CN1258783C - High-dielectric constant and reduction resistant dielectric material for capacitor with basic-metal electrode - Google Patents
High-dielectric constant and reduction resistant dielectric material for capacitor with basic-metal electrode Download PDFInfo
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- CN1258783C CN1258783C CN 02146520 CN02146520A CN1258783C CN 1258783 C CN1258783 C CN 1258783C CN 02146520 CN02146520 CN 02146520 CN 02146520 A CN02146520 A CN 02146520A CN 1258783 C CN1258783 C CN 1258783C
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Abstract
The present invention discloses a high-dielectric constant and reduction resistant dielectric material for a capacitor with a base metal electrode, which belongs to the preparing technical field of a capacitor material. Main components of the material comprise a solid solution Bax (ZrySnzTi1-y-z) O3 of BaTiO3, BaZrO3 and BaSnO3, and a ceramic material composed of a secondary additive and more than one rare earth oxide, the main components can be sintered in two steps in a temperature range of 1000 DEG C to 1350 DEG C and under reducing atmosphere, and the Y5V high-dielectric constant and reduction resistant dielectric material for a capacitor with a base metal electrode is formed, which has good dielectric property and microstructure. The material has a room temperature dielectric constant of 8000 to 15000, a capacitance temperature variance ratio of-82 % to +22%, room temperature dielectric loss not more than 2.5%, alternating current breakdown field strength higher than 4.5 kv/mm, and a ceramic grain size of 500 to 2500mm. The ceramic material and a base metal together can be fired into a monolith capacitor. The present invention is suitable for manufacturing an MLCC material which has the advantages of the large capacity of a base metal electrode and extensive use foreground.
Description
Technical field
The invention belongs to field of capacitor material technology, the particularly a kind of high dielectric of electrodes in base metal, anti-reduction capacitor dielectric material of being used for.
Background technology
Develop rapidly along with electronics industry, miniaturization and lightness become the development trend of each electronic product such as digital camera, mobile phone, notebook computer, palmtop PC etc., these components and parts that require to constitute these electronic equipments must reduce volume and weight, and can adapt to the needs of surface mounting technology (SMD).The components and parts that surface mounting technology requires are chip components and parts, and multilayer ceramic capacitor, multi-layer ceramics inductor and plate resistor are most widely used three major types passive components in the chip component.Multilayer ceramic capacitor (MultilayerCeramic Capacitors) is called for short MLCC, it is that multilayer inner electrode and ceramic body are superimposed, burn till an only stone body altogether, and at the only two ends coating external electrode of stone body, connect with the interior electrode electricity that alternately exposes respectively and form.According to the international EIA of Electronic Industries Association (Electronic Industries Association) standard, Y5V type MLCC is meant that the capacitance with 25 ℃ is a benchmark, within-30 ℃ to+85 ℃ the scope, temperature coefficient of capacitance is between+22%～-82% in temperature, dielectric loss (DF)≤2.5%.Y5V type MLCC divides two big classes by forming: a class is made up of leaded ferroelectric, and is another kind of with BaTiO
3Solid solution be that the non-lead of base material is that ferroelectric is formed.Wherein the latter is because environmental pollution is little, and mechanical strength, ageing resistace, platability and reliability be better than the former, and therefore non-lead is that Y5V type MLCC has broad application prospects.
