CN101333105B - X7RMLCC medium porcelain of thin medium - Google Patents
X7RMLCC medium porcelain of thin medium Download PDFInfo
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- CN101333105B CN101333105B CN 200810138110 CN200810138110A CN101333105B CN 101333105 B CN101333105 B CN 101333105B CN 200810138110 CN200810138110 CN 200810138110 CN 200810138110 A CN200810138110 A CN 200810138110A CN 101333105 B CN101333105 B CN 101333105B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
Abstract
The invention discloses a thin medium X7R MLCC medium ceramic material, comprising the main ingredient BaTiO3; the auxiliary components MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2 and sintering additive glass powder; the RE can be at least one of the Y, Dy, Gd, Er, Tb and Ho; the glass composite comprises K2O, B2O3, ZnO, CaO and SiO2.
Description
Affiliated technical field
The present invention relates to a kind of is the MLCC dielectric ceramic composition and preparation method thereof of base with the barium titanate.
Background technology
Current, along with the fast development to aspects such as miniaturization, high-performance of electrical equipment and electronics, employed laminated ceramic capacitor also faces smaller szie and more jumbo requirement in these equipment.In order to realize smaller szie and large vol more, the thickness of dielectric layers of such laminated ceramic capacitor thins down, and simultaneously stacked quantity is also more and more.At present, BaTiO
3Medium layer reaches more than 300 layers, and its thickness is 3 μ m or littler, so that obtain to have the electrical condenser of ultra-high capacity.In order to produce such laminated ceramic capacitor with ultra-high capacity, key is to make this medium layer thin as far as possible, this just requires the granularity of dielectric ceramic composition thinner, median size can not surpass 0.2 μ m, dielectric ceramic composition for barium phthalate base, it is 0.08～0.18 μ m that its median size requires, preferred 0.1～0.15 μ m.When medium layer became thinner, microtexture had determined dielectric property and reliability.This just requires principal constituent BaTiO
3Have high-crystallinity, regular, the single dispersion of granule-morphology, high purity; While principal constituent and ancillary component not only grain diameter will mate but also want blended very even, make it to be coated on uniformly BaTiO
3The surface, guarantee that porcelain has good core-shell structure, thereby make porcelain have high-k and good TCC.
For principal constituent BaTiO
3, adopt liquid phase method to produce; The barium titanate of liquid phase method production has: single dispersion, fine ceramics, chemical homogeneity are good, high purity, high-crystallinity; Be more suitable in the laminated ceramic capacitor of producing below the thickness of dielectric layers 3 μ m.
For ancillary component MnO
2Or MnAc
2, RE
2O
3, MgO or MgAc
2, TiO
2, require material purity 〉=99.5%, and starting material carried out pre-treatment (MnAc
2, MgAc
2Except), granularity requirements is less than 0.1 μ m, and ancillary component can be coated on the surface of BaTiO3 uniformly like this, forms good core-shell structure, thereby obtains excellent dielectric properties.
Sintering aid glass powder is made up of above-mentioned glass composition, and is the ultrafine powder of particle diameter between 80nm to 200nm.In order to form thickness is 3 μ m or littler film dielectric layer, with the BaTiO of particle diameter in 80nm to 180nm scope
3The base porcelain is as the dielectric slurry, therefore, when the glass powder in joining the dielectric slurry has 1 μ m or bigger particle diameter, then is difficult to evenly make the following thin dielectric layer of thickness 3 μ m; Can reduce simultaneously the sintering temperature of laminated ceramic capacitor.
The concrete implication of the X7R of EIA standard definition is: X represents the low temperature limit-55 ℃ of operation temperature area, 7 represent high temperature limit+125 ℃ of operation temperature area, and the velocity of variation of the electrical capacity of R representative all temperature spots (55 ℃～+ 125 ℃ scope in) in operation temperature area during with respect to 25 ℃ of room temperatures be less than or equal to ± and 15%.
Summary of the invention
The invention provides a kind of is the MLCC dielectric ceramic composition and preparation method thereof of base with the barium titanate.
