CN111574213B - Low-dielectric-constant LTCC material and preparation method thereof - Google Patents

Low-dielectric-constant LTCC material and preparation method thereof Download PDF

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CN111574213B
CN111574213B CN202010350140.7A CN202010350140A CN111574213B CN 111574213 B CN111574213 B CN 111574213B CN 202010350140 A CN202010350140 A CN 202010350140A CN 111574213 B CN111574213 B CN 111574213B
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孙成礼
王铭剑
黄学敏
张树人
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University of Electronic Science and Technology of China
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Abstract

The invention discloses Li2O‑MgO‑SiO2An LTCC material and a preparation method thereof relate to the technical field of electronic materials, and the original ingredients of the LTCC material comprise 98.0-100.0 wt% of Li2O‑MgO‑SiO2Ceramic material and 0.0-2.0 wt% lanthanum boron zinc glass. The LMS ceramic material comprises the following components: li2CO3、MgO、SiO2In molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material of (1); the lanthanum-boron-zinc glass comprises the following raw materials: la not more than 45 wt%2O3≤47wt％、28wt％≤B2O3Less than or equal to 32wt percent, and less than or equal to 21wt percent and less than or equal to 25wt percent of ZnO. The components are subjected to the procedures of weighing, primary ball milling, presintering, sieving, secondary ball milling, granulation, molding and the like, and then are sintered in the air at 850-925 ℃ to prepare the LTCC material. The low-temperature sintering LTCC material provided by the invention has the advantages of low raw material price, extremely low device production cost, lower dielectric constant, higher quality factor and good process stability after detection.

Description

Low-dielectric-constant LTCC material and preparation method thereof
Technical Field
The invention belongs to the technical field of electronic materials and devices, and particularly relates to a low dielectric constant LTCC material and a preparation method thereof.
Background
In recent years, the information-oriented wave mat rolls around the world, and the microwave technology is also developing towards higher frequency due to the rapid development of modern communication technologies such as mobile communication and Wireless Local Area Network (WLAN). The rapid development of the fifth generation mobile communication makes mobile communication devices and portable terminals tend to be small, light, high-frequency, low-power, multifunctional and high-performance, which puts higher demands on microwave circuit components based on microwave dielectric ceramics. The low dielectric constant microwave dielectric material is suitable for designing and manufacturing high-frequency chip components such as filters, antennas, modules and the like due to excellent microwave dielectric property and small high-frequency loss, and has been generally paid attention by related researchers. The research on the low dielectric constant microwave dielectric ceramic material with the relative dielectric constant of 6-20, high quality factor and near-zero resonant frequency temperature coefficient is more and more important. Meanwhile, microelectronic devices, electronic equipment and the like are rapidly developed in the direction of miniaturization, high power, integration and multi-functionalization, and the application requirements in communication systems cannot be met by the traditional device integration process. The design of a multilayer structure based on a Low-Temperature Co-fired Ceramic (LTCC) technology can effectively reduce the volume of a device, and is an important way for realizing the development of the device to miniaturization, light weight, multiple functions, integration and Low cost. LTCC is a technology for realizing high-performance circuit packaging, is generally applied to multi-layer chip circuit modular design, and has the advantages of design diversity, excellent high-frequency performance and the like. LTCC mainly adopts silver (961 ℃) with high conductivity as a conductive medium, so the sintering temperature of LTCC is necessarily lower than the melting point of silver, namely below 960 ℃; when silver wiring is adopted, the silver wiring can not be oxidized in the sintering process, so that electroplating protection is not needed. Research on LTCC technology has become a hotspot in the field of electronic materials and devices today. At present, three methods for reducing the sintering temperature of microwave dielectric ceramic materials are mainly used: A. the superfine powder is used as a raw material, so that the activity of the powder is improved to reduce the sintering temperature, but the cost is higher; B. the preparation process is improved, such as the chemical synthesis method is adopted to reduce the sintering temperature, but the method has complex process and prolonged manufacturing period; C. the low-melting-point oxide or the low-melting-point glass is added as a sintering aid, the oxide or the glass sintering aid forms a liquid phase in the sintering process, the cooling effect is obvious, and the method is low in cost, simple in process and easy for batch production. In general, a third approach is used to implement LTCC technology.
