A low-temperature co-fired ceramic / glass composite material and its preparation method

Abstract

The present invention discloses a low-temperature co-fired ceramic / glass composite material and its preparation method and application, belonging to the technical field of ceramic materials. The present invention uses aluminum oxide (Al2O3) as a ceramic phase, CaO-B2O3-SiO2 (CBS) and zinc-boron glass as a glass phase, and adds K2O, CuO, and Nb2O5. When the low-temperature co-fired ceramic / glass composite material is used to prepare microelectronic components, its firing temperature can be reduced to 800°C to 850°C, and the dielectric constant can be reduced to 7.0-8.5, and the dielectric loss can be reduced to 0.3×10 ‑3 ~0.7×10 ‑3 (1MHz).

Description

Technical Field

[0001] The present invention relates to the technical field of organic resins, and in particular to a low-temperature co-fired ceramic / glass composite material and a preparation method thereof. Background Art

[0002] With the rapid development of microelectronics technology, electronic packaging is also experiencing rapid growth. Electronic packaging provides a variety of functions, including mechanical support, electrical connection, physical protection, external field shielding, stress relief, heat dissipation and moisture resistance, dimensional transitions, and standardization. Integrated circuit chips cannot fully function without packaging. Simultaneously, the continuous improvement of bare chip performance is placing higher demands on electronic packaging.

[0003] Low-temperature co-fired ceramics (LTCC) technology has become one of the fastest-growing and most widely used packaging technologies in recent years. This is primarily due to the low sintering temperature (<1000°C) of LTCC substrate materials, which allows for co-firing with most highly conductive metals, such as Ag, Pd, Au, and Cu. This significantly improves the functionality of the package. Furthermore, thick-film process equipment can be used, significantly reducing costs, achieving a balance between high performance and low cost, meeting the requirements of most packaging applications. While different performance requirements are sought for LTCC materials depending on the application scenario, generally, the lowest possible ceramic firing temperature and dielectric loss are required. Dielectric loss is the energy loss caused by the hysteresis effect of dielectric conductivity and polarization under the influence of an electric field. The lower the dielectric loss of the LTCC material, the lower the signal transmission attenuation during device operation. The low sintering temperature facilitates co-firing with low-melting-point, high-conductivity metals, such as Ag, Pd, Au, and Cu, reducing processing complexity and lowering production costs.

[0004] However, the firing temperature of existing LTCC is generally around 900° C. to 950° C., and still has relatively high dielectric loss. Summary of the Invention

[0005] In response to the above problems, the present invention provides a low-temperature co-fired ceramic / glass composite material and its preparation method and application, which effectively solves the technical problems of high ceramic firing temperature and high dielectric loss in the existing low-temperature co-fired ceramic technology. The present invention uses alumina (Al2O3) as the ceramic phase, CaO-B2O3-SiO2 (CBS) and zinc-boron glass as the glass phase, and effectively reduces the firing temperature when preparing the low-temperature co-fired ceramic / glass composite material by adding K2O, CuO, and Nb2O5, and the prepared low-temperature co-fired ceramic / glass composite material has lower dielectric loss.

[0006] The first object of the present invention is to provide a low-temperature co-fired ceramic / glass composite material, which is made of the following raw materials in parts by mass: 30 to 50 parts of CBS microcrystalline glass, 3 to 6 parts of zinc-boron glass, 50 to 70 parts of aluminum oxide, 4 to 6 parts of Nb2O5; 0.2 to 0.4 parts of K2O, and 3 to 5 parts of CuO; the total part by mass of the CBS microcrystalline glass and aluminum oxide is 100 parts.

[0007] The CBS glass-ceramics includes the following raw materials in percentage by weight: 35wt% to 45wt% CaCO3, 20wt% to 30wt% H3BO3, 25wt% to 35wt% SiO2, and the remainder is impurities, which totals 100%.

[0008] The zinc-boron glass comprises the following raw materials in percentage by mass: 40 wt% to 45 wt% ZnO, 40 wt% to 45 wt% B2O3, 10 wt% to 15 wt% K2O, and 1 wt% to 5 wt% SiO2, which totals 100%.

