CN100390099C - Dielectric ceramic composition and monolithic ceramic capacitor - Google Patents
Dielectric ceramic composition and monolithic ceramic capacitor Download PDFInfo
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- CN100390099C CN100390099C CNB2005800203039A CN200580020303A CN100390099C CN 100390099 C CN100390099 C CN 100390099C CN B2005800203039 A CNB2005800203039 A CN B2005800203039A CN 200580020303 A CN200580020303 A CN 200580020303A CN 100390099 C CN100390099 C CN 100390099C
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Abstract
A dielectric ceramic composition according to the present invention contains a substance represented by general formula 100 (Ba 1-x Ca x ) m TiO 3 + aMnO + bCuO + cRO n (wherein the coefficients 100, a, b, and c each represent a molar ratio; R represents at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; and n represents a number determined by the valence of the rare-earth element R and is a positive number required for maintaining electroneutrality) and a sintering aid. The dielectric ceramic composition satisfies the relationships 0.990<=m<=1.050; 0.01<=x<=0.20; 0.5<=a<=3.5; 0.1<=b<=5.0; and 10<=c<=20, and the amount of the sintering aid represented by d in terms of parts by weight satisfies 0.8<=d<=5.0 with respect to 100 parts by weight of the compound represented by (Ba 1-x Ca x ) m TiO 3. Furthermore, VO 3/2 may be added to increase the breakdown field.
Description
Technical field
The present invention relates to dielectric ceramic composition and monolithic ceramic capacitor, specifically, the monolithic ceramic capacitor that relates to dielectric ceramic composition and show high reliability when under high dc voltage or high frequency and/or high AC voltage, working.
Background technology
Monolithic ceramic capacitor uses under low AC voltage of low frequency or DC low pressure usually.Yet along with the progress of electronics, the miniaturization of electronic component has obtained progress fast.Thereby, also promoted the capacity increase of monolithic ceramic capacitor and further developing of miniaturization.Therefore, be applied to the trend that electric field between a pair of opposite electrode of ceramic condenser is correspondingly just showing as increase.Under these conditions, people have proposed the intensive demand to the improvement of heavy body, low-loss, insulativity and the improvement of reliability.
For this point, patent documentation 1 and patent documentation 2 have been instructed and can have been stood at the high AC voltage of high frequency or dielectric ceramic composition of working under high dc voltage and monolithic ceramic capacitor.
The dielectric ceramic composition described in the patent documentation 1 comprise 100 weight parts by general formula ABO
3+ aR+bM (wherein, ABO
3It is the general formula of expression barium titanate sosoloid; R represents to be selected from least a oxide compound in the group of being made up of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And M represents to be selected from least a oxide compound in the group of being made up of Mn, Ni, Mg, Fe, Al, Cr and Zn) main ingredient of expression and the sintering aid of 0.8～8.0 weight part, the wherein satisfied 0.950≤A/B of A/B (mol ratio), a and b≤1.050,0.12＜a≤0.30 and 0.04≤b≤0.30.The X that it is 0.35mol or less amount that this dielectric ceramic composition can also comprise with respect to every mole of barium titanate sosoloid (Zr, Hf) O
3(wherein, X is selected from least a among Ba, Sr and the Ca), and/or with respect to every mole of barium titanate sosoloid D (wherein, D is at least a oxide compound that is selected from the group of being made up of V, Nb, Ta, Mo, W, Y and Sc) that is 0.02mol or less amount.This dielectric ceramic composition shows 200 or bigger relative permittivity, the low-loss under high frequency and/or high AC voltage and the high specific insulation resistance under high field intensity, satisfy B characteristic and X7R characteristic, and work as it 1, when 300 ℃ or lower sintering, it has long average Time To Failure in high temperature load test.
Anti-reductive action (reduction-resistant) dielectric ceramic of in patent documentation 2, describing comprise 100 weight parts by general formula ABO
3+ aR+bM (wherein, ABO
3It is the general formula of expression barium titanate sosoloid; R represents to be selected from least a oxide compound in the group of being made up of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And M represents to be selected from least a oxide compound in the group of being made up of Mn, Ni, Mg, Fe, Al, Cr and Zn) shown in main ingredient and the sintering aid of 0.2～4.0 weight part, wherein A/B (mol ratio), a and b satisfy 1.000≤A/B 1.035,0.005≤a≤0.12 and 0.005≤b≤0.12.X (Zr, Hf) O that it is 0.20mol or less amount that this dielectric ceramic composition can further comprise with respect to every mole of barium titanate sosoloid
3(wherein, X is selected from least a among Ba, Sr and the Ca), and/or with respect to every mole of barium titanate sosoloid D that is 0.02mol or less amount (wherein, at least a oxide compound in the group formed by V, Nb, Ta, Mo, W, Y, Sc, P, Al and Fe of D).In this dielectric ceramic composition, the crystallographic axis of being determined-25 ℃ or higher temperature range by X-ray diffraction is than the satisfied 1.000≤c/a of c/a≤1.003, and apply in the process of 2Vms/mm that frequency is 1kHz or lower AC field, be lower than under-25 ℃ the temperature, observing relative permittivity and local maximum occurs with respect to temperature variation.This dielectric ceramic composition shows low-loss and generation low in calories under high frequency and/or high AC voltage, and shows stable insulation resistance when applying AC or dc voltage.
Patent documentation 1: the open 2000-103668 of Japanese unexamined patent
Patent documentation 2: the open 2002-50536 of Japanese unexamined patent
Summary of the invention
The problem to be solved in the present invention
Disclosed dielectric ceramic composition has high reliability under high frequency and/or high AC voltage or at high dc voltage in patent documentation 1 and 2.
Yet the electronic component that stronger from now on needs are littler, capacity is bigger is such as monolithic ceramic capacitor, and expects that from now on the frequency and the intensity of institute's applied field will further improve in the course of the work.Therefore, the characteristic of improving under these working conditions has become a urgent task with reliability.
And when the thickness of ceramic layer reduced, operating voltage was close towards voltage breakdown (hereinafter, being known as " BDV ").Therefore, another free-revving engine is to improve the electric field of stupalith when breakdown.
The present invention is based on above-mentioned existing situation and finishes.Its objective is the monolithic ceramic capacitor that a kind of dielectric ceramic composition is provided and constitutes by this dielectric ceramic composition, wherein said dielectric ceramic composition produces low in calories in high frequency and/or high AC voltage or the working process under high dc voltage, its relative permittivity and specific insulation resistance can compare favourably with the relative permittivity and the specific insulation resistance of prior art, and have the high reliability of this future trend that is suitable for further miniaturization and capacity increase.
Except these advantages, the present invention aims to provide a kind of the have higher breakdown field (breakdownfield) and the monolithic ceramic capacitor of high reliability more.
The mode of dealing with problems
Dielectric ceramic composition of the present invention (claim 1) comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cRO
n(wherein, coefficient 100, a, b and c represent mol ratio separately; R represents to be selected from least a element in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And n represents by counting of determining of the valency of rare-earth element R and is to keep the needed positive number of electric neutrality) material and the sintering aid of expression, wherein said dielectric ceramic composition satisfies following relationship:
0.990≤m≤1.050,0.01≤x≤0.20,0.5≤a≤3.5,0.1≤b≤5.0 and 10≤c≤20, and with respect to 100 weight parts by (Ba
1-xCa
x)
mTiO
3The compound of expression, the described sintering aid amount of being represented by d satisfies 0.8≤d≤5.0 according to the weight part meter.
As in the dielectric ceramic composition of claim 2, at (the Ba of every 100mol
1-xCa
x)
mTiO
3In the shown compound, the dielectric ceramic composition of claim 1 comprises 7.0mol or MO still less (wherein, M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn).
As in the dielectric ceramic composition of claim 3, at (the Ba of every 100mol
1-xCa
x)
mTiO
3In the shown compound, claim 1 or 2 dielectric ceramic composition comprise 15mol or X still less (Zr, Hf) O
3(wherein, X is at least a element that is selected from the group of being made up of Ba, Sr and Ca).
As in the dielectric ceramic composition of claim 4, preferably comprise SiO as sintering aid according to each described dielectric ceramic composition in the claim 1 to 3
2
The invention still further relates to the monolithic ceramic capacitor of the above-mentioned dielectric ceramic composition of a kind of fusion.
Monolithic ceramic capacitor of the present invention (claim 5) comprise a plurality of dielectric ceramic layers that are laminated to each other, the interior electrode between described dielectric ceramic layer and with described in the outer electrode that is electrically connected of electrode, wherein said dielectric ceramic layer comprises according to each described dielectric ceramic composition in the claim 1 to 4.
As at the monolithic ceramic capacitor of claim 6, the monolithic ceramic capacitor of claim 5 preferably has the interior electrode that comprises electro-conductive material, and described electro-conductive material contains Ni or Ni alloy or Cu or Cu alloy as main ingredient.
Dielectric ceramic composition of the present invention (claim 7) comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cVO
3/2+ dRO
n(wherein coefficient 100, a, b, c and d represent mol ratio separately; R is at least a element that is selected from the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And n represents by counting of determining of the valency of R and is to keep the needed positive number of electric neutrality) shown in material and sintering aid, wherein said dielectric ceramic composition satisfies and to concern 0.990≤m≤1.050,0.01≤x≤0.20,0.5≤a≤3.5,0.1≤b≤5.0,0.1≤c≤3.0 and 8≤d≤20, wherein with respect to 100 weight parts by (Ba
1-xCa
x)
mTiO
3The compound of expression, the described sintering aid amount of being represented by e satisfies 0.8≤e≤5.0 according to the weight part meter.
Dielectric ceramic composition as claimed in claim 8 is such, every 100mol by (Ba
1-xCa
x)
mTiO
3In the shown compound, the dielectric ceramic composition of claim 1 preferably comprises 7.0mol or MO still less (wherein, M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn).
Dielectric ceramic composition as claimed in claim 9 is such, every 100mol by (Ba
1-xCa
x)
mTiO
3In the shown compound, claim 7 or 8 dielectric ceramic composition preferably comprise 15mol or X still less (Zr, Hf) O
3(wherein, X is at least a element that is selected from the group of being made up of Ba, Sr and Ca).
As the dielectric ceramic composition of claim 10, preferably comprise SiO as sintering aid according to each the described dielectric ceramic composition in the claim 7 to 9
2
The invention still further relates to a kind of monolithic capacitor that contains above-mentioned dielectric ceramic composition.
Monolithic ceramic capacitor of the present invention (claim 11) comprise a plurality of dielectric ceramic layers that are laminated to each other, the interior electrode between described dielectric ceramic layer and with described in the outer electrode that is electrically connected of electrode, wherein said dielectric ceramic layer comprises according to each described dielectric ceramic composition in the claim 7 to 10.
As at the monolithic ceramic capacitor of claim 12, the monolithic ceramic capacitor of claim 11 preferably has the interior electrode that comprises electro-conductive material, and described electro-conductive material contains Ni or Ni alloy or Cu or Cu alloy as main ingredient.
Advantage
According to the invention described in the application's the claim 1 to 6, even when miniaturization from now on and capacity increase further make progress, also can be provided in the work under high dc voltage or high frequency and/or the high AC voltage quantity of heat production low, have specific insulation resistance that can compare favourably and a monolithic ceramic capacitor with high reliability with the dielectric ceramic composition of prior art.
