CN1848317A - Electric assembly - Google Patents
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- CN1848317A CN1848317A CN 200610084042 CN200610084042A CN1848317A CN 1848317 A CN1848317 A CN 1848317A CN 200610084042 CN200610084042 CN 200610084042 CN 200610084042 A CN200610084042 A CN 200610084042A CN 1848317 A CN1848317 A CN 1848317A
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Abstract
A multilayer ceramic capacitor 1 having dielectric layers 2 having barium titanate or barium calcium titanate as a main ingredient. When the dielectric layers are barium titanate, the thickness of the crystal grain boundaries 22 present between adjoining dielectric grains 20 is 1nm or less has a ratio of 30% to 95% of entire particles in the plurality of dielectric grains 20 forming the dielectric layers 2. When the dielectric layers 2 are barium calcium titanate, the thickness of the crystal grain boundaries 22 present between adjoining dielectric grains 20 is 1nm or less has a ratio of 20% to 70% of entire particles in the plurality of dielectric grains 20 forming the dielectric layers 2.
Description
Technical field
The present invention relates to electronic units such as multilayer ceramic capacitor, in more detail, relate to electrical characteristics excellences such as dielectric constant,, also can obtain excellent in temperature characteristic, small-sized jumbo electronic unit that reliability is high even under the thin situation of dielectric layer.
Background technology
In recent years, electric product more and more requires miniaturization and high performance, and incident is to electronic unit also strong request miniaturization and high performance.As the multilayer ceramic capacitor of electronic unit one example, especially require high power capacity and high reliability.
Yet in order to obtain the multilayer ceramic capacitor of small-sized and high power capacity, the thin layerization of dielectric ceramics layer, interior electrode layer is absolutely necessary, and still incident is the reliability variation.On the other hand, in order to obtain the multilayer ceramic capacitor of small-sized and high reliability, must make dielectric ceramics layer, interior electrode layer thickening, but can't obtain high power capacity like this.
As obtaining high power capacity and demonstrating the method for the multilayer ceramic capacitor of high reliability, for example in document 1 (spy opens flat 5-9066 communique), propose to satisfy the X7R characteristic of EIA standard, also demonstrated high-k, and the high dielectric ceramic composition of insulation resistance.Yet, in the method shown in the document 1, for example dielectric ceramics layer thin layer turned to 3 μ m or when following, may not necessarily be met the reliability of market demands.
In addition, in document 2 (spy opens the 2001-316176 communique), disclose by with BaTiO
3Be to use fine material in the dielectric medium powder of principal component, and limit its maximum particle diameter, particle size distribution, thereby obtain fine and demonstrate the method for the dielectric ceramics of good electrical.By with the dielectric ceramics miniaturization, can also obtain high reliability.
Yet, in above-mentioned document 2, the thickness of dielectric ceramics layer is envisioned for 30 μ m, dielectric ceramics layer thin layer turned to 3 μ m or when following, supposition may not necessarily be met the reliability of market demands.For example in document 2, add very many such accessory ingredients of Mn, Mg, if but excessive interpolation additive composition, then owing to reasons such as donor on crystal grain boundary or receptor component segregations, the reliability that can envision laminated ceramic reduces.That is, in the method described in the document 2, at dielectric layer more during thin layer, can envision existence and be the problem that the reliability of representative reduces with the increase of defective insulation, with the life-span.
In addition, in document 3 (spy opens flat 11-302071 communique) and document 4 (spy opens the 2002-29836 communique), disclose by using the B as main material with Ca replacement Ba
1-xCa
xTiO
3Mother metal, thus satisfy the X7R characteristic and obtain the dielectric ceramic composition of high reliability.Yet, big with respect to the capacity deterioration of direct voltage in the described method of these patent documentations, still can't fully satisfy the requirement in market.
Summary of the invention
The present invention makes in view of such present situation, its objective is electrical characteristics excellences such as a kind of dielectric constant is provided, even under the thin situation of dielectric layer, also can obtain excellent in temperature characteristic, electronic units such as small-sized jumbo multilayer ceramic capacitor that reliability is high.
Even the inventor finds to turn under 5 μ m for example or following, 3 μ m or the following situation at the dielectric layer thickness thin layer, THICKNESS CONTROL by the crystal grain boundary between the crystalline particle that will constitute dielectric layer is suitable value, can be met the B characteristic of JIS standard and the electronic units such as X5R characteristic, high reliability and small-sized jumbo multilayer ceramic capacitor of EIA standard, thereby finish the present invention.
Promptly, the electronic unit that the present invention's the 1st viewpoint relates to is that to have with the barium titanate be the electronic unit of the dielectric layer of principal component, it is characterized in that, in a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 1nm or following particle ratio are whole 30%-95%.
In the 1st viewpoint of the present invention, the thickness of the crystal grain boundary that exists between preferred adjacent ceramic particle is that 0.75nm or following particle ratio are whole 40%-90%.
The electronic unit that the present invention's the 2nd viewpoint relates to is to have to pass through Ba
1-xCa
xTiO
3The barium titanate calcium of (0.001≤x≤0.15) expression is the electronic unit of the dielectric layer of principal component, it is characterized in that, in a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 1nm or following particle ratio are whole 20%-70%.
In the 2nd viewpoint of the present invention, the thickness of the crystal grain boundary that exists between preferred adjacent ceramic particle is that 0.75nm or following particle ratio are whole 25%-65%.
In the of the present invention the 1st and the 2nd viewpoint, very few if the thickness of crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, the dielectric constant step-down that then has a dielectric layer is the tendency of insulation resistance lifetime simultaneously.In addition, too much if the thickness of crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, then there is the tendency of lifetime simultaneous temperature characteristic variation of the insulation resistance of dielectric layer.
Dielectric layer thickness is preferably 4.5 μ m or following, and more preferably 3 μ m or following are preferably 2.5 μ m or following especially.The present invention is effective under the thin especially situation of dielectric layer thickness.
The average grain diameter of preferably ceramic particle is 0.3 μ m or following.By reducing particle diameter, can obtain good reliability, still,, be difficult to obtain high dielectric constant by the size effect of insulating particles.Therefore, to the not special definition of the lower limit of particle diameter.Yet, in order to obtain little particle diameter, must use little raw material, if its material powder is more little, is difficult to more handle, thereby is limited to about 0.05 μ m under the average grain diameter of common ceramic particle.
Preferably in dielectric layer, contain magnesium (Mg) oxide as accessory ingredient, with respect to the barium titanate (BaTiO of 100mol
3) or barium titanate calcium (Ba
1-xCa
xTiO
3), the content of Mg oxide is 0～2mol (wherein not comprising 0), more preferably 0～1mol (wherein not comprising 0).
By containing the Mg oxide; can realize the micronize of insulating particles; if but too much as the addition of the MgO of accessory ingredient, though then can realize the micronize of insulating particles, can produce the deterioration of temperature characterisitic, the unfavorable conditions such as reduction of insulation resistance.Therefore, in the scope that can not produce so various electrical characteristics deteriorations, expectation reduces the content of MgO.
Preferably in dielectric layer, contain manganese (Mn) oxide and/or chromium (Cr) oxide as accessory ingredient, with respect to 100mol barium titanate or barium titanate calcium, the total amount of Mn oxide and Cr oxide is 0～0.5mol (wherein not comprising 0), more preferably 0～0.4mol (wherein not comprising 0).
By containing Mn oxide and/or Cr oxide, have the effect of acceleration of sintering, the effect that improves IR (insulation resistance) and the effect in raising high-temperature load life-span, if but their content is too much, then can produce the deterioration of temperature characterisitic, the unfavorable conditions such as reduction of insulation resistance.Therefore, in the scope that can not produce so various electrical characteristics deteriorations, expectation reduces the content of Mn oxide and/or Cr oxide.
Preferably contain terres rares (R) oxide as accessory ingredient in dielectric layer, with respect to 100mol barium titanate or barium titanate calcium, the content of R oxide is 0～4mol (wherein not comprising 0 and 4), and more preferably 0.5～3mol is preferably 0.5～2mol especially.
