CN101880167B - Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system - Google Patents
Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system Download PDFInfo
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- CN101880167B CN101880167B CN 201010204502 CN201010204502A CN101880167B CN 101880167 B CN101880167 B CN 101880167B CN 201010204502 CN201010204502 CN 201010204502 CN 201010204502 A CN201010204502 A CN 201010204502A CN 101880167 B CN101880167 B CN 101880167B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000010953 base metal Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000576 coating method Methods 0.000 title abstract description 21
- 239000011248 coating agent Substances 0.000 title abstract description 15
- 239000000126 substance Substances 0.000 title abstract description 11
- 239000003990 capacitor Substances 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 66
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 50
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical group [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 48
- 238000005245 sintering Methods 0.000 claims description 45
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 31
- 239000012266 salt solution Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
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- 239000010410 layer Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002609 medium Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- -1 silicon alkoxide Chemical class 0.000 claims description 10
- 239000004902 Softening Agent Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000007766 curtain coating Methods 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
- 238000003801 milling Methods 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002612 dispersion medium Substances 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 108010064470 polyaspartate Proteins 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 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
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Abstract
The invention discloses a ceramic powder body which can be taken as a base metal inner electrode multi-layer ceramic wafer type capacitor medium material and a preparation method thereof. Doped elements are evenly coated on the surfaces of barium titanate grains by means of chemical coprecipitation; the main material of the barium titanate BaTiO3 is 90-97mol% of the ceramic powder material; and the use amount of the composite oxide of a nanometer coating later is 3-10mol% of the gross amount of the ceramic powder material. The ceramic powder material is sintered in the reducing atmosphere which is controlled by a nitrogen and hydrogen-mixed humidifying gas within the temperature range of 950-1250 DEG C to obtain an X7R/X5R type MLCC material, wherein the room temperature dielectric constant of the material is 2000-3000, the vessel temperature change rate is less than or equal to +/-15%, the vessel temperature dielectric loss is less than or equal to 2%, the crystalline grain of the ceramic is less than 2000nm, the dielectric loss is small, the evenness of the material is good, and the material is applied to manufacturing a multi-layer ceramic capacitor with large capacity and ultrathin dielectric layer (the depth of the dielectric layer is less than 3mu m).
Description
Technical field
The invention belongs to the electronic ceramics field of capacitor material technology, be specifically related to a kind of base metal internal electrode multi-layer ceramic chip capacitor and dedicated ceramic powder thereof and their preparation method.
Background technology
Laminated ceramic capacitor (Multilayer Ceramic Capacitors) is called for short MLCC.It burns ceramic body and interior electrode alternative stacked as a whole altogether.MLCC is particularly suitable for the chip type surface mount, can greatly improve the circuit packing density, dwindles machine volume, and this outstanding characteristic makes MLCC become in the world maximum, the with fastest developing speed a kind of chip type element of consumption.According to the international EIA of Electronic Industries Association USA (Electronic Industries Association) standard, X7R temperature-stable MLCC refers to take 25 ℃ capacitance as benchmark, in temperature within-55 ℃ to+125 ℃ the scope, temperature coefficient of capacitance (TCC)≤± 15%, dielectric loss (DF)≤2.5%; X5R temperature-stable MLCC refers to take 25 ℃ capacitance as benchmark, in temperature within-55 ℃ to+85 ℃ the scope, temperature coefficient of capacitance≤± 15%, dielectric loss (DF)≤2.5%.Temperature-stable MLCC is by forming minute two large classes: a class is comprised of leaded ferroelectrics, and is another kind of with BaTiO
3The ferroelectrics of the non-plumbous system of base forms.And the latter is because environmentally safe, and mechanical strength and reliability is 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, the base metals such as development Ni, Cu are the important development direction of MLCC as interior electrode (BME) material to replace the precious metals such as Ag, Pd.But oxidation can occur in the 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 semi-conductor behind sintering under neutrality or the reducing atmosphere simultaneously, and enough insulation resistances and good dielectric properties are arranged, need to add the principal elements such as Mg, Mn and regulate.In US Patent No.-005403797A, the essentially consist of stupalith is BaTiO
3-Y
2O
3-MgO-V
2O
5This composition satisfies the X7R performance requriements substantially, and room temperature dielectric constant is more than 2500, but sintering temperature is too high, greater than 1350 ℃; The dielectric temperature coefficient is larger, approaches-15% at-55 ℃; Loss is larger, substantially all is higher than 2.0%.Therefore be not suitable for scale operation.DE-19918091A1 in German Patent, the essentially consist of stupalith 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 requriements, 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 larger, approaches-15% at-55 ℃ or 125 ℃, is not suitable for scale operation.In US Patent No.-20040229746A1, stupalith 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 that greater than 500nm large capacity superthin layer BME-MLCC uses.