According to the described invention of claim 7 to 12, except above-mentioned advantage, can provide to have the higher breakdown field and the monolithic ceramic capacitor of high reliability more.
Description of drawings
Figure 1 shows that the cross-sectional view of an embodiment (first embodiment) of expression monolithic ceramic capacitor of the present invention.
Figure 2 shows that the cross-sectional view of an embodiment (second embodiment) of expression monolithic ceramic capacitor of the present invention.
Label symbol
1,21: monolithic ceramic capacitor
2,22: the dielectric ceramic layer
3,23: laminating material
4,5,24,25: the first and second outer electrodes
6,7,26,27: the first electrolytic coatings
8,9,28, electrode in 29: the first and second
10,11,30,31: the second electrolytic coatings
Embodiment
＜the first embodiment 〉
At first, description is according to the composition of dielectric ceramic composition of the present invention (claim 1～4).
Dielectric ceramic composition of the present invention comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cRO
nThe main ingredient of expression and the sintering aid of d weight part, wherein satisfied 0.990≤m≤1.050,0.01≤x≤0.20,0.5≤a≤3.5,0.1≤b≤5.0,10≤c≤20 and 0.8≤d≤5.0 of concerning of m, x, a, b, c and d.
That is to say, by to wherein with rare earth oxide RO
nMain ingredient (BaCa) TiO with MnO adding dielectric ceramic composition
3In system in the new CuO that adds, can obtain so a kind of dielectric ceramic composition: it suppresses the heat generation in high frequency and/or high AC voltage or the working process under high dc voltage, have the relative permittivity that can compare favourably with prior art and specific insulation resistance and have high reliability; And can be with the dielectric ceramic material that acts on the monolithic ceramic capacitor that needs further miniaturization and further increase capacity from now on.This is because at relatively large rare earth oxide RO
n, i.e. the main ingredient barium calcium titanate (Ba of every 100mol
1-xCa
x)
mTiO
3In contain 10～20mol, play the cause of synergistic effect with initiate CuO.
Rare earth oxide RO
nMajor portion dissolve in (Ba
1-xCa
x)
mTiO
3In the principal phase particulate part, thereby each particle all is divided into and is substantially free of RO
nNuclear and contain RO
nThe shell of sosoloid.Because so a kind of grain pattern, therefore the phase transition temperature of pottery of the present invention from tetragonal spheroidal to the isometric system can not surpass room temperature, and for example this temperature is-80 ℃ approximately.Therefore, at room temperature, crystalline structure is isometric system or approximate isometric system.By inference, suppress the effect of heat generation in the work under high dc voltage or high frequency and/or high AC voltage from this crystalline structure.
Main ingredient (Ba at dielectric ceramic composition
1-xCa
x)
mTiO
3In, (Ba+Ca) the mol ratio m with Ti satisfies 0.990≤m≤1.050.Less than 0.990 o'clock, specific insulation resistance ρ was less than 10 at m
11Ω m, this value has been a low value.Surpass at 1.050 o'clock at m, high temperature load test (170 ℃, DC field intensity: 40kV/mm, dielectric thickness: the average Time To Failure (MTTF) 10 μ m) was less than 150 hours, and this time has been the short time.
At barium calcium titanate (Ba
1-xCa
x)
mTiO
3In Ca content x satisfy 0.01≤x≤0.20 according to its mol ratio.When x less than 0.01 the time, the MTTF in high temperature load test was less than 150 hours, this time has been the short time.Surpass 0.20 at x, relative permittivity is reduced to less than 300.
With respect to 100 (Ba
1-xCa
x)
mTiO
3And the MnO content a according to molar ratio computing satisfies 0.5≤a≤3.5.If a is less than 0.5 or greater than 3.5, then specific insulation resistance ρ becomes and is lower than 10
11Ω m.
With respect to 100 (Ba
1-xCa
x)
mTiO
3And the CuO content b according to molar ratio computing satisfies 0.1≤b≤5.0.If b is less than 0.1, then the MTTF in high temperature load test becomes and is less than 150 hours.Surpass at 5.0 o'clock at b, specific insulation resistance ρ becomes and is lower than 10
11Ω m.
With respect to 100 (Ba
1-xCa
x)
mTiO
3And RO according to molar ratio computing
nContent c satisfies 10≤c≤20.If c is less than 10, then the MTTF in high temperature load test becomes and is less than 100 hours.Surpass at 20 o'clock at c, relative permittivity becomes and is lower than 300.R is selected from least a in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, maybe can be to contain the wherein compound of the appropriate combination of two or more elements.In addition, at RO
nIn n be the number of determining by the valency of rare-earth element R, and expression keeps the needed positive number of electric neutrality.For example, when R is La, n=1.5, and when R is Ce, n=2.
Dielectric ceramic composition of the present invention comprises the sintering aid as auxiliary component of d weight part, wherein with respect to the main ingredient of 100 weight parts, satisfy and concerns 0.8≤d≤5.0.When the content d of sintering aid less than 0.8 the time, the stable sintering difficulty that becomes.When d surpasses 5.0, the MTTF in high temperature load test becomes and is as short as less than 150 hours.Can adopt existing sintering aid as sintering aid, not have special restriction.In the present invention, preferably adopt SiO
2As sintering aid.
And as other component in main ingredient, dielectric ceramic composition of the present invention is preferably at the (Ba of every 100mol
1-xCa
x)
mTiO
3In comprise 7.0mol or MO still less.By MO is added in the main ingredient, relatively dielectric than and the reliability under high-temperature load can improve when not adding MO.When MO content surpassed 7.0mol, the relative permittivity ratio was low when not adding MO, and this situation is not preferred.Herein, M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn.M can be a kind of element or two or more element of suitably selecting from these elements.
As other component in main ingredient, dielectric ceramic composition of the present invention can be at (the Ba of every 100mol
1-xCa
x)
mTiO
3In comprise 15mol or X still less (Zr, Hf) O
3When with X (Zr, Hf) O
3When adding in the main ingredient, than not adding X (Zr, Hf) O
3The time, can obtain higher relative permittivity and high-temperature load reliability.If X is (Zr, Hf) O
3Surpass 15mol, then than not adding X (Zr, Hf) O
3The time, its relative permittivity can reduce unfriendly.Herein, X represents to be selected from least a element in the group of being made up of Ba, Sr and Ca.Although Hf and Zr are at X (Zr, Hf) O
3In ratio do not have special restriction, but consider its preferred 30mol% or littler from the viewpoint of stable sintering.
The method for preparing dielectric ceramic composition of the present invention (claim 1～4) is then described.
Preparation is used for the (Ba of dielectric ceramic composition
1-xCa
x)
mTiO
3The method of material powder does not have particular restriction, as long as can prepare the ceramic composition that above-mentioned general formula is represented.For example, can adopt the dried synthesis method of the mixture calcining of parent material being carried out again solid state reaction.Alternatively, can adopt wet synthesis method, such as hydrothermal synthesis method, hydrolysis method or sol-gel method.
Be used for RO
n, MnO, CuO and SiO
2Starting raw material be not limited to oxide powder, as long as they can prepare dielectric ceramic composition of the present invention, wherein said RO
n, MnO, CuO and SiO
2Be to be added into (Ba
1-xCa
x)
mTiO
3Material powder is the component in the main ingredient.For example, can adopt carboxide powder, alkoxide or organometallic solution or analogue as starting raw material.
By the above-mentioned material powder of sintering, can obtain dielectric ceramic composition of the present invention.
Then, the structure that fusion has the monolithic ceramic capacitor of the present invention (claim 5 and 6) of (claim 1～4) of dielectric ceramic composition of the present invention is described, and the method for preparing this monolithic ceramic capacitor.
In the following description, explain the present invention based on embodiment shown in Figure 1.Fig. 1 is the schematic cross section that illustrates according to the monolithic ceramic capacitor of the present embodiment of the present invention.
As shown in Figure 1, for example, the monolithic ceramic capacitor 1 of the present embodiment comprises the layered product 3 that contains lamination dielectric ceramic layer 2 and inserts electrode 8 and 9 in first and second between the described dielectric ceramic layer 2.On two end faces of layered product 3, form the first external electrode 4 and the second external electrode 5 respectively, and these outer electrodes are electrically connected with electrode 8 and 9 in first and second.
As shown in Figure 1, each in first electrode 8 all extend to the other end (right-hand member) near dielectric ceramic layer 2 from the end (left end in the drawings) of dielectric ceramic layer 2.Each the second inner electrode 9 extends near left end from the right-hand member of dielectric ceramic layer.Electrodes 8 and 9 all are to be made of the conducting metal that for example contains as the Ni of main ingredient in first and second.
As shown in Figure 1, the first external electrode 4 with in layered product 3 first in electrode 8 be electrically connected, and the second external electrode 5 is electrically connected with the second inner electrode 9 in layered product 3.For example, first and second outer electrodes 4 and 5 all constitute by containing as the Cu of main ingredient or the conducting metal of Ag.Coating first electrolytic coating 6 and 7 is coated with second electrolytic coating 10 and 11 then on first and second outer electrodes 4 and 5 the surface.
Since dielectric ceramic composition of the present invention can be in reducing atmosphere sintering, so the interior electrode of electrical condenser preferably is made of the electro-conductive material that contains Ni or its alloy or Cu or its alloy.By this way, interior electrode can low-cost prepare.
Therefore, fusion has the monolithic ceramic capacitor of dielectric ceramic composition of the present invention to have 300 or bigger relative permittivity and 10
11Ω m or bigger specific insulation resistance, and in the process that applies the high AC voltage of high frequency (at 300kHz time 10kVp-p/mm), produce littler heat and have 0.8% or lower dielectric loss.It also high temperature load test (170 ℃, DC field intensity: 40kV/mm, dielectric thickness: had 150 hours 10 μ m) or the MTTF of longer time, thereby show high reliability.
＜embodiment 1-1 〉
In the present embodiment, preparation monolithic ceramic capacitor 1 shown in Figure 1.
At first, preparation high purity powdered form BaCO
3, CaCO
3And TiO
2As main ingredient (Ba
L-xCa
x)
mTiO
3Starting raw material, mix again, with gained improved Ca content x and (Ba+Ca) and the mol ratio m of Ti be illustrated in the table 1.
The powder for preparing is carried out wet mixing in ball mill close.After powder is evenly dispersed, be dried, obtain adjusted powder.
Should adjusted powder at 1,000 ℃ or higher temperature lower calcination, to obtain to satisfy x in the table 1 and the (Ba of m
1-xCa
x)
mTiO
3Powder.
Preparation MnCO
3, CuO, SiO
2, Y
2O
3, La
2O
3, CeO
2, Pr
5O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3And Lu
2O
3Powder, as the starting raw material that is used for auxiliary component.The starting raw material and (Ba that will be used for auxiliary component
1-xCa
x)
mTiO
3Powder mixes, thereby acquisition has the composition of the x shown in the table 1, m, a, b, c and d.In the present embodiment, adopt SiO
2As sintering aid.
Then, the wet mixing in ball mill of prepared powder is closed.After powder is evenly dispersed, be dried, obtain to be used for the material powder of dielectric ceramic composition.
Polyvinyl butyral acetal-based binder and organic solvent are joined in the material powder such as ethanol, and the wet mixing in ball mill of gained mixture is closed, with the soup compound of preparation ceramic powder.
