CN101183610A - Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material - Google Patents
Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material Download PDFInfo
- Publication number
- CN101183610A CN101183610A CNA2007101781342A CN200710178134A CN101183610A CN 101183610 A CN101183610 A CN 101183610A CN A2007101781342 A CNA2007101781342 A CN A2007101781342A CN 200710178134 A CN200710178134 A CN 200710178134A CN 101183610 A CN101183610 A CN 101183610A
- Authority
- CN
- China
- Prior art keywords
- dielectric material
- base metal
- temperature
- barium titanate
- capacitor dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000010953 base metal Substances 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 239000003989 dielectric material Substances 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title claims abstract description 19
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 42
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims description 39
- 239000010410 layer Substances 0.000 claims description 32
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000004615 ingredient Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000280 densification Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007766 curtain coating Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Ceramic Capacitors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a chemical coating prepared dielectric material of base-metal electrode multilayer ceramic capacitor, belonging to the capacitor material preparing technology, which adopts the technical proposal that a plurality of barium titanate grains are coated by the doped elements through chemical coprecipitation; the main ingredient, barium titanate BaTiO3, accounts for 90mol% to 97mol% of the prescription; the amount of nanometer inhibitory coating composite oxide accounts for 3mol% to 10mol% of the total materials. The ceramic material is sintered at a reducing atmosphere controlled by a humidified gas mixture of nitrogen and hydrogen at a temperature between 950 to 1250 DEG C to get a X7R/X5R type MLCC material; wherein the dielectric constant of the material at room temperature is 2000 to 2700; the temperature coefficient of capacitance is less than or equal to positive and negative 15%; the dielectric loss at room temperature is less than or equal to 2%. The ceramic crystal grain under 200nm has low dielectric loss and good material uniformity; the multilayer ceramic capacitor produced with the ceramic crystal grain has the advantages of large capacity, ultrathin dielectric layer and the thickness less than 2um.
Description
Technical field
The invention belongs to the electronic ceramic field of capacitor material technology, particularly a kind of chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material.Be specifically related to coat manufactured is done interior electrode with base metal (for example nickel) ultra-fine brilliant temperature-stable base metal inner electrode multi-layer ceramic wafer type capacitor medium material with chemistry.
Background technology
Multilayer ceramic capacitor (Multilayer Ceramic Capacitors) is called for short MLCC.It is with ceramic body and interior electrode alternative stacked, burns as a whole altogether.MLCC is particularly suitable for the chip type surface-assembled, can improve the circuit packaging density greatly, dwindles machine volume, and this outstanding characteristic makes MLCC become consumption maximum in the world, a kind of chip type element with fastest developing speed.According to the international EIA of Electronic Industries Association (ElectronicIndustries Association) standard, X7R temperature-stable MLCC is meant that the capacitance with 25 ℃ is a benchmark, in temperature within-55 ℃ to+125 ℃ the scope, temperature coefficient of capacitance (TCC)≤± 15%, dielectric loss (DF)≤2.5%; X5R temperature-stable MLCC is meant that the capacitance with 25 ℃ is a benchmark, in temperature within-55 ℃ to+85 ℃ the scope, temperature coefficient of capacitance≤± 15%, dielectric loss (DF)≤2.5%.Temperature-stable MLCC divides two big classes by forming: a class is made up of leaded ferroelectric, and is another kind of with BaTiO
3The ferroelectric of the non-plumbous system of base is formed.And the latter is because environmentally safe, and mechanical strength and reliability be better than the former, and therefore non-lead is BaTiO
3Base temperature-stable MLCC has broad application prospects.