Electronic devices and components miniaturization, high performance development trend require base metal inner electrode multilayer ceramic capacitor (BME-MLCC) towards the future development of large 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 grain-size, and for guaranteeing device reliability, the ceramic crystalline grain size also will be reduced to 200 nanometers from 500 nanometers accordingly, 100 nanometers and even less, and require the size of ceramic crystalline grain even.But, the reduction that reduces often to cause specific inductivity of grain-size, in US Patent No.-62709906B1, when the ceramic crystalline grain size was reduced to 100～200 nanometer, specific inductivity was 1600～1800, all is lower than 2000.Therefore, how more even, carry out element doping effectively, economically, composition, microtexture and the sintering process of control ceramic medium material are problem to be solved by this invention to obtain Ultra-fine Grained, epigranular and high performance MLCC material with the requirement of satisfying large capacity, superthin layer base metal inner electrode multilayer ceramic capacitor.
Summary of the invention
The purpose of this invention is to provide a kind of ceramic powder as the base metal internal electrode multi-layer ceramic chip capacitor dielectric material.
Ceramic powder provided by the present invention is comprised of nuclear core and shell; Described nuclear core is barium carbonate powder, and described shell is the nanometer coating layer that is formed by composite oxides; The molar fraction sum of barium titanate and composite oxides counts 100% in the described ceramic powder, wherein, the molar fraction of barium titanate is 90%-98%, and the molar fraction of composite oxides (that is: the molar fraction sum of each oxide compound in the composition composite oxides) is 2%-10%;
Described composite oxides, its composition comprise following three type oxides: A, B and C;
Wherein, A is expressed as CaTiO
3, CaO, BaO, SrO, at least a among the MgO;
B is expressed as MnO
2, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3In at least a;
C is expressed as SiO
2, B
2O
3, Li
2At least a among the O;
The mol ratio of described A, B, C three type oxides is followed successively by: (0.01-2): (0.01-3): (0.1-6).
The molar fraction of barium titanate is preferably 95%-98% in above-mentioned ceramic powder, and the molar fraction of composite oxides is for being preferably 2%-5%.
Also can comprise the D type oxide in the composition of described composite oxides, certain described composite oxides also can be only by following four type oxides compound composition: A, B, C and D.
Wherein, D represents rare earth oxide Re
2O
3, Re is at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu;
The mol ratio of described A, B, C, D four type oxides can be successively: (0.01-2): (0.01-3): (0.1-6): (0-4); Be preferably (1.8-2): (0.4-1): (0.4-0.8): (0.14-0.55).
The median size of described barium carbonate powder can be 70nm-160nm.
The preparation method of ceramic powder provided by the present invention comprises the steps:
1) with barium carbonate powder take water as dispersion medium, add auxiliary dispersants, ball milling 6h-48h or sand milling 5min-1h obtain barium titanate suspension;
2) a, in described C type oxide, do not contain SiO
2The time, A, B, the corresponding soluble metallic salt of each type oxide of C are followed successively by (0.01-2) according to A, B, all kinds of corresponding metal oxide mol ratios of C: (0.01-3): (0.1-6) weighing, be dissolved in the deionized water, obtain mixed inorganic salt solution A;
B, in described C type oxide, contain SiO
2The time, will remove SiO in the corresponding soluble metallic salt of described category-A oxide compound, the corresponding soluble metallic salt of described category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound and SiO
2Corresponding silicon alkoxide is followed successively by (0.01-2) according to A, B, all kinds of corresponding metal oxide mol ratios of C: (0.01-3): (0.1-6) weighing, then will remove SiO in A, the corresponding soluble metallic salt of category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound is dissolved in the deionized water, obtains mixed inorganic salt solution B; Then with described silicon alkoxide and ethanol, acetic acid, deionized water according to volume ratio 1: (1-15): (1-8): (5-40) mix, obtain silicon sol;
3) A of mixed inorganic salt solution described in the step 2 is added drop-wise in the described barium titanate suspension of step 1, stirs, mix, get mixed solution; The mole number that makes the corresponding metal oxide of metal ion that comes from the mixed solution among the mixed inorganic salt solution A is (2-10) with the ratio of the mole number of barium titanate: (90-98);
Or the B of mixed inorganic salt solution described in the step 2 and silicon sol be added drop-wise to respectively in the described barium titanate suspension of step 1, stir, mix, get mixed solution; The mole number sum that makes the corresponding silicon-dioxide of silicon in the corresponding metal oxide of the metal ion that comes from the mixed solution among the mixed inorganic salt solution B and the silicon sol is (2-10) with the ratio of the mole number of barium titanate: (90-98);
4) in described mixed solution, add ammoniacal liquor, regulate the pH value to 6-11, carry out coprecipitation reaction, obtain the suspension that the surface coats the barium titanate particles of composite oxides;
5) with the oven dry of described suspension, and with the powder that obtains in 300 ℃ of-600 ℃ of sintering 1-6h in air, namely obtain described ceramic powder.
