CN115626822A - Low-temperature sintered microwave dielectric ceramic material and preparation method and application thereof - Google Patents
Low-temperature sintered microwave dielectric ceramic material and preparation method and application thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 48
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- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 22
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- 229910052573 porcelain Inorganic materials 0.000 claims description 7
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000010344 co-firing Methods 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
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- 238000005516 engineering process Methods 0.000 description 8
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Abstract
The invention discloses a low-temperature sintering microwave dielectric ceramic material, a preparation method of the low-temperature sintering microwave dielectric ceramic material and application of the low-temperature sintering microwave dielectric ceramic material in preparing low-temperature co-fired ceramic taking metal Ag as an electrode, wherein the low-temperature sintering microwave dielectric ceramic material has a chemical general formula as follows: zn 1.92 Cu 0.08 GeO 4 ‑y wt.％B 2 O 3 Wherein y =0.25 to 1; ceramic material of the inventionThe sintering temperature is below 960 ℃, the co-firing condition with metal electrode Ag (melting point 961 ℃) is met, zn 1.92 Cu 0.08 GeO 4 +0.5wt.％B 2 O 3 The ceramic material shows good dielectric property after being co-fired with the silver electrode at 940 ℃: epsilon r =7.38, q × f =108500GHz and τ f The temperature is not less than 25.3 ppm/DEG C, and the electronic component can be stacked with the conductive electrode and then subjected to multilayer co-firing to prepare a miniaturized, integrated, multi-adaptability, low-cost and large-scale electronic component; the chemical composition and the preparation process are simple, and the method can be used for industrial production.
Description
Technical Field
The invention belongs to the technical field of microwave dielectric ceramic materials and low-temperature sintering, and particularly relates to a low-temperature sintered microwave dielectric ceramic material and a preparation method and application thereof.
Background
Microwave dielectric ceramics refer to ceramic materials that are used as dielectric materials and perform one or more functions in microwave frequency band circuits. Microwave dielectric ceramics, as a new electronic material, are used in modern communications as resonators, filters, dielectric substrates, dielectric antennas, dielectric guided wave circuits, and the like. The low temperature co-fired ceramic (LTCC) integrates the microwave dielectric material by sintering at low temperature, and can superpose the microwave dielectric material meeting the conditions with the conductive electrode and then carry out multi-layer co-firing to prepare the miniaturized, integrated, multi-adaptability, low-cost and large-scale electronic component. The low temperature preparation under the LTCC technology is widely applied to many fields of microwave technology, such as mobile phones, satellite broadcasting, radars, radio remote control and the like, and realizes the upgrading of electronic components and reduces the energy consumption.
Low dielectric constant microwave dielectric materials, which are widely used in the development of modern communication systems due to their excellent characteristics, are used as substrate materials for microwave integrated circuits or components related to millimeter communication. For substrate material applications, the dielectric material should have a low dielectric constant (ε) r ) To shorten signal delay time, with high quality factor (Q f) to reduce power dissipation and near-zero temperature coefficient of resonance frequency (tau) f ) To produce a temperature resistant device. Recently, electronic components for microwave communication have been reduced in size and increased in performance requirements, and such miniaturization requirements can be achieved using low temperature co-fired ceramic (LTCC) technology. Generally, metallic Ag having a melting point of about 960 c is frequently used as an electrode in LTCC devices because it is very conductive and inexpensive. Microwave dielectric ceramics for LTCC devices must be belowAnd 960 c, because they are sintered at a temperature not higher than the melting point of Ag electrodes during sintering.
With the continuous development of low temperature co-fired ceramic (LTCC) technology, the application and research prospects of microwave dielectric ceramic materials are wider. Three main performance indexes epsilon of microwave dielectric ceramics r 、Q×f、τ f These three properties are mutually restricted. Before conclusion, the microwave dielectric ceramic sintering is basically completed at high temperature. At present, the microwave dielectric ceramic sintered at low temperature can meet three performance requirements of the microwave dielectric ceramic, and the microwave ceramic in pure phase rarely exists. Usually, a low Q f quality factor or τ occurs f The temperature coefficient of the resonance frequency is not close to zero, and the expected requirement cannot be met for practical application. These have restricted the development of low temperature co-fired ceramic technology. The exploration and research of the potential material which can reduce energy consumption through low-temperature sintering and realize LTCC technology and has high microwave dielectric property are the directions of future development and breakthrough.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-temperature sintering microwave dielectric ceramic material which can be sintered at low temperature and simultaneously shows good microwave dielectric property combination and a preparation method thereof, and can be used for preparing low-temperature co-fired ceramic taking metal Ag as an electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-temperature sintered microwave dielectric ceramic material has a chemical formula as follows: zn 1.92 Cu 0.08 GeO 4 -y wt.％B 2 O 3 Wherein y =0.25 to 1.