As R, be preferably a kind of being selected among Sc, Er, Tm, Yb, Lu, Y, Dy, Ho, Tb, Gd and the Eu or 2 kinds or more than, more preferably be selected among Y, Dy and the Ho a kind or 2 kinds or more than.
By containing such R oxide within the limits prescribed, the thickness that can control crystal grain boundary is the ratio of 1nm or following particle, can realize action effect of the present invention.
Preferably in dielectric layer, contain vanadium (V) oxide, tungsten (W) oxide, tantalum (Ta) oxide and/or niobium (Nb) oxide as accessory ingredient, with respect to 100mol barium titanate or barium titanate calcium, the total amount of V oxide, W oxide, Ta oxide and Nb oxide is 0～0.5mol (wherein not comprising 0), more preferably 0～0.3mol (wherein not comprising 0) is preferably 0～0.1mol (wherein not comprising 0) especially.
By containing V oxide, W oxide, Ta oxide and Nb oxide, the effect that improves the high-temperature load life-span is arranged, if but their content is too much, then can produce unfavorable conditions such as temperature characterisitic deterioration, insulation resistance reduction.Therefore, in the scope that can not produce so various electrical characteristics deteriorations, expectation reduces the content of these oxides.
In the 1st viewpoint of the present invention, preferably in dielectric layer, contain glass ingredient.As glass ingredient, be preferably (Ba
1-xCa
x) SiO
3(wherein, x=0.3～0.7).Containing under the situation of this glass ingredient, with respect to the 100mol barium titanate, the content of glass ingredient is 0.5～12mol (wherein not comprising 0.5), more preferably 0.5～6mol (wherein not comprising 0.5 and 6), more preferably 1～4mol.
By containing such glass ingredient within the limits prescribed, the thickness that can control crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, can realize action effect of the present invention.
In the 2nd viewpoint of the present invention, preferably in dielectric layer, contain glass ingredient.As glass ingredient, there is no particular limitation, can use alkaline-earth metals oxide, Li
2O
3, B
2O
3, SiO
2Mixture or (Ba
1-xCa
x) SiO
3(wherein, x=0.3～0.7) etc.
With respect to the barium titanate calcium of 100mol, glass ingredient is 0.5～12mol (wherein not comprising 0.5), 0.5～6mol (wherein not comprising 0.5 and 6) more preferably, preferred especially 1～5mol.
By containing such glass ingredient within the limits prescribed, the thickness that can control crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, can realize action effect of the present invention.
In the present invention, as electronic unit, there is no particular limitation, is preferably to have the multilayer ceramic capacitor that mutual lamination has the element body of above-mentioned dielectric layer and interior electrode layer.As other electronic unit, there is no particular limitation, and illustration has piezoelectric element, chip inductor, chip varistor, chip thermistor, chip-resistance, other mounted on surface (SMD) chip-type electronic component.
Preferred above-mentioned interior electrode layer is a principal component with base metals such as Ni or Ni alloys.
According to electronic unit of the present invention, electrical characteristics excellences such as dielectric constant can be provided, even under the thin situation of dielectric layer, also can obtain excellent in temperature characteristic, electronic units such as small-sized jumbo multilayer ceramic capacitor that reliability is high.
Description of drawings
Below, the present invention will be described based on the execution mode shown in the accompanying drawing.
Fig. 1 is the schematic section of the multilayer ceramic capacitor of the electronic unit that relates to as one embodiment of the present invention,
Fig. 2 is the schematic diagram that constitutes the insulating particles of dielectric layer in the multilayer ceramic capacitor,
Fig. 3 A is the TEM photo that constitutes the insulating particles of dielectric layer in the multilayer ceramic capacitor that relates to of one embodiment of the invention,
Fig. 3 B is the enlarged photograph of the crystal grain boundary shown in Fig. 3 A,
Fig. 4 A is the TEM photo that constitutes the insulating particles of dielectric layer in the multilayer ceramic capacitor that relates to of comparative example of the present invention,
Fig. 4 B is the enlarged photograph of the crystal grain boundary shown in Fig. 4 A,
Fig. 5 A is the TEM photo that constitutes the insulating particles of dielectric layer in the multilayer ceramic capacitor that relates to of one embodiment of the invention,
Fig. 5 B is the enlarged photograph of the crystal grain boundary shown in Fig. 5 A,
Fig. 6 A is the TEM photo that constitutes the insulating particles of dielectric layer in the multilayer ceramic capacitor that relates to of comparative example of the present invention,
Fig. 6 B is the enlarged photograph of the crystal grain boundary shown in Fig. 6 A,
Embodiment
(the 1st execution mode)
The manufacture method of multilayer ceramic capacitor
As shown in Figure 1, the capacity cell main body 10 that has alternatively laminated dielectric layer 2 and interior electrode layer 3 structures as the multilayer ceramic capacitor 1 of an example of electronic unit of the present invention.At the two ends of capacity cell main body 10, form respectively and the pair of external electrodes 4 that is arranged alternately in interior electrode layer 3 conductings of element body 10 inside.Interior electrode layer 3 is lamination in the following manner, makes each end face alternately be exposed to the surface of two relative ends of capacity cell main body 10.
Pair of external electrodes 4 is formed at two ends of capacity cell main body 10, and is connected with the exposed end face of the interior electrode layer 3 that is arranged alternately, thereby constitutes capacitor circuit.
Profile, size to capacitor element main body 10 have no particular limits, can suitably set according to purposes, usually, profile can be set to roughly rectangular shape, size can be set to usually long (0.4～5.6mm) * wide (0.2～5.0mm) * high (about 0.2～1.9mm).
Barium titanate is by composition formula (BaO)
mTiO
2Expression.In addition, in above-mentioned formula,, be 0.990～1.035 to there is no particular limitation for m with mol ratio (A/B value) as the Ti of B site constituent as the Ba of A site constituent.
In the present embodiment, as glass ingredient, can illustration contain the situation of Ba oxide, Ca oxide and Si oxide.The preferred glass composition is with (Ba
1-xCa
x) SiO
3(wherein, x=0.3～0.7) is represented.
In the present embodiment, accessory ingredient contains
The Mg oxide,
One or both of Mn oxide and Cr oxide,
Be selected from V oxide, W oxide, Ta oxide and the Nb oxide a kind or 2 kinds or above and
R (wherein, R be selected among Sc, Er, Tm, Yb, Lu, Y, Dy, Ho, Tb, Gd and the Eu a kind or 2 kinds or more than, be preferably and be selected from more than a kind or 2 kinds of Y, Dy and Ho) oxide.
As shown in Figure 2, the dielectric layer 2 of present embodiment contains a plurality of insulating particless (ceramic particle) 20.The average grain diameter of insulating particles 20 is 0.3 μ m or following.By reducing particle diameter, can obtain good reliability, but because the size effect of insulating particles is difficult to obtain high dielectric constant.Therefore, to the not special definition of the lower limit of particle diameter.Yet, in order to obtain little particle diameter, must use little raw material, if its material powder is more little, is difficult to more handle, thereby is limited to about 0.05 μ m under the average grain diameter of common ceramic particle.
Have crystal grain boundary 22 between insulating particles 20 and insulating particles 20, in the present embodiment, the thickness of the crystal grain boundary 22 that exists between adjacent ceramic particle is that the ratio of 1nm or following particle is whole 30%-95%.Preferably the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that the ratio of 0.75nm or following particle is whole 40%-90%.
If the thickness of crystal grain boundary is that the ratio of 1nm or following or 0.75nm or following particle is very few, then exist the dielectric constant of dielectric layer to reduce the tendency of insulation resistance lifetime simultaneously.In addition, too much if the thickness of crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, then there are the lifetime of insulation resistance of dielectric layer and the tendency that temperature characterisitic worsens.
