CN115340376B - Ceramic substrate for LTCC and preparation method and application thereof - Google Patents
Ceramic substrate for LTCC and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ceramic substrate for LTCC and a preparation method and application thereof, the preparation raw materials of the ceramic substrate for LTCC comprise ZrO 2 、SiO 2 ZnO and B 2 O 3 ；ZrO 2 And SiO 2 The mass ratio of (2-10): 1, a step of; znO and B 2 O 3 The mass ratio of (2) is 1:1 to 5; siO (SiO) 2 And ZnO in a mass ratio of 2.5-4:1. The slurry prepared from the preparation raw materials in the proportion can meet the requirement of 3D printing on the slurry, so that the ceramic substrate for the LTCC with accurate size and complex structure can be prepared by a 3D printing method. The invention also provides a preparation method and application of the ceramic substrate for LTCC.
Description
Technical Field
The invention relates to the technical field of ceramics for LTCC (Low temperature Co-fired ceramic), in particular to a ceramic substrate for LTCC, and a preparation method and application thereof.
Background
With the rapid development of modern information technology, the electronic products are required to be miniaturized, portable, multifunctional, highly reliable, low in cost and the like.
The low temperature co-fired Ceramic technology (Low Temperature Co-natural Ceramic, LTCC) is a popular multi-disciplinary cross-integrated component technology in recent years, and simply, the technology is an electronic packaging technology for realizing low cost, high integration and high performance by firing electrode materials, substrates, electronic devices and the like at 900 ℃ or below according to a pre-designed structure. The excellent electronic and thermo-mechanical properties have become the preferred mode for the integration and modularization of electronic components in the future.
However, the conventional ceramic substrate for LTCC has poor dimensional accuracy, and it is more difficult to obtain a ceramic substrate having a complicated structure.
The ceramic substrate for LTCC adopts a thick film material, and direct-writing printing is used as one of the 3D printing modes, so that the ceramic substrate is suitable for developing new materials and new structures and is an important method for printing multi-component composite materials. At present, the method for preparing intelligent materials, structures, soft robots, flexible electronics and the like is widely applied, but the raw materials for preparing the traditional ceramic substrate for LTCC cannot be directly used for 3D printing, and further the ceramic substrate for LTCC with accurate size and complex structure cannot be formed by means of 3D printing.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the ceramic substrate for the LTCC, and the preparation raw materials of the ceramic substrate can meet the requirement of 3D printing on the raw materials, so that the ceramic substrate for the LTCC with accurate size and complex structure can be prepared by a 3D printing method.
The invention also discloses a preparation method of the ceramic substrate for the LTCC.
The invention also discloses application of the ceramic substrate for LTCC.
According to an embodiment of the first aspect of the present invention, there is provided a ceramic substrate for LTCC, the preparation raw material of the ceramic substrate for LTCC comprising ZrO 2 、SiO 2 ZnO and B 2 O 3 ；
The ZrO 2 And SiO 2 The mass ratio of (2-10): 1, a step of;
the ZnO and B 2 O 3 The mass ratio of (2) is 1:1 to 5;
the saidSiO 2 And ZnO in a mass ratio of 2.5-4.0:1.
The ceramic substrate for LTCC provided by the embodiment of the invention has at least the following beneficial effects:
(1) The ceramic substrate for the LTCC can be prepared by a 3D printing method (stable slurry can be formed, and the ceramic substrate for the LTCC obtained by printing has good performance), and the size precision of the ceramic substrate for the LTCC is high (less than or equal to 100 mu m); and complex patterns can be formed on the ceramic substrate for LTCC.
(2) The metal oxide such as ZnO has higher melting point, the ceramic substrate for LTCC is difficult to be molded in the preparation process, and a certain amount of B is added into the preparation raw material adopted by the invention 2 O 3 Has the function of improving the processing performance of the preparation raw materials.