[0009] As a preferred embodiment, the impurities are 0.5wt% to 2wt% MgO, 1wt% to 2wt% P2O5 and 0.1wt% to 1wt% Na2O in mass percentage.

[0010] A second object of the present invention is to provide a method for preparing the above-mentioned low-temperature co-fired ceramic / glass composite material, comprising the following steps:

[0011] The raw materials of CBS glass-ceramics are weighed according to mass percentage, mixed, melted at 1400-1500° C. to obtain glass liquid, cooled and formed, and ground to obtain CBS glass-ceramics powder.

[0012] The raw materials of zinc-boron glass are weighed according to mass percentage, mixed, melted at 1400-1500° C. to obtain glass liquid, cooled and formed, and ground to obtain zinc-boron glass powder.

[0013] The CBS microcrystalline glass powder and zinc boron glass powder are used as the glass phase, alumina is used as the ceramic phase, Nb2O5, K2O and CuO are added, and then anhydrous ethanol is added, ball milled, and dried to obtain a composite powder.

[0014] The composite powder is granulated and tabletted to obtain a green body, which is heated to 500° C. for the first time and kept warm, and then heated to 800° C. to 850° C. for the second time and sintered to obtain a low-temperature co-fired ceramic / glass composite material.

[0015] As a preferred embodiment, the melting time is 4 to 5 hours.

[0016] As a preferred embodiment, the CBS glass-ceramics powder has a D10 of 0.829 μm, a D50 of 2.363 μm, and a D90 of 5.428 μm.

[0017] As a preferred embodiment, the first heating rate is 1°C / min, and the insulation time is 5 to 6 hours.

[0018] As a preferred embodiment, the second heating rate is 2-5°C / min, and the sintering time is 2-4h.

[0019] As a preferred embodiment, a polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation.

[0020] The third object of the present invention is to provide an application of the above-mentioned low-temperature co-fired ceramic / glass composite material in electromagnetic shielding.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention provides a low-temperature co-fired ceramic / glass composite material, which uses aluminum oxide as a ceramic phase, CBS glass-ceramics and zinc-boron glass as glass phases, and is prepared by adding K2O, CuO, and Nb2O5. The CBS glass-ceramics and zinc-boron glass of the present invention play a key role as glass phases in the densification of the ceramic material. The surface tension of the glass and the wettability of the glass on the ceramic particles are very important. The distribution of the glass at the sintering temperature will affect the sintering densification of the material. The present application uses CBS glass-ceramics and zinc-boron glass as the glass phases. CBS glass-ceramics, as a low-melting-point glass-ceramics, introduces new crystalline phases during the sintering process, increasing the pores in the sintered body. The precipitation of crystalline phases affects the dielectric properties of the material. Zinc-boron glass, as a low-melting-point glass, does not itself undergo crystallization. It provides a liquid phase to promote the densification of the ceramic / glass composite material, which can reduce the sintering temperature to approximately 800°C with minimal impact on the dielectric properties. The present invention adds transition metal oxide Nb2O5, alkali metal compound K2O, and metal oxide CuO to improve the dielectric properties and low-temperature sintering performance of the ceramic / glass composite material, reduce the loss in signal transmission, and reduce production costs. K2O reduces the softening point of glass, reduces the sintering temperature, and promotes liquid phase sintering efficiency. +The large ionic radius effectively reduces ion migration loss at low frequencies, and trace amounts of K2O reduce the dielectric loss of the material. Nb2O5 regulates the precipitated crystal phase, generating calcium niobate at a low sintering temperature. Calcium niobate has low dielectric loss, thereby reducing the dielectric loss of the system. The metal oxide CuO partially enters the glass network, improving the crystallization performance of the glass. The present invention uses the combined effects of K2O, Nb2O5, and CuO to regulate the crystallization process of the glass / ceramic composite material, lower the sintering temperature, and reduce the dielectric loss. The firing temperature can be reduced to 800°C to 850°C, while the dielectric constant is reduced to 7.0 to 8.5 and the dielectric loss is reduced to 0.3×10 -3 ~0.7×10 -3 (1MHz). BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of the preparation process of LTCC material in the present invention.

