CN107176834B - LTCC (Low temperature Co-fired ceramic) ceramic material with medium and high dielectric constant and preparation method thereof - Google Patents

LTCC (Low temperature Co-fired ceramic) ceramic material with medium and high dielectric constant and preparation method thereof Download PDF

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CN107176834B
CN107176834B CN201610141351.3A CN201610141351A CN107176834B CN 107176834 B CN107176834 B CN 107176834B CN 201610141351 A CN201610141351 A CN 201610141351A CN 107176834 B CN107176834 B CN 107176834B
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dielectric constant
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CN107176834A (en
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兰开东
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SHANGHAI JINGCAI NEW MATERIAL TECHNOLOGY Co.,Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped 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 titanium oxides or titanates
    • C04B35/462—Shaped 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 titanium oxides or titanates based on titanates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/14—Silica-free oxide glass compositions containing boron
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass

Abstract

The invention provides an LTCC ceramic material with a medium and high dielectric constant and a preparation method thereof, wherein the LTCC ceramic material with the medium and high dielectric constant comprises the following components in parts by mass: x parts of ZrTiO4Ceramic powder of y parts of BaO-B2O3‑ZnO‑TiO2Glass material, wherein x + y = 100. The LTCC ceramic material with medium and high dielectric constant is in ZrTiO4BaO-B is adopted on the basis of ceramic powder2O3‑ZnO‑TiO2The sintering temperature is reduced by the aid of the glass sintering of the system, low-temperature sintering at 900 ℃ can be realized, the dielectric constant of the prepared LTCC ceramic material with the medium and high dielectric constant is 38-42 at 6GHz, and the low dielectric loss is less than or equal to 3 multiplied by 10‑4. In addition, the preparation method has the advantages of cheap production raw materials, low production cost and simple preparation process. The ceramic material can be used for manufacturing microwave devices such as a low temperature co-fired ceramic system (LTCC), a multilayer dielectric resonator, a microwave antenna, a filter and the like.

Description

LTCC (Low temperature Co-fired ceramic) ceramic material with medium and high dielectric constant and preparation method thereof
Technical Field
The invention belongs to the field of electronic ceramic materials and manufacturing thereof, and particularly relates to a low-cost and medium-high dielectric constant LTCC ceramic material and a preparation method thereof.
Background
The Low Temperature Co-fired Ceramic (LTCC) technology is a novel material technology developed by Houss corporation in 1982, and is an integrated technology which manufactures a required circuit pattern by casting Low Temperature sintered Ceramic powder into a green Ceramic tape with uniform and compact thickness, manufacturing the required circuit pattern by the processes of laser drilling, grouting, circuit screen printing and the like, laminating in multiple layers, and sintering at the Temperature of below 900 ℃ into a three-dimensional passive device. At present, the LTCC technology is widely used for manufacturing electronic components in the fields of microwave communication, semiconductors, photoelectronics and the like, and has the remarkable advantages of high integration level and high performance. In recent years, no matter general electronic complete machines, communication equipment or electronic products of civil consumption type are rapidly developed to methods of miniaturization, light weight, integration, multi-functionalization and high reliability internationally, the LTCC technology is promoted to be widely applied to electronic components such as a patch filter, a resonator, a coupler, an LED display module, a Bluetooth module, an inductor, a capacitor and the like, and the requirement on high-performance LTCC materials is increased. However, the commercial high-performance LTCC materials are mainly monopolized abroad at present, and the key breakthrough is not always made in the field in China, so that the cost of LTCC integrated devices and assemblies developed in China is high, and the application and popularization are not facilitated. Therefore, the development of high performance LTCC materials with proprietary intellectual property rights is imminent.