Based on the consideration that reduces cost, it is the important development direction of MLCC as inner electrode that development base metal such as Ni, Cu and alloy thereof replace noble metals such as Ag, Pd.But oxidation can take place in metal such as Ni, Cu sintering in air, loses the effect as interior electrode, therefore needs to use neutrality or reducing atmosphere.Be to guarantee that the barium titanate based dielectric pottery does not become semiconductor behind sintering under neutrality or the reducing atmosphere simultaneously, and enough insulation resistances and superior dielectric properties are arranged, need to add recipient elements such as Mg, Mn and regulate.At present, in Japan Patent JP-A-63-103861, ceramic material basic composition is BaTiO
3-MnO-MgO-rare earth oxide.The insulation resistance of this composition and dielectric temperature coefficient are influenced by the grain size of barium titanate major ingredient, therefore are difficult to form the dielectric property that obtain temperature stabilization by control material.In U.S. Pat-005403797A, the basic composition of ceramic material is BaTiO
3-Y
2O
3-MgO-V
2O
5This composition satisfies the X7R performance requirement substantially, and room temperature dielectric constant is more than 2500, but sintering temperature is too high, greater than 1350 ℃; The dielectric temperature coefficient is bigger, at-55 ℃ approaching-15%; Loss is bigger, substantially all is higher than 2.0%.Therefore be not suitable for large-scale production.DE-19918091A1 in Deutsche Bundespatent, the basic composition of ceramic material is BaTiO
3-MgO-MnO-V
2O
5-Al
2O
3-Ho
2O
3-BaCO
3-SrO-CaO-CoO-ZrO
2This composition satisfies the X7R performance requirement, and room temperature dielectric constant can be regulated 2000~4000, but sintering temperature is too high, and greater than 1300 ℃, the dielectric temperature coefficient is bigger, and is approaching-15%-55 ℃ or 125 ℃, is not suitable for large-scale production.In U.S. Pat-20040229746A1, ceramic material basic composition is BaTiO
3-Mn
3O
4-Y
2O
3-Ho
2O
3-CaCO
3-SiO
2-B
2O
3-Al
2O
3-MgO-CaO can carry out sintering at 1200 ℃~1300 ℃, but ceramic crystalline grain is unfavorable for the attenuate of dielectric layer greater than 500nm.
Electronic devices and components miniaturization, high performance development trend require base metal inner electrode multilayer ceramic capacitor to develop towards the direction of big capacity, superthin layer.The medium thickness in monolayer constantly reduces, and drops to 2 μ m from 5 μ m, 1 μ m even thinner.This just proposes higher requirement to the ceramic medium material crystallite dimension, and for guaranteeing the reliability of device, the ceramic crystalline grain size also will be reduced to 200 nanometers from 500 nanometers accordingly, 100 nanometers and even littler, and require the size of ceramic crystalline grain even.But, the reduction that reduces often to cause dielectric constant of crystallite dimension, in U.S. Pat-62709906B1, when the ceramic crystalline grain size was reduced to 100~200 nanometers, dielectric constant was 1600~1800, all is lower than 2000.Therefore, how more even, carry out element doping effectively, composition, structure and the sintering process of control ceramic medium material are problem to be solved by this invention to obtain ultra-fine crystalline substance, epigranular and high performance MLCC material with the requirement of satisfying big capacity, superthin layer base metal inner electrode multilayer ceramic capacitor.
Summary of the invention
The object of the present invention is to provide a kind of chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material, it is characterized in that: this material is by chemical coprecipitation the chemical coating method that doped chemical evenly is coated on the barium titanate particles surface to be prepared the ultra-fine brilliant temperature-stable base metal inner electrode multilayer ceramic capacitor dielectric material with high dielectric constant, form described barium titanate BaTiO by barium titanate major ingredient and nanometer coating layer composite oxides
3Major ingredient shared molar fraction in prescription is 90~97mol%; The consumption of described nanometer coating layer composite oxides accounts for 3~10mol% of total amount of material.
Described nanometer coating layer is formed by the oxide of following ingredients is compound:
w A+x B+yC+z D
Wherein A is expressed as CaTiO
3, CaO, BaO, SrO, more than one among the MgO;
B is expressed as MnO
2, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3In more than one;
C represents to comprise SiO
2, B
2O
3, Li
2Among the O more than one;
D represents rare earth oxide Re
2O
3, Re is more than one among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu.
W, x, y, z are that each type oxide is with respect to BaTiO
3Molar fraction, w:0.01~2mol% wherein, x:0.01~3mol%, y:0.1~6mol%, z:0~4mol%.
The step that described chemistry coats preparation nanometer coating barium titanate ceramics material is as follows:
1. be medium with barium carbonate powder with aqueous solvent, ethanol, propyl alcohol or isopropyl alcohol, ball milling 6h~48h obtains finely disseminated barium titanate suspension.
2. with the A of solubility, B, pairing metal nitrate of D type oxide or acetate are weighed in molar ratio, are dissolved in the deionized water mixed inorganic salt solution that obtains clarifying.
3. by volume, with the alkoxide of silicon: ethanol: acetic acid: deionized water=1: (1~15): (1~8): (5~40) mix, and obtain clarifying stable solution;
4. step inorganic solution and step solution 3. 2. is added drop-wise to respectively in the barium titanate suspension, wherein, step inorganic solution 2.: step solution 3.: barium titanate suspension=1~8: 1~4: 10~50 (volume ratios), strong agitation makes to mix;
5. add ammonia spirit, regulate pH value to 6~11,, make each doped chemical evenly be coated on the barium titanate particles surface by coprecipitation reaction;
6. gained suspension is dried;
7. the gained powder obtains required coating barium carbonate powder in 300 ℃~600 ℃ pre-burning 1~6h in air.