With respect to Li2O-MgO-SiO2The (LMS) system has been studied mainly: george et al, in 2009, Journal of the American Society for ceramics (Journal of American Ceramic Society)2MgSiO4Low temperature sintering of ceramics and microwave dielectric properties (Low-Te)mperature Sintering and Microwave Dielectric Properties of Li2MgSiO4Ceramics) is reported, and LMS system microwave dielectric Ceramics have a relative dielectric constant of 5.1 and a dielectric loss tan δ of 5.2 × 10 when f is 8GHz after sintering at 1250 ℃ for 2 hours-4(ii) a Meanwhile, lithium borosilicate glass and lithium magnesium zinc borosilicate glass are respectively added into LMS ceramic, and the sintering temperature is successfully reduced to be about 900 ℃, so that good microwave dielectric property (f is 8GHz) is obtained. Aleena Rose et al, 2018, Applied Surface Science, Li2MgSiO4 pure phase Synthesis and microwave dielectric research and Li2MgSiO4Addition of B2O3，MgF2，WO3Application as substrate material (Synthesis and microwave dielectric stubs of pure Li)2MgSiO4 and B2O3，MgF2，WO3 added Li2MgSiO4for substrate applications), the microwave dielectric properties of LMS ceramics were also investigated: the LMS system was sintered at 1100 ℃ for 6 hours, and when f was 8GHz, the relative dielectric constant was 5.73, and the dielectric loss tan δ was 5.897 × 10-4(ii) a Adding oxide WO into LMS ceramic3Better microwave dielectric properties (f ═ 8GHz) were obtained by sintering at 1100 ℃ for 4 hours.
For Li2O-MgO-SiO2Systems microwave dielectric ceramic systems, although much of the previous research has focused on lowering the sintering temperature, in which some low melting point glasses are paired with Li2O-MgO-SiO2The base microwave dielectric ceramic has unique liquid phase sintering function and can effectively reduce the sintering temperature; however, these studies have not revealed the microwave dielectric properties of LMS-based ceramics at high frequencies, i.e., the Q × f value is not high, or the addition of oxides is not effective in lowering the sintering temperature. The low-temperature sintered microwave dielectric ceramic material used at present is pursuing the characteristics of medium and high dielectric constant, low loss, near-zero resonant frequency temperature coefficient and the like, but in the development of the fifth generation mobile communication at present, a low-cost, simple process, low dielectric constant, high quality factor, low sintering temperature (the sintering temperature is less than 950 ℃) and capability of co-sintering with silver and being co-sintered with silverThe ceramic material does not generate chemical reaction so as to meet the application requirement of the microwave communication industry.
Disclosure of Invention
The invention aims to: in order to solve the problems, the microwave ceramic material which can be sintered at 950 ℃, has low loss, good temperature characteristics and low dielectric constant and the preparation method thereof are provided.
The technical scheme of the invention is as follows: a low dielectric constant LTCC material is provided, comprising Li2O-MgO-SiO2A ceramic main material and a glass additive, characterized in that the Li2O-MgO-SiO2The mass percentage of the ceramic main material is 98.0-100.0%; the glass additive is lanthanum-boron-zinc glass and is 0.0-2.0% by mass.
Preferably, Li2O-MgO-SiO2Ceramic material with Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material.
Preferably, the glass additive composition comprises: la not more than 45 wt%2O3≤47wt％、28wt％≤B2O3≤32wt％、21wt％≤ZnO≤25wt％。
The other technical scheme of the invention is as follows: the preparation method of the low dielectric constant LTCC material comprises the following steps:
step 1: preparation of ceramic Main Material, Li2O-MgO-SiO2Ceramic material with Li2CO3、MgO、SiO2As raw material, according to the mol ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material of (1); mixing the mixed ingredients with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, uniformly crushing, and presintering at 850-930 ℃ for 4 hours to synthesize the Li-based main crystal phase2MgSiO4Li of phase2O-MgO-SiO2A ceramic base material;
step 2: preparing glass additive from La2O3、B2O3And ZnO by mass percent: la of more than or equal to 45%2O3≤47％、28％≤B2O3Mixing materials with the weight percentage of not more than 32 percent and not more than 21 percent and not more than 25 percent of ZnO, mixing the materials with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, presintering at 600-800 ℃ for 4 hours, melting glass residues at 1200-1400 ℃, and finally crushing the prepared glass residues and carrying out ball milling to obtain powder;
and step 3: in Li2O-MgO-SiO2Adding the lanthanum-boron-zinc glass obtained in the step 2 into the main material, wherein the addition amount of the glass additive is 0-2.0 wt%, and mixing and ball-milling by taking deionized water as a medium to obtain Li2O-MgO-SiO2Adding a glass additive into the main material to obtain mixed powder, wherein the powder granularity of the mixed powder is 1-5 mu m;
and 4, step 4: and (3) performing ball milling, drying, sieving, granulating and forming on the mixed powder obtained in the step (3), sintering at 850-930 ℃ in air atmosphere, and preserving heat for 1-4 hours to prepare the low dielectric constant LTCC material.
