CN117069490A - Medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material and preparation method thereof - Google Patents

Medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material and preparation method thereof Download PDF

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CN117069490A
CN117069490A CN202310903021.3A CN202310903021A CN117069490A CN 117069490 A CN117069490 A CN 117069490A CN 202310903021 A CN202310903021 A CN 202310903021A CN 117069490 A CN117069490 A CN 117069490A
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上官端丹
兰开东
李自豪
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Shanghai Jingcai New Material Technology Co ltd
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Abstract

The invention discloses a medium dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material and a preparation method thereof, wherein the ceramic substrate material comprises the following components in percentage by mass: 90-95% BaTi 5 O 11 Ceramics and ceramic dopants, the balance being a low melting point sintering aid; wherein the ceramic dopant is CuO, znO, ceO 2 、V 2 O 5 One or more of the following BaTi 5 O 11 0.5 to 2 percent of ceramic mass; the sintering aid is ZnO-B 2 O 3 ‑SiO 2 ‑BaO‑Li 2 O glass, caO-B 2 O 3 ‑SiO 2 ‑Al 2 O 3 ‑Na 2 CO 3 Glass, mgO-SrO-B 2 O 3 ‑SiO 2 Glass, li 2 O‑SiO 2 ‑CaO‑Al 2 O 3 One or more of the glasses. The invention is characterized in that BaTi 5 O 11 The doping agent is introduced into the ceramic to reduce BaTi 5 O 11 Defects in the ceramic to improve the microwave dielectric properties of the ceramic; simultaneously adding sintering aid to make BaTi 5 O 11 The sintering temperature of the ceramic is reduced from 1100 ℃ to 870-925 ℃ and the glass liquid phase infiltrates the BaTi 5 O 11 Ceramic particles, promoting rearrangement and viscous flow of the ceramic particles, and further realizing BaTi 5 O 11 The low-temperature co-firing of the ceramics improves the bending strength of the material on the premise of ensuring the microwave dielectric property of the material as much as possible.

Description

Medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material and preparation method thereof
Technical Field
The invention relates to the technical field of low-temperature co-fired ceramics, in particular to a medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material and a preparation method thereof.
Background
The microwave dielectric ceramic is a ceramic which is used as a dielectric material in a microwave frequency band circuit so as to realize one or more functions. The microwave dielectric ceramic is used as a core material of electronic elements such as a microwave filter, a microwave dielectric oscillator, a microwave dielectric resonator, a microwave capacitor and the like, and has wide application in the fields of wireless networks, radars, communication and the like. In order to meet the demand for miniaturization of passive devices, multilayer chip components have been developed unprecedentedly. When preparing the multilayer microwave component, the microwave dielectric material needs to be co-fired with the metal electrode material with high conductivity. At present, silver (the melting point is about 961 ℃) is an ideal inner electrode material, and low-temperature cofired ceramics (LTCCs) with excellent development performance have important practical application significance.
BaO-TiO in the 70 s of the 20 th century 2 The binary system microwave ceramic is a great hot research, and the dielectric loss value and the temperature coefficient of the system material are difficult to adjust and are neglected once, but the defects can be improved by doping, multi-component compounding and other methods, and the raw materials are cheap and easy to obtain, so the system material is attracting attention in recent years. Reported in literature, baTi 4 O 9 The ceramic had a dielectric constant of about 37 and a Q.times.f. value of 22700GHz when sintered at 1300 ℃. Single-phase Ba 2 Ti 9 O 20 The ceramic has a relatively high temperature, typically above 1300 ℃, a dielectric constant of about 40 and a Q.times.f. of about 32000GHz. Compared with the former two, baTi 5 O 11 Ceramic materialThe microwave dielectric properties of (C) are more excellent, but the reason for the less related researches is single-phase BaTi 5 O 11 Are difficult to obtain. Tillmanns et al reported by rapid cooling of BaTi 4 O 9 BaTi can be obtained 5 O 11 And (3) phase (C). In 2008, zhou et al in BaCO 3 With TiO 2 1wt% of CuO is added into the raw material, and the monoclinic BaTi is successfully prepared by a solid phase reaction method 5 O 11 The ceramic was sintered at 1100℃and had a dielectric constant of 41.2 and a Q.times.f value of 47430GHz. Subsequently, zhou et al reported BaCu (B 2 O 5 ) Can effectively use BaTi 5 O 11 The ceramic sintering temperature was reduced to 925 c, at which time the dielectric constant of the ceramic was 37.4 and the Q.times.f value was 25502GHz. Proper amount of glass additive can also effectively lower sintering temperature of ceramic, and BaO-ZnO-B is disclosed in patent 201611109678.9 2 O 3 Glass pair BaTi 5 O 11 The sintering temperature of the system material is 875-920 ℃, the system material has medium dielectric constant (30-40) and Q multiplied by f of 20000-30000 GHz.