(3) In the preparation raw materials adopted in the invention, zrO 2 The photocuring efficiency of the subsequent 3D printing can be effectively improved, so that the printed green body can be effectively cured, the change of the size is avoided, and the mechanical property of the ceramic substrate for the LTCC can be improved; siO (SiO) 2 The strength of the ceramic substrate for LTCC can be effectively improved; znO and B 2 O 3 The dielectric property of the ceramic substrate for LTCC can be effectively improved;
the ceramic substrate for LTCC with accurate size, high strength and excellent dielectric property can be obtained by combining the preparation raw materials.
According to some embodiments of the invention, the ZrO 2 And SiO 2 The mass ratio of (2) is 4-6: 1.
according to some embodiments of the invention, the ZnO and B 2 O 3 The mass ratio of (2) is 1:2 to 4.
According to some embodiments of the invention, the SiO 2 And ZnO in a mass ratio of about 2.8 to 3.2:1.
According to some embodiments of the invention, the LTCC ceramic substrate has a pattern.
According to some embodiments of the invention, the pattern comprises at least one of holes, grooves, protrusions. Thus, the ceramic substrate for LTCC can be used for designing more precise integrated electronic components.
According to a second aspect of the present invention, there is provided a method for manufacturing the ceramic substrate for LTCC, the method comprising the steps of:
s1, the ZrO is treated 2 And SiO 2 Mixing, grinding and roasting to obtain a presintered material;
the ZnO and B are mixed 2 O 3 Melting after mixing to obtain an additive;
s2, mixing a solvent with the presintered materials and the additive materials to obtain slurry;
s3, taking the slurry as a raw material, and preparing a blank by adopting a 3D printing method;
s4, sintering the green body.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
in the traditional process, a flat plate-shaped ceramic substrate for LTCC without special patterns needs to be prepared firstly, if special patterns are needed, the ceramic substrate needs to be prepared in later processing, the working time is long, and the size precision of the obtained ceramic substrate for LTCC is difficult to guarantee.
The invention can accurately control the size of the printed blank by combining with the film-free direct-writing 3D printing technology, and can conveniently design and print a hole structure or a special structure, thereby avoiding the subsequent processes of drilling, surface processing and the like; meanwhile, the dimensional accuracy of the ceramic substrate can be guaranteed, and the performance of the ceramic substrate for LTCC can be improved. Meanwhile, the preparation method provided by the invention adopts a 3D printing technology which is mature in industry, is simple to operate and is convenient for commercial application.
According to some embodiments of the invention, the method of mixed milling is wet milling.
According to some embodiments of the invention, the wet milling is performed in a ball mill.
According to some embodiments of the invention, the solvent used for wet milling comprises DMF.
According to some embodiments of the invention, the solvent comprises 10wt% to 20wt% of the wet grinding material.
According to some embodiments of the invention, the wet milling ball mill has a rotational speed of 400rpm to 500rpm.
According to some embodiments of the invention, the wet milling is performed for a period of time ranging from 1h to 2h.
According to some embodiments of the invention, in step S1, the particle size of the material obtained after the mixing and grinding is less than or equal to 100 μm.
The stewing is directly carried out without drying after the mixing and grinding.
According to some embodiments of the invention, in step S1, the constant temperature of the stewing is 700 ℃ to 1000 ℃.
According to some preferred embodiments of the invention, in step S1, the constant temperature of the stewing is 800 ℃ to 900 ℃.
According to some embodiments of the invention, in step S1, the constant temperature duration of the stewing is 1h to 10h.
According to some preferred embodiments of the invention, in step S1, the constant temperature duration of the stewing is 1h to 5h.
According to some embodiments of the invention, in step S1, the roasting is performed under an air atmosphere.
In the roasting process, due to the effect of surface energy, the materials tend to be homogenized, namely, the process of growing small particles and reducing large particles is carried out, and agglomeration cannot occur in the temperature range, so that no additional crushing step is needed, and impurities introduced in the mixing and grinding process can be volatilized in a high-temperature environment.
In conclusion, the roasting can improve the uniformity of the obtained presintered material, refine particles, eliminate agglomeration and eliminate impurities, and is beneficial to the preparation of the slurry in the step S2.
According to some embodiments of the invention, in step S1, the constant temperature of the melting is 1000 ℃ to 1600 ℃.
According to some preferred embodiments of the invention, in step S1, the constant temperature of the melting is 1300 ℃ to 1500 ℃.