Preferably, the ball milling in steps 1 to 4 refers to placing the mixture in a nylon tank, adding zirconia balls, taking deionized water as a medium, and mixing the following materials in mass ratio: ball: wet ball milling was performed on a planetary ball mill at a ratio of 1:4: 1.
Preferably, the addition amount of the lanthanum boron zinc glass in the step 3 is any one of 0.5 wt%, 1.0 wt%, 1.5 wt% and 2.0 wt%; the sintering conditions of the mixed powder green blank in the step 4 are as follows: the sintering time is 2 hours, and the sintering temperature is any one of 850 ℃, 875 ℃, 900 ℃ and 925 ℃.
Preferably, the binder used in granulating the mixed powder in the step 4 is a 5.0 wt% acrylic acid solution.
The invention has the beneficial effects that:
1. the LMS ceramic material comprises the following components: li2CO3、MgO、SiO2In molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material of (1); the lanthanum-boron-zinc glass comprises the following raw materials: la not more than 45 wt%2O3≤47wt％、28wt％≤B2O3Less than or equal to 32wt percent, less than or equal to 21wt percent and less than or equal to 25wt percent of ZnO, low cost of the needed synthetic raw materials, easy obtaining, the granularity of the synthetic materials does not reach the nanometer level, and the preparation process is relatively simple.
2. The LTCC material prepared by the preparation method disclosed by the invention is low in price of raw materials, extremely low in production cost of devices, low in dielectric constant, high in quality factor, good in process stability, relatively low in dielectric constant, high in quality factor at high frequency and excellent in microwave dielectric property.
3. The invention provides a simple, reliable and low-cost preparation method, which is characterized in that glass is added as a sintering aid after a main crystal phase is presintered and synthesized, the sintering aid forms a liquid phase in a subsequent sintering process, and the liquid phase effectively promotes the sintering of ceramics, so that the sintering temperature of the ceramics is reduced to 900 ℃, and the LTCC material has excellent microwave dielectric property, has a lower dielectric constant and a higher quality factor, can be applied at high frequency, and meets the requirements of the microwave communication industry.
4. The preparation method of the invention requires extremely small glass content, i.e. the sintering temperature of the ceramic can be obviously reduced to 900 ℃ by using extremely small glass.
5. In step 3 of the preparation process of the present invention, Li2O-MgO-SiO2The powder particle size of the mixed powder after the glass additive is added into the main material is 1-5 mu m, the nano level is not reached, and the preparation process is easier to realize.
6. The glass additive composition of the invention comprises: 45-47 wt% of La2O3, 28-32 wt% of B2O3 and 21-25 wt% of ZnO, simple components, less requirement in the subsequent preparation process of LTCC materials and material saving.
Drawings
FIG. 1 is Li after pre-firing at 850 deg.C2O-MgO-SiO2XRD diffractogram of;
FIG. 2 is an XRD diffraction analysis chart of samples 1-4 in the low-temperature sintered ceramic material prepared by the invention;
FIG. 3 is an SEM scanning electron microscope image of samples 1-4 in the low-temperature sintered ceramic material prepared by the invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The invention provides a low dielectric constant LTCC material, which comprises Li2O-MgO-SiO2Ceramic main material, and glass additive, the Li2O-MgO-SiO2The mass percentage of the ceramic main material is 98.0-100.0%; the glass additive is lanthanum-boron-zinc glass and is 0.0-2.0% by mass.
Li2O-MgO-SiO2Ceramic material with high purity Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material.