In addition, the thickness of crystal grain boundary is that the ratio of 1nm or following or 0.75nm or following particle for example can be measured according to following mode.That is, at first, observe the zone of 700nm * 500nm by transmission electron microscope (TEM).For the crystal grain boundary of in this zone, observing 22, from three-dimensional point 24 arbitrarily, along crystal grain boundary 22, at the thickness of on the point of 100nm, measuring crystal grain boundary.In a plurality of zones, it is measured, in amounting to 50 points, measure the thickness of crystal grain boundary, by collecting, can be in the hope of its ratio.
Terms and conditions such as the lamination number of dielectric layer 2, thickness, can suitably determine that in the present embodiment, the thin thickness stratification of the dielectric layer 2 of clamping in the pair of internal electrodes layer 3 is 4.5 μ m or following according to purpose, purposes, be preferably 3.0 μ m or following, more preferably 2.5 μ m or following.In the present embodiment, when the thickness of the such dielectric layer 2 of thin layerization, also can keep the various electrical characteristics of capacitor 1, particularly keep enough temperature characterisitics, can improve simultaneously that CR is long-pending, the IR life-span.
At least a or their alloy constitutes by Ni, Pd, Ag, Au, Cu, Pt, Rh, Ru, Ir etc. usually for outer electrode 4.Usually use Cu, Cu alloy, Ni or Ni alloy etc., Ag, Ag-Pd alloy, In-Ga alloy etc.The thickness of outer electrode 4 is suitably determined according to purposes etc., is preferably usually about 10～50 μ m.
The manufacture method of multilayer ceramic capacitor
Below, an example of the method for the multilayer ceramic capacitor 1 of making present embodiment is described.
(1) in the present embodiment, the dielectric layer of preparing to remain to be configured for to form behind the sintering dielectric layer before the sintering of dielectric layer 2 shown in Fig. 1 is with thickener with remain to be configured for to form behind the sintering interior electrode layer thickener of the preceding interior electrode layer of sintering of interior electrode layer 3 shown in Fig. 1.In addition, also prepare the outer electrode thickener.
Dielectric layer prepares by mixing dielectric raw material and organic carrier with thickener.
(1-1) the dielectric raw material that uses in the present embodiment contains the various raw materials that constitute above-mentioned dielectric ceramic composition with the group specified proportion by subtraction.At first, preparation is as barium titanate raw material, glass ingredient raw material and the accessory ingredient raw material of above-mentioned various raw materials.
The barium titanate raw material
As the barium titanate raw material of dielectric layer principal component, use with composition formula (BaO)
mTiO
2The material of expression.The barium titanate raw material that uses in the present embodiment can also obtain by so-called liquid phase method except by the so-called solid phase method.Solid phase method (calcination method) is to use BaCO
3, TiO
2Under the situation as initiation material, these raw materials of quantitative weighing are by mixed calcining, pulverize the method obtain raw material.As liquid phase method, can enumerate oxalate method, hydrothermal synthesis method, alkoxide process, sol-gel process etc.
The glass ingredient raw material
As the glass ingredient raw material, use the material that contains Ba compound, Ca compound and Si compound.Si compound in the glass ingredient raw material plays the effect of sintering aid, and Ca compound and Ba compound exhibits go out to improve the effect of the temperature characterisitic (to the rate of change of the electrostatic capacitance of temperature) of electrostatic capacitance.
The glass ingredient raw material of Shi Yonging can use in the mode of mixture in the present embodiment, also can use in the mode of composite oxides.Wherein, in the present embodiment, preferred use is than the form of the composite oxides of the form fusing point reduction of mixture.
As the mode of mixture, can illustration Ca compound (CaO, CaCO
3Deng)+Si compound (SiO
2Deng)+Ba compound (BaO, BaCO
3Deng) etc.As the mode of composite oxides, can illustration (Ba
1-xCa
x) SiO
3Deng.X in the following formula is preferably 0.3～0.7, and more preferably 0.35～0.50.If x is too small, then there is the tendency of deterioration in temperature characterisitic, if x is excessive, there is the tendency that reduces in dielectric constant.
The accessory ingredient raw material
In the present embodiment, as the accessory ingredient raw material, use
The Mg compound,
Mn compound and Cr compound a kind or 2 kinds,
Be selected from V compound, W compound, Ta compound and Nb compound a kind or 2 kinds or above and
R (wherein, R be selected from Sc, Er, Tm, Yb, Lu, Y, Dy, Ho, Tb, Gd and Eu a kind or 2 kinds or more than, be preferably a kind of being selected from Y, Dy and Ho or 2 kinds or more than) compound.
The Mg compound has the effect of planarization capacity temperature characteristic and suppresses the effect that particle is grown up.Mn compound and Cr compound have the effect of acceleration of sintering, the effect that improves IR (insulation resistance) and the effect in raising high-temperature load life-span.V compound, W compound, Ta compound and Nb compound have the effect that improves the high-temperature load life-span.The R compound mainly demonstrates the effect that improves the high-temperature load life-span.
In addition, so-called Mg compound is meant to form magnesian compound behind magnesium oxide and/or the sintering, so-called Mn compound, be meant the compound that forms manganese oxide behind manganese oxide and/or the sintering, so-called Cr compound is meant the compound that forms chromium oxide behind chromium oxide and/or the sintering.
So-called V compound, be meant the compound that forms vanadium oxide behind vanadium oxide and/or the sintering, so-called W compound, be meant the compound that forms tungsten oxide behind tungsten oxide and/or the sintering, so-called Ta compound, be meant the compound that forms tantalum oxide behind tantalum oxide and/or the sintering, so-called Nb compound is meant the compound that forms niobium oxide behind niobium oxide and/or the sintering.
So-called R compound is meant the compound that forms the R oxide behind R oxide and/or the sintering.
(1-2) then, form by mixing barium titanate raw material, glass ingredient raw material and accessory ingredient raw material, forming finally.
With respect to the above-mentioned barium titanate raw material of 100mol, the combined amount of glass ingredient raw material (ratio) is as described below.
Be converted into BaO at the Ba compound, the Ca compound is converted into CaO, and the Si compound is converted into SiO
2The time, preferred
Ba compound+Ca compound: 0.5～12mol (wherein not comprising 0.5),
Si compound: 0.5～12mol (wherein not comprising 0.5).
More preferably
Ba compound+Ca compound: 0.5～6mol (wherein not comprising 0.5 and 6),
Si compound: 0.5～6mol (wherein not comprising 0.5 and 6),
If the addition of Ba compound, Ca compound, Si compound is very few, then be difficult to densification under lower temperature, can produce harmful effect to temperature characterisitic simultaneously.
In addition, in the present invention, by containing glass ingredient within the limits prescribed, the thickness that can control crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle.
With respect to the above-mentioned barium titanate raw material of 100mol, the combined amount of accessory ingredient raw material (ratio) is as described below.
Be converted into MgO at the Mg compound, the Mn compound is converted into MnO, and the Cr compound is converted into Cr
2O
3, the V compound is converted into V
2O
5, the W compound is converted into WO
3, the Ta compound is converted into Ta
2O
5, the Nb compound is converted into Nb
2O
5, the R compound is converted into R
2O
3The time, preferred
Mg compound: 0～2mol (wherein not comprising 0mol),
Mn compound+Cr compound: 0～0.5mol (wherein not comprising 0mol),
V compound+W compound+Ta compound+Nb compound: 0～0.5mol (wherein not comprising 0mol),
R compound: 0～4mol (wherein not comprising 0mol and 4mol),
More preferably
Mg compound: 0～1mol (wherein not comprising 0mol),
Mn compound+Cr compound: 0～0.4mol (wherein not comprising 0mol),
V compound+W compound+Ta compound+Nb compound: 0.01～0.1mol,
R compound: 0.5～3.5mol.