In order to weaken the damage of the glass auxiliary agent to the mechanical property and microwave property of ceramics, more glass auxiliary agents are used for BaTi 5 O 11 The influence of the sintering property of the ceramic should be reported in order to obtain a more excellent glass aid component, which satisfies the practical application. Experimental results show that ZnO-B 2 O 3 Glass, znO-B 2 O 3 -SiO 2 Glass, baO-ZnO-B 2 O 3 -SiO 2 Glass, B 2 O 3 -ZnO-La 2 O 3 The glass additives can be effective BaO-TiO 2 Sintering temperature of the system. However, the low-melting glass can cause the problems of reduced mechanical strength, mismatching with silver paste, small process tolerance and the like after being introduced. Thus, baTi was developed 5 O 11 The ceramic multi-component glass auxiliary agent has positive significance.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a medium dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material, which comprises the following components in percentage by mass: 90-95% BaTi 5 O 11 Ceramics and ceramic dopants, the balance being a low melting point sintering aid;
wherein the ceramic dopant is CuO, znO, ceO 2 、V 2 O 5 One or more of the following BaTi 5 O 11 0.5 to 2 percent of ceramic mass; to improve BaTi 5 O 11 The microscopic morphology of the ceramic reduces defect formation, thereby improving BT 5 Microwave dielectric properties of ceramics;
the sintering aid is ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 O glass, caO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 Glass, mgO-SrO-B 2 O 3 -SiO 2 Glass, li 2 O-SiO 2 -CaO-Al 2 O 3 One or more of glass; the compatibility between the glass and the matrix ceramic material is good, on one hand, the sintering of the ceramic material can be promoted, and on the other hand, the selected glass has relatively low dielectric loss, and the dielectric property of a material system is positively influenced.
Further, with the ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 The mass percentage of the O glass is calculated as the ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 The O glass comprises: 15 to 25 percent of ZnO and B 2 O 3 30～50％，SiO 2 20～30％，BaO 20～30％，Li 2 O 0～2％。
Further, with the CaO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 The mass percentage of the glass is calculated as the CaO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 The glass comprises: 30-45% of CaO, B 2 O 3 10～20％，SiO 2 35～45％，Al 2 O 3 0～10％，Na 2 CO 3 0～2％。
Further, with the MgO-SrO-B 2 O 3 -SiO 2 The mass percentage of the glass is that the MgO-SrO-B 2 O 3 -SiO 2 The glass comprises: 30-45% of MgO, 0-10% of SrO and B 2 O 3 10～20％，SiO 2 20～50％。
Further, with the Li 2 O-SiO 2 -CaO-Al 2 O 3 The mass percentage of the glass is as follows 2 O-SiO 2 -CaO-Al 2 O 3 The glass comprises: li (Li) 2 O 15～35％，SiO 2 20～35％，CaO 20～35％，Al 2 O 3 5～15％。
The second aspect of the invention provides a preparation method of the medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material, which comprises the following steps:
firstly, weighing doped modified ceramic powder and sintering aid powder according to a proportion, adding a dispersing agent and an organic solvent, ball-milling and mixing for 1-3 hours, adding a plasticizer and a binder, and ball-milling and mixing for 1-3 hours again to obtain a required casting slurry;
cutting the green porcelain tape obtained by casting, and then selecting 10-20 sheets for lamination and isostatic compaction treatment to form a biscuit;
cutting the biscuit into samples, placing the samples on a porous screen plate, then placing the samples into a muffle furnace, slowly heating the samples from room temperature to 450-550 ℃ at a heating rate of 1 DEG/min, preserving heat to completely remove organic components in the samples, then quickly heating the samples to 870-925 ℃ at a heating rate of 5 DEG/min, sintering the samples for 2-4 hours, and cooling the samples to the room temperature along with the furnace to obtain the ceramic substrate.
