阅读说明：本技术 一种低温烧结改性NiO-Ta2O5基微波介质陶瓷材料及其制备方法 (Low-temperature sintering modified NiO-Ta2O5Microwave-based dielectric ceramic material and preparation method thereof ) 是由 邢孟江 曲明山 杨鸿宇 孙成礼 于 2021-11-03 设计创作，主要内容包括：本发明属于电子陶瓷及其制造领域,具体为一种低温烧结改性NiO-Ta-(2)O-(5)基微波介质陶瓷材料及其制备方法。是以离子掺杂改性为指导依据,不仅考虑到以相近半径的离子进行取代,如Zn～(2+)取代Ni～(2+)离子,V～(5+)取代Ta～(5+)离子；同时选择的掺杂氧化物仍具有低熔点的性质。因此可以实现改善NiO-Ta-(2)O-(5)基陶瓷材料微波介电性能的同时仍能降低适宜的烧结温度。在本发明中,通过调节各原料的摩尔含量,直接一次合成了具有低温烧结、温度稳定且微波介电性能优异的NiO-Ta-(2)O-(5)基陶瓷材料,可广泛应用于LTCC技术领域。(The invention belongs to the field of electronic ceramics and manufacture thereof, and particularly relates to low-temperature sintering modified NiO-Ta 2 O 5 A microwave-based dielectric ceramic material and a preparation method thereof. It is based on the guidance of ion doping modification, not only considering the substitution with ions of similar radius, such as Zn 2+ Substitution of Ni 2+ Ion, V 5+ Substituted Ta 5+ Ions; while the doped oxide is selected to still have the property of a low melting point. Thus, improvement of NiO-Ta 2 O 5 The base ceramic material has microwave dielectric performance and proper sintering temperature. In the invention, NiO-Ta with low-temperature sintering, stable temperature and excellent microwave dielectric property is directly synthesized in one step by adjusting the molar content of each raw material 2 O 5 The base ceramic material can be widely applied to the technical field of LTCC.)

1. Low-temperature sintering modified NiO-Ta₂O₅The microwave-based dielectric ceramic material is characterized in that the low-temperature sintering modified NiO-Ta₂O₅The general chemical formula of the microwave dielectric ceramic material is as follows:

(1.587y-0.198xy)ZnO-(2.597y-0.324xy)CuO-(1-x)NiO-(1.855y-0.231xy)B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.2; y is more than or equal to 0.03 and less than or equal to 0.09; prepared by a solid phase method; crystal type is NiTa₂O₆Structure;

the sintering temperature of the microwave dielectric ceramic material is 875-950 ℃, and the microwave dielectric ceramic material is pre-sintered in atmosphere at 850-900 ℃; the dielectric constant is 17 to 21, the Q x f value of the quality factor is 14000 to 23000GHz, and the temperature coefficient of the resonance frequency is 5 to 10 ppm/DEG C.

2. The low temperature sintered modified NiO-Ta of claim 1₂O₅The microwave dielectric ceramic material is characterized in that: when x is 0.15 and y is 0.06, the dielectric constant of the material at the sintering temperature of 925 ℃ is 20.2, the quality factor Q × f is 22417GHz, and the temperature coefficient of resonance frequency is 8.7 ppm/deg.c.

3. Low-temperature sintering modified NiO-Ta₂O₅The preparation method of the microwave-based dielectric ceramic material is characterized by comprising the following steps: the method comprises the following steps:

step 1: ZnO, CuO, NiO and B₂O₃、SnO₂、Ta₂O₅And V₂O₅The powder is represented by the chemical general formula (1.587y-0.198xy) ZnO- (2.597y-0.324xy) CuO- (1-x) NiO- (1.855y-0.231xy) B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅(ii) a (x is 0.1-0.2, y is 0.03-0.09) mixing;

step 2: and (2) putting the powder prepared in the step (1) into a ball milling tank, and adding zirconia balls and deionized water into the ball milling tank according to the following powder: zirconia balls: ball milling is carried out on deionized water according to the mass ratio of 1: 5-7: 3-5, ball milling is carried out for 6-8 hours in a planetary way, the deionized water is taken out and dried in an oven at 80-120 ℃, sieved by a screen mesh of 40-60 meshes and presintered for 3-5 hours in atmosphere at 850-900 ℃;

and step 3: and (3) the powder after the pre-sintering in the step (2) is subjected to powder mixing again according to the following powder: zirconium ball: ball milling is carried out on deionized water according to the mass ratio of 1: 4-6: 1-3, planetary ball milling mixing is carried out for 3-6 hours, the mixture is taken out and dried, and then polyvinyl alcohol solution is added into the obtained powder for granulation;

and 4, step 4: pressing and molding the ceramic raw material prepared in the step 3, removing the binder at 600-650 ℃, and sintering at 875-950 ℃ for 4-6 hours in an atmosphere to obtain the low-temperature sintered modified NiO-Ta₂O₅The microwave dielectric ceramic material.