If the addition of Mg compound is very few, then there is the tendency of unusual particle growth, if too much, then there is the tendency that reduces in relative dielectric constant.If Mn compound and Cr compound add up to addition too many, have the tendency that relative dielectric constant reduces.If the total addition of V compound, W compound, Ta compound and Nb compound is too much, then there is the significantly reduced tendency of IR.If the addition of R compound is too much, then there is the tendency that worsens in agglutinating property.
Afterwards, as required, in ball mill, in decentralized media such as pure water, mix this mixed-powder,, thereby obtain the dielectric raw material by drying.
In addition, the dielectric raw material that is made of mentioned component can use above-mentioned oxide, its mixture, composite oxides, in addition, can also be from form all cpds of above-mentioned oxide, composite oxides by sintering, for example suitably select in carbonate, oxalates, nitrate, hydroxide, the organo-metallic compound etc., mix the back and use.
In addition, the content of each compound can be by its mode of forming that becomes above-mentioned dielectric ceramic composition is determined in the dielectric raw material.
Under the state before coatingization, the average grain diameter of dielectric raw material is preferably 0.3 μ m or following, more preferably about 0.05～0.26 μ m.
Organic carrier is the material that contains adhesive and solvent.As adhesive, can use for example common various adhesives such as ethyl cellulose, polyvinyl butyral resin, acrylic resin.Also there is no particular limitation to solvent, can use organic solvents such as terpineol, butyl carbitol, acetone, toluene, dimethylbenzene, ethanol.
Dielectric layer can mixing dielectric raw material with thickener and in water the carrier of dissolving water-soluble binder form.Water-soluble binder is not particularly limited, and can use polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, water soluble acrylic resin, emulsion etc.
Interior electrode layer with thickener can be by will comprising above-mentioned various conductive metal, alloy electric conducting material or behind sintering, form the various oxides, organo-metallic compound, resin etc. of above-mentioned electric conducting material, mix with above-mentioned organic carrier and prepare.
Outer electrode also can be by preparing with the identical method of thickener with this interior electrode layer with thickener.
There is no particular limitation to the content in the organic carrier in the above-mentioned various thickeners, and common content can be that for example adhesive is about 1～5 weight %, and solvent is about 10～50 weight %.In addition, in various thickeners, can also contain the additive that is selected from various dispersants, plasticizer, dielectric, insulator etc. as required.
(2) then, use the dielectric layer contain above-mentioned dielectric raw material with thickener and interior electrode layer thickener, the preparation lamination raw cook (green chip) of dielectric layer and the preceding interior electrode layer of sintering before the sintering.Then, the annealing operation of carry out unsticking mixture operation, sintering circuit, carrying out as required, thus obtain capacitor element main body 10.Then, in this element body 10, printing or transfer printing outer electrode thickener carry out sintering, form outer electrode 4, thereby make multilayer ceramic capacitor 1.
(the 2nd execution mode)
The 2nd execution mode is the variation execution mode of above-mentioned the 1st execution mode, and only the material of dielectric layer 2 is different with it, and other structure is identical with the 1st execution mode with action effect.Below, only different parts being described, the explanation of same section is omitted.
In the present embodiment, dielectric layer 2 contains with Ba
1-xCa
xTiO
3Barium titanate calcium, glass ingredient and the accessory ingredient of (0.001≤x≤0.15) expression.Barium titanate calcium is with composition formula (BaO)
mTiO
2The compound that is replaced by Ca as the part of the Ba of A site constituent in the barium titanate of expression.If the value of x is too small in the barium titanate calcium, then there is the tendency of deterioration in temperature characterisitic, if excessive, then there is the tendency that reduces in dielectric constant.
As glass ingredient, in the present embodiment, there is no particular limitation, can use alkaline-earth metals oxide, Li
2O
3, B
2O
3, SiO
2Mixture or (Ba
1-xCa
x) SiO
3(wherein, x=0.3～0.7) etc.
In the present embodiment, have crystal grain boundary 22 between insulating particles 20 and insulating particles 20, the thickness of the crystal grain boundary 22 that exists between adjacent ceramic particle is that the ratio of 1nm or following particle is whole 20%-70%.Preferably the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that the ratio of 0.75nm or following particle is whole 25%-65%.
If the thickness of crystal grain boundary is that the ratio of 1nm or following or 0.75nm or following particle is very few, then there is the tendency that reduces in the dielectric constant of dielectric layer.In addition, too much if the thickness of crystal grain boundary is the ratio of 1nm or following or 0.75nm or following particle, then have the tendency of lifetime of the insulation resistance of dielectric layer.
Barium titanate calcium raw material as the dielectric layer principal component can use composition formula Ba
1-xCa
xTiO
3The material of (0.001≤x≤0.15) expression.The barium titanate calcium raw material that uses in the present embodiment can also obtain by so-called liquid phase method except by the so-called solid phase method.Solid phase method (calcination method) is to use BaCO
3, CaCO
3, TiO
2Under the situation as initiation material, these raw materials of quantitative weighing mix, and obtain the method for raw material by calcining, pulverizing.As liquid phase method, can enumerate oxalate method, hydrothermal synthesis method, alkoxide process, sol-gel process etc.
As glass ingredient, there is no particular limitation, can use alkaline-earth metals oxide, Li
2O
3, B
2O
3, SiO
2Mixture or (Ba
1-xCa
x) SiO
3(wherein, x=0.3～0.7) etc.
The glass ingredient raw material of Shi Yonging can use in the mode of mixture in the present embodiment, also can use in the mode of composite oxides.Wherein, in the present embodiment, preferred use is than the form of the composite oxides of the form fusing point reduction of mixture.
As the form of mixture, can illustration Ca compound (CaO, CaCO
3Deng)+Si compound (SiO
2Deng)+Ba compound (BaO, BaCO
3Deng) etc.As the form formula of composite oxides, can illustration (Ba
1-xCa
x) SiO
3Deng.X in the following formula is preferably 0.3～0.7, and more preferably 0.35～0.50.If x is too small, then there is the tendency of deterioration in temperature characterisitic, if x is excessive, then there is the tendency that reduces in dielectric constant.
With respect to the above-mentioned barium titanate calcium raw material of 100mol, the combined amount of glass ingredient raw material (ratio) is as described below.
That is, glass ingredient contains 0.5～12mol (wherein not comprising 0.5), further preferably contains 0.5～6mol (wherein not comprising 0.5 and 6), is preferably 1～5mol especially.
If the addition of glass ingredient is very few, then be difficult to densification under lower temperature, also can produce bad influence simultaneously to temperature characterisitic.
In addition, in the present invention, by containing glass ingredient within the limits prescribed, the thickness that can control crystal grain boundary is the ratio of 1mm or following or 0.75nm or following particle.
With respect to the above-mentioned barium titanate calcium raw material of 100mol, the combined amount of accessory ingredient raw material (ratio) is as described below.
Be converted into MgO at the Mg compound, the Mn compound is converted into MnO, and the Cr compound is converted into Cr
2O
3, the V compound is converted into V
2O
5, the W compound is converted into WO
3, the Ta compound is converted into Ta
2O
5, the Nb compound is converted into Nb
2O
5, the R compound is converted into R
2O
3The time, preferred
Mg compound: 0～2mol (wherein not comprising 0mol),
Mn compound+Cr compound: 0～0.5mol (wherein not comprising 0mol),
V compound+W compound+Ta compound+Nb compound: 0～0.5mol (wherein not comprising 0mol),
R compound: 0～4mol (wherein not comprising 0mol and 4mol),
More preferably
Mg compound: 0～1mol (wherein not comprising 0mol),
Mn compound+Cr compound: 0～0.4mol (wherein not comprising 0mol),
V compound+W compound+Ta compound+Nb compound: 0.01～0.1mol,
R compound: 0.5～3.5mol.
If the addition of Mg compound is very few, then there is the tendency of unusual particle growth, if too much, then there is the tendency that reduces in relative dielectric constant.If the total addition of Mn compound and Cr compound is too many, have the tendency that relative dielectric constant reduces.If the total addition of V compound, W compound, Ta compound and Nb compound is too much, then there is the significantly reduced tendency of IR.If the addition of R compound is too much, then there is the tendency that worsens in agglutinating property.
