CN117303866A - Dielectric constant regulating and controlling method and preparation method of ceramic substrate material - Google Patents

Dielectric constant regulating and controlling method and preparation method of ceramic substrate material Download PDF

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CN117303866A
CN117303866A CN202311052434.1A CN202311052434A CN117303866A CN 117303866 A CN117303866 A CN 117303866A CN 202311052434 A CN202311052434 A CN 202311052434A CN 117303866 A CN117303866 A CN 117303866A
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substrate material
dielectric constant
glass powder
ceramic
ceramic substrate
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海韵
吕子彬
吕金玉
那华
郭恩霞
曹禹
徐博
朱宝京
韩滨
祖成奎
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China Building Materials Academy CBMA
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Abstract

The invention relates to the technical field of ceramic materials, in particular to a dielectric constant regulating and controlling method and a preparation method of a ceramic substrate material, wherein the ceramic substrate material comprises the following components: at least two glass powder bodies with different particle sizes, ceramic powder bodies and an organic carrier; the dielectric constant of the ceramic substrate material is regulated and controlled by regulating the proportion of the glass powder with different particle sizes. The glass powder at least comprises large-particle glass powder with a median particle diameter of 2.5-2.8 microns and small-particle glass powder with a median particle diameter of 1.1-1.4 microns. The invention controls the compactness of the sintering substrate by adjusting the grain size grading of the glass powder in the LTCC slurry, thereby realizing the ceramic substrate material with adjustable dielectric constant under the condition of small fluctuation of mechanical property, and having wide application prospect in the fields of electronic ceramic elements, electronic device packaging and the like.

Description

Dielectric constant regulating and controlling method and preparation method of ceramic substrate material
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a dielectric constant regulating and controlling method and a preparation method of a ceramic substrate material.
Background
The microwave dielectric ceramic is a novel electronic material which is used as a dielectric material in a microwave (300 MHz < f <300 GHz) frequency band and realizes multiple functions. The microwave has the characteristics of short wavelength, high working frequency, strong directivity, strong penetrating power and the like, and plays an important role in the 5G field. The material can be used as a resonator, a filter and a substrate material, and can also realize satellite communication and the like. The dielectric property is the most important property of the microwave dielectric ceramic, including dielectric constant, dielectric loss and the like, and in addition, the microwave dielectric ceramic also has good mechanical property, and in practical application, various performance indexes need to be comprehensively considered.
The low temperature co-fired ceramic, LTCC, is a typical microwave dielectric ceramic technology, has become the mainstream mode of electronic component integration, and is widely applied to wireless communication in the field of high precision. By adjusting the LTCC material system, the component proportion, the additive and the like, ceramic substrate materials with different dielectric constants can be obtained to meet the requirements of different application scenes.
In recent years, although many microwave dielectric materials having different dielectric constants have been developed, the main difficulty in developing new LTCC materials is that not only excellent dielectric properties are satisfied, but also excellent mechanical properties should be provided as a support material for mounting electronic components. At present, for the same material system, the dielectric constant of the ceramic substrate material is changed by adjusting the component proportion and adding the additive, and the mechanical property of the ceramic substrate material is also adversely affected; while the dielectric constant can be adjusted in a small range by surface modification and other methods, additional process flows and cost are added.
Accordingly, there is a need to provide an improved dielectric constant control method while maintaining excellent mechanical properties thereof to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a dielectric constant regulating and controlling method and a preparation method of a ceramic substrate material, wherein the ceramic substrate material with adjustable dielectric constant is obtained by regulating the grain size grading of glass powder in LTCC slurry, and meanwhile, excellent mechanical properties are maintained.
In order to achieve the above object, in a first aspect, the present invention provides a method for controlling a dielectric constant of a ceramic substrate material, where the ceramic substrate material comprises: at least two glass powder bodies with different particle sizes, ceramic powder bodies and an organic carrier; the dielectric constant of the ceramic substrate material is regulated and controlled by regulating the proportion of the glass powder with different particle sizes.
According to the invention, the research shows that the dielectric constant of the glass powder can be regulated and controlled without complex surface modification and other additives, and only the grain size grading of the glass powder is regulated and controlled, and the mechanical property of the glass powder can be ensured, so that the preparation process is obviously simplified, and the preparation cost is reduced.