By scraping the skill in using a kitchen knife in cookery ceramic soup compound being formed thin slice, is the ceramic green thin slice of 14 μ m with preparation thickness, and then, the conductive paste that will contain as the Ni of main ingredient by silk screen printing is coated on this ceramic green thin slice, thus the conductive paste film of electrode in being formed for.
Subsequently,, make it alternately be placed in the side that conductive paste film is extracted as shown in Figure 1, with preparation birth layered product by with the ceramic green sheet lamination.In nitrogen atmosphere, be heated to 350 ℃ temperature with giving birth to layered product,, in reducing atmosphere and under the temperature shown in the table 2, cured 2 hours then so that binding agent is burnt, thus acquisition layered product 3, and wherein said reducing atmosphere contains oxygen partial pressure and is
10
-9～10
-12The H of MPa
2-N
2-H
2The O mixed gas.
Preparation contains B
2O
3-SiO
2The Ag paste of-BaO-base glass powder, and this Ag paste is coated on two end surfaces that the interior electrode 8 and 9 of layered product 3 is exposed.Then, with the Ag paste at N
2Cure under the temperature of atmosphere and 600 ℃, thus form with on two end surfaces of layered product 3 first and second in first and second outer electrodes 4 and 5 that are electrically connected of electrode 8 and 9.Subsequently, two steps were carried out in the surface of first and second outer electrodes 4 and 5 electroplate, form first electrolytic coating 6 and 7 and second electrolytic coating 10 and 11, thereby obtain monolithic ceramic capacitor 1.
The outside dimension of thus obtained monolithic ceramic capacitor 1 is wide 3.2mm, long 4.5mm and thick 0.5mm.The thickness that is inserted in the dielectric ceramic layer between the adjacent interior electrode is 10 μ m.Add up to 5 for what obtain the effective dielectric ceramic layer of electrical capacity, the area of opposite electrode is 2.5 * 10 in every layer
-6m
2With thus obtained sample number into spectrum is that 1～51 monolithic ceramic capacitor is analyzed, to estimate electrical characteristic.The result is table 2 illustrate.
In table 1 and 2, band asterisk sample is outside the present invention's's (claim 1～6) scope.
The method and the evaluation result of the electrical characteristic of estimating monolithic ceramic capacitor will be described now.
A. relative permittivity (ε r) and dielectric loss (tan δ)
Adopt automatic bridge-type meter, in the sample number into spectrum 1～51 each is all applied the signal voltage of 50Vrms/mm (1kHz), to measure electrical capacity (C) and dielectric loss (tan δ).Based on the structure of each monolithic ceramic capacitor, by the observed value calculating relative permittivity (ε r) of electrical capacity.The result is table 2 illustrate.
B. specific insulation resistance (ρ)
Adopt Insulation Resistance Tester, under 25 ℃, each in sample number into spectrum 1～51 all applies the dc voltage 1 minute of 300V, with measurement insulation resistance, and calculates specific insulation resistance (ρ) by this insulation resistance.The result is table 2 illustrate.
C. average Time To Failure (MTTF)
As high temperature load test, under 170 ℃, each in sample number into spectrum 1～51 all applies the dc voltage of 400V, with the variation of measurement insulation resistance with respect to the time.In high temperature load test, each sample all is assumed to when its insulation resistance and becomes 10
6Ω or more hour just fail determines the average Time To Failure of each sample thus.The result is table 2 illustrate.
D. the dielectric loss in applying the high-frequency AC voltage process (tan δ)
For the heat of estimating in applying high-frequency process produces, each in sample number into spectrum 1～51 all applies the signal voltage of 10kVp-p/mm (300kHz), to measure dielectric loss (tan δ).The result is table 2 illustrate.
Table 1
| Sample number into spectrum | m | x | R | a | b | c | d |
| *1 | 0.980 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 2 | 0.990 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 3 | 1.000 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 4 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 5 | 1.030 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 6 | 1.050 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| *7 | 1.060 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| *8 | 1.010 | 0.00 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 9 | 1.010 | 0.01 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 10 | 1.010 | 0.10 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 11 | 1.010 | 0.15 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| 12 | 1.010 | 0.20 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| *13 | 1.010 | 0.25 | Gd | 1.0 | 1.0 | 12 | 1.25 |
| *14 | 1.010 | 0.06 | Gd | 0.0 | 1.0 | 12 | 1.25 |
| *15 | 1.010 | 0.06 | Gd | 0.2 | 1.0 | 12 | 1.25 |
| 16 | 1.010 | 0.06 | Gd | 0.5 | 1.0 | 12 | 1.25 |
| 17 | 1.010 | 0.06 | Gd | 2.0 | 1.0 | 12 | 1.25 |
| 18 | 1.010 | 0.06 | Gd | 3.5 | 1.0 | 12 | 1.25 |
| *19 | 1.010 | 0.06 | Gd | 4.0 | 1.0 | 12 | 1.25 |
| *20 | 1.010 | 0.06 | Gd | 1.0 | 0.0 | 12 | 1.25 |
| 21 | 1.010 | 0.06 | Gd | 1.0 | 0.1 | 12 | 1.25 |
| 22 | 1.010 | 0.06 | Gd | 1.0 | 0.5 | 12 | 1.25 |
| 23 | 1.010 | 0.06 | Gd | 1.0 | 2.0 | 12 | 1.25 |
| 24 | 1.010 | 0.06 | Gd | 1.0 | 5.0 | 12 | 1.25 |
| *25 | 1.010 | 0.06 | Gd | 1.0 | 6.0 | 12 | 1.25 |
| *26 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 9 | 1.25 |
| 27 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 10 | 1.25 |
| 28 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 15 | 1.25 |
| 29 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 18 | 1.25 |
| 30 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 20 | 1.25 |
| *31 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 22 | 1.25 |
| *32 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 0.60 |
| 33 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 0.80 |
| 34 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 2.00 |
| 35 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 3.00 |
| 36 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 5.00 |
| *37 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 6.00 |
| 38 | 1.010 | 0.06 | Y | 1.0 | 1.0 | 12 | 1.25 |
| 39 | 1.010 | 0.06 | La | 1.0 | 1.0 | 12 | 1.25 |
| 40 | 1.010 | 0.06 | Ce | 1.0 | 1.0 | 12 | 1.25 |
| 41 | 1.010 | 0.06 | Pr | 1.0 | 1.0 | 12 | 1.25 |
| 42 | 1.010 | 0.06 | Nd | 1.0 | 1.0 | 12 | 1.25 |
| 43 | 1.010 | 0.06 | Sm | 1.0 | 1.0 | 12 | 1.25 |
| 44 | 1.010 | 0.06 | Eu | 1.0 | 1.0 | 12 | 1.25 |
| 45 | 1.010 | 0.06 | Tb | 1.0 | 1.0 | 12 | 1.25 |
| 46 | 1.010 | 0.06 | Dy | 1.0 | 1.0 | 12 | 1.25 |
| 47 | 1.010 | 0.06 | Ho | 1.0 | 1.0 | 12 | 1.25 |
| 48 | 1.010 | 0.06 | Er | 1.0 | 1.0 | 12 | 1.25 |
| 49 | 1.010 | 0.06 | Tm | 1.0 | 1.0 | 12 | 1.25 |
| 50 | 1.010 | 0.06 | Yb | 1.0 | 1.0 | 12 | 1.25 |
| 51 | 1.010 | 0.06 | Lu | 1.0 | 1.0 | 12 | 1.25 |
Table 2
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Ωm〕 | MTTF〔hr〕 | tanδ〔％〕 (300kHz) |
| *1 | 1200 | 620 | 0.4 | 6.2*10 10 | 120 | 0.8 |
| 2 | 1200 | 620 | 0.4 | 8.3*10 11 | 150 | 0.8 |
| 3 | 1200 | 620 | 0.4 | 7.2*10 11 | 155 | 0.7 |
| 4 | 1225 | 600 | 0.3 | 8.3*10 11 | 160 | 0.6 |
| 5 | 1250 | 580 | 0.5 | 6.5*10 11 | 160 | 0.7 |
| 6 | 1275 | 550 | 0.5 | 6.2*10 11 | 150 | 0.6 |
| *7 | 1300 | 530 | 0.5 | 4.4*10 11 | 130 | 0.6 |
| *8 | 1225 | 600 | 0.2 | 7.2*10 11 | 130 | 0.8 |
| 9 | 1200 | 620 | 0.3 | 7.6*10 11 | 150 | 0.8 |
| 10 | 1200 | 580 | 0.4 | 8.9*10 11 | 160 | 0.6 |
| 11 | 1200 | 550 | 0.3 | 8.2*10 11 | 170 | 0.6 |
| 12 | 1175 | 400 | 0.5 | 8.8*10 11 | 160 | 0.7 |
| *13 | 1175 | 280 | 0.5 | 4.2*10 11 | 150 | 0.7 |
| *14 | 1225 | - | - | 5.2*10 7 | - | - |
| *15 | 1200 | 610 | 0.4 | 7.6*10 10 | 65 | 0.8 |
| 16 | 1200 | 600 | 0.4 | 4.0*10 11 | 150 | 0.8 |
| 17 | 1200 | 580 | 0.3 | 5.1*10 11 | 160 | 0.8 |
| 18 | 1175 | 570 | 0.5 | 5.8*10 11 | 160 | 0.8 |
| *19 | 1175 | 550 | 0.5 | 4.2*10 10 | 130 | 0.8 |
| *20 | 1200 | 610 | 0.3 | 8.6*10 11 | 90 | 0.8 |
| 21 | 1200 | 600 | 0.3 | 6.0*10 11 | 150 | 0.8 |
| 22 | 1200 | 580 | 0.3 | 5.8*10 11 | 155 | 0.6 |
| 23 | 1175 | 570 | 0.5 | 4.8*10 11 | 160 | 0.7 |
| 24 | 1175 | 570 | 0.5 | 4.2*10 11 | 150 | 0.7 |
| *25 | 1175 | 570 | 0.5 | 3.1*10 10 | 90 | 0.7 |
| *26 | 1150 | 800 | 0.7 | 6.9*10 11 | 120 | 1.2 |
| 27 | 1175 | 730 | 0.4 | 5.1*10 11 | 150 | 0.6 |
| 28 | 1225 | 550 | 0.3 | 4.3*10 11 | 160 | 0.6 |
| 29 | 1250 | 480 | 0.3 | 4.1*10 11 | 170 | 0.6 |
| 30 | 1275 | 350 | 0.2 | 6.1*10 11 | 180 | 0.6 |
| *31 | 1300 | 270 | 0.1 | 5.3*10 11 | 200 | 0.6 |
| *32 | Sintering is insufficient | - | - | - | - | - |
| 33 | 1260 | 540 | 0.4 | 3.3*10 12 | 150 | 0.6 |
| 34 | 1150 | 600 | 0.4 | 4.3*10 12 | 160 | 0.7 |
| 35 | 1125 | 580 | 0.4 | 7.4*10 11 | 165 | 0.7 |
| 36 | 1100 | 540 | 0.2 | 7.7*10 11 | 150 | 0.5 |
| *37 | 1100 | 500 | 0.1 | 8.3*10 11 | 120 | 0.5 |
| 38 | 1225 | 570 | 0.2 | 7.4*10 11 | 150 | 0.5 |
| 39 | 1150 | 580 | 0.2 | 7.7*10 11 | 150 | 0.5 |
| 40 | 1150 | 560 | 0.3 | 8.3*10 11 | 150 | 0.6 |
| 41 | 1150 | 550 | 0.3 | 7.4*10 11 | 160 | 0.6 |
| 42 | 1150 | 600 | 0.1 | 7.7*10 11 | 160 | 0.5 |
| 43 | 1175 | 580 | 0.3 | 8.3*10 11 | 156 | 0.5 |
| 44 | 1175 | 590 | 0.2 | 7.4*10 11 | 155 | 0.5 |
| 45 | 1200 | 570 | 0.2 | 7.7*10 11 | 150 | 0.7 |
| 46 | 1200 | 550 | 0.4 | 8.3*10 11 | 170 | 0.8 |
| 47 | 1225 | 600 | 0.3 | 7.4*10 11 | 170 | 0.8 |
| 48 | 1225 | 590 | 0.3 | 7.7*10 11 | 160 | 0.7 |
| 49 | 1225 | 590 | 0.2 | 8.3*10 11 | 155 | 0.7 |
| 50 | 1250 | 800 | 0.3 | 7.4*10 11 | 155 | 0.6 |
| 51 | 1250 | 580 | 0.4 | 7.7*10 11 | 155 | 0.6 |
The result of table 2 shows, is being used for evaluation at (Ba
1-xCa
x)
mTiO
3In in the sample number into spectrum 1～7 of effect of mol ratio m of (Ba+Ca) and Ti, sample number into spectrum 2～6 shows as in the scope of the invention (0.990≤m≤1.050), their dielectric losses when 50Vrms/mm (1kHz) are 0.5% or lower, and keep relative permittivity be 300 or bigger in, have 10
11Ω m or bigger specific insulation resistance.(170 ℃, the DC field intensity: the MTTF 40kV/mm) is 150 hours or longer time, thereby shows high reliability at high temperature load test.Dielectric loss in the high-frequency AC electric current process of the 10kVp-p/mm that applies 300kHz is 0.8% or lower, that is, heat produces few.On the contrary, in the sample number into spectrum 1 and 7 outside the scope of the invention, it is 6.2 * 10 that m shows specific insulation resistance less than 0.990 sample number into spectrum 1
10Ω m is lower than 10
11Ω m.M surpasses 1.050 sample number into spectrum 7 and shows that MTTF is 130 hours in high temperature load test, is lower than 150 hours.