In addition, the present invention is not limited in the above-mentioned execution mode, can carry out various changes within the scope of the invention.
For example, in the above-described embodiment, as electronic unit of the present invention, illustration multilayer ceramic capacitor, but as electronic unit of the present invention, be not limited to multilayer ceramic capacitor, all can so long as have the parts of the dielectric layer that constitutes by the above-mentioned dielectric ceramic composition of forming.
(embodiment)
Below, the present invention will be described based on more detailed embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
The preparation of dielectric raw material
At first, prepare barium titanate raw material, glass ingredient raw material and accessory ingredient raw material.As the barium titanate raw material, use specific area (SSA) to be 6m
2/ g (BaO)
mTiO
2(wherein, m=1.005).The barium titanate raw material is the BaCO with respect to 1.005mol
3, the TiO of preparation 1.000mol
2, these raw materials were passed through the ball mill wet mixed 16 hours, after the drying, under 800 ℃, sintering in air prepared by the ball mill case of wet attrition in 100 hours again.
In addition, SSA is the value by determination of nitrogen adsorption, and m tries to achieve by glass bead method.
Be to use following raw material as the glass ingredient raw material: with BaCO
3, CaCO
3And SiO
2Ratio was according to the rules passed through the ball mill wet mixed 16 hours, and after the drying, sintering in 1150 ℃ of following air passed through the ball mill case of wet attrition 100 hours again, thereby obtained (the Ba as composite oxides
0.6Ca
0.4) SiO
3(below be called BCG).
As the accessory ingredient raw material, using average grain diameter is MgO, MnO (or the Cr of 0.01～0.1 μ m
2O
3), Y
2O
3, V
2O
5
Then, with respect to the barium titanate raw material of 100mol, add as the BCG of glass ingredient raw material, MgO, MnO (or Cr as the accessory ingredient raw material
2O
3), Y
2O
3, V
2O
5, with water as solvent, wet mixed in ball mill (pigment are broken) 16 hours.Then, use heated-air drying down at 130 ℃, thereby obtain the dielectric raw material.
The dielectric raw material contains the BCG:3mol with respect to 100mol barium titanate raw material, Y
2O
3: 0～4mol (with reference to the sample 1～8 of table 1), MgO:0.5mol, MnO:0.2mol (or Cr
2O
3: 0.2mol), V
2O
5: 0.03mol.
Table 1
mol％
| Sample number into spectrum | MgO | MnO | Cr2O3 | Y2O3 | Dy2O3 | Ho2O3 | V2O5 | BCG |
| *1 | 0.5 | 0.2 | 0 | 0 | 0 | 0 | 0.03 | 3 |
| 2 | 0.5 | 0.2 | 0 | 0.5 | 0 | 0 | 0.03 | 3 |
| 3 | 0.5 | 0.2 | 0 | 1 | 0 | 0 | 0.03 | 3 |
| 4 | 0.5 | 0 | 0.2 | 1 | 0 | 0 | 0.03 | 3 |
| 5 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 3 |
| 6 | 0.5 | 0 | 0.2 | 2 | 0 | 0 | 0.03 | 3 |
| **7 | 0.5 | 0.2 | 0 | 3 | 0 | 0 | 0.03 | 3 |
| *8 | 0.5 | 0.2 | 0 | 4 | 0 | 0 | 0.03 | 3 |
| 9 | 0.5 | 0.2 | 0 | 0 | 1 | 0 | 0.03 | 3 |
| 10 | 0.5 | 0.2 | 0 | 0 | 0 | 1 | 0.03 | 3 |
| *11 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 0.5 |
| 12 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 1 |
| 13 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 2 |
| 14 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 4 |
| 15 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 5 |
| *16 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 6 |
* be comparative example
* is a reference example
Then, interpolation polyvinyl butyral resin and ethanol are organic solvent in the dielectric raw material that obtains, and mix with ball mill once more, make its gelatinization make the dielectric layer thickener.
Then, mix Ni particle, 52 weight portion terpineols, 3 weight portion ethyl celluloses, the 0.4 weight portion BTA of 44.6 weight portions,, thereby obtain the interior electrode layer thickener its pulp by triple-roller mill.
The preparation of sintered body
The dielectric layer thickener that use obtains forms raw cook by the scraper plate method on the PET film.Thereon by silk screen print method printing paste for internal electrode.To not print the protection of paste for internal electrode then peels off from the PET film with raw cook; it is about 300 μ m that a plurality of tab laminates are formed thickness; the printing of peeling off from the PET film thereon with expectation number (this moment be 5) lamination the thin slice of paste for internal electrode; lamination protection is used raw cook again; crimping, thus raw cook obtained.In addition, the dielectric layer thickness before the sintering is 3 μ m.
Then, raw cook is cut into the size of regulation, carry out the processing of unsticking mixture, sintering and annealing according to following condition, thereby obtain the chip sintered body.Unsticking mixture treatment conditions are: programming rate: 32.5 ℃/hour, keep temperature: 260 ℃, and temperature hold-time: 8 hours, atmosphere: in air.Sintering condition is: programming rate: 200 ℃/hour, keep temperature: about 1200 ℃ (1180～1280 ℃/with reference to table 2), temperature hold-time: 2 hours, cooling rate: 200 ℃/hour, atmosphere gas: the N of humidification
2+ H
2Mist.Annealing conditions is: programming rate: 200 ℃/hour, keep temperature: 1050 ℃, and temperature hold-time: 2 hours, cooling rate: 200 ℃/hour, atmosphere gas: humidification N
2Gas.In addition, during the humidification of the atmosphere gas when sintering and annealing, use is made as water temperature 20 ℃ humidifier.
The sintered body that obtains is of a size of 3.2mm * 1.6mm * 0.6mm, is 4 in the quantity of the dielectric layer of internal electrode interlayer clamping.
The preparation of capacitor sample and evaluating characteristics
After by sandblast the end face of the chip sintered body of gained being ground, In-Ga is as outer electrode in coating, obtains the sample of the multilayer ceramic capacitor shown in Fig. 1.
To each capacitor sample that obtains, measure the temperature characterisitic (TC), high-temperature load life-span (IR life-span/in table, only be expressed as " life-span ") of relative dielectric constant ε, electrostatic capacitance, the result is shown in the table 2.
For relative dielectric constant ε, at first, to the capacitor sample of gained, under 20 ℃ of fiducial temperatures, by digital LCR meter (YHP4284 that Yokogawa Motor (strain) is made), be that 1kHz, input signal level (mensuration voltage) are mensuration electrostatic capacitance C under the condition of 1Vrms/ μ m in frequency.Then, calculate relative dielectric constant ε (no unit) by the electrostatic capacitance that obtains.
In the present embodiment, relative dielectric constant be preferably 2500 or more than, more preferably 2700 or more than.
For the temperature characterisitic (TC) of electrostatic capacitance, estimate according to the X5R characteristic of EIAJ standard.That is to say, to the capacitor sample, by digital LCR meter (4274A that YHP company makes), in frequency is that 1kHz, input signal level (mensuration voltage) are measured electrostatic capacitance under the condition of 1Vrms, when fiducial temperature was made as 25 ℃, in-55 ℃～85 ℃ temperature range, whether research satisfied X5R characteristic (in ± 15%) with respect to the electrostatic capacitance change rate (Δ C/C) of temperature, situation about satisfying is designated as zero, and ungratified situation is designated as *.
For the high-temperature load life-span, to the capacitor sample, under 150 ℃, apply the direct voltage of 40V, by keeping this state, measure the high-temperature load life-span.This high-temperature load life-span particular importance during to the thin layer dielectric layer.In the present embodiment, will it be the life-span from applying the timing definition that begins to an order of magnitude of insulation resistance reduction.10 capacitor samples are carried out this evaluation, calculate its average life time.In the present embodiment, the IR life-span be preferably 100 hours or more than, more preferably 110 hours or more than.These results are shown in the table 2.
