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CN117049864A - Low-temperature co-fired ceramic green ceramic tape, preparation method, ceramic circuit and application - Google Patents

Low-temperature co-fired ceramic green ceramic tape, preparation method, ceramic circuit and application Download PDF

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CN117049864A
CN117049864A CN202311314493.1A CN202311314493A CN117049864A CN 117049864 A CN117049864 A CN 117049864A CN 202311314493 A CN202311314493 A CN 202311314493A CN 117049864 A CN117049864 A CN 117049864A
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temperature
low
fired ceramic
ceramic
borosilicate glass
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仪凯
陈均优
王琰诏
张庆猛
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GRIMN Engineering Technology Research Institute Co Ltd
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GRIMN Engineering Technology Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
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    • H05K1/0306Inorganic insulating substrates, e.g. ceramic, glass
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365Borosilicate glass
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Abstract

The invention belongs to the technical field of ceramic materials, and particularly relates to a low-temperature co-fired ceramic green ceramic tape, a preparation method, ceramic, a ceramic circuit and application. According to the invention, fine calcium sodium borosilicate glass powder and spherical alumina are selected as inorganic powder in the green ceramic tape, and a mixed solvent, a mixed binder, a corresponding plasticizer and a corresponding dispersing agent are selected as organic components, so that the anisotropic problem of sintering shrinkage of the traditional LTCC green ceramic tape is effectively solved. The low-temperature co-fired ceramic green ceramic tape prepared by the method has a flat and smooth surface, and X, Y, Z sintering shrinkage is 15% +/-0.5%, so that co-firing with gold slurry can be realized at about 850 ℃. The ceramics prepared by adopting the low-temperature co-fired ceramic green ceramic tape of the invention are low-order and low-costThe temperature co-fired ceramic has excellent dielectric properties, and has a dielectric constant of 7-8 at 8GHz and a dielectric loss of less than 3×10 ‑3

Description

Low-temperature co-fired ceramic green ceramic tape, preparation method, ceramic circuit and application
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a low-temperature co-fired ceramic green ceramic tape, a preparation method, ceramic, a ceramic circuit and application.
Background
Along with the rapid development of microelectronic information technology, the electronic complete machine further promotes the miniaturization, integration and high-frequency of electronic components in the aspects of miniaturization, portability, multifunction, digitalization and high reliability, which requires the performances of high propagation speed, high wiring density and the like of the integrated circuit board. Low Temperature Cofired Ceramics (LTCCs) have been widely focused and used for their advantages of good high frequency characteristics, high transmission characteristics, low sintering temperature, and good process compatibility. The LTCC technology is a multilayer circuit technology which is produced in the 80 s of the last century, and is characterized in that firstly raw porcelain powder is adopted to form raw porcelain belts through tape casting, then punching, filling through hole metal slurry, printing circuit patterns and printing resistance are carried out on each layer of raw porcelain belts, and finally, each layer of raw porcelain plates are aligned and laminated, pressed and sintered into a whole at the temperature of 850-900 ℃ to form a multilayer ceramic circuit.
The key factors affecting the quality of LTCC green tapes are the components of the material. The components, content, granularity and morphology of the ceramic powder in the green ceramic tape directly influence the performance of the green ceramic tape. The traditional LTCC green ceramic tape has large sintering shrinkage rate, and is easy to generate mismatch phenomenon in the co-firing process with metal slurry to cause warping, which seriously affects the reliability of the LTCC device and restricts the further development of the LTCC device towards the miniaturization and high reliability.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a low-temperature co-fired ceramic green tape, a preparation method, co-fired ceramic and application thereof, solves the problem of variability of sintering shrinkage of the traditional LTCC green tape, and improves dielectric properties of the LTCC. The invention specifically comprises the following contents:
the low-temperature co-fired ceramic green ceramic tape comprises the following components: 40-70wt% of calcium sodium borosilicate glass, 40-70wt% of spherical alumina and 10-15wt% of casting medium; the average grain diameter of the calcium sodium borosilicate glass is 2-3 mu m; the average particle size of the spherical alumina is 2-5 mu m; the casting medium includes: 80-90 wt% of mixed solvent, 6-12 wt% of binder, 3-8 wt% of plasticizer and 1-3 wt% of dispersing agent.
