CN114804637A - Glass ceramic material with medium and low dielectric constant and preparation method thereof - Google Patents
Glass ceramic material with medium and low dielectric constant and preparation method thereof Download PDFInfo
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
Abstract
Discloses a glass ceramic material with medium and low dielectric constant and low loss, which comprises the following components in percentage by mass: BaTi 4 O 9 53‑63wt％；MgTiO 3 11-25 wt%; 21-26 wt% of low-melting-point glass powder; the low-melting-point glass powder comprises the following components in percentage by mass relative to the total weight of the low-melting-point glass powder: b is 2 O 3 66‑68％；SiO 2 13‑17％；Al 2 O 3 13 to 15 percent; 2 to 5 percent of ZnO. The low-temperature co-fired ceramic substrate prepared by the glass ceramic material has a dielectric constant of 12-16 and a dielectric constant of less than 2 multiplied by 10 ‑3 Dielectric loss and temperature coefficient of resonance frequency within +/-10 ppm/DEG C, and can be used for producing ceramic devices such as filters and the like.
Description
Technical Field
The invention belongs to the technical field of dielectric ceramic materials, and particularly relates to a glass ceramic material with medium and low dielectric constant and low loss and a preparation method thereof.
Background
BaTi 4 O 9 BaO-TiO in 1955 by Rose and Roy at the earliest 2 Is found in the series. In 1971, Masse et al first pointed out BaTi 4 O 9 Can be used as microwave medium porcelain, and further research proves that BaTi 4 O 9 Has excellent microwave dielectric property, epsilon r ≈38，Qf＝38000，τ f 14 ppm/. degree.C, and BaTi 4 O 9 The cost of the synthetic raw materials is low, the preparation process is pollution-free, and the large-scale production is easy to realize.
Due to BaTi 4 O 9 The material has various excellent characteristics and is widely applied to many fields, but the large dielectric constant and the temperature coefficient of the resonant frequency of the material are difficult to meet the requirements of millimeter wave antenna modules, and the high sintering temperature (1250 ℃) of the material cannot meet the requirements of the current low temperature co-fired ceramic (LTCC) material.
Generally, in order to reduce the sintering temperature, low-melting point oxides are often added, but the temperature reduction range is limited, and the sintering temperature cannot reach 900 ℃; the other method is to add low-melting-point glass, but the existence of the glass phase greatly improves the dielectric loss of the material and greatly limits BaTi 4 O 9 The application of ceramics in millimeter wave multilayer devices is developed. Kim DW et al add Zn-B glasses to reduce BaTi 4 O 9 The dielectric properties of dielectric constant 33, Qf 27000, and temperature drift of 7 ppm/DEG C were obtained at 900 ℃. However, the sintering temperature of 900 ℃ is still not the optimum sintering temperature for the current LTCC formulations.
Silver (Ag) is widely used in LTCC substrates and modules during LTCC production. However, the diffusion of Ag in LTCC material matrices remains a concern. During sintering, the metal electrode oxidizes and migrates beyond 875 ℃. Ag diffusion can lead to current leakage, thereby reducing the reliability of the LTCC device.
In summary, the existing glass ceramic materials can not meet the requirements of low loss, near zero temperature drift and low sintering temperature (less than 875 ℃) at the same time.
Therefore, a new glass-ceramic material and a method for preparing the same are needed to solve the above technical problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel glass ceramic material. The glass ceramic material has medium and low dielectric constant and good low-temperature sintering performance, and is suitable for the application in the field of components such as microwave dielectric filters and the like.
The invention relates to a glass ceramic material which comprises the following components in percentage by mass:
BaTi 4 O 9 53-63wt％；
MgTiO 3 11-25wt％；
21-26 wt% of low-melting-point glass powder.