Table 2
| Specimen coding | Sintering temperature (℃) | Dielectric constant | Life-span (h) | The X5R characteristic | Ratio (%) with 1nm or following crystal grain boundary | Ratio (%) with 0.7nm or following crystal grain boundary |
| *1 | 1180 | 3410 | 20 | × | 98 | 94 |
| 2 | 1200 | 3130 | 110 | ○ | 94 | 88 |
| 3 | 1220 | 2790 | 250 | ○ | 74 | 70 |
| 4 | 1220 | 2830 | 200 | ○ | 82 | 66 |
| 5 | 1240 | 2740 | 270 | ○ | 58 | 48 |
| 6 | 1240 | 2700 | 260 | ○ | 44 | 40 |
| **7 | 1260 | 2440 | 280 | ○ | 38 | 34 |
| *8 | ≥1280 | The sintering deficiency | 28 | 16 | ||
| 9 | 1220 | 2710 | 230 | ○ | 56 | 52 |
| 10 | 1220 | 2720 | 220 | ○ | 64 | 52 |
| *11 | ≥1280 | The | 20 | 10 | ||
| 12 | 1260 | 2820 | 140 | ○ | 90 | 80 |
| 13 | 1200 | 2760 | 160 | ○ | 78 | 68 |
| 14 | 1200 | 2640 | 180 | ○ | 62 | 50 |
| 15 | 1180 | 2550 | 150 | ○ | 32 | 26 |
| *16 | 1180 | 2400 | 120 | × | 24 | 8 |
* be comparative example
* is a reference example
Dielectric layer thickness
On the face vertical, cut off the sintered body that obtains, this section is ground, by a plurality of positions of this abradant surface of metal microstructure sem observation with internal electrode.Then, the image by the metal microstructure sem observation is carried out digitized processing, thereby try to achieve the average thickness of the dielectric layer behind the sintering.The average thickness of each sample dielectric layer is 2.5 μ m.
The average grain diameter of the insulating particles in the dielectric layer
Sintered body to gained grinds, apply chemical etching after, observe abradant surface by scanning electron microscope (SEM), by coding (code) method, suppose the ball that is shaped as of insulating particles 20 in the dielectric layer, try to achieve the average grain diameter of this insulating particles.Average grain diameter is 250 mean values that mensuration is counted.Average grain diameter is 0.20～0.26 μ m.
The crystal grain boundary thickness of insulating particles in the dielectric layer
The sintered body that mechanical lapping obtains after applying ion and grinding, by transmission electron microscope (TEM), is measured the thickness of crystal grain boundary by following mode.
By the zone of tem observation 700nm * 500nm, for the crystal grain boundary of in this zone, observing 22, from three-dimensional point 24 arbitrarily, along crystal grain boundary 22, at the thickness of measuring crystal grain boundary 22 every the point of 100nm.In a plurality of zones, measure the thickness of crystal grain boundary 22, in amounting to 50 points, measure the thickness of crystal grain boundary 22.By this measurement result, the thickness that each sample is calculated crystal grain boundary 22 is that the right ratio (%) of 1nm or following particle and the thickness of crystal grain boundary are 0.7nm or the following right ratio (%) of particle.The result is shown in the table 2.
In addition, in table 1 and table 2, the TEM photo of embodiment specimen coding 3 is shown in Fig. 3 A, and its enlarged photograph is shown in Fig. 3 B.In addition, the TEM photo of comparative example specimen coding 8 is shown in Fig. 4 A, and its enlarged photograph is shown in Fig. 4 B.
Estimate 1
Shown in the specimen coding 1～8 of table 2, confirm that thickness at crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 30%-95% satisfies the X5R characteristic of EIA standard, and demonstrate the high reliability under the high-k.In addition, find that more preferably thickness at crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 40%-90% satisfies the X5R characteristic of EIA standard equally, and demonstrate the high reliability (high life) under the high-k more.
When the dielectric portion of relatively representing core and grain boundary portion, insulation resistance is the higher of grain boundary portion usually.Therefore think that the ratio of crystal boundary with 1nm or above thickness is many more, its reliability is just high more.Yet on the other hand, when more identical dielectric portion and grain boundary portion, dielectric constant is that dielectric portion is higher usually.Therefore think that the ratio of crystal boundary with 1nm or following thickness is few more, the dielectric constant of multilayer ceramic capacitor is just high more.In order preferably to be worth in two sides of its reliability and dielectric constant, the ratio of crystal boundary of considering to have 1nm or following thickness (being preferably 0.7nm or following) is in above-mentioned scope.
In addition, according to Y
2O
3The difference of addition, the thickness of confirming crystal grain boundary is that the right ratio regular meeting of particle of 1nm or following (or 0.7nm or following) changes, but as described later shown in other the embodiment, to adding Y
2O
3Method in addition, its ratio also changes.
Shown in the specimen coding 9 and 10 of table 1, except barium titanate raw material, with the addition interpolation Dy of 1mol with respect to 100mol
2O
3Or Ho
2O
3Replace Y
2O
3In addition, the same with the specimen coding 3 of embodiment 1, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 2, confirm there be the tendency identical with embodiment 1.Infer by this embodiment, use other terres rares (Sc, Er, Tm, Yb, Lu, Tb, Gd and Eu) to replace Y, also can obtain same effect.
Shown in the specimen coding 11～16 of table 1, the same with the specimen coding 5 of embodiment 1 except the addition of BCG being changed into the scope of 0.5～6mol, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 2, confirm there be the tendency identical with embodiment 1.That is, the thickness of confirming crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 30%-95% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability under the high-k.In addition, the thickness of more preferably finding crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 40%-90% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability (high life) under the high-k more.
In addition, even confirm to change addition, the Mg amount of glass ingredients such as BCG, the thickness of crystal grain boundary is that the ratio of the particle of 1nm or following (or 0.7nm or following) also changes.
Shown in the specimen coding 3a～3e of table 3, the same with the specimen coding 3 of embodiment 1 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 3, confirm there be the tendency identical with embodiment 1.That is, the thickness of confirming crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 30%-95% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability under the high-k.In addition, the thickness of more preferably finding crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 40%-90% satisfies the X5R characteristic of EIA standard equally, and demonstrates the high reliability (high life) under the high-k more.
In addition, confirm to change sintering temperature, the thickness of crystal grain boundary is that the ratio of the particle of 1nm or following (or 0.7nm or following) also changes.
Table 3
| Specimen coding | Sintering temperature (℃) | Dielectric constant | Life-span (h) | The X5R characteristic | Ratio (%) with 1nm or following crystal grain boundary | Ratio (%) with 0.7nm or following crystal grain boundary |
| *3a | 1180 | 2120 | 50 | ○ | 24 | 18 |
| **3b | 1200 | 2640 | 140 | ○ | 40 | 34 |
| 3c | 1220 | 2790 | 250 | ○ | 74 | 70 |
| 3d | 1240 | 2740 | 160 | ○ | 52 | 50 |
| *3e | 1260 | 2650 | 90 | ○ | 24 | 20 |
| *9a | 1180 | 1990 | 10 | ○ | 12 | 8 |
| **9b | 1200 | 2520 | 110 | ○ | 44 | 30 |
| 9c | 1220 | 2710 | 230 | ○ | 56 | 52 |
| **9d | 1240 | 2690 | 180 | ○ | 42 | 38 |
| *9e | 1260 | 2550 | 50 | ○ | 18 | 6 |
| *10a | 1180 | 2080 | 40 | ○ | 10 | 16 |
| *10b | 1200 | 2480 | 90 | ○ | 28 | 26 |
| 10c | 1220 | 2720 | 220 | ○ | 64 | 52 |
| **10d | 1240 | 2680 | 170 | ○ | 50 | 36 |
| *10e | 1260 | 2590 | 60 | ○ | 26 | 4 |
* be comparative example
* is a reference example
Embodiment 5
Shown in the specimen coding 9a～9e of table 3, the same with the specimen coding 9 of embodiment 1 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 3, confirm there be the tendency identical with embodiment 4.
