CN113929444A

CN113929444A - Blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, and preparation method and application thereof

Info

Publication number: CN113929444A
Application number: CN202111255277.5A
Authority: CN
Inventors: 谭金刚; 罗薇; 余祖高; 罗昌桅; 童建喜; 卢冠宇; 徐俊峰
Original assignee: Jiaxing Glead Electronics Co ltd
Current assignee: Jiaxing Glead Electronics Co ltd
Priority date: 2021-10-27
Filing date: 2021-10-27
Publication date: 2022-01-14
Anticipated expiration: 2041-10-27
Also published as: CN113929444B

Abstract

The invention relates to a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, a preparation method and application thereof, and the blue low-temperature co-fired low-dielectric microwave dielectric ceramic material comprises the following components in percentage by weight: calcium carbonate: 20-40%; silicon dioxide: 20-40%; magnesium oxide: 10-30%; aluminoborosilicate glass: 18-38%; blue colorant: 2-10%; the sum of the above components is 100%. The chip type frequency component prepared by the ceramic material through the LTCC process technology has the characteristics of simple firing process, excellent dielectric property, high mechanical strength, light shielding property and the like.

Description

Blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, and preparation method and application thereof

Technical Field

The invention relates to the technical field of microwave dielectric ceramic materials, in particular to a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, a preparation method and application thereof.

Background

In recent years, with the rapid development of communication technology, the demand for miniaturization, portability, multifunction, digitalization, high frequency, high reliability, and high performance of electronic devices has driven the development of miniaturization, integration, and high frequency of electronic components, and has brought a new explosion point to chip components. The Low Temperature Co-fired Ceramic (LTCC for short) technology has been widely used in the passive device direction and in the new device industry due to its characteristics of good dielectric property, high strength, good heat dissipation, high integration level, flexible design, etc., and becomes a new economic growth point.

And packaging substrates, MEMS sensors, power devices, surface acoustic wave devices, optical communication modules, and the like. The design requirements of small device size, compact structure, multiple functions, stable performance and the like are met, and the passive integration technology becomes a mainstream technology of passive integration. High Temperature Co-fired ceramic (HTCC) and Low Temperature Co-fired ceramic (LTCC) technologies are two relatively mature microelectronic ceramic packaging technologies. The LTCC technology is applied to passive integrated devices and semiconductor packaging.

Blue alumina low-dielectric microwave dielectric ceramic materials are commonly used in LTCC technology, and blue is used as a chip frequency device and has unique appearance advantages. The generally blue-colored low-temperature co-fired ceramic materials generally consist of alumina, a colored oxide and a fluxing agent. The coloring oxide is Co2O3, etc. The flux includes SiO2, B2O3, talc, and the like. Because the sintering temperature of the alumina is high, a large amount of fluxing agent is required to be added to reduce the sintering temperature to 850-900 ℃, and the blue alumina low-temperature co-fired ceramic has the following defects: (1) the signal transmission loss is large, and high-frequency application is limited; (2) the difficulty of the co-firing matching of the ceramic powder and the silver is increased; (3) the large amount of flux causes a relative decrease in mechanical strength.

The silicate ceramic can be co-fired with metal (Ag, Au or Cu, etc.) at about 900 ℃ better by adding a small amount of fluxing agent, has lower loss and higher transmission speed than alumina ceramic, but has bad appearance due to the fact that internal patterns of the surface of the frequency device are leaked out after the silicate material is co-fired with the metal, and the yield of the frequency device is influenced.

If the respective advantages of the characteristics of the alumina and silicate materials can be combined, the respective disadvantages can be avoided, the low-temperature co-fired microwave dielectric ceramic material can be adjusted and optimized, and the LTCC material meeting the application requirements of the frequency device with high transmission speed, low loss and stable characteristics can be developed, so that the LTCC material has great significance and excellent application value.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention provides a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, a second purpose of the invention is to provide a preparation method of the ceramic material, and a third purpose of the invention is to provide application of the ceramic material. The ceramic frequency device prepared by the ceramic material through the LTCC process technology has the characteristics of simple firing process, high mechanical strength, excellent dielectric property, light shielding property and the like.

