WO2022188220A1 - Sio2-series high-frequency low-dielectric low-temperature co-fired ceramic material and preparation method therefor - Google Patents

Sio2-series high-frequency low-dielectric low-temperature co-fired ceramic material and preparation method therefor Download PDF

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WO2022188220A1
WO2022188220A1 PCT/CN2021/084474 CN2021084474W WO2022188220A1 WO 2022188220 A1 WO2022188220 A1 WO 2022188220A1 CN 2021084474 W CN2021084474 W CN 2021084474W WO 2022188220 A1 WO2022188220 A1 WO 2022188220A1
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sio
low
temperature
fired ceramic
ceramic material
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袁烨
童建喜
石珊
张彩霞
李进
徐红梅
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嘉兴佳利电子有限公司
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction

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  • the invention belongs to the field of microwave dielectric ceramic materials, in particular to a SiO2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material and a preparation method thereof.
  • Low-temperature co-firing ceramics is a kind of electronic packaging technology. It completes the spatial wiring of electrodes by stacking and co-firing multiple ceramic diaphragms printed with metal patterns to achieve specific For component function, since silver or copper with high conductivity and low melting point is used for wiring, it needs to be matched with ceramic materials that can be sintered at low temperature below 900 o C or 1000 o C.
  • LTCC technology is widely used in various electronic components, ceramic tubes, RF substrates and modules due to its miniaturization, high integration, high performance and high reliability.
  • the transmission rate of the signal is inversely proportional to the dielectric constant of the material.
  • the dielectric constant of the material is around 6-8, such as Ferro A6-M (dielectric constant 5.9 ⁇ 0.2), DuPont 951 (dielectric constant 7.8) and so on.
  • Ferro A6-M dielectric constant 5.9 ⁇ 0.2
  • DuPont 951 dielectric constant 7.8
  • microwave technology is developing towards higher frequencies, that is, towards the direction of millimeter waves and sub-millimeter waves, which requires low temperature common Fired ceramics have a lower dielectric constant.
  • the commonly used ceramic material with the lowest dielectric constant is SiO 2 .
  • the dielectric constant of crystalline SiO2 is 4.0 ⁇ 4.6
  • the dielectric loss is 0.15%
  • the frequency temperature coefficient ⁇ f is around -15 ppm/°C
  • the sintering temperature is as high as 1650°C.
  • the dielectric constant of amorphous SiO 2 (fused silica) is 3.5-3.8, and the dielectric loss is 0.008%. It is reported in the literature that its ⁇ f is about -10 ppm/°C, and the sintering temperature is generally 1350°C.
  • SiO2 -based low-temperature co-fired ceramic materials can be prepared by introducing sintering aids such as low-melting glass.
  • Patent CN 103011788A uses the low softening point of borosilicate glass and the low dielectric constant (5.1) and low expansion coefficient (4.6 ppm/K) of high-purity ultrafine spherical quartz to develop a low-dielectric, low-expansion, low-temperature co-fired ceramic material .
  • Patent CN 110903078A is a low-temperature co-fired ceramic prepared by using SiO 2 -Li 2 TiO 3 composite ceramic with SiO 2 as the main crystal phase and LBSCA glass, and the dielectric constant is 4.5-5.1.
  • the above patents do not disclose the information on the type of SiO 2 crystal phase.
  • the introduction of additives and low-melting glass can easily act as a mineralizer, which will promote the sintering and cooling process.
  • the polycrystalline transformation of SiO 2 in the process of polycrystalline transformation, due to the change of its internal structure, accompanied by the change of volume (for example, the volume change of cristobalite ⁇ - ⁇ phase transformation process is as high as 3.2%), resulting in a larger volume. Stress often causes micro-cracks or cracks after sintering or in practical applications. In the manufacture of microwave components, it can lead to product failure and scrap or reliability failure and cause serious quality problems, which will greatly limit SiO 2 series low-temperature co-fired ceramics. material application.
  • the first object of the present invention is to provide a SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material, which has good performance and improves the microcracks and cracking problems of the existing ceramic materials.
  • the second object of the invention is to provide a preparation method of a high frequency, low dielectric and low temperature co-fired ceramic material.
  • the present invention adopts the following technical solutions.
  • a SiO2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material is composed of the following components by weight: 30%-50% borosilicate glass, 30%-55% SiO2 , 1%-15%
  • the crystallization control additive ; the sum of the above components is 100%; the crystallization control additive is selected from at least one of ZBS glass frit, ZrO 2 , TiO 2 , Y 2 O 3 , AlN, and crystalline SiO 2 .
  • the crystallization control additive is at least one of ZrO 2 , TiO 2 , Y 2 O 3 , AlN, crystalline SiO 2 and ZBS glass powder, and the weight percentage of ZBS glass powder is not less than 3% .
  • the crystallization control additive is at least one of ZBS glass powder, ZrO 2 , Y 2 O 3 , AlN, crystalline SiO 2 and TiO 2 , and the weight percentage of TiO 2 is 0.5%-4%.
  • the borosilicate glass is composed of the following components by weight: 60%-80% SiO 2 , 10%-30% B 2 O 3 , 1%-5% Al 2 O 3 and 1-12% of alkali metal oxide R 2 O, the sum of the above components is 100%; wherein R is at least one of K, Na and Li.
  • the ZBS glass contains the following components by weight: 7-30% SiO 2 , 20-60% B 2 O 3 , 40-70% ZnO, the sum of the above components is 100% .