The preparation method of the low-temperature sintering microwave dielectric ceramic material comprises the following steps:
step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully ball-milling and mixing the raw materials in a planetary ball mill by taking absolute ethyl alcohol as a medium to obtain uniformly mixed slurry, pouring the ball-milled slurry into a tray, and placing the trayDrying in a drying oven to obtain a dry mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the presintering temperature of 600 ℃ for 4 hours, and reacting to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 According to the mass percentage (99-99.75): (0.25-1), weighing and proportioning, fully ball-milling and mixing the raw materials in a planetary ball mill by taking absolute ethyl alcohol as a medium, putting an inverted raw stock tray after ball milling into an oven and drying to obtain a dry mixture;
step four, adding a binder accounting for 3-7% of the mass of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing compression molding by using a mold;
and step five, placing the green porcelain formed by pressing in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 900-960 ℃ for 5-8 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
Preferably, the ZnO, cuO and GeO are 2 And B 2 O 3 The purity of (2) was 99.99%.
Preferably, the ball milling mixing in the step one is ball milling for 8 hours under the rotating speed condition of 300 r/min.
Preferably, the drying in the first step and the second step is drying at 80 ℃ for 6 hours.
Preferably, the ball milling mixing in the second step is ball milling for 6 hours under the condition of the rotating speed of 300 r/min.
Preferably, the binder in the fourth step is a polyvinyl alcohol solution with a mass concentration of 5%.
The invention also protects the application of the low-temperature sintered microwave dielectric ceramic material in preparing low-temperature co-fired ceramic taking metal Ag as an electrode.
Compared with the prior art, the invention has the following technical effects:
the microwave medium ceramic material formula of the inventionHas excellent combination of microwave dielectric properties, zn 1.92 Cu 0.08 GeO 4 +0.5wt.％B 2 O 3 The microwave dielectric property of the ceramic material at 940 ℃ can reach: epsilon r ＝7.38，Q×f＝108500GHz，τ f ＝-25.3ppm/℃；
The sintering temperature of the microwave dielectric ceramic material is below 960 ℃, the microwave dielectric ceramic material meets the co-firing condition with a metal electrode Ag (melting point 961 ℃), has no chemical reaction with Ag during co-firing, can be used as a potential candidate material of an LTCC technology, and can be stacked with a conductive electrode to perform multilayer co-firing to prepare miniaturized, integrated, multi-adaptability, low-cost and large-scale electronic components; the chemical composition and the preparation process are simple, and the method can be used for industrial production.
Drawings
Fig. 1 is an XRD spectrum of the microwave dielectric ceramic material prepared in examples 1 to 4;
FIG. 2 is an XRD pattern of a low temperature co-fired ceramic material prepared in example 5;
FIG. 3 is an SEM image of a low temperature co-fired ceramic material prepared in example 5;
FIG. 4 is an EDS diagram of a low temperature co-fired ceramic material prepared in example 5.
Detailed Description
The present invention will be explained in further detail with reference to examples.
ZnO, cuO, geO in the following examples 2 And B 2 O 3 The purity of (2) is 99.99%;
the polyvinyl alcohol is 1799 type product produced by Shanghai Aladdin Biotechnology GmbH, and the alcoholysis degree is 98-99%.