In order to achieve the first object, the invention adopts the following technical scheme:

a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material comprises the following components in percentage by weight:

calcium carbonate: 20-40%;

silicon dioxide: 20-40%;

magnesium oxide: 10-30%;

aluminoborosilicate glass: 18-38%;

blue colorant: 2-10%;

the sum of the above components is 100%.

Preferably, the ceramic material comprises the following components in percentage by weight:

calcium carbonate: 23-38%;

silicon dioxide: 25-32%;

magnesium oxide: 12-25%;

aluminoborosilicate glass: 20-32%;

blue colorant: 3-8%;

the sum of the above components is 100%.

Blue colorant selection CoAl₂O₄One or more of Co oxide, Al oxide, Ni oxide, Co oxide, Mn oxide, Cr basic carbonate, Cu basic carbonate, Ni basic carbonate, Co basic carbonate and Mn carbonate; the oxides include lower oxides and higher oxides.

Preferably, the blue colorant comprises the following components in percentage by mass:

CoAl₂O₄：75%～100％；

MO：0～25％；

the sum of the above components is 100%;

wherein MO is metal oxide CuO, NiO, CoO and MnO₂One or more of; wherein CoO and MnO₂May be made of Co respectively₂O₃And MnCO₃Replacing according to equivalent molar quantity conversion of metal atoms; the invention adds CoAl₂O₄The coloring stability for ceramics can be improved.

Preferably, the aluminoborosilicate glass comprises the following components in percentage by mass:

A₂O：0~15%；

RO：0~20%；

Al₂O₃：15~35%；

B₂O₃：10~30%；

SiO₂：30~65%；

the sum of the above components is 100%;

wherein A refers to one or more of alkali metals Li, Na and K; r is one or more of alkaline earth metals Mg, Ca, Sr and Ba.

In order to achieve the second object, the invention adopts the following technical scheme:

a preparation method of a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material comprises the following steps:

1) the preparation method of the silicate ceramic comprises the following steps: the weight ratio is as follows: 23-38% of CaCO₃，25～35％SiO₂12-35% of MgO and CaCO₃、SiO₂MgO, wherein the mass ratio of the materials to the deionized water is 1:1 to 1.5, ZrO is selected₂Grinding balls, mixing materials by a wet method for 4-12h, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1150-1350 ℃ for 3-6h, and grinding and crushing to obtain powder with the particle size D50 of 1.0-2.8 mu m;

2) the preparation method of the aluminoborosilicate glass comprises the following steps: according to the mass ratio: 0 to 15% of A₂O，0～20％RO，15～35％Al₂O₃，10～30％B₂O₃，30～65％SiO₂(ii) a Weighing Li₂CO₃、NaHCO₃Or Na₂CO₃、KHCO₃Or K₂CO₃MgO or basic magnesium carbonate, B₂O₃Or H₃BO₃、BaCO₃、CaCO₃、SrCO₃、Al₂O₃And SiO₂Using ZrO₂Mixing materials for 2-8 h by a ball grinding dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.5-1 h at the melting temperature of 1350-1500 ℃, and then pouring the molten liquid into water for quenching; ball-milling and crushing the obtained glass fragments, and drying to obtain glass powder with the granularity D50 of 1.2-2.8 mu m;

3) and mixing the silicate ceramic powder, the aluminoborosilicate glass and the blue colorant powder according to a required proportion by a wet method, uniformly mixing the materials by the wet method, and drying to obtain the ceramic material.

Preferably, the blue colorant CoAl₂O₄The preparation method comprises the following steps: and (2) according to molar ratio: 1, weighing Al₂O₃And Co₂O₃Raw materials are mixed according to the mass ratio of 1: 1-1.5 adding ethanol, mixing materials by a wet method for 4-12h, drying at 80 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1150-1250 ℃ for 3-6h, and synthesizing CoAl₂O₄Grinding and crushing the main crystal phase to obtain CoAl with the grain diameter D50 of 1.0-2.5 mu m₂O₄And (3) powder.