Further, the dielectric constant of the ceramic substrate material at 5GHz is adjustable within a range of 6.7-7.5, preferably within a range of 6.9-7.5; and the flexural strength fluctuates within the range of 210+/-10 MPa; preferably within the range of 210.+ -.5 MPa. The dielectric constant of the ceramic substrate material can be stable and adjustable within the range of 6.7-7.5, namely, the ceramic substrate material is obtained by repeated preparation of glass powder with the same grain size gradation, and the deviation of the dielectric constant is less than or equal to 0.03, preferably less than or equal to 0.02.
The small change interval of the flexural strength indicates that the change of the grain size grading of the glass powder can lead to different densification degrees of the substrate under the ceramic composition system of the invention, but the wide fluctuation of mechanical properties cannot be caused, which is not realized in the prior art.
Further, the glass powder at least comprises large-particle glass powder with a median particle diameter of 2.5-2.8 microns and small-particle glass powder with a median particle diameter of 1.1-1.4 microns. Preferably, the large-particle glass powder and the small-particle glass powder are the same glass powder. The glass powder with the two particle sizes is selected for compounding, so that the fluctuation degree of the flexural strength can be minimized, and the dielectric constants are changed to different degrees. When the particle diameter of the large-particle glass powder is too large or the particle diameter of the small-particle glass powder is too small, the flexural strength is also greatly affected although the dielectric constant can be changed.
The mass ratio of the large-particle glass powder to the small-particle glass powder is 0:10-10:0, preferably 1:9-9:1.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.5 microns and a small particle glass frit having a median particle size of 1.1 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.6 microns and a small particle glass frit having a median particle size of 1.1 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.7 microns and a small particle glass frit having a median particle size of 1.2 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.8 microns and a small particle glass frit having a median particle size of 1.3 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.8 microns and a small particle glass frit having a median particle size of 1.4 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.5 microns and a small particle glass frit having a median particle size of 1.4 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.7 microns and a small particle glass frit having a median particle size of 1.3 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
In some embodiments, the glass frit comprises a large particle glass frit having a median particle size of 2.6 microns and a small particle glass frit having a median particle size of 1.4 microns in a mass ratio of 1:10, 1:8, 1:6, 1:5, 1:4, 1:2, 1:1, 1:0.8, 1:0.5, 1:0.2, 1:0.1, etc.
According to the invention, the glass powder with different particle sizes is subjected to particle size grading according to a certain proportion, so that the densification degree of the sintered substrate is controlled. After the glass powder with different particle sizes is graded, the glass powder forms different dispersion and accumulation states in the raw porcelain, so that the densification degree of the sintered substrate is different, namely, the sintered substrate has different pore space ratios. Therefore, the ceramic substrate material with adjustable dielectric constant is realized under the condition of small fluctuation of the mechanical property of the ceramic substrate material.
Further, the glass powder is an untreated glass powder, preferably an untreated calcium boron lanthanum glass powder. The invention is based on the research of untreated glass powder, namely, the surface treatment of the glass powder is not needed, and the dielectric constant can be regulated and controlled only by regulating the particle size of the glass powder, so that the preparation process is simplified, and the cost is reduced.
Further, the ceramic powder is selected from one or more of alpha-alumina, beta-alumina and gamma-alumina, and the particle size of the ceramic powder is 3.8-4.0 microns.
Further, the ceramic substrate material comprises the following components in percentage by mass: 15-40wt% of glass powder with at least two different particle sizes, 30-50wt% of ceramic powder and 15-40wt% of organic carrier.
Further, the organic vehicle includes a solvent, a binder, and a plasticizer.
The solvent comprises at least two of ethyl acetate, butyl acetate and isopropanol; the binder comprises at least one of polymethyl methacrylate and polyvinyl butyral; the plasticizer includes at least one of dibutyl phthalate and dioctyl phthalate.
Further, the solvent accounts for 50-85% of the mass of the organic carrier, preferably 68-78%, more preferably 70-75%; the binder accounts for 10-25% of the mass of the organic carrier, preferably 12-20%, more preferably 15-18%; the plasticizer comprises 0.1-20%, preferably 5-15%, more preferably 8-11% of the organic vehicle by weight.