Preferably, the calcium sodium borosilicate glass comprises the following components: caO 0-20wt%, na 2 O 0~5wt%、B 2 O 3 10~30wt%、SiO 2 40~70wt%、Al 2 O 3 0~20wt%、K 2 O 0~8wt%、MgO 1~15wt%、Cr 2 O 3 0.5~1wt%。
Preferably, the mixed solvent is a mixture of two or three of ethanol, toluene and butanone; the binder is a mixture of polymethyl methacrylate and methacrylic acid; the plasticizer is dibutyl phthalate; the dispersing agent is castor oil.
Preferably, the components of the mixed solvent include: 40-60 wt% of ethanol, 20-40 wt% of toluene and 10-30 wt% of butanone; the grouping of the binder includes: 70-80 wt% of polymethyl methacrylate and 20-30 wt% of methacrylic acid.
Preferably, the sintering temperature of the low-temperature co-fired ceramic green ceramic tape is 820-860 ℃ and the sintering shrinkage rate of X, Y, Z is 15% +/-0.5%.
The preparation method of the low-temperature co-fired ceramic green tape comprises the following steps:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Proportionally placing the raw materials into melting equipment, preserving heat for 2-6 hours at 1550-1600 ℃, and then adding deionized water into the melting equipment to obtain transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: crushing the fragments of the calcium sodium borosilicate glass into calcium sodium borosilicate glass powder with the average particle size of 2-3 mu m;
(3) Preparing low-temperature co-fired ceramic powder: the method comprises the steps of (1) forming a mixture of calcium sodium borosilicate glass powder and spherical alumina according to the mass ratio of (40-70): (40-70), ball-milling the mixture together with zirconia balls and ethanol, and then drying to obtain low-temperature co-fired ceramic powder;
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: and adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain the low-temperature co-fired ceramic green tape.
Preferably, the method for crushing the calcium sodium borosilicate glass fragments in the step (2) comprises the following steps: mixing the calcium sodium borosilicate glass fragments with deionized water, taking zirconia balls as a ball milling medium, performing ball milling according to the mass ratio of the calcium sodium borosilicate glass fragments to the zirconia balls to the deionized water= (0.8-1.2): (3.5-4.5): (0.8-1.2), wherein the ball milling time is 8-12 h, and then drying in an oven at 120-140 ℃ for 6-8 h to obtain the calcium sodium borosilicate glass powder with the average particle size of 2-3 mu m.
Preferably, the ball milling method in the step (3) comprises the following steps: mixing and ball milling according to the mass ratio of the mixture of zirconia balls and ethanol= (0.8-1.2) to (3.5-4.5) to (0.8-1.2), wherein the ball milling time is 2-4 hours, and then drying in an oven at 70-90 ℃ for 4-6 hours to obtain the low-temperature co-fired ceramic powder.
Preferably, the ball milling time in the step (4) is 24-36 hours, the drying temperature is 40-60 ℃, and the drying time is 3-4 hours.
A ceramic prepared by adopting the low-temperature co-fired ceramic green ceramic tape.
Preferably, the dielectric constant of the ceramic at 8GHz is 7-8, and the dielectric loss is less than 3 x 10 -3
A ceramic circuit prepared by adopting the low-temperature co-fired ceramic green ceramic tape.
Preferably, the low-temperature co-fired ceramic green tape and the gold slurry are co-fired at 820-860 ℃ to obtain the ceramic circuit.
The application of the ceramic circuit in electronic components.
The invention has the beneficial effects that:
(1) According to the invention, fine calcium sodium borosilicate glass powder and spherical alumina are selected as inorganic powder in the green ceramic tape, and a mixed solvent, a mixed binder, a corresponding plasticizer and a corresponding dispersing agent are selected as organic components, so that the anisotropic problem of sintering shrinkage of the traditional LTCC green ceramic tape is effectively solved. The low-temperature co-fired ceramic green ceramic tape prepared by the method has a flat and smooth surface, and X, Y, Z sintering shrinkage is 15% +/-0.5%, so that co-firing with gold slurry can be realized at about 850 ℃.
