CN110790568A

CN110790568A - Low-dielectric LTCC green tape and preparation method and application thereof

Info

Publication number: CN110790568A
Application number: CN201911197245.7A
Authority: CN
Inventors: 吕洋; 董兆文; 周万丰; 沐方清
Original assignee: CETC 43 Research Institute
Current assignee: CETC 43 Research Institute
Priority date: 2019-11-29
Filing date: 2019-11-29
Publication date: 2020-02-14
Anticipated expiration: 2039-11-29
Also published as: CN110790568B

Abstract

The invention discloses a low-dielectric LTCC green tape and a preparation method and application thereof, wherein the low-dielectric LTCC green tape is composed of powder, a solvent, a dispersant, a binder and a plasticizer, the mass fraction of the powder is 40-60%, the powder is prepared from 10-40 wt% of a glass material, 1-10 wt% of a low-melting-point oxide sintering aid and the balance of a ceramic material, and the chemical composition of the ceramic material is Zn_2‑xSiO_4‑xWherein x = 0.05-0.3. In the invention, Zn is solved by applying the composite addition of the devitrification glass material and the sintering aid_2‑xSiO_4‑xThe low-temperature sintering of the ceramic can improve the mechanical property and high-frequency electrical property of the system.

Description

Low-dielectric LTCC green tape and preparation method and application thereof

Technical Field

The invention belongs to the field of low-temperature co-fired ceramic materials, and particularly relates to a low-dielectric LTCC green tape and a preparation method and application thereof.

Background

With the continuous progress of 5G communication and microwave technology, microwave circuit elements with the characteristics of small size, light weight and multiple functions are more and more concerned by the consumer market of electronic products, and the circuits have the characteristics of high use frequency, low delay and low loss and heat productivity, and provide new and higher requirements for raw materials. The LTCC technology is an important way for realizing the development of microwave components towards the directions of high-density integration, high reliability, high frequency and the like, the LTCC technology is designed for a circuit in a three-dimensional space, and according to the designed structure, electrode materials and dielectric materials are fired at one time through the procedures of punching, through hole filling, printing, laminating and the like on a green ceramic tape, so that the packaging size of a product is greatly reduced. Compared with organic polymer materials, the ceramic material has higher density and more ordered structure, can keep low loss at a higher frequency band, and is widely applied to the field of microwave and millimeter waves.

The common LTCC powder material comprises microcrystalline glass, glass-ceramic and glass-ceramic systems, wherein the microcrystalline glass is generated by crystallizing silicate glass or borosilicate glass in the glass after heat treatment at a certain temperature, and the glass is crystallized into a low-loss phase in the sintering process, so that the material has low dielectric loss. Glass plus ceramic material: the reduction of the sintering temperature of the electronic ceramic material is achieved by adding a low softening point glass to the crystalline ceramic filler. The ceramic is required to have lower dielectric loss and dielectric constant, the glass has lower dielectric constant and lower softening point, so that the glass and the ceramic form better infiltration in the sintering process, and the glass and ceramic LTCC materials are mainly used for low-frequency high-density integration, particularly the high-density and high-reliability field.

Through mixing the powder with binder, organic solvent etc. ball-milling, can make the homogeneous slurry of composition, performance, the slurry is through defoaming, defoaming etc., on even scribbling or flowing the substrate with the slurry again, or on the even scraper support membrane of blade, form even membrane thick liquids and make the slurry into the green tape, form the even biscuit membrane of certain thickness through drying, it is fashioned important form of LTCC powder, the green tape is made into circuit board or electronic component through the follow-up LTCC technology.

The existing low-temperature co-fired material is usually a ceramic + glass system, wherein glass is not crystallized and is only used as a sintering aid to reduce the mechanical strength and the high-frequency electrical property of the system.

Disclosure of Invention

In view of the above, the invention needs to provide a low-dielectric LTCC green tape and a preparation method and application thereof, wherein Zn without impurity phase is prepared in a Zn defect mode_2-xSiO_4-xPure phase, calcium borosilicate glass, CuO, V₂O₅The calcium borosilicate glass is a sintering aid, the glass formula is adjusted to enable the calcium borosilicate glass to have a low glass softening temperature (600-620 ℃), the flowing mass transfer of materials can be promoted at a low temperature, the zinc silicate can be sintered at 850 ℃, and the calcium borosilicate glass can be crystallized into CaSiO at 800-820 DEG C₃And the low-loss phase is adopted, so that fine holes of the sintered ceramic are filled, and the dielectric loss of the material can be reduced. Solves the problem that the glass does not crystallize in the existing ceramic and glass system low-temperature co-fired ceramic material. In the invention, by applying the composite addition of the devitrification glass material and the sintering aid, on the one hand, Zn is solved_2-xSiO_4-xThe low-temperature sintering of the ceramic can improve the mechanical property and high-frequency electrical property of the system.

