阅读说明：本技术 一种微波介电陶瓷材料及其制备方法和用途 (Microwave dielectric ceramic material and preparation method and application thereof ) 是由 肖明 于 2020-07-07 设计创作，主要内容包括：本发明提供了一种微波介电陶瓷材料及其制备方法和用途,微波介电陶瓷材料包括Zn<Sub>3</Sub>B<Sub>2</Sub>O<Sub>6</Sub>和Mg<Sub>3</Sub>B<Sub>2</Sub>O<Sub>6</Sub>两种材料,Zn<Sub>3</Sub>B<Sub>2</Sub>O<Sub>6</Sub>和Mg<Sub>3</Sub>B<Sub>2</Sub>O<Sub>6</Sub>的摩尔比为(1-x):x,其中,x＝0.05～0.40,由按下述摩尔百分比的各组分的氧化物制得：主料ZnO,71.25～45.00％；主料B<Sub>2</Sub>O<Sub>3</Sub>,25.00％；取代料MgO,3.75～30.00％；上述组分的摩尔百分比之和为100％,且所述ZnO与所述MgO的摩尔比为(0.95:0.05)～(0.60:0.40)。该微波介电陶瓷材料具有低介电常数、高品质因数、高相对密度、较稳定的温度特性以及低致密化温度的优异特性。(The invention provides a microwave dielectric ceramic material and a preparation method and application thereof, wherein the microwave dielectric ceramic material comprises Zn 3 B 2 O 6 And Mg 3 B 2 O 6 Two materials, Zn 3 B 2 O 6 And Mg 3 B 2 O 6 The molar ratio of (1-x) to x, wherein x is 0.05-0.40, and the catalyst is prepared from the following oxides of the components in percentage by mole: 71.25-45.00% of ZnO as a main material; main ingredient B 2 O 3 25.00%; 3.75-30.00% of substituted MgO; the sum of the mole percentages of the components is 100 percent, and the mole ratio of the ZnO to the MgO is (0.95:0.05) - (0.60: 0.40). The microwave dielectric ceramic material has the excellent characteristics of low dielectric constant, high quality factor, high relative density, stable temperature characteristic and low densification temperature.)

1. A microwave dielectric ceramic material, characterized by: comprising Zn₃B₂O₆And Mg₃B₂O₆Two materials, Zn₃B₂O₆And Mg₃B₂O₆The molar ratio of (1-x) to x, wherein x is 0.05 to 0.40.

2. A microwave dielectric ceramic material according to claim 1, wherein: prepared from the following oxides of the components in percentage by mole:

71.25-45.00% of ZnO as a main material;

main ingredient B₂O₃，25.00％；

3.75-30.00% of substituted MgO;

the sum of the mole percentages of the components is 100 percent, and the mole ratio of the ZnO to the MgO is (0.95:0.05) - (0.60: 0.40).

3. A microwave dielectric ceramic material according to claim 1, wherein: the molar ratio of the ZnO to the MgO is 60.00% to 15.00%.

4. A preparation method of a microwave dielectric ceramic material is characterized by comprising the following steps: the method comprises the following steps:

s1 preparation of (1-x) Zn by oxide method according to molecular formula molar ratio₃B₂O₆+xMg₃B₂O₆Oxides ZnO, B required for the material₂O₃And MgO, wherein x is 0.05 to 0.40;

s2, preparing the oxide ZnO, B₂O₃Mixing the MgO with deionized water, and carrying out primary ball milling in a planetary ball mill for 11-13 hours;

s3, filtering, drying and sieving, and pre-sintering the obtained powder, wherein the pre-sintering temperature is 840-860 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 3-5 h;

s4, performing secondary ball milling on the pre-sintered material, wherein the secondary ball milling time is 11-13 hours;

s5, filtering, drying, sieving, sintering the obtained powder at a low temperature of 940-960 ℃, at a heating rate of 1-3 ℃/min for 3-5 h, and sintering at a low temperature to obtain the microwave dielectric ceramic material.

5. Use of a microwave dielectric ceramic material according to any one of claims 1 to 2, wherein: the microwave dielectric ceramic material is used for low-temperature co-fired ceramic.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of microwave dielectric ceramic materials, in particular to a microwave dielectric ceramic material and a preparation method and application thereof.

[ background of the invention ]

Low temperature co-fired ceramic (LTCC) technology has attracted extensive interest to researchers due to the ability to perform large scale three-dimensional integration with passive devices. Since the melting point of silver is 961 ℃, the maximum temperature of the LTCC process should be below its melting point. In addition, the materials used in the field of microwave communication should have both a low dielectric constant: (_r) And a high quality factor (Q × f). Therefore, the alloy has low electrical characteristics and processing temperature_rAnd the ceramic with high Q x f and low densification temperature has great potential application value in the field of LTCC.

Zn₃B₂O₆The dielectric properties of the (ZBO) ceramics when fired at 925 ℃ are as follows,_roverall, ZBO ceramics have better sintering and dielectric properties, 6.7, 58,500GHz, 96% relative density. However, the Q.times.f.value of ZBO ceramics still has room for further improvement. Mg (magnesium)₃B₂O₆The dielectric properties of (MBO) ceramics when sintered at 1350 ℃ are as follows,_rrelative density of 7, Q × f 108,000GHz, 97%. Obviously, the Q x f value of MBO ceramic is higher than that of ZBO ceramic, and considering that the densification temperature of ZBO ceramic is lower than that of MBO ceramic, replacing ZnO with MgO is a feasible way to increase the Q x f value of ZBO ceramic and maintain it_rWithout major changes.

Chinese invention publication No. CN103755321A at 20140430 discloses a method for preparing a medium-temperature microwave dielectric ceramic material, which comprises washing kaolin with water, removing impurities, and drying to obtain kaolin powder at S1; s2, taking 87-93.5 wt% of kaolin powder, 3-5 wt% of MgO, 1-3 wt% of CaO, 0.5-1 wt% of ZnO and 2-3.5 wt% of B₂O₃0 to 0.5% of SnO₂Adding the mixture into a ball milling tank, ball milling the mixture for 12 to 16 hours by using a planetary ball mill, uniformly mixing and grinding the mixture, wherein MgO, CaO, ZnO and B₂O₃、SnO₂The modifier is formed, conventional equipment is adopted, one-time sintering is carried out, calcination and melting are not needed, the temperature is reduced from original 1400-1450 ℃ to 1200-1250 ℃ by introducing the modifier, the production cost is reduced, and the requirements of energy conservation and emission reduction are met. The dielectric constant of the warm microwave dielectric ceramic material is between 5.7 and [email protected] and 3GHz, and the warm microwave dielectric ceramic material has low microwave dielectric loss and smaller temperature coefficient of resonant frequency. However, the modifier consists of four components, the component degree of complexity is high, and the sintering temperature is still high.

20180810, Chinese invention CN108383519A, provides a microwave dielectric ceramic material, which is prepared from composite oxide and additive; the general formula of the composite oxide is xMg_1.2Zn_0.8SiO₄+yMg_0.65Zn_0.35Al₂O₄(ii) a Wherein x + y is 1, x is more than or equal to 0.4 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.6. Compared with the prior art, the microwave dielectric ceramic material provided by the invention is prepared from composite oxygen with a specific general formulaPrepared by compounds and additives, realizes the preparation of the microwave dielectric ceramic material Mg₂SiO₄Effective improvement of (1); the microwave dielectric ceramic material has low dielectric constant, extremely high Q & ltf & gt value and good sintering stability, and can realize continuous and adjustable temperature drift to meet various requirements. Experimental results show that the microwave dielectric ceramic material has the relative dielectric constant r of 7-8, the quality factor Q f value of more than or equal to 180000GHz, the temperature drift adjustment range of +10 to +6 ppm/DEG C, stable sintering, and very excellent application value and market potential. However, the dielectric constant and sintering temperature of microwave dielectric ceramic materials are still high, and the use of microwave dielectric ceramic materials in microwave communication devices based on low-temperature co-fired ceramic technology is still limited.

[ summary of the invention ]

In view of the above, the present invention is directed to a microwave dielectric ceramic material, which has the excellent characteristics of low dielectric constant and high quality factor and has simple components, and a preparation method and use thereof.

In a first aspect, the present invention provides a microwave dielectric ceramic material comprising Zn₃B₂O₆And Mg₃B₂O₆Two materials, Zn₃B₂O₆And Mg₃B₂O₆The molar ratio of (1-x) to x, wherein x is 0.05 to 0.40.