The technical solution adopted for the present invention to solve the technical problems is: a kind of thin-medium X7R MLCC dielectric ceramic composition comprises: principal constituent BaTiO
3Ancillary component MnO
2Or MnAc
2, RE
2O
3, MgO or MgAc
2, TiO
2With sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K
2O, B
2O
3, ZnO, CaO, SiO
2
The dielectric ceramic composition composition is expressed from the next:
ABaTiO
3+ b (MnO
2Or MnAc
2)+cRE
2O
3+ d (MgO or MgAc
2)+eTiO
2+ f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, a=100,0.02≤b≤2.0,0≤c≤5.0,0.05≤d≤2.0,0.05≤e≤1.0,0.1≤f≤2.0, and b+c+d+e+f≤2.0,0.995≤Ba/Ti≤1.03; Glass composition is expressed from the next: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
Described composition BaTiO
3Median size be 0.08～0.18 μ m, preferred 0.1～0.15 μ m; Its foreign matter content requires: Na≤10ppm, K≤10ppm, Sr≤200ppm, Fe≤20ppm.
Described composition BaTiO
3BaTiO by liquid phase method production
3Powder provides.
Described composition MnO
2, RE
2O
3, MgO, TiO
2Require purity 〉=99.5% and carry out pre-treatment, require granularity less than 0.1 μ m; Acetate purity 〉=99.5%.
Described glass composition: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80; This glass powder is the ultrafine powder of particle diameter between 80nm to 200nm.
A kind of laminated ceramic capacitor, comprise have medium layer and with the medium layer alternative in the capacitor body of electrode, wherein, described medium layer is a kind of dielectric ceramic composition composition, it contains principal constituent BaTiO
3, and ancillary component MnO
2Or MnAc
2, RE
2O
3, MgO or MgAc
2, TiO
2With sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K
2O, B
2O
3, ZnO, CaO, SiO
2Described dielectric ceramic composition composition is expressed from the next: aBaTiO
3+ b (MnO
2Or MnAc
2)+cRE
2O
3+ d (MgO or MgAc
2)+eTiO
2+ f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, a=100,0.02≤b≤2.0,0≤c≤5.0,0.05≤d≤2.0,0.05≤e≤1.0,0.1≤f≤2.0, and b+c+d+e+f≤2.0,0.995≤Ba/Ti≤1.03; Glass composition is expressed from the next: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
Described laminated ceramic capacitor adopts base metal Ni slurry to be electrode size, 1170～1230 ℃ of sintering temperatures.
Every layer of described medium layer of described laminated ceramic capacitor has the thickness of 1.0～2.0 μ m.
Described laminated ceramic capacitor satisfies the X7R characteristic of EIA standard definition.
Embodiment
A kind of thin-medium X7R MLCC dielectric ceramic composition, it presses BaTiO
3Weight be 100, MnO
2Or MnAc
2Be 0.02～2.0, RE
2O
3Be 0～5.0, MgO or MgAc
2Be 0.05～2.0, TiO
2Be 0.05～1.0, sintering aid is 0.1～2.0, and (MnO
2Or MnAc
2)+RE
2O
3+ (MgO or MgAc
2)+TiO
2+ sintering aid≤2.0,0.995≤Ba/Ti≤1.03.