Above-mentioned steps 3) mole number that makes the corresponding metal oxide of metal ion among the mixed inorganic salt solution A in is preferably (2-5) with the ratio of the mole number of barium titanate: (95-98); Or the ratio of the mole number sum that makes the corresponding silicon-dioxide of silicon in the corresponding metal oxide of the metal ion that comes from the mixed solution among the mixed inorganic salt solution B and the silicon sol and the mole number of barium titanate is for being preferably (2-5): (95-98).
Step 2) also comprises the corresponding soluble metallic salt of D type oxide among the A of mixed inorganic salt solution described in and/or the described mixed inorganic salt solution B; Described D type oxide represents rare earth oxide Re
2O
3, Re is at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu;
A, B, all kinds of corresponding metal oxide mol ratios of C, D are followed successively by (0.01-2) among the described mixed inorganic salt solution A: (0.01-3): (0.1-6): (0-4);
Among the described mixed inorganic salt solution B, A, B, all kinds of corresponding metal oxide mol ratios of D are followed successively by (0.01-2): (0.01-3): (0-4).
Step 1) auxiliary dispersants described in can be at least a in ethanol, propyl alcohol, Virahol, the trimethyl carbinol, ammonium citrate, polyacrylic acid maleic anhydride, polymaleic anhydride, polyacrylic acid, Polyvinylpyrolidone (PVP), long-chain quaternary ammonium hydroxide and the poly aspartic acid; Step 2) silicon alkoxide described in specifically can be tetraethoxy or butyl silicate.
A further object of the present invention provides a kind of base metal inner electrode multilayer ceramic capacitor and preparation method thereof.
Base metal inner electrode multilayer ceramic capacitor provided by the present invention is to prepare according to the method that comprises the steps:
A) in the prepared ceramic powder of the present invention, add organic solvent, binding agent, auxiliary dispersants and softening agent, in mass ratio, ceramic powder: organic solvent: binding agent: auxiliary dispersants: softening agent=(10-60): (3-15): (1-5): (1-10): (1-3), ball milling 6-48 hour, obtain casting slurry;
B) described casting slurry curtain coating becomes dielectric layer, described medium thickness≤5 μ m;
C) mutually superpose with the base-metal inner-electrode layer, produce green compact;
D) binder removal;
E) sintering under reducing atmosphere: passing into volume ratio in the sintering process is 40: 1-15: 1 N
2And H
2Mixed gas, pass into simultaneously water vapor, oxygen partial pressure is controlled at 10
-6～10
-12In the scope of atm, adopt two-part sintering or normal sintering, obtain the sintering idiosome; The method of described two-part sintering is as follows: green compact are first at T
1Under the temperature, be incubated 0-30 minute, then cool to T
2Temperature continues insulation 2-10 hour, wherein T
1＞T
2, i.e. 1250 ℃ 〉=T
1＞T
2〉=950 ℃; The method of described normal sintering is as follows: with green compact constant temperature sintering 2-10 hour under 1050-1250 ℃ of temperature;
F) under the weak oxide condition, anneal: oxygen partial pressure is controlled at 10
-5～10
-2In the scope of atm, make described sintering idiosome 800 ℃-1100 ℃ lower insulations 2-4 hour, then be cooled to room temperature, idiosome obtains annealing;
G) end-blocking, burn end and process: with the end electrode material described annealing idiosome is carried out end-blocking, and in nitrogen atmosphere, is incubated 0.5-2 hour in 600 ℃-800 ℃, behind the naturally cooling, namely obtain base metal inner electrode multilayer ceramic capacitor.
Wherein, step a) described in binding agent specifically can be polyvinyl butyral acetal, described auxiliary dispersants specifically can be phosphoric acid ester, described softening agent specifically can be dibutyl phthalate or dioctyl phthalate (DOP), described organic solvent can be toluene or ethanol; The method of binder removal steps d) is: in 300 ℃ of insulations 20 hours, or be higher than under 300 ℃ the temperature condition insulation 10-20 hour under nitrogen protection in air; Step g) material of end electrode described in specifically can be Cu or Ag.