Further, the ceramic substrate material is LTCC low-temperature co-fired ceramic.
Further, the method for regulating and controlling the dielectric constant of the ceramic substrate material comprises the following steps: (a) The size grading is carried out by using two glass powders with the size, wherein the median diameter of the large glass powder particles is 2.5-2.8 microns, and the median diameter of the small glass powder particles is 1.1-1.4 microns. (b) And ball-milling and mixing the graded glass powder, the ceramic powder and the organic carrier to obtain ceramic slurry. (c) casting the ceramic slurry to obtain a green ceramic tape; (d) And cutting, hot-pressing lamination and sintering the green ceramic tape to obtain the ceramic substrate material.
In a second aspect, the present invention provides a ceramic substrate material with an adjustable dielectric constant, which is obtained by using the regulation method described in any one of the above.
In a third aspect, the present invention provides a method for preparing a ceramic substrate material with an adjustable dielectric constant, comprising:
step one, carrying out grain size grading on at least two glass powders with different grain sizes to obtain graded glass powder;
step two, mixing the solvent, the binder and the plasticizer, and stirring to obtain an organic carrier;
thirdly, ball-milling and mixing the graded glass powder, the ceramic powder and the organic carrier to obtain ceramic slurry;
and step four, carrying out vacuum defoaming treatment on the ceramic slurry, and then casting to obtain the LTCC green ceramic tape.
And fifthly, cutting, laminating, hot pressing and sintering the green ceramic tape to obtain the ceramic substrate material.
Further, the casting speed is 0.5 m/min-1.0 m/min;
the ball milling and mixing time is 36-60h;
the sintering temperature is 845-895 ℃ and the sintering time is 18-36h.
Further, the thickness of the LTCC green tape is 100-130 micrometers, and the number of layers of the LTCC green tape in the laminated layers is 6-12.
The beneficial effects of the invention are as follows:
1. the ceramic substrate material with adjustable dielectric constant provided by the invention has the advantages that the grain size grading of glass powder in ceramic slurry is regulated, and the compactness of a sintered substrate is controlled, so that the ceramic substrate material with adjustable dielectric constant is obtained under the condition of small fluctuation of mechanical properties, and the ceramic substrate material has high production value and research significance, and has wide application prospects in the fields of electronic ceramic elements, electronic device packaging and the like.
2. The invention has low production cost, simple process and controllable reaction conditions, and is suitable for regulating and controlling a large quantity of casting slurry, thereby obtaining a plurality of batches of ceramic substrate materials with adjustable dielectric constants.
3. Under the condition of ensuring that the ceramic powder and other LTCC slurry have the same components, the invention independently adjusts the granularity grading of the glass powder, avoids interference caused by multiple variables, finally obtains ceramic substrate materials with different densification degrees, and achieves the purpose of adjustable dielectric constant.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram showing the distribution of glass powder in a raw porcelain material provided by the invention.
FIG. 2 shows XRD patterns of ceramic substrate materials obtained by sintering at 845 ℃ in examples 3, 4, 7 and 8 of the present invention.
FIG. 3 is a sectional scanning electron micrograph of a ceramic substrate material sintered at 845℃according to examples 3, 4, 7, 8 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a first ceramic substrate material with adjustable dielectric constant prepared by preparing ceramic slurry through size grading of glass powder of a large size and a small size and tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 40g and D of glass frit of 2.5 μm 50 160g of glass powder with the particle size of 1.1 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 7.221 at normal temperature and 5GHz, and the flexural strength is 210.6MPa.
Example 2
The embodiment provides a second ceramic substrate material with adjustable dielectric constant, which is prepared by performing grain size grading on two kinds of glass powder, preparing ceramic slurry, and performing tape casting molding and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 90g and D of glass frit of 2.5 μm 50 110g of glass powder with the particle size of 1.4 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 7.018 at normal temperature and 5GHz, and the flexural strength is 206.3MPa.
Example 3
The third embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry by size grading of glass powder and tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 Glass frit 120g and D at 2.8 microns 50 80g of glass powder with the particle size of 1.1 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 7.508 at normal temperature and 5GHz, and the flexural strength is 209.8MPa.