The preparation method of above-mentioned dielectric ceramic composition, undertaken by following step:
(1) according to the composition of glass powder in the table 1, the corresponding component of weighing joins in zirconium white mill Jie's the ball grinder, add deionized water (material: water=1: 1.2-1.3) mix, ball milling 4 hours, dry, sieve (60 orders or 80 orders), vitrifying (sintering temperature is at 1400 ℃～1500 ℃), aftertreatment;
(2) according to weight percent, with principal constituent, ancillary component (form of slurry) and deionized water (material: water=1: 1.1-1.2) join in the ball grinder that zirconium white mill Jie is housed ball milling 3 hours;
(3) ball milling is good slurry filter, dry, sieve (60 orders or 80 orders);
(4) powder after will sieving is calcined (700 ± 10 ℃);
(5) powder after will calcining joins in the ball grinder that the zirconium white mill is situated between, add deionized water (material: water=1: 1.1-1.2), ball milling 2 hours;
(6) ball milling is good slurry filter, dry, sieve (60 orders or 80 orders);
The glass composition composition sees Table 1:
Table 1
The dielectric ceramic composition composition sees Table 2:
Table 2
Sample is made as follows:
Prepare burden → disperse → filter → dry → sieve → calcine → disperse → filter → dry → sieve → disperse → curtain coating → silk-screen → lamination → lamination → cutting → binder removal → sintering → chamfering → end-blocking → burning end → test
The MLCC sample medium thickness 1.5 μ m that make, the medium number of plies 300, specification 0402
The dielectric properties of sample are tests like this:
By under the condition of 1KHz and 1V, utilizing electric bridge 4278A to measure electric capacity and loss, calculate specific inductivity according to capacity meter then; Utilize insulation resistance instrument TH2683 test insulation resistance IR under the condition of 100V, the test duration is 10s; In-55 ℃ to+125 ℃ scope, utilize temperature profile coefficient (TCC) proofing box to measure the electric capacity of each temperature spot, be that benchmark is according to formula (Δ C/C with 25 ℃ electric capacity
25) calculate changes in capacitance rate under each temperature.
Respectively get 3 on the green compact of one group of different ingredients, sintering, insulation 2h under same burning temperature, dielectric properties are tested in 2 of selections from three, get its mean value, the results are shown in following table 3.
The test result of table 3 ceramic capacitor dielectric sample of the present invention
Annotate:
ε is a specific inductivity
Tan δ is a loss tangent
IR is an insulation resistance
Δ C/C is a rate of temperature change.
Claims (9)
1. a thin-medium X7R MLCC dielectric ceramic composition comprises: principal constituent BaTiO
3Ancillary component MnO
2Or MnAc
2, RE
2O
3, MgO or MgAc
2, TiO
2With sintering aid glass powder, described composition BaTiO
3Median size be 0.08～0.18 μ m, described composition MnO
2, RE
2O
3, MgO, TiO
2Require granularity less than 0.1 μ m, glass powder is the ultrafine powder of particle diameter between 80nm to 200nm; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass powder comprises K
2O, B
2O
3, ZnO, CaO, SiO
2The dielectric ceramic composition composition is expressed from the next:
ABaTiO
3+ b (MnO
2Or MnAc
2)+cRE
2O
3+ d (MgO or MgAc
2)+eTiO
2+ f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, a=100,0.02≤b≤2.0,0≤c≤5.0,0.05≤d≤2.0,0.05≤e≤1.0,0.1≤f≤2.0, and b+c+d+e+f≤2.0,0.995≤Ba/Ti≤1.03; Glass powder is expressed from the next: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
2. a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1 is characterized in that its foreign matter content requirement: Na≤10ppm, K≤10ppm, Sr≤200ppm, Fe≤20ppm.
3. a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1 is characterized in that described composition BaTiO
3BaTiO by liquid phase method production
3Powder provides.
4. a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1 is characterized in that described composition MnO
2, RE
2O
3, MgO, TiO
2Require purity 〉=99.5% and carry out pre-treatment, require granularity less than 0.1 μ m; Acetate purity 〉=99.5%.