  • the SiO 2 is amorphous SiO 2 .
  • the present invention adopts the following technical solutions.
  • the above-mentioned preparation method of a SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material includes the following steps: 1) Preparation of borosilicate glass and ZBS glass.
  • the SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material involved in the present invention is mainly composed of amorphous SiO 2 and borosilicate glass, which can be sintered and dense at a low temperature of 840-900° C.
  • the dielectric constant measured at a frequency of 10GHz It is 4.0-4.5, the dielectric loss is less than 0.3%, the thermal expansion coefficient is 2-4 ppm/K, and the frequency temperature coefficient is about -21ppm/°C. It can be widely used in couplers, power dividers, antennas, Development and manufacture of LTCC devices such as filters.
  • the material of the present invention has the following advantages.
  • the low dielectric constant LTCC material of the present invention has a small frequency temperature coefficient, and in the application of component products, it can ensure that the product can be used in different temperature environments. frequency stability.
  • FIG. 1 is the SEM surface topography of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively.
  • Examples 1-6 preparation of borosilicate glass: SiO 2 , H 3 BO 3 , Li 2 CO 3 , Al 2 O 3 , K 2 CO 3 were weighed according to the mass ratio in Table 1 as borosilicate glass
  • Raw material powder the above components are subjected to wet ball milling for 5 hours with anhydrous ethanol as a medium to obtain raw material powder.
  • the clear glass liquid is quickly poured into deionized water to obtain glass slag.
  • the obtained glass slag is ball-milled and pulverized, and after drying, borosilicate glass powder with a particle size D50 of 1.0-3.0 ⁇ m is obtained.
  • Preparation of ZBS glass powder Weigh SiO 2 , H 3 BO 3 , ZnO as the raw material powder of ZBS glass according to the mass ratio in Table 1, and use absolute ethanol as the medium to pass the above components through wet ball milling for 5 hours and then dry to obtain the raw materials Put the raw material powder into a platinum crucible, place it in a high-temperature resistance furnace at 1100 °C to melt and clarify, and pour the clarified glass liquid into deionized water quickly after 2 hours to obtain glass slag. The obtained glass slag is ball milled and pulverized, and after drying, ZBS glass powder with a particle size D50 of 1.0-3.0 ⁇ m is obtained.
  • Examples 7-16 the material compositions of borosilicate glass, SiO 2 , and crystallization control additives in Table 2 were weighed, ethanol was used as the solvent, and zirconium balls were used as the ball milling medium, and the material: ethanol: zirconium balls was 1: After ball milling at a ratio of 2:10 for 15-20 hours, bake in an oven at 80°C for 15 hours to obtain low-temperature co-fired ceramic powder.
  • the dried low-temperature co-fired ceramic powder is added with a PVA binder with a mass ratio of 20%-30% for granulation and dry pressing to form a round block sample with a diameter of 20mm and a height of 10-12mm. Sintering at 840-900 DEG C, and keeping the temperature for 15-60 min, the low-temperature co-fired ceramics of the present invention are obtained.
  • Table 3 shows the test results of the embodiment of the present invention and the surface cracks after sintering.
  • Example 13 It can be seen from Table 3 that compared with Comparative Example 1, the dielectric constants of Examples 9-12 and 16 are less than 4.5, the dielectric loss is still less than 0.3% at 10 GHz, and the ceramic surface is dense and crack-free after sintering, which can meet the requirements of microwave components. application requirements. Although the dielectric loss of Example 13 is as low as about 0.25%, there are slight cracks on the surface after sintering, and there are risks of cracking of the porcelain body and reliability failure.
  • Figure 1 shows the SEM surface morphologies of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively. It can be seen from the figure that Example 9 basically has no surface cracks and has a denser structure, which greatly improves the performance of the material. and device product strength and reliability.
  • Figure 2 shows the surface XRD analysis of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively. Compared with the SEM surface morphology, the degree of crystallization of cristobalite and the surface microcracks are very large. This patent greatly improves the generation of cracks by controlling the crystallization of cristobalite, preventing the product from failure and scrapping due to cracking of the porcelain body or serious quality problems caused by reliability failure.

Abstract

An SiO 2-series high-frequency low-dielectric low-temperature co-fired ceramic material and a preparation method therefor. The ceramic material is composed of, in percentages by weight, 30-50% of borosilicate glass, 30-55% of SiO 2 and 1-15% of a crystallization controlling additive, wherein the crystallization controlling additive is selected from at least one of a ZBS glass powder, ZrO 2, TiO 2, Y 2O 3, AlN and crystalline SiO 2. The ceramic material can be sintered at a temperature of 840-900ºC for compaction, the dielectric constant thereof is 4.0-4.5 at a high frequency of 10 GHz, and the dielectric loss thereof is less than 0.3%; and same can be widely used in the manufacturing of high-frequency components such as LTCC couplers, power dividers, antennas, filters, etc. By introducing the crystallization controlling additive, the polycrystal transformation of SiO 2 is effectively controlled, the problem of surface cracking of the ceramic is improved, and the reliability of the components is improved.

Description

一种SiO2系高频低介低温共烧陶瓷材料及其制备方法A kind of SiO2 series high frequency low dielectric low temperature co-fired ceramic material and preparation method thereof 技术领域technical field
本发明属于微波介质陶瓷材料领域，具体涉及一种SiO 2系高频低介低温共烧陶瓷材料及其制备方法。 The invention belongs to the field of microwave dielectric ceramic materials, in particular to a SiO2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material and a preparation method thereof.