The concrete processing step of described manufacturing MLCC is as follows:
1. with above-mentioned coating barium titanate powder medium porcelain, add organic solvent, binding agent, dispersant, plasticizer, press mass ratio, dielectric ceramic composition: organic solvent: binding agent: dispersant: plasticizer=(10~60): (3~15): (1~5): (1~10): (1~3), ball milling 6~48 hours obtains casting slurry;
2. curtain coating becomes dielectric layer: medium thickness≤10 μ m;
3. with base-metal inner-electrode layer mutual superposition, produce green compact;
4. binder removal:, in the air, be incubated 20 hours at 300 ℃; If be higher than 300 ℃ of dump temperatures, then use nitrogen protection;
5. sintering under reducing atmosphere: the N that feeds 40: 1 by volume~15: 1 in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-6~ 10
-12In the scope of atm, adopt two-part sintering or normal sintering: (a) " two-part " sintering refers to that two stages are experienced in the densification of green compact, earlier at T
1Under the temperature, of short duration insulation 0~30 minute cools to T then
2Temperature continues insulation 2~10 hours, reaches complete densification, wherein T
1>T
2, i.e. 1250 ℃ 〉=T
1>T
2≤ 950 ℃; (b) normal sintering refers to that green sintering is at T
1Be that direct constant temperature was finished densification process in 2~10 hours under 1050~1250 ℃ of temperature.
6. anneal under the weak oxide condition: furnace temperature is incubated 4 hours at 800 ℃~1100 ℃, and partial pressure of oxygen is controlled at 10
-5~10
-2In the scope of atm;
7. be cooled to room temperature;
8. termination electrode technology: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 600 ℃~800 ℃, and nitrogen protection behind the natural cooling, obtains promptly that electrode is the multi-layer ceramic capacitance dielectric material of base metal in the temperature-stable.
The alkoxide of described silicon is tetraethoxysilane or butyl silicate etc.
Described organic solvent is that toluene or ethanol etc., binding agent are that polyvinyl butyral resin, dispersant are that phosphate, plasticizer are dibutyl phthalate or dioctyl phthalate.
Beneficial effect of the present invention can adopt " two-part " sintering or normal sintering for by technology of the present invention and material prescription under 950 ℃~1250 ℃ temperature, make temperature-stable (X7R/X5R type) the MLCC material of excellent performance.Its room temperature dielectric constant (wafer sample) can be controlled between 2000~2700, satisfies the X7R/X5R performance requirement, and temperature coefficient of capacitance is little, and dielectric loss is little, and has high insulation resistivity, stable performance.Crystallite dimension is less than 200nm, epigranular, and good reliability is applicable to the multilayer ceramic capacitor of producing big capacity, ultra-thin dielectric layer (medium thickness is less than 3 μ m).
Description of drawings
Fig. 1 is corresponding to the transmission electron microscope photo of the barium titanate sample of embodiment 1 coating;
Fig. 2 is corresponding to the temperature characteristics of embodiment 2 samples 1 dielectric constant
Fig. 3 is corresponding to the temperature variant curve of embodiment 2 samples, 1 rate of change of capacitance;
Fig. 4 is corresponding to the stereoscan photograph of embodiment 2 samples 1 sintering rear surface pattern.
Embodiment
The invention provides a kind of chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material.The ultra-fine brilliant temperature-stable base metal inner electrode multilayer ceramic capacitor dielectric material that the method preparation that utilizes chemistry to coat has high dielectric constant.This material is made up of barium titanate major ingredient and nanometer coating layer composite oxides, described barium titanate BaTiO
3Major ingredient shared molar fraction in prescription is 90 ~ 97mol%; The consumption of described nanometer coating layer composite oxides accounts for 3~10mol% of total amount of material.
Described nanometer coating layer is formed by the oxide of following ingredients is compound:
w A+x B+y C+z D
Wherein A is expressed as CaTiO
3, CaO, BaO, SrO, more than one among the MgO;
B is expressed as MnO
2, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3In more than one;
C represents to comprise SiO
2, B
2O
3, Li
2Among the O more than one;
D represents rare earth oxide Re
2O
3, Re is more than one among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu.