Beneficial effect of the present invention is: can be under 950 ℃～1250 ℃ temperature by the ceramic powder that Design and material prescription of the present invention prepares, adopt " two-part " sintering or normal sintering, make temperature-stable (X7R/X5R type) the MLCC material of excellent performance.Its room temperature dielectric constant (wafer sample) can be controlled between 2000～3000, satisfies the X7R/X5R performance requriements, and temperature coefficient of capacitance is little, and dielectric loss is little, and has high insulation resistivity, stable performance.Grain-size is less than 200nm, epigranular, and reliability is strong, and is with low cost, is applicable to produce the laminated ceramic capacitor of large capacity, ultra-thin dielectric layer (medium thickness is less than 3 μ m).
Description of drawings
Fig. 1 is the transmission electron microscope photo of barium carbonate powder of the even coating of embodiment 1 preparation;
Fig. 2 is the temperature characteristics of the specific inductivity of sample 1 among the embodiment 2;
Fig. 3 is the temperature variant curve of the rate of change of capacitance of sample 1 among the embodiment 2;
Fig. 4 is the temperature characteristics of the specific inductivity of sample among the embodiment 4;
Fig. 5 is the temperature variant curve of the rate of change of capacitance of sample among the embodiment 4;
Fig. 6 is the stereoscan photograph of sample sintering rear surface pattern among the embodiment 4.
Embodiment
The invention provides prescription and the method for evening chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material under a kind of aqueous systems.The method of utilizing chemistry to coat is prepared the Ultra-fine Grained temperature-stable base metal inner electrode multilayer ceramic capacitor dielectric materials with high dielectric constant.This material is comprised of barium titanate major ingredient and nanometer coating layer composite oxides, described barium titanate BaTiO
3Major ingredient shared molar fraction in prescription is 90-98mol%; The consumption of described nanometer coating layer composite oxides accounts for the 2-10mol% of total amount of material.
Described nanometer coating layer forms by the oxide compound of following ingredients is compound:
wA+xB+yC+zD
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.
The mol ratio of described A, B, C, D four type oxides can be successively: (0.01-2): (0.01-3): (0.1-6): (0-4); Be preferably (1.8-2): (0.4-1): (0.4-0.8): (0.14-0.55).
Preparation nanometer coating barium titanate ceramics material method is as follows among the following embodiment:
1) with barium carbonate powder take aqueous solvent as medium, add micro-auxiliary dispersants, ball milling 6h～48h, or sand milling 5min～1h obtain finely disseminated barium titanate suspension;
2) with the A of solubility, B, C, the corresponding soluble metallic salt of D type oxide (such as metal nitrate or acetate) is weighed in molar ratio, is dissolved in the deionized water mixed inorganic salt solution that obtains clarifying; If contain SiO in the C type oxide
2The time, then with SiO
2Corresponding silicon alkoxide and ethanol, acetic acid, deionized water are according to volume ratio 1: (1-15): (1-8): (5-40) mix, obtain clarifying stable silicon sol;
3) with step 2) inorganic solution be added drop-wise to violent stirring in the barium titanate suspension, it is mixed; Or with step 2) inorganic solution and step 2) silicon sol be added drop-wise to respectively violent stirring in the barium titanate suspension, it is mixed;
4) add ammonia soln, regulate pH value to 6～11, by coprecipitation reaction, it is surperficial and gained suspension dried to make each doped element evenly be coated on barium titanate particles;
5) the gained powder obtains the barium carbonate powder that required doping agent evenly coats in 400 ℃～700 ℃ pre-burning 1～6h in air.
The concrete technology step of making MLCC among the following embodiment is as follows:
1) above-mentioned coating barium titanate powder medium porcelain, add solvent, binding agent, auxiliary dispersants, softening agent, in mass ratio, dielectric ceramic composition: solvent: binding agent: auxiliary dispersants: softening agent=(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≤5 μ m;
3) mutually superpose with the base-metal inner-electrode layer, produce green compact;
4) binder removal: at 300 ℃, in the air, be incubated 20 hours; If be higher than 300 ℃ of dump temperatures, then use nitrogen protection;
5) sintering under reducing atmosphere: pass into 40: 1 by volume～15: 1 N in the sintering process
2/ H
2, humidification is controlled at 10 with oxygen partial pressure 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, first at T
1Under the temperature, then of short duration insulation 0～30 minute cools to T
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) reoxidize under the weak oxide condition: furnace temperature is incubated 2-4 hour at 800 ℃～1100 ℃, and oxygen partial pressure is controlled at 10
-5～10
-2In the scope of atm, be cooled to room temperature;
7) end electrode technique: end electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 600 ℃ ~ 800 ℃, nitrogen protection, and behind the naturally cooling, namely obtaining the interior electrode of temperature-stable is the multi-layer ceramic capacitance of base metal.
