CN1635592A - High dielectric and reduction resistant ceramic material and prepared ceramic capacitor - Google Patents
High dielectric and reduction resistant ceramic material and prepared ceramic capacitor Download PDFInfo
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Abstract
This invention discloses a high dielectric anti-deoxidize ceramic materials and its process multi-film capacitor. The material component percentage by weight is the following: main transistor phase (Ba1-xCax)a(Ti1-yZry)O3: 97-99%, wherein 0.12<=x<=0.20, 0.10<=y<=0.40, 1.002<=a<=1.02 and the a represents (BaO+CaO)/(TiO2+ZrO2) value and the 0.8-8.20% of assistant component from one or more from Y2O3,MnO2,Yb2O3,ZnO,SiO2,Nb2O5 .
Description
Technical field
The present invention relates to the multilayer chip capacitor (MLCC) of a kind of electron ceramic material and preparation thereof, more particularly, the present invention relates to a kind of high dielectric, the zirconium barium calcium titanate of anti-reduction or the multilayer chip capacitor of barium zirconium titanate ceramic and preparation thereof.
Background technology
Multiple-layer sheet ceramic capacitor (MLCC) is with its small size, high reliability and mount characteristics such as convenient and be used widely in the manufacture process of electronic equipment.Along with the development and the arrival in mobile communication epoch of digitizing technique, various electronic devices and equipment require surface-pasted multiple-layer sheet ceramic capacitor (MLCC) to realize small size and high reliability to miniaturization, the development of high density integrated direction.
In order to realize big capacity, low cost, the microminiaturization of ceramic capacitor (MLCC), at first, require dielectric ceramic material must have very high dielectric constant, also require this dielectric ceramic material to have very strong resistance to reduction energy simultaneously.Because have only when dielectric material has very high dielectric constant, could under the situation of unit are/volume, have enough big electric capacity ability; And production cost and cost in order to reduce capacitor also must adopt comparatively cheap base metal to make the internal and external electrode of capacitor.
Because up to this point, the interior electrode of multiple-layer sheet ceramic capacitor (MLCC) all is printed onto dielectric layer by screen printing technique with the metal paste layer and gets on, alternately carry out above-mentioned printing, lamination, again it compacting, cutting are formed green compact, the base substrate of electrode at high temperature burns altogether in will being printed with layer by layer then, after again the two end electrodes envelope being coated with slurry, become capacitor element with internal and external electrode through final making of Overheating Treatment.And traditional multiple-layer sheet ceramic capacitor (MLCC) sintering in air atmosphere.Not oxidized in the process of high temperature co-firing for electrode in making, the slurry of electrode all adopts the palladium/silver alloy of noble metal in the tradition.Because it is high that the market price of precious metal palladium continues, cause the manufacturing cost of traditional multiple-layer sheet ceramic capacitor (MLCC) also high.
For the cost price of electrode in reducing, can only adopt base metal to be used as the raw material of interior electrode.If but with base metal such as nickel or nickel alloy interior electrode as multiple-layer sheet ceramic capacitor (MLCC), not oxidized and influence the capacitor quality under the capacitor high temperature co-firing in order to prevent base-metal inner-electrode, high temperature co-firing process at the preparation capacitor must be carried out in reducing atmosphere, but the used dielectric material of traditional multiple-layer sheet ceramic capacitor (MLCC) again should not be at sintering under the reducing atmosphere, because traditional dielectric material at high temperature is reduced into semiconductor easily, thereby reduce the insulation resistance of dielectric material, increase dielectric loss, make the quality of multiple-layer sheet ceramic capacitor (MLCC) not reach standard-required.
