Low-temperature co-fired ceramic powder material, preparation method and application thereof

Abstract

The application provides a low-temperature co-fired ceramic powder material and a preparation method and application thereof, and relates to the technical field of electronic ceramic materials.The low-temperature co-fired ceramic powder material provided by the application comprises the following raw material components in parts by weight: borosilicate glass powder 50-60 parts, quartz glass powder 30-40 parts, and powder additives 5-10 parts, wherein the powder additives comprise at least one of Al2O3, ZrO2, MgO and BaO.The low-temperature co-fired ceramic powder material prepared by compounding borosilicate glass powder, quartz glass powder and powder additives has a dielectric constant εr=3.8-4.5 after sintering, a low dielectric loss tan δ=0.001-0.0025, and a resistivity ρ=1.0-9.9*10 12 Ω*cm, the sintering temperature is in the range of 850-900 DEG C, and the density after sintering is good, and can be up to 99.8%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic ceramic materials, and particularly relates to a low-temperature co-fired ceramic powder material and a preparation method and application thereof. BACKGROUND

[0002] Low temperature co-fired ceramic (LTCC) technology is an ideal packaging technology for realizing miniaturization and chipization of electronic components. With the gradual popularization of 5G technology, the requirements for miniaturization and integration of electronic components are increasingly high, and the information capacity and transmission speed required for information transmission are increasingly high. Therefore, when used as a substrate, the low temperature co-fired ceramic (LTCC) material needs to have a lower dielectric constant to reduce signal delay, and when used as a chip inductor, a lower dielectric constant and dielectric loss are also needed to reduce the capacitance and increase the inductance, so as to adapt to high-frequency applications. SUMMARY

[0003] In order to solve the above problems, the main purpose of the present application is to provide a low-temperature co-fired ceramic powder material and a preparation method and application thereof.

[0004] To achieve the above-mentioned purpose, in a first aspect, the present application provides a low-temperature co-fired ceramic powder material, 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 a powder additive, wherein the powder additive comprises at least one of Al2O3, ZrO2, MgO and BaO.

[0005] In the technical scheme of the present application, the low-temperature co-fired ceramic powder material takes quartz glass (SiO2) as the main crystal phase, and on this basis, the powder additive 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 is improved. However, the sintering temperature of the powder material obtained by simply mixing the quartz glass powder and the powder additive is above 1200℃, which is too high and exceeds the maximum temperature (900℃) of matching co-firing with Ag internal electrodes. In the present application, borosilicate glass powder is mixed with quartz glass powder and a powder additive to prepare a low-temperature co-fired ceramic powder material. The introduction of borosilicate glass powder can regulate the sintering temperature of the powder material to the range of 850-900℃, significantly reduce the sintering temperature, so that the powder material can be co-fired with Ag electrodes without Ag diffusion, meet the low-temperature co-firing temperature requirement, and at the same time ensure that other performances are not affected.

[0006] The low-temperature co-fired ceramic powder material prepared by compounding borosilicate glass powder, quartz glass powder and a powder additive has a dielectric constant εr=3.8-4.5, a dielectric loss tanδ=0.001-0.0025 and a resistivity ρ=1.0-9.9×1012 Ω·cm, the sintering temperature is in the range of 850-900℃, and the density after sintering is good, up to 99.8%.

[0007] 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: SiO2, H3BO3, metal oxides and carbonates, and the mass of SiO2 and H3BO3 accounts for 85-92% of the mass of the borosilicate glass powder.

[0008] In the technical scheme of the application, the borosilicate glass powder is prepared by high-temperature melting method with H3BO3, SiO2 and various metal oxides and carbonates, wherein the mass of SiO2 and H3BO3 accounts for 85-92% of the mass of the borosilicate glass powder. Since SiO2 and H3BO3 are low in price, the cost of raw materials can be greatly reduced.

[0009] The borosilicate glass powder of the application can reduce the sintering temperature of the low-temperature co-fired ceramic powder material from above 1200℃ to 850-900℃, and at the same time, since the borosilicate glass powder itself has an ultra-low dielectric constant, it does not significantly increase the dielectric constant of the finally prepared low-temperature co-fired ceramic powder material, ensuring the stable performance of the low-temperature co-fired ceramic powder material.

[0010] As a preferred embodiment of the low-temperature co-fired ceramic powder material, the metal oxides include at least one of ZnO, Al2O3, ZrO2, MgO and TiO2, and the carbonates include at least one of CaCO3, Li2CO3, K2CO3, Na2CO3, SrCO3 and BaCO3.