The invention will be further described below by specific embodiment, but the present invention is not limited thereto.Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent material if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, ceramic powder (namely evenly coating barium carbonate powder)
Barium carbonate powder (grain size is 120nm) take water and auxiliary dispersants as medium ball milling 12h, is obtained barium titanate suspension; According to barium titanate (BaTiO
3) and coating layer composite oxides (CL) 96: 4 and Y: Ce: Mn: Mg: Si: Ca=4: 2: 3: 12: 5: 2 (being mol ratio), take by weighing soluble salt and the tetraethoxy of corresponding weight, adopt Chemical coating method provided by the present invention, make the suspension liquid of the barium titanate particles of coating, obtain the barium carbonate powder that coats after the oven dry.The gained powder sieves behind 550 ℃ of thermal treatment 2h, obtains required ceramic powder.This ceramic powder is comprised of nuclear core and shell; Described nuclear core is barium carbonate powder, and described shell is by Y
2O
3, Ce
2O
3, MnO
2, MgO, SiO
2The formed nanometer coating layer of composite oxides with the CaO composition.Its transmission electron microscope photo is seen Fig. 1.As shown in Figure 1, doping agent evenly is coated on the barium titanate particles surface, and coating thickness is less than 10nm.
Preparation and the dielectric properties test thereof of embodiment 2, ceramic powder (namely evenly coating barium carbonate powder)
The barium carbonate powder that adopts Chemical coating method preparation of the present invention to coat (prepares 3 groups altogether, every group of 500g), wherein the grain size of selected barium carbonate powder is 150nm, and each element mol ratio is Y: Ce: Mn: Mg: Si: Ca=4 in the composite oxides coating layer: 3: 3: 12: 4: 2.Barium titanate (BaTiO
3) with coating layer composite oxides (CL) mol ratio be 95: 5.
After this ceramic powder is pressed into disk, at N
2/ H
2(30: 1, v/v) under the 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 upper silver electrode, and the dielectric properties parameter sees Table 1.Fig. 2 is the rational curve that the dielectric constant with temperature of present embodiment sample 1 changes, and the dielectric curve of sample is smooth as shown in Figure 2, and specific inductivity reaches 2200.Fig. 3 is the temperature variant curve of the rate of change of capacitance of sample 1, and the TCC curve meets the X7R characteristic as shown in Figure 3.
Table 1
| Sample number | Barium titanate particle diameter (nm) | Sintering condition | Specific inductivity (25 ℃) | Dielectric loss | Insulation resistivity (Ω cm*10 12) | Grain-size (nm) | |
| 1 | 150 | 1200℃-2h | 2153 | 0.007 | 5.6 | 168 | X7R |
| 2 | 150 | 1200℃-2h | 2102 | 0.006 | 7.2 | 171 | X7R |
| 3 | 150 | 1200℃-2h | 2112 | 0.007 | 6.7 | 174 | X7R |
Preparation and the dielectric properties test thereof of embodiment 3, ceramic powder (namely evenly coating barium carbonate powder)
Adopt the barium carbonate powder of Chemical coating method preparation coating of the present invention, choose the barium carbonate powder of initial particle average out to 80 nanometers, coat the oxide skin of different element contaminations, various coating layer compositions are as shown in table 2.Various oxide compound total contents account for 3～10mol% of total amount of material, and are as shown in table 3.
After porcelain is pressed into disk, at N
2/ H
2(35: 1, v/v) under the reducing atmosphere, in 1150～1250 ℃ of sintering 2～3h, then under the weak oxide condition in 1050 ℃ annealing 3h.Sample surfaces is carried out electrical performance testing by upper silver electrode, and the dielectric properties parameter sees Table 3.
Table 2
| The coating layer numbering | Composition (element mol ratio) |
| ac1 | Y∶Ce∶Mn∶Mg∶Si∶Ca＝4∶3∶4∶12∶5∶1 |
| ac2 | Y∶Ce∶Mn∶Mg∶Si∶Ca＝5∶0∶4∶12∶5∶2 |
| ac3 | Dy∶Sm∶Mn∶Mg∶Si∶Ba＝5∶2∶4∶12∶5∶1 |
| ac4 | Dy∶Ce∶Mn∶Mg∶Si∶Ca＝3∶1∶4∶16∶6∶2 |
Table 3
| Sample number | Barium titanate particle diameter (nm) | Doping agent | Doping ratio (BaTiO 3∶CL，mole) | Sintering condition | Specific inductivity (25 ℃) | Grain-size (nm) | |
| 4 | 80 | ac1 | 97∶3 | 1220℃-2h | 2401 | 120 | |
| 5 | 80 | ac2 | 96∶4 | 1220℃-2h | 2500 | 117 | X5R |
| 6 | 80 | ac3 | 96∶4 | 1200℃-2h | 2002 | 109 | X7R |
| 7 | 80 | ac4 | 95∶5 | 1200℃-2h | 1870 | 107 | X7R |
Preparation and the dielectric properties test thereof of embodiment 4, ceramic powder (namely evenly coating barium carbonate powder)
The barium carbonate powder that adopts Chemical coating method preparation of the present invention to coat (prepares 2 groups altogether, every group of 20kg), wherein the barium titanate grain size is 160nm, and each element mol ratio is Y: Ce: Mn: Mg: Si: Ca=4 in the composite oxides coating layer: 3: 3: 18: 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
2(30: 1, v/v) under the reducing atmosphere, in 1230 ℃ of sintering 2h, then under the weak oxide condition in 1050 ℃ annealing 2h.Sample surfaces is carried out electrical performance testing by upper silver electrode.
