CN101333105A - X7RMLCC medium porcelain of thin medium - Google Patents
X7RMLCC medium porcelain of thin medium Download PDFInfo
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- CN101333105A CN101333105A CN 200810138110 CN200810138110A CN101333105A CN 101333105 A CN101333105 A CN 101333105A CN 200810138110 CN200810138110 CN 200810138110 CN 200810138110 A CN200810138110 A CN 200810138110A CN 101333105 A CN101333105 A CN 101333105A
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- 229910052573 porcelain Inorganic materials 0.000 title description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 23
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 53
- 239000000919 ceramic Substances 0.000 claims description 26
- 239000003985 ceramic capacitor Substances 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 229910052689 Holmium Inorganic materials 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 abstract 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
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, the BaTiO3 medium 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 BaTiO3 to have 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 the surface of BaTiO3, guarantee that porcelain has good core-shell structure, thereby make porcelain have high-k and good TCC.
For principal constituent BaTiO3, 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 MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2, require material purity 〉=99.5%, and starting material are carried out pre-treatment (except MnAc2, the MgAc2), granularity requirements is less than 0.1 μ m, ancillary component can be coated on the surface of BaTiO3 uniformly like this, form good core-shell structure, thereby obtain 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, the BaTiO3 base porcelain of particle diameter in 80nm to 180nm scope is used as the dielectric slurry, therefore, when the glass powder in joining the dielectric slurry has 1 μ m or bigger particle diameter, then be 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 BaTiO3; Ancillary component MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2 and sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K2O, B2O3, ZnO, CaO, SiO2.
The dielectric ceramic composition composition is expressed from the next:
ABaTiO3+b (MnO2 or MnAc2)+cRE2O3+d (MgO or MgAc2)+eTiO2+f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, and 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: gK2O+hB2O3+iZnO+jCaO+kSiO2, and wherein, g, h, i, j, k satisfy following relation: in mol%, g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
The median size of described composition BaTiO3 is 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 BaTiO3 is provided by the BaTiO3 powder of liquid phase method production.
Described composition MnO2, RE2O3, MgO, TiO2 require purity 〉=99.5% and carry out pre-treatment, require granularity less than 0.1 μ m; Acetate purity 〉=99.5%.
Described glass composition: gK2O+hB2O3+iZnO+jCaO+kSiO2, wherein, g, h, i, j, k satisfy following relation: in mol%, 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 BaTiO3, and ancillary component MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2 and sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K2O, B2O3, ZnO, CaO, SiO2.Described dielectric ceramic composition composition is expressed from the next: aBaTiO3+b (MnO2 or MnAc2)+cRE2O3+d (MgO or MgAc2)+eTiO2+f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, and 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: gK2O+hB2O3+iZnO+jCaO+kSiO2, and wherein, g, h, i, j, k satisfy following relation: in mol%, 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
| Numbering | ε | tanδ*10 -4 | IR*10 10 | Max|ΔC/C| (％) |
| 1 | 2870 | 81 | 10.9 | 12.5 |
| 2 | 2948 | 79 | 11.0 | 13.2 |
| 3 | 2795 | 77 | 9.2 | 12.1 |
| 4 | 3014 | 79 | 7.9 | 13.5 |
| 5 | 3107 | 72 | 8.5 | 11.3 |
| 6 | 2778 | 87 | 9.2 | 12.5 |
| 7 | 2698 | 66 | 11.0 | 11.0 |
| 8 | 2918 | 68 | 10.7 | 12.2 |
| 9 | 3008 | 75 | 9.3 | 13.2 |
| 10 | 2889 | 73 | 10.7 | 13.5 |
| 11 | 2812 | 72 | 11.0 | 11.1 |
| 12 | 2788 | 79 | 11.1 | 10.5 |
| 13 | 2952 | 81 | 11.3 | 10.8 |
| 14 | 3102 | 75 | 11.1 | 10.9 |
| 15 | 3056 | 73 | 11.1 | 12.6 |
| 16 | 2876 | 69 | 10.7 | 11.8 |
| 17 | 2862 | 67 | 8.9 | 10.9 |
| 18 | 2908 | 70 | 10.2 | 11.3 |
| 19 | 2956 | 71 | 10.8 | 11.1 |
| 20 | 2973 | 73 | 10.7 | 11.7 |
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 (10)
1, a kind of thin-medium X7R MLCC dielectric ceramic composition comprises: principal constituent BaTiO3; Ancillary component MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2 and sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K2O, B2O3, ZnO, CaO, SiO2.