Further, the synthesis of the doped modified ceramic powder comprises the following steps: baCO is carried out 3 、TiO 2 Raw material powder and doping agent CuO, znO, ceO 2 、V 2 O 5 One or more of the materials are proportioned and mixed toAlcohol is ball milling medium and mixed for 2-6 hours, then the mixture is dried in an oven at 60-120 ℃, screened by a 20-80 mesh screen, finally presintered in a muffle furnace at 800-950 ℃ for 2-4 hours, cooled with the furnace and taken out; and (3) putting the obtained powder into a ball milling tank again, performing secondary ball milling by taking alcohol as a ball milling medium, performing ball milling for 4-6 hours, and drying to obtain the doped modified ceramic powder.
Further, the sintering aid powder includes: znO-B 2 O 3 -SiO 2 -BaO-Li 2 O glass powder, caO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 Glass powder, mgO-SrO-B 2 O 3 -SiO 2 Glass powder, li 2 O-SiO 2 -CaO-Al 2 O 3 One or more of the glass powder materials.
Further, the dielectric constant of the ceramic substrate is 28-35 under the condition of 5GHz, and the loss is reduced<1.432*10 -3 。
Compared with the prior art, the invention has the following technical effects:
the invention provides a medium dielectric constant low-temperature cofiring microwave dielectric ceramic material and a preparation method thereof, which is characterized in that BaTi 5 O 11 Introduction of CuO, znO, ceO into ceramics 2 、V 2 O 5 One or more dopants of (a) to reduce BaTi 5 O 11 Defects in the ceramic to improve the microwave dielectric properties of the ceramic; simultaneously adding one or more of ZBSB glass, CBS glass, MSBS glass and LSCA glass as sintering auxiliary agent to obtain BaTi 5 O 11 The sintering temperature of the ceramic is reduced from 1100 ℃ to 870-925 ℃ and the glass liquid phase infiltrates the BaTi 5 O 11 Ceramic particles, promoting rearrangement and viscous flow of the ceramic particles, and further realizing BaTi 5 O 11 The low-temperature co-firing of the ceramics improves the bending strength of the material on the premise of ensuring the microwave dielectric property of the material as much as possible.
The ceramic substrate material has low raw material price, simple preparation process condition and can be burned at 870-925 DEG CCompact structure, good matching performance with silver paste and good comprehensive performance. By adjusting BaTi 5 O 11 The mixture ratio of the doping agent and the sintering aid is such that the dielectric constant of the system material is between 28 and 35, and the dielectric loss is 5.7901 x 10 -4 ～1.432*10 -3 The bending strength is more than 130MPa.
Drawings
FIG. 1 is a cross-sectional SEM image of a ceramic substrate of example 3 of the invention;
FIG. 2 is a cross-sectional SEM image of a ceramic substrate of example 4 of the invention;
FIG. 3 is a cross-sectional SEM image of a ceramic substrate of example 6 of the invention;
FIG. 4 is a cross-sectional SEM image of a ceramic substrate of example 8 of the invention;
FIG. 5 is a cross-sectional SEM image of a ceramic substrate of example 10 of the invention;
FIG. 6 is a schematic process flow diagram of a method for preparing a medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material according to the invention.