In addition, the powder is cast into a green tape by adopting a proper casting slurry system, Ag and Au conductors are printed on the green tape, and the green tape material is well matched with the conductor slurry and co-fired, so that the green tape material is suitable for the application field of high-frequency low-dielectric LTCC substrate materials. The problems of low material strength and high dielectric loss in the prior art are solved.

In order to achieve the purpose, the invention adopts the following technical scheme:

the low-dielectric LTCC green tape is composed of powder, a solvent, a dispersing agent, a binder and a plasticizer, wherein the mass fraction of the powder is 40-60%, the powder is prepared from 10-40 wt% of a glass material, 1-10 wt% of a low-melting-point oxide sintering aid and the balance of a ceramic material, and the chemical composition of the ceramic material is Zn_2-xSiO_4-xWherein x is 0.05 to 0.3.

Further, the particle size D50 of the glass material is: 2-2.5 mu m, the glass material is microcrystalline glass, and the composition of the microcrystalline glass at least comprises CaO and B₂O₃、SiO₂、P₂O₅、Na₂O and Li₂O。

Preferably, in the microcrystalline glass, the content of each component is respectively 20-50 wt% of CaO and 10-40 wt% of B₂O₃、15～45wt％SiO₂、0.5～10wt％P₂O₅、0.5～10wt％Na₂O、0.5～10wt％Li₂O。

Further, the low-melting-point oxide sintering aid comprises CuO and V₂O₅Wherein the total content of the low-melting-point oxide sintering aid is less than 5wt% of the ceramic material.

Further, the solvent is a mixture of at least two of toluene, ethanol, isopropanol, butanone and ethyl acetate;

the dispersant is a compound of tributyl phosphate, triolein and triethanolamine;

the plasticizer is a mixture of dibutyl phthalate and polyvinyl alcohol;

the binder is one of polyvinyl butyral and acrylic resin.

Furthermore, the thickness of the low-dielectric LTCC green ceramic tape is 70-200 μm.

The invention also provides a preparation method of the low-dielectric LTCC green tape, which comprises the following steps:

preparing a ceramic material: according to the chemical composition Zn of the ceramic material_2-xSiO_4-xWeighing ZnO and SiO₂As initial powder, mixing the initial powder, ball milling, drying, calcining, ball milling and refining to obtain Zn_2-xSiO_4-xA ceramic material;

preparing a glass material: weighing CaCO according to the proportion₃、SiO₂、H₃BO₃、Al₂O₃、P₂O₅、Na₂CO₃、Li₂CO₃After mixing uniformly, melting and quenching to prepare cullet, then ball-milling and drying to prepare a glass material;

preparing raw porcelain tape slurry: according to the proportionThe Zn is added_2-xSiO_4-xPreparing casting slurry with solid content of 45-65 wt% by ball milling, mixing and defoaming the ceramic material, the glass material, the low-melting-point oxide, the solvent, the plasticizer, the dispersing agent and the binder;

tape casting of the raw porcelain tape: and casting the casting slurry to prepare the low-dielectric LTCC green ceramic tape.

Further, in the preparation process of the ceramic material, alcohol is used as a ball milling medium in the ball milling process, and agate balls are used for ball milling for 4-8 hours; the calcination is carried out at 800-850 ℃ for 12-24 h.

Further, in the preparation process of the green tape slurry, the binder is a pre-mixed colloidal solution, the solvent of the colloidal solution is the same as that of the green tape slurry, and the binder accounts for 30wt% of the colloidal solution.

The invention also provides application of the low-dielectric LTCC green tape in preparation of a high-frequency low-dielectric LTCC substrate material.

