阅读说明：本技术 一种低温共烧陶瓷粉体材料及其制备方法和应用 (Low-temperature co-fired ceramic powder material and preparation method and application thereof ) 是由 黄国洪 党明召 陈涛 崔三川 曹秀华 沓世我 付振晓 于 2021-09-08 设计创作，主要内容包括：本发明提供了一种低温共烧陶瓷粉体材料及其制备方法和应用,涉及电子陶瓷材料技术领域。本发明提供的低温共烧陶瓷粉体材料包括如下重量份数的原料组分：硼硅玻璃粉50-60份、石英玻璃粉30-40份、粉体助剂5-10份,所述粉体助剂包括Al-(2)O-(3)、ZrO-(2)、MgO和BaO中的至少一种。本发明将硼硅玻璃粉、石英玻璃粉和粉体助剂复配制备的低温共烧陶瓷粉体材料烧结后的介电常数εr＝3.8-4.5,介电损耗低tanδ＝0.001-0.0025,电阻率ρ＝1.0-9.9×10～(12)Ω·cm,其烧结温度在850-900℃范围内,烧结后致密度良好,最高可达99.8％。(The invention provides a low-temperature co-fired ceramic powder material and a preparation method and application thereof, relating to the technical field of electronic ceramic materials. The low-temperature co-fired ceramic powder material provided by the invention comprises the following raw material components in parts by weight: 50-60 parts of borosilicate glass powder, 30-40 parts of quartz glass powder and 5-10 parts of powder auxiliary agent, wherein the powder auxiliary agent comprises Al 2 O 3 、ZrO 2 At least one of MgO and BaO. The low-temperature co-fired ceramic powder material prepared by compounding borosilicate glass powder, quartz glass powder and powder auxiliary agent has the dielectric constant Epsilonr of 3.8-4.5, low dielectric loss tan delta of 0.001-0.0025 and resistivity rho of 1.0-9.9 multiplied by 10 after being sintered 12 Omega cm, sintering thereofThe temperature is in the range of 850-900 ℃, the density after sintering is good, and the maximum density can reach 99.8 percent.)

1. The low-temperature co-fired ceramic powder material is characterized by comprising the following raw material components in parts by weight: 50-60 parts of borosilicate glass powder, 30-40 parts of quartz glass powder and 5-10 parts of powder auxiliary agent, wherein the powder auxiliary agent comprises Al₂O₃、ZrO₂At least one of MgO and BaO.

2. The low-temperature co-fired ceramic powder material according to claim 1, wherein the purity of the quartz glass powder is 4N; the borosilicate glass powder comprises the following raw material components: SiO 2₂、H₃BO₃Metal oxide and carbonate, the SiO₂And H₃BO₃The mass of (a) is 85-92% of the mass of the borosilicate glass powder.

3. The low temperature co-fired ceramic powder material of claim 2, wherein the metal oxide comprises ZnO, Al₂O₃、ZrO₂MgO and TiO₂At least one of, the carbonate comprises CaCO₃、Li₂CO₃、K₂CO₃、Na₂CO₃、SrCO₃And BaCO₃At least one of (1).

4. The low-temperature co-fired ceramic powder material according to any one of claims 1 to 3, wherein the borosilicate glass powder comprises the following raw material components in percentage by mass: SiO 2₂ 58-65％、H₃BO₃25-30％、ZnO 0-1wt％、CaCO₃0-1wt％、Al₂O₃ 0-2wt％、Li₂CO₃ 0-1wt％、K₂CO₃0-1.5wt％、Na₂CO₃ 0-2.5wt％、ZrO₂ 0-1wt％、SrCO₃ 0-1wt％、BaCO₃0-1.5 wt%, MgO 0-1 wt% and TiO₂ 0-0.5wt％。

5. As claimed in claim 4The low-temperature co-fired ceramic powder material is characterized in that the borosilicate glass powder comprises the following raw material components in percentage by mass: SiO 2₂ 61.6％、H₃BO₃ 28.2％、ZnO 0.6wt％、CaCO₃ 0.8wt％、Al₂O₃ 1.1wt％、Li₂CO₃ 0.4wt％、K₂CO₃ 1.2wt％、Na₂CO₃2.5wt％、ZrO₂ 0.5wt％、SrCO₃0.9wt％、BaCO₃1.1 wt%, MgO 0.8 wt% and TiO₂0.3wt％。

6. The low-temperature co-fired ceramic powder material according to any one of claims 2 to 5, wherein the preparation method of the borosilicate glass powder comprises the following steps: mixing the raw material components of the borosilicate glass powder with water, performing ball milling discharging, melting and quenching at 1400 ℃ after drying and crushing, sieving with a 60-mesh sieve after crushing, adding water, performing ball milling until the particle size of D50 is 0.7-1.8um, and drying to obtain the borosilicate glass powder.

