CN101913863B - Ceramic dielectric material matched with nickel inner electrode - Google Patents
Ceramic dielectric material matched with nickel inner electrode Download PDFInfo
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- CN101913863B CN101913863B CN 201010236943 CN201010236943A CN101913863B CN 101913863 B CN101913863 B CN 101913863B CN 201010236943 CN201010236943 CN 201010236943 CN 201010236943 A CN201010236943 A CN 201010236943A CN 101913863 B CN101913863 B CN 101913863B
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Abstract
The invention discloses a low-temperature high-frequency ceramic dielectric material matched with a nickel electrode, which consists of a main crystal phase, a property-modifying additive and a sintering fluxing medium. The structural formula of the main crystal phase is (MgaCabSr(1-a-b))nTicZr(1-c)O3, wherein a is more than or equal to 0 and less than or equal to 0.15; b is more than or equal to 0 and less than or equal to 1; c is more than or equal to 0 and less than or equal to 0.15; and m is more than or equal to 0.8 and less than or equal to 1.1. The property-modifying additive is one or more MnO2, Al2O3, CaO and Y2O3. The sintering fluxing medium is one or more SiO2, ZnO, Li2O, K2O and BaO. The material meets EIA standard COG characteristics, and has material uniformity, uniform size distribution, high dispersibility, good molding process and high dielectric properties. When used for manufacturing a multi-layer chip ceramic capacitor, the material is matched with the nickel electrode, and after being sintered, ceramic crystal grains uniformly and compactly grow and a dielectric layer is well matched with the inner electrode, so stress generation is reduced, a Q value of the product is increased and the performance of the product is more stable.
Description
Technical field
The present invention relates to the preparation method of ceramic medium material and gained components and parts, relate in particular to a kind of porcelain of the COG of meeting characteristic, can be in reducing atmosphere sintering, and can with high frequency low permittivity ceramic dielectric material and the preparation MLCC product of nickel inner electrode coupling, especially be fit to the making of small size MLCC.
Background technology
Along with infiltration and the expansion of electronic information technology in each technical field, chip multilayer ceramic capacitor (be called for short MLCC), it is keeping same high-level tempo with large-scale integrated circuit as the important electron element always.Current MLCC Developing Trend in Technology is miniaturization, low pressure high capacity, chip type, high pressure seriation, interior electrode base metalization. wherein particularly noticeable with the large-scale application of base metal nickel electrode MLCC.Nickel electrode MLCC has following principal feature: 1. the nickel electrode cost is low; 2. the electromigration speed of nickle atom or atomic group is little than palladium-silver atoms group, thereby has good electrochemical stability; 3. nickel electrode is to solidity to corrosion and the good heat resistance of scolder, and technology stability is good; 4. nickel electrode MLCC has the impedance frequency characteristic that less equivalent series resistance is become reconciled.The MLCC utilisation technology is developing to the field of mobile communication direction year by year fast according to statistics, and communication class product operating frequency is substantially all more than 500MHz, request signal transmission is very accurate, so high frequency MLCC product Q value is proposed higher requirement. and the Q value of MLCC is relatively low at present. and for example the Q value that records under the 0402N100J500NB0 product 100MHz is 300～500; The Q value that 0201N100J500NB0 records under 100MHz is 300～500; Difficulty satisfies service requirements.
In anti-reduction high frequency MLCC field, still to burn the material of temperature about 1300 ℃, Chinese patent application ZL02151904.8 discloses the MLCC product that a kind of anti-reduction heat is stablized ceramic medium material and reached gained both at home and abroad.The ceramic medium material of its invention comprises principal crystalline phase and ancillary component, and wherein, principal crystalline phase is Mg
aCa
bSr
cBa
1-a-b-cZr
dO
1+2d(0≤a≤1,0≤b≤1,0≤c≤1,0.8≤d≤1.2), ancillary component comprises ZnO, SiO
2, MnO
2, K
2The material of one or more among the O.The specific inductivity of MLCC product is in 20～40 scope, and frequency response characteristic and dielectric properties are good, but the burning temperature of this MLCC product is at 1250 ℃～1350 ℃, causes production cost higher.
Summary of the invention
The technical problem that the present invention need solve provides a kind of sintering temperature of the MLCC of reduction product, saves cost, that enhance competitiveness and the low temperature radio ceramics dielectric material nickel electrode coupling.
For solving the problems of the technologies described above, technical scheme provided by the invention is: a kind of low temperature radio ceramics dielectric material that mates with nickel electrode, to be formed by principal crystalline phase, property-modifying additive, sintering fusing assistant, and the principal crystalline phase structural formula is (Mg
aCa
bSr
(1-a-b))
mTi
cZr
(1-c)O
3, 0≤a≤0.15,0≤b≤1,0≤c≤0.15,0.8≤m≤1.1 wherein, property-modifying additive is MnO
2, Al
2O
3, CaO, Y
2O
3In one or more, the sintering fusing assistant is SiO
2, ZnO, Li
2O, K
2Among O, the BaO one or more.