In order to achieve the third object, the present invention adopts the following technical solutions:

the low-temperature co-fired blue low-dielectric microwave dielectric ceramic material is applied to frequency components, chip filters, chip antennas, chip duplexers, chip power dividers and the like.

In order to meet the requirement of light shielding performance of semiconductor packaging, the formula of the ceramic material contains a blue colorant component, and in addition, the ceramic frequency device prepared by the ceramic material through LTCC process technology has the characteristics of simple firing process, high mechanical strength, excellent dielectric property, light shielding performance and the like, can be better than alumina ceramic in performance, has a light shielding effect better than common silicate ceramic, meets the manufacturing requirements of chip frequency devices such as chip filters, chip antennas, chip duplexers, chip power dividers and the like, and has obvious advantages.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.

FIG. 1 is a scanning electron microscope (magnification 1 ten thousand times) photograph of the ceramic surface obtained by sintering the blue low-temperature co-fired low-dielectric microwave dielectric ceramic material at 880 ℃ for 0.5h in example 1 of the present invention.

Fig. 2 is a physical diagram of a device with the size of 1.6mm by 0.8mm by 0.6mm of a chip antenna and a chip filter which are made of the material of the invention through an LTCC process.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that "and/or" in the present application, such as "feature 1 and/or feature 2" refers to "feature 1" alone, "feature 2" alone, and "feature 1" plus "feature 2" alone.

In addition, in the description of the present application, the meaning of "a plurality" of "one or more" means two or more unless otherwise specified; the range of "numerical value a to numerical value b" includes both values "a" and "b", and "unit of measure" in "numerical value a to numerical value b + unit of measure" represents "unit of measure" of both "numerical value a" and "numerical value b".

The following is a detailed description of embodiments of a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material, a preparation method thereof and applications thereof.

Example 1

Weighing 8 percent of Li according to the proportion (mass ratio)₂

CO

₃10% of MgO, 20% of Al₂O₃20% of B₂O₃And 42% SiO₂(ii) a Using ZrO₂Mixing materials for 5h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.75 h at the melting temperature of 1450 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 1.2 mu m is obtained after drying. Meanwhile, the molar ratio of the raw materials is 2: 1 proportion of Al₂O₃And Co₂O₃According to the mass ratio of the materials to the absolute ethyl alcohol of 1: 1.25 adding ethanol, mixing materials by a wet method for 8h, drying at 80 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1200 ℃ for 4.5h, and synthesizing CoAl₂O₄Grinding and pulverizing the main crystal phase to obtain CoAl with the particle size D50 of 1.7 mu m₂O₄And (3) powder. In proportion (mass)Ratio) 87.5% of CoAl was weighed₂O₄The powder was mixed with 12.5% CuO to make a blue colorant. Weighing 25% of CaCO according to the proportion (mass ratio)₃25% of SiO₂20% of MgO, 24% of aluminoborosilicate glass and 6% of blue colorant, wherein the mass ratio of the materials to the deionized water is 1: 1.25, ZrO is selected₂Grinding balls, mixing materials by a wet method for 8 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1250 ℃ for 4.5 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 1.5 mu m. The silicate ceramic powder can be applied to the preparation of filters.

Example 2

Weighing 15% KHCO according to the proportion (mass ratio)₃20 percent of basic magnesium carbonate and 15 percent of Al₂O₃20% of B₂O₃And 30% SiO₂Using ZrO₂Mixing materials for 8h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 1h at the melting temperature of 1350 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 2.8 mu m is obtained after drying. Meanwhile, the molar ratio of the raw materials is 2: 1 proportion of Al₂O₃And Co₂O₃Adding ethanol according to the mass ratio of the materials to the absolute ethanol of 1:1, mixing the materials by a wet method for 4 hours, drying the materials at 80 ℃, sieving the dried mixture by a 40-mesh sieve, filling the mixture into an alumina crucible, calcining the mixture at 1150 ℃ for 6 hours, and synthesizing the CoAl₂O₄Grinding and pulverizing the main crystal phase to obtain CoAl with the particle size D50 of 1.0 mu m₂O₄And (3) powder. Weighing 23% of CaCO according to the proportion (mass ratio)₃35% of SiO ₂12% MgO, 30% aluminoborosilicate glass and 10% blue colorant. According to the mass ratio of 1:1, ZrO is selected₂Grinding balls, mixing materials by a wet method for 12 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1350 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2.8 mu m. The silicate ceramic powder can be applied to the preparation of a sheet antenna.