[0011] As a preferred embodiment of the low-temperature co-fired ceramic powder material, the borosilicate glass powder comprises the following raw material components in mass percentage: SiO2 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%, BaCO3 0-1.5wt%, MgO 0-1wt% and TiO2 0-0.5wt%.

[0012] As a preferred embodiment of the low-temperature co-fired ceramic powder material, the borosilicate glass powder comprises the following components by mass percentage: SiO2 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%, SrCO3 0.9wt%, BaCO3 1.1wt%, MgO 0.8wt%, and TiO2 0.3wt%.

[0013] 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, ball milling the outfeed, drying and crushing, melting at 1400℃, quenching, crushing and passing through a 60-mesh sieve, ball milling with water to obtain the borosilicate glass powder with a D50 particle size of 0.7-1.8um, and drying.

[0014] In the technical scheme, the molten liquid is obtained by high-temperature melting, and the borosilicate glass is obtained by quenching. The borosilicate glass can reduce the sintering temperature in the final formula, and can ensure the dielectric properties of the finally prepared ceramic powder material when matched with other powders for sintering.

[0015] As a preferred embodiment of the low-temperature co-fired ceramic powder material,

[0016] In the technical scheme, the SiO2 with a purity of 4N is selected as the main crystal phase, so that the dielectric constant of the low-temperature co-fired ceramic powder material can be kept at an ultra-low value, and the dielectric loss can be reduced.

[0017] As a preferred embodiment of the low-temperature co-fired ceramic powder material, the powder aid comprises the following components by weight percentage: Al2O3 3-7 parts, ZrO2 0.5-1.5 parts, MgO 1-3 parts, and BaO 0.5-1.5 parts.

[0018] The inventor found through a large number of experiments that the ratio of the raw materials in the powder aid needs to be strictly controlled within the above range to achieve the best effect. If the ratio of the raw materials in the powder aid exceeds the above range, the density of the low-temperature co-fired ceramic powder material after sintering will be greatly affected.

[0019] In a second aspect, the application further provides a preparation method of a low-temperature co-fired ceramic powder material, comprising the following steps:

[0020] (1) quartz glass powder, powder additives and grinding balls, deionized water are mixed, ball milling is carried out, and after drying, the mixture is pre-sintered at 850-950 DEG C for 1-5h, cooled, crushed, and the powder is sieved through a 200 mesh screen to obtain a pre-sintered powder;

[0021] (2) the pre-sintered powder and borosilicate glass powder are mixed with grinding balls and deionized water, and ball milling is carried out to uniformly mix the powders, and the slurry D50 particle size is controlled to be 0.8-1.5um, and the low-temperature co-fired ceramic powder material is obtained after drying.

[0022] In the technical scheme of the application, the quartz glass powder and the powder additives are pre-sintered at 850-950 DEG C, which can effectively improve the density of the sintered ceramic body of the low-temperature co-fired ceramic powder material prepared finally, thereby improving the processing performance thereof; and the pre-sintering treatment enables the borosilicate glass powder to better match the pre-sintered powder in the subsequent sintering process, thereby improving the dispersion uniformity of the powder.

[0023] 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 additives in step (1): the mass of the grinding balls: the mass of the deionized water = 1:4:0.8; and the total mass of the pre-sintered powder and the borosilicate glass powder in step (2): the mass of the grinding balls: the mass of the deionized water = 1:3:1.2.

[0024] In a third aspect, the application further provides a use of the low-temperature co-fired ceramic powder material in the preparation of a low-temperature co-fired ceramic radio frequency device.

[0025] Compared with the prior art, the application has the following advantages:

[0026] The technical scheme of the application uses quartz glass (SiO2) as the main crystal phase, adds powder additives to improve the density of the sintered ceramic body of the low-temperature co-fired ceramic powder material, improves the processing performance thereof, introduces borosilicate glass powder to adjust the sintering temperature of the powder material to the range of 850-900 DEG C, significantly reduces the sintering temperature, enables the powder material to be matched with Ag electrodes and basically not to diffuse Ag, meets the low-temperature co-firing temperature requirement, and at the same time, ensures that other performances are not affected.

[0027] The low-temperature co-fired ceramic powder material prepared by the application has a dielectric constant εr = 3.8-4.5, a dielectric loss tan δ = 0.001-0.0025, and a resistivity ρ = 1.0-9.9 x 10 12 Ω·cm, the sintering temperature is in the range of 850-900 DEG C, and the sintered density is good, up to 97.5-99.8%. DETAILED DESCRIPTION

[0028] In order to better illustrate the purposes, technical solutions and advantages of the present application, the present application will be further described below through specific examples.