Compared with the prior art, the invention has the following beneficial effects:

1. preparing pure-phase zinc silicate powder by adopting Zn defect method and using Zn_2-xSiO_4-xPure phase as ceramic matrix, Zn_2-xSiO_4-xHas lower dielectric constant of 6.6(10GHz), lower dielectric loss: < 1 x 10^-4(10GHz), and the structure is in a metastable state due to the lattice distortion caused by Zn defect, so that the sintering agent and the glass are easier to sinter.

2. The raw ceramic tape material formula is added with a compounded microcrystalline glass material with low-temperature softening and high-temperature crystallization, and the microcrystalline glass material is generally low in mechanical strength due to the fact that the ratio of glass to a crystallization phase in the system is high. The microcrystalline glass can be sintered and compacted at 850 ℃, and the glass is crystallized in the sintering process to form low-loss CaSiO₃Phase (CaSiO)₃Dielectric loss ofThe loss is less than or equal to 0.001@ 10-12 GHz), so that the dielectric loss of a material system is reduced, and the LTCC substrate material is an excellent LTCC substrate material.

3. CuO and V are added into the formula at the same time₂O₅The sintering aid can obviously reduce the softening point of the glass and promote the low-temperature sintering of the material, and the CuO can induce the crystallization of the glass ceramics in the heat treatment process, and the crystallization is carried out after the ceramic holes are filled with the glass in the later sintering stage, thereby improving the performance of the material system.

4. According to the invention, the multiphase solvent system and the dispersant system are adopted, so that the powder can be well dispersed, the LTCC green tape is easy to prepare, the green tape material is well matched with the Ag conductor and is well co-fired, the dielectric constant of the low-dielectric LTCC green tape material system is 5-8 at 10-15 GHz, the dielectric loss is less than or equal to 0.002, and the application requirement of high-frequency microwave packaging of the LTCC substrate can be met.

Drawings

FIG. 1 is a surface SEM photograph of a low dielectric LTCC green tape of example 2;

FIG. 2 is an SEM of a co-fired cross-section of a low dielectric LTCC green tape and a silver conductor of example 2.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description of specific embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The invention discloses a low-dielectric LTCC green tape which comprises 40-60% by mass of powder, a solvent, a dispersant, a binder and a plasticizer, wherein the low-dielectric LTCC green tape is prepared from 10-40% by weight of a glass material, 1-10% by weight of a low-melting-point oxide sintering aid and the balance of a ceramic materialPrepared by the method, the chemical composition of the ceramic material is Zn_2-xSiO_4-xWherein x is 0.05 to 0.3. According to the invention, the ceramic can keep the original crystal structure through certain ZnO vacancy, the ceramic material without the ZnO second phase is prepared, and the ZnO vacancy enables the crystal lattice of the material to be distorted and to react with the glass more easily, so that the sintering temperature is further reduced.

Further, the particle size D50 of the glass material is: 2-2.5 mu m, the glass material is microcrystalline glass, the ceramic material is used as a filling phase, the high-frequency low-dielectric low-loss glass substrate has the characteristics of high frequency and low dielectric low-loss, and is used as the basis of the application of the substrate material in the field of high-frequency communication, the glass material is microcrystalline glass, the low-temperature sintering of the ceramic filling phase is promoted, and the glass material is crystallized in the later sintering stage, so that the loss of a material system is reduced. In some embodiments of the present invention, the microcrystalline glass has a composition including at least CaO and B₂O₃、SiO₂、P₂O₅And Na₂O and Li₂And O. The particle size of the glass material is also limited, because the particle size D50 is: in some embodiments of the present invention, the glass material having a particle size of 2 to 2.5 μm is preferably in the above range because the glass material can effectively fill the gaps between the ceramic powder particles, and the homogenized glass powder can more easily promote the liquid-phase viscous flow sintering of the ceramic to improve the sintering characteristics.

In some embodiments of the invention, the content of each component in the microcrystalline glass is 20-50 wt% of CaO and 10-40 wt% of B₂O₃、15～45wt％SiO₂、0.5～10wt％P₂O₅、0.5～10wt％Na₂O、0.5～10wt％Li₂And O. This is because the microcrystalline glass in this preferred compounding ratio range has a relatively suitable glass softening point, and therefore, the green tape in the present invention is excellent in properties.

In some embodiments of the present invention, the sintering aid is a low-melting point oxide, and the low-melting point oxide can form a liquid phase at the early stage of sintering, wet and dissolve a solid phase, promote mass transfer between powder bodies, and reduce the sintering temperature of the system.