In sample number into spectrum 8～13, the sample number into spectrum 9～12 of improved Ca content x in the scope of the invention (0.01≤x≤0.20) all satisfies above-mentioned characteristic.On the contrary, in the sample number into spectrum 8 and 13 outside the scope of the invention, improved Ca content x shows 130 hours MTTF less than 0.01 sample number into spectrum 8, and this was than 150 hours weak points.X shows 280 relative permittivity above 0.20 sample number into spectrum 13, and this is lower than 300.
The result of table 2 illustrates, and at the sample number into spectrum 14～19 of the effect that is used for estimating MnO content a, the sample number into spectrum 16～18 within the scope of the invention (0.5≤a≤3.5) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 14,15 and 19 outside the scope of the invention, the sample number into spectrum 14 that does not contain MnO shows low-down specific insulation resistance, thereby can not calculate its ε r etc.A shows 7.6 * 10 less than 0.5 sample number into spectrum 15
10The specific insulation resistance of Ω m, this is lower than 10
11Ω m; And 65 hours MTTF, this result is shorter than 150 hours.A shows 4.2 * 10 above 3.5 sample number into spectrum 19
10The specific insulation resistance of Ω m, this specific insulation resistance is lower than 10
11Ω m.
The result of table 2 illustrates, and at the sample number into spectrum 20～25 of the effect that is used for estimating CuO content b, the sample number into spectrum 21～24 within the scope of the invention (0.1≤b≤5.0) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 20 and 25 outside the scope of the invention, CuO content b shows 90 hours MTTF less than 0.1 sample number into spectrum 20, and this result is shorter than 150 hours.B shows 3.1 * 10 above 5.0 sample number into spectrum 25
10The specific insulation resistance of Ω m, this result is lower than 10
11Ω m.
The result of table 2 illustrates, and is being used to estimate RO
nIn the sample number into spectrum 26～31 of the effect of content c, the sample number into spectrum 27～30 within the scope of the invention (10≤c≤20) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 26 and 31 outside the scope of the invention, RO
nContent c shows 120 hours MTTF less than 10 sample number into spectrum 26, and this result is shorter than 150 hours; And produce high heat, promptly show 1.2% dielectric loss in the process of the AC field of the 10kVp-p/mm that applies 300kHz, c shows 270 relative permittivity above 20.0 sample number into spectrum 31, and this result is lower than 300.
The result of table 2 illustrates, and is being used to estimate sintering aid (SiO
2) in the sample number into spectrum 32～37 of effect of amount d, the sample number into spectrum 33～36 within the scope of the invention (0.8≤d≤5.0) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 32 and 37 outside the scope of the invention, sintering aid content d is less than the abundant sintering of 0.8 sample number into spectrum 32.D shows 120 hours MTTF above 5.0 sample number into spectrum 37, and this result is shorter than 150 hours.
The result of table 2 illustrates, and is being used to estimate RO
n, i.e. in the sample number into spectrum 38～51 of the effect of rare-earth oxidation species, as long as their RO
nContent c all satisfies above-mentioned evaluating characteristics in the scope of the invention (10≤c≤20).
＜embodiment 1-2 〉
In the present embodiment, as shown in table 3, in the sample number into spectrum 4 of embodiment 1-1, further add MO, MO content e changes outside scope in preferable range of the present invention.By the monolithic ceramic capacitor that constitutes by the dielectric ceramic composition of sample number into spectrum 52～62 with the prepared identical with embodiment 1-1.Then, the electrical characteristic of these monolithic ceramic capacitors are estimated in the mode identical with embodiment 1-1.The result is table 4 illustrate.
Table 3
| Sample number into spectrum | m | x | R | a | b | c | | M | e | |
| 4 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | |
| 52 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 1.0 | |
| 53 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 2.0 | |
| 54 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | |
| 55 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 5.0 | |
| 56 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 8.0 | |
| 57 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 7.0 | |
| 58 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 8.0 | |
| 59 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Ni | 3.0 | |
| 60 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Ni | 8.0 | |
| 61 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Zn | 3.0 | |
| 62 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Zn | 8.0 |
Table 4
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Ωm〕 | MTTF 〔hr〕 | tanδ〔％〕 (300kHz) |
| 4 | 1225 | 600 | 0.3 | 8.3*10 11 | 160 | 0.7 |
| 52 | 1200 | 620 | 0.4 | 6.6*10 11 | 180 | 0.8 |
| 53 | 1200 | 620 | 0.4 | 7.2*10 11 | 175 | 0.7 |
| 54 | 1225 | 630 | 0.3 | 6.3*10 11 | 180 | 0.7 |
| 55 | 1225 | 600 | 0.4 | 8.5*10 11 | 190 | 0.7 |
| 56 | 1200 | 600 | 0.3 | 4.2*10 11 | 190 | 0.7 |
| 57 | 1175 | 600 | 0.3 | 5.5*10 11 | 190 | 0.7 |
| 58 | 1175 | 550 | 0.3 | 5.2*10 11 | 200 | 0.6 |
| 59 | 1200 | 600 | 0.3 | 5.4*10 11 | 180 | 0.6 |
| 60 | 1200 | 550 | 0.4 | 6.6*10 11 | 190 | 0.7 |
| 61 | 1200 | 620 | 0.4 | 8.6*10 11 | 180 | 0.6 |
| 62 | 1225 | 560 | 0.4 | 5.6*10 11 | 190 | 0.7 |
The result of table 4 illustrates, (the Ba of every 100mol
1-xCa
x)
mTiO
3The sample number into spectrum 52～57 that contains 7.0mol or MgO still less shows longer MTTF than the sample number into spectrum 4 that does not contain MgO.The sample number into spectrum 58 that MgO content exceeds preferable range of the present invention shows long MTTF, but unfriendly, its relative permittivity is lower than the relative permittivity of sample number into spectrum 4.Wherein be added into NiO rather than MgO sample number into spectrum 59 and 60 and the sample number into spectrum 61 and 62 that wherein is added into ZnO rather than MgO also show the result that can be comparable to the sample that contains MgO.
＜embodiment 1-3 〉
In the present embodiment, as shown in table 5, in the sample number into spectrum 4 of embodiment 1-1, further add X (Zr, Hf) O
3, and X (Zr, Hf) O
3Content f change outside this scope in preferable range of the present invention.By the monolithic ceramic capacitor that constitutes by the dielectric ceramic composition of sample number into spectrum 63～77 with the prepared identical with embodiment 1-1.Then, in the mode identical, estimate the electrical characteristic of these monolithic ceramic capacitors 1 with embodiment 1-1.The result is table 6 illustrate.
Table 5
| Sample number into spectrum | m | x | R | a | b | c | d | M | | X | f | |
| 4 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | Ba | 0.0 | |
| 63 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | Ba | 6.0 | |
| 64 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | Ba | 9.0 | |
| 65 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | Ba | 12.0 | |
| 66 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.258 | - | 0.0 | Ba | 15.0 | |
| 67 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | - | 0.0 | Ba | 18.0 | |
| 68 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 0.0 | |
| 69 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 6.0 | |
| 70 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 9.0 | |
| 71 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 12.0 | |
| 72 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 15.0 | |
| 73 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Mg | 3.0 | Ba | 18.0 | |
| 74 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Ni | 3.0 | Sr | 12.0 | |
| 75 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Ni | 3.0 | Sr | 18.0 | |
| 76 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Zn | 3.0 | Ca | 12.0 | |
| 77 | 1.010 | 0.06 | Gd | 1.0 | 1.0 | 12 | 1.25 | Zn | 3.0 | Ca | 18.0 |
Table 6
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Ωm〕 | MTTF 〔hr〕 | tanδ〔％〕 (300kHz) |
| 4 | 1225 | 600 | 0.3 | 8.3*10 11 | 160 | 0.7 |
| 63 | 1225 | 620 | 0.4 | 8.2*10 11 | 170 | 0.6 |
| 64 | 1225 | 660 | 0.4 | 6.2*10 11 | 170 | 0.6 |
| 65 | 1225 | 650 | 0.3 | 6.4*10 11 | 180 | 0.6 |
| 66 | 1250 | 600 | 0.4 | 7.5*10 11 | 190 | 0.6 |
| 67 | 1250 | 550 | 0.3 | 4.2*10 11 | 190 | 0.6 |
| 68 | 1200 | 630 | 0.3 | 8.9*10 11 | 190 | 0.6 |
| 69 | 1200 | 650 | 0.4 | 7.3*10 11 | 200 | 0.7 |
| 70 | 1200 | 650 | 0.4 | 8.8*10 11 | 200 | 0.7 |
| 71 | 1225 | 670 | 0.4 | 8.6*10 11 | 200 | 0.7 |
| 72 | 1225 | 630 | 0.4 | 8.5*10 11 | 190 | 0.7 |
| 73 | 1225 | 580 | 0.3 | 5.3*10 11 | 190 | 0.6 |
| 74 | 1200 | 660 | 0.3 | 7.7*10 11 | 190 | 0.6 |
| 75 | 1225 | 620 | 0.4 | 5.6*10 11 | 195 | 0.6 |
| 76 | 1200 | 660 | 0.4 | 8.3*10 11 | 190 | 0.6 |
| 77 | 1225 | 580 | 0.4 | 4.1*10 11 | 195 | 0.6 |
The result of table 6 illustrates, (the Ba of every 100mol
1-xCa
x)
mTiO
3Contain 15mol or X still less (Zr, Hf) O
3Sample number into spectrum 63～66 than not containing Ba (Zr, Hf) O
3Sample number into spectrum 4, have longer MTTF.Ba (Zr, Hf) O
3The sample number into spectrum 67 that content surpasses preferable range of the present invention shows long MTTF, but unfriendly, its relative permittivity is than not containing Ba (Zr, Hf) O
3The relative permittivity of sample number into spectrum 4 low.
