing rapidly towards miniaturization, high frequency, and high integration, placing more stringent requirements on the dielectric properties of substrate materials. Silicon dioxide (SiO2), as a typical inorganic non-metallic material, exhibits irreplaceable application potential in the field of high-frequency millimeter-wave substrates due to its extremely low dielectric constant and dielectric loss, excellent insulation properties, chemical stability, and thermal stability. It has become one of the most promising core substrate materials in current millimeter-wave communication equipment and precision electronic packaging. However, silicon dioxide itself has significant performance limitations. Its bending strength is relatively low, and it is prone to cracking and breakage under mechanical impact during complex assembly processes, vibration under special working conditions, and thermal stress. This severely limits its promotion and application in special working conditions such as aerospace, automotive electronics, and high-end precision instruments where high mechanical performance requirements for substrates are necessary. Summary of the Invention

[0003] This invention proposes a silica-based composite multilayer ceramic substrate and its preparation method, which solves the problem of low bending strength of silica-based composite multilayer ceramic substrates in related technologies.

[0004] The technical solution of the present invention is as follows: This invention proposes a silica-based composite multilayer ceramic substrate, comprising the following raw materials in parts by weight: 90-100 parts of boron-zinc composite coated silica, 8-10 parts of aluminum nitride, 3-5 parts of sintering aid, 2-4 parts of toughening aid, 2-3 parts of dispersant, 5-9 parts of binder, 1-2 parts of plasticizer, and 100-150 parts of solvent; The boron-zinc composite coated silica comprises the following raw materials in parts by weight: 100 parts silica, 6-10 parts zinc nitrate hexahydrate, and 8-12 parts boron trioxide.

[0005] As a further technical solution, the mass ratio of zinc nitrate hexahydrate to boron trioxide is 4:5.

[0006] As a further technical solution, the preparation method of the boron-zinc composite coated silica includes the following steps: A1. Disperse silica and silane coupling agent in an aqueous ethanol solution to obtain a silica suspension; A2. Disperse zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; A3. Mix boron trioxide with the silica suspension, then add zinc precursor solution, adjust the pH to 6.0~7.0, age, filter, wash, dry and calcine to obtain boron-zinc composite coated silica.

[0007] As a further technical solution, in step A1, the mass of the silane coupling agent is 3% to 5% of the mass of silicon dioxide.

[0008] As a further technical solution, in step A1, the silane coupling agent is silane coupling agent KH-550.

[0009] As a further technical solution, in step A1, the mass-to-volume ratio of silicon dioxide and ethanol aqueous solution is 1g:15mL; the mass fraction of ethanol in the ethanol aqueous solution is 80%.

[0010] As a further technical solution, in step A2, the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1.

[0011] As a further technical solution, in step A2, the mass-to-volume ratio of zinc nitrate hexahydrate and anhydrous ethanol is 1g:8mL.

[0012] As a further technical solution, in step A3, the calcination temperature is 500~700℃ and the time is 2~4h.

[0013] As a further technical solution, the toughening agent includes zirconium oxide and a stabilizer; the stabilizer includes gallium oxide and yttrium oxide.

[0014] The present invention relates to a silicon dioxide-based composite multilayer ceramic substrate using a combination of zirconium oxide, gallium oxide, and yttrium oxide as toughening agents. Zirconia undergoes a martensitic phase transformation from a tetragonal to a monoclinic phase during ceramic stress and crack propagation, resulting in a phase transformation toughening effect accompanied by a volume effect, effectively consuming crack propagation energy and inhibiting crack extension. Gallium oxide and yttrium oxide, as composite stabilizers, stabilize the high-temperature tetragonal phase structure of zirconium oxide, ensuring that the phase transformation toughening mechanism continues to function during sintering and use, thereby improving the fracture toughness of the silicon dioxide-based composite multilayer ceramic substrate.

[0015] As a further technical solution, the mass ratio of zirconium oxide to stabilizer is 8~10:1.

[0016] As a further technical solution, the mass ratio of gallium oxide to yttrium oxide is 1~3:6.

[0017] As a further technical solution, the sintering aid includes one or more of magnesium oxide, yttrium oxide, and calcium oxide.

[0018] As a further technical solution, the dispersant is acrylic acid.

[0019] As a further technical solution, the adhesive is polyvinyl butyral.

[0020] As a further technical solution, the plasticizer includes one or more of butyl benzyl phthalate, dioctyl phthalate, and dimethyl phthalate.