Technical Field

The invention belongs to the field of electronic ceramics and manufacture thereof, and relates to low-temperature sintering modified NiO-Ta₂O₅A microwave-based dielectric ceramic material and a preparation method thereof.

Background

Along with the development of mobile communication towards high frequency, the importance of electronic components such as dielectric filters, dielectric resonator antennas, dielectric waveguides and the like is remarkable, and the microwave dielectric ceramic can play a role in the range of 300MHz to 300GHz and is a key basic material widely used for preparing the electronic components at present.

The traditional microwave equipment is heavy and expensive, and the communication industry is developed to the present, and the occupied space of a circuit system is required to be as small as possible. As a novel three-dimensional integrated package interconnection technology, a low temperature co-fired ceramic (LTCC) technology provides a reliable solution for preparing a ceramic module or an integrated circuit with embedded electrodes because it satisfies high frequency applications, and therefore, development of a ceramic system applied to the LTCC technology becomes a key point of research in this field.

NiO-Ta with tetragonal Tri-rutile crystal structure₂O₅The microwave dielectric property of the ceramic material at 1400 ℃ is as follows: epsilon_r＝25，Q×f＝31200GHz，τ_f26 ppm/DEG C, but cannot be co-fired with Ag or Cu electrodes in LTCC technology (the co-firing with Ag electrodes needs not more than 950℃; the co-firing with Cu electrodes needs not more than 1000℃ and is carried out in a reducing atmosphere) due to an excessively high sintering temperature, and the temperature coefficient of resonance frequency tau_fThe value is also large (tau)_fValues between. + -. 10 ppm/. degree.C. represent excellent temperature stability). No reference to NiO-Ta has been found so far₂O₅Low temperature sintering exploration of ceramics. Thus, the NiO-Ta is reduced₂O₅The sintering temperature of the base ceramic and the maintenance of the microwave dielectric properties are important points which need to be paid attention.

Disclosure of Invention

Aiming at the problems or the defects existing in the prior art, the prior NiO-Ta is solved₂O₅The invention provides a low-temperature sintering modified NiO-Ta, which solves the problem that ceramics cannot be co-sintered with Ag or Cu electrodes in an LTCC technology due to overhigh sintering temperature₂O₅The microwave-based dielectric ceramic material and the preparation method thereof realize low dielectric constant while maintaining excellent microwave dielectric propertyThe temperature of the material is stable by the warm sintering, and the material can be widely applied to the technical field of LTCC.

The invention provides a low-temperature sintering modified NiO-Ta₂O₅The microwave dielectric ceramic material has a chemical general formula as follows:

(1.587y-0.198xy)ZnO-(2.597y-0.324xy)CuO-(1-x)NiO-(1.855y-0.231xy)B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅(ii) a Wherein x is more than or equal to 0.1 and less than or equal to 0.2; y is more than or equal to 0.03 and less than or equal to 0.09; prepared by a solid phase method; crystal type is NiTa₂O₆Structure;

the sintering temperature of the microwave dielectric ceramic material is 875-950 ℃, and the microwave dielectric ceramic material is pre-sintered in atmosphere at 850-900 ℃; the dielectric constant is 17 to 21, the Q x f value of the quality factor is 14000 to 23000GHz, and the temperature coefficient of the resonance frequency is 5 to 10 ppm/DEG C.

Preferably, when x is 0.15 and y is 0.06, the dielectric constant of the material at the sintering temperature of 925 ℃ is 20.2, the quality factor Q × f value is 22417GHz, and the temperature coefficient of resonance frequency is 8.7 ppm/DEG C, and the material can be widely used in the field of LTCC technology.

The low-temperature sintering modified NiO-Ta₂O₅The preparation method of the microwave dielectric ceramic material comprises the following steps:

step 1: ZnO, CuO, NiO and B₂O₃、SnO₂、Ta₂O₅And V₂O₅The powder is represented by the chemical general formula (1.587y-0.198xy) ZnO- (2.597y-0.324xy) CuO- (1-x) NiO- (1.855y-0.231xy) B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅(ii) a (x is 0.1-0.2, y is 0.03-0.09) mixing;

step 2: and (2) putting the powder prepared in the step (1) into a ball milling tank, and adding zirconia balls and deionized water into the ball milling tank according to the following powder: zirconia balls: ball milling is carried out on deionized water according to the mass ratio of 1: 5-7: 3-5, ball milling is carried out for 6-8 hours in a planetary way, the deionized water is taken out and dried in an oven at 80-120 ℃, sieved by a screen mesh of 40-60 meshes and presintered for 3-5 hours in atmosphere at 850-900 ℃;

and step 3: and (3) the powder after the pre-sintering in the step (2) is subjected to powder mixing again according to the following powder: zirconium ball: ball milling is carried out on deionized water according to the mass ratio of 1: 4-6: 1-3, planetary ball milling mixing is carried out for 3-6 hours, the mixture is taken out and dried, and then polyvinyl alcohol solution is added into the obtained powder for granulation;

and 4, step 4: pressing and molding the ceramic raw material prepared in the step 3, removing the binder at 600-650 ℃, and sintering at 875-950 ℃ for 4-6 hours in an atmosphere to obtain the low-temperature sintered modified NiO-Ta₂O₅The microwave dielectric ceramic material.