The result of table 6 illustrates, wherein to the (Ba of 100mol
1-xCa
x)
mTiO
3In add 3molMgO and in preferable range of the present invention, add Ba (Zr, Hf) O
3Sample number into spectrum 68～73 show also longer MTTF.Ba (Zr, Hf) O
3The sample number into spectrum 73 of content outside preferable range of the present invention shows long MTTF, but unfriendly, and its relative permittivity is lower than the sample number into spectrum 4 of embodiment 1-1.Contain NiO or ZnO rather than MgO and contain Sr (Zr, Hf) O
3Or Ca (Zr, Hf) O
3Rather than Ba (Zr, Hf) O
3Sample show to be comparable to and contain MgO and Ba (Zr, Hf) O
3The result of sample.
Should be noted that the present invention is limited by the foregoing description never.
＜the second embodiment 〉
The composition of dielectric ceramic composition of the present invention (claim 7～10) is described now.
Dielectric ceramic composition of the present invention comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cVO
3/2+ dRO
nThe main ingredient of expression and the sintering aid of e weight part, wherein satisfied 0.99≤m≤1.05,0.01≤x≤0.20,0.5≤a≤3.5,0.1≤b≤5.0,0.1≤c≤3.0,0.8≤d≤20 and 0.8≤e≤5.0 of concerning of m, x, a, b, c, d and e.
Main ingredient (Ba at dielectric ceramic composition
1-xCa
x)
mTiO
3In the mol ratio m of (Ba+Ca) and Ti satisfy 0.99≤m≤1.050.Less than 0.990 o'clock, specific insulation resistance ρ was low excessively at m, and it is less than 10
11Ω m.Surpass at 1.050 o'clock at m, high temperature load test (170 ℃, DC field intensity: 40kV/mm, dielectric thickness: the average Time To Failure (MTTF) 10 μ m) is short, for example, less than 150 hours.
At barium calcium titanate (Ba
1-xCa
x)
mTiO
3Ca content x according to the mole meter than satisfying 0.01≤x≤0.20.When x less than 0.01 the time, the MTTF in high temperature load test is short, it was less than 150 hours.Surpass at 0.20 o'clock at x, relative permittivity is reduced to less than 300.
With respect to 100 (Ba
1-xCa
x)
mTiO
3MnO content a satisfy 0.5≤a≤3.5 according to molar ratio computing.If a is less than 0.5, then the MTTF in high temperature load test is short, promptly less than 150 hours.Surpass at 3.5 o'clock at a, specific insulation resistance ρ becomes and is lower than 10
11Ω m.
With respect to 100 (Ba
1-xCa
x)
mTiO
3CuO content b satisfy 0.1≤b≤5.0 according to molar ratio computing.If b is less than 0.1, then MTTF becomes and is shorter than 150 hours.Surpass at 5.0 o'clock at b, then specific insulation resistance ρ becomes less than 10
11Ω m.
With respect to 100 (Ba
1-xCa
x)
mTiO
3VO
3/2Content satisfies 0.1≤c≤3.0 according to molar ratio computing.When c less than 0.1 the time, BDV (frequency: 60Hz, dielectric thickness: 10 μ m) be reduced to less than 0.92kVrms.On the contrary, surpass at 3.0 o'clock at c, specific insulation resistance is reduced to less than 10
11Ω m.Annotate " VO
3/2" the expression valency is 3 vanadium oxide.Yet the valency of vanadium is not critical to the present invention.For example, can adopt different valencys, as VO
5/2, only otherwise damaging purpose of the present invention gets final product.
With respect to 100 (Ba
1-xCa
x)
mTiO
3RO
nContent d satisfies 8≤d≤20 according to molar ratio computing.When d less than 8 the time, the MTTF in high temperature load test was as short as less than 100 hours.When d greater than 20 the time, relative permittivity is reduced to less than 300.R can be at least a element that is selected from the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, perhaps can be the composition that contains the appropriate combination of two or more elements.In addition, RO
nIn n be the number of determining by the valency of rare-earth element R, and expression keeps the needed positive number of electric neutrality.For example, when R is La, n=1.5, and when R is Ce, n=2.
Dielectric ceramic composition of the present invention comprises the sintering aid of e weight part as auxiliary component, wherein with respect to the main ingredient of 100 weight parts, satisfy and concerns 0.8≤e≤5.0.When sintering aid content e less than 0.8 the time, the stable sintering difficulty that becomes.When e surpassed 5.0, the MTTF in high temperature load test became and is as short as less than 150 hours.Can adopt existing sintering aid as sintering aid, this does not have particular restriction.In the present invention, preferably adopt SiO
2As sintering aid.
As other component in main ingredient, dielectric ceramic composition of the present invention is preferably at the (Ba of every 100mol
1-xCa
x)
mTiO
3In comprise 7.0mol or MO still less.By MO is joined in the main ingredient, make when not adding MO, can improve relative dielectric than and the reliability under high-temperature load.When MO content surpassed 7.0mol, relative permittivity became when not adding MO low, and this result is not preferred.Herein, M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn.M can be a kind of element or the two or more element of suitably selecting from these elements.
As other component in main ingredient, dielectric ceramic composition of the present invention can be at (the Ba of every 100mol
1-xCa
x)
mTiO
3In comprise 15mol or X still less (Zr, Hf) O
3When with X (Zr, Hf) O
3When joining in the main ingredient, than not adding X (Zr, Hf) O
3The time, its relative permittivity and the reliability under high-temperature load can be enhanced.If X is (Zr, Hf) O
3Surpass 15mol, then unfriendly, than not adding X (Zr, Hf) O
3The time, its relative permittivity reduces.Herein, X represents to be selected from least a element in the group of being made up of Ba, Sr and Ca.Although at X (Zr, Hf) O
3In Hf and the ratio of Zr do not have particular restriction, but consider its preferred 30mol% or lower from the viewpoint of stable sintering.
As mentioned above, by to containing main ingredient (BaCa) TiO
3, rare earth oxide RO
nWith new CuO and the VO of adding in the system of MnO
3/2Can obtain so a kind of dielectric ceramic composition: can be suppressed in the working process under high dc voltage or high frequency and/or the high AC voltage and produce heat, show the relative permittivity and the specific insulation resistance that can be comparable to existing composition, and have the reliability of high breakdown field and improvement.Dielectric ceramic composition of the present invention can be with acting on the further dielectric ceramic material of the monolithic ceramic capacitor of increase of further miniaturization of expection and capacity.
Dielectric ceramic of the present invention comprises the relatively large i.e. rare earth oxide RO of 8～20mol
n, thereby this pottery is pressed onto high pressure in can being suitable for; Yet, rare earth oxide RO
nMajor part dissolve in (Ba
1-xCa
x)
mTiO
3In the principal phase particulate part, thereby each particle all is divided into and does not contain RO substantially
nNuclear and contain RO
nThe shell of sosoloid.Because so a kind of grain pattern, therefore the phase inversion temperature of pottery of the present invention from tetragonal spheroidal to the isometric system can not surpass room temperature, and for example, this temperature is-80 ℃ approximately.Therefore, at room temperature, crystalline structure is isometric system or approximate isometric system.According to estimates, being suppressed at the effect that produces heat in the working process under high dc voltage or high frequency and/or the high AC voltage is from this crystalline structure.
Especially, by comprising local dissolution at (Ba
1-xCa
x)
mTiO
3In rare-earth element R O
nWith initiate CuO and VO
3/2Synergy, can improve breakdown field.This may be because initiate VO
3/2Changed the ratio between the electric field part that is applied to intragranular electric field part and is applied to crystal boundary in the existence on the crystal boundary of ceramic structure.Another kind of to estimate to have the factor that helps to improve breakdown field be the existence of CuO, because the existence of CuO has improved ceramic homogeneity, thereby reduced the electrostrictive effect in high electric field application process.
Then, the method that is used to prepare dielectric ceramic composition of the present invention (claim 7～10) is described.
Preparation is used for the (Ba of dielectric ceramic composition
1-xCa
x)
mTiO
3The method of material powder does not have special restriction, as long as can prepare the ceramic composition shown in the above-mentioned general formula.For example, can adopt the dried synthesis method of the mixture calcining of parent material being carried out again solid state reaction.Alternatively, can adopt wet synthesis method, such as hydrothermal synthesis method, hydrolysis method or sol-gel method.
Be used for RO
n, MnO, CuO, VO
3/2And SiO
2Starting raw material be not limited to oxide powder, as long as they can prepare dielectric ceramic composition of the present invention, wherein said RO
n, MnO, CuO, VO
3/2And SiO
2Be to be added into (Ba
1-xCa
x)
mTiO
3Material powder is the component in the main ingredient.For example, can adopt carboxide powder, alkoxide or organometallic solution or analogue as starting raw material.
By the above-mentioned material powder of sintering, can obtain dielectric ceramic composition of the present invention.
Then, the structure that fusion has the monolithic ceramic capacitor of the present invention (claim 11 and 12) of dielectric ceramic composition of the present invention (claim 7～10) is described, and the method for preparing this monolithic ceramic capacitor.
In the following description, explain the present invention based on embodiment shown in Figure 2.Fig. 2 is the schematic cross section that illustrates according to the monolithic ceramic capacitor of the present embodiment of the present invention.
As shown in Figure 2, for example, the monolithic ceramic capacitor 21 of the present embodiment comprises the layered product 23 that contains lamination dielectric ceramic layer 22 and inserts electrode 28 and 29 in first and second between the described dielectric ceramic layer 22.On two end faces of layered product 23, form the first external electrode 24 and the second external electrode 25 respectively, and these outer electrodes are electrically connected with electrode 28 and 29 in first and second.
As shown in Figure 2, each in first electrode 28 all extend to the other end (right-hand member) near dielectric ceramic layer 22 from the end (left end in the drawings) of dielectric ceramic layer 22.Each the second inner electrode 29 extends near left end from the right-hand member of dielectric ceramic layer.Electrodes 28 and 29 all are to be made of the conducting metal that for example contains as the Ni of main ingredient in first and second.
As shown in Figure 2, the first external electrode 24 with in layered product 23 first in electrode 28 be electrically connected, and the second external electrode 25 is electrically connected with the second inner electrode 29 in layered product 23.For example, first and second outer electrodes 24 and 25 all constitute by containing as the Cu of main ingredient or the conducting metal of Ag.Coating first electrolytic coating 26 and 27 is coated with second electrolytic coating 30 and 31 then on first and second outer electrodes 24 and 25 the surface.