The low-melting-point glass powder comprises the following components in percentage by mass relative to the total weight of the low-melting-point glass powder:
in the low-melting-point glass frit: the glass composition is added with SiO with higher content 2 And B 2 O 3 Since they are formed bodies and intermediates of glass networks, respectively, have high binding energy and are not easily polarized under the action of an external electric field, the glass can exhibit a low dielectric constant and dielectric loss, and devitrification of the glass can be suppressed. Al (Al) 2 O 3 Adding proper amount of Al as glass network intermediate oxide 2 O 3 Can reduce the crystallization tendency of glass and greatly improve the chemical stability, thermal stability, mechanical strength and hardness of the glass. Zn in ZnO 2+ The field intensity of the glass is higher, and the glass generates obvious ordered effect on surrounding oxygen ions, thereby generating potential phase splitting tendency, accelerating the crystallization speed of the glass, and achieving the effect of reducing the melting temperature and the transition temperature of the glass.
The invention also provides a preparation method of the glass ceramic material, which comprises the following steps (1): mixing the formula amount of BaTi 4 O 9 、MgTiO 3 Mixing the low-melting-point glass powder, ball milling, drying and sieving to obtain the glass ceramic material.
Wherein, during ball milling, the mass ratio of the materials to the water to the zirconia balls is 1:1.5:3, the diameter of the zirconia balls is 1.5mm, the ball milling speed is 300-350 r/min, and the ball milling time is 2-5 h.
Wherein the drying temperature is 80-180 ℃, and the drying time is 3-12 h.
Wherein the sieving mesh is 80 meshes.
The preparation method of the glass ceramic material further comprises the following steps: prior to step (1) one or more of the following steps (i), (ii) and (iii) are performed:
(i) obtaining BaTi 4 O 9 A step (2);
(ii) obtaining MgTiO 3 A step (2);
(iii) and obtaining the low-melting-point glass powder.
Wherein the step (i) is to prepare BaTi by a solid phase synthesis method 4 O 9 Which comprises the following steps: weighing BaCO according to the stoichiometric ratio of 1:4 3 And TiO 2 Adding 0.6-1.5 wt% of ammonium polyacrylate dispersant, ball milling and mixing according to the material-water ratio of 1:1.5, spray granulating by using a spray dryer (the inlet temperature is controlled to be 250 +/-5 ℃, the outlet temperature is controlled to be 120 +/-5 ℃, the rotation speed of an atomizer is 10800 +/-5 r/min), and then calcining at high temperature of 1050- 4 O 9 A material.
Wherein the step (ii) is to prepare MgTiO by solid phase synthesis 3 Comprises the following steps: weighing Mg (OH) according to the stoichiometric ratio of 1:3 2 And TiO 2 Adding 0.6-1.5 wt% of ammonium polyacrylate dispersant, ball milling and mixing according to the ratio of material to water of 1:1.5, spray granulating by using a spray dryer (the inlet temperature is controlled to be 250 +/-5 ℃, the outlet temperature is controlled to be 120 +/-5 ℃, the rotation speed of an atomizer is 10800 +/-5 r/min), and then calcining at high temperature, wherein the calcining temperature is 950- 3 A material.
Wherein the step (iii) is a step of preparing the low melting point glass frit, and comprises the following steps: weighing corresponding raw materials according to glass components, uniformly mixing, melting at high temperature to prepare glass molten slurry, cooling to form sheet glass by a pair of rollers, rolling to form coarse glass by a ceramic pair of rollers, and then preparing the coarse glass into glass powder by dry crushing and airflow crushing to obtain the required low-melting-point glass powder.
The invention provides glass ceramic slurry which comprises the glass ceramic material and an organic auxiliary agent.
Wherein, the content of the glass ceramic material in the glass ceramic slurry is 35-53 wt% in percentage by mass.
Wherein the organic auxiliary agent comprises one or more of a dispersing agent, a defoaming agent, a binder, a plasticizer or a dissolving agent.
Wherein the content of the first and second substances,
the dispersing agent comprises one or more of ammonium polyacrylate, phosphate ester, ethoxy compound and fresh fish oil;
the defoaming agent comprises one or more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene;
the binder comprises one or more of PVA, PVB, polymethyl acrylate, ethyl cellulose, acrylic emulsion and ammonium polyacrylate salt;
the plasticizer comprises one of polyethylene glycol, phthalate and glycol;
the dissolving agent comprises one or more of water, ethanol, methyl ethyl ketone, trichloroethylene, toluene and xylene.
The invention also provides a preparation method of the glass ceramic slurry, which comprises the steps of adding the organic auxiliary agent into the glass ceramic material and uniformly mixing.