7. The low-temperature co-fired ceramic powder material of claim 1, wherein the powder auxiliary agent comprises the following components in parts by weight: al (Al)₂O₃3-7 parts of ZrO₂0.5-1.5 parts of MgO, 1-3 parts of BaO and 0.5-1.5 parts of BaO.

8. The method for preparing a low-temperature co-fired ceramic powder material according to any one of claims 1 to 7, comprising the following steps:

(1) mixing quartz glass powder, powder auxiliary agent, grinding balls and deionized water, ball-milling and discharging, drying, pre-burning at 850-950 ℃ for 1-5h, cooling, crushing, and sieving the powder with a 200-mesh sieve to obtain pre-burned powder;

(2) and mixing the pre-sintered powder and borosilicate glass powder with a grinding ball and deionized water, then carrying out ball milling to ensure that the powder is uniformly mixed, controlling the particle size of the slurry D50 to be 0.8-1.5um, and drying to obtain the low-temperature co-fired ceramic powder material.

9. The method according to claim 8, wherein the total mass of the silica glass powder and the powder assistant in the step (1) is as follows: grinding ball quality: deionized water with the mass ratio of 1:4: 0.8; the total mass of the pre-sintered powder and the borosilicate glass powder in the step (2) is as follows: grinding ball quality: deionized water mass 1:3: 1.2.

10. Use of the low-temperature co-fired ceramic powder material according to any one of claims 1 to 7 in the preparation of a low-temperature co-fired ceramic radio frequency device.

Technical Field

The invention relates to the technical field of electronic ceramic materials, in particular to a low-temperature co-fired ceramic powder material and a preparation method and application thereof.

Background

Low Temperature Co-fired Ceramics (LTCC) technology is an ideal packaging technology for realizing miniaturization and chip-type electronic components. With the increasing popularization of the 5G technology, the demand for miniaturization and integration of electronic components is higher, the information amount is increased, and the demand for the capacity and transmission speed of information to be transmitted is higher. Therefore, low temperature co-fired ceramic (LTCC) materials need a lower dielectric constant to reduce signal delay when used as a substrate, and also need a lower dielectric constant and dielectric loss to meet high frequency band applications when used as a chip inductor in order to reduce capacitance and increase inductance.

Disclosure of Invention

In order to solve the problems, the invention mainly aims to provide a low-temperature co-fired ceramic powder material and a preparation method and application thereof.

In order to achieve the purpose, the invention provides a low-temperature co-fired ceramic powder material in a first aspect, which comprises the following raw material components in parts by weight: 50-60 parts of borosilicate glass powder, 30-40 parts of quartz glass powder and 5-10 parts of powder auxiliary agent, wherein the powder auxiliary agent comprises Al₂O₃、ZrO₂At least one of MgO and BaO.

In the technical scheme of the invention, the low-temperature co-fired ceramic powder material is quartz glass (SiO)₂) Is a main crystal phase, and on the basis, the powder auxiliary agent is added to improve the density of the final sintered ceramic body of the low-temperature co-fired ceramic powder material, so that the processing performance of the ceramic body is improved. But is prepared by mixing quartz glass powder and powder auxiliary agentThe sintering temperature of the obtained powder material is over 1200 ℃, the sintering temperature is too high and exceeds the highest temperature (900 ℃) for matching and co-firing with the Ag inner electrode, the borosilicate glass powder, the quartz glass powder and the powder auxiliary agent are mixed to prepare the low-temperature co-fired ceramic powder material, the introduction of the borosilicate glass powder can regulate the sintering temperature of the powder material to be within the range of 850-plus-one 900 ℃, the sintering temperature is obviously reduced, the powder material can be matched and co-fired with the Ag electrode, Ag diffusion basically does not occur, the low-temperature co-firing temperature requirement is met, and meanwhile, other performances can be ensured to be unaffected.