Detailed Description
The invention is further described below with reference to the drawings and specific examples, which are not intended to be limiting. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention provides a medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material, which comprises the following components in percentage by mass: 90-95% BaTi 5 O 11 Ceramics and ceramic dopants, the balance being a low melting point sintering aid B;
wherein the ceramic dopant is CuO, znO, ceO 2 、V 2 O 5 One or more of the materials with the mass of BaTi 5 O 11 0.5 to 2 percent of the ceramic quality so as to improve BaTi 5 O 11 The microscopic morphology of the ceramic reduces defect formation, thereby improving BT 5 Microwave dielectric properties of ceramics;
the sintering aid is ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 O glass, caO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 Glass, mgO-SrO-B 2 O 3 -SiO 2 Glass, li 2 O-SiO 2 -CaO-Al 2 O 3 One or more of glass; the compatibility between the glass and the matrix ceramic material is good, on one hand, the sintering of the ceramic material can be promoted, and on the other hand, the selected glass has relatively low dielectric loss, which has positive influence on the dielectric property of a material system.
Preferably as ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 Mass percent of O glass, znO-B 2 O 3 -SiO 2 -BaO-Li 2 The O glass comprises: 15 to 25 percent of ZnO and B 2 O 3 30～50％，SiO 2 20～30％，BaO 20～30％，Li 2 O0-2%. With CaO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 CaO-B based on mass percentage of glass 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 The glass comprises: 30-45% of CaO, B 2 O 3 10～20％，SiO 2 35～45％，Al 2 O 3 0～10％，Na 2 CO 3 0 to 2 percent. With MgO-SrO-B 2 O 3 -SiO 2 MgO-SrO-B in mass percent of glass 2 O 3 -SiO 2 The glass comprises: 30-45% of MgO, 0-10% of SrO and B 2 O 3 10～20％，SiO 2 20-50%. By Li 2 O-SiO 2 -CaO-Al 2 O 3 Glass mass percent, li 2 O-SiO 2 -CaO-Al 2 O 3 The glass comprises: li (Li) 2 O 15～35％，SiO 2 20～35％，CaO 20～35％，Al 2 O 3 5～15％。
The invention also provides a preparation method of the medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material, which comprises the following steps:
step 1, pre-synthesis of doped modified ceramic powder
BaCO is carried out 3 、TiO 2 Raw material powder and doping agent CuO, znO, ceO 2 、V 2 O 5 Mixing one or more of the materials according to a proportion, proportioning, mixing for 2-6 hours by taking alcohol as a ball milling medium, then placing the mixture into a baking oven at 60-120 ℃, drying, sieving by using a 20-80 mesh screen, finally presintering for 2-4 hours in a muffle furnace at 800-950 ℃, cooling along with the furnace, and taking out; and (3) putting the obtained powder into a ball milling tank again, performing secondary ball milling by taking alcohol as a ball milling medium, performing ball milling for 4-6 hours, and drying to obtain the doped modified ceramic powder.
Step 2.1 ZBSB glass (ZnO-B) 2 O 3 -SiO 2 -BaO-Li 2 O glass) powder preparation
ZnO, B 2 O 3 、SiO 2 、BaO、Li 2 Weighing and proportioning according to a set proportion, wherein ZnO is 15-25%, B 2 O 3 30～50％，SiO 2 20～30％，BaO 20～30％，Li 2 O0-2%; then placing the prepared raw materials into a three-roll mixer, and mixing for 8-12 hours to obtain uniformly mixed powder; pouring the mixed powder into a platinum crucible to fuse for 1-3 hours, wherein the glass fusing temperature is 1200-1500 ℃, and finally pouring the fused glass melt into deionized water to quench to obtain glass slag; finally, placing the glass slag into an alumina ball milling tank, adding a proper amount of high-purity alcohol, ball milling for 6-12 hours, then drying for 4-8 hours at 80-120 ℃, and sieving with a 20-80 mesh screen to obtain the required glass powder.
Step 2.2 CBS glass (CaO-B) 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 Glass) powder preparation
CaO, B 2 O 3 、SiO 2 、Al 2 O 3 、Na 2 CO 3 Weighing ingredients according to a set proportion, wherein CaO accounts for 30-45%, B 2 O 3 10～20％，SiO 2 35～45％，Al 2 O 3 0～10％，Na 2 CO 3 0 to 2 percent; then placing the prepared raw materials into a three-roll mixer, and mixing for 8-12 hours to obtain uniformly mixed powder; and mixing the powderPouring the molten glass into a platinum crucible to fuse for 1 to 3 hours, wherein the glass fusing temperature is 1200 to 1550 ℃, and finally pouring the fused glass into deionized water to quench to obtain glass slag; finally, placing the glass slag into an alumina ball milling tank, adding a proper amount of high-purity alcohol, ball milling for 6-12 hours, then drying for 4-8 hours at 80-120 ℃, and sieving with a 20-80 mesh screen to obtain the required glass powder.