The invention also provides a raw porcelain tape which is prepared by tape casting the glass ceramic slurry.
The invention also provides a low-temperature co-fired ceramic substrate, which comprises the sintered glass ceramic material; or comprises sintering the above glass ceramic slurry; or comprises sintered green tape as described above.
The invention also provides a preparation method of the low-temperature co-fired ceramic substrate, which comprises the step of sintering the glass ceramic material, the glass ceramic slurry or the green ceramic tape into the low-temperature co-fired ceramic substrate.
The preparation method of the low-temperature co-fired ceramic substrate comprises the following steps:
(1) forming the glass ceramic material or the glass ceramic slurry into a green body, or preparing a raw ceramic tape by using the glass ceramic slurry;
(2) and heating the green body or the green porcelain tape from room temperature to 250 ℃ at a first heating rate in an air atmosphere, heating from 250 ℃ to 350 ℃ at a second heating rate, heating from 350 ℃ to 860-875 ℃ at a third heating rate, and keeping the temperature for 2-4 hours, wherein the first heating rate, the second heating rate and the third heating rate are 1-5 ℃/min, and the first heating rate, the second heating rate and the third heating rate can be the same or different from each other.
The invention also provides the application of the glass ceramic material, the glass ceramic slurry, the green ceramic tape and the low-temperature co-fired ceramic substrate in preparing ceramic devices.
The invention also provides a ceramic device comprising the above sintered glass-ceramic material; or comprises the above sintered glass ceramic slurry; or comprises the above green ceramic tape after sintering; or the low-temperature co-fired ceramic substrate.
Wherein the ceramic device includes a filter or the like.
The beneficial technical effects of the invention are embodied in the following aspects:
1. for the low-temperature co-fired ceramic substrate prepared by the glass ceramic material, the SPDR method is used, the dielectric constant is measured to be 12-16 under the 10GHz test frequency, and the dielectric loss is less than 2 multiplied by 10 -3 Under the test frequency of 15GHz, the temperature coefficient of the resonance frequency of-40-110 ℃ is measured to be within +/-10 ppm/DEG C, so that the dielectric constant is low and the loss is low, and the dielectric constant can be used for producing filters and the likeA ceramic device.
2. For the glass ceramic material prepared by the invention, the glass has a lower softening point (522-537 ℃), so that the glass ceramic material can be sintered into ceramic at a calcination temperature lower than the diffusion of silver paste, and the glass ceramic material can be more selectively matched with the silver paste in the subsequent preparation process of substrates and devices.
3. The glass ceramic material prepared by the invention contains BaTi after being sintered 4 O 9 A crystalline phase, and Zn 2 Ti 3 O 8 、Mg 2 SiO 4 、Mg 3 (BO 3 ) 2 And thus, the glass-ceramic material has a small dielectric loss and a near-zero temperature coefficient of resonance frequency.
Drawings
FIG. 1 is a TMA curve of the glass-ceramic material prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) According to BaTi 4 O 9 53 wt%, low melting point glass powder A22 wt%, MgTiO 3 Mixing materials according to the content ratio of 25 wt%, and preparing raw materials: water: the mass ratio of the zirconia balls is 1:1.5:3, adding water and zirconia balls according to the proportion, controlling the diameter of the zirconia balls to be 1.5mm, controlling the ball milling rotation speed to be 300r/min, carrying out ball milling for 5h, then drying for 3h at 180 ℃ until the materials are completely dried, and sieving by using a 80-mesh sieve to obtain the glass ceramic material for later use;
(2) and adding the obtained glass ceramic material into an organic carrier to prepare slurry, wherein the dispersant, the defoamer, the binder, the plasticizer and the dissolving agent in the organic carrier are respectively ammonium polyacrylate, emulsified silicone oil, polymethyl acrylate, polyethylene glycol and ethanol, and the glass ceramic material accounts for 35 wt% of the slurry.
(3) And preparing the slurry into a green ceramic tape by tape casting, then heating the green ceramic tape from room temperature to 250 ℃ at a heating rate of 3 ℃/min under the air atmosphere, then heating from 250 ℃ to 350 ℃ at a heating rate of 1 ℃/min, finally heating from 350 ℃ to 875 ℃ at a heating rate of 4 ℃/min, carrying out heat preservation sintering for 4h, and sintering to prepare the substrate, thus obtaining the required low-temperature co-fired ceramic substrate.