背景技术Background technique
低温共烧陶瓷技术（Low-temperature co-firing ceramics，LTCC）是电子封装技术的一种，它通过将多个印有金属图案的陶瓷膜片堆叠共烧，完成电极的空间布线，实现特定的元器件功能，由于采用高导电率低熔点的银或铜做布线，需要对应能在900 oC或1000 oC以下低温烧结的陶瓷材料与之匹配。LTCC技术因其小型化、集成度高、高性能和高可靠性等特点而广泛应用于各类电子元器件、陶瓷管壳、射频基板和模组等产品中。 Low-temperature co-firing ceramics (LTCC) is a kind of electronic packaging technology. It completes the spatial wiring of electrodes by stacking and co-firing multiple ceramic diaphragms printed with metal patterns to achieve specific For component function, since silver or copper with high conductivity and low melting point is used for wiring, it needs to be matched with ceramic materials that can be sintered at low temperature below 900 o C or 1000 o C. LTCC technology is widely used in various electronic components, ceramic tubes, RF substrates and modules due to its miniaturization, high integration, high performance and high reliability.
在微波技术中，信号的传输速率与材料的介电常数成反比，为了降低信号在传输过程中的延迟，通常希望材料的介电常数越低越好。目前常用的材料介电常数在6-8左右，如Ferro A6-M（介电常数5.9±0.2），DuPont 951（介电常数7.8）等。但是随着移动通信、无线通信、卫星通讯和导航、电子对抗和雷达等领域技术的迅速发展，微波技术朝着更高频率，即向着毫米波和亚毫米波的方向发展，这就要求低温共烧陶瓷具备更低介电常数。In microwave technology, the transmission rate of the signal is inversely proportional to the dielectric constant of the material. In order to reduce the delay of the signal in the transmission process, it is generally desirable that the dielectric constant of the material be as low as possible. At present, the dielectric constant of commonly used materials is around 6-8, such as Ferro A6-M (dielectric constant 5.9±0.2), DuPont 951 (dielectric constant 7.8) and so on. However, with the rapid development of technologies in the fields of mobile communication, wireless communication, satellite communication and navigation, electronic countermeasures and radar, microwave technology is developing towards higher frequencies, that is, towards the direction of millimeter waves and sub-millimeter waves, which requires low temperature common Fired ceramics have a lower dielectric constant.
目前介电常数最低的常用陶瓷材料为SiO 2。通常结晶SiO 2的介电常数在4.0~4.6，介电损耗0.15%，频率温度系数τf在-15 ppm/℃左右，烧结温度高达1650℃。而无定型SiO 2（熔融石英）的介电常数在3.5-3.8，介电损耗0.008%，文献报道其τf在-10 ppm/℃左右，烧结温度一般为1350℃。 At present, the commonly used ceramic material with the lowest dielectric constant is SiO 2 . Usually, the dielectric constant of crystalline SiO2 is 4.0~4.6, the dielectric loss is 0.15%, the frequency temperature coefficient τf is around -15 ppm/°C, and the sintering temperature is as high as 1650°C. The dielectric constant of amorphous SiO 2 (fused silica) is 3.5-3.8, and the dielectric loss is 0.008%. It is reported in the literature that its τf is about -10 ppm/℃, and the sintering temperature is generally 1350℃.
结晶SiO 2和无定型SiO 2都是实现低介材料的理想原料，而无定型SiO 2在介电损耗方面更具优势，是低介低温共烧陶瓷材料开发的优选基料。通常可通过引入低熔点玻璃等烧结助剂来制备SiO 2系的低温共烧陶瓷材料。专利CN 103011788A利用硼硅酸盐玻璃的低软化点和高纯超细球形石英的低介电常数（5.1）和低膨胀系数（4.6 ppm/K），开发了一种低介低膨胀低温共烧陶瓷材料。专利CN 110903078A 利用SiO 2为主晶相的SiO 2-Li 2TiO 3复合陶瓷与LBSCA玻璃制得的低温共烧陶瓷，介电常数4.5-5.1。但是以上专利都未披露SiO 2晶相种类信息，而在SiO 2材料体系中，通常情况下助剂和低熔点玻璃的引入极易起到矿化剂作用，在烧结和降温冷却过程中会促进SiO 2的多晶转变，在发生多晶转变的过程中，由于其内部结构发生了变化，伴随着体积的变化（如方石英α-β相转变过程中体积变化高达3.2%）产生较大的应力，往往会在烧结后或者实际应用中出现微裂纹或者开裂现象，在微波元器件制造中可导致产品失效报废或者可靠性失效引起严重的质量问题，这将大大限制SiO 2系低温共烧陶瓷材料的应用。 Both crystalline SiO 2 and amorphous SiO 2 are ideal raw materials for realizing low-dielectric materials, while amorphous SiO 2 has more advantages in dielectric loss and is the preferred base material for the development of low-dielectric and low-temperature co-fired ceramic materials. Generally, SiO2 -based low-temperature co-fired ceramic materials can be prepared by introducing sintering aids such as low-melting glass. Patent CN 103011788A uses the low softening point of borosilicate glass and the low dielectric constant (5.1) and low expansion coefficient (4.6 ppm/K) of high-purity ultrafine spherical quartz to develop a low-dielectric, low-expansion, low-temperature co-fired ceramic material . Patent CN 110903078A is a low-temperature co-fired ceramic prepared by using SiO 2 -Li 2 TiO 3 composite ceramic with SiO 2 as the main crystal phase and LBSCA glass, and the dielectric constant is 4.5-5.1. However, the above patents do not disclose the information on the type of SiO 2 crystal phase. In the SiO 2 material system, the introduction of additives and low-melting glass can easily act as a mineralizer, which will promote the sintering and cooling process. The polycrystalline transformation of SiO 2 , in the process of polycrystalline transformation, due to the change of its internal structure, accompanied by the change of volume (for example, the volume change of cristobalite α-β phase transformation process is as high as 3.2%), resulting in a larger volume. Stress often causes micro-cracks or cracks after sintering or in practical applications. In the manufacture of microwave components, it can lead to product failure and scrap or reliability failure and cause serious quality problems, which will greatly limit SiO 2 series low-temperature co-fired ceramics. material application.