In the above-mentioned molten condition range, the uniform fusion between additive components can be maximally ensured, and agglomeration between particles can be maximally avoided.
According to some embodiments of the invention, in step S1, the constant temperature period of the melting is 2h to 10h.
According to some preferred embodiments of the invention, in step S1, the constant temperature duration of the melting is 3h to 7h.
According to some embodiments of the invention, in step S1, cooling the resulting molten product after said melting is further comprised;
preferably, the cooling time period is about 30 minutes.
Further preferably, the temperature of the cooled material is 10-40 ℃; it will be appreciated that the specific temperature may be about 30 ℃.
According to some embodiments of the invention, the method further comprises crushing the additive.
According to some embodiments of the invention, the method of crushing comprises ball milling.
According to some embodiments of the invention, the ball milling time is 0.5h to 10h.
According to some preferred embodiments of the invention, the duration of the ball milling is 2h to 5h.
According to some embodiments of the invention, the crushed additive has a particle size of less than or equal to 100 μm.
According to some embodiments of the invention, in step S2, the solvent comprises at least one of DMF (N, N-dimethylformamide) and ethyl acetate.
According to some embodiments of the invention, in step S2, the duration of the mixing is 1h to 10h.
According to some embodiments of the invention, in step S2, the mixing is performed by means of mechanical stirring; preferably, the rotation speed of the mechanical stirring is 80-150 rpm; further preferably, in the apparatus for mechanical stirring, the dispersion plate has a size of 25cm (equivalent to a stirring paddle), the mixing cylinder has a diameter of 35cm (container),
according to some embodiments of the invention, in step S2, the slurry has a solids content of 78wt% to 85wt%.
According to some embodiments of the invention, in step S2, the slurry has a solids content of about 80wt%.
According to some embodiments of the invention, the method of preparing further comprises performing digital modeling of the 3D printing prior to step S3.
According to some embodiments of the invention, the digital modeling may be implemented by means of commercial drawing software, the main function of which is to define the structure of the product obtained by 3D printing, such as length, width, height, pattern structure, etc., and more particularly to define the movement track of the printer nozzle in 3D printing.
According to some embodiments of the invention, in step S3, the 3D printing method is a modulo-free direct writing 3D printing method; preferably, the instrument used is a modulo-free direct-write 3D printing device.
According to some embodiments of the invention, the non-mold direct-write 3D printing apparatus employs a servo stepper motor; therefore, the repeated positioning accuracy is less than or equal to 100 mu m, the XY line width motion resolution accuracy is less than or equal to 10 mu m, and the layer thickness resolution is less than or equal to 20 mu m, so that the printing accuracy is fully ensured; further, the dimensional accuracy of the obtained ceramic substrate for LTCC was confirmed.
According to some embodiments of the invention, in step S4, the sintering comprises a first stage sintering and a second stage sintering.
According to some embodiments of the invention, the constant temperature of the first stage sintering is 400 ℃ to 600 ℃.
According to some preferred embodiments of the invention, the constant temperature of the first stage sintering is 500 ℃ to 600 ℃.
According to some embodiments of the invention, the first stage sintering has a constant temperature duration of 0.5h to 5h.
According to some preferred embodiments of the invention, the first stage sintering has a constant temperature duration of 1h to 3h.
According to some embodiments of the invention, the constant temperature of the second stage sintering is 600 ℃ to 850 ℃.
According to some preferred embodiments of the invention, the constant temperature of the second stage sintering is 700 ℃ to 800 ℃.
According to some embodiments of the invention, the second stage sintering has a constant temperature duration of 1h to 10h.
According to some preferred embodiments of the invention, the second stage sintering has a constant temperature duration of 2h to 5h.
According to some embodiments of the invention, in step S4, the sintering is performed under an air atmosphere.
Under the above sintering conditions, the size of the ceramic substrate for LTCC and the size of the green body are almost the same, i.e., the sintering process has little influence on the size of the ceramic substrate for LTCC, which further ensures the dimensional accuracy of the resulting ceramic substrate for LTCC.
According to some embodiments of the invention, the method further comprises polishing the sintered product after step S4.