Since dielectric ceramic composition of the present invention can be in reducing atmosphere sintering, so the interior electrode of electrical condenser preferably is made of the electro-conductive material that contains Ni or its alloy or Cu or its alloy.By this way, interior electrode can low-cost prepare.
Therefore, fusion has the monolithic ceramic capacitor of dielectric ceramic composition of the present invention to have 300 or bigger relative permittivity and 10
11Ω m or bigger specific insulation resistance, and in the process that applies the high AC voltage of high frequency (at 300kHz time 10kVp-p/mm), produce littler heat and have 0.8% or lower dielectric loss.It also has high to 0.92kVrms or bigger BDV (dielectric thickness: 10 μ m) in the application process of AC field, and (170 ℃ of high temperature load tests, DC field intensity: 40kV/mm, dielectric thickness: had 150 hours 10 μ m) or MTTF for more time, thereby show high reliability.
＜embodiment 2-1 〉
In the present embodiment, preparation monolithic ceramic capacitor 21 shown in Figure 2.
At first, preparation high purity powdered form BaCO
3, CaCO
3And TiO
2As main ingredient (Ba
1-xCa
x)
mTiO
3Starting raw material, mix again, with gained improved Ca content x and (Ba+Ca) and the mol ratio m of Ti be illustrated in the table 7.
The powder for preparing is carried out wet mixing in ball mill close.After powder is evenly dispersed, be dried, to obtain adjusted powder.
Should adjusted powder at 1,000 ℃ or higher temperature lower calcination, to obtain to satisfy x in the table 7 and the (Ba of m
1-xCa
x)
mTiO
3Powder.
Preparation MnCO
3, CuO, V
2O
3, SiO
2, SiO
2, Y
2O
3, La
2O
3, CeO
2, Pr
5O
11, Nd
2O
3, Sm
2O
3, Eu
2O
3, Gd
2O
3, Tb
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3And Lu
2O
3Powder, as the starting raw material that is used for auxiliary component.The starting raw material and (Ba that will be used for auxiliary component
1-xCa
x)
mTiO
3Powder mixes, thereby acquisition has the composition of the x shown in the table 7, m, a, b, c and d.In the present embodiment, adopt SiO
2As sintering aid.
Then, the wet mixing in ball mill of prepared powder is closed.After powder is evenly dispersed, be dried, obtain to be used for the material powder of dielectric ceramic composition.
Polyvinyl butyral acetal-based binder and organic solvent are joined in the material powder such as ethanol, and the wet mixing in ball mill of gained mixture is closed, with the soup compound of preparation ceramic powder.
By scraping the skill in using a kitchen knife in cookery ceramic soup compound is formed thin slice, with preparation thickness is the ceramic green thin slice of 14 μ m, then, the conductive paste that will contain as the Ni of main ingredient by silk screen printing is coated on this ceramic green thin slice, thus the conductive paste film of electrode in being formed for forming.
Subsequently,, make it alternately be placed in the side that conductive paste film is removed as shown in Figure 2, with preparation birth layered product by with the ceramic green sheet lamination.In nitrogen atmosphere, be heated to 350 ℃ temperature with giving birth to layered product,, in reducing atmosphere and under the temperature shown in the table 8, cured 2 hours then so that binding agent is burnt, thus acquisition layered product 23, and it is 10 that wherein said reducing atmosphere contains oxygen partial pressure
-9～10
-12The H of MPa
2-N
2-H
2The O mixed gas.
Preparation contains B
2O
3-SiO
2The Ag paste of-BaO-base glass powder, and this Ag paste is coated on two end surfaces of the interior electrode 28 that wherein exposes layered product 23 and 29.Then, with the Ag paste at N
2Cure under the temperature of atmosphere and 600 ℃, thus form with on two end surfaces of layered product 23 first and second in first and second outer electrodes 24 and 25 that are electrically connected of electrode 28 and 29.Subsequently, two stages were carried out in the surface of first and second outer electrodes 24 and 25 electroplate (two-step plating), form first electrolytic coating 26 and 27 and second electrolytic coating 30 and 31, thereby obtain monolithic ceramic capacitor 21.
The outside dimension of thus obtained monolithic ceramic capacitor 21 is wide 3.2mm, long 4.5mm and thick 0.5mm.The thickness that is inserted in the dielectric ceramic layer between the adjacent interior electrode is 10 μ m.Effectively obtain electrical capacity the dielectric ceramic layer add up to 5, and the area of opposite electrode is 2.5 * 10 in every layer
-6m
2With thus obtained sample number into spectrum is that 1～57 monolithic ceramic capacitor is analyzed, to estimate electrical characteristic.The result is table 7 illustrate.
In table 7 and 8, band asterisk sample is outside the present invention's's (claim 7～12) scope.
The method and the evaluation result of the electrical characteristic of estimating monolithic ceramic capacitor will be described now.
A. relative permittivity (ε r) and dielectric loss (tan δ)
Adopt automatic bridge-type meter, each sample in the his-and-hers watches 7 all applies the signal voltage of 50Vrms/mm (1kHz), to measure electrical capacity (C) and dielectric loss (tan δ).Based on the structure of each monolithic ceramic capacitor, by the observed value calculating relative permittivity (ε r) of electrical capacity.The result is table 8 illustrate.
B. specific insulation resistance (ρ)
Adopt Insulation Resistance Tester, under 25 ℃, each sample in table 7 all applies the dc voltage 1 minute of 300V, with measurement insulation resistance, and calculates specific insulation resistance (ρ) by this insulation resistance.The result is table 8 illustrate.
C. average Time To Failure (MTTF)
As high temperature load test, under 170 ℃, each sample in table 7 all applies the dc voltage of 400V, with the variation of measurement insulation resistance with respect to the time.In high temperature load test, each sample all is assumed to when its insulation resistance and becomes 10
6Ω or more hour just fail determines the average Time To Failure of each sample thus.The result is table 8 illustrate.
D. the dielectric loss in applying the high-frequency AC voltage process (tan δ)
Each sample in table 7 all is applied to the signal voltage of the 10kVp-p-p/mm under the 300kHz, and with measurement dielectric loss (tan δ), thereby the heat of estimating in applying high-frequency process produces.The result is table 8 illustrate.
E.BDV
Adopt AC to puncture the AC field that tester each sample in table 7 all applies 60Hz, to estimate BDV.Advancing the speed of voltage is 50V/sec.
Table 7
| Sample number into spectrum | m | x | R | a | b | c | d | e |
| *1 | 0.98 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 2 | 0.98 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 3 | 1.00 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 4 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 5 | 1.03 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 6 | 1.05 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| *7 | 1.06 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| *8 | 1.01 | 0.00 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 9 | 1.01 | 0.01 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 10 | 1.01 | 0.10 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 11 | 1.01 | 0.15 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 12 | 1.01 | 0.20 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| *13 | 1.01 | 0.25 | Gd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| *14 | 1.01 | 0.06 | Gd | 0.0 | 1.0 | 1.0 | 12 | 1.25 |
| *15 | 1.01 | 0.06 | Gd | 0.2 | 1.0 | 1.0 | 12 | 1.25 |
| 16 | 1.01 | 0.06 | Gd | 0.5 | 1.0 | 1.0 | 12 | 1.25 |
| 17 | 1.01 | 0.06 | Gd | 2.0 | 1.0 | 1.0 | 12 | 1.25 |
| 18 | 1.01 | 0.06 | Gd | 3.5 | 1.0 | 1.0 | 12 | 1.25 |
| *19 | 1.01 | 0.06 | Gd | 4.0 | 1.0 | 1.0 | 12 | 1.25 |
| *20 | 1.01 | 0.06 | Gd | 1.0 | 0.0 | 1.0 | 12 | 1.25 |
| 21 | 1.01 | 0.06 | Gd | 1.0 | 0.1 | 1.0 | 12 | 1.25 |
| 22 | 1.01 | 0.06 | Gd | 1.0 | 0.5 | 1.0 | 12 | 1.25 |
| 23 | 1.01 | 0.06 | Gd | 1.0 | 2.0 | 1.0 | 12 | 1.25 |
| 24 | 1.01 | 0.06 | Gd | 1.0 | 5.0 | 1.0 | 12 | 1.25 |
| *25 | 1.01 | 0.06 | Gd | 1.0 | 6.0 | 1.0 | 12 | 1.25 |
| *26 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.0 | 12 | 1.25 |
| 27 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.1 | 12 | 1.25 |
| 28 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.2 | 12 | 1.25 |
| 29 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 |
| 30 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 3.0 | 12 | 1.25 |
| *31 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 3.5 | 12 | 1.25 |
| *32 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 7 | 1.25 |
| 33 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 8 | 1.25 |
| 34 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 10 | 1.25 |
| 35 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 15 | 1.25 |
| 36 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 20 | 1.25 |
| *3 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 22 | 1.25 |
| *38 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 0.80 |
| 39 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 0.80 |
| 40 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 2.00 |
| 41 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 3.00 |
| 42 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 5.00 |
| *43 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 1.0 | 12 | 6.00 |
