LTCC material with low dielectric constant and low dielectric loss and preparation method thereof

Abstract

The invention relates to an electronic component material technology, and aims to provide an LTCC (Low Temperature Co-Fired Ceramic) material with low dielectric constant and low dielectric loss and a preparation method thereof. The LTCC material is prepared from zinc borosilicate glass and zinc borosilicate microcrystalline glass with different softening point ranges, a ceramic filler, silicate and a metal oxide through ball milling, mixing, modeling and sintering, and the material contains Zn2SiO4 with a devitrified phase. According to the invention, two kinds of zinc borosilicate glass with different softening points are adopted as cooling assistants, and a devitrified phase Zn2SiO4 is generated through reaction in the sintering process, so that the problem of large dielectric loss of a composite system caused by more glass phases can be effectively improved; by flexibly regulating and controlling the content of each component and the components of the auxiliary materials, the sintering characteristics of the glass internal component regulation and control material are optimized, and the success rate of matching and co-firing of the material and silver is further improved; meanwhile, the sintering window is relatively wide, so that good quality stability of the product is favorably kept; the dielectric loss of the composite system is reduced by doping the nucleating agent, and the volume shrinkage process of the material is regulated and controlled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic component materials, and in particular to a low-dielectric constant and low-dielectric loss LTCC material and a preparation method thereof. BACKGROUND

[0002] Some popular application scenarios such as 5G / 6G communication, vehicle-mounted network, and wearable devices have high-speed and large-capacity network requirements, and therefore a new generation of high-speed wireless network needs to develop towards millimeter waves with large bandwidth and high rate. With the use of wireless spectrum covering microwave, millimeter wave, and even higher frequency bands, the platform of low-temperature co-fired ceramic (LTCC) technology for passive integration and passive / active integration and modular technology will have greater development space. Therefore, there are great opportunities and challenges for related materials and devices, especially in solving the basic needs of LTCC powders for higher frequency applications.

[0003] For millimeter wave applications, with the reduction of wavelength and circuit size, device miniaturization is no longer a difficulty, and low dielectric constant and low dielectric loss of materials are more important. For example, a lower dielectric constant medium substrate is needed under millimeter wave. Although the dielectric constant of the LTCC material depends on the frequency range in which it operates, to improve the transmission rate, the dielectric constant of the medium substrate should be as small as possible, and the dielectric constant of the substrate material for microwave low frequency is generally less than 10.0. At the same time, the material suitable for microwave low frequency will significantly increase the loss under millimeter wave, and millimeter wave applications require materials with lower dielectric loss (tanδ<0.001).

[0004] At present, the LTCC commercial products are represented by American Ferro-A6M, Dupont-951, Dupont-9K7, etc., among which American Ferro has also developed an LTCC material with a dielectric constant of 4.10 (@10.0 GHz). Domestic LTCC materials mainly target Ferro A6M and Dupont 951, and there are also corresponding reports on low-dielectric and low-loss LTCC materials for millimeter wave applications. For example, Chinese invention patent CN113372103 A discloses an LTCC ceramic powder composed of borosilicate-based glass and calcium borosilicate glass, which has a dielectric constant as low as about 5.48 and a high-frequency dielectric loss as low as about 0.0001. Chinese invention patent CN118459089 A reports an LTCC material composed of soft and hard borosilicate glass powder, which has a millimeter wave dielectric constant less than 4.5 and a dielectric loss less than 0.005. Although the above-mentioned materials have basically met the application requirements of millimeter wave technology in terms of dielectric constant or dielectric loss, it is difficult to have both low dielectric constant (less than 5.0) and low dielectric loss (less than 0.001), and the LTCC material prepared has poor bending strength due to high glass content, which also limits its further application in future millimeter wave technology.

[0005] At present, the low dielectric LTCC materials mainly include glass / ceramic composite system, glass-ceramic system and low-fired ceramic system. Among them, the glass / ceramic composite system has high dielectric loss and low Q value because of no crystallization during the glass sintering process; the glass-ceramic system has low dielectric loss and good high-frequency performance, but the selection and control of the crystalline phase during the sintering process are extremely high, and the technical barrier is large; and the low-fired ceramic system has few commercial products. In summary, for the LTCC material applied to the millimeter wave technology, it is difficult to simultaneously have low dielectric constant and low loss dielectric performance by selecting any of the above systems.

[0006] The present application proposes a new scheme to solve the above technical problems. SUMMARY

[0007] The technical problem solved by the present application is to overcome the deficiencies in the prior art and provide a LTCC material with low dielectric constant and low dielectric loss and a preparation method thereof.

[0008] To solve the technical problem, the solution of the present application is:

[0009] A LTCC material with low dielectric constant and low dielectric loss is provided, which is obtained by ball milling, shaping and sintering of zinc borosilicate glass with a softening point of 450-500 DEG C, zinc borosilicate glass-ceramic with a softening point of 550-600 DEG C and auxiliary materials, and contains Zn2SiO4 crystalline phase in the LTCC material.

[0010] The raw material components for preparing the LTCC material specifically include: 5-10 parts of zinc borosilicate glass, 30-50 parts of zinc borosilicate glass-ceramic, 40-60 parts of ceramic filler, 0-5 parts of silicate and 0.1-1 parts of metal oxide; the above parts are all mass parts.

[0011] As a preferred scheme of the present application, the zinc borosilicate glass is prepared from the following mass parts of each raw material component: 30-50 parts of ZnO, 20-40 parts of B2O3, 10-20 parts of SiO2, 0-5 parts of Al2O3, 0-5 parts of BaO, 0-2 parts of Na2O, 0-2 parts of Li2O and 0-2 parts of K2O.

[0012] As a preferred scheme of the present application, the zinc borosilicate glass-ceramic is prepared from the following mass parts of each raw material component: 50-60 parts of ZnO, 10-20 parts of B2O3, 20-35 parts of SiO2, 0-10 parts of Al2O3, 0-1 parts of Na2O, 0-1 parts of Li2O and 0-1 parts of K2O.

[0013] As a preferred scheme of the present application, in the adjuvant, the ceramic filler is SiO2; the silicate is one of Zn2SiO4, Mg2SiO4, CaSiO3, Mg2Al4Si5O 18 , CaAl2Si2O8, CaMgSi2O6 or a mixture of at least two thereof; and the metal oxide is one of ZrO2, TiO2, Cr2O3, Fe2O3, GeO2, Nd2O3, Sm2O3, Ta2O3, MoO3, WO3 or a mixture of at least two thereof.

[0014] As a preferred scheme of the present application, the ceramic filler is amorphous or crystalline; and the particle size distribution of the other raw material components satisfies the following conditions: the D 10 particle size of the zinc borosilicate glass is 0.2-0.3 microns, the D 50 particle size is 0.5-1 micron, the D 90 particle size is 2-3 microns; the D 10 particle size of the zinc borosilicate glass-ceramics is 0.5-1 micron, the D 50 particle size is 1-2 microns, the D 90 particle size is 3-5 microns; the D 10 particle size of the ceramic filler is 0.5-1 micron, the D 50 particle size is 2-4 microns, the D 90 particle size is 7-10 microns; the D 10 particle size of the silicate is 0.3-0.6 microns, the D 50 particle size is 1-2 microns, the D 90 particle size is 3-5 microns; the D 10 particle size of the metal oxide is 0.3-0.6 microns, the D 50 particle size is 1-2 microns, the D 90 particle size is 3-5 microns.