According to a third aspect of the present invention, there is provided an application of the ceramic substrate for LTCC in electronic component manufacturing.
The application adopts all the technical schemes of the ceramic substrate for LTCC of the embodiment, so that the ceramic substrate for LTCC has at least all the beneficial effects brought by the technical schemes of the embodiment.
Unless otherwise specified, "about" in the present invention means that the allowable error is within.+ -. 2%, for example, about 100 actually means 100.+ -. 2% X100, that is, 98 to 102.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows the appearance of a ceramic substrate blank for LTCC obtained in step D4 of example 1 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present invention, it should be understood that the direction or positional relationship indicated with respect to the description of the orientation, such as up, down, etc., is based on the direction or positional relationship shown in the drawings, is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Example 1
The ceramic substrate for LTCC is prepared by the specific preparation method:
D1. preparation of presintering materials: weighing ZrO 2 1400g and SiO 2 600g were wet milled in a ball mill for 1.5h, in which the solvent DMF: zrO (ZrO) 2 +SiO 2 The ratio of the materials is 3:17 (mass ratio), the rotating speed of the ball mill is 450rpm, ball milling beads made of stainless steel are arranged in a ball milling tank, the particle size of the mixture after grinding is less than or equal to 100 mu m, and the mixture is directly roasted at 840 ℃ for 2.0 hours without drying to prepare a presintered material;
preparation of additives: weighing 200g of ZnO and B 2 O 3 800g, mixing and then carrying out high-temperature melting, wherein the constant temperature of the high-temperature melting is 1000 ℃, and the constant temperature and the heat preservation time are as follows: 4.5h;
annealing for 30min after the constant temperature and the heat preservation time are finished, specifically placing in air, naturally cooling, and keeping the temperature of the material at about 30 ℃ after 30 min;
ball milling is carried out on the annealed product, the ball milling time is 3 hours, and the particle size of the additive after ball milling is less than or equal to 100 mu m.
D2. Preparation of the mixture: mixing the presintered material obtained in the step D1, the additive, 700g of DMF and 78g of ethyl acetate, and then fully mixing for 2.5h (mechanical stirring at a speed of 100rpm, wherein the diameter of a dispersing disc in a stirrer is 20cm, and the diameter of a charging barrel is 30 cm), so as to obtain mixed slurry capable of being used for the non-mould direct-writing 3D printing;
D3. adding the mixed slurry obtained in the step D2 into a charging barrel of a film-free direct-writing 3D printer;
3D print program settings (digital modeling): setting a 3D printing program, mainly setting the length and width of a pre-printed blank to be 100mm, 100mm and 2.5mm, then setting a special double-ring structure on the surface, wherein a unit of the periodic structure is a concave double ring, the outer diameter of the large ring is 22mm, the inner diameter of the large ring is 18mm, the outer diameter of the small ring is 14mm, the inner diameter of the small ring is 10mm, the depth of the small ring is 1mm, and setting a printing path;
D4. printing: starting a film-free direct-writing 3D printer to print layer by layer, and printing out a blank, wherein the appearance of the obtained blank is shown in figure 1;
D5. sintering the green body obtained in the step D4 for 1h at the temperature of 600 ℃, and then sintering for 2.0h at the temperature of 750 ℃;
D6. preparing a finished product: and D5, polishing the surface of the component obtained in the step D5 to obtain the ceramic substrate for LTCC.
The dimension of the green body obtained in the step D4 and the dimension of the sintered product obtained in the step D5 are also tested by adopting a level meter measurement method; the result shows that the sintering process of step D5 has little effect on the size of the ceramic substrate for LTCC.
The ceramic substrate for LTCC prepared in this example had a firing shrinkage of about 1.0%. The specific test method comprises the following steps: the LTCC substrate was tested for variations in length and width before and after sintering. Carrying out formula calculation on sintering|L 1 -L 0 /L 0 * Calculating 100% | to obtain the maximum value of two values, wherein the angle is marked as 1 and represents the value after sintering, the angle is marked as 0 and represents the value before sintering, for example, the length and the width are 20cm before sintering, 19.8cm after sintering, and the shrinkage is 0.2/20=1%;
from the above results, the preparation process of the present invention has little influence on the size of the ceramic substrate for LTCC, i.e. the ceramic substrate for LTCC with higher dimensional accuracy can be obtained by means of 3D printing.