Still further, in some embodiments of the invention, the low melting point oxide comprises CuO and V₂O₅Wherein the content of the low melting point oxide is less than 5wt% of the ceramic material.

In some embodiments of the present invention, the solvent is a mixture of at least two or more of toluene, ethanol, isopropanol, butanone, ethyl acetate;

the plasticizer is a mixture of dibutyl phthalate and polyvinyl alcohol;

the binder is one of polyvinyl butyral and acrylic resin.

The invention also discloses a preparation method of the low-dielectric LTCC green tape, which comprises the following steps:

preparing raw porcelain tape slurry: the Zn is mixed according to the proportion_2-xSiO_4-xPreparing casting slurry by ball milling, mixing and defoaming a ceramic material, the glass material, a sintering aid, a solvent, a plasticizer, a dispersant and a binder;

Preferably, in the preparation process of the ceramic material, alcohol is used as a ball milling medium in the ball milling, and agate balls are used for ball milling for 4-8 hours; the calcination is carried out at 800-850 ℃ for 12-24 h.

In some embodiments of the present invention, the melting and quenching specifically comprises melting the uniformly mixed material in a platinum crucible, and then pouring the molten glass into deionized water to quench.

In some embodiments of the present invention, during the preparation of the green tape slurry, the binder is a pre-mixed colloidal solution, a solvent of the colloidal solution is the same as a solvent of the green tape slurry, and a mass fraction of the binder in the colloidal solution is 30 wt%.

The casting technology for preparing the green porcelain band by casting the green porcelain band slurry is known by those skilled in the art, the specific casting parameters can be adjusted according to different casting systems, in some embodiments of the invention, the casting speed is 0.05-0.15 m/min, and the height of a scraper is 0.25-0.35 mm.

The technical solution of the present invention will be more clearly and completely described below with reference to more specific examples.

Example 1

a. Preparing a ceramic material: weighing 71.4 wt% of ZnO and 28.6 wt% of SiO according to the mass ratio₂As the initial powder, the initial powder takes alcohol as a ball milling medium, agate balls are adopted for ball milling for 6h, then drying is carried out, and calcination is carried out for 4h at 1150 ℃. Ball-milling and refining the calcined powder to obtain Zn_1.91SiO_3.91A ceramic material.

b. Preparing a glass material: weighing 43.6 wt% CaCO₃、15.2wt％H₃BO₃、34.3％SiO₂、2.2wt％Al₂O₃、2.7wt％P₂O₅，0.8wt％Na₂CO₃、1.2wt％Li₂CO₃Mixing, melting at 1400 deg.C in platinum crucible, directly pouring molten glass into deionized water, quenching to obtain milky fluffy glass cullet, and mixingBall milling the glass cullet to obtain a particle size D50: 1-1.5 mu m, and drying to obtain the microcrystalline glass.

c. Preparing a raw porcelain tape: weighing 42 wt% of microcrystalline glass and 58 wt% of Zn_1.91SiO_3.91Ceramic material, 1.5 wt% CuO, 1.5 wt% V₂O₅And (5) uniformly mixing the powder in a roller mill for 12 hours to obtain powder. The powder and solvent system were weighed as follows:

TABLE 1 Green porcelain band composition formula

Component (A)

Powder body

Ethanol

Toluene

Phosphoric acid tributyl ester

Binder

Triolein

Weight (D)

80g

16g

12g

2g

15g

3.5g

Wherein the binder is a mixed solution of ethanol, toluene and PVB, and the mass ratio of the solvent (the sum of the ethanol and the toluene) to the PVB is 7: 3. after weighing, the slurry is ball-milled for 24h in a roller mill and defoamed for 10min, the height of a casting scraper is 0.27mm, the casting speed is 0.12m/min, and the slurry is cast into a low dielectric LTCC green tape with the thickness of 127 mu m.