[0015] The present application further provides a preparation method of the aforementioned LTCC material, comprising the following steps:

[0016] (1) zinc borosilicate glass preparation: the respective raw material components are weighed according to the mass fraction, mixed, smelted, quenched, ground, dried, sieved and passivated to obtain the powder-like zinc borosilicate glass;

[0017] (2) zinc borosilicate glass-ceramic preparation: the respective raw material components are weighed according to the mass fraction, mixed, smelted, quenched, ground, dried, sieved and passivated to obtain the powder-like zinc borosilicate glass-ceramic;

[0018] (3) the respective raw material components of the LTCC material are weighed according to the mass fraction, and the porcelain powder is obtained through wet ball milling; the porcelain powder is mixed with an appropriate amount of binder, granulated, and shaped to obtain the green body;

[0019] (4) According to the set sintering procedure, the green compact is heated to temperature, then degassing is carried out, and then sintering and temperature maintaining are carried out after re-heating, and the sintering is completed after cooling; in this process, the crystalline phase Zn2SiO4 is nucleated and grown in the glass phase, and finally the LTCC material with low dielectric constant and low dielectric loss is obtained.

[0020] As a preferred scheme of the present application, in the step (1), the melting temperature is controlled to be 1200-1400 ℃ when preparing the zinc borosilicate glass, and the temperature is maintained for 1-2 h; after the glass liquid is obtained by melting, it is poured into deionized water at 20-35 ℃ for quenching; the quenched glass, deionized water and grinding balls are added into a grinding tank for fine grinding, dried, and passed through a 40-mesh sieve; the passivation treatment temperature is 200-400 ℃, and the temperature maintaining time is 2-5 h.

[0021] As a preferred scheme of the present application, in the step (2), the melting temperature is controlled to be 1300-1500 ℃ when preparing the zinc borosilicate glass-ceramic, and the temperature is maintained for 1-2 h; after the glass liquid is obtained by melting, it is poured into deionized water at 20-35 ℃ for quenching; the quenched glass, deionized water and grinding balls are added into a grinding tank for fine grinding, dried, and passed through a 40-mesh sieve; the passivation treatment temperature is 200-400 ℃, and the temperature maintaining time is 2-5 h.

[0022] As a preferred scheme of the present application, in the step (3), the binder is one of PVA, PVB, octadecane and paraffin wax, or a mixture of at least two thereof.

[0023] As a preferred scheme of the present application, in the step (4), the heating rate from heating the green compact to the degassing process is controlled to be 0.5-2 ℃ / min, the temperature is controlled to be 400-500 ℃ when degassing, and the temperature maintaining time is 1-2 h; the heating rate from the degassing process to the sintering process is controlled to be 8-15 ℃ / min, the temperature is controlled to be 850-900 ℃ when sintering, and the temperature maintaining time is 10-30 min; the cooling rate from the completion of sintering to cooling to room temperature is controlled to be 2-5 ℃ / min.

[0024] Principle of the application:

[0025] 1. The current traditional low-dielectric and low-loss LTCC material is mainly a glass / ceramic composite system, generally using a low-softening-point glass to play a role in reducing temperature by liquid-phase sintering, but this method will lead to high dielectric loss of the prepared LTCC material due to the introduction of the glass phase.

[0026] Therefore, researchers often consider the technical idea of mixing two or more glass / ceramic materials. However, in the general understanding of those skilled in the art, the performance of multiple materials is usually considered in such research work, and then the combination is used on this basis. Therefore, in order to achieve the purpose of preparing a low dielectric constant and low dielectric loss LTCC material, they first think of selecting a low dielectric constant glass / ceramic material and a low dielectric loss glass / ceramic material, and then performing combination experiments of two or more materials, so as to obtain the optimal product with both properties. However, in fact, low dielectric constant glass / ceramic materials usually have a high content of glass phase. Although such glass generally has a low dielectric constant, the dielectric loss of the material is high due to the amorphous phase of the glass during the sintering process. In order to maintain a low dielectric loss of the material after sintering, low dielectric loss glass / ceramic materials generally have a low amount of glass phase (<10%) or use microcrystalline glass instead of traditional amorphous glass, which usually has the problems of high sintering temperature and difficult to control crystallization. This leads to the problems of deterioration of the overall dielectric loss of the material, high sintering temperature, and uncontrollable sintering process after the combination and sintering of the two types of materials. Therefore, according to the inertial technical research and development idea of simple performance superposition, it is impossible to obtain a LTCC material with both properties.

[0027] 2、The present application proposes a new idea, using two different softening point zinc borosilicate glasses as cooling aids, including low softening point zinc borosilicate glass and high softening point zinc borosilicate microcrystalline glass, to overcome the problem that the LTCC material prepared by the prior art cannot simultaneously consider low dielectric constant and low dielectric loss performance.

[0028] Among them, the low softening point zinc borosilicate glass is amorphous, and due to its low glass softening point, it plays a role in reducing the sintering temperature of the composite system in the early sintering stage, and a small amount of Zn2SiO4 is generated by reacting with the ceramic phase in the later sintering stage. In addition to playing a role in reducing the sintering temperature, the high softening point zinc borosilicate microcrystalline glass mainly reacts and crystallizes in the sintering process, and the crystalline phase is Zn2SiO4. Since the crystalline phase is nucleated and grown in the glass phase, there is no obvious glass / ceramic interface between the crystalline phase and the glass phase, and the dielectric loss of the material is small. At the same time, the crystalline phase Zn2SiO4 has a high Q value, which can effectively improve the problem of high dielectric loss of the composite system due to the large amount of glass phase, and plays a role in reducing the dielectric loss of the composite system.

[0029] The application also uses ceramic fillers, and various silicates and metal oxides as auxiliary materials, wherein the ceramic filler is SiO2, which mainly plays three roles in the composite system: (1) SiO2, as a microwave dielectric ceramic material with the lowest known dielectric constant (the dielectric constant of SiO2 is 3.8), can effectively reduce the overall dielectric constant of the composite system; (2) SiO2 dissolves in the glass phase in the later sintering stage, can react with zinc borosilicate glass to generate more Zn2SiO4, thereby reducing the dielectric loss of the material; (3) SiO2 can also play a network supplementing role in the glass network, thereby preventing zinc borosilicate glass from producing pores inside due to excessive crystallization, leading to deterioration of dielectric loss. In addition, the addition of silicates and metal oxides can also be used as seeds and nucleating agents to promote the precipitation of Zn2SiO4 during sintering, thereby reducing the overall dielectric loss of the material.

[0030] Therefore, the application breaks through the simple superposition of raw material characteristics in traditional technical thinking, and through long-term observation and research, based on a large number of experiments, it is summarized that different softening point glass materials are used to obtain new crystallization phase components after mixing, thereby obtaining a composite material that can simultaneously consider low dielectric constant and low dielectric loss performance.