W, x, y, z are that each type oxide is with respect to BaTiO
3Molar fraction, w:0 wherein.01~2mol%,x:0.01~3mol%,y:0.1~6mol%,z:0~4mol%。
The step that described chemistry coats preparation nanometer coating barium titanate ceramics material is as follows:
1. be medium with barium carbonate powder with aqueous solvent, ethanol, propyl alcohol or isopropyl alcohol, ball milling 6h~48h obtains finely disseminated barium titanate suspension.
2. with the A of solubility, B, pairing metal nitrate of D type oxide or acetate are weighed in molar ratio, are dissolved in the deionized water mixed inorganic salt solution that obtains clarifying.
3. by volume, with tetraethoxysilane or butyl silicate: ethanol: acetic acid: deionized water=1: (1~15): (1~8): (5~40) mix, and obtain clarifying stable solution;
4. step inorganic solution and step solution 3. 2. is added drop-wise to respectively in the barium titanate suspension, wherein, step inorganic solution 2.: step solution 3.: barium titanate suspension=1~8: 1~4: 10~50 (volume ratios), strong agitation makes to mix;
5. add ammonia spirit, regulate pH value to 6~11,, make each doped chemical evenly be coated on the barium titanate particles surface by coprecipitation reaction;
6. gained suspension is dried;
7. the gained powder obtains required coating barium carbonate powder in 300 ℃~600 ℃ pre-burning 1 ~ 6h in air.
The concrete processing step of described manufacturing MLCC is as follows:
1. with above-mentioned coating barium titanate powder medium porcelain, add organic solvent, binding agent, dispersant, plasticizer, press mass ratio, dielectric ceramic composition: organic solvent: binding agent: dispersant: plasticizer=(10~60): (3~15): (1~5): (1~10): (1~3), ball milling 6~48 hours obtains casting slurry;
2. curtain coating becomes dielectric layer: medium thickness≤10 μ m;
3. with base-metal inner-electrode layer mutual superposition, produce green compact;
4. binder removal:, in the air, be incubated 20 hours at 300 ℃; If be higher than 300 ℃ of dump temperatures, then use nitrogen protection;
5. sintering under reducing atmosphere: the N that feeds 40: 1 by volume~15: 1 in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-6~ 10
-12In the scope of atm, adopt two-part sintering or normal sintering: (a) " two-part " sintering refers to that two stages are experienced in the densification of green compact, earlier at T
1Under the temperature, of short duration insulation 0~30 minute cools to T then
2Temperature continues insulation 2~10 hours, reaches complete densification, wherein T
1>T
2, i.e. 1250 ℃ 〉=T
1>T
2〉=950 ℃; (b) normal sintering refers to that green sintering is at T
1Be that direct constant temperature was finished densification process in 2~10 hours under 1050~1250 ℃ of temperature.
6. anneal under the weak oxide condition: furnace temperature is incubated 4 hours at 800 ℃~1100 ℃, and partial pressure of oxygen is controlled at 10
-5~10
-2In the scope of atm;
7. be cooled to room temperature;
8. termination electrode technology: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 600 ℃~800 ℃, and nitrogen protection behind the natural cooling, obtains promptly that electrode is the multi-layer ceramic capacitance dielectric material of base metal in the temperature-stable.
Further specify as follows below for embodiment:
Embodiment 1 coats the preparation of barium carbonate powder.With barium titanate (grain size is 120nm) is medium ball milling 12h with ethanol, according to barium titanate (BaTiO
3) with coating layer composite oxides (CL) 96: 4 and Y: Ce: Mn: Mg: Si: Ca=4: 1: 3: 12: 5: 2 (being mol ratio) took by weighing the soluble-salt and the tetraethoxysilane of corresponding weight.By chemical coating method technology of the present invention, make the barium titanate particles suspension-turbid liquid of coating, the barium carbonate powder that must coat after the oven dry.The gained powder sieves behind 500 ℃ of heat treatment 2h, obtains required dielectric material.Fig. 1 is the transmission electron microscope photo of the barium titanate particles of coating.