Step 2.3 MSBS glass (MgO-SrO-B) 2 O 3 -SiO 2 Glass) powder preparation
Will MgO, srO, B 2 O 3 、SiO 2 Weighing ingredients according to a set proportion, wherein 30-45% of MgO and 0-10% of SrO are mixed, and B 2 O 3 10～20％，SiO 2 20-50%; then placing the prepared raw materials into a three-roll mixer, and mixing for 8-12 hours to obtain uniformly mixed powder; pouring the mixed powder into a platinum crucible to fuse for 1-3 hours, wherein the glass fusing temperature is 1200-1550 ℃, and finally pouring the fused glass melt into deionized water to quench to obtain glass slag; finally, placing the glass slag into an alumina ball milling tank, adding a proper amount of high-purity alcohol, ball milling for 6-12 hours, then drying for 4-8 hours at 80-120 ℃, and sieving with a 20-80 mesh screen to obtain the required glass powder.
Step 2.4 LSCA glass (Li) 2 O-SiO 2 -CaO-Al 2 O 3 Glass) powder preparation
Li is mixed with 2 O、SiO 2 、CaO、Al 2 O 3 Weighing ingredients according to a set proportion, wherein Li 2 O 15～35％，SiO 2 20～35％，CaO 20～35％，Al 2 O 3 5-15%; then placing the prepared raw materials into a three-roll mixer, and mixing for 8-12 hours to obtain uniformly mixed powder; pouring the mixed powder into a platinum crucible to fuse for 1-3 hours, wherein the glass fusing temperature is 1200-1450 ℃, and finally pouring the fused glass melt into deionized water to quench to obtain glass slag; finally, placing the glass slag into an alumina ball milling tank, adding a proper amount of high-purity alcohol, ball milling for 6-12 hours, then drying for 4-8 hours at 80-120 ℃, and sieving with a 20-80 mesh screen to obtain the required glassAnd (5) powder.
Step 3, preparing raw porcelain belt by tape casting method
Weighing the pre-synthesized powder in the step 1 and one or more sintering aid powder in the steps 2.1, 2.2, 2.3 and 2.4 in proportion, adding 40-60% of solvent and 0.2-0.8% of dispersing agent in the total mass fraction of the powder, and mixing and ball milling for 1-3 hours; then adding 8-12% of plasticizer and 3-7% of binder in the total mass percent of the system, mixing and ball milling for 1-3 hours, finally carrying out vacuum defoaming to prepare casting slurry, and casting the casting slurry into the green ceramic tape by using casting equipment.
Wherein the solvent is a mixed solvent of butanone and isopropanol; the binder is polyvinyl butyral (PVB) or polymethacrylate; the dispersing agent is castor oil or triolein; the plasticizer is one or two of dioctyl phthalate, polyethylene glycol and dibutyl phthalate.
Step 4, preparing the low-temperature co-fired microwave dielectric ceramic substrate
Cutting the green ceramic tape prepared in the step 3 into 80mm square green ceramic chips, selecting 10-20 chips for lamination, and forming a biscuit under the conditions of 20MPa and 70 ℃ by using an isostatic pressing method; cutting the biscuit into samples with the size of 60mm, placing the samples on a porous screen plate, and then placing the samples into a muffle furnace; slowly heating the furnace temperature from room temperature to 450-550 ℃, keeping the temperature for 2 hours at a heating rate of 1 DEG/min, removing organic components in the sample after finishing the glue discharging process, then quickly heating to 870-925 ℃ at a heating rate of 5 DEG/min, sintering for 2-4 hours, and cooling to room temperature along with the furnace to obtain the required ceramic substrate; the substrate was tested for dielectric constant and dielectric loss at 5 GHz.