因此如何控制无定型SiO 2的多晶转变是制备SiO 2系低温共烧陶瓷的关键，华中科技大学硕士论文“添加剂对熔融石英陶瓷析晶和致密化的影响”***阐述了B 4C、B 2O 3、TiB 2等对熔融石英陶瓷析晶性能和烧结性能的影响，发现B 4C、B 2O 3、TiB 2可以避免熔融石英的析晶，但是烧结温度高达1350℃以上，无法实现陶瓷材料与Ag等金属的低温共烧。 Therefore, how to control the polycrystalline transformation of amorphous SiO 2 is the key to the preparation of SiO 2 series low - temperature co-fired ceramics. The effects of 2 O 3 and TiB 2 on the crystallization and sintering properties of fused silica ceramics. It is found that B 4 C, B 2 O 3 and TiB 2 can avoid the devitrification of fused silica, but the sintering temperature is as high as 1350℃, which cannot be achieved. Low temperature co-firing of ceramic materials with metals such as Ag.
综上所述，制备SiO 2系低温共烧陶瓷的技术路线上比较容易实现，但是如何利用无定型SiO 2优异的介电性能并控制其在烧结过程中的多晶转变，避免材料的体积变化造成陶瓷材料开裂是一个亟待解决的难题。 To sum up, the technical route of preparing SiO2 -based low-temperature co-fired ceramics is relatively easy to achieve, but how to utilize the excellent dielectric properties of amorphous SiO2 and control its polycrystalline transformation during sintering to avoid the volume change of the material The cracking of ceramic materials is an urgent problem to be solved.
技术问题technical problem
为了解决上述技术问题，本发明的第一目的是提供一种SiO 2系高频低介低温共烧陶瓷材料，该材料性能较好，且改善了现有陶瓷材料的微裂纹和开裂问题，本发明的第二目的是提供一种高频低介低温共烧陶瓷材料的制备方法。 In order to solve the above-mentioned technical problems, the first object of the present invention is to provide a SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material, which has good performance and improves the microcracks and cracking problems of the existing ceramic materials. The second object of the invention is to provide a preparation method of a high frequency, low dielectric and low temperature co-fired ceramic material.
技术解决方案technical solutions
为了实现上述第一个发明的目的，本发明采用以下技术方案。In order to achieve the purpose of the above-mentioned first invention, the present invention adopts the following technical solutions.
一种SiO 2系高频低介低温共烧陶瓷材料，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、1%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂选自ZBS玻璃粉、ZrO 2、TiO 2、Y 2O 3、AlN、结晶SiO 2中的至少一种。 A SiO2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material is composed of the following components by weight: 30%-50% borosilicate glass, 30%-55% SiO2 , 1%-15% The crystallization control additive; the sum of the above components is 100%; the crystallization control additive is selected from at least one of ZBS glass frit, ZrO 2 , TiO 2 , Y 2 O 3 , AlN, and crystalline SiO 2 .
作为优选方案，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、3%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂为ZrO 2、TiO 2、Y 2O 3、AlN、结晶SiO 2中的至少一种以及ZBS玻璃粉，且ZBS玻璃粉的重量百分比不低于3%。 As a preferred solution, it is composed of the following components by weight: 30%-50% borosilicate glass, 30%-55% SiO 2 , 3%-15% crystallization control additive; the sum of the above components is 100%; the crystallization control additive is at least one of ZrO 2 , TiO 2 , Y 2 O 3 , AlN, crystalline SiO 2 and ZBS glass powder, and the weight percentage of ZBS glass powder is not less than 3% .
作为优选方案，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、0.5%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂为ZBS玻璃粉、ZrO 2、Y 2O 3、AlN、结晶SiO2中的至少一种以及TiO 2，且TiO 2的重量百分比为0.5%-4%。 As a preferred solution, it is composed of the following components by weight: 30%-50% borosilicate glass, 30%-55% SiO 2 , 0.5%-15% crystallization control additive; the sum of the above components The crystallization control additive is at least one of ZBS glass powder, ZrO 2 , Y 2 O 3 , AlN, crystalline SiO 2 and TiO 2 , and the weight percentage of TiO 2 is 0.5%-4%.
作为优选方案，所述的硼硅酸盐玻璃由以下重量百分比的组分构成：60%-80%的SiO 2，10%-30%的B 2O 3，1%-5%的Al 2O 3和1-12%的碱金属氧化物R 2O，上述组分的总和为100%；其中R为K、Na、Li中的至少一种。 As a preferred solution, the borosilicate glass is composed of the following components by weight: 60%-80% SiO 2 , 10%-30% B 2 O 3 , 1%-5% Al 2 O 3 and 1-12% of alkali metal oxide R 2 O, the sum of the above components is 100%; wherein R is at least one of K, Na and Li.