[0024] Figure 2 This is a cross-sectional SEM image of the low-temperature co-fired ceramic / glass composite material after sintering. DETAILED DESCRIPTION

[0025] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention is further described below with reference to specific examples, but the examples are not intended to limit the present invention. The following experimental and detection methods are conventional methods unless otherwise specified; the reagents and raw materials are commercially available unless otherwise specified.

[0026] For low-temperature co-fired ceramic materials, the preparation process generally requires the lowest possible ceramic firing temperature and the realization of low dielectric loss of the ceramic material. The lower the dielectric loss of the LTCC material, the lower the attenuation of signal transmission during device operation; the low sintering temperature facilitates the co-firing of the material with metals with low melting points and high electrical conductivity, such as Ag, Pd, Au, Cu, etc., reducing process difficulty and reducing production costs. However, the firing temperature of existing low-temperature co-fired ceramics is generally around 900℃~950℃, and there is still a high dielectric loss. In response to the above technical problems, the present invention provides a low-temperature co-fired ceramic / glass composite material and its preparation method and application.

[0027] The technical solution of the present invention is described in detail below.

[0028] The present invention first provides a low-temperature co-fired ceramic / glass composite material, which is made of the following raw materials in parts by mass: 30-50 parts of CBS microcrystalline glass, 3-6 parts of zinc-boron glass, 50-70 parts of aluminum oxide, 54-6 parts of Nb2O5; 0.2-0.4 parts of K2O, and 3-5 parts of CuO.

[0029] The CBS glass-ceramics includes the following raw materials in percentage by weight: 35wt% to 45wt% CaCO3, 20wt% to 30wt% H3BO3, 25wt% to 35wt% SiO2, and the remainder is impurities, which totals 100%.

[0030] The zinc-boron glass comprises the following raw materials in percentage by mass: 40 wt% to 45 wt% ZnO, 40 wt% to 45 wt% B2O3, 10 wt% to 15 wt% K2O, and 1 wt% to 5 wt% SiO2, which totals 100%.

[0031] In the above technical solution, alumina (Al2O3) is used as the ceramic phase, CaO-B2O3-SiO2 (CBS) and zinc boron glass are used as the glass phase, and by adding K2O, CuO, and Nb2O5, the firing temperature of the prepared low-temperature co-fired ceramic / glass composite material can be reduced to 750°C to 850°C when used to prepare microelectronic components. At the same time, the dielectric constant is reduced to 7.0 to 8.5, and the dielectric loss is reduced to 0.3×10 -3 ~0.7×10 -3 (1MHz).

[0032] It should be noted that the total mass fraction of the CBS glass-ceramics and aluminum oxide is 100 parts.

[0033] To further reduce dielectric loss, the impurities include 0.5-2% by weight of MgO, 1-2% by weight of P2O5, and 0.1-1% by weight of Na2O. MgO and Na2O act as glass network modifiers in the CBS glass-ceramics, disrupting and damaging the glass network integrity and promoting crystallization. P2O5, acting as a nucleating agent in the CBS glass-ceramics, promotes phase separation and crystallization. By promoting crystallization, the glass-ceramics improves its microwave dielectric properties, thereby reducing dielectric loss.

[0034] The present invention also provides a method for preparing the above-mentioned low-temperature co-fired ceramic / glass composite material, comprising the following steps:

[0035] The raw materials of CBS glass-ceramics are weighed according to mass percentage, mixed, melted at 1400-1500° C. for 4-5 hours to obtain glass liquid, cooled, formed, and ground to obtain CBS glass-ceramics powder.

[0036] The raw materials of zinc-boron glass are weighed according to mass percentage, mixed, melted at 1400-1500° C. for 4-5 hours to obtain glass liquid, cooled, formed, and ground to obtain zinc-boron glass powder.