Square green ceramic tiles 80mm are subjected to 30-40 layers of cross lamination, a biscuit is manufactured through an isostatic pressing method, then the biscuit is cut into strips 5 x 45mm, and then the strips are placed into a muffle furnace; the furnace temperature is slowly increased from room temperature to 450-550 ℃, the temperature increasing rate is 1 DEG/min, the heat preservation is carried out for 2 hours, the glue discharging process is completed, the organic components in the sample are removed, then the temperature is rapidly increased to 870-925 ℃ at the temperature increasing rate of 5 DEG/min, the sintering is carried out for 2-4 hours, the ceramic sample is cooled to room temperature along with the furnace, and the ceramic strip to be tested is tested for bending strength by using a universal testing machine.
Examples
The invention provides examples 1-10, wherein the component proportions (mass percentages) of the low-temperature co-fired microwave dielectric ceramic substrate are shown in table 1:
TABLE 1
Note that: the same individual glass composition used in the 10 examples above was consistent, for example: the LSCA glass was included in both examples 4 and 9, and the composition ratios of the LSCA glass were the same.
In addition, the solvent, the binder, the dispersing agent and the plasticizer only play a role of a carrier, organic materials can fully react and volatilize in the process of discharging glue, inorganic materials (glass and ceramic) are unchanged in the process, and the organic materials are mainly glass ceramic in the process of sintering, and the LTCC substrate is sintered after the process is finished. Therefore, the LTCC raw material tape with smooth appearance, no cracking and good toughness can be prepared by adjusting the proportion of organic materials in the casting slurry, and the solvent, the binder, the dispersing agent and the plasticizer in the embodiment are not excessively limited.
The ceramic substrates of examples 1-10 were tested and the dielectric and mechanical properties results are shown in Table 2:
TABLE 2
Examples example Sintering temperature Sintering time Dielectric constant Dielectric loss Flexural Strength
1 900℃ 2h 32.8065 1.0780*10 -3 144.7MPa
2 900℃ 2h 30.9522 6.8698*10 -4 147.3MPa
3 900℃ 2h 29.9506 5.7901*10 -4 159.5MPa
4 900℃ 2h 29.7303 7.7062*10 -4 153.0MPa
5 900℃ 2h 34.3439 8.5841*10 -4 149.4MPa
6 925℃ 4h 35.5157 9.7901*10 -4 155.1MPa
7 925℃ 4h 33.1341 8.9918*10 -4 148.9MPa
8 925℃ 4h 34.0078 9.0111*10 -4 150.4MPa
9 870℃ 2h 28.0236 1.4320*10 -3 137.2MPa
10 870℃ 2h 30.1595 1.2364*10 -3 138.5MPa
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the embodiments and scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious variations may be made using the teachings and illustrations of the present invention, and that such variations are intended to be included within the scope of the present invention.

Claims (9)

1. The medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material is characterized by comprising the following components in percentage by mass: 90-95% BaTi 5 O 11 Ceramics and ceramic dopants, the balance being a low melting point sintering aid;
wherein the ceramic dopant is CuO, znO, ceO 2 、V 2 O 5 One or more of the following BaTi 5 O 11 0.5 to 2 percent of ceramic mass; to improve BaTi 5 O 11 The microcosmic appearance of the ceramic reduces the defect formation, thereby improving BaTi 5 O 11 Microwave dielectric properties of ceramics;
the sintering aid is ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 O glass, caO-B 2 O 3 -SiO 2 -Al 2 O 3 -
Na 2 CO 3 Glass, mgO-SrO-B 2 O 3 -SiO 2 Glass, li 2 O-SiO 2 -CaO-Al 2 O 3 One or more of glass; the saidThe compatibility between the glass and the matrix ceramic material is good, on one hand, the sintering of the ceramic material can be promoted, and on the other hand, the selected glass has relatively low dielectric loss, and the dielectric property of a material system is positively influenced.