Example 2
(1) According to BaTi 4 O 9 57 wt%, low melting point glass powder B24 wt%, MgTiO 3 Mixing materials according to the content ratio of 19 wt%, and preparing raw materials: water: the mass ratio of the zirconia balls is 1:1.5:3, adding water and zirconia balls according to the proportion, controlling the diameter of the zirconia balls to be 1.5mm, controlling the ball milling rotation speed to be 320r/min, carrying out ball milling for 3h, then drying for 3h at 180 ℃ until the materials are completely dried, and sieving by using a 80-mesh sieve to obtain the glass ceramic material for later use;
(2) and adding the obtained glass ceramic material into an organic carrier to prepare slurry, wherein the dispersant, the defoamer, the binder, the plasticizer and the dissolving agent in the organic carrier are respectively ammonium polyacrylate, polyoxypropylene, PVB, polyethylene glycol and toluene, and the glass ceramic material accounts for 47 wt% of the slurry.
(3) And preparing the slurry into a green ceramic tape by tape casting, then heating the green ceramic tape from room temperature to 250 ℃ at a heating rate of 3 ℃/min under the air atmosphere, then heating from 250 ℃ to 350 ℃ at a heating rate of 1 ℃/min, finally heating from 350 ℃ to 870 ℃ at a heating rate of 4 ℃/min, carrying out heat preservation sintering for 2h, and sintering to prepare the substrate, thus obtaining the required low-temperature co-fired ceramic substrate.
Example 3
(1) According to BaTi 4 O 9 60 wt%, low melting point glass powder C26 wt%, MgTiO 3 Mixing materials according to the content ratio of 14 wt%, and preparing raw material materials: water: the mass ratio of the zirconia balls is 1:1.5:3, controlling the diameter of the zirconia balls to be 1.5mm and the ball milling speed to be 340r/min, carrying out ball milling for 3h, then drying for 10h at 100 ℃ until the zirconia balls are completely dried, and sieving by using a 80-mesh sieve to obtain the glassGlass ceramic material for standby;
(2) adding the obtained glass ceramic material into an organic carrier to prepare slurry, wherein the dispersant, the defoamer, the binder, the plasticizer and the dissolving agent in the organic carrier are respectively phosphate ester, polyoxypropylene glycerol ether, polymethyl acrylate, polyethylene glycol and xylene, and the glass ceramic material accounts for 49 wt% of the slurry.
(3) And preparing the slurry into a green ceramic tape by tape casting, then heating the green ceramic tape from room temperature to 250 ℃ at a heating rate of 3 ℃/min under the air atmosphere, then heating from 250 ℃ to 350 ℃ at a heating rate of 1 ℃/min, finally heating from 350 ℃ to 865 ℃ at a heating rate of 4 ℃/min, carrying out heat preservation sintering for 3h, and sintering to prepare the substrate, thus obtaining the required low-temperature co-fired ceramic substrate.
Example 4
(1) According to BaTi 4 O 9 63 wt%, low melting point glass powder D25 wt%, MgTiO 3 Mixing materials according to the content ratio of 12 wt%, and preparing raw materials: water: the mass ratio of the zirconia balls is 1:1.5:3, adding water and zirconia balls according to the proportion, controlling the diameter of the zirconia balls to be 1.5mm, controlling the ball milling rotation speed to be 310r/min, carrying out ball milling for 4h, then drying for 12h at 80 ℃ until the materials are completely dried, and sieving by using a 80-mesh sieve to obtain the glass ceramic material for later use;
(2) adding the obtained glass ceramic material into an organic carrier to prepare slurry, wherein the dispersant, the defoamer, the binder, the plasticizer and the dissolving agent in the organic carrier are respectively an ethoxy compound, polyoxypropylene glycerol ether, polymethyl acrylate, ethylene glycol, toluene, and the glass ceramic material accounts for 53 wt% of the slurry.