(2) The ceramic prepared by the low-temperature co-fired ceramic green ceramic tape is low-order low-temperature co-fired ceramic, has excellent dielectric property, and has a dielectric constant of 7-8 and a dielectric loss of less than 3 x 10 at 8GHz -3
(3) After punching, filling and printing, the low-temperature co-fired ceramic green ceramic tape disclosed by the invention can be co-fired with gold paste at 850 ℃ to form a ceramic circuit, and the prepared ceramic circuit is applied to electronic components, so that the electrical performance of the electronic components can be improved, and the LTCC (Low temperature Co-fired ceramic) device is further developed towards the miniaturization and high reliability directions.
Drawings
FIG. 1 is a microscopic topography of a ceramic sintered from a green tape of a low temperature cofired ceramic as disclosed herein;
FIG. 2 is a micrograph of a ceramic circuit of the present disclosure;
fig. 3 is a physical diagram of a ceramic circuit according to the present disclosure.
Detailed Description
The invention will now be described in detail with reference to figures 1-3 and the detailed description. FIG. 1 is a microscopic topography of a ceramic sintered from a green tape of a low temperature cofired ceramic as disclosed herein; FIG. 2 is a micrograph of a ceramic circuit of the present disclosure; fig. 3 is a physical diagram of a ceramic circuit according to the present disclosure. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
The low-temperature co-fired ceramic green ceramic tape comprises the following components: 40-70 wt% (e.g., 42wt%, 45wt%, 48wt%, 50wt%, 55wt%, 60wt%, 65wt%, 68wt%, etc.), and 10-15 wt% (e.g., 10.5wt%, 11wt%, 12wt%, 13wt%, 14wt%, 14.5wt%, etc.) of the casting medium. The calcium sodiumThe borosilicate glass has an average particle diameter of 2 to 3 [ mu ] m (e.g., 2.1 [ mu ] m, 2.2 [ mu ] m, 2.4 [ mu ] m, 2.6 [ mu ] m, 2.8 [ mu ] m, etc.); the average particle diameter of the spherical alumina is 2 to 5 [ mu ] m (e.g., 2.1 [ mu ] m, 2.2 [ mu ] m, 2.5 [ mu ] m, 3 [ mu ] m, 3.5 [ mu ] m, 4 [ mu ] m, 4.5 [ mu ] m, etc.); the casting medium includes: 80-90 wt% (e.g., 82wt%, 84wt%, 86wt%, 88wt%, 89wt%, etc.), 6-12 wt% (e.g., 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 11.5wt%, etc.), 3-8 wt% (e.g., 3.2wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 6wt%, 7wt%, etc.), 1-3 wt% (e.g., 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.2wt%, 2.5wt%, 2.8wt%, etc.) of a plasticizer. The calcium sodium borosilicate glass comprises the following components: caO 0 to 20wt% (for example, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 15wt%, 18wt%, etc.), na 2 O0-5 wt% (e.g., 1wt%, 2wt%, 3wt%, 4wt%, 4.5wt%, etc.), B 2 O 3 10 to 30wt% (e.g., 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, etc.), siO 2 40 to 70wt% (e.g., 42wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 68wt%, etc.), al 2 O 3 0 to 20wt% (e.g., 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 15wt%, 18wt%, etc.), K 2 0 to 8wt% of O (e.g., 1wt%, 2wt%, 3wt%, 5wt%, 6wt%, 7wt%, 8wt%, etc.), 1 to 15wt% of MgO (e.g., 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, etc.), cr 2 O 3 0.5 to 1wt% (e.g., 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, etc.). The mixed solvent component comprises: 40-60 wt% of ethanol (e.g., 42wt%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt%, 58wt%, etc.), 20-40 wt% of toluene (e.g., 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 38wt%, etc.), 10-30 wt% of butanone (e.g., 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, etc.); the grouping of the binder includes: 70-80 wt% (e.g., 72wt%, 74wt%, 76wt%, 78wt%, 79wt%, 80wt%, etc.) of polymethyl methacrylate, 20-30 wt% (e.g., 22wt%, 24wt%, 26wt%, 28wt%, 29wt%, etc.) of methacrylic acid; the plasticizer is dibutyl phthalate; the dispersing agent is castor oil.