作为优选方案，所述的ZBS玻璃包含以下重量百分比的组分：7-30%的SiO 2，20-60%的B 2O 3，40-70%的ZnO，上述组分的总和为100%。 As a preferred solution, the ZBS glass contains the following components by weight: 7-30% SiO 2 , 20-60% B 2 O 3 , 40-70% ZnO, the sum of the above components is 100% .
作为优选方案，所述的SiO 2为无定型SiO 2。 As a preferred solution, the SiO 2 is amorphous SiO 2 .
为了实现上述第二个发明的目的，本发明采用以下技术方案。In order to achieve the purpose of the second invention, the present invention adopts the following technical solutions.
如上所述的一种SiO 2系高频低介低温共烧陶瓷材料的制备方法，包括以下步骤：1）硼硅酸盐玻璃、ZBS玻璃制备。 The above-mentioned preparation method of a SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material includes the following steps: 1) Preparation of borosilicate glass and ZBS glass.
按质量百分比：60%-80%的SiO 2，10%-30%的B 2O 3，1%-5%的Al 2O 3，1-12%的碱金属氧化物R 2O，称取SiO 2、H 3BO 3、Al 2O 3、Li 2CO 3或者Na 2CO 3或者K 2CO 3，将上述组分以无水乙醇作为介质通过湿法球磨4-8h，然后烘干，将上述原料粉装入铂金坩埚内，加热到1400-1550℃熔融，保温0.5-2h后倒入水中淬冷，将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的硼硅酸盐玻璃粉体。 By mass percentage: 60%-80% SiO 2 , 10%-30% B 2 O 3 , 1%-5% Al 2 O 3 , 1-12% alkali metal oxide R 2 O, weighed SiO 2 , H 3 BO 3 , Al 2 O 3 , Li 2 CO 3 or Na 2 CO 3 or K 2 CO 3 , the above components are subjected to wet ball milling with absolute ethanol as a medium for 4-8 hours, and then dried, Put the above-mentioned raw material powder into a platinum crucible, heat it to 1400-1550 ℃ to melt, pour it into water for quenching after holding for 0.5-2 hours, and perform ball milling to pulverize the obtained glass slag. After drying, the particle size D50 is 1.0-3.0 μm. borosilicate glass powder.
按质量百分比：7-30%的SiO 2，20-60%的B 2O 3，40-70%的ZnO，称取SiO 2、H 3BO 3、ZnO，将上述组分以无水乙醇作为介质通过湿法球磨4-8h，然后烘干，将上述原料粉装入铂金坩埚内，加热到1050-1300℃熔融，保温0.5-2h后倒入水中淬冷，将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的ZBS玻璃粉体。 By mass percentage: 7-30% SiO 2 , 20-60% B 2 O 3 , 40-70% ZnO, weigh SiO 2 , H 3 BO 3 , ZnO, and use absolute ethanol as the above components. The medium is subjected to wet ball milling for 4-8 hours, and then dried. The above-mentioned raw material powder is put into a platinum crucible, heated to 1050-1300 ℃ to melt, kept for 0.5-2 hours and then poured into water for quenching, and the obtained glass slag is ball-milled and pulverized , ZBS glass powder with particle size D50 of 1.0-3.0 μm is obtained after drying.
2）将质量百分比为30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、1%-15%的析晶控制添加剂混合，以乙醇作为溶剂，球磨15-20h后烘干，得到低温共烧陶瓷粉。 2) Mix 30%-50% by mass of borosilicate glass, 30%-55% SiO 2 , and 1%-15% crystallization control additive, use ethanol as a solvent, ball mill for 15-20h and then bake dry to obtain low-temperature co-fired ceramic powder.
3）将烘干的低温共烧陶瓷粉加入20%-30%的PVA粘结剂进行造粒并干压成型成直径20mm，高度10-12mm的圆块样品，在840-900℃烧结，保温15-60min，即得到SiO 2系高频低介低温共烧陶瓷材料。 3) Add 20%-30% PVA binder to the dried low-temperature co-fired ceramic powder for granulation and dry pressing to form a round block sample with a diameter of 20mm and a height of 10-12mm, sintered at 840-900 ℃, and kept warm In 15-60min, the SiO 2 series high-frequency, low-medium and low-temperature co-fired ceramic material is obtained.
有益效果beneficial effect
本发明涉及的SiO 2系高频低介低温共烧陶瓷材料主要由无定型SiO 2和硼硅酸玻璃组成，可以在840-900℃下低温烧结致密，在10GHz频率下测得的介电常数为4.0-4.5，介电损耗小于0.3%，热膨胀系数为2-4 ppm/K，频率温度系数为-21ppm/℃左右，可广泛应用于高频通讯领域的耦合器、功分器、天线、滤波器等LTCC器件的开发和制造。 The SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material involved in the present invention is mainly composed of amorphous SiO 2 and borosilicate glass, which can be sintered and dense at a low temperature of 840-900° C. The dielectric constant measured at a frequency of 10GHz It is 4.0-4.5, the dielectric loss is less than 0.3%, the thermal expansion coefficient is 2-4 ppm/K, and the frequency temperature coefficient is about -21ppm/℃. It can be widely used in couplers, power dividers, antennas, Development and manufacture of LTCC devices such as filters.
与现有技术相比，本发明材料具有以下优势。Compared with the prior art, the material of the present invention has the following advantages.