[0021] As a further technical solution, the solvent includes one or both of toluene and ethanol.

[0022] This invention also proposes a method for preparing a silica-based composite multilayer ceramic substrate, which includes the following steps: S1. Mix the raw materials of the silicon dioxide-based composite multilayer ceramic substrate to obtain a mixed slurry; S2. The mixed slurry is cast into a tape to obtain a cast strip; S3. The cast tape is subjected to cutting, lamination, debinding and calcination to obtain a silicon dioxide-based composite ceramic substrate.

[0023] As a further technical solution, in step S3, the lamination temperature is 50~70℃ and the pressure is 10~20MPa.

[0024] As a further technical solution, in step S3, the calcination temperature is 1300~1400℃ and the time is 3~6h.

[0025] The working principle and beneficial effects of this invention are as follows: This invention discloses a silica-based composite multilayer ceramic substrate using boron-zinc composite-coated silica as the main matrix material, which can significantly improve the flexural strength of the silica-based composite multilayer ceramic substrate. This boron-zinc composite-coated silica can uniformly coat zinc oxide and boron oxide on the surface of silica particles, forming a low-melting-point liquid phase during sintering. This effectively reduces the sintering temperature of the silica-based composite multilayer ceramic substrate, promotes the densification of the ceramic matrix, reduces internal porosity and defects, and improves the interfacial bonding between silica and components such as aluminum nitride, thereby synergistically improving the flexural strength of the silica-based composite multilayer ceramic substrate. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] In the following examples and comparative examples, the particle size of silicon dioxide was 1 μm; the particle size of aluminum nitride was 2 μm; the particle size of magnesium oxide was 0.5 μm; the particle size of zirconium oxide was 0.5 μm; the particle size of yttrium oxide was 0.3 μm; the particle size of gallium oxide was 0.5 μm; and the density of polyvinyl butyral was 1.07 g / cm³. 3 .

[0028] Example 1 A silica-based composite multilayer ceramic substrate comprises the following raw materials in parts by weight: 90 parts boron-zinc composite coated silica, 8 parts aluminum nitride, 3 parts magnesium oxide, 2 parts toughening agent, 2 parts acrylic acid, 5 parts polyvinyl butyral, 1 part butyl benzyl phthalate, and 100 parts toluene; the toughening agent comprises zirconium oxide and a stabilizer in a mass ratio of 8:1; the stabilizer is yttrium oxide. The preparation method of boron-zinc composite coated silica includes the following steps: A1. Disperse 100 parts of silica and 3 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 6 portions of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1 g:8 mL. A3. Mix 12 parts of boron trioxide and silica suspension, add zinc precursor solution, adjust pH to 6.0, age, filter, wash and dry, and calcine at 500℃ for 4 hours to obtain boron-zinc composite coated silica. A method for preparing a silica-based composite multilayer ceramic substrate includes the following steps: S1. Mix the raw materials of the silica-based composite multilayer ceramic substrate to obtain a mixed slurry; S2. The mixed slurry is cast into a tape. S3. After the cast tape is cut and stacked to 10 layers, it is laminated at a temperature of 50℃ and a pressure of 20MPa, then the adhesive is removed, and finally it is calcined at 1300℃ for 6 hours to obtain a silicon dioxide-based composite ceramic substrate.

[0029] Example 2 A silica-based composite multilayer ceramic substrate comprises the following raw materials in parts by weight: 95 parts boron-zinc composite coated silica, 9 parts aluminum nitride, 4 parts yttrium oxide, 3 parts toughening agent, 2.5 parts acrylic acid, 7 parts polyvinyl butyral, 1.5 parts dioctyl phthalate, and 125 parts ethanol; the toughening agent comprises zirconium oxide and a stabilizer in a mass ratio of 9:1; the stabilizer is yttrium oxide. The preparation method of boron-zinc composite coated silica includes the following steps: A1. Disperse 100 parts of silica and 4 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 6 portions of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1 g:8 mL. A3. Mix 12 parts of boron trioxide and silica suspension, add zinc precursor solution, adjust pH to 6.5, age, filter, wash, dry, and calcine at 600℃ for 3 hours to obtain boron-zinc composite coated silica. A method for preparing a silica-based composite multilayer ceramic substrate includes the following steps: S1. Mix the raw materials of the silica-based composite multilayer ceramic substrate to obtain a mixed slurry; S2. The mixed slurry is cast into a tape. S3. After the cast tape is cut and stacked to 10 layers, it is laminated at a temperature of 60℃ and a pressure of 15MPa, then the adhesive is removed, and finally it is calcined at 1350℃ for 5 hours to obtain a silicon dioxide-based composite ceramic substrate.