At the problems referred to above some technical solutions are arranged also, as disclosing a kind of interchange safety ceramic capacitor in the Chinese patent 95106291.3, the ceramic dielectric operating weight percentage of this capacitor is: the batch mixes of strontium titanates 40～64%, lead oxide 10～20%, bismuth oxide 11～15%, titanium dioxide 10～15%, cerium oxide 0.2～1.0% is even, the poly-vinyl alcohol solution granulating and forming that adds total weight 10～20%, under 1000 and 1300 ℃ of high temperature, divide after baking 2 hours then, make the ceramic dielectric finished product; According to its experimental data, though its dielectric constant can be up to 2000～13500, the dielectric temperature coefficient is not good, exceeds standard to some extent, and adopts raw material containing lead, is unfavorable for environmental protection.The manufacture method of its electrode is for being that " after drying under the C, electrode material also remains precious metal, and cost is higher 150 for the electrocondution slurry of Main Ingredients and Appearance being coated with full on two parallel side of ceramic dielectric finished product with silver oxide and frit.
A kind of dielectric ceramic material, preparation method and multilayer ceramic capacitor of anti-reduction are and for example disclosed in the Chinese patent 99801726.4.This technology adopts nickeliferous interior electrode to make multilayer ceramic capacitor, and the unlikely prolongation of polishing step for preventing from interior electrode end is exposed has prepared a kind of anti-reduction dielectric ceramic material simultaneously, and its ceramic material is made into and comprises with [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y) O
2] composite oxides represented of formula are as the calcined materials of principal component, 0≤x≤1,0≤y≤0.10 and 0.75≤m≤1.04 wherein, and add MgO or rare earth oxide based on principal component 0.001-10mol%, get through sintering.This ceramic material also comprises the SiO of scheduled volume
2With BaO and/or CaO and MnO as auxiliary element.But indexs such as the dielectric constant of the capacitor that further this dielectric material of disclosure employing is made in this piece file, dielectric temperature coefficient, insulation resistance are so be difficult to estimate its advance.
Summary of the invention
At above-mentioned the deficiencies in the prior art, one of purpose of the present invention is that a kind of high dielectric, anti-reduction ceramic material will be provided, this high dielectric ceramic material not only has very high dielectric constant, and has good resistance to reduction energy and insulation resistivity and dielectric temperature coefficient;
Two of purpose of the present invention is that a kind of chip multilayer ceramic capacitor will be provided, and this capacitor adopts cheap base metal as inner electrode, and can reach very high dielectric constant and insulation resistivity, and the dielectric temperature coefficient meets the Y5V standard of EIA.
For this reason, one of technical solution of the present invention is a kind of high dielectric, anti-reduction ceramic material, and its composition is respectively by weight percentage: principal crystalline phase (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3: 97～99%, wherein, 0.12≤x≤0.20,0.10≤y≤0.40,1.002≤a≤1.02, and a is (BaO+CaO)/(TiO
2+ ZrO
2) value; 0.8～8.20% auxiliary element comprises Y in addition
2O
3, MnO
2, Yb
2O
3, ZnO, SiO
2, Nb
2O
5In one or more; The granularity of this ceramic material is less than 1.0 μ m.
Main raw material(s) of the present invention is zirconium barium calcium titanate or barium zirconium phthalate, adopt one or more special chemical methods synthetic in advance, these methods comprise hydro thermal method, molten salt growth method or coprecipitation, these chemical methods can make zirconium barium calcium titanate or barium zirconium phthalate keep high reaction activity and high, can make porcelain body fully burn ripe at 1200～1250 ℃.
At principal component (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3In, the y value need be controlled at 0.10～0.40.With the increase of zirconium content, the material resistance to reduction strengthens, and Curie point is negative partially.This be because: the Zr ionic valence condition be difficult for to change, Ti ionic valence condition (Ti
4+, Ti
3+) at high temperature variable.The intervention of the Zr ion of fixed price in the material will make the Ti-O interchain deadening of conduction disconnected, so can only do the short distance migration by the electronics of donor impurity introducing between several atoms, is difficult to form electricity and leads.Because this localization electronics is subjected to the influence of spontaneous polarization field, away from equilibrium location produces polarization, with the stack of spontaneous polarization field, the material ferroelectricity is strengthened, and dielectric constant raises.
(Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3Be the principal component of this porcelain, a value is (BaO+CaO)/(TiO
2+ ZrO
2) mol ratio, be called A/B again, wherein A is the molal quantity of (BaO+CaO), B is (TiO
2+ ZrO
2) molal quantity.The a value is to influence BaTiO
3The factor of pottery electric strength, the excessive porcelain of the relative B value of A value helps the aplitic texture of pottery, helps the raising of electric strength.A/B preferably crosses weight range 1.002～1.02.And the zirconium barium calcium titanate that the employing chemical method makes or the A/B of barium zirconium phthalate are 1.000, as the principal crystalline phase raw material, and also must be by adding the A/B that Ca regulates this raw material.Because perovskite structure (ABO
3) quite tight, Ca becomes that to fill out be that the possibility of ion is very little, replaces the A position so the existing way of Ca is likely, mainly plays anti-reduction, makes microscopic particles even simultaneously.The present invention adopts aforementioned chemical method to prepare zirconium barium calcium titanate or barium zirconium phthalate, again with CaCO
3Or Ca (NO
3)
2Form Ca is joined earlier or subsequently with adding of other auxiliary elements, under 1200～1250 ℃ of temperature, burn shortening and get principal crystalline phase.
Principal crystalline phase is made the back or is made in the process, and Mn is with MnO
2Or MnCO
3Form add, other auxiliary element adds with oxide form.
Add an amount of MnO
2Can effectively suppress BaTiO
3Semiconducting, make the porcelain body medium in the reducing atmosphere sintering, can obtain good insulation performance resistance.This is because manganese is mainly with Mn in reducing atmosphere
2+Form exists, and Mn
2+With Ti
4+Radius be more or less the same Mn
2+Might occupy the Ti of B position
4+The main effect that is subjected to of free electron is played in the position, has suppressed free electronic concentration, like this Ti
4+Just can not be because trapped electron and become Ti in large quantities
3+And make BaTiO
3Be ceramic semiconducting, thereby strengthened ceramic resistance to reduction.In addition, MnO
2To the formation of crystal boundary, the drift of Curie point also has certain influence.Suitable addition is 0.05～0.5% (wt%).Very few, porcelain body is by semiconducting; Too much, can cause loss to increase, Curie point is negative partially.
Add an amount of ZnO, SiO
2Deng porcelain body can be burnt till under lower temperature, make the crystal grain densification, crystal boundary is easy to form, and obtains higher dielectric constant, lower loss.ZnO and/or SiO
2The permission addition be 0.05～5.0% (wt%), suitable addition is 0.5～1.9% (wt%).ZnO and/or SiO
2Very few, porcelain body must burn ripe 1300 ℃ of ability; ZnO and/or SiO
2Too much, can cause loss to increase, crystal boundary worsens, the Curie point polarization.
An amount of Y
2O
3Interpolation, can effectively suppress growing up of crystal grain, crystallite dimension is controlled at below the 0.5 μ m, and then guarantees to produce the capacitor of the higher number of plies; Under the thin situation of the thickness of dielectric layers of capacitor, still can keep its good insulation, withstand voltage, thermal shock characteristic.Simultaneously, the uniformity of crystal grain is also very important.Y
2O
3Suitable addition be 0.1～0.8% (wt%).
This ceramic medium material is the above-mentioned various helper components that add in principal component as sintering aid, after evenly mixing, and by the powder that certain technology processes, powder granularity normal distribution, D
50＜1.0 μ m.