Fig. 4 is the rational curve that the dielectric constant with temperature of two groups of samples of present embodiment changes, and two groups of samples have identical curve as shown in Figure 4, is slightly difference of specific inductivity, in the error allowed band.Fig. 5 is the temperature variant curve of rate of change of capacitance of two groups of samples of present embodiment, and two groups of sample TCC curves meet the X7R characteristic and are consistent fully as shown in Figure 5, and illustrative experiment repeatability is very good.Fig. 6 be sample at stereoscan photograph and the grain size statistics of sintering rear surface pattern, ceramic crystalline grain size homogeneous as seen from the figure, the about 200nm of average grain size; Do not embodied good repeatability between on the same group.
Adopt the chemical coated powder of embodiment 4 preparations, through curtain coating (3.5 microns of diaphragm thickness), print electrode, lamination, sintering, the techniques such as burning end are prepared international standard 0402 dimensions, the BMEMLCC device of capacity 1 microfarad.The BMEMLCC device sintering temperature of this Chemical coating method preparation is 1200 ℃, and the medium thickness in monolayer is 2.5 μ m behind the sintering, and room temperature dielectric constant reaches 3600, and all characteristics satisfy the X7R standard, and average grain size is less than 200nm.
Above-described embodiment is in 950 ℃～1250 ℃ temperature range, even coating barium carbonate powder provided by the present invention is adopted normal sintering, namely can prepare the nanocrystalline barium titanate barium base base-metal inner-electrode MLCC porcelain that satisfied temperature stable form X7R/X5R type performance index require by lower cost.The room temperature dielectric constant of wafer sample can be controlled at 2100～3000, and temperature coefficient of capacitance is less than ± 15%, and dielectric loss is less than 2%.Insulation resistivity is greater than 10
12Ω cm, voltage breakdown is greater than 5KV/mm, and crystal grain is less than 200nm.
Adopt the dielectric material of this Chemical coating method preparation to 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 profile satisfies the X7R standard, and average grain size is less than 200nm.This material can be applied to large capacity, superthin layer (medium thickness is less than 3 μ m) laminated ceramic capacitor, is a kind of BME-MLCC material with wide application prospect.
Claims (12)
1. a ceramic powder is comprised of nuclear core and shell; Described nuclear core is barium carbonate powder, and described shell is the nanometer coating layer that is formed by composite oxides; The molar fraction sum of barium titanate and composite oxides counts 100% in the described ceramic powder, and wherein the molar fraction of barium titanate is 90%-98%, and the molar fraction of composite oxides is 2%-10%;
Described composite oxides, its composition comprise following three type oxides: A, B and C,
Wherein, A is expressed as CaTiO
3, CaO, BaO, SrO, at least a among the MgO;
B is expressed as MnO
2, Co
2O
3, Co
3O
4, Fe
2O
3, Y
2O
3In at least a;
C is expressed as SiO
2, B
2O
3, Li
2At least a among the O;
The mol ratio of described A, B, C three type oxides is followed successively by: (0.01-2): (0.01-3): (0.1-6);
The particle diameter of described barium carbonate powder is 70nm-200nm;
The preparation method of described ceramic powder comprises the steps:
1) with barium carbonate powder take water as dispersion medium, add auxiliary dispersants, ball milling 6h-48h or sand milling 5min-1h obtain barium titanate suspension;
2) a, in described C type oxide, do not contain SiO
2The time, A, B, the corresponding soluble metallic salt of each type oxide of C are followed successively by (0.01-2) according to oxide mol ratio: (0.01-3): (0.1-6) weighing, be dissolved in the deionized water, obtain mixed inorganic salt solution A;
B, in described C type oxide, contain SiO
2The time, will remove SiO in the corresponding soluble metallic salt of described category-A oxide compound, the corresponding soluble metallic salt of described category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound and SiO
2Corresponding silicon alkoxide is followed successively by (0.01-2) according to A, B, all kinds of oxide mol ratios of C: (0.01-3): (0.1-6) weighing, then will remove SiO in A, the corresponding soluble metallic salt of category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound is dissolved in the deionized water, obtains mixed inorganic salt solution B; Then with described silicon alkoxide and ethanol, acetic acid, deionized water according to volume ratio 1: (1-15): (1-8): (5-40) mix, obtain silicon sol;
