CN114751734B - Dielectric material for low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and preparation method thereof - Google Patents

Dielectric material for low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and preparation method thereof Download PDF

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CN114751734B
CN114751734B CN202210472445.4A CN202210472445A CN114751734B CN 114751734 B CN114751734 B CN 114751734B CN 202210472445 A CN202210472445 A CN 202210472445A CN 114751734 B CN114751734 B CN 114751734B
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CN114751734A (en
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邢孟江
曲明山
杨鸿宇
乔峰
阮丽梅
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University of Electronic Science and Technology of China
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Abstract

The invention belongs to the field of electronic ceramics and manufacturing thereof, in particular to a dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and a preparation method thereof; by adding Mg to 0.17 Nb 0.33 Ti 0.5 O 2 Composite ion V is introduced into the main material 5+ Ta and the like 5+ Partial substitution of ions is carried out, and a modifier A is additionally doped 2 CO 3 ‑BO‑C 2 O 3 ‑SiO 2 (a=na, li; b=cao, mgO, cuO; c=b, nd), provides a negative permittivity temperature coefficient of-330±30ppm/°c while significantly reducing the sintering temperature and reduces the loss degradation factor due to the modifier, producing a dielectric material for a radio frequency MLCC with low loss, low cost and good process stability.

Description

Dielectric material for low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and preparation method thereof
Technical Field
The invention belongs to the field of electronic ceramics and manufacturing thereof, and relates to a dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and a preparation method thereof.
Background
In recent years, with the rapid development of the fifth generation mobile communication technology (5G), the demand for electronic components has also shifted to high performance, high frequency, and miniaturization. The chip type multilayer ceramic capacitor (Multi-layer Ceramic Capacitors, MLCC) has the advantages of being applicable to high frequency or ultrahigh frequency, small in volume, large in specific volume, long in service life, high in safety and the like, plays a great role in the communication field, and the demand of the chip type multilayer ceramic capacitor is increased year by year.
The MLCC is composed of three parts, namely an inner electrode, an end electrode and a ceramic dielectric layer, wherein the inner electrode (such as an Ag electrode) and the ceramic dielectric layer are mutually parallel to form a main body, and the end electrode is generally of a three-layer structure: the innermost layer plays a role of linking and leads out an inner electrode; the middle is a barrier layer which mainly prevents Ag from being corroded by molten soldering tin during welding; the outermost layer isAnd (5) welding a layer. Ceramic capacitors are often classified by the temperature coefficient of permittivity τ of the dielectric ceramic employed ε And (3) representing. Ceramic dielectrics can be generally classified into three major classes, class I, class ii and class iii ceramics according to the american society for electronics RS-198 standard. Among them, the class I ceramic capacitor has high stability and low loss characteristics, and is most widely used in radio frequency and microwave communication. The naming rules are different according to the dielectric constant temperature characteristics, for example, the ceramic capacitor with S2G temperature characteristics means that the ceramic capacitor has temperature drift of minus 330+/-30 ppm/DEG C in the temperature range (-55 ℃ -85 ℃), and the dielectric ceramic capacitor can be used for preparing circuits of phase control radar T/R components, radio frequency power amplifiers, transmitters and the like to play roles of coupling, coordination, filtering and the like.
Common type I ceramic capacitor is made of TiO 2 Based, e.g. ZnO-MgO-TiO 2 Based on BaO-TiO 2 Is BaO-La 2 O 3 -TiO 2 And the like, but the sintering temperature of the system is too high (more than or equal to 1350 ℃), and the energy consumption and the cost are increased. Many systems surround TiO 2 Development, such as improving dielectric properties and lowering sintering temperature by ion doping or multiphase compounding, increases practicality.
By means of (Mg) 1/3 Nb 2/3 ) 4+ Composite ion substituted TiO 2 When the substitution amount is low, rutile structure Mg is formed 0.17 Nb 0.33 Ti 0.5 O 2 Indicating that the complex ion does not cause TiO 2 Structural changes, the sintering temperature of the ceramic is also found to be reduced to a certain extent through literature reports, and accordingly, the dielectric properties are also deteriorated: epsilon r 80 to 8500GHz; although researchers have also studied Mg 0.17 Ta 0.33 Ti 0.5 O 2 Ceramics with excellent dielectric properties: epsilon r 65, Q×f-18000 GHz, but the sintering temperature is still high (1250 ℃), which is not suitable for practical application.