1.较低的介电常数，并在高频下具有较低的介电损耗；2.通过引入析晶控制添加剂，可有效地控制SiO 2的多晶转变，从而显著改善了烧结后陶瓷的微裂纹和表面开裂问题，规避产品应用中的可靠性风险；3.本发明的低介电常数LTCC材料具有较小的频率温度系数，在元器件产品应用中，可保证产品在不同使用温度环境下的频率稳定性。 1. Lower dielectric constant and lower dielectric loss at high frequency; 2. By introducing crystallization control additives, the polycrystalline transformation of SiO2 can be effectively controlled, thereby significantly improving the ceramic properties after sintering. The problem of micro-cracks and surface cracking can avoid the reliability risk in product application; 3. The low dielectric constant LTCC material of the present invention has a small frequency temperature coefficient, and in the application of component products, it can ensure that the product can be used in different temperature environments. frequency stability.
附图说明Description of drawings
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的限定。The accompanying drawings that constitute a part of the present application are used to provide further understanding of the present application, and the schematic embodiments and descriptions of the present application are used to explain the present application and do not constitute a limitation to the present application.
图1分别为实施例9、13和对比例1的低温共烧陶瓷材料的SEM表面形貌图。FIG. 1 is the SEM surface topography of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively.
图2别为实施例9、13和对比例1的低温共烧陶瓷材料的表面XRD分析图。2 is the surface XRD analysis diagram of the low temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively.
本发明的实施方式Embodiments of the present invention
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，下面通过参考附图描述的实施例是示例的，旨在用于解释本发明，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, examples of the embodiments are shown in the accompanying drawings, and the embodiments described below with reference to the accompanying drawings are exemplary and are intended to explain the present invention, but should not be construed as an explanation of the present invention. limit.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图和实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用以限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
实施例1-6，硼硅酸盐玻璃制备：按表1质量配比称取SiO 2， H 3BO 3， Li 2CO 3， Al 2O 3， K 2CO 3作为硼硅酸盐玻璃的原料粉，将上述组分以无水乙醇作为介质通过湿法球磨5h后烘干得到原料粉，将原料粉装入铂金坩埚内，置于1450℃的高温电阻炉内熔融、澄清，2h后将澄清的玻璃液快速倒入去离子水中，得到玻璃碎渣。将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的硼硅酸盐玻璃粉。 Examples 1-6, preparation of borosilicate glass: SiO 2 , H 3 BO 3 , Li 2 CO 3 , Al 2 O 3 , K 2 CO 3 were weighed according to the mass ratio in Table 1 as borosilicate glass Raw material powder, the above components are subjected to wet ball milling for 5 hours with anhydrous ethanol as a medium to obtain raw material powder. The clear glass liquid is quickly poured into deionized water to obtain glass slag. The obtained glass slag is ball-milled and pulverized, and after drying, borosilicate glass powder with a particle size D50 of 1.0-3.0 μm is obtained.
ZBS玻璃粉的制备：按表1质量配比称取SiO 2， H 3BO 3， ZnO作为ZBS玻璃的原料粉，将上述组分以无水乙醇作为介质通过湿法球磨5h后烘干得到原料粉，将原料粉装入铂金坩埚内，置于1100℃的高温电阻炉内熔融、澄清，2h后将澄清的玻璃液快速倒入去离子水中，得到玻璃碎渣。将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的ZBS玻璃粉。 Preparation of ZBS glass powder: Weigh SiO 2 , H 3 BO 3 , ZnO as the raw material powder of ZBS glass according to the mass ratio in Table 1, and use absolute ethanol as the medium to pass the above components through wet ball milling for 5 hours and then dry to obtain the raw materials Put the raw material powder into a platinum crucible, place it in a high-temperature resistance furnace at 1100 °C to melt and clarify, and pour the clarified glass liquid into deionized water quickly after 2 hours to obtain glass slag. The obtained glass slag is ball milled and pulverized, and after drying, ZBS glass powder with a particle size D50 of 1.0-3.0 μm is obtained.
表1。Table 1.
Figure 153012dest_path_image001
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Figure 153012dest_path_image001
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实施例7-16 ，称取如下表2的硼硅酸盐玻璃、SiO 2、析晶控制添加剂的材料组成，以乙醇作为溶剂，锆球作为球磨介质，以材料：乙醇：锆球为1:2:10的比例球磨15-20h后，在80℃的烘箱中烘15h，得到低温共烧陶瓷粉。 In Examples 7-16 , the material compositions of borosilicate glass, SiO 2 , and crystallization control additives in Table 2 were weighed, ethanol was used as the solvent, and zirconium balls were used as the ball milling medium, and the material: ethanol: zirconium balls was 1: After ball milling at a ratio of 2:10 for 15-20 hours, bake in an oven at 80°C for 15 hours to obtain low-temperature co-fired ceramic powder.
表2。Table 2.
Figure 295280dest_path_image002
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Figure 295280dest_path_image002
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将烘干的低温共烧陶瓷粉加入质量比为20%-30%的PVA粘结剂进行造粒并干压成型成直径20mm，高度10-12mm的圆块样品。在840-900℃烧结，保温15-60min，即得到本发明的低温共烧陶瓷。The dried low-temperature co-fired ceramic powder is added with a PVA binder with a mass ratio of 20%-30% for granulation and dry pressing to form a round block sample with a diameter of 20mm and a height of 10-12mm. Sintering at 840-900 DEG C, and keeping the temperature for 15-60 min, the low-temperature co-fired ceramics of the present invention are obtained.