The barium carbonate powder that embodiment 2 is coated by chemical coating method prepared of the present invention, wherein the barium titanate grain size is respectively 120nm, 135nm, 150nm, each element mol ratio is Y: Ce: Mn: Mg: Si: Ca=3 in the composite oxides coating layer: 2: 3: 12: 4: 2.Barium titanate (BaTiO
3) with coating layer composite oxides (CL) mol ratio be 95: 5.After this porcelain is pressed into disk, at N
2/ H
2Under (30: 1) reducing atmosphere, in 1200 ℃ of sintering 2h, then under the weak oxide condition in 1050 ℃ annealing 2h.Sample surfaces is carried out electrical performance testing by last silver electrode, and the dielectric property parameter sees Table 1.What the curve of Fig. 2 provided is the characteristic curve of the dielectric constant with temperature variation of present embodiment sample 1, and Fig. 3 provides the temperature variant curve of rate of change of capacitance of sample 1.Fig. 4 is the stereoscan photograph of sample 1 at sintering rear surface pattern, ceramic crystalline grain size homogeneous, and average grain size is 150 nanometers.
Table 1
Sample number | Diameter of particle (nm) | Sintering condition | Dielectric constant (25 ℃) | Crystallite dimension (nm) | Specification |
1 | 120 | 1200℃-2h | 2222 | 150 | X7R |
2 | 135 | 1200℃-2h | 2206 | 160 | |
3 | 150 | 1200℃-2h | 2534 | 172 | X5R |
Table 2
The coating layer numbering | Composition (element mol ratio) |
CL1 | Y∶Mn∶Mg∶Si∶Ca=4∶3∶12∶4∶1 |
CL2 | Y∶Ce∶Mn∶Mg∶Si∶Ca=5∶1∶3∶10∶5∶2 |
CL3 | Dy∶Sm∶Mn∶Mg∶Si∶Ba=5∶1∶4∶12∶5∶1 |
CL4 | Dy∶Ce∶Mn∶Mg∶Si∶Ca=3∶1∶4∶11∶6∶2 |
Table 3
Sample number | Barium titanate particle diameter (nm) | Dopant | Doping ratio (BaTiO 3∶ CL,mole) | Sintering condition | Dielectric constant (25 ℃) | Crystallite dimension (nm) | Specification |
4 | 110 | CL1 | 97∶3 | 1200℃-2h | 2056 | 153 | X7R |
5 | 110 | CL2 | 96∶4 | 1170℃-3h | 2139 | 157 | X7R |
6 | 120 | CL3 | 96∶4 | 1200℃-2h | 2364 | 190 | X7R |
7 | 135 | CL1 | 94∶6 | 1200℃-2h | 2609 | 162 | X5R |
8 | 150 | CL4 | 95∶5 | 1180℃-3h | 2144 | 185 | X7R |
9 | 150 | CL2 | 97∶3 | 1230℃-2h | 2576 | 193 | X5R |
Embodiment 4 adopts chemical coating method technology of the present invention, is that the composite oxide layer of CL2~CL4 coats barium titanate with the composition, and is as shown in table 4.After the gained porcelain is pressed into disk, under reducing atmosphere, adopt " two-part " sintering, be cooled to 950 ℃~1100 ℃ insulation 2~8h rapidly after being warming up to 1200 ℃~1250 ℃, then under the weak oxide condition in 900 ℃~1000 ℃ annealing 3h.Sample surfaces is carried out electrical performance testing by last silver electrode, and the dielectric property parameter sees Table 4.
Table 4
Sample number | Barium titanate particle diameter (nm) | Dopant | Doping ratio (BaTiO 3∶ CL,mole) | Sintering condition | Dielectric constant (25 ℃) | Crystallite dimension (nm) |
|
10 | 110 | CL2 | 93∶7 | 1220℃-0min, 1080℃-4h | 2105 | 145 | X7R |
11 | 120 | CL4 | 95∶5 | 1180℃-0min, 1050℃-6h | 2231 | 169 | X7R |
12 | 135 | CL3 | 96∶4 | 1220℃-10min, 950℃-5h | 2472 | 153 | X5R |
13 | 110 | CL2 | 97∶3 | 1200℃-10min, 950℃-8h | 2368 | 141 | X7R |
The foregoing description adopts " two-part " sintering or normal sintering in 950 ℃~1250 ℃ temperature range, prepare the nanocrystalline barium titanate barium base base-metal inner-electrode MLCC porcelain that satisfied temperature stable type X7R/X5R type performance index require.The room temperature dielectric constant of MLCC (wafer sample) can be controlled at 2000~2700, and temperature coefficient of capacitance is less than ± 15%, and dielectric loss is less than 2%.Insulation resistivity is greater than 10
12Ω cm, puncture voltage is greater than 5KV/mm, and crystal grain is less than 200nm.Adopt this dielectric material can be fired into the base metal internal electrode multi-layer ceramic chip capacitor that thickness of dielectric layers is 2.5 μ m at 1200 ℃, room temperature dielectric constant reaches 3600, and temperature characterisitic satisfies the X5R standard, and average grain size is less than 200nm.This material can be applied to big capacity, superthin layer (medium thickness is less than 3 μ m) multilayer ceramic capacitor, is a kind of MLCC material with wide application prospect.