[0030] Example 3 A silica-based composite multilayer ceramic substrate comprises the following raw materials in parts by weight: 100 parts boron-zinc composite coated silica, 10 parts aluminum nitride, 5 parts calcium oxide, 4 parts toughening agent, 3 parts acrylic acid, 9 parts polyvinyl butyral, 2 parts dimethyl phthalate, and 150 parts ethanol; the toughening agent comprises zirconium oxide and a stabilizer in a mass ratio of 10:1; the stabilizer is yttrium oxide. The preparation method of boron-zinc composite coated silica includes the following steps: A1. Disperse 100 parts of silica and 5 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 6 portions of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1 g:8 mL. A3. Mix 12 parts of boron trioxide and silica suspension, add zinc precursor solution, adjust pH to 7.0, age, filter, wash, dry, and calcine at 700℃ for 2 hours to obtain boron-zinc composite coated silica. A method for preparing a silica-based composite multilayer ceramic substrate includes the following steps: S1. Mix the raw materials of the silica-based composite multilayer ceramic substrate to obtain a mixed slurry; S2. The mixed slurry is cast into a tape. S3. After the cast tape is cut and stacked to 10 layers, it is laminated at a temperature of 70℃ and a pressure of 10MPa, then the adhesive is removed, and finally it is calcined at 1400℃ for 3 hours to obtain a silicon dioxide-based composite ceramic substrate.

[0031] Example 4 Compared with Example 1, the only difference in this example is that the preparation method of boron-zinc composite coated silica in this example includes the following steps: A1. Disperse 100 parts of silica and 3 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 8 portions of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1 g:8 mL. A3. Mix 10 parts of boron trioxide with the suspension, then add zinc precursor solution, adjust the pH to 6.0 with 2 mol / L ammonia water, age, filter, wash, dry, and calcine at 500℃ for 4 hours to obtain boron-zinc composite coated silica.

[0032] Example 5 Compared with Example 1, the only difference in this example is that the preparation method of boron-zinc composite coated silica in this example includes the following steps: A1. Disperse 100 parts of silica and 3 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 10 parts of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1g:8mL. A3. Mix 8 parts of boron trioxide with the suspension, then add zinc precursor solution, adjust the pH to 6.0 with 2 mol / L ammonia water, age, filter, wash, dry, and calcine at 500℃ for 4 hours to obtain boron-zinc composite coated silica.

[0033] Example 6 Compared with Example 1, the only difference in this example is that the stabilizer in this example includes gallium oxide and yttrium oxide in a mass ratio of 1:6.

[0034] Example 7 Compared with Example 1, the only difference in this example is that the stabilizer in this example includes gallium oxide and yttrium oxide in a mass ratio of 2:6.

[0035] Example 8 Compared with Example 1, the only difference in this example is that the stabilizer in this example includes gallium oxide and yttrium oxide in a mass ratio of 3:6.

[0036] Example 9 The only difference between this embodiment and Example 1 is that the stabilizer in this embodiment is gallium oxide.

[0037] Comparative Example 1 Compared with Example 1, the only difference in this comparative example is that the boron-zinc composite coated silica is replaced with an equal amount of boron-coated silica. The method for preparing boron-coated silica includes the following steps: A1. Disperse 100 parts of silica and 3 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Mix 18 parts of boron trioxide and silica suspension, adjust the pH to 6.0 with 2 mol / L ammonia water, age the mixture, filter, wash and dry it, and then calcine it at 500℃ for 4 hours to obtain boron-coated silica.

[0038] Comparative Example 2 Compared with Example 1, the only difference in this comparative example is that boron-zinc composite coated silica is replaced with an equal amount of zinc coated silica. The preparation method of zinc-coated silica includes the following steps: A1. Disperse 100 parts of silica and 3 parts of silane coupling agent KH-550 in an 80% (w / w) aqueous ethanol solution to obtain a silica suspension; the mass-volume ratio of silica to aqueous ethanol solution is 1 g: 15 mL. A2. Disperse 18 portions of zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; the mass ratio of zinc nitrate hexahydrate to citric acid is 1.5:1; the mass-volume ratio of zinc nitrate hexahydrate to anhydrous ethanol is 1 g:8 mL. A3. The zinc precursor solution was mixed with the silica suspension, the pH was adjusted to 6.0 with 2 mol / L ammonia, aged, filtered, washed and dried, and then calcined at 500℃ for 4 hours to obtain zinc-coated silica.