Further: in the low temperature radio ceramics dielectric material of above-mentioned and nickel electrode coupling, by mole per-cent, principal crystalline phase is that 80～93mol%, property-modifying additive are 1.5～12mol%, sintering fusing assistant 2.5～11.4mol%.Count by molar, the composition of property-modifying additive in whole ceramic medium material is MnO
20.5～3.0mol%, Al
2O
31.0～3.0mol%, CaO 0～2.0mol%, Y
2O
30～4.0mol%.Count by molar, the composition of sintering fusing assistant in whole ceramic medium material is SiO
21.0～4.5mol%, ZnO 1.0～3.5mol%, Li
2O 0～0.8mol%, K
2O 0～0.6mol%, BaO 0.5～2.0mol%.
The present invention compared with prior art has following beneficial technical effects: provided by the invention under reducing atmosphere (the Mg of sintering
aCa
bSr
(1-a-b))
mTi
cZr
(1-c)O
3The non-ferroelectricity media ceramic of system, the ceramic material method that preparation process and those skilled in the art use always is basic identical, preferred main crystal phase material can be to have adopted quick pre-burning solid phase method technology, obtains the grain refining main crystal phase material, and principal crystalline phase is stable and high reactivity.Be about to that main crystal phase material is put into the microwave sintering kiln or the long stove of high temperature tunnel is warmed up to the high-temperature zone temperature by room temperature, soak again, cool to room temperature at last, described temperature-rise period is 3～5 hours, described insulating process is 2.5～5 hours, described room temperature is 20 ± 20 ℃, and described high-temperature zone temperature is 1100 ± 50 ℃.Compare with conventional solid-state method technology, in fast the pre-burning process time shortens 15 hours, and products obtained therefrom uniform particles, grain refining, and save energy.Certainly this dielectric material is suitable for traditional pre-sinter process too.So the low temperature radio ceramics dielectric material with the nickel electrode coupling of the present invention has resistance to reduction, can form matched well with nickel electrode, has solved the difficult problem that nickel inner electrode and stupalith burn altogether.Properties-correcting agent, sintering solubility promoter adopt not leaded (Pb), cadmium (Cd), mercury (Hg), chromium (Cr
+ 6) wait the harmful element that is unfavorable for environmental protection, make porcelain realize sintering down at 1100～1250 ℃, save production cost, better with interior electrode matching, be fit to small size MLCC production, the 0402N100J500NB0 product Q value test of producing all can reach 500～800 under 100MHZ, satisfy the requirement of communication class electronics substantially.And this low temperature radio ceramics dielectric material sintering porcelain body grain growing evenly, fine and close, inclusion-free and few defective, stablize with the element function of this material manufacturing.
Embodiment
Purport of the present invention is to adopt (Mg
aCa
bSr
(1-a-b))
mTi
cZr
(1-c)O
3System is as principal crystalline phase, adds property-modifying additive, sintering fusing assistant, obtains a kind of stupalith of the COG of meeting characteristic, has characteristics such as environmental protection, dispersion of materials height, moulding process are good, and good with the nickel inner electrode coupling, high frequency performance is stablized.And when making the MLCC product, can be implemented in 1100～1250 ℃ of sintering temperatures in the reducing atmosphere.Below in conjunction with embodiment content of the present invention is described in further detail, mentioned content is not limitation of the invention among the embodiment, and material prescription is selected to suit measures to local conditions and the result is not had substantial influence.
At first, the general planning of summary material prescription of the present invention: a kind of low temperature radio ceramics dielectric material that mates with nickel electrode, formed by principal crystalline phase, property-modifying additive, sintering fusing assistant, it is characterized in that: the principal crystalline phase structural formula is (Mg
aCa
bSr
(1-a-b))
mTi
cZr
(1-c)O
3, 0≤a≤0.15,0≤b≤1,0≤c≤0.15,0.8≤m≤1.1 wherein, property-modifying additive is MnO
2, Al
2O
3, CaO, Y
2O
3In one or more, the sintering fusing assistant is SiO
2, ZnO, Li
2O, K
2Among O, the BaO one or more.
Embodiment
A kind of low temperature radio ceramics dielectric material that mates with nickel electrode, principal crystalline phase is Mg
0.05Ca
0.6Sr
0.35Ti
0.13Zr
0.87O
3Material.Add property-modifying additive and sintering aid as shown in table 1 by predetermined proportion then.
Table 1: principal crystalline phase, property-modifying additive, sintering fusing assistant prescription are formed
Next, make the MLCC porcelain by the porcelain technological process of production that those skilled in the art use always, in the making flow process of chip MLCC, add organic binder bond and ethanol equal solvent earlier, thereby formation slurry, the slurry curtain coating is made into diaphragm, electrode in diaphragm printing nickel, the alternately laminated required number of plies forms green compact MLCC chip, then at 200～400 ℃ of heat-treated green compact MLCC chips, to get rid of organic binder bond and solvent, MLCC chip sintering 2.5～5 hours in 1100～1250 ℃ of temperature reducing atmospheres is handled through surface finish, seals up pair of outer copper Cu electrode again at the two ends of chip, outer electrode is connected with internal electrode, thermal treatment outer electrode in 700～900 ℃ of temperature ranges again through technologies such as electroplating processes, obtains the MLCC product.