2. The medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material according to claim 1, wherein the ZnO-B is used for preparing 2 O 3 -SiO 2 -BaO-Li 2 The mass percentage of the O glass is calculated as the ZnO-B 2 O 3 -SiO 2 -BaO-Li 2 The O glass comprises: 15 to 25 percent of ZnO and B 2 O 3 30～50％，SiO 2 20～30％，BaO20～30％，Li 2 O0～2％。
3. The medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material according to claim 1, wherein the CaO-B is used as the material 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 The mass percentage of the glass is calculated as the CaO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 The glass comprises: 30-45% of CaO, B 2 O 3 10～20％，SiO 2 35～45％，Al 2 O 3 0～10％，Na 2 CO 3 0～2％。
4. The medium-dielectric constant low-temperature co-fired microwave dielectric ceramic substrate material according to claim 1, wherein the MgO-SrO-B is used as the material 2 O 3 -SiO 2 The mass percentage of the glass is that the MgO-SrO-B 2 O 3 -SiO 2 The glass comprises: 30-45% of MgO, 0-10% of SrO and B 2 O 3 10～20％，SiO 2 20～50％。
5. The medium-permittivity low-temperature co-fired microwave dielectric ceramic substrate material according to claim 1, wherein said Li 2 O-SiO 2 -CaO-Al 2 O 3 The mass percentage of the glass is as follows 2 O-SiO 2 -CaO-Al 2 O 3 The glass comprises: li (Li) 2 O15～35％，SiO 2 20～35％，CaO20～35％，Al 2 O 3 5～15％。
6. A method for preparing a medium dielectric constant low temperature co-fired microwave dielectric ceramic substrate material according to any one of claims 1 to 5, comprising the following steps:
firstly, weighing doped modified ceramic powder and sintering aid powder according to a proportion, adding a dispersing agent and an organic solvent, ball-milling and mixing for 1-3 hours, adding a plasticizer and a binder, and ball-milling and mixing for 1-3 hours again to obtain a required casting slurry;
cutting the green porcelain tape obtained by casting, and then selecting 10-20 sheets for lamination and isostatic compaction treatment to form a biscuit;
cutting the biscuit into samples, placing the samples on a porous screen plate, then placing the samples into a muffle furnace, slowly heating the samples from room temperature to 450-550 ℃ at a heating rate of 1 DEG/min, preserving heat to completely remove organic components in the samples, then quickly heating the samples to 870-925 ℃ at a heating rate of 5 DEG/min, sintering the samples for 2-4 hours, and cooling the samples to the room temperature along with the furnace to obtain the ceramic substrate.
7. The method of claim 6, wherein the synthesis of the doped modified ceramic powder comprises the steps of: baCO is carried out 3 、TiO 2 Raw material powder and doping agent CuO, znO, ceO 2 、V 2 O 5 Mixing one or more of the materials according to a proportion, proportioning, mixing for 2-6 hours by taking alcohol as a ball milling medium, then placing the mixture into a baking oven at 60-120 ℃, drying, sieving by using a 20-80 mesh screen, finally presintering for 2-4 hours in a muffle furnace at 800-950 ℃, cooling along with the furnace, and taking out; and (3) putting the obtained powder into a ball milling tank again, performing secondary ball milling by taking alcohol as a ball milling medium, performing ball milling for 4-6 hours, and drying to obtain the doped modified ceramic powder.
8. The method of preparing as claimed in claim 6, wherein the sintering aid powder comprises: znO-B 2 O 3 -SiO 2 -BaO-Li 2 O glass powder, caO-B 2 O 3 -SiO 2 -Al 2 O 3 -Na 2 CO 3 Glass powder, mgO-SrO-B 2 O 3 -SiO 2 Glass powder, li 2 O-SiO 2 -CaO-Al 2 O 3 One or more of the glass powder materials.
9. The method according to claim 6, wherein the ceramic substrate has a dielectric constant of 28 to 35 and a loss at 5GHz<1.432*10 -3 。
CN202310903021.3A 2023-07-21 2023-07-21 Medium-dielectric-constant low-temperature co-fired microwave dielectric ceramic substrate material and preparation method thereof Pending CN117069490A (en)

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