[0039] Comparative Example 3 Compared with Example 1, the only difference in this comparative example is that the boron-zinc composite coated silica is replaced with an equal amount of silica.

[0040] Experimental Example 1 The silica-based composite ceramic substrates prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to bending strength tests according to the test method (three-point bending method) specified in standard GB / T6569-2006 "Test Method for Bending Strength of Fine Ceramics". The sample size was 40mm×4mm×3mm, and the lower support span was 30mm. The test results are shown in Table 1. Table 1. Bending strength test results of silica-based composite ceramic substrates

[0041] The results in Table 1 show that the addition of boron-zinc composite coated silica in this invention can improve the bending strength of silica-based composite ceramic substrates.

[0042] Experiment Example 2 The silica-based composite ceramic substrates prepared in Examples 1, 6-9 were subjected to fracture toughness testing according to the test method specified in standard GB / T 23806-2009 "Test Method for Fracture Toughness of Fine Ceramics - Single-sided Precracked Beam (SEPB) Method". A three-point bending model was used, and the sample I had dimensions of 18 mm × 4 mm × 3 mm. The test results are shown in Table 2. Table 2. Fracture toughness test results of silica-based composite ceramic substrates

[0043] The results in Table 2 show that the addition of toughening agents composed of zirconium oxide and stabilizers (including gallium oxide and yttrium oxide) can improve the fracture toughness of silicon dioxide-based composite ceramic substrates.

[0044] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A silicon dioxide-based composite multilayer ceramic substrate, characterized in that, The raw materials include the following components by weight: 90-100 parts boron-zinc composite coated silica, 8-10 parts aluminum nitride, 3-5 parts sintering aid, 2-4 parts toughening aid, 2-3 parts dispersant, 5-9 parts binder, 1-2 parts plasticizer, and 100-150 parts solvent. The boron-zinc composite coated silica comprises the following raw materials in parts by weight: 100 parts silica, 6-10 parts zinc nitrate hexahydrate, and 8-12 parts boron trioxide.

2. The silicon dioxide-based composite multilayer ceramic substrate according to claim 1, characterized in that, The mass ratio of zinc nitrate hexahydrate to boron trioxide is 4:

5.

3. The silicon dioxide-based composite multilayer ceramic substrate according to claim 1, characterized in that, The preparation method of the boron-zinc composite coated silica includes the following steps: A1. Disperse silica and silane coupling agent in an aqueous ethanol solution to obtain a silica suspension; A2. Disperse zinc nitrate hexahydrate and citric acid in anhydrous ethanol to obtain a zinc precursor solution; A3. Mix boron trioxide with the silica suspension, then add zinc precursor solution, adjust the pH to 6.0~7.0, age, filter, wash, dry and calcine to obtain boron-zinc composite coated silica.

4. The silicon dioxide-based composite multilayer ceramic substrate according to claim 1, characterized in that, The toughening agent includes zirconium oxide and a stabilizer; the stabilizer includes gallium oxide and yttrium oxide.

5. The silicon dioxide-based composite multilayer ceramic substrate according to claim 4, characterized in that, The mass ratio of zirconium oxide to stabilizer is 8~10:

1.

6. The silicon dioxide-based composite multilayer ceramic substrate according to claim 4, characterized in that, The mass ratio of gallium oxide to yttrium oxide is 1~3:

6.

7. The silicon dioxide-based composite multilayer ceramic substrate according to claim 1, characterized in that, The sintering aids include one or more of magnesium oxide, yttrium oxide, and calcium oxide.

8. A method for preparing a silica-based composite multilayer ceramic substrate, used to prepare a silica-based composite multilayer ceramic substrate as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Mix the raw materials of the silicon dioxide-based composite multilayer ceramic substrate to obtain a mixed slurry; S2. The mixed slurry is cast into a tape to obtain a cast strip; S3. The cast tape is subjected to cutting, lamination, debinding and calcination to obtain a silicon dioxide-based composite ceramic substrate.

9. The method for preparing a silica-based composite multilayer ceramic substrate according to claim 8, characterized in that, In step S3, the lamination temperature is 50~70℃ and the pressure is 10~20MPa.

10. The method for preparing a silicon dioxide-based composite multilayer ceramic substrate according to claim 8, characterized in that, In step S3, the calcination temperature is 1300~1400℃ and the time is 3~6h.

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