[0037] The CBS microcrystalline glass powder and zinc boron glass powder are used as the glass phase, alumina is used as the ceramic phase, Nb2O5, K2O and CuO are added, and then anhydrous ethanol is added, ball milled, and dried to obtain a composite powder.

[0038] A polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation and tableting to obtain a green body. The green body is heated to 500°C at a rate of 1°C / min for the first time and kept warm for 5 to 6 hours. The green body is heated to 800°C to 850°C for the second time at a rate of 2°C / min to 5°C / min and sintered for 2 to 4 hours to obtain a low-temperature co-fired ceramic / glass composite material.

[0039] It should be noted that the D10, D50 and D90 of the CBS glass-ceramics powder are 0.829 μm, 2.363 μm and 5.428 μm, respectively.

[0040] The technical effects of the present invention are described below with reference to specific embodiments.

[0041] Example 1

[0042] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramics, 3 parts of zinc-boron glass, 65 parts of aluminum oxide, 55 parts of Nb2O, 0.2 parts of K2O, and 4 parts of CuO.

[0043] The CBS glass-ceramics includes the following raw materials in percentage by weight: 44 wt% CaCO3, 26 wt% H3BO3, 28 wt% SiO2, 1 wt% P2O5, 0.5 wt% MgO, and 0.5 wt% Na2O.

[0044] The zinc-boron glass includes the following raw materials in percentage by weight: 42 wt % ZnO, 42 wt % B2O3, 13 wt % K2O, and 3 wt % SiO2.

[0045] The preparation method of the above-mentioned low temperature co-fired ceramic / glass composite material is as follows: Figure 1 As shown, the following steps are included:

[0046] S1. Take a sample of 44wt% CaCO3, 26wt% H3BO3, 28wt% SiO2, 1wt% P2O5, 0.5wt% MgO, and 0.5wt% Na2O and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to fully mix them. After the mixed slurry is dried, the powder is placed in a platinum crucible. The crucible containing the powder is placed in a high-temperature furnace and kept warm at 1400°C for 4 hours to obtain a high-temperature molten glass liquid.

[0047] S2. Take samples of 42wt% ZnO, 42wt% B2O3, 13wt% K2O, and 3wt% SiO2 and put them into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to mix them thoroughly. After drying the mixed slurry, put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400℃ for 4h to obtain high-temperature molten glass liquid.

[0048] S3. The glass liquids obtained in S1 and S2 are poured into deionized water respectively for cooling and quenching to obtain glass blocks of uneven size. The obtained glass blocks are crushed to obtain glass powder, thereby obtaining CBS microcrystalline glass powder and zinc-boron glass powder.

[0049] S4. The obtained CBS microcrystalline glass powder, zinc-boron glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide, and metal oxide copper oxide are ball-milled in anhydrous ethanol at a speed of 280 r / min for 6 hours to obtain a mixed slurry, which is dried to obtain a composite powder, and a polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation, and tablets are pressed to obtain a green body, and the green body is heated to 500°C at a rate of 1°C / min for the first time, kept warm for 5-6 hours, and heated to 800°C at a rate of 5°C / min for a second time, and sintered for 2 hours to obtain a low-temperature co-fired ceramic / glass composite material.

[0050] Test: The sintered ceramic wafer was silvered on both sides. The performance of the wafer was tested by impedance analyzer 4291A. The results were as follows: dielectric constant 8.00, dielectric loss 0.4×10 -3 (1MHz).

[0051] Example 2

[0052] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramics, 3 parts of zinc-boron glass, 65 parts of aluminum oxide, 55 parts of Nb2O, 0.2 parts of K2O, and 4 parts of CuO.

[0053] The CBS glass-ceramics includes the following raw materials in percentage by weight: 44 wt% CaCO3, 26 wt% H3BO3, 28 wt% SiO2, 1 wt% P2O5, 0.5 wt% MgO, and 0.5 wt% Na2O.

[0054] The zinc-boron glass includes the following raw materials in percentage by weight: 42 wt % ZnO, 42 wt % B2O3, 13 wt % K2O, and 3 wt % SiO2.