Example 1
Step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully mixing the raw materials in a planetary ball mill for 8 hours by using absolute ethyl alcohol as a medium at a speed of 300r/min to obtain uniformly mixed slurry, pouring the slurry subjected to ball milling into a tray, putting the tray into an oven, and drying the tray for 6 hours to obtain a dry mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the temperature of 600 ℃ for 4 hours to react to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 Weighing and proportioning according to the mass percentage of 99.75;
step four, adding a binder accounting for 3% of the mass of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing column pressing molding by using a mold;
and step five, placing the green porcelain formed by pressing in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 900 ℃ for 6 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
Example 2
Step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully mixing the raw materials in a planetary ball mill for 8 hours by using absolute ethyl alcohol as a medium at a speed of 300r/min to obtain uniformly mixed slurry, pouring the slurry subjected to ball milling to a tray, putting the tray into an oven at a temperature of 80 ℃, and drying for 6 hours to obtain a dried mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the presintering temperature of 600 ℃ for 4 hours, and reacting to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 Weighing and proportioning according to the mass percentage of 99.56 hours, obtaining a dry mixture;
step four, adding a binder accounting for 5% of the mass of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing compression molding by using a mold;
and step five, placing the green porcelain pressed and formed in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 940 ℃ for 5 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
Example 3
Step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully mixing the raw materials in a planetary ball mill for 8 hours by using absolute ethyl alcohol as a medium at a speed of 300r/min to obtain uniformly mixed slurry, pouring the slurry subjected to ball milling to a tray, putting the tray into an oven at a temperature of 80 ℃, and drying for 6 hours to obtain a dried mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the temperature of 600 ℃ for 4 hours to react to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 Weighing and proportioning the raw materials according to the mass percentage of 99.25 to 0.75, fully mixing the raw materials in a ball mill in a planetary ball mill for 6 hours at 300r/min by taking absolute ethyl alcohol as a medium, putting an inverted tray of the ball-milled raw stock in an oven at 80 ℃, and drying for 6 hours to obtain a dry mixture;
step four, adding a binder with the mass of 7% of that of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing column pressing molding by using a mold;
and step five, placing the green porcelain formed by pressing in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 960 ℃ for 7 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
Example 4
Step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully mixing the raw materials in a planetary ball mill for 8 hours by using absolute ethyl alcohol as a medium at a speed of 300r/min to obtain uniformly mixed slurry, pouring the slurry subjected to ball milling into a tray, putting the tray into an oven, and drying the tray for 6 hours to obtain a dry mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the presintering temperature of 600 ℃ for 4 hours, and reacting to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 Weighing and proportioning according to the mass percentage of 99, taking absolute ethyl alcohol as a medium, performing ball milling on the raw materials in a planetary ball mill for 6 hours at a speed of 300r/min, fully mixing the raw materials, inverting a tray after ball milling, putting the inverted tray into an oven for 80 ℃, and drying the tray for 6 hours to obtain a dry mixture;
step four, adding a binder with the mass of 6% of that of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing column pressing molding by using a mold;
and step five, placing the green porcelain formed by pressing in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 920 ℃ for 8 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
Example 5
Step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully mixing the raw materials in a planetary ball mill for 8 hours by using absolute ethyl alcohol as a medium at a speed of 300r/min to obtain uniformly mixed slurry, pouring the slurry subjected to ball milling to a tray, putting the tray into an oven at a temperature of 80 ℃, and drying for 6 hours to obtain a dried mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the temperature of 600 ℃ for 4 hours to react to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 Weighing and proportioning according to the mass percent of 99.5;
step four, adding a binder accounting for 5% of the mass of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing compression molding by using a mold;
and step five, placing the green porcelain formed by pressing in the step four in a muffle furnace for high-temperature sintering at 940 ℃ for 5 hours to obtain the low-temperature co-fired ceramic material.
And (3) performing phase analysis on the sintered ceramic sample by using a powder X-ray diffraction method, performing structural analysis on the ceramic sample by using a scanning electron microscope, and performing microwave dielectric property evaluation by using a cylindrical dielectric resonator method.
Fig. 1 is an XRD spectrum of the microwave dielectric ceramic material prepared in examples 1 to 4; FIG. 1 shows that all samples detected a single phase and a second phase, indicating the addition of B 2 O 3 To the parent Zn 2 GeO 4 Limited phase formation and crystallization;
FIG. 2 is an XRD pattern of a low temperature co-fired ceramic material prepared in example 5; FIG. 2 demonstrates the chemical compatibility of the ceramic with silver cofiring at 940 deg.C, and only Zn is detected in FIG. 2 2 GeO 4 And Ag (PDF # 87-0597) diffraction peaks, indicating that no chemical reaction occurred between the ceramic and Ag.
FIG. 3 is an SEM image of a low temperature co-fired ceramic material prepared in example 5; FIG. 4 is an EDS diagram of a low temperature co-fired ceramic material prepared in example 5; as shown in FIGS. 3 and 4, zn was obtained 1.92 Cu 0.08 GeO 4 -0.5wt.％B 2 O 3 Microstructure and acquisition of distributed elements; SEM atlas shows that the ceramic material microstructure is relatively uniform and compact; EDS diagram shows elements constituting the materialThe components comprise O, zn, ge and Ag, which shows that the ceramic and the Ag do not have chemical reaction; SEM and EDS analysis, further confirming the coexistence of silver with the ceramic matrix; and large grains (highlighted with # symbol) were identified as Ag, most importantly, zn 1.92 Cu 0.08 GeO 4 +0.5wt.％B 2 O 3 The ceramic has good chemical compatibility with Ag at 940 ℃, which is consistent with the result obtained by XRD, and is a potential ceramic material capable of meeting the application requirements of LTCC.