ZrTiO4The ceramic material is originally rich, has low cost, is a good microwave dielectric material, has higher dielectric constant (Epsilon r-43) and low microwave loss tg delta-1 multiplied by 10-4) And the like. But ZrTiO4The ceramic has high sintering temperature (1500 ℃) and can not be directly co-sintered with low-melting-point metals such as Ag, Cu and the like, and the practical application requirement can not be met. In order to reduce the sintering temperature, low-melting-point oxides are usually added, but the temperature reduction range is limited, and the sintering temperature can not reach 900 ℃; the other method is to add low-melting-point glass, but the existence of the glass phase greatly improves the dielectric loss of the material and greatly limits ZrTiO4The application of ceramics in microwave multilayer devices is developed.
In conclusion, the middle-high dielectric constant, low loss and practical LTCC ceramic material and the preparation method thereof become the focus of research.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a middle and high dielectric constant LTCC ceramic material and a preparation method thereof, so as to realize a low-loss and practical middle and high dielectric constant LTCC ceramic material and a preparation method thereof.
In order to achieve the above and other related objects, the present invention provides a medium and high dielectric constant LTCC ceramic material, which is a glass ceramic material prepared by compounding glass and ceramic, wherein the medium and high dielectric constant LTCC ceramic material comprises the following components in parts by mass: x parts of ZrTiO4Ceramic powder of y parts of BaO-B2O3-ZnO-TiO2A glass material, wherein x + y is 100.
As a preferable scheme of the LTCC ceramic material with medium and high dielectric constant of the present invention, the LTCC ceramic material with medium and high dielectric constant comprises the following components in parts by mass: 65-75 parts of ZrTiO425-35 parts of BaO-B2O3-ZnO-TiO2A glass material.
As a preferable mode of the LTCC ceramic material with medium and high dielectric constant, BaO-B is2O3-ZnO-TiO2The glass material comprises the following components in percentage by mass: 25 to 35 percent of BaO and 20 to 40 percent of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3。
As a preferable scheme of the LTCC ceramic material with the medium and high dielectric constant, the LTCC ceramic material with the medium and high dielectric constant has the dielectric constant of 38-42 and the dielectric loss of less than or equal to 3 multiplied by 10 at room temperature and the test frequency of 6GHz-4。
The present invention adopts the above glass system because of the glass (BaO-B)2O3-ZnO-TiO2) The system has lower glass softening temperature (650 ℃), glass materials with different softening temperatures can be obtained by adjusting the content of different components in the glass, and the content and proportion of glass powder in the low-temperature co-fired ceramic material can be changed to achieve the aim of controlling the sintering temperature of the material; while the BaO-B2O3-ZnO-TiO2The glass of the system has higher dielectric constant and lower loss, and meets the requirements of low-dielectric low-temperature co-fired ceramic materials.
BaO-B used in the present invention2O3-ZnO-TiO2Glass, B2O3Is a former of a glass network structure, B2O3The glass melting temperature is reduced, the viscosity of the glass is too high when the content is lower than 20%, and the chemical stability of the glass is poor when the content is higher than 40%; BaO is beneficial to improving the chemical stability of the glass and reducing the melting temperature of the glass, and the melting temperature of the glass is higher when the melting temperature is lower than 20 percent; ZnO is beneficial to regulating the chemical stability of the glass, and the content is too high, thus being not beneficial to forming the glass; TiO 22Has the function of adjusting the dielectric constant and the crystallization capacity of the glass, and a proper amount of TiO2The microwave dielectric property of the glass and the LTCC material is improved.
BaO-B used in the present invention2O3-ZnO-TiO2The glass is prepared through proportioning the glass components, mixing in a V-type mixer by a dry method, melting the obtained uniform powder in a platinum crucible at 1250 ℃ for 2 hours, then pouring the glass liquid into water to quench, wet-grinding the obtained cullet into slurry in a roller ball mill, wherein the granularity D50 of the glass powder is about 2.0um, and then drying the glass slurry to obtain the glass powder.