The glass additive comprises the following components: la not more than 45 wt%2O3≤47wt％、28wt％≤B2O3≤32wt％、21wt％≤ZnO≤25wt％。
The invention also provides a preparation method of the low dielectric constant LTCC material, which comprises the following steps:
step 1: preparation of ceramic Main Material, Li2O-MgO-SiO2Ceramic material with Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material of (1); mixing the mixed ingredients with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, uniformly crushing, and presintering at 850-930 ℃ for 4 hours to synthesize the Li-based main crystal phase2MgSiO4Li of phase2O-MgO-SiO2A ceramic base material;
step 2: preparing glass additive from La2O3、B2O3And ZnO by mass percent: la of more than or equal to 45%2O3≤47％、28％≤B2O3Mixing materials of not more than 32 percent and not more than 21 percent and not more than 25 percent of ZnO, mixingMixing the prepared materials with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, presintering at 600-800 ℃ for 4 hours, melting glass slag at 1200-1400 ℃, and finally grinding the prepared glass slag and carrying out ball milling to obtain powder;
and step 3: in Li2O-MgO-SiO2Adding the lanthanum-boron-zinc glass obtained in the step 2 into the main material, wherein the addition amount of the glass additive is 0.0-2.0 wt%, and mixing and ball-milling by taking deionized water as a medium to obtain Li2O-MgO-SiO2Adding a glass additive into the main material to obtain mixed powder, wherein the powder granularity of the mixed powder is 1-5 mu m;
and 4, step 4: and (3) performing ball milling, drying, sieving, granulating and forming on the mixed powder obtained in the step (3), sintering at 850-930 ℃ in air atmosphere, and preserving heat for 1-4 hours to prepare the low dielectric constant LTCC material.
The ball milling in each step is to place the mixture into a nylon tank, add zirconia balls, take deionized water as a medium, and mix the following materials in mass ratio: ball: wet ball milling was carried out on a planetary ball mill with water at a ratio of 1:4:1, and the milling time varied depending on the slurry.
The addition amounts of the lanthanum, boron and zinc glass in the step 3 are respectively as follows: 0.5 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%; the sintering conditions of the mixed powder green blank in the step 4 are as follows: the sintering time is 2 hours, and the sintering temperature is 850 ℃, 875 ℃, 900 ℃ and 925 ℃ respectively.
And the binder used in the mixture granulation in the step 4 is 5.0 wt% of acrylic acid solution.
The following are specific examples of the low dielectric constant LTCC material of the present invention:
example 1
The low dielectric constant LTCC material is prepared from 100 mass percent of Li2MgSiO4Composition of Li2MgSiO4The molar ratio of each component in the composition is Li2O:MgO:SiO2The sintering conditions were 1250 ℃/2h, 1: 1.
The low dielectric constant LTCC material is prepared by the following preparation method:
preparation of Li2MgSiO4，Li2O-MgO-SiO2Ceramic material with Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4Ceramic main material (chemical equation is Li)2CO3+MgO+SiO2＝Li2MgSiO4) (ii) a Mixing the mixed ingredients with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, uniformly crushing, and presintering at 850-930 ℃ for 4 hours to synthesize the Li-based main crystal phase2MgSiO4Li of phase2O-MgO-SiO2A ceramic base.
Example 2
A low dielectric constant LTCC material comprises the following components in percentage by mass: 0.5% lanthanum boron zinc glass, 99.5% Li2MgSiO4Ceramic powder;
the lanthanum-boron-zinc glass comprises the following specific components in percentage by mass: 45.00% La2O3、30.00％B2O325.00% ZnO; said Li2MgSiO4The molar ratio of each component in the ceramic powder is Li2O:MgO:SiO2＝1:1:1。
The preparation method of example 2 comprises the following steps:
step 1: according to the component proportion requirement of the lanthanum-boron-zinc glass (45.00 percent of La)2O3、30.00％B2O325.00% ZnO), adding La2O3、B2O3ZnO powder was uniformly mixed ((chemical formula Li)2CO3+MgO+SiO2＝Li2MgSiO4) ); ball-milling the uniformly mixed powder for 4h, then drying and sieving, pre-burning for 4h at 700 ℃, melting for 1h at 1200 ℃, then cooling with a furnace to obtain glass slag, and crushing the glass slag to obtain lanthanum-boron-zinc glass powder;
and 2, step: in molar ratio of Li2O:MgO:SiO2Mixing the ingredients in a ratio of 1:1:1, and then mixing the ingredients in the following ratio: ball: wet ball milling with water in the weight ratio of 1 to 4 to 1, stoving and sieving, pre-sintering at 850 deg.c for 3 hr to obtain Li2MgSiO4Ceramic powder;
and step 3: according to mass percent Li2MgSiO499.5 percent of ceramic powder and 0.5 percent of lanthanum-boron-zinc glass are mixed, and the mixture comprises the following materials: ball: performing secondary ball milling on water in a mass ratio of 1:4:1, and then drying and sieving the powder for later use;
and 4, step 4: adding a certain amount of 5 wt% acrylic acid solution into the powder obtained in the step 3 for granulation; the obtained granules are subjected to dry pressing forming, wherein the forming pressure is 10Mpa, and the diameter and the height of a formed green sample are 15mm and 8mm respectively; and (3) sintering the obtained green body sample in a muffle furnace in an atmospheric atmosphere at the sintering temperature of 850 ℃ for 2 hours, and cooling along with the furnace to obtain the low dielectric constant LTCC material.