With lead is that ferroelectric ceramic is compared, barium titanate and solid-solution material thereof need higher temperature sintering (1100 ℃～1350 ℃), therefore the multilayer ceramic capacitor formed of such material is in air during sintering, needs to use noble metal (metal such as Pt, Au, Pd, Ag and alloy thereof etc.) as interior electrode.These noble metal fancy prices have improved the production cost of MLCC greatly, and utilizing cheap metal material to replace noble metal becomes the important channel that reduces the MLCC cost as inner electrode.Base-metal inner-electrode material commonly used comprises Ni, Fe, Co, Cu and their alloy, when sintering in air, interior electrode base metal among the MLCC can be by airborne dioxygen oxidation, generate the not oxide of easy conductive, lose effect, so the sintering of base-metal inner-electrode MLCC must use neutrality or reducing atmosphere as interior electrode.Simultaneously be semiconductor in order to guarantee that the barium titanate based dielectric pottery is not reduced into during sintering under neutrality or reducing atmosphere, and there are enough insulation property and higher resistance to wear characteristic, the sintering of base-metal inner-electrode MLCC generally adopts the two-part sintering, promptly earlier in 1100 ℃～1350 ℃ higher temperature ranges, carry out sintering, obtain fine and close only stone body, the partial pressure of oxygen of sintering atmosphere is between 10
-6～10
-12Pa under 1000 ℃～1100 ℃ temperature, has 10 then
-3～10
-8Anneal in the atmosphere of Pa partial pressure of oxygen,, guarantee the reliability of MLCC to improve the insulation resistance and the breakdown characteristics of pottery.Atmosphere in the sintering process is generally by nitrogen, hydrogen and water vapour, and perhaps nitrogen, carbon monoxide and carbon dioxide are formed, and obtains sintering atmosphere and annealing atmosphere with specific partial pressure of oxygen by the component of adjusting mist.At present, in U.S. Pat 5361187, the Y5V media ceramic adopts (Ba
1-xCa
x) (Ti
1-y-zSn
yZr
z) O
3Based solid solution is a major ingredient, has obtained higher room temperature dielectric constant (8000～19000), but can only be in air sintering, limited the application of such material in base-metal inner-electrode MLCC.U.S. Pat 6078494 adopts the (Ba of modification
xCa
y) (Ti
zZr
w) O
3The perovskite ferroelectric ceramic has obtained Y5V type Gao Jie (〉=20000) pottery of anti-reduction, but its composition is very complicated, the process conditions harshness, and the crystallite dimension of pottery big (3～5 μ m), the room temperature dielectric loss is bigger, is not suitable for being used in the high-performance multilayer ceramic capacitor that manufacturing single-layer medium thickness is lower than 10 μ m.
Summary of the invention
It is easy to the purpose of this invention is to provide preparation technology, it is simply adjustable to fill a prescription, sintering condition is easily controlled, a kind of high dielectric of electrodes in base metal, anti-reduction capacitor dielectric material of being used for that dielectric property are good, this material is made up of major ingredient solid solution and secondary additive, it is characterized in that: described major ingredient solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3By barium titanate BaTiO
3With barium zirconate BaZrO
3And barium stannate BaSnO
3Form, 0.995≤x≤1.01,0.10≤y≤0.20,0≤z≤0.10 wherein, shared molal quantity is 96～98mol% in prescription; The consumption of described secondary additive accounts for 2～4mol% of total amount of material, comprises CaO, TiO
2, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide M
2O
3, or the presoma of secondary additive; Described each material in the proportioning of mole is: CaO:0.3～1.0mol%; TiO
2: 0.1～0.5mol%; SiO
2: 0～0.5mol%; Li
2O:0.2～1.5mol%; MnO
2: 0.4～1.4mol%; ZnO:0.8～2.5mol%; Re
2O
3: 0.2～1.2mol%.
The particle size of the composition material of described major ingredient solid solution requires less than 1000nm; The powdery granule dimensional requirement of described secondary additive is less than 600nm; The presoma of secondary additive requires to mix the dry deposition in back in the mode of solution, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling in addition.
The presoma of described secondary additive comprises carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide: four butanols titaniums or calcium ethoxide or ethanol zinc.
Described rare earth oxide M
2O
3Middle M representative: La-lanthanum, Ce-cerium, Pr-praseodymium, Nd-neodymium, Sm-samarium, Eu-europium, Gd-gadolinium, Tb-terbium, Dy-dysprosium, Ho-holmium, Er-erbium, Tm-thulium, Yb-ytterbium, Lu-lutetium, and Y-yttrium.
The concrete processing step of making multilayer ceramic capacitor-MLCC is as follows:
(1) pulverous brium carbonate, zirconium dioxide, tin ash and titanium dioxide being mixed mutually, is medium with water, and zirconia ball is situated between for mill, and ball milling is 24 hours in the nylon jar;
(2) with the said mixture of oven dry in 1100 ℃＜T≤1200 ℃, 10
-7～1.2 * 10
-12The low oxygen that divides is depressed calcining, synthetic solid solution major ingredient with perovskite structure;
(3) presoma of described secondary additive requires to mix the dry deposition in back in the mode of solution, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling in addition.