[0055] The preparation method of the above-mentioned low temperature co-fired ceramic / glass composite material is as follows: Figure 1 As shown, the following steps are included:

[0056] S1. Take a sample of 44wt% CaCO3, 26wt% H3BO3, 28wt% SiO2, 1wt% P2O5, 0.5wt% MgO, and 0.5wt% Na2O and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to fully mix them. After the mixed slurry is dried, the powder is placed in a platinum crucible. The crucible containing the powder is placed in a high-temperature furnace and kept warm at 1400°C for 4 hours to obtain a high-temperature molten glass liquid.

[0057] S2. Take samples of 42wt% ZnO, 42wt% B2O3, 13wt% K2O, and 3wt% SiO2 and put them into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to mix them thoroughly. After drying the mixed slurry, put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400℃ for 4h to obtain high-temperature molten glass liquid.

[0058] S3. The glass liquids obtained in S1 and S2 are poured into deionized water respectively for cooling and quenching to obtain glass blocks of uneven size. The obtained glass blocks are crushed to obtain glass powder, thereby obtaining CBS microcrystalline glass powder and zinc-boron glass powder.

[0059] S4. The obtained CBS microcrystalline glass powder, zinc-boron glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide and metal oxide copper oxide are ball-milled in anhydrous ethanol at a speed of 280 r / min for 6 hours to obtain a mixed slurry, which is dried to obtain a composite powder, and a polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation, and tablets are pressed to obtain a green body, and the green body is heated to 500°C at a rate of 1°C / min for the first time, kept warm for 5-6 hours, and heated to 850°C for a second time at a rate of 5°C / min, and sintered for 2 hours to obtain a low-temperature co-fired ceramic / glass composite material.

[0060] Test: The sintered ceramic wafer was silvered on both sides. The performance of the wafer was tested by impedance analyzer 4291A. The results were as follows: dielectric constant 7.00, dielectric loss 0.7×10 -3 (1MHz).

[0061] Compared with Example 1, Example 2 only increases the sintering temperature from 800°C to 850°C, and the dielectric constant of the low-temperature co-fired ceramic / glass composite material decreases from 8.00 to 7.00, and the dielectric loss decreases from 0.4×10 -3 (1MHz) increased to 0.7×10 -3 (1MHz), therefore, the increase of sintering temperature will lead to a decrease in the dielectric constant of the material and an increase in the dielectric loss.

[0062] Example 3

[0063] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramics, 3 parts of zinc-boron glass, 65 parts of aluminum oxide, 55 parts of Nb2O, 0.2 parts of K2O, and 4 parts of CuO.

[0064] The CBS glass-ceramics includes the following raw materials in percentage by weight: 45 wt% CaCO3, 26 wt% H3BO3, 25 wt% SiO2, 1.5 wt% P2O5, 1.5 wt% MgO, and 1 wt% Na2O.

[0065] The zinc-boron glass includes the following raw materials in percentage by weight: 41 wt % ZnO, 42 wt % B2O3, 13 wt % K2O, and 4 wt % SiO2.

[0066] The method for preparing the above-mentioned low-temperature co-fired ceramic / glass composite material comprises the following steps:

[0067] S1. Take a sample of 45wt% CaCO3, 26wt% H3BO3, 25wt% SiO2, 1.5wt% P2O5, 1.5wt% MgO, and 1wt% Na2O and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to fully mix them. After drying the mixed slurry, put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400℃ for 4h to obtain high-temperature molten glass liquid.

[0068] S2. Take a sample of 41wt% ZnO, 42wt% B2O3, 13wt% K2O, and 4wt% SiO2 and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to mix them thoroughly. After the mixed slurry is dried, the powder is placed in a platinum crucible. The crucible containing the powder is placed in a high-temperature furnace and kept warm at 1400°C for 4 hours to obtain high-temperature molten glass liquid.

[0069] S3. The glass liquids obtained in S1 and S2 are poured into deionized water respectively for cooling and quenching to obtain glass blocks of uneven size. The obtained glass blocks are crushed to obtain glass powder, thereby obtaining CBS microcrystalline glass powder and zinc-boron glass powder.