The low-temperature co-fired ceramic material provided by the invention comprises the following ceramic powder: ZrTiO4Ceramic powder. ZrTiO4The ceramic has the advantages of high dielectric constant and low dielectric loss (dielectric constant ε r-43, tg δ -1 × 10)-4) By adjusting ZrTiO4Ceramic powder and BaO-B2O3-ZnO-TiO2The different proportions of the glass can adjust the sintering temperature to be lower than 900 ℃, and the dielectric constant of the LTCC material is adjusted to be within the range of 38-42.
The low-temperature co-fired ceramic material provided by the invention comprises the following processes: the glass powder and the ceramic powder are mixed according to a certain proportion, then the mixture is ball-milled in a roller ball mill by a wet method until the granularity D50 is between 2.0um, then the slurry is dried and crushed to prepare the low-temperature co-fired ceramic powder, and the powder can be kept at 870-plus-material 900 ℃ for 30 minutes and is matched with electrode materials such as Ag slurry and the like for co-firing.
The low-temperature co-fired ceramic material provided by the invention has good dielectric property, physical, chemical and mechanical properties and the like. The low-temperature co-fired ceramic material obtained by the invention has the dielectric constant of 38-42 at 6GHz and the dielectric loss less than or equal to 3 multiplied by 10-4。
The invention also provides a preparation method of the LTCC ceramic material with the medium and high dielectric constant, which comprises the following steps:
1) with ZrTiO4Ceramic powder and BaO-B2O3-ZnO-TiO2The glass material is used as an initial raw material and comprises the following components in parts by mass: 65-75 parts of ZrTiO425-35 parts of BaO-B2O3-ZnO-TiO2A glass material;
2) mixing the ingredients with alcohol serving as a solvent, ball-milling for 1-2 hours by using a sand mill, controlling the granularity of slurry to be D50-2.5 um, and drying;
3) and adding a binder to granulate, performing compression molding, and finally sintering to prepare the LTCC ceramic material with medium and high dielectric constant.
As a preferable scheme of the preparation method of the LTCC ceramic material with medium and high dielectric constant, in the step 1), the ZrTiO is adopted4The ceramic powder is prepared by the following preparation method:
1-1) with ZrO2And TiO2The raw materials are used as initial raw materials, and a batch is formed according to a molar ratio of 1: 1;
1-2) mixing the batch with deionized water in a mass ratio of 1:2, ball-milling for 2-3 hours by a wet planetary ball mill, sieving and drying; then evenly crushing the mixture and calcining the mixture to form a calcined material;
1-3) mixing the calcined material and deionized water according to the mass ratio of 1:1.5, ball-milling for 2-3 hours by a planetary ball mill, sieving and drying to obtain the ZrTiO4Ceramic powder.
As a preferable embodiment of the method for preparing the LTCC ceramic material with medium and high dielectric constant of the present invention, in the step 1-2), the calcination temperature is 1200 ℃ to 1250 ℃, and the calcination time is 2 hours to 3 hours.
As a preferable scheme of the preparation method of the LTCC ceramic material with medium and high dielectric constant, in the step 1), the BaO-B2O3-ZnO-TiO2The glass material comprises the following components in percentage by mass: 25 to 35 percent of BaO and 20 to 40 percent of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3Weighing the above components in proportion, dry-mixing the components, putting the mixture into a crucible, melting the mixture at 1250 ℃ for 1 to 3 hours to form glass liquid, quenching the glass liquid, drying and grinding the glass liquid to obtain the BaO-B2O3-ZnO-TiO2A glass material.
As a preferable embodiment of the method for preparing the LTCC ceramic material with medium and high dielectric constant of the present invention, in the step 2), the ingredients and the alcohol are mixed in a mass ratio of 1:1.
As a preferable embodiment of the preparation method of the LTCC ceramic material with medium and high dielectric constant of the present invention, in the step 3), the binder is PVB solution with a concentration of 2 wt% to 5 wt%, and the amount of the additive is 4 wt% to 8 wt% by mass ratio.
As a preferable scheme of the preparation method of the LTCC ceramic material with medium and high dielectric constant, in the step 3), the sintering temperature is 870-900 ℃, the sintering atmosphere is atmospheric atmosphere, and the sintering time is 20-40 minutes.