Correspondingly, another technical solution of the present invention is a kind of process for preparing above-mentioned high dielectric, anti-reduction ceramic material, and the percentage by weight of this ceramic material consists of: principal crystalline phase (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3: 97～99%, x, y, a satisfy 0.12≤x≤0.20,0.10≤y≤0.40,1.002≤a≤1.02 respectively in the formula, and a is (BaO+CaO)/(TiO
2+ ZrO
2) value; All the other auxiliary compositions 0.5～8.20% comprise and are selected from Y
2O
3, MnO
2, Yb
2O
3, ZnO, SiO
2, Nb
2O
5In one or more, and the Ca in the principal crystalline phase is with CaCO
3Or Ca (NO
3)
2Form add CaCO
3Or Ca (NO
3)
2The percentage by weight of addition in described ceramic material be 0.5～5%; Mn is with MnO in the auxiliary composition
2Or MnCO
3Form add, other composition adds with oxide form.Form the zirconium barium calcium titanate of principal crystalline phase or barium zirconium phthalate and be to adopt and comprise hydro thermal method, molten salt growth method, coprecipitation and make.Principal crystalline phase is in 800 ℃～1200 ℃ scopes principal crystalline phase raw material calcining 2 to 3 hours to be got.Give burning through the principal crystalline phase raw material and obtain thermodynamically stable principal crystalline phase,, make high dielectric of the present invention, anti-reduction ceramic material again with the common mixing of auxiliary element, refinement, calcining.
One after the other, another technical solution of the present invention is a kind of multilayer ceramic capacitor, the interior electrode that comprises dielectric layer, replaces mutually with dielectric layer, and the termination electrode that is connected with interior electrode, wherein dielectric layer adopts anti-reduction, the high dielectric ceramic material of following composition to make: (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3: 97～99%, x, y, a satisfy 0.12≤x≤0.20,0.10≤y≤0.40,1.002≤a≤1.02 respectively in the formula, and a is (BaO+CaO)/(TiO
2+ ZrO
2) value; All the other compositions of 0.5～8.20% are selected from Y
2O
3, MnO
2, Yb
2O
3, ZnO, SiO
2, Nb
2O
5In one or more.Interior electrode adopt nickel or nickel alloy slurry coating on the dielectric layer then in reducing atmosphere sintering make.The sintering temperature of whole multi-layer capacitor is 1200 ℃～1250 ℃.
Make into the capacitor that model specification is 0805F104 with the design of this ceramic medium material, behind 1200～1250 ℃ of sintering, dielectric constant can reach 12000 in the nitrogen and hydrogen mixture atmosphere, and loss angle tangent is less than 160 * 10
-4@20 μ m, the capacity rate of temperature change is+22%～-72%, meets EIA standard Y5V temperature characterisitic.
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment
The multilayer ceramic capacitor that ceramic medium material of the present invention makes is to be example with the 0805F104 specifications and models, but the present invention is not limited to this kind specifications and models.
Embodiment 1
Preparation process comprises the preparation of principal crystalline phase, the preparation of ceramic dielectric powder and the preparation of multilayer chip capacitor.
The preparation process of principal crystalline phase comprises: the initial raw material that chemical method is synthetic through adjusting Ca content, obtain (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3, drying, pulverizing back 800 ℃ to 1200 ℃ calcinings 2 to 3 hours, are obtained required principal crystalline phase.
The preparation process of ceramic dielectric powder is: add helper component again as sintering aid, anti-reducing agent in above-mentioned raw material, the quality percentage composition of each helper component is listed in table 1.After mixing through ball milling, again by processing such as drying, sintering, get final product powder granularity distribution normal state, D
50The ceramic powder of＜1.0 μ m.
The preparation of multilayer chip capacitor: with above-mentioned anti-reduction ceramic powder material as dielectric material, the design model specification is the multi-layer capacitor of 0805F104: after adopting traditional casting technique to produce the diaphragm of 5～30 μ m, adopt screen printing technique electrode in the double exposure on the multilayer diaphragm, electrode size is the nickel alloy slurry that contains 0.1～10% inorganic additive.The multilayer diaphragm is repressed, and cutting forms green compact.