It is not difficult to find out in combination with the above-mentioned state of the art Mg 0.17 Nb 0.33 Ti 0.5 O 2 The base ceramic has the problems of poor comprehensive dielectric properties and the like, and cannot be realizedExcellent dielectric properties are maintained at lower sintering temperatures. The method is necessary to be improved, and a method which has the advantages of simple and controllable process, low material dielectric loss and capability of being co-fired with the Ag inner electrode is developed<950 ℃ and stable dielectric constant temperature coefficient, so as to meet the application requirements of the radio frequency communication industry.
Disclosure of Invention
The invention aims to provide a dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor and a preparation method thereof, so as to overcome the defect of Mg 0.17 Nb 0.33 Ti 0.5 O 2 The technical disadvantage of low sintering temperature and excellent dielectric properties cannot be considered.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor comprises a ceramic material and a modifier;
the chemical general formula of the ceramic material is Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 ；
The formula of the modifier is A 2 CO 3 -BO-C 2 O 3 -SiO 2 (42:12:36:10 wt.%) wherein a 2 CO 3 From 16wt.% Na 2 CO 3 With 26wt.% Li 2 CO 3 Composition; BO consists of 4wt.% MgO with 8wt.% CuO; c (C) 2 O 3 From 32wt.% of B 2 O 3 With 4wt.% Nd 2 O 3 Composition;
the formula of the dielectric material for the multilayer ceramic capacitor is Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 +x wt.% modifier, wherein x in the modifier has a value range of 1.ltoreq.x.ltoreq.2; is prepared by a solid phase method, and the main crystal phase is rutile type Mg 0.17 Nb 0.33 Ti 0.5 O 2 The structure is that the sintering temperature is 850-900 ℃; dielectric constant of 58-71 and dielectric loss of 2X 10 -4 ～5×10 -4 The Q multiplied by f value of the quality factor is 8000-18000 GHz, and the temperature coefficient of the dielectric constant is stable and fullThe temperature characteristics of the S2G are (-55 ℃ to 334 ppm/DEGC; 85 ℃ to 338 ppm/DEGC).
Preferably, when x=1, the dielectric constant of the material is 70.6 at 900 ℃ sintering temperature, dielectric loss is as low as 2.2×10 -4 The Q×f value of the quality factor is as high as 17822GHz.
The preparation method of the dielectric material for the low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor comprises the following steps:
step 1, mgO and TiO are mixed together 2 、Nb 2 O 5 、V 2 O 5 Ta and Ta 2 O 5 According to the chemical general formula Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 Batching;
step 2: loading the powder prepared in the step 1 into a ball milling tank, performing planetary ball milling for 4-6 hours according to the mass ratio of the powder to zirconium balls to deionized water of 1:5-7:3-5, drying the mixed slurry in an oven after ball milling is finished, and sieving the dried slurry with a screen mesh of 40-100 meshes; presintering the sieved powder in the atmosphere of 900-1100 ℃ for 3-5 hours;
step 3, na is carried out 2 CO 3 、Li 2 CO 3 、MgO、CuO、B 2 O 3 、Nd 2 O 3 And SiO 2 Raw powder materials of the glass powder are respectively prepared according to the mass ratio of 16:26:4:8:32:4:10, planetary ball milling is carried out for 6-8 hours according to the mass ratio of the powder materials to the zirconium balls to the alcohol of 1:5-7:4-6, after the ball milling is carried out, the ball milling material is dried, presintering is carried out for 3-6 hours at 600-650 ℃, then the temperature is raised to 1400-1500 ℃ for melting for 3-5 hours, the melted glass is quickly poured into deionized water for cooling, and the cooled glass material is ground into uniform fine powder, so that the modifier is obtained;
step 4, the modifier prepared in the step 3 is prepared according to Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 Content of +x wt.% modifier (x=1 to 2) Mg of step 2 is added 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 Presintering materialAnd again according to the powder: zirconium ball: performing planetary ball milling for 3-5 hours with the mass ratio of deionized water being 1:5-7:3-5, and adding a polyvinyl alcohol solution into the powder after the ball milling materials are dried for bonding granulation;
step 5, pressing and molding the ceramic raw material prepared in the step 4, discharging glue for 3-5 hours at 600-650 ℃ at a heating rate of 2-5 ℃/min, heating to 850-900 ℃ at the same rate, and preserving heat for 4-6 hours to obtain the low-temperature sintered Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 A dielectric ceramic material.