[0029] Example 1

[0030] The raw materials for preparing the borosilicate glass powder in this example include the following components in percentage by mass: SiO261.6%, H3BO328.2%, ZnO 0.6wt%, CaCO30.8wt%, Al2O31.1wt%, Li2CO30.4wt%, K2CO31.2wt%, Na2CO32.5wt%, ZrO20.5wt%, SrCO30.9wt%, BaCO31.1wt%, MgO 0.8wt%, and TiO20.3wt%.

[0031] The preparation method of the borosilicate glass powder in this example includes the following steps:

[0032] (1) The raw material powders are loaded into a nylon ball mill jar according to the above-mentioned ratio, and planetary ball milling is performed in the ball mill jar for 5h at a ratio of total mass of powder: mass of zirconia balls: mass of deionized water = 1:8:1, and the deionized water is discharged, and the powder is completely dried at 100℃;

[0033] (2) The dried powder is broken up and loaded into a platinum crucible, melted at a high temperature of 1400℃, and quenched using a glass sheeting machine, and the quenched glass is pulverized using an air flow pulverizer, and the pulverized glass powder is sieved through a 60-mesh sieve, and the sieved glass powder, zirconia balls and deionized water are planetary ball milled in an agate jar at a ratio of 1:5:1 until the D50 particle size is 0.7-1.8um, and the deionized water is discharged, and the powder is completely dried at 100℃ to obtain the borosilicate glass powder.

[0034] Example 2

[0035] The raw material composition for preparing the low-temperature co-fired ceramic powder material in this example is shown in Table 1;

[0036] The preparation method of the low-temperature co-fired ceramic powder material in this example includes the following steps:

[0037] (1) 4N-grade quartz glass powder and powder additives are weighed, and planetary ball milling is performed in an agate crucible at a ratio of total mass of quartz glass powder and powder additives: mass of zirconia grinding balls: mass of deionized water = 1:4:0.8 for 3h, and the deionized water is discharged, and the powder is dried at 100℃, loaded into an alumina crucible, pre-fired at 850-950℃ for 2h, and after cooling, the pre-fired powder is obtained by breaking up and sieving through a 200-mesh sieve;

[0038] (2) Put the pre-sintered powder and the borosilicate glass powder prepared in Example 1 into a sand mill, and perform superfine grinding for 3 h at a ratio of the total mass of the pre-sintered powder and the borosilicate glass powder: the mass of the grinding ball: the mass of deionized water = 1:3:1.2, so as to mix the powders uniformly. The slurry D50 particle size is controlled to be 0.8-1.5 um, and then the slurry is dried at 100°C until completely dry, to obtain the low-temperature co-fired ceramic powder material.

[0039] Examples 3-4

[0040] The raw material composition of the low-temperature co-fired ceramic powder material prepared in Examples 3-4 is shown in Table 1.

[0041] The preparation method of the low-temperature co-fired ceramic powder material in Examples 3-4 is the same as that in Example 2.

[0042] Comparative Examples 1-6

[0043] The raw material composition of the low-temperature co-fired ceramic powder material prepared in Comparative Examples 1-6 is shown in Table 1.

[0044] The preparation method of the low-temperature co-fired ceramic powder material in Comparative Examples 1-6 is the same as that in Example 2.

[0045] Comparative Example 7

[0046] The raw material composition of the low-temperature co-fired ceramic powder material prepared in Comparative Example 7 is shown in Table 1.

[0047] The preparation method of the low-temperature co-fired ceramic powder material in Comparative Example 7 is basically the same as that in Example 2, except that the pre-sintering treatment is not performed in step (1) of Comparative Example 7.

[0048] Experimental Example 1

[0049] The ceramic powder materials prepared in Examples 2-10 and Comparative Examples 1-5 are granulated by adding 4wt% PVB ethanol solution at a ratio of the ceramic powder: PVB = 10g:2ml, and then pressed into round sheet samples with a thickness of 1.5-2mm under a pressure of 1-4MPa. The samples are sintered at a temperature of 850-900°C for 0.5h, to obtain the samples. The electrical properties after sintering at the respective optimal sintering temperatures are shown in Table 1, wherein the capacitance and tanδ at 1MHz are tested by using an Agilent E4980A precision bridge instrument. The insulation resistance is tested by using a Japanese RIKEN SM7110 insulation resistance tester, and then converted into the insulation resistivity by using a formula; and the density data is obtained by selecting an arbitrary cross-section of the ceramic body, taking a scanning electron microscope picture, drawing a diagonal line on the 500X scanning electron microscope picture, and then calculating the area S1 of the pores passing through the diagonal line. The density of the ceramic body is calculated by using the formula (1-S1 / S 总 )×100%.