2, a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1 is characterized in that the dielectric ceramic composition composition is expressed from the next:
ABaTiO3+b (MnO2 or MnAc2)+cRE2O3+d (MgO or MgAc2)+eTiO2+f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, and 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: gK2O+hB2O3+iZnO+jCaO+kSiO2, and wherein, g, h, i, j, k satisfy following relation: in mol%, g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
3, according to claim 1,2 described a kind of thin-medium X7R MLCC dielectric ceramic compositions, the median size that it is characterized in that described composition BaTiO3 is 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.
4, according to claim 1,2,3 described a kind of thin-medium X7R MLCC dielectric ceramic compositions, it is characterized in that described composition BaTiO 3 is provided by the BaTiO3 powder of liquid phase method production.
5,, it is characterized in that described composition MnO2, RE2O3, MgO, TiO2 require purity 〉=99.5% and carry out pre-treatment, require granularity less than 0.1 μ m according to claim 1,2,3,4 described a kind of thin-medium X7R MLCC dielectric ceramic compositions; Acetate purity 〉=99.5%.
6, a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1, it is characterized in that described glass composition: gK2O+hB2O3+iZnO+jCaO+kSiO2, 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.
7, a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 1, it is characterized in that 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 BaTiO3, and ancillary component MnO2 or MnAc2, RE2O3, MgO or MgAc2, TiO2 and sintering aid glass powder; RE is selected among Y, Dy, Gd, Er, Tb, the Ho at least a; Glass composition comprises K2O, B2O3, ZnO, CaO, SiO2.Described dielectric ceramic composition composition is expressed from the next: aBaTiO3+b (MnO2 or MnAc2)+cRE2O3+d (MgO or MgAc2)+eTiO2+f sintering aid, wherein, a, b, c, d, e, f satisfy following relation: in wt%, and 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: gK2O+hB2O3+iZnO+jCaO+kSiO2, and wherein, g, h, i, j, k satisfy following relation: in mol%, g+h+i+j+k=100,2≤g≤10,5≤h≤20,10≤i≤25,0≤j≤25,50≤k≤80.
8, a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 7 is characterized in that described laminated ceramic capacitor, adopts base metal Ni slurry to be electrode size, sintering temperature 1170-1230 ℃.
9, according to claim 7,8 described a kind of thin-medium X7R MLCC dielectric ceramic compositions, it 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.
10, a kind of thin-medium X7R MLCC dielectric ceramic composition according to claim 7 is characterized in that described laminated ceramic capacitor satisfies the X7R characteristic of EIA standard definition.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011029286A1 (en) * | 2009-09-10 | 2011-03-17 | 中国矿业大学(北京) | Composite sintering agent and method for preparing nano crystalline ceramics at low temperature using the same |
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| CN114999817A (en) * | 2022-06-20 | 2022-09-02 | 山东国瓷功能材料股份有限公司 | Dielectric material for thin dielectric X7R characteristic MLCC and preparation method thereof |
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| JP2800017B2 (en) * | 1989-04-05 | 1998-09-21 | 株式会社村田製作所 | Multilayer ceramic capacitors |
| JP4252665B2 (en) * | 1999-04-08 | 2009-04-08 | アイファイヤー アイピー コーポレイション | EL element |
| US6556422B2 (en) * | 2000-07-05 | 2003-04-29 | Samsung Electro-Mechanics Co., Ltd. | Dielectric ceramic composition, multi-layer ceramic capacitor using the same, and manufacturing method therefor |
| CN1971783B (en) * | 2006-12-04 | 2010-11-24 | 天津大学 | Barium titanate based metal-dielectric composite ceramic capacitor medium and its preparing method |
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2008
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| 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 |
| CN106747420A (en) * | 2016-12-27 | 2017-05-31 | 山东国瓷功能材料股份有限公司 | A kind of X5R types multilayer ceramic capacitor thin-medium material and preparation method thereof |
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| CN108329027A (en) * | 2018-02-13 | 2018-07-27 | 西北大学 | One kind having the fine grain energy-storing dielectric ceramic material and preparation method thereof of double-deck " core-shell " structure |
| 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 |
| CN114999817A (en) * | 2022-06-20 | 2022-09-02 | 山东国瓷功能材料股份有限公司 | Dielectric material for thin dielectric X7R characteristic MLCC and preparation method thereof |
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