With above-mentioned green compact 1200 ℃ of sintering in the nitrogen and hydrogen mixture atmosphere, after handling through surface finish again, envelope is coated with copper alloy or nickel alloy slurry at the termination electrode position, and after 800～900 ℃ of heat treatments of nitrogen atmosphere, handle through three layers of electroplating technology, form the termination electrode of copper-nickel-tin or nickel-nickel-tin structure.Terminal electrode paste uses copper alloy or the nickel alloy slurry contain 1～20% inorganic additive.Use its performance of correlate meter testing of equipment then, each sample performance is listed in table 2.
Table 1
| Sample | Principal component (Ba 1-xCa x) a(Ti 1-yZr y)O 3Form | The quality percentage composition (wt%) of each helper component | |||||||||
| ??1-x | ??x | ??1-y | ??y | ??a | ?ZnO | ??SiO 2 | ??MnO 2 | ??Y 2O 3 | ??Yb 2O 3 | ??Nb 2O 5 | |
| ????1 | ??0.98 | ??0.02 | ??0.70 | ??0.3 | ??1.010 | ??- | ??0.90 | ??0.30 | ??0.60 | ??- | ??- |
| ????2 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.010 | ??0.1 | ??0.70 | ??0.40 | ??0.50 | ??0.2 | ??- |
| ????3 | ??0.94 | ??0.06 | ??0.90 | ??0.1 | ??1.010 | ??0.1 | ??0.50 | ??0.20 | ??0.70 | ??- | ??0.2 |
| ????4 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.012 | ??0.1 | ??0.80 | ??0.30 | ??0.40 | ??- | ??0.7 |
| ????5 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.014 | ??- | ??0.60 | ??0.20 | ??0.20 | ??0.4 | ??- |
| ????6 | ??0.96 | ??0.04 | ??0.60 | ??0.4 | ??1.016 | ??0.4 | ??0.60 | ??0.30 | ??0.30 | ??- | ??0.6 |
| ????7 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.010 | ??0.2 | ??0.50 | ??0.20 | ??0.20 | ??0.4 | ??- |
| ????8 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.010 | ??0.2 | ??0.50 | ??0.40 | ??0.50 | ??0.3 | ??0.4 |
| ????9 | ??0.96 | ??0.04 | ??0.80 | ??0.2 | ??1.010 | ??0.3 | ??0.50 | ??0.50 | ??0.20 | ??- | ??- |
Table 2
| Sample | Sintering temperature (℃) | Dielectric constant | Loss angle tangent | Temperature coefficient (%) | Resistivity (Ω .cm) |
| ????1 | ????1240 | ????9000 | ????140×10 -4 | ????+18～-65 | ????＞10 11 |
| ????2 | ????1220 | ????10200 | ????150×10 -4 | ????+20～-64 | ?????＞10 11 |
| ????3 | ????1230 | ????10300 | ????120×10 -4 | ????+17～-65 | ????＞10 11 |
| ????4 | ????1230 | ????9300 | ????130×10 -4 | ????+14～-67 | ????＞10 11 |
| ????5 | ????1220 | ????12000 | ????120×10 -4 | ????+12～-68 | ????＞10 11 |
| ????6 | ????1210 | ????11300 | ????130×10 -4 | ????+20～-70 | ????＞10 11 |
| ????7 | ????1250 | ????10500 | ????100×10 -4 | ????+18～-71 | ????＞10 11 |
| ????8 | ????1230 | ????10450 | ????110×10 -4 | ????+12～-69 | ????＞10 11 |
| ????9 | ????1220 | ????11560 | ????120×10 -4 | ????+14～-68 | ????＞10 11 |
Embodiment 2
Preparation process comprises the preparation of principal crystalline phase, the preparation of ceramic dielectric powder and the preparation of multilayer chip capacitor.
The preparation process of principal crystalline phase comprises: the Ba (Ti that initial raw material chemical method is synthetic
1-yZr
y) O
3Calcined 2 to 3 hours at 800 ℃ to 1200 ℃ dry, pulverizing back, obtains required principal crystalline phase raw material.