Example 3

Weighing 15% of Na according to the proportion (mass ratio)₂CO₃20% of MgO and 15% of Al₂O₃10% of B₂O₃And 40% SiO₂Using ZrO₂Mixing materials for 5h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.5h at the melting temperature of 1500 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 1.2 mu m is obtained after drying. Meanwhile, the molar ratio of the raw materials is 2: 1 proportion of Al₂O₃And Co₂O₃Adding ethanol according to the mass ratio of the material to the absolute ethanol of 1: 1.5, mixing the materials by a wet method to obtain a mixture 12h h, drying the mixture at 80 ℃, sieving the dried mixture with a 40-mesh sieve, loading the mixture into an alumina crucible, calcining the mixture at 1250 ℃ for 3 hours to synthesize CoAl₂O₄Grinding and pulverizing the main crystal phase to obtain CoAl with the particle size D50 of 2.5 mu m₂O₄And (3) powder. And 75 percent of CoAl by mass percent₂O₄And 25 percent of NiO are uniformly mixed to prepare the blue colorant. Weighing 20% of CaCO according to the proportion (mass ratio)₃25% of SiO ₂12% MgO, 30% aluminoborosilicate glass and 8% blue colorant. According to the mass ratio of 1:1, ZrO is selected₂Grinding balls, mixing materials by a wet method for 12 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1350 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2.8 mu m. The silicate ceramic powder can be applied to the preparation of a sheet duplexer.

Example 4

Weighing 20% KHCO according to the proportion (mass ratio)₃20 percent of basic magnesium carbonate and 15 percent of Al₂O₃10% of H₃BO₃And 35% SiO₂Using ZrO₂Mixing materials for 5h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.75 h at the melting temperature of 1450 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 1.2 mu m is obtained after drying. Meanwhile, the molar ratio of the raw materials is 2: 1 proportion of Al₂O₃And Co₂O₃According to the mass ratio of the materials to the absolute ethyl alcohol of 1: 1.25 adding ethanol, mixing materials by a wet method for 8h, drying at 80 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1200 ℃ for 4.5h, and synthesizing CoAl₂O₄Grinding and pulverizing the main crystal phase to obtain CoAl with the particle size D50 of 1.7 mu m₂O₄And (3) powder. Weighing 87.5 percent of CoAl according to the proportion (mass ratio)₂O₄The powder was mixed with 12.5% CoO to make a blue colorant. Weighing 25% of CaCO according to the proportion (mass ratio)₃25% of SiO₂20% of MgO, 24% of aluminoborosilicate glass and 6% of blue colorant, wherein the mass ratio of the materials to the deionized water is 1: 1.2, ZrO is selected₂Grinding balls, mixing materials by a wet method for 6 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1200 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2 microns. The silicate ceramic powder can be applied to the preparation of a sheet type power divider.

Example 5

Based on example 1, Li in the preparation of glass powder₂CO₃By changing to K₂CO₃And MgO is replaced by basic magnesium carbonate. Changing CuO in preparation of blue colorant to MnO₂. The finally prepared silicate ceramic powder is applied to preparing a sheet filter.

Example 6

Based on example 1, the composition of the silicate ceramic powder was finally changed to: 23% of calcium carbonate, 20% of magnesium oxide and 22% of SiO₂30% of aluminoborosilicate glass and 5% of a blue colorant.

Example 7

Based on example 1, the composition of the silicate ceramic powder was finally changed to: 25% of calcium carbonate and 25% of SiO₂15% magnesium oxide, 30% aluminoborosilicate glass and 5% blue colorant.

Example 8

Based on example 1, the composition of the silicate ceramic powder was finally changed to: 28% of calcium carbonate, 12% of magnesium oxide and 25% of SiO₂32% of aluminum boron siliconAcid salt glass and 3% blue colorant.