The sintering temperature of the low-temperature co-fired ceramic green tape prepared by the method is 820-860 ℃ (such as 830 ℃, 835 ℃, 840 ℃, 845 ℃, 846 ℃, 848 ℃, 849 ℃, 850 ℃ and the like), and the sintering shrinkage rate of X, Y, Z is 15% ± 0.5% (such as 14.5%, 14.8%, 15.0%, 15.2%, 15.4%, 15.5% and the like).
The preparation method of the low-temperature co-fired ceramic green tape comprises the following steps:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Placing raw materials in a melting device according to a proportion, preserving heat for 2-6 hours (such as 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.5 hours, 4 hours, 5 hours, 5.5 hours and the like) at 1550-1600 ℃ (such as 1552 ℃, 1555 ℃, 1556 ℃, 1558 ℃ and 1559 ℃ and the like), and then adding deionized water into the melting device to obtain transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: mixing calcium sodium borosilicate glass fragments with deionized water, taking zirconia balls as a ball milling medium, ball milling according to the mass ratio of (3.5-4.5) to (0.8-1.2) of (0.8:3.5:0.8, 0.9:3.8:1, 1:4:1, 1.1:4.2:1.2, 1.2:4.5:1.2 and the like) of the calcium sodium borosilicate glass fragments to the zirconia balls according to the mass ratio of the deionized water= (8.5-1.2), and then drying in an oven (for example, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h, 7.8 m and the like) at 120-140 ℃ (for example, 122 ℃, 125 ℃, 128 ℃, 130 ℃, 132 ℃, 135 ℃ and the like) for 8-12 h (for example, the average particle size of the calcium sodium silicate glass particles of 2.2 μm, 2 μm, and the glass particles of 2.2 μm, and the like, wherein the ball milling time is 8-12 μm;
(3) Preparing low-temperature co-fired ceramic powder: mixing and ball milling (the specific proportion can be 0.8:3.5:0.8, 0.9:3.8:1, 1:4:1, 1.1:4.2, 1.2:4.5, 1.2:70, etc.) the calcium sodium borosilicate glass powder and the spherical alumina according to the mass ratio of (40-70) (the specific proportion can be 40:40, 40:50, 45:60, 50:65, 60:70, 70:70, etc.), mixing and ball milling (the specific proportion can be 0.8:3.5:0.8, 0.9:3.8:1, 1:4.2:1.2, 1.2:4.5:1.2, etc.), the ball milling time is 2-4 hours (for example, 2.5 hours, 2.8 hours, 3 hours, 3.2 hours, 3.5 hours, 3.8 hours, etc.), the mixing and ball milling (for example, 72 ℃ at a temperature of 75 ℃ at a temperature of 78 ℃, 82 ℃ and a temperature of 88 ℃ and the like), and drying in an oven (for example, 4.5 hours, 5 hours, and the like);
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain a low-temperature co-fired ceramic green ceramic tape; the ball milling time is 24-36 h (such as 25h, 28h, 30h, 32h, 34h, 35h, etc.), the drying temperature is 40-60 ℃ (such as 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃ etc.), and the drying time is 3-4 h (such as 3.2h, 3.4h, 3.5h, 3.6h, 3.8h, 4h, etc.).
A ceramic (microstructure is shown in figure 1) prepared by adopting the low-temperature co-fired ceramic green ceramic tape. The dielectric constant of the ceramic at 8GHz is 7-8, and the dielectric loss is less than 3 multiplied by 10 -3
A ceramic circuit (as shown in figures 2 and 3) prepared by using the low temperature co-fired ceramic green tape. The preparation method of the ceramic circuit comprises the following steps: and co-firing the low-temperature co-fired ceramic green tape with gold slurry at 820-860 ℃ (e.g. 830 ℃, 835 ℃, 840 ℃, 845 ℃, 846 ℃, 848 ℃, 849 ℃, 850 ℃ and the like) to obtain the ceramic circuit. The ceramic circuit can be applied to electronic components.