Further, the microwave dielectric ceramic material is prepared from the following oxides in percentage by mole:

71.25-45.00% of ZnO as a main material;

main ingredient B₂O₃，25.00％；

3.75-30.00% of substituted MgO;

the sum of the mole percentages of the components is 100 percent, and the mole ratio of the ZnO to the MgO is (0.95:0.05) - (0.60: 0.40). Wherein 60.00% to 15.00% is preferred.

In a second aspect, the present invention provides a method for preparing a microwave dielectric ceramic material, comprising the following steps:

s1, useOxide method, preparing (1-x) Zn according to molecular formula molar ratio₃B₂O₆+xMg₃B₂O₆Oxides ZnO, B required for the material₂O₃And MgO, wherein x is 0.05 to 0.40;

s2, mixing the oxide with deionized water, and performing primary ball milling in a planetary ball mill for 11-13 hours;

s3, filtering, drying and sieving, and pre-sintering the obtained powder, wherein the pre-sintering temperature is 840-860 ℃, the heating rate is 1-3 ℃/min, and the heat preservation time is 3-5 h;

s4, performing secondary ball milling on the pre-sintered material, wherein the secondary ball milling time is 11-13 hours;

s5, filtering, drying, sieving, sintering the obtained powder at a low temperature of 940-960 ℃, at a heating rate of 1-3 ℃/min for 3-5 h, and sintering at a low temperature to obtain the microwave dielectric ceramic material.

In a third aspect, the invention provides a use of a microwave dielectric ceramic material, which is applied to the field of low-temperature co-fired ceramics.

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

(1) the microwave dielectric ceramic material of the invention replaces ZnO with proper MgO, only adopts MgO as a substituting agent, and has relatively low component complexity. So that the ZBO ceramic has excellent characteristics of low dielectric constant, high quality factor, high relative density and low densification temperature, wherein the dielectric constant_rIt was 6.47, the Q × f quality factor was 89,600GHz, and the relative density was 96.7%.

(2) The microwave dielectric ceramic material can realize the densification sintering of the microwave dielectric ceramic at 950 ℃ under the condition of not adding any low-melting-point sintering aid.

The microwave dielectric ceramic material can solve the following key technical problems in the fields of microwave devices based on a low-temperature co-firing technology and the like: firstly, the loss of the microwave device to signals during working is effectively reduced through high quality factor, so that the performance of the microwave device can be greatly improved; secondly, the delay time of signal transmission is effectively reduced through a lower dielectric constant, so that the real-time performance of signals is improved; thirdly, the densification temperature is lower than the melting point (961 ℃) of silver, so that low-temperature sintering can be realized without adding sintering aids, and the deterioration of electrical properties caused by adding the sintering aids is avoided.

[ description of the drawings ]

FIG. 1 is a flow chart of a method for preparing a microwave dielectric ceramic material according to the present invention;

FIG. 2 is a scanning electron microscope image of the microwave dielectric ceramic material of comparative example 1 after sintering;

FIG. 3 is a scanning electron micrograph of the microwave dielectric ceramic material of example 1 after sintering;

FIG. 4 is a scanning electron micrograph of a microwave dielectric ceramic material sintered according to example 2;

FIG. 5 is a scanning electron micrograph of a microwave dielectric ceramic material according to example 3 after sintering;

FIG. 6 is a scanning electron micrograph of a microwave dielectric ceramic material according to example 4 after sintering;

FIG. 7 is a scanning electron micrograph of a microwave dielectric ceramic material according to example 5 after sintering;

FIG. 8 is a scanning electron micrograph of the microwave dielectric ceramic material of example 6 after sintering.

FIG. 9 is a scanning electron micrograph of a microwave dielectric ceramic material according to example 7 after sintering.

[ detailed description ] embodiments

The embodiment of the invention provides a microwave dielectric ceramic material, a preparation method and application thereof, and aims to provide a microwave dielectric ceramic material, a preparation method and application thereof.

In order to solve the above problems, the technical solution in the embodiments of the present invention has the following general idea: by Zn₃B₂O₆And Mg₃B₂O₆Two materials, Zn₃B₂O₆And Mg₃B₂O₆In a molar ratio of (1-x): x, whichWherein x is 0.05 to 0.40. In the prepared raw materials, ZnO is replaced by proper MgO, so that the ZBO ceramic has excellent characteristics of low dielectric constant, high quality factor, high relative density and low densification temperature, and the densification sintering of the microwave dielectric ceramic can be realized at 950 ℃ without adding any low-melting-point sintering aid, thereby avoiding the deterioration of electrical properties caused by the addition of the sintering aid.