Example 9

Based on example 1, the composition of the silicate ceramic powder was finally changed to: 23% of calcium carbonate and 25% of SiO ₂12% magnesium oxide, 32% aluminoborosilicate glass and 8% blue colorant.

Example 10

Based on example 1, the composition of the silicate ceramic powder was finally changed to: 37 percent of calcium carbonate and 20 percent of SiO₂20% magnesium oxide, 20% aluminoborosilicate glass and 3% blue colorant.

Comparative example 11

Weighing 20% KHCO according to the proportion (mass ratio)₃20 percent of basic magnesium carbonate and 15 percent of Al₂O₃10% of H₃BO₃And 35% SiO₂Using ZrO₂Mixing materials for 5h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.75 h at the melting temperature of 1450 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 1.2 mu m is obtained after drying. Weighing 37 percent of CaCO according to the proportion (mass ratio)₃20% of SiO₂20% MgO, 20% aluminoborosilicate glass and 3% Co₂O₃. According to the mass ratio of 1: 1.2, ZrO is selected₂Grinding balls, mixing materials by a wet method for 6 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1200 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2 microns. The silicate ceramic powder can be applied to the preparation of a sheet type power divider.

Comparative example 12

Weighing 15% of Na according to the proportion (mass ratio)₂CO₃20% of MgO and 15% of Al₂O₃10% of B₂O₃And 40% SiO₂Using ZrO₂Mixing materials for 5h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.5h at the melting temperature of 1500 ℃, and then pouring the molten liquid into water for quenching; the obtained glass culletThe blocks are ball-milled and crushed, and the glass powder with the granularity D50 of 1.2 mu m is obtained after drying. Weighing 20% of CaCO according to the proportion (mass ratio)₃25% of SiO ₂12% MgO, 30% aluminoborosilicate glass and 8% Co₂O₃According to the mass ratio of 1:1, ZrO is selected₂Grinding balls, mixing materials by a wet method for 12 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1350 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2.8 mu m. The silicate ceramic powder can be applied to the preparation of a sheet duplexer.

Comparative example 13

Weighing 15% KHCO according to the proportion (mass ratio)₃20 percent of basic magnesium carbonate and 15 percent of Al₂O₃20% of B₂O₃And 30% SiO₂Using ZrO₂Mixing materials for 8h by a ball milling dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 1h at the melting temperature of 1350 ℃, and then pouring the molten liquid into water for quenching; the obtained glass fragments are ball-milled and crushed, and the glass powder with the granularity D50 of 2.8 mu m is obtained after drying. Weighing 23% of CaCO according to the proportion (mass ratio)₃35% of SiO ₂12% MgO, 30% aluminoborosilicate glass and 10% Co₂O₃. According to the mass ratio of 1:1, ZrO is selected₂Grinding balls, mixing materials by a wet method for 12 hours, drying at 120 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1350 ℃ for 6 hours, and grinding and crushing to obtain silicate ceramic powder with the particle size D50 of 2.8 mu m. The silicate ceramic powder can be applied to the preparation of a sheet antenna.

The powders prepared in the examples 1 to 10 and the comparative examples 1 to 3 were subjected to dry pressing and sintering at 850 ℃ for 0.5h in an air atmosphere to prepare ceramic round blocks, ceramic round sheets and ceramic test strips, which were subjected to microwave dielectric property (test condition: 8.5GHz), density, thermal conductivity and bending strength tests, and the test results are summarized in Table 1.

TABLE 1

As can be seen from Table 1, compared with comparative ratios of 11 to 13, the blue low-temperature co-fired low-dielectric microwave dielectric ceramic materials prepared in examples 1 to 10 have low dielectric loss at high frequency (8.5GHz), which is 20 to 42 × 10^-4The composite material has high mechanical strength and bending strength of 300-400 MPa. Can meet the requirements of various chip frequency devices. The ceramic frequency device prepared by the ceramic material through the LTCC process technology has the characteristics of simple firing process, high mechanical strength, excellent dielectric property, light shading property and the like, can be better than alumina ceramic in performance, is better than common silicate ceramic in light shading effect, meets the manufacturing requirements of chip frequency devices such as chip filters, chip antennas, chip duplexers, chip power dividers and the like, and has obvious advantages.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments without departing from the principle and spirit of the present invention, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the technical scope of the present invention.