Example 4
The fourth embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry by size grading of glass powder and tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 160g and D of glass frit of 2.8 microns 50 40g of glass powder with the particle size of 1.4 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 6.912 at normal temperature and 5GHz, and the flexural strength is 205.2MPa.
Example 5
The fifth embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry by size grading of glass powder of two sizes and tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 40g and D of glass frit of 2.6 μm 50 160g of glass powder with the particle size of 1.1 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 7.205 at normal temperature and 5GHz, and the flexural strength is 211.4MPa.
Example 6
The sixth embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry through size grading of glass powder of two sizes, tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Weighing D respectively by electronic balance 50 160g and D of glass frit of 2.5 microns 50 40g of glass powder with the particle size of 1.3 microns is added into a mixer to be mixed, and the mixture is mixed for 10min at the normal temperature of 25 ℃;
(2) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(3) 240g of alpha-alumina powder and 200g of graded glass powder are weighed by an electronic balance and added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(4) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(5) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 6.903 at normal temperature and 5GHz, and the flexural strength is 207.7MPa.
Example 7
The seventh embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry through size grading of glass powder of a large size and a small size, tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(2) Separately weighing 240g of alpha-alumina powder by an electronic day scale, and D 50 200g of glass powder with the particle size of 2.6 microns is added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(3) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(4) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 6.702 at normal temperature and 5GHz, and the flexural strength is 208.1MPa.
Example 8
The seventh embodiment provides a ceramic substrate material with adjustable dielectric constant obtained by preparing ceramic slurry through size grading of glass powder of a large size and a small size, tape casting forming and sintering, and a preparation method thereof, and the specific steps are as follows:
(1) Respectively weighing 120g of ethyl acetate, 120g of butyl acetate, 55g of acrylic resin and 30g of dioctyl phthalate in a ball milling tank by using an electronic day, adding a ball milling medium, and premixing for 4 hours at the normal temperature of 25 ℃ to obtain an organic carrier which is uniformly dispersed and has no undissolved particles;
(2) Separately weighing 240g of alpha-alumina powder by an electronic day scale, and D 50 200g of glass powder with the particle size of 1.3 microns is added into a ball milling tank which is provided with an organic carrier in advance, and ball milling is carried out for 36 hours at the normal temperature of 25 ℃.
(3) The ceramic slurry is subjected to vacuum defoaming treatment, and then the LTCC green ceramic tape with the thickness of 120 micrometers is obtained at the casting speed of 0.8 m/min.
(4) Cutting the green porcelain belt, stacking 8 layers of porcelain belts, hot-pressing to obtain a bar block, placing the bar block in a sintering furnace, and heating the bar block to 845 ℃ in a gradient way, wherein the total sintering time is 20 hours.
The dielectric constant of the ceramic substrate material obtained by testing is 7.306 at normal temperature and 5GHz, and the flexural strength is 212.4MPa.
Table 1 particle size grading of examples 1-8
Dielectric constant test and flexural strength test method
Dielectric constant: and testing by using a Keysight E5080B resonant cavity network analyzer to obtain the dielectric constant of the sample at 5GHz, wherein the testing precision is within +/-0.02.
Flexural strength: referring to a national standard GB/T6569-2006 fine ceramic bending strength test method, preparing a three-point bending test sample of a sintered substrate, and carrying out three-point bending strength test on an E42 universal tester of the MTS company in the United states, wherein the stress surface of the test sample is polished by diamond, the test span is 15mm, and the moving speed of a pressure head is 0.5mm/min, so that the maximum bending strength of the test sample is obtained.