5. a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1 is characterized in that described glass powder: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
6. laminated ceramic capacitor, comprise have medium layer and with the medium layer alternative in the capacitor body of electrode, wherein, the medium layer material is a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1, it contains principal constituent BaTiO
3, and ancillary component MnO
2Or MnAc
2, RE
2O
3, MgO or MgAc
2, TiO
2With sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K
2O, B
2O
3, ZnO, CaO, SiO
2Described dielectric ceramic composition composition is expressed from the next: aBaTiO
3+ b (MnO
2Or MnAc
2)+cRE
2O
3+ d (MgO or MgAc
2)+eTiO
2+ f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, a=100,0.02≤b≤2.0,0≤c≤5.0,0.05≤d≤2.0,0.05≤e≤1.0,0.1≤f≤2.0, and b+c+d+e+f≤2.0,0.995≤Ba/Ti≤1.03; Glass composition is expressed from the next: gK
2O+hB
2O
3+ iZnO+jCaO+kSiO
2, wherein, g, h, i, j, k satisfy following relation: in mol%, and g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
7. a kind of laminated ceramic capacitor according to claim 6 is characterized in that described laminated ceramic capacitor, adopts base metal Ni slurry to be electrode size, sintering temperature 1170-1230 ℃.
8. a kind of laminated ceramic capacitor according to claim 6 is characterized in that every layer of described medium layer of described laminated ceramic capacitor has the thickness of 1.0～2.0 μ m.
9. a kind of laminated ceramic capacitor according to claim 6 is characterized in that described laminated ceramic capacitor satisfies the X7R characteristic of EIA standard definition.
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|---|---|---|---|---|
| CN101654366B (en) * | 2009-09-10 | 2012-10-24 | 中国矿业大学(北京) | Composite sintering agent and method for preparing nano crystalline ceramics at low temperature |
| CN102020465A (en) * | 2010-11-04 | 2011-04-20 | 仙桃市中星电子材料有限公司 | Multilayered ceramic capacitor medium ceramic material with reducing resistance |
| CN106747420B (en) * | 2016-12-27 | 2020-01-07 | 山东国瓷功能材料股份有限公司 | Thin dielectric material for X5R type multilayer ceramic capacitor and preparation method thereof |
| CN108329027B (en) * | 2018-02-13 | 2020-10-27 | 西北大学 | Fine-grain energy storage medium ceramic material with double-layer core-shell structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117326A (en) * | 1989-04-05 | 1992-05-26 | Murata Manufacturing Co., Ltd. | Monolithic ceramic capacitor |
| CN1300522A (en) * | 1999-04-08 | 2001-06-20 | Tdk株式会社 | El element |
| CN1332131A (en) * | 2000-07-05 | 2002-01-23 | 三星电机株式会社 | Dielectric ceramic composition, ceramic capacitor using the same and manufacture thereof |
| CN1971783A (en) * | 2006-12-04 | 2007-05-30 | 天津大学 | Barium titanate based metal-dielectric composite ceramic capacitor medium and its preparing method |
-
2008
- 2008-07-01 CN CN 200810138110 patent/CN101333105B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117326A (en) * | 1989-04-05 | 1992-05-26 | Murata Manufacturing Co., Ltd. | Monolithic ceramic capacitor |
| CN1300522A (en) * | 1999-04-08 | 2001-06-20 | Tdk株式会社 | El element |
| CN1332131A (en) * | 2000-07-05 | 2002-01-23 | 三星电机株式会社 | Dielectric ceramic composition, ceramic capacitor using the same and manufacture thereof |
| CN1971783A (en) * | 2006-12-04 | 2007-05-30 | 天津大学 | Barium titanate based metal-dielectric composite ceramic capacitor medium and its preparing method |
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| CB03 | Change of inventor or designer information |
Inventor after: Si Liuqi Inventor after: Zhang Bing Inventor after: Zhang Xi Inventor before: Zhang Bing Inventor before: Chen Shichun Inventor before: Zhang Peng Inventor before: Ying Hong Inventor before: Wu Suwen |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG BING CHEN SHICHUN ZHANG PENG YING HONG WU SUWEN TO: SI LIUQI ZHANG BING ZHANG XI |
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Effective date of registration: 20180328 Address after: Wulian Industrial Road Fenggang Town Industrial Park in Dexing city of Dongguan province Guangdong 523696 Building 1 room B Patentee after: Dongguan sinocera Shu Pu electronic technology limited company Address before: 257091 the middle of the galaxy, Dongying high tech Zone, Shandong Province Patentee before: Shandong Sinocera Functional Material Co., Ltd. |