As described above, the LTCC ceramic material with medium and high dielectric constant and the preparation method thereof of the present invention have the following beneficial effects: the invention provides a new method for preparing ZrTiO4A novel LTCC microwave ceramic material with medium and high dielectric constant and low loss and a preparation method thereof. The LTCC ceramic material with medium and high dielectric constant is in ZrTiO4BaO-B is adopted on the basis of ceramic powder2O3-ZnO-TiO2The sintering temperature is reduced by the aid of the glass sintering of the system, low-temperature sintering at 900 ℃ can be realized, the dielectric constant of the prepared LTCC ceramic material with the medium and high dielectric constant is 38-42 at 6GHz, and the low dielectric loss is less than or equal to 3 multiplied by 10-4. In addition, the preparation method has the advantages of cheap production raw materials, low production cost and simple preparation process. The ceramic material can be used for manufacturing microwave devices such as a low temperature co-fired ceramic system (LTCC), a multilayer dielectric resonator, a microwave antenna, a filter and the like.
Drawings
FIG. 1 is a schematic flow chart of the steps of the preparation method of the LTCC ceramic material with medium and high dielectric constant according to the present invention.
FIG. 2 is a graph showing the variation of microwave dielectric properties of the LTCC ceramic material with medium and high dielectric constant according to the BBZT glass doped amount in example 2 of the present invention.
FIG. 3 is a graph showing the microwave dielectric properties of the LTCC ceramic material with middle and high dielectric constant according to the embodiment 2 of the present invention as a function of the sintering temperature.
FIG. 4 is SEM image of the matching co-fired interface between the LTCC ceramic material with medium and high dielectric constant and the Ag electrode material.
Description of the element reference numerals
S11-S13 Steps 1-step 3)
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 4. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the type, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example 1
The embodiment provides an LTCC ceramic material with a medium and high dielectric constant, which is a glass ceramic material prepared by compounding glass and ceramic, wherein the LTCC ceramic material with the medium and high dielectric constant comprises the following components in parts by mass: x parts of ZrTiO4Ceramic powder of y parts of BaO-B2O3-ZnO-TiO2A glass material, wherein x + y is 100.
By way of example, the medium-high dielectric constant LTCC ceramic material comprises the following components in parts by mass: 65-75 parts of ZrTiO425-35 parts of BaO-B2O3-ZnO-TiO2A glass material.
As an example, the BaO-B2O3-ZnO-TiO2The glass material comprises the following components in percentage by mass: 25 to 35 percent of BaO and 20 to 40 percent of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3。
The present invention adopts the above glass system because of the glass (BaO-B)2O3-ZnO-TiO2) The system has lower glass softening temperature (650 ℃), glass materials with different softening temperatures can be obtained by adjusting the content of different components in the glass, and the content and proportion of glass powder in the low-temperature co-fired ceramic material can be changed to achieve the aim of controlling the sintering temperature of the material; while the BaO-B2O3-ZnO-TiO2The glass of the system has higher dielectric constant and lower loss, and meets the requirements of low-dielectric low-temperature co-fired ceramic materials. BaO-B used in the present invention2O3-ZnO-TiO2Glass, B2O3Is a former of a glass network structure, B2O3The glass melting temperature is reduced, the viscosity of the glass is too high when the content is lower than 20%, and the chemical stability of the glass is poor when the content is higher than 40%; BaO is beneficial to improving the chemical stability of the glass and reducing the melting temperature of the glass, and the melting temperature of the glass is higher when the melting temperature is lower than 20 percent; ZnO is beneficial to regulating the chemical stability of the glass, and the content is too high, thus being not beneficial to forming the glass; TiO 22Has the function of adjusting the dielectric constant and the crystallization capacity of the glass, and a proper amount of TiO2The microwave dielectric property of the glass and the LTCC material is improved. BaO-B used in the present invention2O3-ZnO-TiO2The glass is prepared through proportioning the glass components, mixing in a V-type mixer by a dry method, melting the obtained uniform powder in a platinum crucible at 1250 ℃ for 2 hours, then pouring the glass liquid into water to quench, wet-grinding the obtained cullet into slurry in a roller ball mill, wherein the granularity D50 of the glass powder is about 2.0um, and then drying the glass slurry to obtain the glass powder.