[0031] Compared with the prior art, the application has the following beneficial effects:

[0032] (1) The traditional glass / ceramic composite system has the problems of low strength and unsatisfactory dielectric loss due to high glass content, and the crystallization process of the glass-ceramic system is usually difficult to control and the material has poor acid corrosion resistance (for example, Ferro A6M material), based on the design of the above material system, the dielectric performance, mechanical properties and material plating properties of the material are considered, based on the strategy of glass / ceramic composite system + glass-ceramic system synergistic sintering, SiO2 is selected as a low dielectric filler, low softening point zinc borosilicate glass and high softening point zinc borosilicate glass-ceramic are used as cooling and dielectric loss reducing aids during sintering into porcelain, and finally a LTCC material with low dielectric constant and dielectric loss is obtained.

[0033] (2) Based on the zinc borosilicate glass system, different physical properties of zinc borosilicate glass can be obtained by flexibly adjusting the glass component content and auxiliary material composition, and under the premise of not changing the composition of the LTCC material system, the sintering characteristics of the material can be controlled by optimizing the internal components of the glass, thereby further improving the success of the silver matching co-sintering of the material.

[0034] (3) By adjusting the doping ratio of low softening point zinc borosilicate glass, high softening point zinc borosilicate glass-ceramic and ceramic fillers, a series of LTCC materials with low dielectric constant and dielectric loss can be obtained, and the sintering window of the material is wide, which is beneficial to maintaining good quality stability of the product.

[0035] (4) The present application dopes ZrO2, TiO2, Cr2O3, Fe2O3, GeO2, Nd2O3, Sm2O3, Ta2O3, MoO3, WO3, etc. as nucleating agents of the zinc borosilicate glass / zinc borosilicate glass ceramic / SiO2 composite system, on the one hand, it is conducive to promoting the crystallization of zinc borosilicate glass ceramic in the sintering process, reducing the dielectric loss of the composite system; on the other hand, in the co-firing process with silver, the crystallization process of the composite system can be controlled by the different doping amounts of nucleating agents, and then the volume shrinkage process of the material is controlled, preventing the warping defects after co-firing with silver, greatly improving the success of silver paste matching. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 XRD pattern of the LTCC material in Examples 1-4.

[0037] Figure 2 Cross-sectional SEM image of the silver paste matching product further prepared by the LTCC material in Example 1. DETAILED DESCRIPTION

[0038] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not used to limit the scope of the present application. In addition, it should be understood that after reading the content taught by the present application, those skilled in the art can make various modifications or changes to the present application, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

[0039] 1、Summary of the implementation scheme of the present application

[0040] The present application first provides a LTCC material with low dielectric constant and low dielectric loss, which is obtained by ball milling, shaping and sintering of zinc borosilicate glass with a softening point of 450-500℃, zinc borosilicate glass ceramic with a softening point of 550-600℃ and auxiliary materials, and contains Zn2SiO crystalline phase in the LTCC material. The raw material components for preparing the LTCC material specifically include: zinc borosilicate glass 5-10 parts, zinc borosilicate glass ceramic 30-50 parts, ceramic filler 40-60 parts, silicate 0-5 parts, and metal oxide 0.1-1 part; the above parts are all mass parts.

[0041] The zinc borosilicate glass is prepared from the following raw material components in mass fraction: 30-50 parts of ZnO, 20-40 parts of B2O3, 10-20 parts of SiO2, 0-5 parts of Al2O3, 0-5 parts of BaO, 0-2 parts of Na2O, 0-2 parts of Li2O, and 0-2 parts of K2O; and the zinc borosilicate glass ceramic is prepared from the following raw material components in mass fraction: 50-60 parts of ZnO, 10-20 parts of B2O3, 20-35 parts of SiO2, 0-10 parts of Al2O3, 0-1 part of Na2O, 0-1 part of Li2O, and 0-1 part of K2O.

[0042] As optional examples, in the adjuvant, the ceramic filler is SiO2; the silicate is one of Zn2SiO4, Mg2SiO4, CaSiO3, Mg2Al4Si5O 18 , CaAl2Si2O8, CaMgSi2O6 or a mixture of at least two thereof; and the metal oxide is one of ZrO2, TiO2, Cr2O3, Fe2O3, GeO2, Nd2O3, Sm2O3, Ta2O3, MoO3, WO3 or a mixture of at least two thereof. The ceramic filler is amorphous or crystalline; and the particle size distribution of the other raw material components satisfies the following conditions: the D 10 particle size of the zinc borosilicate glass is 0.2-0.3 microns, the D 50 particle size is 0.5-1 micron, the D 90 particle size is 2-3 microns; the D 10 particle size of the zinc borosilicate glass ceramic is 0.5-1 micron, the D 50 particle size is 1-2 microns, the D 90 particle size is 3-5 microns; the D 10 particle size of the ceramic filler is 0.5-1 micron, the D 50 particle size is 2-4 microns, the D 90 particle size is 7-10 microns; and the D 10 particle size of the silicate or metal oxide is 0.3-0.6 micron, the D 50 particle size is 1-2 microns, the D 90 particle size is 3-5 microns.

[0043] The present application further provides a preparation method of the aforementioned LTCC material, comprising the following steps:

[0044] (1) Preparation of zinc borosilicate glass: the raw material components are weighed according to the mass fraction, mixed, melted, quenched, ground, dried, sieved, and passivated to prepare the zinc borosilicate glass in powder form;

[0045] As an example, when the zinc borosilicate glass is prepared, the melting temperature is controlled to be 1200-1400℃, and the temperature is kept for 1-2h; after the glass liquid is obtained by melting, the glass liquid is poured into deionized water at 20-35℃ for quenching; the quenched glass, deionized water and grinding balls are added into a grinding tank for fine grinding, drying and sieving through a 40-mesh sieve; the passivation treatment temperature is 200-400℃, and the temperature is kept for 2-5h.

[0046] (2) Zinc borosilicate glass-ceramic is prepared by weighing the components according to the mass fraction, mixing, melting, quenching, grinding, drying, sieving and passivation treatment, and the zinc borosilicate glass-ceramic in powder form is obtained;

[0047] As an example, when the zinc borosilicate glass is prepared, the melting temperature is controlled to be 1200-1400℃, and the temperature is kept for 1-2h; after the glass liquid is obtained by melting, the glass liquid is poured into deionized water at 20-35℃ for quenching; the quenched glass, deionized water and grinding balls are added into a grinding tank for fine grinding, drying and sieving through a 40-mesh sieve; the passivation treatment temperature is 200-400℃, and the temperature is kept for 2-5h.

[0048] (3) The components of the LTCC material are weighed according to the mass fraction, and the ceramic powder is obtained by wet ball milling; the ceramic powder is mixed with an appropriate amount of binder, granulated, and shaped to obtain a green body;

[0049] As an example, the binder is one of PVA, PVB, octadecane and paraffin, or a mixture of at least two of them.

[0050] (4) According to the set sintering program, the green body is heated and then degreased, heated again and sintered, and then cooled after sintering is completed; in this process, the crystalline phase Zn2SiO4 is nucleated and grown in the glass phase, and finally the LTCC material with low dielectric constant and low dielectric loss is obtained.