Examples 3 to 5
The difference between the embodiments 3-5 and the embodiment 2 lies in that the mixing ratio of the Li2MgSiO4 ceramic powder and the lanthanum boron zinc glass is different, and the sintering temperature is 850 ℃.
The mixing ratio of the Li2MgSiO4 ceramic powder to the lanthanum boron zinc glass in example 3: 1.0 percent of lanthanum boron zinc glass and 99.0 percent of Li2MgSiO4 ceramic powder.
Li in example 42MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.5% lanthanum boron zinc glass, 98.5% Li2MgSiO4And (3) ceramic powder.
Li in example 52MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 2.0 percent of lanthanum boron zinc glass and 98.0 percent of Li2MgSiO4 ceramic powder.
Examples 6, 10 and 14
The compositions of the mixes in examples 6, 10, 14 are the same as in example 2: 0.5% lanthanum boron zinc glass, 99.5% Li2MgSiO4The ceramic powders were different in the sintering temperature, 875 ℃ for example 6, 900 ℃ for example 10 and 925 ℃ for example 14.
Examples 7 to 9
The sintering temperatures of examples 7 to 9 and 6 were 875 ℃ respectively, except for the components of the mixture in example 7Li2MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.0% lanthanum boron zinc glass, 99.0% Li2MgSiO4Ceramic powder; li in example 82MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.5% lanthanum boron zinc glass, 98.5% Li2MgSiO4Ceramic powder; li in example 92MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 2.0% lanthanum boron zinc glass, 98.0% Li2MgSiO4And (3) ceramic powder.
Examples 11 to 13
The sintering temperatures of examples 11 to 13 and 10 were the same and 900 ℃ respectively, except for the components of the mixture, Li in example 112MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.0% lanthanum boron zinc glass, 99.0% Li2MgSiO4Ceramic powder; li in example 122MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.5% lanthanum boron zinc glass, 98.5% Li2MgSiO4Ceramic powder; li in example 132MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 2.0% lanthanum boron zinc glass, 98.0% Li2MgSiO4And (3) ceramic powder.
Examples 15 to 17
The sintering temperatures of examples 15 to 17 and 14 were the same, and were all 925 ℃, except for the components of the mixture, Li in example 152MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.0% lanthanum boron zinc glass, 99.0% Li2MgSiO4Ceramic powder; li in example 162MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 1.5% lanthanum boron zinc glass, 98.5% Li2MgSiO4Ceramic powder; li in example 172MgSiO4The mixing ratio of the ceramic powder to the lanthanum-boron-zinc glass is as follows: 2.0% lanthanum boron zinc glass, 98.0% Li2MgSiO4And (3) ceramic powder.
Table 1 shows the percentage of the mixture, the sintering conditions, the dielectric constant and the Qxf value adopted by the low dielectric constant LTCC ceramic materials of the embodiments 1-17 in the invention.
TABLE 1
Figure BDA0002471656130000101
Figure BDA0002471656130000111
With reference to table 1, in examples 10 to 13, as the mass percentage of the LBZ glass in the LMS microwave dielectric ceramic material increases, the sintering temperature is fixed at 900 ℃, and the dielectric constant of the material system generally increases, but when the mass percentage of the glass is greater than 1%, the dielectric constant hardly changes, but the quality factor obviously increases and then decreases. By analyzing the reason, the SEM in fig. 3 shows that (the upper left sample 1 in fig. 3 is the SEM of example 10, the upper right sample 2 is the SEM of example 11, the lower left sample 3 is the SEM of example 12, and the lower right sample 4 is the SEM of example 13), there are a lot of pores and the grains are not normally grown in sample 1 (i.e., example 10) in fig. 3, the structure is dense and the grains are normally grown in sample 2 (i.e., example 11) and sample 3 (i.e., example 12), compared to that there are many liquid phases formed by glass in sample 3 (i.e., example 12) and the grains are all melted in sample 4 (i.e., example 13) although there are no many pores; the method is mainly characterized in that along with the increase of the glass content in the system, liquid phases which are beneficial to sintering are increased, so that the system not only forms phases at a lower temperature, but also has compact and uniform crystal grains with a certain glass content and only has few pores; however, excessive glass melts the grains, which affects the normal growth of the grains and thus the microwave dielectric properties. Meanwhile, from the X-ray diffraction analysis charts (respectively shown as samples 1 to 4) of examples 10 to 13 shown in FIG. 2, it can be found that at the sintering temperature of 900 ℃, with the increase of the glass content in the sample, there are diffraction peaks gradually increasing around 26 degrees, which is similar to Li2MgSiO4The diffraction peaks corresponding to the standard cards are inconsistent, which shows that the sample has the precipitation of a second phase in the sintering process, and the system has the defect that the second phase is not consistentThe introduction of new impurities is the reason for deteriorating the microwave dielectric properties.