[0070] S4. The obtained CBS microcrystalline glass powder, zinc-boron glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide and metal oxide copper oxide are ball-milled in anhydrous ethanol at a speed of 280r / min for 6h to obtain a mixed slurry, which is dried to obtain a composite powder. A polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation. Subsequently, the green blank with a diameter of 12mm and a thickness of about 1mm is dry-pressed through a mold. The green blank is then placed in a muffle furnace for debinding and sintering. The debinding process is heated to 500℃ for the first time at a rate of 1℃ / min and kept warm for 5h. Subsequently, the temperature is heated to 800℃ for the second time at a rate of 2℃ / min and kept warm for 3h for sintering to obtain a low-temperature co-fired ceramic / glass composite material.

[0071] Test: The sintered ceramic wafer was silvered on both sides. The performance of the wafer was tested by impedance analyzer 4291A. The results were as follows: dielectric constant 7.72, dielectric loss 0.3×10 -3 (1MHz).

[0072] Figure 2 This is a cross-sectional SEM image of the sintered low-temperature co-fired ceramic / glass composite material prepared in Example 3 of the present invention. Figure 2 It can be seen that the microstructure of the low-temperature co-fired ceramic / glass composite material of the present invention is relatively dense and has no large pores.

[0073] Example 4

[0074] A low-temperature co-fired ceramic / glass composite material is made from the following raw materials in parts by mass: 35 parts of CBS glass-ceramics, 3 parts of zinc-boron glass, 65 parts of aluminum oxide, 55 parts of Nb2O, 0.2 parts of K2O, and 4 parts of CuO.

[0075] The CBS glass-ceramics includes the following raw materials in percentage by weight: 40 wt% CaCO3, 28 wt% H3BO3, 30 wt% SiO2, 1.0 wt% P2O5, 0.5 wt% MgO, and 0.5 wt% Na2O.

[0076] The zinc-boron glass includes the following raw materials in percentage by weight: 41 wt % ZnO, 42 wt % B2O3, 13 wt % K2O, and 4 wt % SiO2.

[0077] The method for preparing the above-mentioned low-temperature co-fired ceramic / glass composite material comprises the following steps:

[0078] S1. Take a sample of 40wt% CaCO3, 28wt% H3BO3, 30wt% SiO2, 1.0wt% P2O5, 0.5wt% MgO, and 0.5wt% Na2O and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to fully mix them. After drying the mixed slurry, put the powder into a platinum crucible, put the crucible with the built-in powder into a high-temperature furnace, and keep it warm at 1400℃ for 4h to obtain high-temperature molten glass liquid.

[0079] S2. Take a sample of 41wt% ZnO, 42wt% B2O3, 13wt% K2O, and 4wt% SiO2 and put it into a planetary ball mill. Use a nylon ball mill jar with built-in zirconium balls and anhydrous ethanol as the ball milling medium to mix them thoroughly. After the mixed slurry is dried, the powder is placed in a platinum crucible. The crucible containing the powder is placed in a high-temperature furnace and kept warm at 1400°C for 4 hours to obtain high-temperature molten glass liquid.

[0080] S3. The glass liquids obtained in S1 and S2 are poured into deionized water respectively for cooling and quenching to obtain glass blocks of uneven size. The obtained glass blocks are crushed to obtain glass powder, thereby obtaining CBS microcrystalline glass powder and zinc-boron glass powder.

[0081] S4. The obtained CBS microcrystalline glass powder, zinc-boron glass powder, alumina ceramic powder, alkali metal oxide potassium oxide, transition metal oxide niobium pentoxide and metal oxide copper oxide are ball-milled in anhydrous ethanol at a speed of 280r / min for 6h to obtain a mixed slurry, which is dried to obtain a composite powder. A polyvinyl alcohol solution with a mass concentration of 5% is added to the composite powder for granulation. Subsequently, the green body is dry-pressed into a disc-shaped green body with a diameter of 12mm and a thickness of about 1mm through a mold. The green body is then placed in a muffle furnace for debinding and sintering. The debinding process is heated to 500℃ for the first time at a speed of 1℃ / min and kept warm for 5h. Subsequently, the temperature is heated to 825℃ for the second time at a speed of 2℃ / min and kept warm for 4h for sintering to obtain a low-temperature co-fired ceramic / glass composite material.