[0051] As an example, the heating rate from heating the green body to the degreasing process is controlled to be 0.5-2℃ / min, the temperature is controlled to be 400-500℃ during degreasing, and the temperature is kept for 1-2h; the heating rate from the degreasing process to the sintering process is controlled to be 8-15℃ / min, the temperature is controlled to be 850-900℃ during sintering, and the temperature is kept for 10-30min; the cooling rate from the completion of sintering to room temperature is controlled to be 2-5℃ / min.

[0052] 2. Specific embodiments and comparative examples

[0053] The low dielectric constant LTCC material and the preparation method thereof of the present application are further described below through some specific embodiments and comparative examples.

[0054] Example 1

[0055] (1) Preparation of low softening point zinc borosilicate glass. The following components were mixed: 50 parts of ZnO, 30 parts of B2O3, 10 parts of SiO2, 5 parts of Al2O3, 3 parts of BaO, and 2 parts of Li2O. The mixture was then uniformly mixed by dry mixing, melted at 1200°C, and kept for 1 hour. The melted glass liquid was then rapidly poured into deionized water at 20°C for quenching. Finally, the quenched glass slag, ethanol, and grinding balls were added into a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. The mixture was then dried, sieved through a 40-mesh sieve, and passivated at 200°C for 2 hours to obtain glass powder. The particle size distribution of the obtained glass powder was D 10 0.20 microns, D 50 0.50 microns, D 90 3.0 microns, and the softening point of the glass was as shown in Table 1.

[0056] (2) Preparation of high softening point zinc borosilicate glass. The following components were mixed: 50 parts of ZnO, 10 parts of B2O3, 28 parts of SiO2, 10 parts of Al2O3, 1 part of Na2O, and 1 part of Li2O. The mixture was then uniformly mixed by dry mixing, melted at 1300°C, and kept for 1 hour. The melted glass liquid was then rapidly poured into deionized water at 20°C for quenching. Finally, the quenched glass slag, ethanol, and grinding balls were added into a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. The mixture was then dried, sieved through a 40-mesh sieve, and passivated at 200°C for 2 hours to obtain glass powder. The particle size distribution of the obtained glass powder was D 10 0.50 microns, D 50 1.0 microns, D 90 3.0 microns, and the softening point of the glass was as shown in Table 1.

[0057] (3) Preparation of LTCC ceramic powder. The following components were mixed: 10 parts of low softening point zinc borosilicate glass, 30 parts of high softening point zinc borosilicate glass-ceramics, 54 parts of SiO2, 5 parts of Zn2SiO4, and 1 part of ZrO2. The particle size distribution of the SiO2 was D 10 0.50 microns, D 50 2.0 microns, D 90 7.0 microns, and the particle size distribution of the Zn2SiO4 was D 10 0.30 microns, D 50 1.0 microns, D 90 3.0 microns, and the particle size distribution of the ZrO2 was D 10 0.30 microns, D 50 1.0 microns, D 90 3.0 microns. The mixture was then mixed in a ratio of powder:ethanol:grinding balls = 1:2:10, ball-milled for 17 hours, discharged, dried, sieved through a 40-mesh sieve, and LTCC ceramic powder was obtained.

[0058] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The prepared ceramic powder is granulated with 5% PVA aqueous solution, briquetted, and sintered, wherein the temperature rising rate of degassing is 0.5°C / min, the degassing temperature is 400°C, the holding time is 1 h, the sintering temperature rising rate is 8°C / min, the sintering temperature is 880°C, the holding time is 30 min, and the temperature falling rate is 2°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, and the results are shown in Table 2.

[0059] Example 2

[0060] (1) Preparation of low softening point zinc borosilicate glass. The following components are prepared: 30 parts of ZnO, 40 parts of B2O3, 20 parts of SiO2, 1 part of Al2O3, 5 parts of BaO, 2 parts of Na2O, and 2 parts of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1400°C for 2 h. Then, the melted glass liquid is quickly poured into 35°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 400°C for 5 h. The prepared glass powder has a particle size distribution of D 10 0.3 microns, D 50 1.0 micron, D 90 2.0 microns, and a glass softening point as shown in Table 1.

[0061] (2) Preparation of high softening point zinc borosilicate glass. The following components are prepared: 60 parts of ZnO, 10 parts of B2O3, 20 parts of SiO2, 9 parts of Al2O3, and 1 part of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1500°C for 2 h. Then, the melted glass liquid is quickly poured into 35°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 400°C for 5 h. The prepared glass powder has a particle size distribution of D 10 1.0 micron, D 50 2.0 micron, D 90 5.0 micron, and a glass softening point as shown in Table 1.

[0062] (3) Preparation of LTCC ceramic powder. 5 parts of low softening point zinc borosilicate glass, 34.9 parts of high softening point zinc borosilicate glass-ceramics, 60 parts of SiO2, and 0.1 parts of TiO2 are taken, wherein the SiO2 has a particle size distribution of D 10 1.0 micron, D 50 4.0 micron, D 90Particle size 10.0 microns, Ti02particle size distribution D 10 Particle size 0.6 microns, D 50 Particle size 2.0 microns, D 90 Particle size 5.0 microns. Then, the ingredients were mixed in a ratio of powder: ethanol: grinding balls = 1:2:10, ball-milling was performed for 17 h, the product was discharged, dried, and sieved through a 40-mesh screen to obtain the LTCC ceramic powder.

[0063] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above was granulated using 5% PVB solution, briquetted, and sintered, wherein the temperature rising rate for degassing was 2°C / min, the degassing temperature was 500°C, the holding time was 2 h, the temperature rising rate for sintering was 15°C / min, the sintering temperature was 900°C, the holding time was 30 min, and the temperature falling rate was 5°C / min. Finally, the sintered LTCC material was obtained, and its dielectric properties were tested, with the results shown in Table 2.

[0064] Example 3

[0065] (1) Preparation of low softening point zinc borosilicate glass. The ingredients were mixed in the following proportions: 50 parts of ZnO, 30 parts of B203, 13 parts of Si02, 5 parts of BaO, and 2 parts of Na20. After dry mixing, the mixture was melted at 1340°C for 2 h. Then, the molten glass liquid was quickly poured into 30°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls were added to a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. After drying and sieving through a 40-mesh screen, the glass powder was passivated at 300°C for 4 h. The particle size distribution of the prepared glass powder was D 10 Particle size 0.2 microns, D 50 Particle size 1.0 microns, D 90 Particle size 2.23 microns, and the glass softening point is shown in Table 1.

[0066] (2) Preparation of high softening point zinc borosilicate glass. The ingredients were mixed in the following proportions: 50 parts of ZnO, 20 parts of B203, 28 parts of Si02, 1 part of Na20, and 1 part of Li20. After dry mixing, the mixture was melted at 1450°C for 1.5 h. Then, the molten glass liquid was quickly poured into 25°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls were added to a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. After drying and sieving through a 40-mesh screen, the glass powder was passivated at 280°C for 5 h. The particle size distribution of the prepared glass powder was D 10 Particle size 0.54 microns, D 50 Particle size 1.42 microns, D 90 Particle size 5.0 microns, and the glass softening point is shown in Table 1.