Claims

1. A blue low-temperature co-fired low-dielectric microwave dielectric ceramic material is characterized in that: the ceramic material comprises the following components in percentage by weight:

calcium carbonate: 20-40%;

silicon dioxide: 20-40%;

magnesium oxide: 10-30%;

aluminoborosilicate glass: 18-38%;

blue colorant: 2-10%;

the sum of the above components is 100%.

2. The blue low-temperature co-fired low-dielectric microwave dielectric ceramic material as claimed in claim 1, wherein the ceramic material comprises the following components in percentage by weight:

calcium carbonate: 23-38%;

silicon dioxide: 25-32%;

magnesium oxide: 12-25%;

aluminoborosilicate glass: 20-32%;

blue colorant: 3-8%;

the sum of the above components is 100%.

3. The blue low-temperature co-fired low-dielectric microwave dielectric ceramic material as claimed in claim 1 or 2, wherein the blue colorant comprises the following components in percentage by mass:

CoAl₂O₄：75%～100％；

MO：0～25％；

the sum of the above components is 100%;

wherein MO is metal oxide CuO, NiO, CoO and MnO₂One or more of; wherein CoO and MnO₂May be made of Co respectively₂O₃And MnCO₃Replacing by equivalent molar quantity of metal atoms.

4. A blue low-temperature co-fired low-dielectric microwave dielectric ceramic material according to any one of claims 1 to 3, wherein the aluminoborosilicate glass comprises, in mass percent:

A₂O：0~15%；

RO：0~20%；

Al₂O₃：15~35%；

B₂O₃：10~30%；

SiO₂：30~65%；

the sum of the above components is 100%;

5. The preparation method of the blue low-temperature co-fired low-dielectric microwave dielectric ceramic material according to any one of claims 1 to 4, characterized by comprising the following steps:

2) the preparation method of the aluminoborosilicate glass comprises the following steps: according to the mass ratio: 0 to 15% of A₂O，0～20％RO，15～35％Al₂O₃，10～30％B₂O₃，30～65％SiO₂(ii) a Weighing Li₂CO₃、NaHCO₃Or Na₂CO₃、KHCO₃Or K₂CO₃MgO or basic magnesium carbonate, B₂O₃Or H₃BO₃、BaCO₃、CaCO₃、SrCO₃、Al₂O₃And SiO₂Using ZrO₂Mixing materials for 2-8 h by a ball grinding dry method, then putting the mixed powder into a platinum crucible, keeping the temperature and homogenizing for 0.5-1 h at the melting temperature of 1350-1500 ℃, and then pouring the molten liquid into water for quenching; the resulting glass fragmentsPerforming ball milling and crushing, and drying to obtain glass powder with the granularity D50 of 1.2-2.8 mu m;

6. The method for preparing a blue low-temperature co-fired low-dielectric microwave dielectric ceramic material as claimed in claim 5, wherein a blue colorant CoAl₂O₄The preparation method comprises the following steps: and (2) according to molar ratio: 1, weighing Al₂O₃And Co₂O₃Raw materials are mixed according to the mass ratio of 1: 1-1.5 adding ethanol, mixing materials by a wet method for 4-12h, drying at 80 ℃, sieving the dried mixture by a 40-mesh sieve, loading into an alumina crucible, calcining at 1150-1250 ℃ for 3-6h, and synthesizing CoAl₂O₄Grinding and crushing the main crystal phase to obtain CoAl with the grain diameter D50 of 1.0-2.5 mu m₂O₄And (3) powder.

7. The use of the blue low-temperature co-fired low-dielectric microwave dielectric ceramic material according to any one of claims 1 to 4, wherein the low-temperature co-fired ceramic material is used as a frequency device, a chip filter, a chip antenna, a chip duplexer, a chip power divider, and the like.