(3) And preparing the slurry into a green ceramic tape by tape casting, then heating the green ceramic tape from room temperature to 250 ℃ at a heating rate of 3 ℃/min under the air atmosphere, then heating from 250 ℃ to 350 ℃ at a heating rate of 1 ℃/min, finally heating from 350 ℃ to 860 ℃ at a heating rate of 4 ℃/min, carrying out heat preservation sintering for 4h, and sintering to prepare the substrate, thus obtaining the required low-temperature co-fired ceramic substrate.
Example 5
In the same manner as in example 2, only the contents of the components in the glass-ceramic material were different, BaTi 4 O 9 53 wt%, low melting point glass powder B24 wt%, MgTiO 3 23wt％。
Example 6
In the same manner as in example 2, only the contents of the components in the glass-ceramic material were different, BaTi 4 O 9 55 wt%, low melting point glass powder B24 wt%, MgTiO 3 21wt％。
Example 7
In the same manner as in example 2, only the contents of the components in the glass-ceramic material were different, BaTi 4 O 9 60 wt%, low melting point glass powder B24 wt%, MgTiO 3 16wt％。
Comparative example 1
Like example 2, only the main phase BaTi 4 O 9 Exchanged to CaTiO 3 。
Comparative example 2
As in example 2, only the additive MgTiO 3 By Mg having a smaller dielectric constant 2 SiO 4 。
The specific components of the low-melting glass frit A, B, C, D used in examples 1 to 7 and comparative examples 1 to 2 are shown in table 1 below.
TABLE 1 compositions A-D of low-melting glass frits used in examples and comparative examples
For the low temperature co-fired ceramic substrates obtained in the above examples and comparative examples, the dielectric constant and dielectric loss were measured at 10GHz test frequency using the SPDR method, and the temperature coefficient of resonance frequency (temperature drift) at-40 to 110 ℃ was measured at 15GHz test frequency, and the results are shown in Table 2.
TABLE 2 results of performance test of examples and comparative examples
| Examples | Dielectric constant | Loss tangent | Temperature drift (ppm/. degree.C.) |
| 1 | 13 | 1.8×10 -3 | -9 |
| 2 | 14 | 1.4×10 -3 | 3 |
| 3 | 15 | 1.6×10 -3 | 7 |
| 4 | 16 | 1.7×10 -3 | 10 |
| 5 | 12 | 1.1×10 -3 | -5 |
| 6 | 13 | 1.3×10 -3 | -2 |
| 7 | 15 | 1.7×10 -3 | 5 |
| Comparative example 1 | 35 | 2.5×10 -3 | 36 |
| Comparative example 2 | 10 | 1.1×10 -3 | 2 |
As can be seen from Table 2, the examples of the present invention all obtained dielectric constants of 12 to 16, less than 2X 10 -3 And a temperature coefficient of resonance frequency within + -10 ppm/deg.C. While using CaTiO 3 Substitute for BaTi 4 O 9 The dielectric constant, dielectric loss and temperature drift of comparative example 1 are all significantly higher than the range of the present invention; with Mg 2 SiO 4 Substitute for MgTiO 3 The dielectric constant of comparative example 2 was too low to satisfy the requirements of the present invention.
In addition, referring to fig. 1, when the TMA curve of the glass ceramic material prepared in example 2 is observed, the sintering temperature of the formula powder is 869 ℃, which is lower than the calcination temperature of silver paste diffusion.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The glass ceramic material comprises the following components in percentage by mass:
BaTi 4 O 9 53-63wt％；
MgTiO 3 11-25wt％；
21-26 wt% of low-melting-point glass powder;
the low-melting-point glass powder comprises the following components in percentage by mass relative to the total weight of the low-melting-point glass powder:
2. the glass-ceramic material of claim 1, wherein the glass-ceramic material has a dielectric constant of 12 to 16 and a dielectric loss of less than 2 x 10 at a test frequency of 10GHz -3 And the temperature coefficient of the resonance frequency in the temperature range of-40-110 ℃ is within +/-10 ppm/DEG C under the test frequency of 15 GHz.
3. A method for the preparation of a glass-ceramic material according to claim 1 or 2, comprising the steps of: mixing the formula amount of BaTi 4 O 9 、MgTiO 3 Mixing the low-melting-point glass powder, ball milling, drying and sieving to obtain the glass ceramic material.