The ceramic substrate for LTCC prepared in this example had a planar warpage of 0.8%. The method specifically adopts a meter-striking measurement method: the surface-beating measuring method is to put the measured part and micrometer on a standard flat plate, take the standard flat plate as a measuring reference plane, and measure the measured part and micrometer point by point along the actual surface or along several straight directions.
From this, it is understood that there is little influence on the warpage of the component during the sintering process of step D5, which further increases the dimensional accuracy of the ceramic substrate for LTCC prepared by the present invention.
The ceramic substrate for LTCC obtained in this example had a flexural strength of 73MPa. In particular, the method comprises the steps of, flexural strength testing was performed on an Instron1195 universal materials tester, made in english. The loading rate was 0.5mm/min as measured by the three-point bending method. Each data was tested for 5 bars and then averaged.
The dielectric constant and dielectric loss of the ceramic substrate for LTCC obtained in this example were measured by the coaxial line method with the frequency range of 1-18Ghz, and the specific results were: the dielectric constant is 3 to 5.6; dielectric loss of 1.1-1.4X10 -3 。
Comparative example 1
The ceramic substrate for LTCC is prepared by the comparative example, and the specific preparation method comprises the following steps:
D1. preparation of presintering materials: by FeO and SiO 2 As raw materials, 1400g of FeO and SiO are weighed 2 600g is subjected to wet grinding in a grinding machine, and is roasted for 3.5 hours at 900 ℃ after grinding to prepare a presintered material;
preparation of additives: weighing ZrO 2 200g and Al 2 O 3 800g, mixing and then carrying out high-temperature melting, wherein the constant temperature of the high-temperature melting is 750 ℃; the constant temperature and the heat preservation time are 3 hours;
annealing for 40min after the constant temperature and the heat preservation are finished;
ball milling is carried out on the annealed product, and the ball milling time is 2 hours;
D2. preparation of the mixture: mixing the presintered material obtained in the step D1 and an additive material with a mixed solvent formed by 700g of DMF and 78g of ethyl acetate, and then fully mixing for 2.5 hours to obtain a mixture;
D3. adding the mixed slurry obtained in the step D2 into a charging barrel of a film-free direct-writing 3D printer;
3D print program settings (digital modeling): setting a 3D printing program, mainly setting the length and width of a pre-printed blank to be 20mm x 0.4mm, and setting a printing path;
D4. printing: starting a DLP 3D printer to print layer by layer, and printing out a blank;
D5. sintering the green body obtained in the step D4 at 800 ℃ for 1h, and sintering at 950 ℃ for 2h; the surface appearance is rough after sintering, and certain warping exists;
D6. preparing a finished product: and D5, polishing the surface of the component obtained in the step D5 to obtain the ceramic substrate for LTCC.
With reference to the test method of example 1, the ceramic substrate for LTCC obtained in this comparative example was measured:
the sintering shrinkage is about 1.2%;
the plane warpage is about 0.8%;
the bending strength is about 75MPa;
the dielectric constant is 2 to 4.5;
dielectric loss of 1.2-1.9X10 -3 The method comprises the steps of carrying out a first treatment on the surface of the Dielectric properties of the material are not better than those of ZrO with mass fraction 2 -Si0 2 -ZnO-B 2 0 3 A material system.
As is clear from comparison of the results of example 1 and comparative example 1, on the basis that the substrate size for LTCC obtained in example 1 is significantly higher than that of comparative example 1, a lower sintering shrinkage and a comparable degree of warpage are also obtained as compared with comparative example 1, thus demonstrating that the preparation raw material system employed in example 1 has higher dimensional accuracy as compared with comparative example 1; as is clear from the comparison of the dielectric constant and the dielectric loss, the example has more excellent dielectric properties than the comparative example 1.