| 44 | 1.01 | 0.06 | Y | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 45 | 1.01 | 0.06 | La | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 46 | 1.01 | 0.06 | Co | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 47 | 1.01 | 0.06 | Pr | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 48 | 1.01 | 0.06 | Nd | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 49 | 1.01 | 0.06 | Sm | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 50 | 1.01 | 0.06 | Eu | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 51 | 1.01 | 0.06 | Tb | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 52 | 1.01 | 0.06 | Dy | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 53 | 1.01 | 0.06 | Ho | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 54 | 1.01 | 0.06 | Er | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 55 | 1.01 | 0.06 | Tm | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 58 | 1.01 | 0.06 | Yb | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
| 57 | 1.01 | 0.06 | Lu | 1.0 | 1.0 | 1.0 | 12 | 1.25 |
Table 8
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Ωm〕 | MTTF〔h〕 | tanδ〔％〕 (300kHz) | BDV[kV mm] |
| *1 | 1200 | 650 | 0.2 | 8.5*10 10 | 120 | 0.7 | 0.50 |
| 2 | 1200 | 630 | 0.2 | 6.7*10 11 | 150 | 0.7 | 0.93 |
| 3 | 1200 | 620 | 0.2 | 7.2*10 11 | 155 | 0.7 | 0.92 |
| 4 | 1225 | 600 | 0.2 | 8.3*10 11 | 160 | 0.7 | 0.94 |
| 5 | 1250 | 580 | 0.7 | 6.5*10 11 | 160 | 1.2 | 0.92 |
| 6 | 1275 | 550 | 0.7 | 6.2*10 11 | 150 | 1.2 | 0.93 |
| *7 | 1300 | 530 | 0.7 | 4.4*10 11 | 100 | 1.2 | 0.92 |
| *8 | 1225 | 600 | 0.2 | 2.1*10 11 | 130 | 0.8 | 0.94 |
| 9 | 1200 | 620 | 0.3 | 7.7*10 11 | 150 | 0.8 | 0.94 |
| 10 | 1200 | 580 | 0.3 | 8.9*10 11 | 150 | 0.6 | 0.93 |
| 11 | 1200 | 540 | 0.3 | 9.2*10 11 | 160 | 0.8 | 0.94 |
| 12 | 1175 | 400 | 0.5 | 8.6*10 11 | 160 | 0.7 | 0.95 |
| *13 | 1175 | 280 | 0.5 | 5.5*10 12 | 150 | 0.7 | 0.99 |
| *14 | 1225 | - | - | 3.4*10 7 | - | - | - |
| *15 | 1200 | 610 | 0.5 | 7.6*10 11 | 40 | 0.6 | 0.62 |
| 16 | 1200 | 600 | 0.5 | 5.2*10 11 | 150 | 0.6 | 0.93 |
| 17 | 1200 | 580 | 0.2 | 5.3*10 11 | 100 | 0.6 | 0.96 |
| 18 | 1175 | 570 | 0.2 | 5.8*10 11 | 100 | 0.6 | 0.93 |
| *19 | 1175 | 540 | 0.2 | 4.2*10 10 | 80 | 0.6 | 0.45 |
| *20 | 1200 | 610 | 0.3 | 6.9*10 11 | 130 | 0.6 | 0.92 |
| 21 | 1200 | 600 | 0.3 | 8.0*10 11 | 150 | 0.6 | 0.93 |
| 22 | 1200 | 620 | 0.3 | 5.9*10 11 | 155 | 0.6 | 0.92 |
| 23 | 1175 | 500 | 0.2 | 5.9*10 11 | 160 | 0.7 | 0.92 |
| 24 | 1175 | 450 | 0.2 | 4.5*10 11 | 150 | 0.7 | 0.94 |
| *25 | 1175 | 400 | 0.2 | 2.2*10 11 | 50 | 0.7 | 0.48 |
| *26 | 1150 | 630 | 0.7 | 7.9*10 11 | 150 | 0.7 | 0.72 |
| 27 | 1175 | 600 | 0.2 | 5.2*10 11 | 150 | 0.6 | 0.92 |
| 28 | 1225 | 580 | 0.2 | 4.5*10 11 | 150 | 0.6 | 0.93 |
| 29 | 1250 | 550 | 0.1 | 3.2*10 11 | 150 | 0.6 | 0.95 |
| 30 | 1250 | 430 | 0.1 | 2.4*10 11 | 160 | 0.6 | 0.96 |
| *31 | 1250 | - | - | 5.3*10 11 | - | - | - |
| *32 | 1150 | 800 | 0.3 | 5.9*10 11 | 80 | 1.2 | 0.92 |
| 33 | 1175 | 730 | 0.3 | 8.8*10 11 | 150 | 0.6 | 0.92 |
| 34 | 1225 | 550 | 0.3 | 5.4*10 11 | 150 | 0.6 | 0.93 |
| 35 | 1250 | 480 | 0.3 | 4.2*10 11 | 160 | 0.6 | 0.96 |
| 36 | 1275 | 350 | 0.4 | 4.1*10 11 | 160 | 0.6 | 0.96 |
| *37 | 1300 | 270 | 0.4 | 3.3*10 11 | 170 | 0.6 | 0.94 |
| *38 | Sintering is insufficient | - | - | - | - | - | - |
| 39 | 1250 | 540 | 0.5 | 3.3*10 11 | 150 | 0.6 | 0.93 |
| 40 | 1150 | 600 | 0.4 | 4.3*10 11 | 160 | 0.7 | 0.92 |
| 41 | 1125 | 580 | 0.4 | 7.4*10 11 | 155 | 0.7 | 0.94 |
| 42 | 1100 | 540 | 0.2 | 7.7*10 11 | 150 | 0.5 | 0.93 |
| *43 | 1100 | 500 | 0.1 | 8.3*10 11 | 90 | 0.5 | 0.93 |
| 44 | 1225 | 570 | 0.2 | 7.4*10 11 | 150 | 0.5 | 0.92 |
| 45 | 1150 | 580 | 0.2 | 7.7*10 11 | 150 | 0.5 | 0.92 |
| 46 | 1150 | 560 | 0.3 | 8.3*10 11 | 150 | 0.6 | 0.93 |
| 47 | 1150 | 550 | 0.3 | 7.4*10 11 | 160 | 0.8 | 0.93 |
| 48 | 1150 | 600 | 0.1 | 7.7*10 11 | 155 | 0.5 | 0.92 |
| 49 | 1175 | 580 | 0.3 | 8.3*10 11 | 155 | 0.5 | 0.92 |
| 50 | 1175 | 590 | 0.2 | 7.4*10 11 | 155 | 0.5 | 0.92 |
| 51 | 1200 | 570 | 0.2 | 7.7*10 11 | 150 | 0.7 | 0.93 |
| 52 | 1200 | 550 | 0.4 | 8.3*10 11 | 150 | 0.8 | 0.93 |
| 53 | 1225 | 600 | 0.3 | 7.4*10 11 | 150 | 0.6 | 0.93 |
| 54 | 1225 | 590 | 0.3 | 7.7*10 11 | 160 | 0.7 | 0.93 |
| 55 | 1225 | 590 | 0.2 | 8.3*10 11 | 155 | 0.7 | 0.92 |
| 56 | 1250 | 600 | 0.3 | 7.4*10 11 | 155 | 0.6 | 0.93 |
| 57 | 1250 | 580 | 0.4 | 7.7*10 11 | 155 | 0.6 | 0.93 |
The result of table 8 shows, is being used for evaluation at (Ba
1-xCa
x)
mTiO
3In in the sample number into spectrum 1～7 of effect of mol ratio m of (Ba+Ca) and Ti, sample number into spectrum 2～6 shows as in the scope of the invention (0.990≤m≤1.050), their dielectric losses when 50Vrms/mm (1kHz) are 0.8% or lower, and keep relative permittivity be 300 or bigger in, have 10
11Ω m or bigger specific insulation resistance.(170 ℃, the DC field intensity: the MTTF 40kV/mm) is 150 hours or longer time, thereby shows high reliability at high temperature load test.Dielectric loss in the high-frequency AC electric current process of the 10kVp-p/mm that applies 300kHz is 0.8% or lower, thereby heat produces little.The BDV height is to 0.92kVrms.On the contrary, in the sample number into spectrum 1 and 7 outside the scope of the invention, it is 6.5 * 10 that m shows specific insulation resistance less than 0.990 sample number into spectrum 1
10Ω m, this result is lower than 10
11Ω m.M surpasses 1.050 sample number into spectrum 7 and shows that MTTF is 100 hours in high temperature load test, and this result is lower than 150 hours.
In sample number into spectrum 8～13, the sample number into spectrum 9～12 of improved Ca content x in the scope of the invention (0.01≤x≤0.20) all satisfies above-mentioned characteristic.On the contrary, in the sample number into spectrum 8 and 13 outside the scope of the invention, improved Ca content x shows 130 hours MTTF less than 0.01 sample number into spectrum 8, and this result was than 150 hours weak points.X shows 280 relative permittivity above 0.20 sample number into spectrum 13, and this result is lower than 300.
The result of table 8 illustrates, and at the sample number into spectrum 14～19 of the effect that is used for estimating MnO content a, the sample number into spectrum 16～18 within the scope of the invention (0.5≤a≤3.5) all satisfies above-mentioned characteristic.On the contrary, in the sample number into spectrum 14,15 and 19 outside the scope of the invention, the sample number into spectrum 14 that does not contain MnO shows low-down specific insulation resistance, thereby can not calculate its ε r etc.A shows 7.6 * 10 less than 0.5 sample number into spectrum 15
10The specific insulation resistance of Ω m, this result is lower than 10
11Ω m; And 40 hours MTTF, this result is shorter than 150 hours.A shows 4.2 * 10 above 3.5 sample number into spectrum 19
10The specific insulation resistance of Ω m, this specific insulation resistance is lower than 10
11Ω m.
The result of table 8 illustrates, and at the sample number into spectrum 20～25 of the effect that is used for estimating CuO content b, the sample number into spectrum 21～24 within the scope of the invention (0.1≤b≤5.0) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 20 and 25 outside the scope of the invention, CuO content b shows 130 hours MTTF less than 0.1 sample number into spectrum 20, and this result is shorter than 150 hours.B shows 2.2 * 10 above 5.0 sample number into spectrum 25
10The specific insulation resistance of Ω m, this result is lower than 10
11Ω m.
The result of table 8 illustrates, and is being used to estimate VO
3/2In the sample number into spectrum 26～31 of the effect of content c, the sample number into spectrum 27～30 within the scope of the invention (0.1≤c≤3.0) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 26 and 31 outside the scope of the invention, do not contain VO
3/2Sample number into spectrum 26 show the BDV of 0.72kVrms, this result is unsatisfactory.C shows low-down specific insulation resistance above 3.0 sample number into spectrum 31, and can not calculate its ε r etc.
Result shown in the table 8 illustrates, and is being used to estimate RO
nIn the sample number into spectrum 32～37 of the effect of content d, the sample number into spectrum 33～36 in the scope of the invention (8≤d≤20) all satisfies above-mentioned characteristic.On the contrary, in the sample number into spectrum 32 and 37 outside the scope of the invention, RO
nContent c shows 80 hours MTTF less than 8 sample number into spectrum 32, and this result is shorter than 150 hours; And in the process of the AC field of the 10kVp-p/mm that applies 300kHz, produce high calorie, promptly show 1.2% dielectric loss.D shows 270 relative permittivity above 20.0 sample number into spectrum 37, and this result is lower than 300.
The result of table 8 illustrates, and is being used to estimate sintering aid (SiO
2) the sample number into spectrum 38～43 of effect of amount e in, the sample number into spectrum 39～42 in the scope of the invention (0.8≤e≤5.0) all satisfies above-mentioned evaluating characteristics.On the contrary, in the sample number into spectrum 38 and 43 outside the scope of the invention, sintering aid content e is less than the abundant sintering of 0.8 sample number into spectrum 38.E shows 90 hours MTTF above 5.0 sample number into spectrum 43, and this result is shorter than 150 hours.
The result of table 8 illustrates, and is used to estimate RO
nThe sample number into spectrum 44～57 that is the effect of rare-earth oxidation species all satisfies above-mentioned evaluating characteristics, as long as their RO
nContent d (8≤d≤20) within the scope of the invention gets final product.
＜embodiment 2-2 〉
In the present embodiment, as shown in table 9, in the sample number into spectrum 29 of embodiment 2-1, further add MO, MO content f changes outside scope in preferable range of the present invention.By the monolithic ceramic capacitor that constitutes by the dielectric ceramic composition of sample number into spectrum 58～68 with the prepared identical with embodiment 2-1.Then, the electrical characteristic of these monolithic ceramic capacitors 21 are estimated in the mode identical with embodiment 2-1.The result is table 10 illustrate.