[0067] (3) LTCC ceramic powder preparation. Take 9 parts of low softening point zinc borosilicate glass, 50 parts of high softening point zinc borosilicate glass, 40 parts of SiO2, and 1 part of Cr2O3, wherein the particle size distribution of SiO2 is D 10 particle size 0.68 microns, D 50 particle size 2.36 microns, D 90 particle size 7.46 microns, and the particle size distribution of Cr2O3 is D 10 particle size 0.6 microns, D 50 particle size 2.0 microns, D 90 particle size 5.0 microns. Then, according to the ratio of powder: ethanol: grinding ball = 1:2:10, ball milling is carried out for 17 h, the material is discharged, dried, and sieved through a 40-mesh sieve to obtain the LTCC ceramic powder.

[0068] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with octadecane, briquetted, and sintered, wherein the temperature rising rate of degassing is 0.8°C / min, the degassing temperature is 450°C, the holding time is 1 h, the sintering temperature rising rate is 10°C / min, the sintering temperature is 850°C, the holding time is 10 min, and the temperature falling rate is 3°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, and the results are shown in Table 2.

[0069] Example 4

[0070] (1) Preparation of low softening point zinc borosilicate glass. The components are mixed according to the following proportions: 49 parts of ZnO, 20 parts of B2O3, 20 parts of SiO2, 5 parts of Al2O3, 2 parts of Na2O, 2 parts of Li2O, and 2 parts of K2O. After dry mixing, the mixture is melted at 1350°C for 1.5 h. Then, the molten glass is quickly poured into 30°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added to a grinding tank in a ratio of 1:1:5, and the mixture is ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 300°C for 4 h. The particle size distribution of the prepared glass powder is D 10 particle size 0.22 microns, D 50 particle size 0.76 microns, D 90 particle size 2.23 microns, and the glass softening point is shown in Table 1.

[0071] (2) Preparation of high softening point zinc borosilicate glass. The following components are mixed: 52 parts of ZnO, 12 parts of B2O3, 35 parts of SiO2, 0.2 parts of Na2O, 0.5 parts of Li2O, and 0.3 parts of K2O. After being mixed uniformly, the mixture is melted at 1400°C for 2 hours. The melted glass is then rapidly poured into deionized water at 25°C for quenching. The quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. The glass powder is then passivated at 300°C for 4 hours. The prepared glass powder has a particle size distribution of D 10 0.62 microns, D 50 1.49 microns, D 90 3.96 microns, and a glass softening point as shown in Table 1.

[0072] (3) Preparation of LTCC ceramic powder. 10 parts of low softening point zinc borosilicate glass, 41 parts of high softening point zinc borosilicate glass-ceramics, 47 parts of SiO2, 1 part of Mg2Al4Si5O 18 0.5 parts of Fe2O3, and 0.5 parts of ZrO2 are mixed, wherein the SiO2 has a particle size distribution of D 10 0.64 microns, D 50 2.46 microns, D 90 6.37 microns, and the Mg2Al4Si5O 18 has a particle size distribution of D 10 0.60 microns, D 50 2.0 microns, D 90 5.0 microns, and the Fe2O3 has a particle size distribution of D 10 0.50 microns, D 50 1.23 microns, D 90 3.26 microns. The mixture is then ground in a planetary ball mill for 17 hours at a powder:ethanol:grinding ball ratio of 1:2:10. After drying, the mixture is sieved through a 40-mesh sieve to obtain the LTCC ceramic powder.

[0073] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with octadecane / paraffin (mass ratio 1:1), briquetted, and sintered, wherein the degassing temperature is 450°C, the degassing rate is 1.0°C / min, the sintering temperature is 876°C, the sintering rate is 14°C / min, the sintering time is 10 min, and the cooling rate is 2.8°C / min. The sintered LTCC material is obtained, and its dielectric properties are tested. The results are shown in Table 2.

[0074] Example 5

[0075] (1) Preparation of low softening point zinc borosilicate glass. The following components were mixed: 52 parts of ZnO, 28 parts of B2O3, 11 parts of SiO2, 4 parts of Al2O3, 3 parts of BaO, 1 part of Na2O, and 1 part of K2O. The mixture was then uniformly mixed by dry mixing, melted at 1400°C for 1 hour, and then rapidly poured into deionized water at 25°C for quenching. The quenched glass slag, ethanol, and grinding balls were then added to a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. The mixture was then dried, sieved through a 40-mesh sieve, and then passivated at 280°C for 2 hours to obtain a glass powder with a particle size distribution of D10= 0.26 microns, D50= 0.87 microns, and D90= 2.88 microns. 10 D10= 0.26 microns, D50= 0.87 microns, and D90= 2.88 microns. 50 D10= 0.26 microns, D50= 0.87 microns, and D90= 2.88 microns. 90 D10= 0.26 microns, D50= 0.87 microns, and D90= 2.88 microns.

[0076] (2) Preparation of high softening point zinc borosilicate glass. The following components were mixed: 55 parts of ZnO, 10 parts of B2O3, 25 parts of SiO2, 7 parts of Al2O3, 1 part of Na2O, 1 part of Li2O, and 1 part of K2O. The mixture was then uniformly mixed by dry mixing, melted at 1480°C for 1.5 hours, and then rapidly poured into deionized water at 25°C for quenching. The quenched glass slag, ethanol, and grinding balls were then added to a grinding tank in a ratio of 1:1:5, and the mixture was ground in a planetary ball mill. The mixture was then dried, sieved through a 40-mesh sieve, and then passivated at 350°C for 3 hours to obtain a glass powder with a particle size distribution of D10= 0.58 microns, D50= 1.30 microns, and D90= 4.12 microns. 10 D10= 0.58 microns, D50= 1.30 microns, and D90= 4.12 microns. 50 D10= 0.58 microns, D50= 1.30 microns, and D90= 4.12 microns. 90 D10= 0.58 microns, D50= 1.30 microns, and D90= 4.12 microns.

[0077] (3) Preparation of LTCC ceramic powder. The following components were mixed: 10 parts of low softening point zinc borosilicate glass, 40 parts of high softening point zinc borosilicate glass-ceramics, 48 parts of SiO2, 0.5 parts of Mg2SiO4, 1 part of CaSiO3, 0.3 parts of GeO2, and 0.2 parts of WO3. The SiO2 had a particle size distribution of D10= 0.70 microns, D50= 2.50 microns, and D90= 8.55 microns, the Mg2SO4 had a particle size distribution of D10= 0.6 microns, D50= 1.2 microns, and D90= 3.12 microns, the CaSiO3 had a particle size distribution of D10= 0.38 microns, D50= 1.38 microns, and D90= 4.57 microns, and the GeO2 had a particle size distribution of D10= 0.45 microns, D50= 1.28 microns, and D90= 3.27 microns. The mixture was then ground in a planetary ball mill for 17 hours, dried, sieved through a 40-mesh sieve, and then passivated at 350°C for 3 hours to obtain an LTCC ceramic powder.

[0078] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The prepared ceramic powder is granulated with 5% PVA aqueous solution, briquetted, and sintered, wherein the temperature rising rate of degassing is 1.2°C / min, the degassing temperature is 450°C, the holding time is 1.5h, the sintering temperature rising rate is 10°C / min, the sintering temperature is 870°C, the holding time is 10min, and the temperature falling rate is 3°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, and the results are shown in Table 2.