Example 2

a. Preparing a ceramic material: 69.7 wt% of ZnO and 30.3 wt% of SiO were weighed₂As the initial powder, the initial powder takes alcohol as a ball milling medium, agate balls are adopted for ball milling for 6h, then drying is carried out, and calcination is carried out for 4h at 1150 ℃. Ball-milling and refining the calcined powder to obtain Zn_1.79SiO_3.79A ceramic material.

b. Preparing a glass material: weighing 43.1 wt% CaCO₃、18.2wt％H₃BO₃、31.8％SiO₂、2.2wt％Al₂O₃、2.7wt％P₂O₅，0.8wt％Na₂CO₃、1.2wt％Li₂CO₃Mixing, melting in a platinum crucible at 1400 ℃, directly pouring the molten glass into deionized water for quenching to obtain milky fluffy cullet, and ball-milling the cullet until the particle size is D50: 1-1.5 mu m, and drying to obtain the microcrystalline glass.

c. Preparing a raw porcelain tape: weighing 45wt% of microcrystalline glass and 52 wt% of Zn_1.79SiO_3.79Ceramic material, 1.2 wt% CuO, 1.8 wt% V₂O₅And (5) uniformly mixing the powder in a roller mill for 12 hours to obtain powder. Weighing the powder and a solvent system according to table 1, wherein the binder is a mixed solution of ethanol, toluene and PVB, and the mass ratio of the solvent (the sum of ethanol and toluene) to the PVB is 7: 3. after weighing, the slurry was ball milled on a roller mill for 24 h. And defoaming for 10min, wherein the height of a casting scraper is 0.27mm, the casting speed is 0.12m/min, and the low-dielectric LTCC green tape with the thickness of 127 mu m is formed by casting.

Example 3

a. Preparing a ceramic material: weighing 70.8 wt% ZnO and 28.6 wt% SiO₂As initial powder, alcohol is used as a ball milling medium, agate balls are adopted to dry after ball milling for 6h, and calcination is carried out for 4h at 1150 ℃. Ball-milling and refining the calcined powder to obtain Zn_1.89SiO_3.89Ceramic materialA material.

b. Preparing a glass material: weighing 42.8 wt% CaCO₃、13.7wt％H₃BO₃、37.7％SiO₂、1.6wt％Al₂O₃、2.2wt％P₂O₅，0.8wt％Na₂CO₃、1.2wt％Li₂CO₃Mixing, melting in a platinum crucible at 1400 ℃, directly pouring the molten glass into deionized water for quenching to obtain milky fluffy cullet, and ball-milling the cullet until the particle size is D50: 1-1.5 mu m, and drying to obtain the microcrystalline glass.

c. Preparing a raw porcelain tape: weighing 53 wt% of microcrystalline glass and 44 wt% of Zn_2-xSiO_4-xCeramic material, 1.5 wt% CuO, 1.5 wt% V₂O₅And (5) uniformly mixing the powder in a roller mill for 12 hours. The powder and solvent systems were weighed according to the system in table 1 and the slurry was ball milled on a roller mill for 24 h. And defoaming for 10min, wherein the height of a casting scraper is 0.27mm, the casting speed is 0.12m/min, and the low-dielectric LTCC green tape with the thickness of 127 mu m is formed by casting.

The low dielectric green LTCC tapes prepared in examples 1-3 were cut into single layer LTCC green tapes of the same size and the desired electrode pattern was printed on the LTCC green tape surface by screen printing, followed by positioning and lamination of 20 single layer LTCC green tapes and hot isostatic pressing (3500psi, 70 ℃) to form a green body. And then putting the green body of the LTCC substrate formed by hot isostatic pressing into a muffle furnace, heating to 450 ℃ at the speed of 1.5 ℃/min, preserving the heat for 60 minutes to remove organic matters in the sample, and heating to 850 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes, thus obtaining the LTCC substrate sample.

The ceramic sheets obtained by laminating and sintering the blank green ceramic tapes prepared in the three embodiments are laser-scribed into wafers with the diameter of 10mm, silver electrodes are coated on the upper and lower surfaces of the wafers and sintered for 30min at 550 ℃, and the dielectric constant and the dielectric loss of the material under 1MHz are tested by an impedance analyzer. The ceramic powder of the three examples is granulated and pressed into a cylinder with the diameter of 10mm and the height of 6-7 mm, the same curve as that of the green tape sintering is adopted to obtain cylinder samples of the three examples, and the dielectric constant and the dielectric loss of the samples under the microwave frequency band are tested by a parallel plate resonant cavity method. The properties of the fired ceramics of the three examples are shown in Table 2:

TABLE 2 sintered ceramic Properties

Note: in Table 2^aThe sintering shrinkage test method comprises the following steps: and measuring the length/width (X/Y direction) and the thickness (Z direction) of the biscuit blank by adopting a micrometer or a measuring tool meeting the precision requirement, and measuring the length, the width and the thickness of the sintered mature porcelain after sintering. The sintering shrinkage in the X/Y direction is obtained by subtracting the length of the green body from the length of the cooked porcelain and dividing the difference by the length of the green body; the sintering shrinkage in the Z direction is the thickness of the green body subtracted from the thickness of the porcelain, and the difference is divided by the thickness of the green body.