The low-temperature co-fired ceramic powder material prepared by compounding borosilicate glass powder, quartz glass powder and powder auxiliary agent has the dielectric constant Epsilonr of 3.8-4.5, low dielectric loss tan delta of 0.001-0.0025 and resistivity rho of 1.0-9.9 multiplied by 10 after being sintered¹²Omega-cm, the sintering temperature is in the range of 850-900 ℃, the density after sintering is good, and the maximum density can reach 99.8 percent.

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the purity of the quartz glass powder is 4N; the borosilicate glass powder comprises the following raw material components: SiO 2₂、H₃BO₃Metal oxide and carbonate, the SiO₂And H₃BO₃The mass of the boron silicon glass powder accounts for 85-92% of that of the boron silicon glass powder;

in the technical scheme of the invention, the borosilicate glass powder is prepared by H₃BO₃、SiO₂Prepared by high-temperature melting method together with various metal oxides and carbonates, wherein SiO is₂And H₃BO₃The mass of (a) is 85-92% of the mass of the borosilicate glass powder, since SiO is₂And H₃BO₃The price is low, so the cost of raw materials can be greatly reduced.

The borosilicate glass powder can reduce the sintering temperature of the low-temperature co-fired ceramic powder material from more than 1200 ℃ to 850-900 ℃, and meanwhile, because the borosilicate glass powder has an ultralow dielectric constant, the dielectric constant of the finally prepared low-temperature co-fired ceramic powder material cannot be obviously improved, and various properties of the low-temperature co-fired ceramic powder material are ensured to be stable.

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the metal oxide comprises ZnO and Al₂O₃、ZrO₂MgO and TiO₂At least one of, the carbonate comprises CaCO₃、Li₂CO₃、K₂CO₃、Na₂CO₃、SrCO₃And BaCO₃At least one of (1).

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the borosilicate glass powder comprises the following raw material components in percentage by mass: SiO 2₂ 58-65％、H₃BO₃ 25-30％、ZnO 0-1wt％、CaCO₃ 0-1wt％、Al₂O₃ 0-2wt％、Li₂CO₃ 0-1wt％、K₂CO₃ 0-1.5wt％、Na₂CO₃ 0-2.5wt％、ZrO₂ 0-1wt％、SrCO₃ 0-1wt％、BaCO₃0-1.5 wt%, MgO 0-1 wt% and TiO₂ 0-0.5wt％。

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the borosilicate glass powder comprises the following raw material components in percentage by mass: SiO 2₂ 61.6％、H₃BO₃ 28.2％、ZnO 0.6wt％、CaCO₃ 0.8wt％、Al₂O₃ 1.1wt％、Li₂CO₃ 0.4wt％、K₂CO₃ 1.2wt％、Na₂CO₃ 2.5wt％、ZrO₂ 0.5wt％、SrCO₃0.9wt％、BaCO₃1.1 wt%, MgO 0.8 wt% and TiO₂ 0.3wt％。

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the preparation method of the borosilicate glass powder comprises the following steps: mixing the raw material components of the borosilicate glass powder with water, performing ball milling discharging, melting and quenching at 1400 ℃ after drying and crushing, sieving with a 60-mesh sieve after crushing, adding water, performing ball milling until the particle size of D50 is 0.7-1.8um, and drying to obtain the borosilicate glass powder.

According to the technical scheme, the molten liquid is prepared through high-temperature melting, the borosilicate glass is obtained through quenching, the sintering temperature of the prepared borosilicate glass can be reduced in a final formula, and the borosilicate glass is matched and sintered with other powder, so that the dielectric property of the finally prepared ceramic powder material can be guaranteed.

As a preferred embodiment of the low-temperature co-fired ceramic powder material.

In the technical scheme of the invention, SiO with the purity of 4N is selected₂As the main crystal phase, the dielectric constant of the low-temperature co-fired ceramic powder material can be kept at an ultra-low value, and the dielectric loss of the low-temperature co-fired ceramic powder material is reduced.

As a preferred embodiment of the low-temperature co-fired ceramic powder material, the powder auxiliary agent comprises the following components in parts by weight: al (Al)₂O₃3-7 parts of ZrO₂0.5-1.5 parts of MgO, 1-3 parts of BaO and 0.5-1.5 parts of BaO.

Through a large number of experimental researches, the inventor finds that the proportion of each raw material in the powder auxiliary agent needs to be strictly controlled within the range to synergistically exert the optimal effect, and the density of the low-temperature co-fired ceramic powder material prepared by exceeding the addition range can be greatly influenced after sintering.