Claims (9)
1. chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material, it is characterized in that: this material is by chemical coprecipitation the chemical coating method that doped chemical evenly is coated on the barium titanate particles surface to be prepared the ultra-fine brilliant temperature-stable base metal inner electrode multilayer ceramic capacitor dielectric material with high dielectric constant, this material is made up of barium titanate major ingredient and nanometer coating layer composite oxides, described barium titanate BaTiO
3Major ingredient shared molar fraction in prescription is 90~97mol%; The consumption of described nanometer coating layer composite oxides accounts for 3~10mol% of total amount of material.
2. according to the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 1 capacitor dielectric material, it is characterized in that: described nanometer coating layer is formed by the oxide of following ingredients is compound:
w A+x B+y C+z D
Wherein A is expressed as CaTiO
3, CaO, BaO, SrO, more than one among the MgO;
B is expressed as MnO
2, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3In more than one;
C represents to comprise SiO
2, B
2O
3, Li
2Among the O more than one;
D represents rare earth oxide Re
2O
3, Re is more than one among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu;
W, x, y, z are that each type oxide is with respect to BaTiO
3Molar fraction, w:0.01~2mol% wherein, x:0.01~3mol%, y:0.1~6mol%, z:0~4mol%.
3. the method for a chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material is characterized in that: the step that described preparation nanometer coats barium carbonate powder is as follows:
1. be medium with barium carbonate powder with aqueous solvent, ethanol, propyl alcohol or isopropyl alcohol, ball milling 6h~48h obtains finely disseminated barium titanate suspension;
2. with the A of solubility, B, pairing metal nitrate of D type oxide or acetate are weighed in molar ratio, are dissolved in the deionized water mixed inorganic salt solution that obtains clarifying;
3. by volume, with the alkoxide of silicon: ethanol: acetic acid: deionized water=1: (1~15): (1~8): (5~40) mix, and obtain clarifying stable solution;
4. step inorganic solution and step solution 3. 2. is added drop-wise to respectively in the barium titanate suspension, wherein, step inorganic solution 2.: step solution 3.: barium titanate suspension=1~8: 1~4: 10~50 (volume ratios), strong agitation makes to mix;
5. add ammonia spirit, regulate pH value to 6~11,, make each doped chemical evenly be coated on the barium titanate particles surface by coprecipitation reaction;
6. gained suspension is dried;
7. the gained powder obtains required coating barium carbonate powder in 300 ℃~600 ℃ pre-burning 1~6h in air.
4. according to the method for the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 3 capacitor dielectric material, it is characterized in that: the processing step of described manufacturing multi-layer ceramic chip capacitor dielectric material is as follows:
1. with above-mentioned coating barium titanate powder medium porcelain, add organic solvent, binding agent, dispersant, plasticizer, press mass ratio, dielectric ceramic composition: organic solvent: binding agent: dispersant: plasticizer=(10~60): (3~15): (1~5): (1~10): (1~3), ball milling 6~48 hours obtains casting slurry;
2. curtain coating becomes dielectric layer: medium thickness≤10 μ m;
3. with base-metal inner-electrode layer mutual superposition, produce green compact;
4. binder removal:, in the air, be incubated 20 hours at 300 ℃; If be higher than 300 ℃ of dump temperatures, then use nitrogen protection;
5. sintering under reducing atmosphere: feed N in the sintering process
2/ H
2(40: 1~15: 1), humidification is controlled at 10 with partial pressure of oxygen simultaneously
-6~10
-12In the scope of atm, adopt two-part sintering or normal sintering: (a) " two-part " sintering refers to that two stages are experienced in the densification of green compact, earlier at T
1Under the temperature, of short duration insulation 0~30 minute cools to T then
2Temperature continues insulation 2~10 hours, reaches complete densification, wherein T
1>T
2, i.e. 1250 ℃ 〉=T
1>T
2〉=950 ℃; (b) normal sintering refers to that green sintering is at T
1Be that direct constant temperature was finished densification process in 2~10 hours under 1050~1250 ℃ of temperature;
6. anneal under the weak oxide condition: furnace temperature is incubated 4 hours at 800 ℃~1100 ℃, and partial pressure of oxygen is controlled at 10
-5~10
-2In the scope of atm;
7. be cooled to room temperature;
8. termination electrode technology: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 600 ℃~800 ℃, and nitrogen protection behind the natural cooling, obtains promptly that electrode is the multi-layer ceramic capacitance dielectric material of base metal in the temperature-stable.