(4) pulverizing of solid solution major ingredient: with water is medium, and zirconia ball is situated between for mill, and ball milling is 48 hours in the nylon jar, obtains the major ingredient powder of particle size less than 1000nm;
(5) above-mentioned solid solution powder is mixed mutually with the secondary additive, add suitable organic solvent n-propyl acetate, binding agent polyvinyl butyral resin, plasticizer dioctyl phthalate, dispersant ammonium polyacrylate, with zirconia ball is mill ball milling 48 hours that are situated between in the nylon jar, obtains casting slurry;
(6) become dielectric layer with above-mentioned casting slurry curtain coating: medium thickness is 10 μ m or below the 10 μ m;
(7) printing base-metal inner-electrode layer on above-mentioned dielectric layer, the curtain coating dielectric layer mutual superposition of electrode is cut after the hot pressing in will being printed on again, forms the MLCC green compact;
(8) binder removal: in 300 ℃～340 ℃ temperature range, insulation is 20 hours in air, gets rid of the organic substance in the MLCC green compact, and the programming rate of binder removal process is not higher than 10 ℃/h;
(9) sintering under reducing atmosphere: feed N in the sintering process
2/ H
2/ H
2The mist of O is controlled at 10 with partial pressure of oxygen
-6～10
-12In the scope of Pa, Control for Kiln Temperature is in 1100 ℃＜T＜1350 ℃;
(10) anneal under the weak oxide condition: furnace temperature is incubated 2～4 hours in 1000 ℃＜T＜1100 ℃, and partial pressure of oxygen is controlled at 10
-3～10
-8In the scope of Pa;
(11) coating termination electrode: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 700 ℃～850 ℃, and nitrogen protection behind the natural cooling, promptly obtains Y5V type base metal inner electrode multilayer ceramic capacitor.
Beneficial effect of the present invention is for by material prescription of the present invention, can and be lower than 1350 ℃ sintering temperature and goes out the high dielectric of Y5V type of excellent performance, anti-reduction capacitor dielectric material at 1200 ℃.Its room temperature dielectric constant can be controlled at 8,000～15, between 000,-30 ℃～+ 85 ℃ range content temperature rates of change are between+22%～-82%, satisfy the EIA-Y5V requirement, room temperature dielectric loss≤2.5%, the alternating current breakdown field intensity is higher than 4.5kV/mm, the ceramic crystalline grain size is between 500nm～2,500nm.Be applicable to that manufacturing is the thin layer (≤10 μ m) of inner electrode, the high number of plies, jumbo multilayer ceramic capacitor with the base metal.
Description of drawings
Fig. 1 is the dielectric constant and the variation of temperature curve of embodiment 1 sample;
Fig. 2 is the microstructure photograph of the natural surface of embodiment 1 sample;
Fig. 3 is the dielectric constant and the variation of temperature curve of embodiment 2 samples;
Fig. 4 is the microstructure photograph of the natural surface of embodiment 2 samples;
Fig. 5 is the dielectric constant and the variation of temperature curve of embodiment 3 samples;
Fig. 6 is the microstructure photograph of the natural surface of embodiment 3 samples.
Embodiment
The present invention is that a kind of preparation technology is easy, and it is simply adjustable to fill a prescription, and sintering condition is easily controlled, the high dielectric that is used for electrodes in base metal that dielectric property are good, anti-reduction capacitor dielectric material, and this material is by barium titanate BaTiO
3With barium zirconate BaZrO
3And barium stannate BaSnO
3Solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3Form described major ingredient solid solution Ba with secondary additive
x(Zr
ySn
zTi
1-y-z) O
3, shared molal quantity is 96～98mol% in prescription; The consumption of described secondary additive accounts for 2～4mol% of total amount of material.0.995≤x≤1.01,0.10≤y≤0.20,0≤z≤0.10 wherein, the particle size of major ingredient requires less than 1000nm.Described secondary additive comprises CaO, TiO
2, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide M
2O
3, or the presoma of secondary additive: comprise carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide (four butanols titaniums, calcium ethoxide, ethanol zinc etc. are not determined at a certain alkoxide).Described each material mixture ratio is (in mole): CaO:0.3～1.0mol%; TiO
2: 0.1～0.5mol%; SiO
2: 0～0.5mol%; Li
2O:0.2～1.5mol%; MnO
2: 0.4～1.4mol%; ZnO:0.8～2.5mol%:Re
2O
3: 0.2～1.2mol%.
Rare earth oxide M
2O
3Middle M representative: La-lanthanum, Ce-cerium, Pr-praseodymium, Nd-neodymium, Sm-samarium, Eu-europium, Gd-gadolinium, Tb-terbium, Dy-dysprosium, Ho-holmium, Er-erbium, Tm-thulium, Yb-ytterbium, Lu-lutetium, and Y-yttrium.