According to the results, the preparation raw materials are suitable for 3D printing technology by adjusting the types and the proportions of the preparation raw materials, and the ceramic substrate for LTCC has higher dimensional accuracy and also has very rich surface patterns after the steps of sintering and the like, so that the ceramic substrate for LTCC is more suitable for the preparation of integrated electronic elements.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (13)
1. A ceramic substrate for LTCC is characterized in that the preparation raw material of the ceramic substrate for LTCC is ZrO 2 、SiO 2 ZnO and B 2 O 3 ；
The ZrO 2 And SiO 2 The mass ratio of (2-10): 1, a step of;
the ZnO and B 2 O 3 The mass ratio of (2) is 1: 1-5;
the SiO is 2 The mass ratio of ZnO to ZnO is 2.5-4.0:1;
the ceramic substrate for LTCC is prepared by a preparation method comprising the following steps:
s1, the ZrO is treated 2 And SiO 2 Mixing, grinding and roasting to obtain a presintered material;
the ZnO and B are mixed 2 O 3 Melting after mixing to obtain an additive;
s2, mixing a solvent with the presintered materials and the additive materials to obtain slurry;
s3, taking the slurry as a raw material, and preparing a blank by adopting a 3D printing method;
s4, sintering the green body.
2. The ceramic substrate for LTCC according to claim 1, wherein the ZrO 2 And SiO 2 The mass ratio of (2) is 4-6: 1.
3. the ceramic substrate for LTCC according to claim 1, wherein the ZnO and B 2 O 3 The mass ratio of (2) is 1: 2-4.
4. The ceramic substrate for LTCC according to claim 1, wherein the constant temperature of the baking in step S1 is 700 ℃ to 1000 ℃.
5. The ceramic substrate for LTCC according to claim 1, wherein the constant temperature period of the stewing is 1h to 10h.
6. The ceramic substrate for LTCC according to claim 1, wherein the constant temperature of the melting in step S1 is 1000 ℃ to 1600 ℃.
7. The ceramic substrate for LTCC according to claim 1, wherein the constant temperature period of melting is 2h to 10h.
8. The ceramic substrate for LTCC according to claim 1, wherein the preparing method further comprises crushing the additive.
9. The ceramic substrate for LTCC according to claim 1, wherein the manufacturing method further comprises performing digital modeling of the 3D printing before step S3.
10. The ceramic substrate for LTCC according to claim 1, wherein the sintering includes a first stage sintering and a second stage sintering in step S4.
11. The ceramic substrate for LTCC according to claim 10, wherein the constant temperature of the first stage sintering is 400 ℃ to 600 ℃.
12. The ceramic substrate for LTCC according to claim 10, wherein the constant temperature of the second stage sintering is 600 ℃ to 850 ℃.
13. Use of a ceramic substrate for LTCC according to any one of claims 1-12 in the manufacture of electronic components.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06199541A (en) * | 1993-01-05 | 1994-07-19 | Matsushita Electric Ind Co Ltd | Glass-ceramic composition |
| JPH08175869A (en) * | 1994-12-22 | 1996-07-09 | Kyocera Corp | Glass-ceramic sintered body and its production |
| GB0308032D0 (en) * | 2003-04-08 | 2003-05-14 | Wang Tianhe | Porous ceramic pattened substrates |
| JP2005179105A (en) * | 2003-12-18 | 2005-07-07 | Tdk Corp | Dielectric ceramic composition, electronic component, and method for manufacturing the same |
| JP2005213138A (en) * | 2004-01-30 | 2005-08-11 | Korea Inst Of Science & Technology | Low temperature firing high dielectric constant ceramic composition |
| JP2007015878A (en) * | 2005-07-06 | 2007-01-25 | Murata Mfg Co Ltd | Ceramic composition, ceramic substrate, and electronic component |
| CN101671163A (en) * | 2008-09-09 | 2010-03-17 | 奥斯兰姆有限公司 | Ltcc layer stack |