TABLE 2 dielectric constant and flexural Strength for examples 1-8
As can be seen from tables 1 and 2, in the particle size interval defined in the present invention, the ratio of the amounts of the two particle size glass powders is mainly affected on the dielectric constant. For example, the ratio of the amounts used in examples 1 and 5 was the same, the dielectric constant was the same, and the ratio of the amounts used in examples 4 and 6 was the same, the dielectric constant was the same. And it can be seen from examples 3 and 4 that when the content of the glass powder with large particle size is far higher than that of the glass powder with small particle size (the ratio of the two glass powders is not less than 4), the glass powder with small particle size is difficult to completely fill the pores formed by the glass powder with large particle size, so that the porosity is higher, the dielectric constant is correspondingly reduced, but the breaking strength is not obviously reduced, which indicates that the glass powder with two particle sizes has a certain synergism on mechanical properties so as to offset the influence of the pores on the strength. When the content of the glass powder with large particle size is close to that of the glass powder with small particle size (the ratio of the two is about 1.3-1.6), the porosity is lower, and the dielectric constant is correspondingly larger.
Fig. 1 is a schematic diagram showing the distribution of glass powder in a raw porcelain material provided by the invention. a is the distribution state of large-particle glass powder, alumina powder and air holes, b is the distribution state of small-particle glass powder, alumina powder and air holes, and c is the distribution state of large-particle glass powder, small-particle glass powder, alumina powder and air holes.
Fig. 2 shows XRD patterns of ceramic substrate materials obtained by sintering at 845 ℃ in examples 3, 4, 7 and 8 provided by the invention. The comparison shows that the crystallization peak positions and the intensities of the examples 3, 4, 7 and 8 are similar, and the crystallization peak positions and the intensities are not obviously changed, so that no new crystal phase is generated after the granularity grading of the glass powder is changed, which is an important precondition for ensuring that the mechanical properties of a material system are not obviously changed.
Fig. 3 is a sectional scanning electron microscope photograph of a ceramic substrate material obtained by sintering at 845 ℃ in examples 3, 4, 7 and 8 provided by the invention, and it can be observed that glass powders with different particle sizes have pores with different sizes on microcosmic inside a sample after graded sintering.
The organic binder is completely ablated during sintering, and the densification of the substrate is accomplished primarily by the flow of the liquid glass phase and rearrangement of the ceramic particles. After the glass powder with different particle sizes is graded, the glass powder forms different dispersion and accumulation states in the raw porcelain, so that the densification degree of the sintered substrate is different, namely, the sintered substrate has different pore space ratios.
An empirical formula is calculated according to the dielectric constants of multiphase materials with randomly arranged constituent materials:
lnε＝V 1 lnε 1 +V 2 lnε 2 (1)
wherein: epsilon is the dielectric constant of the material, epsilon 1 For the electrical constant, ε of constituent material 1 2 Is the dielectric constant of component material 2, V 1 V as the volume fraction of the constituent material 1 2 Is the volume fraction of the constituent material 2. It can be seen that the dielectric constant of the multiphase material and the groupsThe dielectric constant of the fraction is closely related to the volume fraction. As can be seen from FIG. 1, the samples of the different examples have substantially identical precipitated crystalline phases and relative contents, the dielectric constant of alumina is 9.8, and the main crystalline phase LaBO 3 The dielectric constant of the material is 11.8, the dielectric constant of air is about 1 and is far smaller than that of various crystalline phases and glass phases, so that the higher the pore ratio is, the lower the dielectric constant of the sample is. Therefore, the ceramic substrate material with adjustable dielectric constant is prepared by carrying out grain size grading on the two glass powders according to a certain proportion and controlling the densification degree of the sintered substrate. Meanwhile, as can be seen from the flexural strength test results of the present invention, under the particle size grading defined by the present invention, the flexural strength does not decrease significantly even due to the change of the pore ratio.
In order to further verify the stability effect of the particle size fraction of the present invention, the present invention conducted multiple sets of particle size fraction experiments, the particle size fractions being shown in Table 3.