The low-temperature co-fired ceramic material provided by the invention comprises the following ceramic powder: ZrTiO4Ceramic powder. ZrTiO4The ceramic has the advantages of high dielectric constant and low dielectric loss (dielectric constant ε r-43, tg δ -1 × 10)-4) By adjusting ZrTiO4Ceramic powder and BaO-B2O3-ZnO-TiO2Different ratio of glassFor example, the sintering temperature can be adjusted to be lower than 900 ℃, and the dielectric constant of the LTCC material can be adjusted to be within the range of 38-42.
The low-temperature co-fired ceramic material provided by the invention comprises the following processes: the glass powder and the ceramic powder are mixed according to a certain proportion, then the mixture is ball-milled in a roller ball mill by a wet method until the granularity D50 is between 2.0um, then the slurry is dried and crushed to prepare the low-temperature co-fired ceramic powder, and the powder can be kept at the temperature of 870 plus materials and 900 ℃ for 30 minutes and is matched with electrode materials such as Ag slurry and the like for co-firing, as shown in figure 4.
The low-temperature co-fired ceramic material provided by the invention has good dielectric property, physical, chemical and mechanical properties and the like. The low-temperature co-fired ceramic material obtained by the invention has the dielectric constant of 38-42 at 6GHz and the dielectric loss less than or equal to 3 multiplied by 10-4。
As shown in fig. 1, the present invention further provides a preparation method of an LTCC ceramic material with a medium and high dielectric constant, comprising the following steps:
1) with ZrTiO4Ceramic powder and BaO-B2O3-ZnO-TiO2The glass material is used as an initial raw material and comprises the following components in parts by mass: 65-75 parts of ZrTiO425-35 parts of BaO-B2O3-ZnO-TiO2A glass material;
2) mixing the ingredients with alcohol serving as a solvent, ball-milling for 1-2 hours by using a sand mill, controlling the granularity of slurry to be D50-2.5 um, and drying;
3) and adding a binder to granulate, performing compression molding, and finally sintering to prepare the LTCC ceramic material with medium and high dielectric constant.
As an example, in the step 1), the ZrTiO4The ceramic powder is prepared by the following preparation method:
1-1) with ZrO2And TiO2The raw materials are used as initial raw materials, and a batch is formed according to a molar ratio of 1: 1;
1-2) mixing the batch with deionized water in a mass ratio of 1:2, ball-milling for 2-3 hours by a wet planetary ball mill, sieving and drying; then evenly crushing the mixture and calcining the mixture to form a calcined material;
1-3) mixing the calcined material and deionized water according to the mass ratio of 1:1.5, ball-milling for 2-3 hours by a planetary ball mill, sieving and drying to obtain the ZrTiO4Ceramic powder.
As an example, in the step 1-2), the calcination temperature is 1200 ℃ to 1250 ℃, and the calcination time is 2 hours to 3 hours.
As an example, in the step 1), the BaO-B2O3-ZnO-TiO2The glass material comprises the following components in percentage by mass: 25 to 35 percent of BaO and 20 to 40 percent of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3Weighing the above components in proportion, dry-mixing the components, putting the mixture into a crucible, melting the mixture at 1250 ℃ for 1 to 3 hours to form glass liquid, quenching the glass liquid, drying and grinding the glass liquid to obtain the BaO-B2O3-ZnO-TiO2A glass material.
As an example, in the step 2), the ingredients are mixed with alcohol in a mass ratio of 1:1.
As an example, in the step 3), the binder is a PVB solution with a concentration of 2 wt% to 5 wt%, and the additive amount is 4 wt% to 8 wt% in a mass ratio.