The powdery granule dimensional requirement is less than 600nm in the above-mentioned secondary additive, (solvent generally is water, ethanol, acetate or their mixture with solution in the presoma requirement of described secondary additive, for salts soluble in water such as carbonate, acetate, nitrate, solvent is selected water for use, can select ethanol for use for alkoxide, separate to prevent water, acetate, oxalates etc. can be selected the aqueous solution of acetic acid or acetic acid for use as solvent) mode mix the dry deposition in back, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling in addition.
The concrete processing step of making MLCC is as follows:
(1) pulverous brium carbonate, zirconium dioxide, tin ash and titanium dioxide being mixed mutually, is medium with water, and zirconia ball is situated between for mill, and ball milling is 24 hours in the nylon jar;
(2) with the said mixture of oven dry in 1100 ℃＜T≤1200 ℃, 10
-7～1.2 * 10
-12The low oxygen that divides is depressed calcining, synthetic solid solution major ingredient with perovskite structure;
(3) pulverizing of solid solution major ingredient: with water is medium, and zirconia ball is situated between for mill, and ball milling is 48 hours in the nylon jar, obtains the major ingredient powder of particle size less than 1000nm;
(4) above-mentioned solid solution powder being mixed mutually with the secondary additive, add suitable organic solvent, binding agent, plasticizer, dispersant etc., is mill ball milling 48 hours that are situated between in the nylon jar with zirconia ball, obtains casting slurry;
(5) become dielectric layer with above-mentioned casting slurry curtain coating: medium thickness is 10 μ m or below the 10 μ m;
(6) printing base-metal inner-electrode layer on above-mentioned dielectric layer, the curtain coating dielectric layer mutual superposition of electrode is cut after the hot pressing in will being printed on again, forms the MLCC green compact;
(7) binder removal: in 300 ℃～340 ℃ temperature range, insulation is 20 hours in air, gets rid of the organic substance in the MLCC green compact, and the programming rate of binder removal process is not higher than 10 ℃/h;
(8) sintering under reducing atmosphere: feed N in the sintering process
2/ H
2/ H
2The mist of O is controlled at 10 with partial pressure of oxygen
-6～10
-12In the scope of Pa, Control for Kiln Temperature: be warmed up to 1250 ℃ with 200 ℃/hour speed, temperature retention time is 2 hours;
(9) anneal under the weak oxide condition: furnace temperature is incubated 2～4 hours in 1000 ℃＜T＜1100 ℃, and partial pressure of oxygen is controlled at 10
-3～10
-8In the scope of Pa;
(10) coating termination electrode: termination electrode is Cu or Ag, and furnace temperature is incubated 1 hour at 700 ℃～850 ℃, and nitrogen protection behind the natural cooling, promptly obtains Y5V type base metal inner electrode multilayer ceramic capacitor.
Further specify as follows below again for embodiment:
Embodiment 1, earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=1.005 wherein, y=0.13, z=0.04) synthetic perovskite solid solution, 1150 ℃ of synthesis temperatures, the particle size of solid solution is 570nm after the ball mill grinding.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 96mol%; CaO:0.4mol%; TiO
2: 0.5mol%; SiO
2: 0.2mol%; Li
2O:0.4mol%; MnO
2: 0.6mol%; ZnO:1.4mol%; Sm
2O
3: 0.3mol%; Dy
2O
3: the weighing of 0.2mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive n-propyl acetate, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, and behind the binder removal, sintering under reducing atmosphere (feeds N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-11Pa is warmed up to 1260 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 2 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 1.What the curve of Fig. 1 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 2 provides the microstructure of sample natural surface, and crystallite dimension is between 1500～2000nm.
The electric property parameter of table 1 sample 1
| The major ingredient composition | Sintering condition | TCC(％) (-30℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝15℃) | tgδ(％) (25℃) | ρ25℃ (Ω·cm) | E B25℃ (ACkV/mm) |
| Ba 1.005(Zr 0.13Sn 0.04Ti 0.83)O 3 | 1260 ℃ * 2 hours | -62.8 | 12200 | -70.4 | +9.4 | 1.30 | 2.0×10 11 | 4.9 |
Embodiment 2, earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=1.002 wherein, y=0.17, z=O) synthetic perovskite solid solution, 1150 ℃ of synthesis temperatures, the particle size of solid solution is 410nm after the ball mill grinding.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 97mol%; CaO:0.3mol%; TiO
2: 0.1mol%; SiO
2: 0.2mol%; Li
2O:0.2mol%; MnO
2: 0.5mol%; ZnO:1.2mol%; Nd
2O
3: 0.2mol%; La
2O
3: the weighing of 0.3mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive n-propyl acetate, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, and behind the binder removal, sintering under reducing atmosphere (feeds N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-11Pa is warmed up to 1220 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 3 hours at 1100 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 2.What the curve of Fig. 3 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 4 provides the microstructure of the fresh section of sample, and crystallite dimension is between 800～1000nm.