[0079] Example 6

[0080] (1) Preparation of low softening point zinc borosilicate glass. The following components are prepared: 45 parts of ZnO, 32 parts of B2O3, 13 parts of SiO2, 4 parts of Al2O3, 4 parts of BaO, 1 part of Na2O, and 1 part of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1350°C for 1.3h. Then, the melted glass liquid is quickly poured into 30°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 350°C for 2h. The prepared glass powder has a particle size distribution of D 10 0.25 microns, D 50 0.83 microns, D 90 2.87 microns, and the glass softening point is shown in Table 1.

[0081] (2) Preparation of high softening point zinc borosilicate glass. The following components are prepared: 57 parts of ZnO, 10 parts of B2O3, 28 parts of SiO2, 4 parts of Al2O3, 0.5 parts of Li2O, and 0.5 parts of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1400°C for 2h. Then, the melted glass liquid is quickly poured into 25°C deionized water for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 300°C for 5h. The prepared glass powder has a particle size distribution of D 10 0.61 microns, D 50 1.62 microns, D 90 4.00 microns, and the glass softening point is shown in Table 1.

[0082] (3) Preparation of LTCC ceramic powder. 10 parts of low softening point zinc borosilicate glass, 39 parts of high softening point zinc borosilicate glass-ceramics, 48 parts of SiO2, 1 part of CaAl2Si2O8, 1.5 parts of CaMgSi2O6, 0.3 parts of Nd2O3, and 0.2 parts of Sm2O3 are taken, wherein the particle size distribution of SiO2 is D 10Particle size 0.67 micron, D 50 Particle size 2.42 micron, D 90 Particle size 7.46 micron, CaAl2Si2O8particle size distribution is D 10 Particle size 0.50 micron, D 50 Particle size 1.37 micron, D 90 Particle size 3.96 micron, CaMgSi2O6particle size distribution is D 10 Particle size 0.49 micron, D 50 Particle size 1.81 micron, D 90 Particle size 4.36 micron, Nd2O3particle size distribution is D 10 Particle size 0.45 micron, D 50 Particle size 1.31 micron, D 90 Particle size 3.36 micron, Sm2O3particle size distribution is D 10 Particle size 0.55 micron, D 50 Particle size 1.41 micron, D 90 Particle size 4.36 micron. Then according to the powder: ethanol: grinding ball = 1:2:10 ratio, ball milling 17h, discharge, drying, 40 mesh sieve, to get the LTCC ceramic powder.

[0083] (4) Preparation of low dielectric constant, low dielectric loss LTCC material. The ceramic powder prepared above is granulated with paraffin, briquetting, sintering, wherein the degassing temperature is 450℃, the degassing heating rate is 0.5℃ / min, the holding time is 1h, the sintering temperature is 860℃, the sintering heating rate is 10℃ / min, the holding time is 30min, the cooling rate is 3℃ / min, finally the sintered LTCC material is obtained, and its dielectric properties are tested, the results are shown in Table 2.

[0084] Example 7

[0085] (1) Preparation of low softening point zinc borosilicate glass. According to the following components: 43 parts of ZnO, 32 parts of B2O3, 12 parts of SiO2, 5 parts of Al2O3, 4 parts of BaO, 2 parts of Na2O, 1 part of Li2O, 1 part of K2O, then after dry mixing uniformly, melting at 1250℃, holding for 2h. Then the molten glass liquid is quickly poured into 30℃ deionized water for quenching, finally the quenched glass slag, ethanol, grinding balls are added into the grinding tank in the ratio of 1:1:5, placed in the planetary ball mill for grinding, and dried, passed through a 40 mesh sieve, and finally the glass powder is passivated at 300℃ for 4h, and the prepared glass powder has a particle size distribution of D 10 Particle size 0.28 micron, D 50 Particle size 0.82 micron, D 90 Particle size 2.43 micron, the glass softening point is shown in Table 1.

[0086] (2) Preparation of high softening point zinc borosilicate glass. The following components were prepared: 52 parts of ZnO, 13 parts of B2O3, 30 parts of SiO2, 3 parts of Al2O3, 0.5 parts of Na2O, 1.5 parts of Li2O, and then the mixture was uniformly mixed by dry mixing, and then melted at 1400°C for 1.5 h. Subsequently, the molten glass liquid was quickly poured into deionized water at 25°C for quenching, and finally the quenched glass slag, ethanol and grinding balls were added into the grinding tank in a ratio of 1:1:5, and then placed in a planetary ball mill for grinding and drying, and then sieved through a 40-mesh sieve, and finally the glass powder was passivated at 350°C for 5 h. The prepared glass powder had a particle size distribution of D 10 particle size 0.58 microns, D 50 particle size 1.49 microns, D 90 particle size 3.97 microns, and the glass softening point is shown in Table 1.

[0087] (3) Preparation of LTCC ceramic powder. 10 parts of low softening point zinc borosilicate glass, 35 parts of high softening point zinc borosilicate glass-ceramics, 54 parts of SiO2, 0.3 parts of Ta2O3, 0.2 parts of MoO3, 0.4 parts of WO3, and 0.1 parts of ZrO2 were prepared, wherein the particle size distribution of SiO2 was D 10 particle size 0.70 microns, D 50 particle size 2.43 microns, D 90 particle size 7.52 microns, and the particle size distribution of Ta2O3 was D 10 particle size 0.56 microns, D 50 particle size 1.64 microns, D 90 particle size 3.85 microns, and the particle size distribution of MoO3 was D 10 particle size 0.43 microns, D 50 particle size 1.74 microns, D 90 particle size 4.85 microns, and the particle size distribution of WO3 was D 10 particle size 0.37 microns, D 50 particle size 1.54 microns, D 90 particle size 3.45 microns, and the particle size distribution of ZrO2 was D 10 particle size 0.52 microns, D 50 particle size 1.45 microns, D 90 particle size 4.36 microns. Then the powder:ethanol:grinding ball was prepared in a ratio of 1:2:10, ball milled for 17 h, discharged, dried, and sieved through a 40-mesh sieve to obtain the LTCC ceramic powder.

[0088] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with octadecane, briquetted, and sintered, wherein the temperature rising rate for degassing is 1°C / min, the degassing temperature is 450°C, the holding time is 1 h, the sintering temperature rising rate is 10°C / min, the sintering temperature is 900°C, the holding time is 15 min, and the temperature falling rate is 3°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, as shown in Table 2.

[0089] Example 8

[0090] (1) Preparation of low softening point zinc borosilicate glass. The following components are prepared: 38 parts of ZnO, 38 parts of B2O3, 11 parts of SiO2, 5 parts of Al2O3, 5 parts of BaO, 1 part of Na2O, 1 part of Li2O, and 1 part of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1300°C for 2 h. Subsequently, the molten glass liquid is rapidly poured into deionized water at 25°C for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 300°C for 4 h. The prepared glass powder has a particle size distribution of D 10 0.24 microns, D 50 0.79 microns, D 90 2.43 microns, and a glass softening point as shown in Table 1.