[0050] Table 1. Raw material composition and performance test results (raw material composition is in parts by mass)

[0051]

[0052] As can be seen from Table 1, the performance of each of Examples 2-4 meets the requirements and satisfies the following conditions: sintering temperature of 850-900℃, tanδ@1MHz of 0.0010-0.0025, εr@1MHz of 3.8-4.5, insulation resistivity of 1.0-9.9×10 12 , and density of 97.5%-99.8%;

[0053] In Comparative Example 1, the amount of quartz glass is reduced, and the other components remain unchanged. The sintering temperature of the prepared powder material is low, only 800℃, the tanδ@1MHz is high, 0.0035, and the εr@1MHz is 4.8, which is increased;

[0054] In Comparative Example 2, no Al2O3 is added, and the electrical properties can meet the required range, but the density of the sample is low, only 95.4%;

[0055] In Comparative Example 3, no ZrO2 is added, and the sintering temperature is low, 825℃, and the density of the sample is low, only 95.7%;

[0056] In Comparative Example 4, no MgO is added, and the sintering temperature and electrical properties can meet the required range, but the density of the sample is low, 96.3%;

[0057] In Comparative Example 5, no BaO is added, and the sintering temperature and electrical properties can meet the required range, but the density of the sample is low, 95.9%;

[0058] In Comparative Example 6, the amount of borosilicate glass is reduced, and the prepared powder material needs to be sintered at 1000℃ to form porcelain, and the sintered sample cracks;

[0059] In Comparative Example 7, Al2O3, ZrO2, MgO, and BaO are not pre-sintered with SiO2 at 850-950℃, which not only affects the uniformity of small material dispersion, but also leads to poor matching sintering of the powder with the subsequent borosilicate glass, affecting the density.

[0060] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A low temperature co-fired ceramic powder material, characterized by, The raw material components include the following weight parts: borosilicate glass powder 50-60 parts, quartz glass powder 35-40 parts, and powder additive 5-10 parts; The powder additive includes the following weight parts of components: Al2O3 3-7 parts, ZrO2 0.5-1.5 parts, MgO 1-3 parts, and BaO 0.5-1.5 parts; The preparation method of the low-temperature co-fired ceramic powder material includes the following steps: (1) After mixing the quartz glass powder, the powder additive, the grinding balls, and deionized water, ball milling is performed, and after drying, the mixture is pre-fired at 850-950°C for 1-5 hours, cooled, crushed, and sieved through a 200-mesh screen to obtain pre-fired powder; (2) After mixing the pre-fired powder and the borosilicate glass powder with the grinding balls and deionized water, ball milling is performed to uniformly mix the powders, the slurry D50 particle size is controlled to be 0.8-1.5um, and after drying, the low-temperature co-fired ceramic powder material is obtained.

2. The low temperature co-fired ceramic powder material of claim 1, wherein, The purity of the quartz glass powder is 4N; the borosilicate glass powder includes the following raw material components: SiO2, H3BO3, metal oxides, and carbonates, and the mass of SiO2 and H3BO3 accounts for 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 oxides include at least one of ZnO, Al2O3, ZrO2, MgO, and TiO2, and the carbonates include at least one of CaCO3, Li2CO3, K2CO3, Na2CO3, SrCO3, and BaCO3.

4. The low temperature co-fired ceramic powder material of any one of claims 1-3, wherein, The borosilicate glass powder includes the following raw material components in mass percentage: SiO2 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%, BaCO3 0-1.5wt%, MgO 0-1wt%, and TiO2 0-0.5wt%.

5. The low temperature co-fired ceramic powder material of claim 4, wherein, The borosilicate glass powder includes the following raw material components in mass percentage: SiO2 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%, SrCO3 0.9wt%, BaCO3 1.1wt%, MgO 0.8wt%, and TiO2 0.3wt%.

6. The low temperature co-fired ceramic powder material of any one of claims 2-5, wherein, The preparation method of the borosilicate glass powder comprises the following steps: mixing each raw material component of the borosilicate glass powder with water, ball milling the mixture, drying and crushing, melting at 1400 o C under, quenching, crushing, passing through a 60-mesh screen, ball milling with water until the D50 particle size is 0.7-1.8 um, and drying to obtain the borosilicate glass powder.

7. The low temperature co-fired ceramic powder material of claim 1, wherein, The total mass of the quartz glass powder and the powder additive in step (1) is 1:4:0.8 of the mass of the grinding balls and deionized water; and the total mass of the pre-fired powder and the borosilicate glass powder in step (2) is 1:3:1.2 of the mass of the grinding balls and deionized water.

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

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