5. according to the method for claim 3 a chemical coating prepared base metal internal electrode multi-layer ceramic chip formula capacitor dielectric material, it is characterized in that: the alkoxide of described silicon is tetraethoxysilane or butyl silicate.
6. according to the method for the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 4 capacitor dielectric material, it is characterized in that: described organic solvent is toluene or ethanol.
7. according to the method for the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 4 capacitor dielectric material, it is characterized in that: described binding agent is a polyvinyl butyral resin.
8. according to the method for the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 4 capacitor dielectric material, it is characterized in that: described dispersant is a phosphate.
9. according to the method for the described chemical coating prepared base metal internal electrode multi-layer ceramic chip formula of claim 4 capacitor dielectric material, it is characterized in that: described plasticizer is dibutyl phthalate or dioctyl phthalate.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2007101781342A CN101183610B (en) | 2007-11-27 | 2007-11-27 | Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material |
US12/277,994 US20090135546A1 (en) | 2007-11-27 | 2008-11-25 | Nano complex oxide doped dielectric ceramic material, preparation method thereof and multilayer ceramic capacitors made from the same |
US14/106,168 US9266781B2 (en) | 2007-11-27 | 2013-12-13 | Nano complex oxide doped dielectric ceramic material, preparation method thereof and multilayer ceramic capacitors made from the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2007101781342A CN101183610B (en) | 2007-11-27 | 2007-11-27 | Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101183610A true CN101183610A (en) | 2008-05-21 |
CN101183610B CN101183610B (en) | 2010-12-15 |
Family
ID=39448823
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2007101781342A Active CN101183610B (en) | 2007-11-27 | 2007-11-27 | Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101183610B (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101880167A (en) * | 2010-06-11 | 2010-11-10 | 清华大学 | Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system |
CN102336571A (en) * | 2010-07-28 | 2012-02-01 | 深圳振华富电子有限公司 | Manufacture method for chip ceramic element |
CN106505144A (en) * | 2016-10-17 | 2017-03-15 | 奈申(上海)智能科技有限公司 | Multilayer electric card ceramic component and preparation method thereof |
CN106966719A (en) * | 2017-04-13 | 2017-07-21 | 广东工业大学 | A kind of barium phthalate base X8R ceramic materials and preparation method thereof, ceramic capacitor |
CN110117188A (en) * | 2019-03-18 | 2019-08-13 | 武汉理工大学 | A kind of high-overpressure resistance barium titanate base composite ceramic dielectric material and preparation method thereof |
CN112919901A (en) * | 2021-02-06 | 2021-06-08 | 四川建筑职业技术学院 | Ceramic glass dielectric composite material and preparation process thereof |
CN113443910A (en) * | 2021-07-21 | 2021-09-28 | 广东工业大学 | Barium strontium titanate ceramic material matched with base metal internal electrode and preparation method thereof |
CN114188155A (en) * | 2021-12-02 | 2022-03-15 | 清华大学 | X7R/X8R dielectric powder suitable for ultrathin base metal inner electrode multilayer ceramic capacitor and preparation method thereof |
CN114255986A (en) * | 2022-01-07 | 2022-03-29 | 中国矿业大学 | Ultra-wide temperature-stable high-dielectric-constant ceramic capacitor dielectric material and preparation method thereof |
CN114758889A (en) * | 2022-03-15 | 2022-07-15 | 福建火炬电子科技股份有限公司 | High-capacity thin-layer ceramic capacitor, dielectric material 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 |
CN116206898A (en) * | 2023-03-09 | 2023-06-02 | 成都宏科电子科技有限公司 | Manufacturing method of high-voltage piece type multilayer ceramic dielectric capacitor and capacitor |
CN116462500A (en) * | 2023-04-19 | 2023-07-21 | 杭州兴容科技有限公司 | X7R characteristic thin-layer BME ceramic dielectric material and preparation method thereof |
-
2007
- 2007-11-27 CN CN2007101781342A patent/CN101183610B/en active Active
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101880167A (en) * | 2010-06-11 | 2010-11-10 | 清华大学 | Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system |
CN101880167B (en) * | 2010-06-11 | 2013-02-13 | 清华大学 | Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system |
CN102336571A (en) * | 2010-07-28 | 2012-02-01 | 深圳振华富电子有限公司 | Manufacture method for chip ceramic element |