For example, in the step 3), the sintering temperature is 870 ℃ to 900 ℃, the sintering atmosphere is an atmospheric atmosphere, and the sintering time is 20 minutes to 40 minutes.
Example 2
The present embodiment provides a medium-high dielectric constant LTCC ceramic material and a preparation method thereof, the basic scheme is as in embodiment 1, wherein:
BaO-B2O3-ZnO-TiO2the glass material is prepared by melting according to the following components (BBZT-1): BaO 33%, B2O330％，ZnO20％，TiO215％，MgO+Al2O32 percent; the melting temperature is 1250 ℃, the melting time is 2 hours, the glass is poured into water for quenching, and the wet grinding is carried out until the particle size D50 is about 2.0 um.
The low-temperature co-fired ceramic material comprises the following components in percentage by weight: ZrTiO465-75% of ceramic powder and 25-35% of BBZT-1 glass% of the total weight of the composition. The mixture is wet-milled until the particle size D50 is about 2.0 um.
The obtained low-temperature co-fired ceramic material is sintered at 870-900 ℃, the temperature is kept for 30 minutes, and the measured material performance at 6GHz is as follows: the dielectric constant is 38-40, and the dielectric loss is less than or equal to 3.0 multiplied by 10-4As shown in fig. 2 and 3.
The composition is as follows: ZrTiO475% of ceramic powder and 30% of BBZT-1 glass, sintering at 890 ℃, keeping the temperature for 30 minutes, and measuring the material performance at 6GHz as follows: dielectric constant of 39.1 and dielectric loss of 2.88X 10-4。
The LTCC ceramic material powder with the medium and high dielectric constant can be insulated for 30 minutes at 870-900 ℃, is matched with electrode materials such as Ag paste and the like for co-firing, and obtains good sintering quality, as shown in figure 4.
Example 3
The present embodiment provides a medium-high dielectric constant LTCC ceramic material and a preparation method thereof, the basic scheme is as in embodiment 1, wherein:
BaO-B2O3-ZnO-TiO2the glass material is prepared by melting according to the following components (BBZT-2): BaO 30%, B2O330％，ZnO20％，TiO218％，MgO+Al2O32 percent; the melting temperature is 1250 ℃, the melting time is 2 hours, the glass is poured into water for quenching, and the wet grinding is carried out until the particle size D50 is about 2.0 um.
The low-temperature co-fired ceramic material comprises the following components in percentage by weight: ZrTiO465-75% of ceramic powder and 25-35% of BBZT-1 glass. The mixture is wet-milled until the particle size D50 is about 2.0 um.
The obtained low-temperature co-fired ceramic material is sintered at 870-900 ℃, the temperature is kept for 30 minutes, and the measured material performance at 6GHz is as follows: the dielectric constant is 39-41, and the dielectric loss is less than or equal to 3.0 multiplied by 10-4。
The composition is as follows: ZrTiO475% of ceramic powder and 25% of BBZT-2 glass, and sintering at 890 ℃, keeping the temperature for 30 minutes, wherein the material properties measured at 6GHz are as follows: dielectric constant of 40.2 and dielectric loss of 2.65X 10-4。
Example 4
The present embodiment provides a medium-high dielectric constant LTCC ceramic material and a preparation method thereof, the basic scheme is as in embodiment 1, wherein:
BaO-B2O3-ZnO-TiO2the glass material is prepared by melting according to the following components (BBZT-3): BaO 25%, B2O330％，ZnO20％，TiO223％，MgO+Al2O32 percent; the melting temperature is 1250 ℃, the melting time is 2 hours, the glass is poured into water for quenching, and the wet grinding is carried out until the particle size D50 is about 2.0 um.
The low-temperature co-fired ceramic material comprises the following components in percentage by weight: ZrTiO465-75% of ceramic powder and 25-35% of BBZT-1 glass. The mixture is wet-milled until the particle size D50 is about 2.0 um.