Example 1
(1) Weighing 6kg of CaO and 6kg of Na according to the weight percentage 2 O 2kg、B 2 O 3 16kg、SiO 2 67kg、Al 2 O 3 4kg、K 2 O 2kg、MgO 2.5kg、Cr 2 O 3 0.5 kg, placing the weighed powder into a platinum crucible, preserving heat for 3 hours at 1550-1600 ℃, and pouring into deionized water to obtain transparent and uniform glass fragments;
(2) Mixing glass slag with deionized water, and taking zirconia balls as ball milling media according to the following steps: ball: ball milling is carried out for 10 hours in a ratio of deionized water=1:4:1, and then the ball milling is carried out in a baking oven at 130 ℃ for 6 hours, so that glass powder with an average particle size of 1-3 mu m is obtained;
(3) The weight portion ratio is 50:50, glass powder and alumina powder form a mixture, and ethanol medium is added according to the mixture: zirconia balls: mixing and ball milling ethanol=1:3:1 for 3 hours, and then placing the mixture in an oven at 80 ℃ for 5 hours to obtain low-temperature co-fired ceramic powder;
(4) Adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, ball milling for 28 hours, vacuum defoaming, casting and forming, and drying to obtain a green ceramic tape, wherein: the drying temperature is 50 ℃, the drying time is 4 hours, the prepared green porcelain tape is sliced and laminated, and then the green porcelain tape is subjected to pressure maintaining for 10 minutes at 70 ℃ and 20Mpa in a hot press, so that the viscosity of the slurry is ensured to be 1-2 Pa.S.
Table 1 contents of the components of the low temperature co-fired ceramic green tape of calcium sodium borosilicate glass-alumina
Cutting the green ceramic tape after lamination and hot pressing into required size, placing in an electric furnace, discharging glue, heating to a set temperature, and sintering at a constant temperature. The specific steps of sintering are as follows: heating the low-temperature co-fired ceramic material from room temperature to 450 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, heating to 850 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes to obtain the ceramic. The performance test for the sintered magnet is shown in table 2.
TABLE 2 sintering and dielectric Properties of Low temperature Co-fired ceramic green tape of calcium sodium borosilicate glass-alumina
Example 2
The preparation method of the low-temperature co-fired ceramic green tape comprises the following steps:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Proportionally placing the raw materials into a melting device, preserving heat at 1552 ℃ for 2.5h, and then adding deionized water into the melting deviceThe sub water is used for obtaining transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: mixing the calcium sodium borosilicate glass fragments with deionized water, ball-milling the mixture according to the mass ratio of the zirconia balls to the deionized water=1:4:0.9 by taking zirconia balls as a ball-milling medium, wherein the ball-milling time is 11 hours, and then drying the mixture in a drying oven at 125 ℃ for 7 hours to obtain calcium sodium borosilicate glass powder with the average particle size of 2.5 mu m;
(3) Preparing low-temperature co-fired ceramic powder: the preparation method comprises the steps of (1) forming a mixture by calcium sodium borosilicate glass powder and spherical alumina according to the mass ratio of 55:62, mixing and ball milling according to the mass ratio of the mixture to zirconia balls to ethanol=1:4:1, wherein the ball milling time is 2.5 hours, and then drying in a drying oven at 75 ℃ for 4.5 hours to obtain low-temperature co-fired ceramic powder;
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain a low-temperature co-fired ceramic green ceramic tape; the ball milling time is 25 hours, the drying temperature is 45 ℃, and the drying time is 3.2 hours.
The dielectric constant of the ceramic prepared by the low-temperature co-fired ceramic green ceramic tape prepared by the embodiment is 7.2 at 8GHz, and the dielectric loss is less than 3 multiplied by 10 -3 . And co-firing the low-temperature co-fired ceramic green ceramic tape and the gold slurry at 825 ℃ to obtain the ceramic circuit. The ceramic circuit can be applied to electronic components.