TABLE 1 Zn 1.92 Cu 0.08 GeO 4 -y wt.％B 2 O 3 Microwave dielectric properties corresponding to each component of the microwave dielectric ceramic material (y = 0.25-1).
As can be seen from Table 1, zn 1.92 Cu 0.08 GeO 4 -0.5wt.％B 2 O 3 The formula has the best microwave dielectric property: epsilon r ＝7.38，Q×f＝108500GHz，τ f = 25.3 ppm/DEG C, and can be cofired with Ag at low temperature.
The microwave dielectric ceramic material prepared by the invention has excellent dielectric property combination, can be sintered at a low temperature of below 960 ℃, can be used as a potential ceramic material for realizing LTCC technology, and can be stacked with a conductive electrode and then subjected to multilayer co-firing to prepare miniaturized, integrated, multi-adaptive, low-cost and large-scale electronic components. The chemical composition and the preparation process are simple, and the method can be used for industrial production.
Other embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and all such modifications and equivalents may be resorted to without departing from the spirit and scope of the invention.
Claims (8)
1. A low-temperature sintered microwave dielectric ceramic material is characterized in that the chemical general formula is as follows: zn 1.92 Cu 0.08 GeO 4 -y wt.％B 2 O 3 Wherein y =0.25 to 1.
2. A method of preparing a low temperature sintered microwave dielectric ceramic material as claimed in claim 1, comprising the steps of:
step one, according to a chemical general formula Zn 1.92 Cu 0.08 GeO 4 In the stoichiometric ratio, znO, cuO and GeO are weighed 2 Fully ball-milling and mixing the raw materials in a planetary ball mill by taking absolute ethyl alcohol as a medium to obtain uniformly mixed slurry, pouring the ball-milled slurry into a tray, and drying in an oven to obtain a dry mixed raw material;
step two, placing the dry mixed raw material prepared in the step one in a muffle furnace for high-temperature presintering at the temperature of 600 ℃ for 4 hours to react to obtain single-phase Zn 1.92 Cu 0.08 GeO 4 ；
Step three: the single-phase Zn prepared in the second step 1.92 Cu 0.08 GeO 4 And B 2 O 3 According to the mass percentage (99-99.75): (0.25-1), weighing and proportioning, fully ball-milling and mixing the raw materials in a planetary ball mill by taking absolute ethyl alcohol as a medium, putting an inverted tray of the primary pulp after ball milling into an oven for drying, and obtaining a dry mixture;
step four, adding a binder accounting for 3-7% of the mass of the dry mixture prepared in the step three into the dry mixture, uniformly mixing, granulating, and then performing compression molding by using a mold;
and step five, placing the green porcelain pressed and formed in the step four in a muffle furnace for high-temperature sintering at the sintering temperature of 900-960 ℃ for 5-8 hours to obtain the low-temperature sintered microwave dielectric ceramic material.
3. A method for preparing a low temperature sintered microwave dielectric ceramic material as claimed in claim 2, wherein said ZnO, cuO, geO 2 And B 2 O 3 The purity of (2) was 99.99%.
4. The method for preparing a low temperature sintered microwave dielectric ceramic material as claimed in claim 2, wherein the ball milling mixing in the step one is ball milling for 8 hours at a rotation speed of 300 r/min.
5. The method for preparing a low temperature sintered microwave dielectric ceramic material as claimed in claim 2, wherein the drying in the first and second steps is drying at 80 ℃ for 6 hours.
6. The method for preparing low temperature sintering microwave dielectric ceramic material according to claim 2, wherein the ball milling and mixing in step two is ball milling for 6 hours at a rotation speed of 300 r/min.
7. The method for preparing microwave dielectric ceramic material by low temperature sintering according to claim 2, wherein the binder in the fourth step is polyvinyl alcohol solution with mass concentration of 5%.
8. Use of the low-temperature sintered microwave dielectric ceramic material of claim 1 in the preparation of a low-temperature co-fired ceramic with metal Ag as an electrode.
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