The preparation process of ceramic dielectric powder is: add Ca content conditioning agent and other helper component such as sintering aid, anti-reducing agent etc. in above-mentioned raw material, the quality percentage composition of each helper component is listed in table 3.After mixing through ball milling, again by certain technology processing, get final product powder granularity distribution normal state, D
50The ceramic powder of＜1.0 μ m.
The preparation of multilayer chip capacitor: with above-mentioned anti-reduction ceramic medium material as dielectric material, design model specification: 0805F104, adopts traditional casting technique to produce the diaphragm of 5～30 μ m after, adopt the interior electrode of screen printing technique double exposure, repressed again, cutting forms green compact.Electrode size uses the nickel alloy slurry contain 0.1～10% inorganic additive.
With green compact 1250 ℃ of sintering in the nitrogen and hydrogen mixture atmosphere, after handling through surface finish again, envelope copper alloy or nickel alloy terminal electrode paste.And after 800～900 ℃ of heat treatments of nitrogen atmosphere, handle through three layers of electroplating technology, form the termination electrode of copper-nickel-tin or nickel-nickel-tin structure.Terminal electrode paste uses copper alloy or the nickel alloy slurry contain 1～20% inorganic additive.。Use its performance of correlate meter testing of equipment then, each sample performance is listed in table 4.
Table 3
| Sample | Principal component Ba (Ti 1-yZr y)O 3Form | ??????????????????????????CaCO 3. the quality percentage composition (wt%) of each helper component | |||||||
| ????1-y | ????y | ????CaCO 3 | ????ZnO | ????SiO 2 | ????MnO 2 | ????Y 2O 3 | ????Yb 2O 3 | ????Nb 2O 5 | |
| ????1 | ????0.80 | ????0.20 | ????0.5 | ????0.4 | ????0.90 | ????0.30 | ????0.60 | ????- | ????- |
| ????2 | ????0.80 | ????0.20 | ????0.7 | ????0.1 | ????0.80 | ????0.30 | ????0.50 | ????0.2 | ????- |
| ????3 | ????0.80 | ????0.20 | ????0.9 | ????- | ????0.70 | ????0.30 | ????0.70 | ????- | ????0.2 |
| ????4 | ????0.90 | ????0.10 | ????1.2 | ????0.3 | ????0.20 | ????0.50 | ????0.40 | ????- | ????- |
| ????5 | ????0.70 | ????0.30 | ????1.4 | ????0.2 | ????0.40 | ????0.40 | ????0.20 | ????0.4 | ????- |
| ????6 | ????0.60 | ????0.40 | ????2.0 | ????0.1 | ????0.30 | ????0.30 | ????0.30 | ????- | ????0.6 |
| ????7 | ????0.80 | ????0.20 | ????3.0 | ????0.2 | ????0.50 | ????0.20 | ????0.50 | ????- | ????- |
| ????8 | ????0.80 | ????0.20 | ????3.5 | ????- | ????0.50 | ????0.40 | ????0.70 | ????0.3 | ????0.4 |
| ????9 | ????0.80 | ????0.20 | ????4.0 | ????0.2 | ????0.50 | ????0.50 | ????0.20 | ????- | ????- |
Table 4
| Sample | Sintering temperature (℃) | Dielectric constant | Loss angle tangent | Temperature coefficient (%) | Resistivity (Ω .cm) |
| ????1 | ????1210 | ????9200 | ????140×10 -4 | ????+12～-65 | ????＞10 11 |
| ????2 | ????1220 | ????9200 | ????150×10 -4 | ????+21～-64 | ????＞10 11 |
| ????3 | ????1240 | ????10200 | ????120×10 -4 | ????+13～-65 | ????＞10 11 |
| ????4 | ????1230 | ????12000 | ????120×10 -4 | ????+16～-67 | ????＞10 11 |
| ????5 | ????1250 | ????10200 | ????120×10 -4 | ????+11～-68 | ????＞10 11 |
| ????6 | ????1210 | ????11250 | ????130×10 -4 | ????+21～-70 | ????＞10 11 |
| ????7 | ????1220 | ????11500 | ????100×10 -4 | ????+19～-71 | ????＞10 11 |
| ????8 | ????1230 | ????10400 | ????110×10 -4 | ????+18～-69 | ????＞10 11 |
| ????9 | ????1220 | ????11500 | ????110×10 -4 | ????+15～-68 | ????＞10 11 |
By table 2,4 as seen, anti-reduction ceramic medium material of the present invention is suitable for sintering in the nitrogen and hydrogen mixture atmosphere, and sintering temperature is between 1200 ℃ to 1250 ℃, and dielectric constant can be up to 12000 (0805F104), and loss angle tangent is less than 160 * 10
-4@20 μ m, resistivity is greater than＞10
11Ω .cm, temperature coefficient meet EIA standard Y5V temperature characterisitic between+22%～-72%.