3) A of mixed inorganic salt solution described in the step 2 is added drop-wise in the described barium titanate suspension of step 1, stirs, mix, get mixed solution; The mole number that makes the corresponding metal oxide of metal ion that comes from the mixed solution among the mixed inorganic salt solution A is (2-10) with the ratio of the mole number of barium titanate: (90-98);
Or the B of mixed inorganic salt solution described in the step 2 and silicon sol be added drop-wise to respectively in the described barium titanate suspension of step 1, stir, mix, get mixed solution; The mole number sum that makes the corresponding silicon-dioxide of silicon in the corresponding metal oxide of the metal ion that comes from the mixed solution among the mixed inorganic salt solution B and the silicon sol is (2-10) with the ratio of the mole number of barium titanate: (90-98);
4) in described mixed solution, add ammoniacal liquor, regulate the pH value to 6-11, carry out coprecipitation reaction, obtain the suspension that the surface coats the barium titanate particles of composite oxides;
5) with the oven dry of described suspension, and with the powder that obtains in 300 ℃ of-600 ℃ of sintering 1-6h in air, namely obtain described ceramic powder.
2. ceramic powder according to claim 1, it is characterized in that: the molar fraction of barium titanate is 95%-98% in the described ceramic powder, the molar fraction of composite oxides is 2%-5%.
3. ceramic powder according to claim 1 and 2 is characterized in that: described composite oxides are by described three type oxides compound composition: A, B and C.
4. ceramic powder according to claim 1 and 2 is characterized in that: described composite oxides are by following four type oxides compound composition: A, B, C and D;
Wherein, D represents rare earth oxide Re
2O
3, Re is at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu;
The mol ratio of described A, B, C, D four type oxides is followed successively by: (0.01-2): (0.01-3): (0.1-6): (0-4).
5. the application of arbitrary described ceramic powder in preparation base metal internal electrode multi-layer ceramic chip electrical condenser among the claim 1-4.
6. prepare the method for the described ceramic powder of claim 1, comprise the steps:
1) with barium carbonate powder take water as dispersion medium, add auxiliary dispersants, ball milling 6h-48h or sand milling 5min-1h obtain barium titanate suspension;
2) a, in described C type oxide, do not contain SiO
2The time, A, B, the corresponding soluble metallic salt of each type oxide of C are followed successively by (0.01-2) according to oxide mol ratio: (0.01-3): (0.1-6) weighing, be dissolved in the deionized water, obtain mixed inorganic salt solution A;
B, in described C type oxide, contain SiO
2The time, will remove SiO in the corresponding soluble metallic salt of described category-A oxide compound, the corresponding soluble metallic salt of described category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound and SiO
2Corresponding silicon alkoxide is followed successively by (0.01-2) according to A, B, all kinds of oxide mol ratios of C: (0.01-3): (0.1-6) weighing, then will remove SiO in A, the corresponding soluble metallic salt of category-B oxide compound and the C type oxide
2The corresponding soluble metallic salt of outer oxide compound is dissolved in the deionized water, obtains mixed inorganic salt solution B; Then with described silicon alkoxide and ethanol, acetic acid, deionized water according to volume ratio 1: (1-15): (1-8): (5-40) mix, obtain silicon sol;
3) A of mixed inorganic salt solution described in the step 2 is added drop-wise in the described barium titanate suspension of step 1, stirs, mix, get mixed solution; The mole number that makes the corresponding metal oxide of metal ion that comes from the mixed solution among the mixed inorganic salt solution A is (2-10) with the ratio of the mole number of barium titanate: (90-98);
Or the B of mixed inorganic salt solution described in the step 2 and silicon sol be added drop-wise to respectively in the described barium titanate suspension of step 1, stir, mix, get mixed solution; The mole number sum that makes the corresponding silicon-dioxide of silicon in the corresponding metal oxide of the metal ion that comes from the mixed solution among the mixed inorganic salt solution B and the silicon sol is (2-10) with the ratio of the mole number of barium titanate: (90-98);
4) in described mixed solution, add ammoniacal liquor, regulate the pH value to 6-11, carry out coprecipitation reaction, obtain the suspension that the surface coats the barium titanate particles of composite oxides;
5) with the oven dry of described suspension, and with the powder that obtains in 300 ℃ of-600 ℃ of sintering 1-6h in air, namely obtain described ceramic powder.