The electric property parameter of table 2 sample 2
| The major ingredient composition | Sintering condition | TCC(％) (-30℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝10℃) | tgδ(％) (25℃) | ρ25℃ (Ω·cm) | E B25℃ (ACkV/mm) |
| Ba 1.002(Zr 0.17Ti 0.83)O 3 | 1220 ℃ * 2 hours | -49.4 | 8816 | -65.3 | +9.3 | 1.07 | 3.2×10 11 | 5.1 |
Embodiment 3, earlier according to Ba
x(Zr
ySn
zTi
1-y-z) O
3(x=0.998 wherein, y=0.14, z=0.08) synthetic perovskite solid solution, 1150 ℃ of synthesis temperatures, the particle size of solid solution is 650nm after the ball mill grinding.Then according to Ba
x(Zr
ySn
zTi
1-y-z) O
3Solid solution: 97mol%; CaO:0.8mol%; TiO
2: 0.2mol%; SiO
2: 0mol%; Li
2O:0.2mol%; MnO
2: 0.4mol%; ZnO:1.0mol%; Yb
2O
3: 0.2mol%; Ho
2O
3: the weighing of 0.2mol% proportioning.Above-mentioned material is mixed, add ball milling after the suitable organic additive n-propyl acetate, the casting film-forming sheet with the stack of printing Ni electrode, is made the MLCC green compact then, and behind the binder removal, sintering under reducing atmosphere (feeds N in the sintering process
2/ H
2, humidification is controlled at 10 with partial pressure of oxygen simultaneously
-11Pa is warmed up to 1300 ℃ with 200 ℃/hour speed, and temperature retention time is 2 hours), annealing under the weak oxide condition then, (furnace temperature is incubated 4 hours at 1050 ℃, and partial pressure of oxygen is controlled to be 10
-7Pa).Blackening Cu termination electrode (furnace temperature is incubated 1 hour, nitrogen protection at 850 ℃) afterwards.Above-mentioned multilayer ceramic capacitor is carried out performance test, and the electric property parameter sees Table 3.What the curve of Fig. 5 provided is the change curve of present embodiment sample dielectric constant with temperature, and Fig. 6 provides the microstructure of sample natural surface, and crystallite dimension is between 1500～2500nm.
The electric property parameter of table 3 sample 3
| The major ingredient composition | Sintering condition | TCC(％) (-30℃) | Dielectric constant (25 ℃) | TCC(％) (85℃) | TCC(％) (T C＝15℃) | Tgδ(％) (25℃) | ρ 25℃ (Ω·cm) | E B25℃ (ACkV/mm) |
| Ba 0.998(Zr 0.14Sn 0.08Ti 0.78)O 3 | 1220 ℃ * 2 hours | -66.7 | 13610 | -72.2 | +8.9 | 1.58 | 2.8×10 11 | 4.7 |
The foregoing description has prepared the high dielectric of barium titanate solid solution base base-metal inner-electrode that satisfies the EIA-Y5V performance index and require, anti-reduction capacitor dielectric material in the temperature range of 1100 ℃＜T≤1200 ℃.Its room temperature dielectric constant can be controlled between 8000 to 1,5000, and-30 ℃～+ 85 ℃ temperature coefficient of capacitance are between+22%～-82%, and dielectric loss is less than 2.5%.Insulation resistivity is about 10
11Ω cm, ac breakdown voltage is greater than 4.5KV/mn.Utilize prescription of the present invention and technology, it is wide to obtain sintering range, and performance is adjustable, stability and the good anti-reduction barium titanate solid solution base Y5V type MLCC material of reproducibility.And the uniform crystal particles of material, the ceramic crystalline grain size is between 500nm～2,500nm.Can be applied to big capacity, superthin layer (medium thickness is less than 10 μ m) multilayer ceramic capacitor is a kind of MLCC material with wide application prospect.
Above-mentioned Fig. 1～Fig. 6 is corresponding to the temperature characteristics of each sample dielectric constant of embodiment 1～3 and surperficial microstructure.The probe temperature of Jie's temperature characteristics is-55 ℃～+ 125 ℃.