[0091] (2) Preparation of high softening point zinc borosilicate glass. The following components are prepared: 50 parts of ZnO, 15 parts of B2O3, 29 parts of SiO2, 5 parts of Al2O3, 0.2 parts of Na2O, 0.5 parts of Li2O, and 0.3 parts of K2O. After being uniformly mixed by dry mixing, the mixture is melted at 1350°C for 2 h. Subsequently, the molten glass liquid is rapidly poured into deionized water at 30°C for quenching. Finally, the quenched glass slag, ethanol, and grinding balls are added into a grinding tank in a ratio of 1:1:5, and are ground in a planetary ball mill. After drying, the mixture is sieved through a 40-mesh sieve. Finally, the glass powder is passivated at 300°C for 4 h. The prepared glass powder has a particle size distribution of D 10 0.64 microns, D 50 1.56 microns, D 90 3.91 microns, and a glass softening point as shown in Table 1.

[0092] (3) Preparation of LTCC ceramic powder. 10 parts of low softening point zinc borosilicate glass, 41 parts of high softening point zinc borosilicate glass-ceramics, 48 parts of SiO2, and 1 part of Sm2O3 are prepared, wherein the SiO2 has a particle size distribution of D 10 0.68 microns, D 50 2.66 microns, D 90Particle size 6.47 microns, Sm2O3 particle size distribution is D 10 Particle size 0.51 microns, D 50 Particle size 1.33 microns, D 90 Particle size 3.46 microns. Then according to the ratio of powder: ethanol: grinding ball = 1:2:10, ball milling for 17h, discharging, drying, and passing through a 40 mesh sieve to obtain the LTCC ceramic powder.

[0093] (4) Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with octadecane, briquetted, and sintered, wherein the temperature rising rate for degassing is 1.0°C / min, the degassing temperature is 450°C, the holding time is 2h, the temperature rising rate for sintering is 12°C / min, the sintering temperature is 890°C, the holding time is 20min, and the temperature falling rate is 3°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, and the results are shown in Table 2.

[0094] Comparative Example 1

[0095] The low softening point zinc borosilicate glass prepared in Example 1 is taken as the raw material of the LTCC ceramic powder, and the specific ratio of the LTCC ceramic powder is as follows: 50 parts of low softening point zinc borosilicate glass, 49 parts of SiO2, and 1 part of ZrO2, wherein the particle size distribution of SiO2 is D 10 Particle size 0.70 microns, D 50 Particle size 2.50 microns, D 90 Particle size 8.55 microns, ZrO2 particle size distribution is D 10 Particle size 0.45 microns, D 50 Particle size 1.28 microns, D 90 Particle size 3.27 microns. Then according to the ratio of powder: ethanol: grinding ball = 1:2:10, ball milling for 17h, discharging, drying, and passing through a 40 mesh sieve to obtain the LTCC ceramic powder.

[0096] Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with 5% PVA aqueous solution, briquetted, and sintered, wherein the temperature rising rate for degassing is 1°C / min, the degassing temperature is 450°C, the holding time is 2h, the temperature rising rate for sintering is 15°C / min, the sintering temperature is 830°C, the holding time is 10min, and the temperature falling rate is 3°C / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested, and the results are shown in Table 2.

[0097] Comparative Example 2

[0098] The low softening point zinc borosilicate glass prepared in Example 1 is taken as the raw material of the LTCC ceramic powder, and the specific ratio of the LTCC ceramic powder is as follows: 50 parts of low softening point zinc borosilicate glass, 49 parts of SiO2, and 1 part of ZrO2, wherein the particle size distribution of SiO2 is D 10Particle size 0.70 micron, D 50 Particle size 2.50 micron, D 90 Particle size 8.55 micron, ZrO2 particle size distribution is D 10 Particle size 0.45 micron, D 50 Particle size 1.28 micron, D 90 Particle size 3.27 micron. Then according to the ratio of powder: ethanol: grinding ball = 1:2:10, ball milling for 17h, discharging, drying, and passing through a 40 mesh sieve to obtain the LTCC ceramic powder.

[0099] Preparation of low dielectric constant and low dielectric loss LTCC material. The ceramic powder prepared above is granulated with 5% PVA aqueous solution, briquetted, and sintered, wherein the temperature rising rate for degassing is 1℃ / min, the degassing temperature is 450℃, the holding time is 2h, the sintering temperature rising rate is 8℃ / min, the sintering temperature is 950℃, the holding time is 30min, and the temperature falling rate is 3℃ / min. Finally, the sintered LTCC material is obtained, and its dielectric properties are tested. The results are shown in Table 2.

[0100] 3. Test results and analysis

[0101] (1) According to the provisions of GBT 28195-2011 standard, the softening points of zinc borosilicate glass and zinc borosilicate glass-ceramics in each example and comparative example are tested. The results are shown in Table 1.

[0102] Table 1 Glass softening points in different examples

[0103]

[0104] As shown in Table 1, by flexibly adjusting the glass formula, the low softening point zinc borosilicate glass obtained has a softening point of 450-500℃, and the high softening point zinc borosilicate glass-ceramics has a softening point of 550-600℃.

[0105] (2) According to the provisions of GBT 26537-2011 and GBT 6569-2006 standards, the dielectric constant, dielectric loss, bending strength and sintering temperature of the LTCC material prepared in each example and comparative example are tested. The results are shown in Table 2.

[0106] Table 2 Properties of sintered samples in different examples

[0107] As shown in Table 2, in Example 1-Example 8, the dielectric constant of all sintered LTCC materials is less than 5, the dielectric loss is less than 0.001, and the sintering temperature is lower than 900℃. After sintering, Zn2SiO4 crystals are precipitated in the material. In Figure 1In the figure, the XRD patterns of the LTCC materials in Examples 1-4 are further shown to illustrate the precipitation of Zn2SiO4crystals. The "1Zn2SiO4" in the upper right corner of the figure indicates the precipitation peak of Zn2SiO4identified by the symbol "1", which is marked on the curve of Example 4 as an example. The lowermost curve in the figure and "PDF #96-900-7628 Zn2SiO4" represent the standard PDF card of Zn2SiO4.

[0108] The dielectric constant of the material in Example 2 is as low as 4.45, and the material maintains a dielectric loss of 6.15 x 10 -4 The dielectric loss of the material in Comparative Example 1 is significantly deteriorated compared to Example 1 because only low-softening-point zinc borosilicate glass is added. In Comparative Example 2, only high-softening-point zinc borosilicate glass is added, but the sintering temperature is 950°C, which is close to the melting point of Ag, which is not conducive to the later silver paste matching, and therefore cannot be used as an LTCC material.

[0109] Compared with the LTCC materials prepared by various typical processes in the industry, the product prepared by the present application has the advantages of low dielectric constant and low dielectric loss. For example, the LTCC material described in Chinese Invention Patent CN118459089 A has a dielectric constant of 4.5 and a dielectric loss of <0.005; the LTCC material described in Chinese Invention Patent CN110436894 A has a dielectric constant of 6-10@11GHz and a dielectric loss of <0.002@11GHz; the LTCC material described in Chinese Invention Patent CN117682768 A has a dielectric constant of <5 and a dielectric loss of <0.003; the commercial product of Ferro A6M-E type has a dielectric constant of 5.9±0.2 and a dielectric loss of <0.002; the commercial product of Dupont 951 type has a dielectric constant of 7.8±0.2 and a dielectric loss of 0.006; the commercial product of Vibrantz Confidential MW 5.8U type has a dielectric constant of 5.9 and a dielectric loss of 0.001. In summary, the LTCC materials prepared by various processes in the prior art are difficult to have both low dielectric constant and low dielectric loss.