Claims (10)
1, a kind of high dielectric, anti-reduction ceramic material, the principal crystalline phase in this ceramic material is (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3, its percentage by weight in this ceramic material is formed: 97～99%, and x, y, a satisfy 0.12≤x≤0.20,0.10≤y≤0.40,1.002≤a≤1.02 respectively in the formula, and a is (BaO+CaO)/(TiO
2+ ZrO
2) value.
2, high dielectric as claimed in claim 1, anti-reduction ceramic material is characterized in that in described ceramic material, percentage by weight is 0.5～8.20% auxiliary element in addition, and this auxiliary element is for being selected from Y
2O
3, MnO
2, Yb
2O
3, ZnO, SiO
2And Nb
2O
5In one or more.
3, high dielectric as claimed in claim 1 or 2, anti-reduction ceramic material is characterized in that the granularity of described ceramic material is less than 1.0 μ m.
4, high dielectric as claimed in claim 2, anti-reduction ceramic material is characterized in that by weight percentage, described auxiliary element contains: 0.1～0.8% Y
2O
3, 0.05～0.50% MnO
2, 0.0～0.6% Yb
2O
3, 0.0～0.4% ZnO, 0.5～1.5% SiO
2With 0.0～0.7% Nb
2O
5
5, high dielectric as claimed in claim 1, anti-reduction ceramic material is characterized in that described principal crystalline phase is zirconium barium calcium titanate or the barium zirconium phthalate that adopts hydro thermal method, molten salt growth method or coprecipitation to make.
6, high dielectric as claimed in claim 1, anti-reduction ceramic material is characterized in that the Ca in the described principal crystalline phase is with CaCO
3Or Ca (NO
3)
2Form add CaCO
3Or Ca (NO
3)
2The percentage by weight of addition in described ceramic material be 0.5～5%.
7, high dielectric as claimed in claim 2, anti-reduction ceramic material is characterized in that the Mn in the described auxiliary composition is with MnO
2Or MnCO
3Form add, other composition adds with oxide form.
8, a kind of chip multilayer ceramic capacitor of making by high dielectric, anti-reduction ceramic material, this capacitor comprises dielectric layer and interior electrode, it is characterized in that, the percentage by weight of the dielectric layer of described capacitor consists of: (Ba
1-xCa
x)
a(Ti
1-yZr
y) O
3: 97～99%, x, y, a satisfy 0.12≤x≤0.20,0.10≤y≤0.40,1.002≤a≤1.02 respectively in the formula, and a is (BaO+CaO)/(TiO
2+ ZrO
2) value; All the other are for being selected from Y
2O
3, MnO
2, Yb
2O
3, ZnO, SiO
2, Nb
2O
5In one or more.
9, chip multilayer ceramic capacitor as claimed in claim 8 is characterized in that, the interior electrode of described capacitor is nickel or nickel alloy material.