Embodiment 6
Shown in the specimen coding 10a～10e of table 3, the same with the specimen coding 1O of embodiment 1 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 3, confirm there be the tendency identical with embodiment 4.
Embodiment 7
Except using barium titanate calcium replacement barium titanate,, carry out same evaluation with embodiment 1 the same sintered body sample and the capacitor sample of preparing.Below, only the part different with embodiment 1 being described in detail, the declaratives of common ground omit.
The dielectric raw material is by preparing as following mode.
At first, prepare barium titanate calcium raw material, glass ingredient raw material and accessory ingredient raw material.
As the barium titanate calcium raw material, use by the synthetic Ba of liquid phase method
1-xCa
xTiO
3(0.001≤x≤O.15).
As the glass ingredient raw material, by mixing BaO, the SiO of 60mol% of 10mol%
2, 10mol% TiO
2Li with 20mol%
2O
3, calcining prepares.
As the accessory ingredient raw material, using average grain diameter is MgO, MnO (or the Cr of 0.01～0.1 μ m
2O
3) Y
2O
3, V
2O
5
Then,, add above-mentioned glass ingredient raw material and accessory ingredient raw material with respect to 100mol barium titanate calcium raw material, with water as solvent, by ball mill wet mixed (pigment are broken) 16 hours.Then, under 130 ℃, carry out heated-air drying, thereby obtain the dielectric raw material.
In the dielectric raw material, with respect to 100mol barium titanate calcium raw material, contain glass ingredient: 3mol, Y
2O
3: 0～4mol (with reference to the sample 21～28 of table 4), MgO:0.5mol, MnO:0.2mol (or Cr
2O
3: 0.2mol), V
2O
5: O.03mol.
Table 4
mol％
| Specimen coding | MgO | MnO | Cr2O3 | Y2O3 | Dy2O3 | Ho2O3 | V2O5 | Glass ingredient |
| *21 | 0.5 | 0.2 | 0 | 0 | 0 | 0 | 0.03 | 3 |
| 22 | 0.5 | 0.2 | 0 | 0.5 | 0 | 0 | 0.03 | 3 |
| 23 | 0.5 | 0.2 | 0 | 1 | 0 | 0 | 0.03 | 3 |
| 24 | 0.5 | 0 | 0.2 | 1 | 0 | 0 | 0.03 | 3 |
| 25 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 3 |
| 26 | 0.5 | 0 | 0.2 | 2 | 0 | 0 | 0.03 | 3 |
| **27 | 0.5 | 0.2 | 0 | 3 | 0 | 0 | 0.03 | 3 |
| *28 | 0.5 | 0.2 | 0 | 4 | 0 | 0 | 0.03 | 3 |
| 29 | 0.5 | 0.2 | 0 | 0 | 0.5 | 0 | 0.03 | 3 |
| 30 | 0.5 | 0.2 | 0 | 0 | 1 | 0 | 0.03 | 3 |
| 31 | 0.5 | 0.2 | 0 | 0 | 2 | 0 | 0.03 | 3 |
| 32 | 0.5 | 0.2 | 0 | 0 | 0 | 1 | 0.03 | 3 |
| *33 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 0.5 |
| 34 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 1 |
| 35 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 2 |
| 36 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 4 |
| **37 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 5 |
| *38 | 0.5 | 0.2 | 0 | 2 | 0 | 0 | 0.03 | 6 |
* be comparative example
* is a reference example
The relative dielectric constant of sintered body sample and capacitor sample, IR life-span, X5R characteristic are shown in the table 5 in the present embodiment.
Table 5
| Specimen coding | Sintering temperature (℃) | Dielectric constant | Life-span (h) | The X5R characteristic | Ratio (%) with 1nm or following crystal grain boundary | Ratio (%) with 0.7nm or following crystal grain boundary |
| *21 | 1180 | 3390 | 20 | × | 78 | 74 |
| 22 | 1200 | 3100 | 120 | ○ | 68 | 60 |
| 23 | 1220 | 2820 | 280 | ○ | 44 | 40 |
| 24 | 1220 | 2800 | 220 | ○ | 42 | 34 |
| 25 | 1240 | 2730 | 250 | ○ | 34 | 30 |
| 26 | 1240 | 2610 | 240 | ○ | 30 | 26 |
| **27 | 1260 | 2330 | 210 | ○ | 26 | 20 |
| *28 | ≥1280 | The sintering deficiency | 18 | 2 | ||
| 29 | 1220 | 2740 | 160 | ○ | 56 | 48 |
| 30 | 1220 | 2760 | 280 | ○ | 36 | 34 |
| 31 | 1240 | 2700 | 300 | ○ | 30 | 26 |
| 32 | 1240 | 2750 | 230 | ○ | 32 | 26 |
| *33 | ≥1280 | The sintering deficiency | 14 | 2 | ||
| 34 | 1240 | 2780 | 150 | ○ | 60 | 54 |
| 35 | 1200 | 2730 | 180 | ○ | 44 | 34 |
| 36 | 1200 | 2720 | 150 | ○ | 36 | 30 |
| **37 | 1180 | 2800 | 170 | ○ | 22 | 16 |
| *38 | 1180 | 2360 | 120 | × | 16 | 14 |
* be comparative example
* is a reference example
Dielectric layer thickness
On the face vertical, cut off the sintered body that obtains, this section is ground, by a plurality of positions of this abradant surface of metal microstructure sem observation with internal electrode.Then, the image by the metal microstructure sem observation is carried out digitized processing, thereby try to achieve the average thickness of the dielectric layer behind the sintering.The average thickness of each sample dielectric layer is 2.5 μ m.
The average grain diameter of the insulating particles in the dielectric layer
Sintered body to gained grinds, apply chemical etching after, observe abradant surface by scanning electron microscope (SEM), by compiling method, suppose the sphere that is shaped as of insulating particles 20 in the dielectric layer, measure the average grain diameter of this insulating particles.Average grain diameter is 250 mean values that mensuration is counted.Average grain diameter is 0.20～0.26 μ m.
The crystal grain boundary thickness of insulating particles in the dielectric layer
The sintered body that mechanical lapping obtains after applying ion and grinding, by transmission electron microscope (TEM), is measured the thickness of crystal grain boundary by following mode.
Zone by tem observation 700nm * 500nm.For the crystal grain boundary of in this zone, observing 22, from three-dimensional point 24 arbitrarily, along crystal grain boundary 22, at the thickness of on the point of 100nm, measuring crystal grain boundary 22.In a plurality of zones, measure the thickness of crystal grain boundary 22, in amounting to 50 points, measure the thickness of crystal grain boundary 22.By this measurement result, the thickness that each sample is calculated crystal grain boundary 22 is that the right ratio (%) of 1nm or following particle and the thickness of crystal grain boundary 22 are 0.7nm or the following right ratio (%) of particle.The result is shown in the table 5.
In addition, in table 4 and table 5, the TEM photo of embodiment specimen coding 23 is shown in Fig. 5 A, and its enlarged photograph is shown in Fig. 5 B.In addition, the TEM photo of comparative example specimen coding 28 is shown in Fig. 6 A, and its enlarged photograph is shown in Fig. 6 B.
In the present embodiment, relative dielectric constant be preferably 2300 or more than, more preferably 2500 or more than, 2700 or more than.In addition, in the present embodiment, the IR life-span be preferably 100 hours or more than, more preferably 120 hours or more than.
Shown in the specimen coding 21～28 of table 5, the thickness of confirming crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 20%-70% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability under the high-k.In addition, the thickness of more preferably finding crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 25%-65% satisfies the X5R characteristic of EIA standard equally, and demonstrates the high reliability (high life) under the high-k more.