In a second aspect, the invention further provides a preparation method of the low-temperature co-fired ceramic powder material, which comprises the following steps:

(1) mixing quartz glass powder, powder auxiliary agent, grinding balls and deionized water, performing ball milling discharging, drying, presintering at 850-950 ℃ for 1-5h, cooling, crushing, and sieving the powder with a 200-mesh sieve to obtain presintering powder;

(2) and mixing the pre-sintered powder and borosilicate glass powder with a grinding ball and deionized water, then carrying out ball milling to ensure that the powder is uniformly mixed, controlling the particle size of the slurry D50 to be 0.8-1.5um, and drying to obtain the low-temperature co-fired ceramic powder material.

According to the technical scheme, the quartz glass powder and the powder auxiliary agent are subjected to presintering treatment at 850-950 ℃, so that the density of the finally prepared low-temperature co-fired ceramic powder material sintered ceramic body can be effectively improved, and the processing performance of the ceramic body is improved; and the pre-sintering treatment is carried out, so that the borosilicate glass powder can be better matched with the pre-sintering powder in the subsequent sintering process, and the dispersion uniformity of the powder is improved.

As a preferred embodiment of the preparation method of the low-temperature co-fired ceramic powder material, the total mass of the quartz glass powder and the powder auxiliary agent in the step (1) is as follows: grinding ball quality: deionized water with the mass ratio of 1:4: 0.8; the total mass of the pre-sintered powder and the borosilicate glass powder in the step (2) is as follows: grinding ball quality: deionized water mass 1:3: 1.2.

In a third aspect, the invention further provides an application of the low-temperature co-fired ceramic powder material in preparation of a low-temperature co-fired ceramic radio frequency device.

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

the technical proposal of the invention is that quartz glass (SiO)₂) The main crystal phase is added with the powder auxiliary agent to improve the density of the final sintered ceramic body of the low-temperature co-fired ceramic powder material, so that the processing performance of the ceramic body is improved, and then the borosilicate glass powder is introduced to regulate and control the sintering temperature of the powder material to be within the range of 850-900 ℃, so that the sintering temperature is obviously reduced, the powder material can be matched with an Ag electrode for co-firing, Ag diffusion is basically avoided, the low-temperature co-firing temperature requirement is met, and meanwhile, other performances can be ensured not to be influenced.

The sintered low-temperature co-fired ceramic powder material prepared by the invention has the dielectric constant epsilon r of 3.8-4.5, the dielectric loss low tan delta of 0.001-0.0025 and the resistivity rho of 1.0-9.9 multiplied by 10¹²Omega-cm, the sintering temperature is in the range of 850-900 ℃, and the density after sintering is good and can reach 97.5-99.8%.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following specific examples.

Example 1

The raw materials for preparing the borosilicate glass powder comprise the following components in percentage by mass: SiO 2₂ 61.6％、H₃BO₃ 28.2％、ZnO 0.6wt％、CaCO₃ 0.8wt％、Al₂O₃ 1.1wt％、Li₂CO₃ 0.4wt％、K₂CO₃1.2wt％、Na₂CO₃ 2.5wt％、ZrO₂ 0.5wt％、SrCO₃ 0.9wt％、BaCO₃1.1 wt%, MgO 0.8 wt% and TiO₂ 0.3wt％。

The preparation method of the borosilicate glass powder comprises the following steps:

(1) and (2) filling the raw material powder into a nylon ball milling tank according to the proportion, wherein the weight ratio of the raw material powder to the total weight of the powder is as follows: the mass of the zirconia balls is as follows: carrying out planetary ball milling for 5 hours in a ball milling tank according to the mass ratio of the deionized water to 1:8:1, discharging the deionized water, and drying at 100 ℃ until the deionized water is completely dried;

(2) crushing the dried powder, putting the crushed powder into a platinum crucible, melting the powder at a high temperature of 1400 ℃, quenching the powder by using a glass sheet bundling machine, crushing the quenched glass by using a jet mill, sieving the crushed glass by using a 60-mesh sieve, carrying out planetary ball milling on the sieved glass powder, zirconia balls and deionized water in an agate tank according to the ratio of 1:5:1 until the particle size of D50 is 0.7-1.8um, discharging the material by using deionized water, and drying the discharged material at 100 ℃ until the borosilicate glass powder is completely dried to obtain the borosilicate glass powder.