[0110] The present application further carries out silver paste matching experiments on the LTCC material prepared in Example 1, wherein the silver powder in the selected silver paste has a solid content of 87%, and the cross-sectional SEM detection results of the silver paste matching product are shown in Figure 2 As can be seen from a and b in Figure 2 , all silver electrodes are well matched with the substrate, and no silver shrinkage, silver running and other defects are generated. As can be seen from Figure 2As can be seen from the middle C, the LTCC material substrate after sintering is sintered to be dense, and white grains are precipitated, and it can be known from the XRD pattern that the grains are Zn2SiO4, which can effectively reduce the dielectric loss of the material. Therefore, according to the above experimental data, the low-softening-point zinc-boron-silicon glass as a cooling aid and the high-softening-point zinc-boron-silicon glass as a loss reduction aid are used, and after sintering with SiO2, the LTCC material with low dielectric constant and low dielectric loss can be prepared, and the material has a suitable sintering window, which is helpful to widen the regulation interval in the later silver paste matching.

[0111] The above is a further detailed description of the present application in combination with specific preferred embodiments, and the specific implementation of the present application cannot be limited to these descriptions. For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of equivalent substitutions or obvious variations can be made, and the performance or use is the same, which should be regarded as belonging to the protection scope of the present application.

Claims

1. A LTCC material having both low dielectric constant and low dielectric loss, characterized in that: It is obtained by mixing zinc borosilicate glass with a softening point of 450-500℃, zinc borosilicate glass-ceramics with a softening point of 550-600℃ and auxiliary materials through ball milling, shaping and sintering. The LTCC material contains Zn2SiO4 in the crystallized phase. The raw material components used to prepare the LTCC material specifically include: 5-10 parts of zinc borosilicate glass, 30-50 parts of zinc borosilicate glass-ceramics, 40-60 parts of ceramic filler, 0-5 parts of silicate, and 0.1-1 parts of metal oxide; the above parts are all by mass.

2. The LTCC material according to claim 1, characterized in that The zinc borosilicate glass is prepared from the following raw material components in parts by mass: 30-52 parts of ZnO, 20-40 parts of B2O3, 10-20 parts of SiO2, 0-5 parts of Al2O3, 0-5 parts of BaO, 0-2 parts of Na2O, 0-2 parts of Li2O, and 0-2 parts of K2O.

3. The LTCC material according to claim 1, characterized in that The zinc borosilicate glass-ceramics is prepared from the following raw material components in parts by mass: 50-60 parts of ZnO, 10-20 parts of B2O3, 20-35 parts of SiO2, 0-10 parts of Al2O3, 0-1 part of Na2O, 0-1 part of Li2O, and 0-1 part of K2O.

4. The LTCC material according to claim 1, characterized in that Among the auxiliary materials, the ceramic filler is SiO2; the silicate is Zn2SiO4, Mg2SiO4, CaSiO3, Mg2Al4Si5O 18 , CaAl2Si2O8, CaMgSi2O6 or a mixture of at least two thereof; the metal oxide is one or a mixture of at least two thereof: ZrO2, TiO2, Cr2O3, Fe2O3, GeO2, Nd2O3, Sm2O3, Ta2O3, MoO3 or WO3.

5. The LTCC material according to claim 1, characterized in that The ceramic filler is amorphous or crystalline; the particle size distribution of other raw material components meets the following conditions: D of zinc borosilicate glass 10 Particle size 0.2~0.3 microns, D 50 Particle size 0.5~1 micron, D 90 Particle size 2~3 microns; D of zinc borosilicate glass-ceramics 10 Particle size 0.5~1 micron, D 50 Particle size 1~2 microns, D 90 Particle size 3~5 microns; D of ceramic filler 10 Particle size 0.5~1 micron, D 50 Particle size 2~4 microns, D 90 Particle size 7~10 microns; silicate D 10 Particle size 0.3~0.6 microns, D 50 Particle size 1~2 microns, D 90 Particle size 3~5 microns; D of metal oxide 10 Particle size 0.3~0.6 microns, D 50 Particle size 1~2 microns, D 90 Particle size 3~5 microns.

6. The method for preparing the LTCC material according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Preparation of zinc borosilicate glass: The raw material components are weighed according to their mass fractions, mixed, melted, quenched, ground, dried, sieved and passivated to obtain powdered zinc borosilicate glass; (2) Preparation of zinc borosilicate glass-ceramics: The raw material components are weighed according to their mass fractions, mixed, melted, quenched, ground, dried, sieved and passivated to obtain powdered zinc borosilicate glass-ceramics; (3) Weighing the raw material components of the LTCC material by mass, and subjecting them to wet ball milling to obtain porcelain powder; mixing the porcelain powder with an appropriate amount of binder, and subjecting them to granulation and forming to obtain a green embryo; (4) According to the set sintering program, the green body is heated and heated to remove the binder, and then heated again and sintered and kept warm. After sintering, the temperature is lowered. In this process, the crystallized phase Zn2SiO4 nucleates and grows in the glass phase, and finally an LTCC material with both low dielectric constant and low dielectric loss is obtained.

7. The method according to claim 6, characterized in that In the step (1), when preparing zinc borosilicate glass, the melting temperature is controlled to be 1200-1400°C and the temperature is kept at this temperature for 1-2 hours; after the glass liquid is obtained by melting, it is poured into deionized water at 20-35°C for quenching; the quenched glass, deionized water and grinding balls are added to a grinding jar for fine grinding, drying and passing through a 40-mesh sieve; the passivation treatment temperature is 200-400°C and the temperature is kept at this temperature for 2-5 hours.

8. The method according to claim 6, characterized in that In the step (2), when preparing zinc borosilicate glass-ceramics, the melting temperature is controlled to be 1300-1500°C and kept warm for 1-2 hours; after the glass liquid is melted, it is poured into deionized water at 20-35°C for quenching; the quenched glass, deionized water and grinding balls are added to a grinding jar for fine grinding, drying and passing through a 40-mesh sieve; the passivation treatment temperature is 200-400°C and the insulation time is 2-5 hours.

9. The method according to claim 6, characterized in that In the step (3), the binder is one or a mixture of at least two of PVA, PVB, octadecane, and paraffin.

10. The method according to claim 6, characterized in that In the step (4), the heating rate from heating the green embryo to the debinding process is controlled to be 0.5~2°C / min, the temperature during debinding is controlled to be 400~500°C, and the holding time is 1~2h; the heating rate from the debinding process to the sintering process is controlled to be 8~15°C / min, the temperature during sintering is controlled to be 850~900°C, and the holding time is 10~30min; the cooling rate from the completion of sintering to cooling to room temperature is controlled to be 2~5°C / min.

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