4. A glass-ceramic paste comprising the glass-ceramic material according to claim 1 or 2 and an organic auxiliary agent.
5. The glass ceramic slurry according to claim 4, wherein the glass ceramic material is contained in the glass ceramic slurry in an amount of 35 to 53% by mass.
6. The glass ceramic slurry according to claim 4 or 5, wherein the organic auxiliary agent comprises one or more of a dispersant, a defoamer, a binder, a plasticizer or a dissolving agent.
7. A green tape made by casting the glass ceramic slurry of any one of claims 4 to 6.
8. A low temperature co-fired ceramic substrate comprising the glass-ceramic material of claim 1 or 2 sintered; or comprising a sintered glass-ceramic paste according to any of claims 4 to 6; or comprising sintered green tape according to claim 7.
9. Use of the glass-ceramic material of claim 1 or 2, the glass-ceramic paste of any one of claims 4 to 6, the green tape of claim 7, or the low temperature co-fired ceramic substrate of claim 8 for the preparation of a ceramic device.
10. A ceramic device comprising the sintered glass-ceramic material of claim 1 or 2; or comprising a sintered glass-ceramic paste according to any of claims 4 to 6; or comprising sintered green tape according to claim 7; or comprising a low temperature co-fired ceramic substrate as claimed in claim 8.
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| CN202110118746.2A CN114804637B (en) | 2021-01-28 | 2021-01-28 | Glass ceramic material with medium-low dielectric constant and preparation method thereof |
| TW110133105A TWI761286B (en) | 2021-01-28 | 2021-09-06 | A kind of glass ceramic material with medium and low dielectric constant and preparation method thereof |
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| CN202110118746.2A CN114804637B (en) | 2021-01-28 | 2021-01-28 | Glass ceramic material with medium-low dielectric constant and preparation method thereof |
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| US5059566A (en) * | 1988-12-27 | 1991-10-22 | Kabushiki Kaisha Toshiba | High-dielectric constant ceramic composite and ceramic capacitor elements |
| CN1334255A (en) * | 2000-07-21 | 2002-02-06 | 株式会社村田制作所 | Insulation ceramic press block |
| CN1771211A (en) * | 2003-04-21 | 2006-05-10 | 旭硝子株式会社 | Non-lead glass for forming dielectric, glass ceramic composition for forming dielectric, dielectric, and process for producing laminated dielectric |
| CN1819980A (en) * | 2004-05-06 | 2006-08-16 | 旭硝子株式会社 | Method for producing laminated dielectric |
| CN105143127A (en) * | 2013-04-18 | 2015-12-09 | 费罗公司 | Low melting glass composition |
| CN111377721A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Low-temperature co-fired ceramic material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3121990B2 (en) * | 1994-07-25 | 2001-01-09 | 京セラ株式会社 | Glass-ceramic substrate |
| GB2371775B (en) * | 2000-12-19 | 2002-12-31 | Murata Manufacturing Co | Composite multilayer ceramic electronic parts and method of manfacturing the same |
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2021
- 2021-01-28 CN CN202110118746.2A patent/CN114804637B/en active Active
- 2021-09-06 TW TW110133105A patent/TWI761286B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5059566A (en) * | 1988-12-27 | 1991-10-22 | Kabushiki Kaisha Toshiba | High-dielectric constant ceramic composite and ceramic capacitor elements |
| CN1334255A (en) * | 2000-07-21 | 2002-02-06 | 株式会社村田制作所 | Insulation ceramic press block |
| CN1771211A (en) * | 2003-04-21 | 2006-05-10 | 旭硝子株式会社 | Non-lead glass for forming dielectric, glass ceramic composition for forming dielectric, dielectric, and process for producing laminated dielectric |
| CN1819980A (en) * | 2004-05-06 | 2006-08-16 | 旭硝子株式会社 | Method for producing laminated dielectric |
| CN105143127A (en) * | 2013-04-18 | 2015-12-09 | 费罗公司 | Low melting glass composition |
| CN111377721A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Low-temperature co-fired ceramic material and preparation method thereof |
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| TW202229195A (en) | 2022-08-01 |
| TWI761286B (en) | 2022-04-11 |
| CN114804637B (en) | 2024-01-30 |
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