10, chip multilayer ceramic capacitor as claimed in claim 8 is characterized in that, described ceramic capacitor comprises the dielectric layer material through reducing atmosphere and 1200-1250 ℃ of temperature sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117578 CN1635592A (en) | 2003-12-29 | 2003-12-29 | High dielectric and reduction resistant ceramic material and prepared ceramic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310117578 CN1635592A (en) | 2003-12-29 | 2003-12-29 | High dielectric and reduction resistant ceramic material and prepared ceramic capacitor |
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| CN102531592A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
| CN102584233A (en) * | 2012-01-11 | 2012-07-18 | 深圳顺络电子股份有限公司 | Medium and high dielectric constant low temperature co-fired ceramic material and preparation method thereof |
| CN103910525A (en) * | 2012-12-28 | 2014-07-09 | 佳能株式会社 | Piezoelectric Material, Piezoelectric Element, And Electronic Apparatus |
| CN104276819A (en) * | 2013-07-12 | 2015-01-14 | 佳能株式会社 | Piezoelectric Material, Piezoelectric Element, And Electronic Apparatus |
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| CN106518067A (en) * | 2016-10-27 | 2017-03-22 | 盐城工学院 | Ceramic composition, ceramic as well as preparation method and application of ceramic |
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| CN102531592B (en) * | 2011-11-10 | 2014-10-29 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
| CN102531592A (en) * | 2011-11-10 | 2012-07-04 | 厦门万明电子有限公司 | Reduction-resistant Y5P ceramic capacitor dielectric porcelain |
| CN102584233A (en) * | 2012-01-11 | 2012-07-18 | 深圳顺络电子股份有限公司 | Medium and high dielectric constant low temperature co-fired ceramic material and preparation method thereof |
| CN102584233B (en) * | 2012-01-11 | 2013-12-25 | 深圳顺络电子股份有限公司 | Medium and high dielectric constant low temperature co-fired ceramic material and preparation method thereof |
| US9144971B2 (en) | 2012-12-28 | 2015-09-29 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric element, and electronic apparatus |
| CN103910525A (en) * | 2012-12-28 | 2014-07-09 | 佳能株式会社 | Piezoelectric Material, Piezoelectric Element, And Electronic Apparatus |
| CN103910525B (en) * | 2012-12-28 | 2016-05-25 | 佳能株式会社 | Piezoelectric, piezoelectric element and electronic installation |
| US9159903B2 (en) | 2013-07-12 | 2015-10-13 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric element, and electronic equipment |
| CN104276822A (en) * | 2013-07-12 | 2015-01-14 | 佳能株式会社 | Piezoelectric material, piezoelectric element, and electronic apparatus |
| US9166140B2 (en) | 2013-07-12 | 2015-10-20 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric element, and electronic device |
| CN104276819A (en) * | 2013-07-12 | 2015-01-14 | 佳能株式会社 | Piezoelectric Material, Piezoelectric Element, And Electronic Apparatus |
| CN104276822B (en) * | 2013-07-12 | 2017-05-10 | 佳能株式会社 | Piezoelectric material, piezoelectric element, and electronic apparatus |
| US9722170B2 (en) | 2013-07-12 | 2017-08-01 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric element, and electronic device |
| US9761788B2 (en) | 2013-07-12 | 2017-09-12 | Canon Kabushiki Kaisha | Piezoelectric material, piezoelectric element, and electronic apparatus |
| CN106518067A (en) * | 2016-10-27 | 2017-03-22 | 盐城工学院 | Ceramic composition, ceramic as well as preparation method and application of ceramic |
| CN111635223A (en) * | 2020-06-16 | 2020-09-08 | 广东国华新材料科技股份有限公司 | Composite microwave dielectric ceramic and preparation method thereof |
| CN111635223B (en) * | 2020-06-16 | 2022-03-22 | 广东国华新材料科技股份有限公司 | Composite microwave dielectric ceramic and preparation method thereof |
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