The meaning of each parameter representative is as follows in table 1～table 3:
TCC (30 ℃): temperature coefficient of capacitance in the time of-30 ℃; TCC (85 ℃): temperature coefficient of capacitance in the time of 85 ℃;
Tg δ (25 ℃): dielectric loss during room temperature, test frequency are 1kHz, test voltage 1.0V;
TCC (T) %=100 * (ε (T)-ε (25 ℃))/ε (25 ℃): temperature coefficient of capacitance;
ρ (25 ℃): room temperature resistivity, test condition are direct voltage 100V, keep 60s;
E
b(25 ℃): room temperature alternating current breakdown field intensity, AC field frequency are 50Hz.
Claims (4)
1. one kind is used for the high dielectric of electrodes in base metal, anti-reduction capacitor dielectric material, and this material is made up of major ingredient solid solution and secondary additive, it is characterized in that: described major ingredient solid solution Ba
x(Zr
ySn
zTi
1-y-z) O
3By barium titanate BaTiO
3With barium zirconate BaZrO
3And barium stannate BaSnO
3Form, 0.995≤x≤1.01,0.10≤y≤0.20,0≤z≤0.10 wherein, shared molal quantity is 96～98mol% in prescription; The consumption of described secondary additive accounts for 2～4mol% of total amount of material, comprises CaO, TiO
2, SiO
2, Li
2O, MnO
2, ZnO and one or more rare earth oxide M
2O
3, or the presoma of secondary additive; Each material of secondary additive in the proportioning of mole is: CaO:0.3～1.0mol%; TiO
2: 0.1～0.5mol%; SiO
2: 0～0.5mol%; Li
2O:0.2～1.5mol%; MnO
2: 0.4～1.4mol%; ZnO:0.8～2.5mol%; M
2O
3: 0.2～1.2mol%.
2. according to the described high dielectric of electrodes in base metal, the anti-reduction capacitor dielectric material of being used for of claim 1, it is characterized in that: the particle size of the composition material of described major ingredient solid solution requires less than 1000nm; Described secondary additive particles of powder dimensional requirement is less than 600nm; The presoma of secondary additive requires to mix the dry deposition in back in the mode of solution, then deposit is carried out calcination processing at 800 ℃～900 ℃, and ball milling in addition.
3. according to the described high dielectric of electrodes in base metal, the anti-reduction capacitor dielectric material of being used for of claim 1, it is characterized in that: the presoma of described secondary additive comprises carbonate, hydroxide, oxalates, acetate, nitrate, citrate and alkoxide: four butanols titaniums or calcium ethoxide or ethanol zinc.
4. according to the described high dielectric of electrodes in base metal, the anti-reduction capacitor dielectric material of being used for of claim 1, it is characterized in that: described rare earth oxide M
2O
3Middle M representative: La-lanthanum, Ce-cerium, Pr-praseodymium, Nd-neodymium, Sm-samarium, Eu-europium, Gd-gadolinium, Tb-terbium, Dy-dysprosium, Ho-holmium, Er-erbium, Tm-thulium, Yb-ytterbium, Lu-lutetium, and Y-yttrium.
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|---|---|---|---|---|
| US20070131142A1 (en) * | 2005-10-21 | 2007-06-14 | E.I. Du Pont Denemours And Company, Inc. | Barium Titanate Thin Films with Titanium Partially Substituted by Zirconium, Tin or Hafnium |
| CN101376591B (en) * | 2007-08-30 | 2012-08-22 | 中国科学院福建物质结构研究所 | Novel barium stannate-lead ferroelectric and piezoelectic ceramic, and preparation thereof |
| JP5217405B2 (en) * | 2007-12-11 | 2013-06-19 | Ｔｄｋ株式会社 | Dielectric porcelain composition and electronic component |
| TWI471884B (en) * | 2012-10-09 | 2015-02-01 | Murata Manufacturing Co | Laminated ceramic electronic parts and manufacturing method thereof |
| CN107382308A (en) * | 2017-07-17 | 2017-11-24 | 天津大学 | A kind of anti-reduced form dielectric material of high-k |
| CN114133238B (en) * | 2021-11-02 | 2022-09-16 | 广东省先进陶瓷材料科技有限公司 | Ceramic dielectric material and preparation method and application thereof |
| CN116041060B (en) * | 2023-02-08 | 2023-09-22 | 福建火炬电子科技股份有限公司 | Base metal pulse energy storage ceramic dielectric material, ceramic capacitor and preparation method thereof |
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