Example 2

The composition of the raw materials for preparing the low-temperature co-fired ceramic powder material is shown in table 1;

the preparation method of the low-temperature co-fired ceramic powder material comprises the following steps:

(1) weighing 4N-grade quartz glass powder and powder auxiliary agent, and placing the materials in an agate crucible according to the total mass of the quartz glass powder and the powder auxiliary agent: the quality of the zirconia grinding ball is as follows: carrying out planetary ball milling for 3h according to the mass ratio of the deionized water to 1:4:0.8, discharging the deionized water, drying at 100 ℃, putting into an alumina crucible, presintering at 850-;

(2) weighing the pre-sintered powder and the borosilicate glass powder prepared in the embodiment 1 in a sand mill, wherein the total mass of the pre-sintered powder and the borosilicate glass powder is as follows: grinding ball quality: and carrying out superfine grinding for 3h according to the mass ratio of the deionized water to 1:3:1.2 to uniformly mix the powder, controlling the particle size of the slurry D50 to be 0.8-1.5um, and drying at 100 ℃ until the powder is completely dried to obtain the low-temperature co-fired ceramic powder material.

Examples 3 to 4

Examples 3-4 the raw material compositions for preparing low temperature co-fired ceramic powder materials are shown in table 1;

examples 3-4 the preparation method of the low temperature co-fired ceramic powder material is the same as example 2.

Comparative examples 1 to 6

Comparative examples 1-6 the raw material compositions for preparing low temperature co-fired ceramic powder materials are shown in table 1;

comparative examples 1-6 the preparation method of the low temperature co-fired ceramic powder material is the same as that of example 2.

Comparative example 7

The raw material composition of the low-temperature co-fired ceramic powder material prepared in comparative example 7 is shown in table 1;

comparative example 7 the preparation method of the low-temperature co-fired ceramic powder material is basically the same as that of example 2, except that: comparative example 7 no pre-firing treatment was performed in step (1).

Experimental example 1

The ceramic powder materials prepared in examples 2-10 and comparative examples 1-5 were prepared according to the following ceramic powder: PVB 10 g: adding 4 wt% of PVB ethanol solution at the proportion of 2ml for granulation, pressing into a wafer sample with the thickness of 1.5-2mm under the condition of 1-4 MPa, sintering at the temperature of 850-. The electrical properties of the different formulations after sintering at the respective optimum sintering temperatures are shown in table 1, wherein the capacitance and tan δ at 1MHz were measured using an Agilent E4980A precision bridge instrument. The insulation resistance is tested by an SM7110 insulation resistance tester which is arranged daily, and then is converted into insulation resistivity through a formula; the density data is obtained by selecting any porcelain section position to shoot a scanning electron microscope picture, taking the scanning electron microscope picture under the condition of 500X as an auxiliary diagonal line, drawing out the air holes passed by the diagonal line and measuring and calculating the area S₁From the formula (1-S)₁/S_{General assembly}) The density of the porcelain body can be calculated by multiplying 100 percent.

TABLE 1 raw material composition and Performance test results (raw material composition in parts by mass)

As can be seen from Table 1, the properties of examples 2 to 4 meet the requirements, and the following conditions are satisfied: the sintering temperature is 850-¹²The density is 97.5 to 99.8 percent;

in the comparative example 1, the addition amount of quartz glass is reduced, other components are kept unchanged, the sintering temperature of the prepared powder material is low and is only 800 ℃, the tan delta @1MHz is high and is 0.0035, and the epsilon r @1MHz is 4.8, so that the sintering temperature is increased;

comparative example 2 without Al addition₂O₃Under the condition of (1), the electrical performance can reach the required range, but the compactness of the sample is lower and is only 95.4 percent;

comparative example 3 in which ZrO was not added₂Under the condition of (1), the sintering temperature is lower and is 825 ℃, and the density of the sample is lower and is only 95.7 percent;

in the comparative example 4, under the condition of not adding MgO, the sintering temperature and the electrical property can reach the required range, but the density of the sample is lower and is 96.3 percent;

in the comparative example 5, under the condition of not adding BaO, the sintering temperature and the electrical property can reach the required range, but the compactness of the sample is lower and is 95.9 percent;

in the comparative example 6, the addition amount of borosilicate glass is reduced, the prepared powder material can be sintered into porcelain only after being heated to 1000 ℃, and a sintered sample has a cracking phenomenon;

comparative example 7 due to Al₂O₃、ZrO₂MgO, BaO, and SiO₂No presintering is carried out at 850-950 ℃, which not only influences the uniformity of small material dispersion, but also causes the poor matching sintering condition of the powder and the subsequent borosilicate glass and influences the compactness.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.