[0082] Test: The sintered ceramic wafer was silvered on both sides. The performance of the wafer was tested by impedance analyzer 4291A. The results were as follows: dielectric constant 8.07, dielectric loss 0.7×10 -3 (1MHz).

[0083] In summary, the low-temperature co-fired ceramic / glass composite material provided by the present invention has a significantly lower sintering temperature of 1500°C than that of alumina ceramic material, has lower energy consumption, and has a dielectric constant of 6.26 and a dielectric loss of 1.00×10-1 compared to pure CBS microcrystalline glass sintered at 850°C. -3(1MHz), the dielectric properties have been significantly improved, with excellent dielectric properties: dielectric constant 7.0 ~ 8.5, dielectric loss 0.3 × 10 -3 ~0.7×10 -3 (1MHz). It has a wide range of applications and stable performance. It can be used to manufacture microwave components such as resonators, filters, and dielectric ceramic substrates. The preparation process is simple and can be industrialized for mass production.

[0084] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A low temperature co-fired ceramic / glass composite material, characterized in that: Made from the following raw materials in parts by mass: 30-50 parts of CBS glass-ceramics, 3-6 parts of zinc-boron glass, 50-70 parts of aluminum oxide, 54-6 parts of Nb2O5, 0.2-0.4 parts of K2O, and 3-5 parts of CuO; the total parts by mass of the CBS glass-ceramics and aluminum oxide is 100 parts; The CBS glass-ceramics comprises the following raw materials in percentage by weight: 35 wt% to 45 wt% CaCO3, 20 wt% to 30 wt% H3BO3, 25 wt% to 35 wt% SiO2, and the remainder is impurities, totaling 100%; the impurities are 0.5 wt% to 2 wt% MgO, 1 wt% to 2 wt% P2O5, and 0.1 wt% to 1 wt% Na2O in percentage by weight; The zinc-boron glass includes the following raw materials in percentage by weight: 40wt%~45wt% ZnO, 40wt%~45wt% B2O3, 10wt%~15wt% K2O, and 1wt%~5wt% SiO2, which totals 100%.

2. A method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 1, characterized in that: The following steps are involved: Weigh the raw materials of CBS glass-ceramics according to their mass percentages, mix them, melt them at 1400°C to 1500°C to obtain glass liquid, cool them into shape, and grind them to obtain CBS glass-ceramics powder; Weigh the raw materials of zinc-boron glass according to mass percentage, mix them, melt them at 1400-1500° C. to obtain glass liquid, cool them into shape, grind them, and obtain zinc-boron glass powder; The CBS glass-ceramics powder and zinc-boron glass powder are used as the glass phase, alumina is used as the ceramic phase, Nb2O5, K2O and CuO are added, and then anhydrous ethanol is added, ball milled, and dried to obtain a composite powder; The composite powder is granulated and tabletted to obtain a green body, which is heated to 500° C. for the first time and kept warm, and then heated to 800° C. to 850° C. for the second time and sintered to obtain a low-temperature co-fired ceramic / glass composite material.

3. The method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 2, characterized in that: The melting time is 4h~5h.

4. The method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 2, characterized in that: The D10, D50 and D90 of the CBS glass-ceramic powder are 0.829 μm, 2.363 μm and 5.428 μm, respectively.

5. The method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 2, characterized in that: The first heating rate is 1°C / min, and the holding time is 5h-6h.

6. The method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 2, characterized in that: The second heating rate is 2°C / min to 5°C / min, and the sintering time is 2h to 4h.

7. The method for preparing the low-temperature co-fired ceramic / glass composite material according to claim 2, characterized in that: A polyvinyl alcohol solution with a mass concentration of 5% was added to the composite powder for granulation.

8. Use of the low-temperature co-fired ceramic / glass composite material according to claim 1 in electromagnetic shielding.

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