Example 3
The preparation method of the low-temperature co-fired ceramic green tape comprises the following steps:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Proportionally placing the raw materials into melting equipment, preserving heat at 1555 ℃ for 4 hours, and then adding deionized water into the melting equipment to obtain transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: mixing the calcium sodium borosilicate glass fragments with deionized water, ball-milling the mixture according to the mass ratio of the zirconia balls to the deionized water=1.1:3.8:1 by taking the zirconia balls as a ball milling medium, wherein the ball milling time is 10 hours, and then drying the mixture in a 130 ℃ oven for 7.5 hours to obtain calcium sodium borosilicate glass powder with the average particle diameter of 2 mu m;
(3) Preparing low-temperature co-fired ceramic powder: mixing and ball milling calcium sodium borosilicate glass powder and spherical alumina according to the mass ratio of 60:50, mixing and ball milling according to the mass ratio of the mixture to zirconia balls to ethanol=0.9:3.7:1.1 for 3.5 hours, and then drying in an oven at 80 ℃ for 5.5 hours to obtain low-temperature co-fired ceramic powder;
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain a low-temperature co-fired ceramic green ceramic tape; the ball milling time is 30 hours, the drying temperature is 50 ℃, and the drying time is 3.8 hours.
The dielectric constant of the ceramic prepared by the low-temperature co-fired ceramic green ceramic tape prepared by the embodiment is 7.8 at 8GHz, and the dielectric loss is less than 2 multiplied by 10 -3 . And co-firing the low-temperature co-fired ceramic green ceramic tape and the gold paste at 840 ℃ to obtain the ceramic circuit. The ceramic circuit can be applied to electronic components.
Example 4
The preparation method of the low-temperature co-fired ceramic green tape comprises the following steps:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Proportionally placing the raw materials into melting equipment, preserving heat for 6 hours at 1600 ℃, and then adding deionized water into the melting equipment to obtain transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: mixing the calcium sodium borosilicate glass fragments with deionized water, ball-milling the mixture according to the mass ratio of the zirconia balls to the deionized water=1.2:3.5:0.8 by taking the zirconia balls as a ball milling medium, wherein the ball milling time is 12 hours, and then drying the mixture in a 140 ℃ oven for 6-8 hours to obtain calcium sodium borosilicate glass powder with the average particle size of 2-3 mu m;
(3) Preparing low-temperature co-fired ceramic powder: mixing and ball milling calcium sodium borosilicate glass powder and spherical alumina according to the mass ratio of 70:40, mixing and ball milling zirconia balls according to the mass ratio of the mixture to ethanol=0.8:4.5:0.9 for 4 hours, and then drying in a 90 ℃ oven for 6 hours to obtain low-temperature co-fired ceramic powder;
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain a low-temperature co-fired ceramic green ceramic tape; the ball milling time is 36 hours, the drying temperature is 60 ℃, and the drying time is 4 hours.
The dielectric constant of the ceramic prepared by the low-temperature co-fired ceramic green ceramic tape prepared by the embodiment is 8 at 8GHz, and the dielectric loss is less than 1.5x10 -3 . And co-firing the low-temperature co-fired ceramic green ceramic tape and the gold paste at 860 ℃ to obtain the ceramic circuit. The ceramic circuit can be applied to electronic components.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (14)

1. The low-temperature co-fired ceramic green tape is characterized by comprising the following components: 40-70wt% of calcium sodium borosilicate glass, 40-70wt% of spherical alumina and 10-15wt% of casting medium; the average grain diameter of the calcium sodium borosilicate glass is 2-3 mu m; the average particle size of the spherical alumina is 2-5 mu m; the casting medium includes: 80-90 wt% of mixed solvent, 6-12 wt% of binder, 3-8 wt% of plasticizer and 1-3 wt% of dispersing agent.
2. The low temperature co-fired ceramic green tape of claim 1, wherein the calcium sodium borosilicate glass comprises: caO 0-20wt%, na 2 O 0~5wt%、B 2 O 3 10~30wt%、SiO 2 40~70wt%、Al 2 O 3 0~20wt%、K 2 O 0~8wt%、MgO 1~15wt%、Cr 2 O 3 0.5~1wt%。
3. The low-temperature co-fired ceramic green tape according to claim 1, wherein the mixed solvent is a mixture of two or three of ethanol, toluene and butanone; the binder is a mixture of polymethyl methacrylate and methacrylic acid; the plasticizer is dibutyl phthalate; the dispersing agent is castor oil.