This MLCC product has the advantages that capacity is stable, performance is good, when 25 ℃ of room temperatures, utilizes the HP4278 electric bridge, and at 1MHz, 1.0V (AC) is test MLCC product capacity, loss down; Utilize the SF2512 machine that insulate fast, apply the DC voltage rating 10 seconds of 100V, the test insulation resistance; Utilize high-low temperature chamber, between-55～+ 125 ℃, the test temperature coefficient of permittivity; The MLCC test parameter of 1～11 material prescription correspondence of product performance test parameter such as table 2.
Table 2: the MLCC 0402N100J500NB0 particular product performance parameters that makes according to above-mentioned ceramic medium material
Annotate: it is the wide 0.5mm of long 1.0mmx that 0402N100J500NB0 represents the MLCC product, and capacity is 10pF, operating voltage 50V.
Claims (1)
1. a low temperature radio ceramics dielectric material that mates with nickel electrode is made up of principal crystalline phase, property-modifying additive, sintering fusing assistant, and it is characterized in that: the principal crystalline phase structural formula is (Mg
aCa
bSr
(1-a-b))
mTi
cZr
(1-c)O
3, a=0.05 wherein, 0≤b≤1,0≤c≤0.15,0.8≤m≤1.1, property-modifying additive is MnO
2, Al
2O
3, CaO, Y
2O
3In one or more, the sintering fusing assistant is SiO
2, ZnO, Li
2O, K
2Among O, the BaO one or more; By mole per-cent, principal crystalline phase is that 80～93mol%, property-modifying additive are 1.5～12mol%, sintering fusing assistant 2.5～11.4mol%;
Count by molar, the composition of property-modifying additive in whole ceramic medium material is MnO
20.5～3.0mol%, Al
2O
31.0～3.0mol%, CaO 0～2.0mol%, Y
2O
30～4.0mol%;
Count by molar, the composition of sintering fusing assistant in whole ceramic medium material is SiO
21.0～4.5mol%, ZnO 1.0～3.5mol%, Li
2O 0～0.8mol%, K
2O 0～0.6mol%, BaO0.5～2.0mol%.
2
.The low temperature radio ceramics dielectric material that mates with nickel electrode according to claim 1, it is characterized in that: preferred main crystal phase material is to have adopted quick pre-burning solid phase method technology earlier, described quick pre-burning solid phase method technology is main crystal phase material to be put into the microwave sintering kiln or the long stove of high temperature tunnel is warmed up to the high-temperature zone temperature by room temperature, soak again, cool to room temperature at last, described temperature-rise period is 3～5 hours, described insulating process is 2.5～5 hours, described room temperature is 20 ± 20 ℃, and described high-temperature zone temperature is 1100 ± 50 ℃.
Priority Applications (1)
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|---|---|---|---|
| CN 201010236943 CN101913863B (en) | 2010-07-23 | 2010-07-23 | Ceramic dielectric material matched with nickel inner electrode |
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|---|---|---|---|
| CN 201010236943 CN101913863B (en) | 2010-07-23 | 2010-07-23 | Ceramic dielectric material matched with nickel inner electrode |
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| CN101913863A CN101913863A (en) | 2010-12-15 |
| CN101913863B true CN101913863B (en) | 2013-07-03 |
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|---|---|---|---|---|
| TWI648240B (en) * | 2017-10-27 | 2019-01-21 | 信昌電子陶瓷股份有限公司 | Low dielectric constant dielectric porcelain powder composition which is ultra-low temperature sintered in a reducing atmosphere and Preparation method and temperature-compensated |
| CN109516803A (en) * | 2018-11-22 | 2019-03-26 | 广东风华高新科技股份有限公司 | A kind of ultrathin membrane nickel electrode type multilayer ceramic capacitor Y5V characteristic dielectric material and preparation method thereof |
| CN112521129A (en) * | 2020-12-25 | 2021-03-19 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Low-dielectric-constant ceramic dielectric material for low-temperature sintered MLCC and preparation method thereof |
| CN114694898B (en) * | 2022-06-01 | 2022-10-14 | 西北工业大学 | Preparation method of MLCC nickel inner electrode slurry |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317459A (en) * | 2000-04-07 | 2001-10-17 | 株式会社村田制作所 | Non-reducing dielectric ceramic, and single-block ceramic capacitor using such ceramic |
| CN101343178A (en) * | 2008-08-14 | 2009-01-14 | 广东风华高新科技股份有限公司 | (ZrSnZnNb)TiO4 microwave ceramic dielectric material and preparation thereof |
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| JPH0831284B2 (en) * | 1986-11-14 | 1996-03-27 | 株式会社村田製作所 | Dielectric ceramic composition for non-reducing temperature compensation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317459A (en) * | 2000-04-07 | 2001-10-17 | 株式会社村田制作所 | Non-reducing dielectric ceramic, and single-block ceramic capacitor using such ceramic |
| CN101343178A (en) * | 2008-08-14 | 2009-01-14 | 广东风华高新科技股份有限公司 | (ZrSnZnNb)TiO4 microwave ceramic dielectric material and preparation thereof |
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