The invention is different from the reported technologies in the prior art: i.e. by applying to the NiO-Ta after burn-in₂O₅CuO and V are added into the material₂O₅、B₂O₃The oxides are used as sintering aids to realize the purpose of sintering into porcelain at low temperature under the action of liquid phase, but the ions are doped and modified as guidance basis, and not only the ions with similar radiuses are considered to be substituted to realize the preparation of solid solution ceramics, such as Zn²⁺Substitution of Ni²⁺Ion, V⁵⁺Substituted Ta⁵⁺Ion, (Ni)_1/3Ta_2/3)⁴⁺Composite ion coating Sn⁴⁺Substitution, the synergistic effect among different ions can improve the comprehensive microwave dielectric property; meanwhile, the selected doped oxide still has the property of low melting point, so that the NiO-Ta synthesized at lower temperature can be improved₂O₅The purpose of the main crystal phase of the material is to ensure that the ceramic material keeps excellent microwave dielectric property and can still reduce the sintering temperature.

The invention provides a modified NiO-Ta capable of being sintered at low temperature₂O₅The base ceramic material has the chemical general formula of (1.587y-0.198xy) ZnO- (2.597y-0.324xy) CuO- (1-x) NiO- (1.855y-0.231xy) B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅By adjusting the molar content of each raw material, NiO-Ta with low-temperature sintering, stable temperature and excellent microwave dielectric property is directly synthesized in one step₂O₅The base ceramic material can be widely applied to the technical field of LTCC.

Drawings

Figure 1 XRD diffraction pattern corresponding to example 3;

FIG. 2 corresponds to the SEM topography of example 3.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and examples.

Step 1, adding ZnO, CuO, NiO and B₂O₃、SnO₂、Ta₂O₅And V₂O₅The powder is represented by the chemical general formula (1.587y-0.198xy) ZnO- (2.597y-0.324xy) CuO- (1-x) NiO- (1.855y-0.231xy) B₂O₃-3xSnO₂-(1-x)Ta₂O₅-(0.284y-0.035xy)V₂O₅(x is 0.15 and y is 0.06), and the materials are prepared according to a molar ratio;

step 2, mixing the powder weighed in the step 1, placing the mixture into a ball milling tank, and adding the mixture into zirconia balls and deionized water according to the following powder ratio: zirconia balls: carrying out planetary ball milling for 6 hours in a deionized water mass ratio of 1:6:3, then drying in an oven at 100 ℃, sieving by using a 60-mesh sieve, and then presintering for 3 hours in an atmosphere at 900 ℃;

and 3, putting the pre-sintered powder into a ball milling tank for secondary ball milling, and mixing the powder: zirconia balls: carrying out planetary ball milling for 4 hours at the mass ratio of the deionized water to the deionized water of 1:6:2, taking out and drying, and adding a polyvinyl alcohol solution into the obtained powder for granulation;

step 4, putting the granulated powder intoThe obtained product is dried and pressed into a cylinder under the pressure of 20MPa, then the cylinder block is kept at 650 ℃ for 2 hours to remove the binder, and then the temperature is raised to 875 ℃ to 950 ℃ for 4 hours, and finally the modified NiO-Ta under the low-temperature sintering condition is prepared₂O₅The microwave dielectric ceramic material has the following chemical formula molar ratio: ZnO-CuO-NiO-B₂O₃-SnO₂-Ta₂O₅-V₂O₅(3.7:6.1:33.7:4.3:17.8:33.7:0.7mol％)。

In order to better illustrate the effect of the invention, the preparation method comprises the following steps4 parts of example samples are obtained. FIG. 1 is the XRD diffraction pattern of example 3, after searching the phase composition of the ceramic and NiTa₂O₆The standard card JCPDS card No.32-0702 corresponds to the ceramic material, and the existence of a second phase diffraction peak is not found in the system at the moment, so that the ceramic material belongs to NiTa₂O₆A solid solution of the structure.

FIG. 2 is the SEM topography of example 3, which shows that the grain growth of the ceramic sample is sufficient, and the grain boundary is clearly visible, which indicates that the low-temperature sintering property is good, but the micro-pores still exist.

The compositions and microwave dielectric properties of the examples are as follows:

table 1 shows the composition of the sample groups of the examples

Table 2 shows the microwave dielectric properties of the samples of each example

From the data presented in tables 1 and 2, it can be seen that when x is 0.15 and y is 0.06, the modified NiO-Ta is obtained when the sintering temperature is in the range of 875 to 925 ℃₂O₅The dielectric constant and the Q x f value of the base ceramic material show a tendency of increasing and then decreasing, and the optimal values are obtained at 925 ℃: epsilon_r＝20.2，tanδ＝4.1×10^-4，Q×f＝22417GHz，τ_fCompared with the prior literature report, the sintering temperature is greatly reduced, and the excellent temperature stability and microwave dielectric property are maintained, so that the method can be widely applied to the technical field of LTCC.