^bThe test of the dielectric constant and the dielectric loss of the ceramic is divided into two frequency bands, and the test under the frequency band of 1MHz is referred to 5.11.1 in GB/T5593-1996 electronic component structure ceramic material; the test under the frequency band of 14 GHz-16 GHz refers to GB/T7265.2-1987 open cavity method for testing the complex dielectric constant of solid dielectric microwave.

The low-dielectric LTCC green tape in the embodiment 2 and the LTCC ceramic substrate manufactured by the green tape are respectively subjected to SEM representation, and fig. 1 is an SEM image of the low-dielectric LTCC green tape, so that the ceramic material is compact in shape and free of continuous pores during sintering at 850 ℃, and the fact that the sintering compactness of the ceramic is remarkably improved by adopting the microcrystalline glass material is shown. Fig. 2 is a cross section SEM of low dielectric LTCC green tape co-fired with an Ag electrode material, and it can be seen from the figure that the interface between the Ag conductor layer and the ceramic material is clear, and there is no obvious phenomenon of silver diffusion or interface reaction between the conductor and the substrate, which indicates that the formula system of ceramic + glass ceramics is suitable for co-firing of the LTCC substrate and the conductor lamination.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The low-dielectric LTCC green tape is characterized by comprising 40-60% of powder, a solvent, a dispersant, a binder and a plasticizer, wherein the powder is prepared from 10-40 wt% of a glass material, 1-10 wt% of a low-melting-point oxide sintering aid and the balance of a ceramic material, and the chemical composition of the ceramic material is Zn_2-xSiO_4-xWherein x = 0.05-0.3.

2. The low dielectric LTCC green tape of claim 1, wherein the glass material has a particle size D50 of: 2-2.5 mu m, the glass material is microcrystalline glass, and the composition of the microcrystalline glass at least comprises CaO and B₂O₃、SiO₂、P₂O₅、Na₂O and Li₂O。

3. The low dielectric LTCC green tape of claim 2, wherein the microcrystalline glass comprises 20-50 wt% CaO and 10-40 wt% B₂O₃、15~45wt%SiO₂、0.5~10wt%P₂O₅、0.5~10wt%Na₂O、0.5~10wt%Li₂O。

4. The low dielectric LTCC green tape of claim 1, wherein the low melting point oxide sintering aid comprises CuO and V₂O₅Wherein the total content of the low-melting-point oxide sintering aidLess than 5wt% of the ceramic material.

5. The low dielectric LTCC green tape of claim 1, wherein the solvent is a mixture of at least two of toluene, ethanol, isopropanol, methyl ethyl ketone, and ethyl acetate;

the plasticizer is a mixture of dibutyl phthalate and polyvinyl alcohol;

the binder is one of polyvinyl butyral and acrylic resin.

6. The low dielectric LTCC green tape of claim 1, wherein the low dielectric LTCC green tape has a thickness of 70 μm to 200 μm.

7. The method of making the low dielectric LTCC green tape of any one of claims 1-6, comprising the steps of:

preparing raw porcelain tape slurry: the Zn is mixed according to the proportion_2-xSiO_4-xCarrying out ball milling, mixing and defoaming on a ceramic material, the glass material, the low-melting-point oxide, a solvent, a plasticizer, a dispersing agent and a binder to prepare casting slurry with the solid content of 45-65 wt%;

8. The preparation method of claim 7, wherein in the preparation process of the ceramic material, alcohol is used as a ball milling medium for ball milling, and agate balls are used for ball milling for 4-8 hours; the calcination is carried out at 800-850 ℃ for 12-24 h.

9. The method according to claim 7, wherein the binder is a pre-mixed colloidal solution during the preparation of the green tape slurry, the solvent of the colloidal solution is the same as that of the green tape slurry, and the binder is present in the colloidal solution in a mass fraction of 30 wt%.

10. Use of the low dielectric LTCC green tape of any one of claims 1 to 6 for the preparation of a high frequency low dielectric LTCC substrate material.