Table 9
| Sample number into spectrum | m | x | R | a | b | c | d | | M | f | |
| 29 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | |
| 58 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 1.0 | |
| 59 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 2.0 | |
| 60 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | |
| 61 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 5.0 | |
| 62 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 6.0 | |
| 63 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 7.0 | |
| 64 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 8.0 | |
| 65 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Ni | 3.0 | |
| 66 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Ni | 8.0 | |
| 67 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Zn | 3.0 | |
| 68 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Zn | 8.0 |
Table 10
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Qm〕 | MTTF 〔h〕 | tanδ〔％〕 (300kHz) | BDV[kV mm] |
| 29 | 1250 | 550 | 0.1 | 3.2*10 11 | 150 | 0.6 | 0.95 |
| 58 | 1200 | 620 | 0.2 | 6.8*10 11 | 170 | 0.8 | 0.93 |
| 59 | 1200 | 630 | 0.2 | 7.2*10 11 | 175 | 0.7 | 0.92 |
| 60 | 1225 | 620 | 0.2 | 6.3*10 11 | 180 | 0.7 | 0.95 |
| 61 | 1225 | 480 | 0.2 | 8.5*10 11 | 190 | 0.7 | 0.95 |
| 62 | 1200 | 350 | 0.2 | 5.5*10 11 | 180 | 0.7 | 0.94 |
| 63 | 1175 | 310 | 0.1 | 5.3*10 11 | 180 | 0.7 | 0.94 |
| 64 | 1175 | 220 | 0.1 | 4.2*10 11 | 180 | 0.6 | 0.96 |
| 65 | 1200 | 600 | 0.2 | 5.4*10 11 | 180 | 0.6 | 0.92 |
| 66 | 1200 | 220 | 0.1 | 6.6*10 11 | 180 | 0.7 | 0.93 |
| 67 | 1200 | 620 | 0.3 | 8.6*10 11 | 180 | 0.6 | 0.93 |
| 68 | 1225 | 200 | 0.1 | 5.6*10 11 | 180 | 0.7 | 0.97 |
The result of table 10 illustrates, (the Ba of every 100mol
1-xCa
x)
mTiO
3The sample number into spectrum 58～63 that contains 7.0mol or MgO still less shows longer MTTF than the sample number into spectrum 29 that does not contain MgO.The sample number into spectrum 64 that MgO content exceeds preferable range of the present invention shows long MTTF, but unfriendly, its relative permittivity is lower than the relative permittivity of sample number into spectrum 29.Wherein be added into NiO rather than MgO sample number into spectrum 65 and 66 and the sample number into spectrum 67 and 68 that wherein is added into ZnO rather than MgO also show the result that can be comparable to the sample that contains MgO.
＜embodiment 2-3 〉
In the present embodiment, as shown in table 11, in the sample number into spectrum 29 of embodiment 2-1, further add X (Zr, Hf) O
3, and X (Zr, Hf) O
3Content g change outside scope in preferable range of the present invention.By the monolithic ceramic capacitor that constitutes by the dielectric ceramic composition of sample number into spectrum 69～83 with the prepared identical with embodiment 2-1.Then, in the mode identical, estimate the electrical characteristic of these monolithic ceramic capacitors 21 with embodiment 2-1.The result is table 12 illustrate.
Table 11
| Sample number into spectrum | m | x | R | a | b | c | d | e | M | | X | g | |
| 29 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 0.0 | |
| 69 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 6.0 | |
| 70 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 9.0 | |
| 71 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 12.0 | |
| 72 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 15.0 | |
| 73 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | - | 0.0 | Ba | 18.0 | |
| 74 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 0.0 | |
| 75 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 6.0 | |
| 76 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 9.0 | |
| 77 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 12.0 | |
| 78 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 15.0 | |
| 79 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Mg | 3.0 | Ba | 18.0 | |
| 80 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Ni | 3.0 | Sr | 12.0 | |
| 81 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Ni | 3.0 | Sr | 18.0 | |
| 82 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Zn | 3.0 | Ca | 12.0 | |
| 83 | 1.01 | 0.06 | Gd | 1.0 | 1.0 | 0.5 | 12 | 1.25 | Zn | 3.0 | Ca | 18.0 |
Table 12
| Sample number into spectrum | Stoving temperature (℃) | εr | tanδ〔％〕 (1kHz) | ρ〔Qm〕 | MTTF 〔h〕 | tanδ〔％〕 (300kHz) | BDV[kV mm] |
| 29 | 1250 | 550 | 0.1 | 3.2*10 11 | 150 | 0.6 | 0.95 |
| 69 | 1225 | 620 | 0.1 | 8.1*10 11 | 170 | 0.6 | 0.93 |
| 70 | 1225 | 650 | 0.1 | 6.0*10 11 | 170 | 0.6 | 0.92 |
| 71 | 1225 | 640 | 0.1 | 6.7*10 11 | 170 | 0.5 | 0.96 |
| 72 | 1225 | 440 | 0.1 | 7.5*10 11 | 170 | 0.6 | 0.97 |
| 73 | 1225 | 290 | 0.1 | 4.1*10 11 | 180 | 0.6 | 0.99 |
| 74 | 1200 | 630 | 0.2 | 8.9*10 11 | 180 | 0.6 | 0.92 |
| 75 | 1200 | 640 | 0.2 | 7.3*10 11 | 180 | 0.7 | 0.92 |
| 76 | 1200 | 650 | 0.2 | 8.7*10 11 | 180 | 0.7 | 0.92 |
| 77 | 1225 | 640 | 0.2 | 8.6*10 11 | 180 | 0.7 | 0.93 |
| 78 | 1225 | 440 | 0.2 | 8.5*10 11 | 180 | 0.7 | 0.93 |
| 79 | 1225 | 290 | 0.1 | 5.2*10 11 | 170 | 0.6 | 0.96 |
| 80 | 1200 | 630 | 0.1 | 7.7*10 11 | 180 | 0.6 | 0.94 |
| 81 | 1225 | 280 | 0.1 | 5.6*10 11 | 180 | 0.6 | 0.96 |
| 82 | 1200 | 630 | 0.2 | 8.0*10 11 | 180 | 0.6 | 0.92 |
| 83 | 1225 | 250 | 0.1 | 4.1*10 11 | 170 | 0.6 | 0.96 |
The result of table 12 illustrates, (the Ba of every 100mol
1-xCa
x)
mTiO
3Contain 15mol or X still less (Zr, Hf) O
3Sample number into spectrum 69～72 than not containing Ba (Zr, Hf) O
3Sample number into spectrum 29, have longer MTTF.Ba (Zr, Hf) O
3The sample number into spectrum 73 that content surpasses preferable range of the present invention shows long MTTF, but unfriendly, its relative permittivity is than not containing Ba (Zr, Hf) O
3The relative permittivity of sample number into spectrum 29 low.
The result of table 12 illustrates, wherein to the (Ba of every 100mol
1-xCa
x)
mTiO
3Middle Ba (Zr, Hf) O that adds 3mol MgO and adding
3Sample number into spectrum 74～78 in preferable range of the present invention shows longer MTTF.Ba (Zr, Hf) O
3The sample number into spectrum 79 of content outside preferable range of the present invention shows long MTTF, but unfriendly, and its relative permittivity is lower than the sample number into spectrum 29 of embodiment 2-1.Contain NiO or ZnO rather than MgO and contain Sr (Zr, Hf) O
3Or Ca (Zr, Hf) O
3Rather than Ba (Zr, Hf) O
3Sample show to be comparable to and contain MgO and Ba (Zr, Hf) O
3The result of sample.
Should be noted that the present invention never is subjected to the restriction of above-mentioned each embodiment.
Industrial usability
According to the present invention, can obtain such monolithic ceramic capacitor: produce little heat in its course of work under high frequency and/or high AC voltage or high frequency dc voltage, have relative dielectric constant and the insulativity that can compare favourably with background technology, and show high reliability.
In addition, according to the present invention, can obtain to have higher breakdown field and the monolithic ceramic capacitor of high reliability more.
Therefore, the present invention can be widely used in and relates in the monolithic ceramic capacitor that uses in various Electrical and Electronic devices and the technical field of the dielectric ceramic compositions that is used for these devices.
Claims (12)
1. dielectric ceramic composition, it comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cRO
nThe material and the sintering aid of expression, wherein, coefficient 100, a, b and c represent mol ratio separately; R represents to be selected from least a element in the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And n represents by counting of determining of the valency of rare-earth element R and is to keep the needed positive number of electric neutrality,
Wherein said dielectric ceramic composition satisfies following relationship:
0.990≤m≤1.050，
0.01≤x≤0.20，
0.5≤a≤3.5，
0.1≤b≤5.0 Hes
10≤c≤20，
Wherein with respect to 100 weight parts by (Ba
1-xCa
x)
mTiO
3The compound of expression, the described sintering aid amount of being represented by d satisfies 0.8≤d≤5.0 according to the weight part meter.
2. according to the dielectric ceramic composition of claim 1, wherein every 100mol by (Ba
1-xCa
x) mTiO
3In the shown compound, comprise 7.0mol or MO still less, wherein M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn.
3. according to the dielectric ceramic composition of claim 1 or 2, wherein every 100mol by (Ba
1-xCa
x)
mTiO
3In the shown compound, comprise 15mol or X still less (Zr, Hf) O
3, wherein X is at least a element that is selected from the group of being made up of Ba, Sr and Ca.
4. according to the dielectric ceramic composition of claim 1 or 2, wherein said sintering aid is SiO
2
5. monolithic ceramic capacitor, its comprise a plurality of dielectric ceramic layers that are laminated to each other, the interior electrode between described dielectric ceramic layer and with described in the outer electrode that is electrically connected of electrode, wherein said dielectric ceramic layer comprises according to each described dielectric ceramic composition in the claim 1 to 4.
6. the monolithic ceramic capacitor of claim 5, wherein said in electrode comprise electro-conductive material, and described electro-conductive material contains Ni or Ni alloy or Cu or Cu alloy as main ingredient.
7. dielectric ceramic composition, it comprises by general formula 100 (Ba
1-xCa
x)
mTiO
3+ aMnO+bCuO+cVO
3/2+ dRO
nShown material and sintering aid, wherein coefficient 100, a, b, c and d represent mol ratio separately; R is at least a element that is selected from the group of being made up of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; And n represents by counting of determining of the valency of R and is to keep the needed positive number of electric neutrality,
Wherein said dielectric ceramic composition satisfies relation:
0.990≤m≤1.050，
0.01≤x≤0.20，
0.5≤a≤3.5，
0.1≤b≤5.0，
0.1≤c≤3.0 and
8≤d≤20，
Wherein with respect to 100 weight parts by (Ba
1-xCa
x)
mTiO
3The compound of expression, the described sintering aid amount of being represented by e satisfies 0.8≤e≤5.0 according to the weight part meter.
8. according to the dielectric ceramic composition of claim 7, wherein every 100mol by (Ba
1-xCa
x)
mTiO
3In the shown compound, comprise 7.0mol or MO still less, wherein, M represents to be selected from least a element in the group of being made up of Mg, Ni and Zn.
9. according to the dielectric ceramic composition of claim 7 or 8, wherein every 100mol by (Ba
1-xCa
x)
mTiO
3In the shown compound, comprise 15mol or X still less (Zr, Hf) O
3, wherein X is at least a element that is selected from the group of being made up of Ba, Sr and Ca
10. according to the dielectric ceramic composition of claim 7 or 8, wherein said sintering aid is SiO
2
11. monolithic ceramic capacitor, its comprise a plurality of dielectric ceramic layers that are laminated to each other, the interior electrode between described dielectric ceramic layer and with described in the outer electrode that is electrically connected of electrode, wherein said dielectric ceramic layer comprises according to each described dielectric ceramic composition in the claim 7 to 10.
12. according to the monolithic ceramic capacitor of claim 11, wherein said interior electrode comprises electro-conductive material, described electro-conductive material contains as the Ni of main ingredient or Ni alloy or Cu or Cu alloy.
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