7. method according to claim 6 is characterized in that: step 3) in make the corresponding metal oxide of metal ion among the mixed inorganic salt solution A the ratio of mole number and the mole number of barium titanate be (2-5): (95-98); Or the ratio of the mole number sum that makes the corresponding silicon-dioxide of silicon in the corresponding metal oxide of the metal ion that comes from the mixed solution among the mixed inorganic salt solution B and the silicon sol and the mole number of barium titanate is (2-5): (95-98).
8. it is characterized in that: step 2 according to claim 6 or 7 described methods) described in also comprise the corresponding soluble metallic salt of D type oxide among mixed inorganic salt solution A and/or the described mixed inorganic salt solution B; Described D type oxide represents rare earth oxide Re
2O
3, Re is at least a among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the Lu;
A, B, all kinds of corresponding metal oxide mol ratios of C, D are followed successively by (0.01-2) among the described mixed inorganic salt solution A: (0.01-3): (0.1-6): (0-4);
Among the described mixed inorganic salt solution B, A, B, all kinds of corresponding metal oxide mol ratios of D are followed successively by (0.01-2): (0.01-3): (0-4).
9. method according to claim 8 is characterized in that: step 1) described in the particle diameter of barium carbonate powder be 70nm-200nm; Described auxiliary dispersants is at least a in ethanol, propyl alcohol, Virahol, the trimethyl carbinol, ammonium citrate, polyacrylic acid maleic anhydride, polymaleic anhydride, polyacrylic acid, Polyvinylpyrolidone (PVP), long-chain quaternary ammonium hydroxide and the poly aspartic acid; Step 2) silicon alkoxide described in is tetraethoxy or butyl silicate.
10. prepare the method for base metal inner electrode multilayer ceramic capacitor, comprise the steps:
A) in the claim 1-4 in arbitrary described ceramic powder, add organic solvent, binding agent, auxiliary dispersants and softening agent, in mass ratio, ceramic powder: organic solvent: binding agent: auxiliary dispersants: softening agent=(10-60): (3-15): (1-5): (1-10): (1-3), ball milling 6-48 hour, obtain casting slurry;
B) described casting slurry curtain coating becomes dielectric layer, described medium thickness≤5 μ m;
C) mutually superpose with the base-metal inner-electrode layer, produce green compact;
D) binder removal;
E) sintering under reducing atmosphere: passing into volume ratio in the sintering process is 40: 1-15: 1 N2 and the mixed gas of H2, pass into simultaneously water vapor, and oxygen partial pressure is controlled at 10
-6～10
-12In the scope of atm, adopt two-part sintering or normal sintering, obtain sintered body; The method of described two-part sintering is as follows: green compact are first at T
1Under the temperature, be incubated 0-30 minute, then cool to the T2 temperature and continue insulation 2-10 hour, wherein T
1＞T
2, that is, and 1250 ℃ 〉=T
1＞T
2〉=950 ℃; The method of described normal sintering is as follows: with green compact constant temperature sintering 2-10 hour under 1050-1250 ℃ of temperature;
F) under the weak oxide condition, anneal: oxygen partial pressure is controlled at 10
-5～10
-2In the scope of atm, make described sintered body 800 ℃-1100 ℃ lower insulations 2-4 hour, then be cooled to room temperature, base substrate obtains annealing;
G) end-blocking, burn end and process: with the end electrode material described annealing base substrate is carried out end-blocking, and in nitrogen atmosphere, is incubated 0.5-2 hour in 600 ℃-800 ℃, behind the naturally cooling, namely obtain base metal inner electrode multilayer ceramic capacitor.
11. method according to claim 10 is characterized in that: step a) described in binding agent be polyvinyl butyral acetal, described auxiliary dispersants is phosphoric acid ester, described softening agent is dibutyl phthalate or dioctyl phthalate (DOP); The method of binder removal steps d) is: in 300 ℃ of insulations 20 hours, or be higher than under 300 ℃ the temperature condition insulation 10-20 hour under nitrogen protection in air; Step g) material of end electrode described in is Cu or Ag.
12. the base metal inner electrode multilayer ceramic capacitor that claim 10 or 11 described methods prepare.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1461022A (en) * | 2003-06-27 | 2003-12-10 | 清华大学 | Basic metal electrode multilayer cermaic capcitor medium material and its preparation method |
| CN1854105A (en) * | 2004-12-31 | 2006-11-01 | 电子科技大学 | Nanometer ceramic-material doping agent, ceramic capacitor media material and production thereof |
| CN101183610A (en) * | 2007-11-27 | 2008-05-21 | 清华大学 | Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material |
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