It is known that the ceramic forming of low temperature sintered ceramics is accomplished by means of a liquid phase sintering mechanism, i.e. the glass frit should have a wetting effect on the ceramic matrix, so that the ceramic is dissolved in the glass liquid phase and the "dissolve-precipitate" process is completed, thus realizing low temperature densification. However, the matching property (including the advantages of wettability and solubility) of glass to ceramic has uniqueness and uniqueness, and a glass auxiliary matched with the ceramic matrix needs to be found aiming at the specific ceramic matrix. The invention prepares a glass modifier matched with Mg-Ti-Nb ceramic to obtain a dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor, and adopts a mode of combining an ion substitution process and a doping modifier by adopting the following steps of 0.17 Nb 0.33 Ti 0.5 O 2 Composite ion V is introduced into the main material 5+ Ta and the like 5+ Partial substitution of ions is carried out, and a modifier A is additionally doped 2 CO 3 -BO-C 2 O 3 -SiO 2 (a=na, li; b=cao, mgO, cuO; c=b, nd), provides a negative permittivity temperature coefficient of-330±30ppm/°c while significantly reducing the sintering temperature and reduces the loss degradation factor due to the modifier, producing a dielectric material for a radio frequency MLCC with low loss, low cost and good process stability.
Drawings
Figure 1 corresponds to the XRD pattern of example 3;
fig. 2 corresponds to the SEM topography of example 3.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples.
Step 1: mgO, tiO 2 、Nb 2 O 5 、V 2 O 5 Ta and the like 2 O 5 According to the chemical general formula Mg 0.17 Nb 0.33 Ti 0.5 O 2 Batching;
step 2: filling the powder prepared in the step 1 into a ball milling tank and mixing the powder: zirconium ball: the mass ratio of deionized water is 1:6:5, planetary ball milling is carried out for 6 hours, the mixed slurry is placed into an oven for drying after ball milling is finished, and then a 100-mesh screen is used for sieving. Presintering the sieved powder in the atmosphere at 950 ℃ for 5 hours;
step 3: na is mixed with 2 CO 3 、Li 2 CO 3 、MgO、CuO、B 2 O 3 、Nd 2 O 3 And SiO 2 Raw powders of (2) are respectively prepared according to the mass ratio of 16:26:4:8:32:4:10, and then the raw powders are prepared according to the following steps: zirconium ball: performing planetary ball milling for 6 hours with the mass ratio of alcohol being 1:6:5, drying the materials after ball milling, presintering the materials at 650 ℃ for 4 hours, then heating to 1500 ℃ for melting for 5 hours, rapidly pouring the melted glass into deionized water for cooling, and grinding the cooled glass material into uniform fine powder to obtain the modifier;
step 4: the modifier prepared in the step 3 is prepared according to Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 Content of +x wt.% modifier (x=1 to 2) Mg of step 2 is added 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 In the presintering material, and again according to the powder: zirconium ball: performing planetary ball milling for 4 hours with the mass ratio of deionized water being 1:6:4, and adding 8% polyvinyl alcohol solution as a binder into the powder after the ball milling material is dried to granulate;
step 5: pressing the ceramic raw material obtained in the step 4 to form, and then heating to 650 ℃ at a heating rate of 3 ℃/minDischarging the glue for 4 hours at the temperature, then heating to 850-900 ℃ at the same speed, and preserving heat for 6 hours to obtain the low-temperature sintered Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 A dielectric ceramic material.
To better illustrate the effect of the invention, 6 samples of the examples were prepared according to the procedure described above. FIG. 1 is an XRD diffraction pattern of example 3, showing the phase composition and Mg of the ceramic after searching 0.17 Nb 0.33 Ti 0.5 O 2 Corresponding to the standard card JCPDS card No.40-0366, when the existence of the second phase diffraction peak is not found in the system, the ceramic of the type is indicated to belong to Mg 0.17 Nb 0.33 Ti 0.5 O 2 Structure is as follows.
Fig. 2 is an SEM morphology of example 3, at which the grain size was small and micro-pores were present.
The composition and microwave dielectric properties of each example were as follows:
table 1 shows the components of the sample groups of the examples
Table 2 shows the dielectric properties of the samples of the examples
From the data shown in tables 1 and 2, it can be seen that in example 3, the modified Mg was obtained at a sintering temperature of 900 DEG C 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 The dielectric constant and Q x f value of the ceramic material are optimized: epsilon r ＝70.6，tanδ＝2.2×10 -4 ，Q×f＝17822GHz，τ ε Compared with the prior art, the sintering temperature is greatly reduced and the dielectric loss is kept low at the same time, the dielectric constant temperature coefficient is stable within the range of-55 ℃ to 85 ℃, and the method is suitable for industrial application.
In summary, the dielectric material for the multilayer ceramic capacitor can meet the application requirements of the radio frequency ceramic capacitor with the current S2G temperature characteristic, has simple and controllable preparation process and low material dielectric loss, can be co-fired with an Ag inner electrode (< 950 ℃), has stable dielectric constant temperature coefficient, and can be widely applied to the radio frequency communication industry.