4. A low temperature co-fired ceramic green tape according to claim 3, wherein the composition of the mixed solvent comprises: 40-60 wt% of ethanol, 20-40 wt% of toluene and 10-30 wt% of butanone; the grouping of the binder includes: 70-80 wt% of polymethyl methacrylate and 20-30 wt% of methacrylic acid.
5. The low-temperature co-fired ceramic green tape according to claim 3, wherein the sintering temperature of the low-temperature co-fired ceramic green tape is 820-860 ℃ and the sintering shrinkage rate of X, Y, Z is 15% ± 0.5%.
6. A method for preparing a low temperature co-fired ceramic green tape according to any one of claims 1 to 5, comprising the steps of:
(1) Preparing calcium sodium borosilicate glass: caO, na 2 O、B 2 O 3 、SiO 2 、Al 2 O 3 、K 2 O、MgO、Cr 2 O 3 Proportionally placing the raw materials into melting equipment, preserving heat for 2-6 hours at 1550-1600 ℃, and then adding into the melting equipmentIonized water to obtain transparent and uniform calcium sodium borosilicate glass fragments;
(2) Preparing calcium sodium borosilicate glass powder: crushing the fragments of the calcium sodium borosilicate glass into calcium sodium borosilicate glass powder with the average particle size of 2-3 mu m;
(3) Preparing low-temperature co-fired ceramic powder: the method comprises the steps of (1) forming a mixture of calcium sodium borosilicate glass powder and spherical alumina according to the mass ratio of (40-70): (40-70), ball-milling the mixture together with zirconia balls and ethanol, and then drying to obtain low-temperature co-fired ceramic powder;
(4) Preparing a low-temperature co-fired ceramic green porcelain tape: and adding a solvent, a binder, a plasticizer and a dispersing agent into the low-temperature co-fired ceramic powder, and then sequentially performing ball milling, vacuum defoamation, tape casting and forming and drying to obtain the low-temperature co-fired ceramic green tape.
7. The method for preparing low-temperature co-fired ceramic according to claim 6, wherein the method for crushing the calcium sodium borosilicate glass fragments in the step (2) is as follows: mixing the calcium sodium borosilicate glass fragments with deionized water, taking zirconia balls as a ball milling medium, performing ball milling according to the mass ratio of the calcium sodium borosilicate glass fragments to the zirconia balls to the deionized water= (0.8-1.2): (3.5-4.5): (0.8-1.2), wherein the ball milling time is 8-12 h, and then drying in an oven at 120-140 ℃ for 6-8 h to obtain the calcium sodium borosilicate glass powder with the average particle size of 2-3 mu m.
8. The method for preparing low-temperature co-fired ceramic according to claim 6, wherein the ball milling method in the step (3) is as follows: mixing and ball milling according to the mass ratio of the mixture of zirconia balls and ethanol= (0.8-1.2) to (3.5-4.5) to (0.8-1.2), wherein the ball milling time is 2-4 hours, and then drying in an oven at 70-90 ℃ for 4-6 hours to obtain the low-temperature co-fired ceramic powder.
9. The method for preparing low-temperature co-fired ceramic according to claim 6, wherein the ball milling time in the step (4) is 24-36 h, the drying temperature is 40-60 ℃, and the drying time is 3-4 h.
10. A ceramic prepared using the low temperature cofired ceramic green tape of any one of claims 1 to 5.
11. The ceramic of claim 10, wherein the ceramic has a dielectric constant of 7-8 and a dielectric loss of less than 3 x 10 at 8GHz -3
12. A ceramic circuit prepared using the low temperature co-fired ceramic green tape of any of claims 1-5.
13. A method for manufacturing a ceramic circuit according to claim 12, wherein the low temperature co-fired ceramic green tape and the gold paste are co-fired at 820-860 ℃ to obtain the ceramic circuit.
14. Use of the ceramic circuit of claim 12 in an electronic component.
CN202311314493.1A 2023-10-11 2023-10-11 Low-temperature co-fired ceramic green ceramic tape, preparation method, ceramic circuit and application Pending CN117049864A (en)

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Application publication date: 20231114