表3为本发明实施例测试结果及烧结后表面裂纹情况。Table 3 shows the test results of the embodiment of the present invention and the surface cracks after sintering.
表3。table 3.
Figure 321005dest_path_image003
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Figure 321005dest_path_image003
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由表3可知，相比较对比例1，实施例9-12、16的介电常数小于4.5，在10GHz下介电损耗依然小于0.3%，并且烧结后陶瓷表面致密无裂纹，可满足微波元器件的应用要求。实施例13虽然介电损耗很低只有0.25%左右，但是烧结后表面存在轻微裂纹，存在瓷体开裂和可靠性失效方面的风险。It can be seen from Table 3 that compared with Comparative Example 1, the dielectric constants of Examples 9-12 and 16 are less than 4.5, the dielectric loss is still less than 0.3% at 10 GHz, and the ceramic surface is dense and crack-free after sintering, which can meet the requirements of microwave components. application requirements. Although the dielectric loss of Example 13 is as low as about 0.25%, there are slight cracks on the surface after sintering, and there are risks of cracking of the porcelain body and reliability failure.
图1分别为实施例9、13和对比例1的低温共烧陶瓷材料的SEM表面形貌，从图中可以看出，实施例9的基本无表面裂纹，结构更加致密，这大大提高了材料和器件产品的强度和可靠性。图2分别为实施例9、13和对比例1的低温共烧陶瓷材料的表面XRD分析，与SEM表面的形貌对比，方石英（cristobalite）的析晶程度与表面微裂纹存在着很大的关系，本专利通过控制方石英的析晶大大改善了裂纹的产生，防止产品因瓷体开裂而失效报废或者可靠性失效引起严重的质量问题。Figure 1 shows the SEM surface morphologies of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively. It can be seen from the figure that Example 9 basically has no surface cracks and has a denser structure, which greatly improves the performance of the material. and device product strength and reliability. Figure 2 shows the surface XRD analysis of the low-temperature co-fired ceramic materials of Examples 9, 13 and Comparative Example 1, respectively. Compared with the SEM surface morphology, the degree of crystallization of cristobalite and the surface microcracks are very large. This patent greatly improves the generation of cracks by controlling the crystallization of cristobalite, preventing the product from failure and scrapping due to cracking of the porcelain body or serious quality problems caused by reliability failure.
以上内容是结合具体的优选实施例对本发明所做的进一步详细说明，不能认定本发明的具体实施只限于这些说明。本发明所属领域的技术人员根据本发明的上述内容作出的非本质的改进和调整均属于本发明的保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be considered that the specific implementation of the present invention is limited to these descriptions. Non-essential improvements and adjustments made by those skilled in the art according to the above content of the present invention belong to the protection scope of the present invention.

Claims (7)

  1. 一种SiO 2系高频低介低温共烧陶瓷材料，其特征在于，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、1%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂选自ZBS玻璃粉、ZrO 2、TiO 2、Y 2O 3、AlN、结晶SiO 2中的至少一种。 A SiO2 -based high-frequency, low-dielectric and low-temperature co-fired ceramic material, characterized in that it is composed of the following components by weight: 30%-50% borosilicate glass, 30%-55% SiO2 , 1 %-15% of crystallization control additives; the sum of the above components is 100%; the crystallization control additives are selected from ZBS glass powder, ZrO 2 , TiO 2 , Y 2 O 3 , AlN, crystalline SiO 2 . at least one.
  2. 根据权利要求1所述的一种SiO 2系高频低介低温共烧陶瓷材料，其特征在于，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、3%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂为ZrO 2、TiO 2、Y 2O 3、AlN、结晶SiO 2中的至少一种以及ZBS玻璃粉，且ZBS玻璃粉的重量百分比不低于3%。 A SiO 2 series high frequency, low dielectric and low temperature co-fired ceramic material according to claim 1, characterized in that it is composed of the following components by weight: 30%-50% borosilicate glass, 30%- 55% SiO 2 , 3%-15% crystallization control additives; the sum of the above components is 100%; the crystallization control additives are ZrO 2 , TiO 2 , Y 2 O 3 , AlN, crystalline SiO 2 At least one of and ZBS glass powder, and the weight percentage of ZBS glass powder is not less than 3%.
  3. 根据权利要求1所述的一种SiO 2系高频低介低温共烧陶瓷材料，其特征在于，由以下重量百分比的组分构成：30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、0.5%-15%的析晶控制添加剂；上述组分的总和为100%；所述的析晶控制添加剂为ZBS玻璃粉、ZrO 2、Y 2O 3、AlN、结晶SiO2中的至少一种以及TiO 2，且TiO 2的重量百分比为0.5%-4%。 A SiO 2 series high frequency, low dielectric and low temperature co-fired ceramic material according to claim 1, characterized in that it is composed of the following components by weight: 30%-50% borosilicate glass, 30%- 55% SiO 2 , 0.5%-15% crystallization control additive; the sum of the above components is 100%; the crystallization control additive is ZBS glass powder, ZrO 2 , Y 2 O 3 , AlN, crystalline SiO2 At least one of TiO 2 and TiO 2 , and the weight percentage of TiO 2 is 0.5%-4%.