Claims (2)

1. A dielectric material for a low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor is characterized in that: comprises a ceramic material and a modifier;
the chemical general formula of the ceramic material is Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 ；
The formula of the modifier is A 2 CO 3 -BO-C 2 O 3 -SiO 2 The mass ratio is 42:12:36:10, wherein A is as follows 2 CO 3 From 16wt.% Na 2 CO 3 With 26wt.% Li 2 CO 3 Composition; BO consists of 4wt.% MgO with 8wt.% CuO; c (C) 2 O 3 From 32wt.% of B 2 O 3 With 4wt.% Nd 2 O 3 Composition;
the formula of the dielectric material for the multilayer ceramic capacitor is Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 +1wt.% modifier, obtained by solid phase method, having a main crystalline phase of rutile Mg 0.17 Nb 0.33 Ti 0.5 O 2 The dielectric constant of the material is 70.6 at 900 ℃ sintering temperature, and the dielectric loss is as low as 2.2 multiplied by 10 -4 The Q multiplied by f value of the quality factor is as high as 17822GHz, the temperature coefficient of the dielectric constant is stable and meets the S2G temperature characteristic, and the temperature is minus 55℃: τ ε ＝-334ppm/℃；85℃：τ ε ＝-338ppm/℃。
2. The method for preparing the dielectric material for the low-temperature sintered Mg-Ti-Nb multilayer ceramic capacitor, as recited in claim 1, is characterized in that: the method comprises the following steps:
step 1, mgO and TiO are mixed together 2 、Nb 2 O 5 、V 2 O 5 Ta and Ta 2 O 5 According to the chemical general formula Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 Batching;
step 2: loading the powder prepared in the step 1 into a ball milling tank, performing planetary ball milling for 4-6 hours according to the mass ratio of the powder to zirconium balls to deionized water of 1:5-7:3-5, drying the mixed slurry in an oven after ball milling is finished, and sieving the dried slurry with a screen mesh of 40-100 meshes; presintering the sieved powder in the atmosphere of 900-1100 ℃ for 3-5 hours;
step 3, na is carried out 2 CO 3 、Li 2 CO 3 、MgO、CuO、B 2 O 3 、Nd 2 O 3 And SiO 2 Raw powder materials of the glass powder are respectively prepared according to the mass ratio of 16:26:4:8:32:4:10, planetary ball milling is carried out for 6-8 hours according to the mass ratio of the powder materials to the zirconium balls to the alcohol of 1:5-7:4-6, after the ball milling is carried out, the ball milling material is dried, presintering is carried out for 3-6 hours at 600-650 ℃, then the temperature is raised to 1400-1500 ℃ for melting for 3-5 hours, the melted glass is quickly poured into deionized water for cooling, and the cooled glass material is ground into uniform fine powder, so that the modifier is obtained;
step 4, the modifier prepared in the step 3 is prepared according to Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 +x wt.% modifier, mg added in step 2 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 In the presintering material, the value range of x in the modifier is more than or equal to 1 and less than or equal to 2; and again according to the powder: zirconium ball: performing planetary ball milling for 3-5 hours with the mass ratio of deionized water being 1:5-7:3-5, and adding polymer into the powder after the ball milling materials are driedBinding and granulating the vinyl alcohol solution;
step 5, pressing and molding the ceramic raw material prepared in the step 4, discharging glue for 3-5 hours at 600-650 ℃ at a heating rate of 2-5 ℃/min, heating to 850-900 ℃ at the same rate, and preserving heat for 4-6 hours to obtain the low-temperature sintered Mg 0.17 (Nb 0.32 V 0.08 Ta 0.6 ) 0.33 Ti 0.5 O 2 A dielectric ceramic material.
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