CN106505144A (en) * | 2016-10-17 | 2017-03-15 | 奈申(上海)智能科技有限公司 | Multilayer electric card ceramic component and preparation method thereof |
CN106966719A (en) * | 2017-04-13 | 2017-07-21 | 广东工业大学 | A kind of barium phthalate base X8R ceramic materials and preparation method thereof, ceramic capacitor |
CN110117188B (en) * | 2019-03-18 | 2022-03-25 | 武汉理工大学 | Barium titanate-based composite ceramic dielectric material with high pressure resistance and preparation method thereof |
CN110117188A (en) * | 2019-03-18 | 2019-08-13 | 武汉理工大学 | A kind of high-overpressure resistance barium titanate base composite ceramic dielectric material and preparation method thereof |
CN112919901A (en) * | 2021-02-06 | 2021-06-08 | 四川建筑职业技术学院 | Ceramic glass dielectric composite material and preparation process thereof |
CN113443910A (en) * | 2021-07-21 | 2021-09-28 | 广东工业大学 | Barium strontium titanate ceramic material matched with base metal internal electrode and preparation method thereof |
CN114188155A (en) * | 2021-12-02 | 2022-03-15 | 清华大学 | X7R/X8R dielectric powder suitable for ultrathin base metal inner electrode multilayer ceramic capacitor and preparation method thereof |
CN114255986A (en) * | 2022-01-07 | 2022-03-29 | 中国矿业大学 | Ultra-wide temperature-stable high-dielectric-constant ceramic capacitor dielectric material and preparation method thereof |
CN114758889A (en) * | 2022-03-15 | 2022-07-15 | 福建火炬电子科技股份有限公司 | High-capacity thin-layer ceramic capacitor, dielectric material 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 |
CN116206898A (en) * | 2023-03-09 | 2023-06-02 | 成都宏科电子科技有限公司 | Manufacturing method of high-voltage piece type multilayer ceramic dielectric capacitor and capacitor |
CN116462500A (en) * | 2023-04-19 | 2023-07-21 | 杭州兴容科技有限公司 | X7R characteristic thin-layer BME ceramic dielectric material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN101183610B (en) | 2010-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101183610B (en) | Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material | |
CN101182201B (en) | Nano doping dielectric material for preparing base-metal inner-electrode multi-layer ceramic sheet type capacitor | |
CN101880167B (en) | Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system | |
US9266781B2 (en) | Nano complex oxide doped dielectric ceramic material, preparation method thereof and multilayer ceramic capacitors made from the same | |
CN101088960B (en) | Electronic device, dielectric ceramic composition and the production method | |
CN100508084C (en) | Thin crystal base metal internal electrode multilayer ceramic sheet type capacitor medium material | |
CN100497251C (en) | Electronic device, dielectric ceramic composition and the production method | |
CN101104558A (en) | Electronic device, dielectric ceramic composition and production method thereof | |
CN100556853C (en) | Electronic unit, dielectric ceramic composition and manufacture method thereof | |
CN103288452B (en) | Dielectric ceramic composition and electronic device | |
CN1404080A (en) | Dielectric material for thermostable laminated ceramic capacitor with basic-metal inner electrode | |
CN1983478B (en) | Electronic part, dielectric porcelain composition and producing method thereof | |
KR102608243B1 (en) | Ceramic dielectric and ceramic electronic component and device | |
KR102442888B1 (en) | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor | |
JP5146475B2 (en) | Dielectric ceramic composition and ceramic electronic component | |
KR20180027358A (en) | Multilayer ceramic capacitor and manufacturing method of multilayer ceramic capacitor | |
CN106505144A (en) | Multilayer electric card ceramic component and preparation method thereof | |
CN114188155A (en) | X7R/X8R dielectric powder suitable for ultrathin base metal inner electrode multilayer ceramic capacitor and preparation method thereof | |
CN101093749A (en) | Dielectric ceramic composition, electronic device and the production method | |
CN113582683A (en) | BaTiO for X8R MLCC3Preparation method of base ceramic material | |
JP2012028568A (en) | Multilayer semiconductor ceramic capacitor with varistor function | |
CN100570771C (en) | Electrodes in base metal medium material for multilayer ceramic capacitors and preparation method thereof | |
CN1461023A (en) | Ultrathin temperature stable type multilayer ceramic capacitor dielectric material and its sintering process | |
JP6107367B2 (en) | Multilayer electronic components | |
JP5541318B2 (en) | Dielectric ceramic composition and ceramic electronic component |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |