Low dielectric constant wollastonite-based low temperature co-fired ceramic material and its manufacturing method

Abstract

The present invention discloses a low dielectric constant wollastonite-based low temperature co-fired ceramic material and its manufacturing method, which relates to the technical field of electronic materials. The composition of this ceramic material is Ca x SiO3+awt%SiO2+bwt%R2O+cwt%Bi2O3+dwt%B2O3+ewt%MO (in the formula, 0.9≦x≦1.1, 0

Description

[Technical Field]

[0001] The present invention relates to the technical field of electronic materials, and more particularly to a wollastonite-based low-temperature co-fired ceramic material with a low dielectric constant and a method for producing the same. [Background technology]

[0002] Low-temperature co-fired ceramics (LTCC) is an electronic packaging technology that encompasses LTCC materials and device design, with LTCC being the foundation and key to its success. With the rapid development of 5G communications technology in recent years, microwave technology is moving toward higher frequencies, such as millimeter and submillimeter waves. This places increasingly higher demands on LTCC materials, including a low dielectric constant to reduce signal delay during transmission and a high Q factor (1 / tangent) to reduce device insertion loss and ensure good frequency selectivity. In addition to being able to be co-fired with metallic conductive materials such as Ag and Cu at 900°C, LTCC materials must also possess sufficient mechanical strength, environmental reliability, and corrosion resistance from electroplating or electroless plating solutions.

[0003] Currently, research into high-frequency, low-dielectric-constant, low-temperature co-fired ceramic materials includes three main systems: glass-ceramics, glass-ceramics, and ceramic additives. Glass-ceramics require strict control of material crystallization during the sintering process, placing relatively strict demands on the process. Currently, only FEERO's A6M material is widely used. Glass-ceramic systems require a large amount of glass to achieve low-temperature sintering of ceramics, but this results in a rapid increase in material loss. Unlike glass-ceramic systems, which can introduce a low dielectric constant, ceramic additives generally have difficulty achieving a low dielectric constant.

[0004] (Ca,Mg)SiO3-based microwave dielectric ceramics have good dielectric properties and low material costs. Patent CN103193389B describes blending at least two types of magnesium oxide, calcium oxide, or silicon oxide at 1500-1800°C to form a glass. The total amount of magnesium oxide, calcium oxide, and silicon oxide is 100 mol%, and then materials such as CaTiO3, MgTiO3, ZrTiO4, and TiO2 are added. The material is melted at 1500-1800°C and fired at 900°C. This method is complex, has a high dielectric constant, and requires two melting steps to form a glass, resulting in a low Q×f value. Patent application CN112759378A describes a low-temperature co-fired ceramic material, CaO-MgO-TiO2-SiO2, made by directly calcining a mixture of calcium carbonate, magnesium oxide, titanium dioxide, silicon dioxide, manganese oxide, lithium oxide, and bismuth oxide, followed by sintering at 860-880°C. Lithium oxide and bismuth oxide are added as sintering aids to the components and combined with TiO2 to form the eutectic material Li2TiO3 (900°C). This method involves adding all raw materials to the calcination process, which can lead to uncontrollable reactions between the components during calcination, resulting in complex and uncertain phases. Furthermore, the material has a dielectric constant of 9.5±0.1 and a low Q×f value. The materials described in the patent all have dielectric constants above 9, limiting their use in low-dielectric-constant, high-frequency applications. Invention patent CN200410039848.1 reports a formulation and manufacturing process for low-temperature sintering microwave dielectric ceramics, using a (Ca,Mg)SiO3 system as the main component, CaTiO3 to adjust the frequency temperature coefficient, and Li2CO3 and V2O5 as sintering aids. This low-temperature sintering microwave dielectric ceramic material can be co-fired with silver electrodes and has a dielectric constant of 8-10 and a quality factor Qf > 25,000 GHz. This material has been mass-produced. However, this material has the following drawbacks: (1) While the low-melting-point oxide V2O5 has excellent sintering properties and can significantly reduce the sintering temperature of (Ca,Mg)SiO3 ceramics, it is highly toxic and harmful to humans, failing to meet the increasingly important demands for environmental protection.(2) V2O5 forms a liquid phase during the sintering process, promoting ceramic sintering and facilitating the short-distance diffusion of silver electrodes. This increases the risk of interlayer circuit short-circuiting due to silver migration, leading to a significant problem of poor product reliability.

Summary of the Invention

Problems to be Solved by the Invention

[0005] To solve the above technical problems, the first object of the present invention is to provide a low-dielectric-constant wollastonite-based low-temperature co-fired ceramic material with a low dielectric constant, a high Q×f value, a low frequency temperature coefficient, and capable of low-temperature sintering. The second object of the present invention is to provide a low-dielectric-constant wollastonite-based low-temperature co-fired ceramic material and its manufacturing method that adopt a synthesis route of synthesizing the main-phase ceramic, then manufacturing the oxide sintering aid, and finally performing low-temperature sintering. This manufacturing method has a simple sintering process and good reproducibility.

Means for Solving the Problems

[0006] To achieve the above first object, the present invention adopts the following technical means. A low-dielectric-constant wollastonite-based low-temperature co-fired ceramic material, the composition formula of this low-temperature co-fired ceramic material is Ca x SiO3 + awt%SiO2 + bwt%R2O + cwt%Bi2O3 + dwt%B2O3 + ewt%MO (where 0.9 ≦ x ≦ 1.1, 0 < a ≦ 30, 1 ≦ b ≦ 5, 0 < c ≦ 3, 0 < d ≦ 6, 0 ≦ e ≦ 10, and a, b, c, d, and e are respectively the mass fractions of SiO2, RO, Bi2O3, B2O3, and MO phases with respect to Ca x SiO3, R2O is at least one of Li2O and K2O, MO is one or more of ZnO, MgO, BaO, CoO, CuO, La2O3, and MnO2, SiO2 is at least one of quartz and fused quartz).

[0007] As a preferred technical solution, the composition of the main-phase ceramic material is Ca x SiO3 (where 0.9 ≦ x ≦ 1.0).

[0008] As a preferred technical solution, SiO2 is fused quartz.

[0009] To achieve the above second object, the present invention adopts the following technical means. A method for manufacturing a low dielectric constant wollastonite-based low-temperature co-fired ceramic material, comprising: 1) Synthesis of the main-phase ceramic Ca x SiO3: Weigh raw materials CaCO3 and SiO2 according to the stoichiometric ratio of the chemical formula Ca x SiO3, use Deionized water as a solvent, mix with a ball mill for 16 - 24 h, dry, sieve through a 40-mesh sieve, uniformly pulverize, put into an alumina crucible, calcine at 900°C - 1300°C for 2 - 4 h to synthesize the main-phase ceramic, pulverize and use as a ceramic substrate; 2) Synthesis of the sintering aid: bwt%RO + cwt%Bi2O3 + dwt%B2O3 + ewt%MO (where 1 ≦ b ≦ 5, 0 < c ≦ 3, 0 < d ≦ 6, 0 ≦ e ≦ 10, b, c, d, and e are the mass fractions of the RO, Bi2O3, B2O3, and MO phases with respect to Ca x SiO3 respectively), weigh the raw materials of Li2CO3, K2CO3, Bi2O3, B2O3 or H3BO3, ZnO, MgO or Mg(OH)2, BaCO3, CoO or Co2O3, CuO, La2O3, MnO2 / MnCO3 according to the mass fraction ratio, add ethanol at a mass ratio of the mixed material to absolute ethanol of 1:1 - 1:1.5, mix with a wet method for 16 - 24 h, dry at 80°C, sieve the dried mixed material through a 40-mesh sieve, put into an alumina crucible, calcine at 500 - 700°C for 2 - 4 h, pulverize and use as the sintering aid; 3) The manufactured main-phase Ca x SiO3 ceramic, SiO2 and the oxide sintering aid are Ca xSiO3 + awt% SiO2 + bwt% RO + cwt% Bi2O3 + dwt% B2O3 + ewt% MO (where a, b, c, d and e are Ca x and mixing the materials in a ball mill using ZrO2 balls as milling media and ethanol as a solvent in a blending ratio of 0.1 to 0.5 (where 0.1 to 0.5 mass fractions of SiO2, RO, Bi2O3, B2O3 and MO phases relative to SiO3), mixing and drying for 16 to 24 hours, adding a polyvinyl alcohol binder with a content of 5 to 8 wt%, pulverizing and granulating the mixture, sieving the mixture, and then press-molding it at a pressure of 80 to 120 MPa to form a body having a diameter of 20 mm and a thickness of 10 mm, and firing it in an air atmosphere at 850 to 950°C for 1 to 3 hours to obtain the low-dielectric-constant wollastonite-based low-temperature co-fired ceramic material. [Effects of the Invention]

[0010] Compared with the prior art, the material of the present invention has the following advantages: 1. The present invention provides a simple, reliable, and low-cost manufacturing method. The main phase ceramic and sintering additives are synthesized separately, followed by the production of low-temperature co-fired ceramics. This method allows reliable control of the composition of the main phase ceramic, and also ensures that the sintering additives are synthesized as compounds with low eutectic points (below 700°C), such as Li2O(K2O)-Bi2O3-B2O3. Compared to conventional techniques, the main phase ceramic phase synthesized by this method is easier to control, has a better temperature-lowering effect for eutectic compounds, and has excellent dielectric properties. 2. The present invention designs and optimizes the calcium to silicon ratio of the main phase ceramic and studies its influence on the dielectric properties of the material. In particular, the main phase ceramic Ca x When SiO3 has a value of 0.9≦x≦1, the material has excellent dielectric properties. This is because the calcination process generates not only the wollastonite phase (CaSiO3) but also the Ca2SiO4 phase, which has a large dielectric loss. Excess SiO2 is advantageous in promoting the synthesis of the wollastonite phase, further improving the dielectric properties of the material. 3. Fused quartz and Ca xWhen SiO3 ceramic is used in a composite, the dielectric constant of the material can be effectively reduced due to the low dielectric constant of fused quartz. At the same time, fused quartz easily forms a liquid phase during the sintering process, which has the effect of wetting the powder particles and promoting sintering. 4. The present invention achieves a synergistic temperature reduction by introducing composite oxides, and by controlling the amounts of alkali metal oxides and Bi2O3 added, prevents the risk of interlayer short circuits due to silver migration, which is highly likely to occur when co-firing ceramic materials and silver electrodes. Furthermore, to avoid the complicated manufacturing process of glass additives, which makes it difficult to control batch stability, the present invention performs a pre-mixing and firing process on the various sintering additive oxides introduced. This solves the problem of high slurry viscosity due to crosslinking reactions between free hydroxyl groups in oxides such as B2O3 and powder and hydroxyl groups in binders such as PVB during ceramic casting slurry production, which prevents the production of high-quality ceramic green sheets. 5. The present invention provides a wollastonite-based low-temperature co-fired ceramic material with a dielectric constant of less than 7.5, a Q×f value greater than 20,000 GHz, and an absolute value of the temperature coefficient of frequency of less than 35 ppm / °C, which meets the requirements for low dielectric constant, low loss, and low temperature coefficient of frequency required for millimeter-wave devices. [Brief explanation of the drawings]

[0011] The drawings in the specification that form a part of this application are provided to provide a further understanding of the invention. The illustrative examples of the invention and the description thereof are intended to illustrate the invention and not to limit it. [Figure 1] 1 is an XRD diffraction pattern of the ceramic in Example 2. [Figure 2] 1 is a SEM scanning electron microscope photograph of a fired ceramic sample of Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail, examples of which are shown in the drawings. The embodiments described with reference to the drawings are illustrative and are intended to explain the present invention only, and should not be construed as limiting the present invention.

[0013] In order to clarify and clarify the objectives, technical means and advantages of the present invention, the present invention will be described in detail below with reference to the drawings and examples. It should be understood that the specific examples described herein are only for the purpose of illustrating the present invention, and are not intended to limit the present invention.

[0014] Example 1 1) Synthesis of the main phase: Chemical formula Ca 0.98 Weigh the raw materials CaCO3 and quartz in the SiO3 weighing ratio, Deionized water The mixture was mixed in a ball mill for 24 hours using this as a solvent, dried, and then sieved through a 40-mesh sieve to uniformly crush the mixture. The mixture was then placed in an alumina crucible and fired at 1200°C for 3 hours to synthesize the main phase ceramic. 2) Synthesis of sintering aid: The mass fraction ratio of the main phase ceramic was 3wt% Li2O+2wt% Bi2O3+3wt% B2O3+3wt% ZnO. Raw materials such as Li2CO3, Bi2O3, H3BO3, and ZnO were weighed, and the mixture was mixed with anhydrous ethanol in a mass ratio of 1:1. The mixture was mixed for 16 hours using a wet method and dried at 80°C. The dried mixture was sieved through a 40-mesh sieve, placed in an alumina crucible, fired at 600°C for 3 hours, and then crushed to be used as the sintering aid. 3) Main phase Ca 0.98 SiO3 ceramic was mixed with 3.0 wt% fused quartz and sintering aids synthesized in the previous process, based on the mass fraction of the main phase ceramic. ZrO2 balls were used as milling media and ethanol as solvent. The mixture was mixed and dried in a ball mill for 16 hours. An 8 wt% polyvinyl alcohol binder was added and pulverized. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 850°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0015] Example 2 1) Synthesis of the main phase: Weigh out the raw materials CaCO3 and quartz in the ratio of the chemical formula CaSiO3, Deionized water The mixture was mixed in a ball mill for 24 hours using this as a solvent, dried, and then sieved through a 40-mesh sieve to uniformly crush the mixture. The mixture was then placed in an alumina crucible and fired at 1250°C for 3 hours to synthesize the main phase ceramic. 2) Synthesis of sintering aid: The mass fraction ratio of the main phase ceramic was 1.5wt% Li2O + 1wt% K2O + 0.5wt% Bi2O3 + 2.5wt% B2O3 + 3wt% BaO + 2wt% MnO2. Raw materials such as Li2CO3, K2CO3, Bi2O3, H3BO3, BaCO3, and MnO2 were weighed, and the mixture was mixed with anhydrous ethanol in a mass ratio of 1:1. The mixture was mixed for 16 hours using a wet method and dried at 80°C. The dried mixture was sieved through a 40-mesh sieve, placed in an alumina crucible, fired at 650°C for 3 hours, and then crushed to be used as the sintering aid. 3) The main phase CaSiO3 ceramic was mixed with 3.5 wt% fused quartz and a sintering aid synthesized in a previous process, based on the mass fraction of the main phase ceramic. The mixture was then mixed in a ball mill using ZrO2 balls as milling media and ethanol as the solvent for 16 hours, dried, and then crushed and granulated with 8 wt% polyvinyl alcohol binder. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 900°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated. Figure 1 shows the XRD pattern of the fired ceramic, which consists mainly of CaSiO3 and a small amount of SiO2.

[0016] Example 3 1) Synthesis of the main phase: Chemical formula Ca 1.02 Weigh the raw materials CaCO3 and quartz in the SiO3 weighing ratio, Deionized water The mixture was mixed in a ball mill for 24 hours using this as a solvent, dried, and then sieved through a 40-mesh sieve to uniformly crush the mixture. The mixture was then placed in an alumina crucible and fired at 1300°C for 3 hours to synthesize the main phase ceramic. 2) Synthesis of sintering aid: The mass fraction ratio of the main phase ceramic was 2.5wt% Li2O+1wt% Bi2O3+2.5wt% B2O3+2wt% MgO. Raw materials such as Li2CO3, Bi2O3, H3BO3, and MgO were weighed, and the mixture was mixed with anhydrous ethanol in a mass ratio of 1:1. The mixture was mixed for 16 hours using a wet method and dried at 80°C. The dried mixture was sieved through a 40-mesh sieve, placed in an alumina crucible, fired at 700°C for 3 hours, and then crushed to be used as the sintering aid. 3) Main phase Ca 1.02 SiO3 ceramic was mixed with 5.0 wt% fused quartz and the sintering aid synthesized in the previous process, based on the mass fraction of the main phase ceramic. ZrO2 balls were used as milling media and ethanol as the solvent. The mixture was mixed and dried in a ball mill for 16 hours. An 8 wt% polyvinyl alcohol binder was added and the mixture was pulverized and granulated. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 850°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0017] Example 4 1) Synthesis of the main phase: Weigh out the raw materials CaCO3 and quartz in the ratio of the chemical formula CaSiO3, Deionized water The mixture was mixed in a ball mill for 24 hours using this as a solvent, dried, and then sieved through a 40-mesh sieve to uniformly crush the mixture. The mixture was then placed in an alumina crucible and fired at 1200°C for 3 hours to synthesize the main phase ceramic. 2) Synthesis of sintering aid: The mass fraction ratio of the main phase ceramic was 4wt% Li2O+1.5wt% Bi2O3+4wt% B2O3+1wt% La2O3+2wt% CuO. Raw materials such as Li2CO3, Bi2O3, H3BO3, La2O3, and CuO were weighed, and the mixture was mixed with anhydrous ethanol in a mass ratio of 1:1. The mixture was mixed for 16 hours using a wet method and dried at 80°C. The dried mixture was sieved through a 40-mesh sieve, placed in an alumina crucible, fired at 600°C for 3 hours, and then crushed to be used as the sintering aid. 3) The main phase CaSiO3 ceramic was mixed with 2.0 wt% fused quartz and sintering aids synthesized in the previous process, based on the mass fraction of the main phase ceramic. ZrO2 balls were used as milling media and ethanol as solvent. The mixture was mixed and dried for 16 hours in a ball mill. An 8 wt% polyvinyl alcohol binder was added and granulated. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa pressure. This was then fired at 880°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated. Figure 2 shows a scanning electron microscope image of the cross section of the ceramic sample, demonstrating the excellent density of this low-temperature co-fired ceramic.

[0018] Example 5 1) Synthesis of the main phase: Chemical formula Ca 0.95 Weigh the raw materials CaCO3 and fused quartz in the SiO3 weighing ratio, Deionized water The mixture was mixed in a ball mill for 24 hours using this as a solvent, dried, and then sieved through a 40-mesh sieve to uniformly crush the mixture. The mixture was then placed in an alumina crucible and fired at 1100°C for 3 hours to synthesize the main phase ceramic. 2) Synthesis of sintering aid: The mass fraction ratio of the main phase ceramic was 3.75wt% Li2O+2.5wt% Bi2O3+3.75wt% B2O3+1wt% CoO+2wt% CuO. Raw materials such as Li2CO3, Bi2O3, H3BO3, CoO, and CuO were weighed, and the mixture was mixed with anhydrous ethanol in a mass ratio of 1:1. The mixture was mixed for 16 hours using a wet method and dried at 80°C. The dried mixture was sieved through a 40-mesh sieve, placed in an alumina crucible, fired at 650°C for 3 hours, and then crushed to be used as the sintering aid. 3) Main phase Ca 0.95SiO3 ceramic was mixed with 10.0 wt% fused quartz and the sintering aid synthesized in the previous process, based on the mass fraction of the main phase ceramic. ZrO2 balls were used as milling media and ethanol was used as the solvent. The mixture was mixed and dried for 16 hours in a ball mill. An 8 wt% polyvinyl alcohol binder was added and the mixture was pulverized and granulated. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 850°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0019] Example 6 The main phase Ca synthesized in Example 5 0.95 SiO3 ceramic was mixed with quartz having a mass fraction of 10.0 wt% of the main phase ceramic and the sintering aid synthesized in Example 5. The mixture was mixed in a ball mill using ZrO2 balls as milling medium and ethanol as solvent for 16 hours and dried. After adding 8 wt% polyvinyl alcohol binder, the mixture was pulverized and granulated. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 880°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0020] Example 7 The main-phase CaSiO3 ceramic synthesized in Example 2 was mixed with fused quartz with a mass fraction of 7.0 wt% of the main-phase ceramic and the sintering aid synthesized in Example 2. The mixture was then mixed in a ball mill using ZrO2 balls as milling medium and ethanol as solvent for 16 hours, dried, and then crushed and granulated with 8 wt% polyvinyl alcohol binder. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa. This was then fired at 850°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0021] (Comparative Example 1) The main phase CaSiO3 ceramic synthesized in Example 2 was mixed with the sintering aid synthesized in Example 2, mixed in a ball mill using ZrO2 balls as milling medium and ethanol as solvent for 16 hours, dried, and then crushed and granulated with 8 wt% polyvinyl alcohol binder. After sieving, a 20 mm diameter, 10 mm thick body was produced at 100 MPa pressure. This was then fired at 930°C in an air atmosphere for 3 hours to obtain a low-temperature co-fired ceramic material, and its dielectric properties were evaluated.

[0022] Table 1 shows the evaluation results of the dielectric properties of the materials corresponding to the comparative example and examples 1 to 7. The dielectric properties were measured using an Agilent 8719ET network analyzer to measure the dielectric constant ε r The values ​​of Q×f and the temperature coefficient of frequency τ of the sample were evaluated. f =(f110-f25) / (f25x85), where f110 and f25 are the resonant center frequencies of the sample at 110°C and 25°C, respectively. [Table 1] The low-temperature co-fired ceramic materials listed in the table above have a dielectric constant of less than 7.5, a Q×f value greater than 20,000 GHz, and an absolute value of a frequency temperature coefficient of less than 35 ppm / °C. They meet the low dielectric constant, low loss, and low frequency temperature coefficient requirements of millimeter-wave devices. Compared to the comparative example, the addition of fused silica reduces the sintering temperature, increases the Q×f value of the material, and improves the frequency temperature coefficient.

[0023] It should be noted that in describing the present invention, terms such as "comprises," "including," and the like are intended to cover a non-exclusive inclusion, further including certain other processes, methods, materials, etc. not expressly described. An "embodiment" or a "specific embodiment," etc., means that the specific feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention.

[0024] Therefore, in the above, the invention has been described using specific examples, but it should be understood that the above examples are used to understand the method and core matters of the invention and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions, and variations to the above examples within the scope of the present invention without departing from the principles and gist of the present invention. Any simple modification, equivalent change, and modification made to the above examples in accordance with the technical essence of the present invention shall be regarded as falling within the protection scope of the present invention.

[0025] (Appendix) (Appendix 1) A low dielectric constant wollastonite-based low-temperature co-fired ceramic material, and the composition formula of this low-temperature co-fired ceramic material is Ca x SiO3 + awt%SiO2 + bwt%R2O + cwt%Bi2O3 + dwt%B2O3 + ewt%MO (where 0.9 ≤ x ≤ 1.1, 0 < a ≤ 30, 1 ≤ b ≤ 5, 0 < c ≤ 3, 0 < d ≤ 6, 0 ≤ e ≤ 10, and a, b, c, d, and e are respectively the mass fractions of SiO2, RO, Bi2O3, B2O3, and MO phases relative to Ca x SiO3, R2O is at least one of Li2O and K2O, MO is one or more of ZnO, MgO, BaO, CoO, CuO, La2O3, and MnO2, SiO2 is at least one of quartz and fused quartz). A low dielectric constant wollastonite-based low-temperature co-fired ceramic material characterized by the above.

[0026] (Appendix 2) The composition of the main phase ceramic material is Ca x SiO3 (where 0.9 ≤ x ≤ 1.0). The low dielectric constant wollastonite-based low-temperature co-fired ceramic material according to Appendix 1, characterized by the above.

[0027] (Appendix 3) The SiO2 is fused quartz. The low dielectric constant wollastonite-based low-temperature co-fired ceramic material according to Supplementary Note 1, characterized in that...

[0028] (Supplementary Note 4) A method for manufacturing the low dielectric constant wollastonite-based low-temperature co-fired ceramic material according to Supplementary Note 1, comprising: 1) Synthesis of the main phase ceramic Ca x SiO3: Weigh the raw materials CaCO3 and SiO2 according to the stoichiometric ratio of the chemical formula Ca x SiO3, use Deionized water as a solvent, mix with a ball mill for 16 - 24 h and dry, then sieve through a 40-mesh sieve, uniformly pulverize, put into an alumina crucible, and calcine at 900 °C - 1300 °C for 2 - 4 h to synthesize the main phase ceramic, pulverize and use as a ceramic substrate; 2) Synthesis of the sintering aid: bwt%RO + cwt%Bi2O3 + dwt%B2O3 + ewt%MO (where 1 ≤ b ≤ 5, 0 < c ≤ 3, 0 < d ≤ 6, 0 ≤ e ≤ 10, and b, c, d, and e are the mass fraction ratios of RO, Bi2O3, B2O3, and MO phases to Ca x SiO3 respectively), weigh the raw materials of Li2CO3, K2CO3, Bi2O3, B2O3 or H3BO3, ZnO, MgO or Mg(OH)2, BaCO3, CoO or Co2O3, CuO, La2O3, MnO2 / MnCO3 according to the mass fraction ratio, add ethanol at a mass ratio of the mixed material to absolute ethanol of 1:1 - 1:1.5, mix by the wet method for 16 - 24 h and dry at 80 °C, sieve the dried mixed material through a 40-mesh sieve, put into an alumina crucible, calcine at 500 - 700 °C for 2 - 4 h, pulverize and use as a sintering aid; 3) The manufactured main phase Ca x SiO3 ceramic, SiO2 and the oxide sintering aid are mixed according to Ca x SiO3 + awt%SiO2 + bwt%RO + cwt%Bi2O3 + dwt%B2O3 + ewt%MO (where a, b, c, d, and e are the mass fraction ratios of Ca xthe mixture is mixed in a ball mill using ZrO2 balls as milling media and ethanol as a solvent, and mixed for 16 to 24 hours, dried, and then pulverized and granulated with a polyvinyl alcohol binder content of 5 to 8% by weight, and sieved, and then pressed under a pressure of 80 to 120 MPa to form a body having a diameter of 20 mm and a thickness of 10 mm, and then fired in an air atmosphere at 850 to 950°C for 1 to 3 hours to obtain the low dielectric constant wollastonite-based low temperature co-fired ceramic material; A method for producing a low dielectric constant wollastonite-based low temperature co-fired ceramic material, comprising:

Claims

1. A low dielectric constant wollastonite-based low-temperature co-fired ceramic material having Ca x SiO 3 as the main phase ceramic material, the formulation of which is as follows: Ca ｘ SiO ３ + wt% SiO ２ +bwt%R ２ O+cwt%Bi ２ O ３ + dwt% B ２ O ３ + e wt % MO (where 0.9≦x≦1.1, 0<a≦30, 1≦b≦5, 0<c≦3, 0<d≦6, 0≦e≦10, and a, b, c, d, and e are Ca ｘ SiO ３ SiO ２ , R2O, Bi ２ O ３ , B ２ O ３ and the mass fraction of the MO phase, R ２ O is Li ２ O.K. ２ O, MO is ZnO, MgO, BaO, CoO, CuO, La ２ O ３ , MnO ２ and one or more of: SiO ２ is at least one of quartz and fused silica; A wollastonite-based low-temperature co-fired ceramic material with a low dielectric constant.

2. The composition of the main phase ceramic material is Ca ｘ SiO ３ (Wherein, 0.9≦x≦1.0) 2. The low dielectric constant wollastonite-based low temperature co-fired ceramic material according to claim 1.

3. The SiO ２ is fused silica, 2. The low dielectric constant wollastonite-based low temperature co-fired ceramic material according to claim 1.

4. 2. A method for producing a low dielectric constant wollastonite-based low temperature co-fired ceramic material according to claim 1, comprising: 1) Main phase ceramic Ca ｘ SiO ３ Synthesis of: Chemical formula Ca ｘ SiO ３ The raw material CaCO ３ and SiO ２ weighing the mixture, mixing it in a ball mill with deionized water as a solvent for 16 to 24 hours, drying it, sieving it through a 40-mesh sieve to uniformly crush it, putting it into an alumina crucible, firing it at 900°C to 1300°C for 2 to 4 hours to synthesize a main phase ceramic, and crushing it to use it as a ceramic substrate; 2) Synthesis of sintering aid: The sintering aid is bwt% R2O + cwt% Bi ２ O ３ + dwt% B ２ O ３ + e wt% MO, and then adding the mixed material and absolute ethanol in a mass ratio of 1:1 to 1:1.5, mixing them by a wet method for 16 to 24 hours, drying them at 80°C, and then sieving them through a 40 mesh sieve after drying them, placing them in an alumina crucible, firing them at 500 to 700°C for 2 to 4 hours, and then pulverizing them to be used as a sintering aid; the source of R2O is Li2CO3 and / or K2CO3, the source of B2O3 is B2O3 and / or H3BO3, and the source of MO is at least one selected from ZnO, MgO, Mg(OH)2, BaCO3, CoO, Co2O3, CuO, La2O3, MnO2, and MnCO3; 3) Ca ｘ SiO ３ + wt% SiO ２ +bwt%R 2 O+cwt%Bi ２ O ３ + dwt% B ２ O ３ The main phase ceramic Ca x SiO 3 and SiO 2 produced in the step 1) of synthesizing the main phase ceramic Ca x SiO 3 and the sintering aid produced in the step 2) of synthesizing the sintering aid were mixed in a mass fraction ratio of 0.1 wt % MO. ２ Mixing the mixture in a ball mill for 16 to 24 hours using balls as milling media and ethanol as a solvent, drying, adding 5 to 8 wt% of polyvinyl alcohol binder, pulverizing and granulating, then sieving, pressing the mixture into a body at a pressure of 80 to 120 MPa, and firing in an air atmosphere at 850 to 950°C for 1 to 3 hours to obtain a low-dielectric-constant wollastonite-based low-temperature co-fired ceramic material; A method for producing a low dielectric constant wollastonite-based low temperature co-fired ceramic material, comprising:

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