TABLE 3 particle size grading of examples 9-20
TABLE 4 dielectric constant and flexural Strength for examples 9-20
Examples Dielectric constant Flexural strength (MPa)
Implementation of the embodimentsExample 9 7.219 210.2
Example 10 7.214 210.8
Example 11 7.031 206.9
Example 12 7.022 206.1
Example 13 7.493 209.4
Example 14 7.502 210.1
Example 15 6.918 205.8
Example 16 6.924 205.0
Example 17 6.781 208.9
Example 18 7.256 211.9
Example 19 6.325 178.8
Example 20 6.482 186.5
As can be seen from Table 4, when the mass ratio is the same, the fluctuation of the dielectric constant is less than 0.02 and the flexural strength fluctuates within the range of 210.+ -. 5MPa in the particle size interval defined by the present invention. When the proportion is changed, the dielectric constant is changed, which shows that the invention can adjust the dielectric constant and maintain the strength through the granularity grading of the glass powder. When the granularity is out of the limit of the invention, the dielectric constant is greatly changed, the flexural strength is obviously reduced, and the higher application requirement is difficult to meet.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. The method for regulating and controlling the dielectric constant of the ceramic substrate material is characterized by comprising the following components: at least two glass powder bodies with different particle sizes, ceramic powder bodies and an organic carrier; the dielectric constant of the ceramic substrate material is regulated and controlled by regulating the proportion of the glass powder with different particle sizes.
2. The method for controlling the dielectric constant of the ceramic substrate material according to claim 1, wherein the dielectric constant of the ceramic substrate material at 5GHz is adjustable within a range of 6.7-7.5, and the flexural strength fluctuates within a range of 210+/-10 MPa; preferably within the range of 210.+ -.5 MPa.
3. The method for controlling the dielectric constant of a ceramic substrate material according to claim 1 or 2, wherein the glass powder at least comprises large-particle glass powder with a median particle size of 2.5-2.8 microns and small-particle glass powder with a median particle size of 1.1-1.4 microns;
the mass ratio of the large-particle glass powder to the small-particle glass powder is 0:10-10:0.
4. The method for controlling the dielectric constant of the ceramic substrate material according to claim 1 or 2, wherein the glass powder is calcium-boron-lanthanum glass powder;
and/or the ceramic powder is selected from one or more of alpha-alumina, beta-alumina and gamma-alumina, and the particle size of the ceramic powder is 3.8-4.0 microns.
5. The method for controlling the dielectric constant of a ceramic substrate material according to any one of claims 1 to 4, wherein the components of the ceramic substrate material comprise, in mass percent: 15-40wt% of glass powder with at least two different particle sizes, 30-50wt% of ceramic powder and 15-40wt% of organic carrier.
6. The method for controlling dielectric constant of ceramic substrate material according to any one of claims 1 to 5, wherein the organic vehicle comprises a solvent, a binder and a plasticizer;
the solvent comprises at least two of ethyl acetate, butyl acetate and isopropanol; the binder comprises at least one of polymethyl methacrylate and polyvinyl butyral; the plasticizer includes at least one of dibutyl phthalate and dioctyl phthalate.
7. The method for controlling the dielectric constant of a ceramic substrate material according to claim 6, wherein the solvent accounts for 50-85% of the mass of the organic carrier; the binder accounts for 10-25% of the mass of the organic carrier; the plasticizer accounts for 5-15% of the organic vehicle;
and/or the ceramic substrate material is LTCC low-temperature co-fired ceramic.
8. A ceramic substrate material with an adjustable dielectric constant, characterized in that it is obtained by the regulation method according to any one of claims 1 to 7.
9. A method of preparing the dielectric constant adjustable ceramic substrate material of claim 8, comprising:
step one, carrying out grain size grading on at least two glass powders with different grain sizes to obtain graded glass powder;
step two, mixing the solvent, the binder and the plasticizer, and stirring to obtain an organic carrier;
step three, mixing the graded glass powder, the ceramic powder and the organic carrier to obtain ceramic slurry;
and step four, carrying out vacuum defoaming treatment on the ceramic slurry, and then casting to obtain the LTCC green ceramic tape.
And fifthly, cutting, laminating, hot pressing and sintering the green ceramic tape to obtain the ceramic substrate material.
10. The method for producing a ceramic substrate material with an adjustable dielectric constant according to claim 9, wherein the casting speed is 0.5m/min to 1.0m/min;
the ball milling and mixing time is 36-60h;
the sintering temperature is 845-895 ℃ and the sintering time is 18-36h;
and/or the thickness of the LTCC green tape is 100-130 micrometers, and the number of layers of the LTCC green tape in the laminated layers is 6-12.
CN202311052434.1A 2023-08-21 2023-08-21 Dielectric constant regulating and controlling method and preparation method of ceramic substrate material Pending CN117303866A (en)

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