  4. 根据权利要求1~3所述的一种SiO 2系高频低介低温共烧陶瓷材料，其特征在于，所述的硼硅酸盐玻璃由以下重量百分比的组分构成：60%-80%的SiO 2，10%-30%的B 2O 3，1%-5%的Al 2O 3和1-12%的碱金属氧化物R 2O，上述组分的总和为100%；其中R为K、Na、Li中的至少一种。 A SiO 2 series high frequency, low dielectric and low temperature co-fired ceramic material according to claims 1 to 3, wherein the borosilicate glass is composed of the following components by weight: 60%-80% SiO 2 , 10%-30% B 2 O 3 , 1%-5% Al 2 O 3 and 1-12% alkali metal oxide R 2 O, the sum of the above components is 100%; wherein R is at least one of K, Na, and Li.
  5. 根据权利要求1~3所述的SiO 2系高频低介低温共烧陶瓷材料，其特征在于，所述的ZBS玻璃包含以下重量百分比的组分：7-30%的SiO 2，20-60%的B 2O 3，40-70%的ZnO，上述组分的总和为100%。 The SiO 2 series high-frequency, low-dielectric and low-temperature co-fired ceramic material according to claims 1 to 3, wherein the ZBS glass comprises the following components by weight: 7-30% SiO 2 , 20-60 wt % % B 2 O 3 , 40-70% ZnO, the sum of the above components is 100%.
  6. 根据权利要求1~3所述的SiO 2系高频低介低温共烧陶瓷材料，其特征在于，所述的SiO 2为无定型SiO 2。 The SiO 2 based high frequency, low dielectric and low temperature co-fired ceramic material according to claims 1 to 3, wherein the SiO 2 is amorphous SiO 2 .
  7. 根据权利要求1所述的一种SiO 2系高频低介低温共烧陶瓷材料的制备方法，其特征在于，包括以下步骤： A kind of preparation method of SiO2 series high-frequency, low-medium and low-temperature co-fired ceramic material according to claim 1, is characterized in that, comprises the following steps:
    硼硅酸盐玻璃、ZBS玻璃制备Preparation of borosilicate glass and ZBS glass
    按质量百分比：60%-80%的SiO 2，10%-30%的B 2O 3，1%-5%的Al 2O 3，1-12%的碱金属氧化物R 2O，称取SiO 2、H 3BO 3、Al 2O 3、Li 2CO 3或者Na 2CO 3或者K 2CO 3，将上述组分以无水乙醇作为介质通过湿法球磨4-8h，然后烘干，将上述原料粉装入铂金坩埚内，加热到1400-1550℃熔融，保温0.5-2h后倒入水中淬冷，将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的硼硅酸盐玻璃粉体； By mass percentage: 60%-80% SiO 2 , 10%-30% B 2 O 3 , 1%-5% Al 2 O 3 , 1-12% alkali metal oxide R 2 O, weighed SiO 2 , H 3 BO 3 , Al 2 O 3 , Li 2 CO 3 or Na 2 CO 3 or K 2 CO 3 , the above components are subjected to wet ball milling with absolute ethanol as a medium for 4-8 hours, and then dried, Put the above-mentioned raw material powder into a platinum crucible, heat it to 1400-1550 ℃ to melt, pour it into water for quenching after holding for 0.5-2 hours, and perform ball milling to pulverize the obtained glass slag. After drying, the particle size D50 is 1.0-3.0 μm. borosilicate glass powder;
    按质量百分比：7-30%的SiO 2，20-60%的B 2O 3，40-70%的ZnO，称取SiO 2、H 3BO 3、ZnO，将上述组分以无水乙醇作为介质通过湿法球磨4-8h，然后烘干，将上述原料粉装入铂金坩埚内，加热到1050-1300℃熔融，保温0.5-2h后倒入水中淬冷，将得到的玻璃渣进行球磨粉碎，经烘干后得到粒度D50为1.0~3.0μm的ZBS玻璃粉体； By mass percentage: 7-30% SiO 2 , 20-60% B 2 O 3 , 40-70% ZnO, weigh SiO 2 , H 3 BO 3 , ZnO, and use absolute ethanol as the above components. The medium is subjected to wet ball milling for 4-8 hours, and then dried. The above-mentioned raw material powder is put into a platinum crucible, heated to 1050-1300 ℃ to melt, kept for 0.5-2 hours and then poured into water for quenching, and the obtained glass slag is ball-milled and pulverized , ZBS glass powder with particle size D50 of 1.0~3.0μm is obtained after drying;
    将质量百分比为30%-50%的硼硅酸盐玻璃、30%-55%的SiO 2、1%-15%的析晶控制添加剂混合，以乙醇作为溶剂，球磨15-20h后烘干，得到低温共烧陶瓷粉； Mix 30%-50% by mass of borosilicate glass, 30%-55% SiO 2 , and 1%-15% crystallization control additive, use ethanol as a solvent, ball mill for 15-20h and then dry, Obtain low temperature co-fired ceramic powder;
    将烘干的低温共烧陶瓷粉加入20%-30%的PVA粘结剂进行造粒并干压成型成直径20mm，高度10-12mm的圆块样品，在840-900℃烧结，保温15-60min，即得到SiO 2系高频低介低温共烧陶瓷材料。 The dried low-temperature co-fired ceramic powder is added with 20%-30% PVA binder for granulation and dry pressing to form a round block sample with a diameter of 20mm and a height of 10-12mm, sintered at 840-900 ℃, and kept at a temperature of 15- After 60 min, the SiO 2 series high-frequency, low-medium and low-temperature co-fired ceramic material was obtained.
PCT/CN2021/084474 2021-03-10 2021-03-31 Sio2-series high-frequency low-dielectric low-temperature co-fired ceramic material and preparation method therefor WO2022188220A1 (en)

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