Li in the present invention2O-MgO-SiO2And Li2MgSiO4The expressions of (a) explain:
Li2O-MgO-SiO2it is shown that the components of the system, generally raw materials, i.e. not pre-fired; li2MgSiO4Indicating that the sample has been pre-fired and has a composition of Li2MgSiO4Such a compound.
The particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples throughout the description of the embodiments of the invention.
In the description of the embodiments of the present invention, it should be understood that "-" and "-" indicate the same range of two numerical values, and the range includes the endpoints. For example, "A-B" means a range greater than or equal to A and less than or equal to B. "A to B" means a range of not less than A and not more than B.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. Those skilled in the art will appreciate that the present invention is not limited to the particular embodiments described herein, and that various obvious changes, rearrangements and substitutions will now be apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.

Claims (4)

1. A low dielectric constant LTCC material comprises Li2O-MgO-SiO2A ceramic main material and a glass additive, characterized in that the Li2O-MgO-SiO2The mass percentage of the ceramic main material is 98.0-99.0%; the glass additive is lanthanum-boron-zinc glass, and the mass percent is 1.0-2.0%;
Li2O-MgO-SiO2ceramic base material with Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2The main crystal phase synthesized by the method is Li (1: 1: 1)2MgSiO4The ceramic main material of (1);
the glass additive comprises the following components: la not more than 45 wt%2O3≤47wt％、28wt％≤B2O3≤32wt％、21wt％≤ZnO≤25wt％。
2. A preparation method of a low dielectric constant LTCC material is characterized by comprising the following steps:
step 1: preparation of ceramic Main Material, Li2O-MgO-SiO2Ceramic base material with Li2CO3、MgO、SiO2As raw material, according to the molar ratio of Li2CO3:MgO:SiO2Synthesis of Li as main crystal phase 1:1:12MgSiO4The ceramic main material of (1); mixing the mixed ingredients with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, uniformly crushing, and presintering at 850-930 ℃ for 4 hours to synthesize the Li-based main crystal phase2MgSiO4Li of phase2O-MgO-SiO2A ceramic base material;
step 2: preparing glass additive from La2O3、B2O3And ZnO by mass percent: la of more than or equal to 45%2O3≤47％、28％≤B2O3Mixing materials with the weight percentage of not more than 32 percent and not more than 21 percent and not more than 25 percent of ZnO, mixing the materials with deionized water, carrying out wet ball milling for 2-5 hours, drying, sieving, presintering at 600-800 ℃ for 4 hours, melting glass residues at 1200-1400 ℃, and finally crushing the prepared glass residues and carrying out ball milling to obtain powder;
and step 3: in Li2O-MgO-SiO2Adding the lanthanum-boron-zinc glass obtained in the step 2 into the main material, wherein the adding amount of the glass additive is 1.0-2.0 wt%, and mixing and ball-milling by taking deionized water as a medium to obtain Li2O-MgO-SiO2Adding a glass additive into the main material to obtain mixed powder, wherein the powder granularity of the mixed powder is 1-5 mu m;
and 4, step 4: and (3) performing ball milling, drying, sieving, granulating and molding on the mixed powder obtained in the step (3), sintering at 875-925 ℃ in air atmosphere, and preserving heat for 2 hours to prepare the low dielectric constant LTCC material.
3. The preparation method of the low dielectric constant LTCC material as claimed in claim 2, wherein the ball milling mentioned in the steps 1 to 4 is to put the mixture into a nylon tank, add zirconia balls, use deionized water as a medium, and mix the materials in mass ratio: ball: wet ball milling was performed on a planetary ball mill at a ratio of 1:4: 1.
4. The method for preparing a low dielectric constant LTCC material according to claim 2, wherein the binder used in the step 4 for granulating the mixed powder is a 5.0 wt% acrylic acid solution.
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