| CN103130498A (en) * | 2013-01-29 | 2013-06-05 | 东莞市凯昶德电子科技股份有限公司 | Method for manufacturing ceramic substrate for low temperature co-fired ceramic (LTCC) |
| CN104744034A (en) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | Composition, glass-ceramic composite material, glass-ceramic composite material skeleton and their preparation methods and use |
| CN110256060A (en) * | 2019-07-09 | 2019-09-20 | 嘉兴佳利电子有限公司 | A kind of high frequency low-k low-temperature co-burning ceramic material and preparation method |
| CN111333333A (en) * | 2020-03-03 | 2020-06-26 | 江苏新砺河磨具科技有限公司 | Preparation method of low-temperature co-fired ceramic material for 3D printing molding |
| WO2021256408A1 (en) * | 2020-06-17 | 2021-12-23 | 株式会社村田製作所 | Glass, glass ceramic, and laminated ceramic electronic component |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100506731B1 (en) * | 2002-12-24 | 2005-08-08 | 삼성전기주식회사 | Low temperature sinterable dielectric composition, multilayer ceramic capacitor, ceramic electronic device |
| WO2008018408A1 (en) * | 2006-08-09 | 2008-02-14 | Murata Manufacturing Co., Ltd. | Glass-ceramic composition, sintered galss-ceramic, and laminated ceramic electronic components |
| WO2012015015A1 (en) * | 2010-07-29 | 2012-02-02 | 旭硝子株式会社 | Glass ceramic composition, substrate for light-emitting element, and light-emitting device |
| KR101179330B1 (en) * | 2010-07-30 | 2012-09-03 | 삼성전기주식회사 | Low temperature co-fired ceramic composition, low temperature co-fired ceramic substrate comprising the same and method for manufacturing the same |
| US10179749B2 (en) * | 2016-08-30 | 2019-01-15 | Shenzhen Sunlord Electronics Co., Ltd. | Low-temperature co-fired ceramic material and preparation method thereof |
-
2022
- 2022-06-28 CN CN202210740274.9A patent/CN115340376B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06199541A (en) * | 1993-01-05 | 1994-07-19 | Matsushita Electric Ind Co Ltd | Glass-ceramic composition |
| JPH08175869A (en) * | 1994-12-22 | 1996-07-09 | Kyocera Corp | Glass-ceramic sintered body and its production |
| GB0308032D0 (en) * | 2003-04-08 | 2003-05-14 | Wang Tianhe | Porous ceramic pattened substrates |
| JP2005179105A (en) * | 2003-12-18 | 2005-07-07 | Tdk Corp | Dielectric ceramic composition, electronic component, and method for manufacturing the same |
| JP2005213138A (en) * | 2004-01-30 | 2005-08-11 | Korea Inst Of Science & Technology | Low temperature firing high dielectric constant ceramic composition |
| JP2007015878A (en) * | 2005-07-06 | 2007-01-25 | Murata Mfg Co Ltd | Ceramic composition, ceramic substrate, and electronic component |
| CN101671163A (en) * | 2008-09-09 | 2010-03-17 | 奥斯兰姆有限公司 | Ltcc layer stack |
| CN103130498A (en) * | 2013-01-29 | 2013-06-05 | 东莞市凯昶德电子科技股份有限公司 | Method for manufacturing ceramic substrate for low temperature co-fired ceramic (LTCC) |
| CN104744034A (en) * | 2013-12-27 | 2015-07-01 | 比亚迪股份有限公司 | Composition, glass-ceramic composite material, glass-ceramic composite material skeleton and their preparation methods and use |
| CN110256060A (en) * | 2019-07-09 | 2019-09-20 | 嘉兴佳利电子有限公司 | A kind of high frequency low-k low-temperature co-burning ceramic material and preparation method |
| CN111333333A (en) * | 2020-03-03 | 2020-06-26 | 江苏新砺河磨具科技有限公司 | Preparation method of low-temperature co-fired ceramic material for 3D printing molding |
| WO2021256408A1 (en) * | 2020-06-17 | 2021-12-23 | 株式会社村田製作所 | Glass, glass ceramic, and laminated ceramic electronic component |
Non-Patent Citations (1)
| Title |
|---|
| Phase Evolution and Properties of Li2O-Al2O3-SiO2-Based Glass-Ceramic for LTCC Applications;ZhenJun Qing等;Key Engineering Materials;第257-261页 * |
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