The obtained low-temperature co-fired ceramic material is sintered at 870-900 ℃, the temperature is kept for 30 minutes, and the measured material performance at 6GHz is as follows: the dielectric constant is 39-42, the dielectric loss is less than or equal to 3.0 multiplied by 10-4。
The composition is as follows: ZrTiO475% of ceramic powder and 25% of BBZT-3 glass, and sintering at 890 ℃, keeping the temperature for 30 minutes, wherein the material properties measured at 6GHz are as follows: dielectric constant of 41.3 and dielectric loss of 2.45X 10-4。
Example 5
The present embodiment provides a medium-high dielectric constant LTCC ceramic material and a preparation method thereof, the basic scheme is as in embodiment 1, wherein:
BaO-B2O3-ZnO-TiO2the glass material is prepared by melting according to the following components (BBZT-4): BaO 30%, B2O325％，ZnO25％，TiO218％，MgO+Al2O32 percent; the melting temperature is 1250 ℃, the melting time is 2 hours, the glass is poured into water for quenching, and the wet grinding is carried out until the particle size D50 is about 2.0 um.
The low-temperature co-fired ceramic material comprises the following components in percentage by weight: ZrTiO465-75% of ceramic powder and 25-35% of BBZT-1 glass. The mixture is wet-milled until the particle size D50 is about 2.0 um.
The obtained low-temperature co-fired ceramic material is sintered at 870-900 ℃, the temperature is kept for 30 minutes, and the measured material performance at 6GHz is as follows: the dielectric constant is 39-41, and the dielectric loss is less than or equal to 3.0 multiplied by 10-4。
The composition is as follows: zrTiO470% of ceramic powder and 30% of BBZT-4 glass, sintering at 890 ℃, keeping the temperature for 30 minutes, and measuring the material performance at 6GHz as follows: dielectric constant of 39.5 and dielectric loss of 2.55X 10-4。
Example 6
The present embodiment provides a medium-high dielectric constant LTCC ceramic material and a preparation method thereof, the basic scheme is as in embodiment 1, wherein:
BaO-B2O3-ZnO-TiO2the glass material is prepared by melting according to the following components (BBZT-5): BaO 30%, B2O320％，ZnO30％，TiO218％，MgO+Al2O32 percent; the melting temperature is 1250 ℃, the melting time is 2 hours, the glass is poured into water for quenching, and the wet grinding is carried out until the particle size D50 is about 2.0 um.
The low-temperature co-fired ceramic material comprises the following components in percentage by weight: ZrTiO465-75% of ceramic powder and 25-35% of BBZT-1 glass. The mixture is wet-milled until the particle size D50 is about 2.0 um.
The obtained low-temperature co-fired ceramic material is sintered at 870-900 ℃, the temperature is kept for 30 minutes, and the measured material performance at 6GHz is as follows: the dielectric constant is 39-41, and the dielectric loss is less than or equal to 3.0 multiplied by 10-4。
The composition is as follows: ZrTiO470% of ceramic powder and 30% of BBZT-5 glass, sintering at 890 ℃, keeping the temperature for 30 minutes, and measuring the material performance at 6GHz as follows: a dielectric constant of 39.6 and a dielectric loss of 2.35X 10-4。
As described above, the LTCC ceramic material with medium and high dielectric constant and the preparation method thereof of the present invention comprise the following components by mass: x parts of ZrTiO4Ceramic powder of y parts of BaO-B2O3-ZnO-TiO2A glass material, wherein x + y is 100. The LTCC ceramic material with medium and high dielectric constant is in ZrTiO4BaO-B is adopted on the basis of ceramic powder2O3-ZnO-TiO2The sintering temperature is reduced by the aid of the glass sintering of the system, low-temperature sintering at 900 ℃ can be realized, the dielectric constant of the prepared LTCC ceramic material with the medium and high dielectric constant is 38-42 at 6GHz, and the low dielectric loss is less than or equal to 3 multiplied by 10-4. In addition, the present inventionThe preparation method has the advantages of cheap production raw materials, low production cost and simple preparation process. The ceramic material can be used for manufacturing microwave devices such as a low temperature co-fired ceramic system (LTCC), a multilayer dielectric resonator, a microwave antenna, a filter and the like.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (7)

1. The LTCC ceramic material with the medium and high dielectric constant is characterized in that the LTCC ceramic material with the medium and high dielectric constant has the dielectric constant of 38-42 and the dielectric loss of less than or equal to 3 multiplied by 10 at room temperature and the test frequency of 6GHz-4(ii) a The LTCC ceramic material with the medium and high dielectric constant comprises, by mass, x parts of ZrTiO4Ceramic powder and y parts of BaO-B2O3-ZnO-TiO2A glass material, wherein x is 65-75, y is 25-35, and x + y is 100; the BaO-B2O3-ZnO-TiO2The glass material comprises, by mass, 25-35% of BaO and 20-40% of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3。
2. The preparation method of the LTCC ceramic material with the medium and high dielectric constant is characterized by comprising the following steps:
1) with ZrTiO4Ceramic powder and BaO-B2O3-ZnO-TiO2The glass material is used as an initial raw material and comprises the following components in parts by mass: 65-75 parts of ZrTiO425-35 parts of BaO-B2O3-ZnO-TiO2A glass material; the BaO-B2O3-ZnO-TiO2Glass materials are measured according to mass ratio and packagedComprises 25 to 35 percent of BaO and 20 to 40 percent of B2O310 to 30 percent of ZnO and 15 to 30 percent of TiO2And not more than 2% of MgO + Al2O3Weighing the above components in proportion, dry-mixing the components, putting the mixture into a crucible, melting the mixture at 1250 ℃ for 1 to 3 hours to form glass liquid, quenching the glass liquid, drying and grinding the glass liquid to obtain the BaO-B2O3-ZnO-TiO2A glass material;
2) mixing the ingredients with alcohol serving as a solvent, ball-milling for 1-2 hours by using a sand mill, controlling the granularity of slurry to be D50-2.5 um, and drying;
3) and adding a binder to granulate, performing compression molding, and finally sintering to prepare the LTCC ceramic material with medium and high dielectric constant.
3. The method for preparing a medium and high dielectric constant LTCC ceramic material according to claim 2, wherein the method comprises the following steps: in the step 1), the ZrTiO4The ceramic powder is prepared by the following preparation method:
1-1) with ZrO2And TiO2The raw materials are used as initial raw materials, and a batch is formed according to a molar ratio of 1: 1;
1-2) mixing the batch with deionized water in a mass ratio of 1:2, ball-milling for 2-3 hours by a wet planetary ball mill, sieving and drying; then evenly crushing the mixture and calcining the mixture to form a calcined material;
1-3) mixing the calcined material and deionized water according to the mass ratio of 1:1.5, ball-milling for 2-3 hours by a planetary ball mill, sieving and drying to obtain the ZrTiO4Ceramic powder.
4. A method for preparing a LTCC ceramic material with a medium and high dielectric constant as claimed in claim 3, wherein: in the step 1-2), the calcining temperature is 1200-1250 ℃, and the calcining time is 2-3 hours.
5. A method for preparing a LTCC ceramic material with a medium and high dielectric constant as claimed in claim 3, wherein: in the step 2), the ingredients and alcohol are mixed in a mass ratio of 1:1.
6. A method for preparing a LTCC ceramic material with a medium and high dielectric constant as claimed in claim 3, wherein: in the step 3), the adhesive is a PVB solution with a concentration of 2 wt% to 5 wt%, and the additive amount is 4 wt% to 8 wt% in terms of mass ratio.
7. A method for preparing a LTCC ceramic material with a medium and high dielectric constant as claimed in claim 3, wherein: in the step 3), the sintering temperature is 870-900 ℃, the sintering atmosphere is atmospheric atmosphere, and the sintering time is 20-40 minutes.
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