When the dielectric portion of relatively representing core and grain boundary portion, insulation resistance is the higher of grain boundary portion usually.Therefore think that the ratio of crystal boundary with 1nm or above thickness is many more, its reliability is just high more.Yet on the other hand, when more identical dielectric portion and grain boundary portion, dielectric constant is that dielectric portion is higher usually.Therefore think that the ratio of crystal boundary with 1nm or following thickness is few more, the dielectric constant of multilayer ceramic capacitor is just high more.In order preferably to be worth in two sides of its reliability and dielectric constant, the ratio of crystal boundary of considering to have 1nm or following (preferred 0.7nm or following) thickness is in above-mentioned scope.
In addition, according to Y
2O
3The difference of addition, the thickness of confirming crystal grain boundary is that the right ratio regular meeting of particle of 1nm or following (or 0.7nm or following) changes, but as described later shown in other the embodiment, to adding Y
2O
3Method in addition, its ratio also changes.
Embodiment 8
Shown in the specimen coding 29～32 of table 4,, add Dy except pressing the addition shown in the table 4 with respect to the barium titanate calcium raw material of 100mol
2O
3Or Ho
2O
3Replace Y
2O
3In addition, the same with the specimen coding 23 of embodiment 7, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 5, confirm there be the tendency identical with embodiment 7.Infer by this embodiment, use other terres rares (Sc, Er, Tm, Yb, Lu, Tb, Gd and Eu) to replace Y, also can obtain same effect.
Embodiment 9
Shown in the specimen coding 33～38 of table 4, the same with the specimen coding 25 of embodiment 7 except the addition of glass ingredient being changed into the scope of 0.5～6mol, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 5, confirm there be the tendency identical with embodiment 7.That is, the thickness of confirming crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 20%-70% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability under the high-k.In addition, the thickness of more preferably finding crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 25%-65% satisfies the X5R characteristic of EIA standard equally, and demonstrates the high reliability (high life) under the high-k more.
In addition, even confirm to change addition, the Mg amount of glass ingredient, the thickness of crystal grain boundary is that the right ratio of particle of 1nm or following (or 0.7nm or following) also changes.
Shown in the specimen coding 23a～23e of table 6, the same with the specimen coding 23 of embodiment 7 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 6, confirm there be the tendency identical with embodiment 7.That is, the thickness of confirming crystal grain boundary is that 1nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 20%-70% satisfies the X5R characteristic of EIA standard, and demonstrates the high reliability under the high-k.In addition, the thickness of more preferably finding this crystal grain boundary is that 0.7nm or the following right ratio of particle are that the multilayer ceramic capacitor of whole 25%-65% satisfies the X5R characteristic of EIA standard equally, and demonstrates the high reliability (high life) under the high-k more.
In addition, confirm to change sintering temperature, the thickness of crystal grain boundary is that the right ratio of particle of 1nm or following (or 0.7nm or following) changes.
Table 6
| Specimen coding | Sintering temperature (℃) | Dielectric constant | Life-span (h) | The X5R characteristic | Ratio (%) with 1nm or following crystal grain boundary | Ratio (%) with 0.7nm or following crystal grain boundary |
| *23a | 1180 | 2090 | 70 | ○ | 8 | 8 |
| **23b | 1200 | 2580 | 140 | ○ | 24 | 18 |
| 23c | 1220 | 2820 | 280 | ○ | 44 | 36 |
| **23d | 1240 | 2650 | 210 | ○ | 22 | 16 |
| *23e | 1260 | 2490 | 90 | ○ | 18 | 8 |
| *30a | 1180 | 1880 | 20 | ○ | 6 | 6 |
| **30b | 1200 | 2500 | 150 | ○ | 26 | 20 |
| 30c | 1220 | 2760 | 280 | ○ | 36 | 30 |
| **30d | 1240 | 2660 | 180 | ○ | 28 | 22 |
| *30e | 1260 | 2500 | 50 | ○ | 18 | 10 |
| *32a | 1180 | 2020 | 60 | ○ | 12 | 8 |
| *32b | 1200 | 2360 | 80 | ○ | 24 | 18 |
| 32c | 1220 | 2750 | 230 | ○ | 32 | 26 |
| **32d | 1240 | 2650 | 170 | ○ | 22 | 16 |
| *32e | 1260 | 2540 | 60 | ○ | 14 | 0 |
* be comparative example
* is a reference example
Embodiment 11
Shown in the specimen coding 30a～30e of table 6, the same with the specimen coding 30 of embodiment 7 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 6, confirm there be the tendency identical with embodiment 10.
Embodiment 12
Shown in the specimen coding 32a～32e of table 6, the same with the specimen coding 32 of embodiment 7 except sintering temperature being changed into 1180 ℃～1260 ℃, preparation sintered body sample and capacitor sample carry out same evaluation.As shown in table 6, confirm there be the tendency identical with embodiment 10.
Claims (22)
1, a kind of electronic unit, it is that to have with the barium titanate be the electronic unit of the dielectric layer of principal component, it is characterized in that,
In a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 1nm or following particle ratio are whole 30%-95%.
2, a kind of electronic unit, it is that to have with the barium titanate be the electronic unit of the dielectric layer of principal component, it is characterized in that,
In a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 0.75nm or following particle ratio are whole 40%-90%.
3, the electronic unit described in claim 1 or 2, wherein above-mentioned dielectric layer thickness are 3 μ m or following.
4, the electronic unit described in claim 1 or 2, wherein the average grain diameter of above-mentioned ceramic particle is 0.3 μ m or following.
5, the electronic unit described in claim 1 or 2 is characterized in that, in above-mentioned dielectric layer, contains magnesium oxide as accessory ingredient, and with respect to the 100mol barium titanate, the content of magnesium oxide is 0～2mol (wherein not comprising 0).
6, the electronic unit described in claim 1 or 2 is characterized in that, in above-mentioned dielectric layer, contains Mn oxide and/or chromated oxide as accessory ingredient, with respect to the 100mol barium titanate, is converted into MnO and Cr
2O
3, the total amount of Mn oxide and chromated oxide is 0～0.5mol (wherein not comprising 0).
7, the electronic unit described in claim 1 or 2 is characterized in that, in above-mentioned dielectric layer, contains rare-earth oxide as accessory ingredient, and with respect to the 100mol barium titanate, the content of rare-earth oxide is 0～4mol (wherein not comprising 0 and 4).
8, the electricity described in claim 1 or 2 is in parts, it is characterized in that, in above-mentioned dielectric layer, contain barium oxide, tungsten oxide, tantalum pentoxide and/or niobium oxide as accessory ingredient, with respect to the 100mol barium titanate, the total amount of barium oxide, tungsten oxide, tantalum pentoxide and niobium oxide is 0～0.5mol (wherein not comprising 0).
9, the electronic unit described in claim 1 or 2 is characterized in that, in above-mentioned dielectric layer, contains glass ingredient, and with respect to the 100mol barium titanate, the content of glass ingredient is 0.5～12mol.
10, the electronic unit described in claim 1 or 2, it is to have the multilayer ceramic capacitor that mutual lamination has the element body of above-mentioned dielectric layer and interior electrode layer.
11, the electronic unit described in claim 10, wherein above-mentioned interior electrode layer are principal component with the base metal.
12, a kind of electronic unit, it is to have with Ba
1-xCa
xTiO
3The barium titanate calcium of (0.001≤x≤0.15) expression is the electronic unit of the dielectric layer of principal component, it is characterized in that,
In a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 1nm or following particle ratio are whole 20%-70%.
13, a kind of electronic unit, it is to have with Ba
1-xCa
xTiO
3The barium titanate calcium of (0.001≤x≤0.15) expression is the electronic unit of the dielectric layer of principal component, it is characterized in that,
In a plurality of ceramic particles that form above-mentioned dielectric layer, the thickness of the crystal grain boundary that exists between adjacent ceramic particle is that 0.75nm or following particle ratio are whole 25%-65%.
14, the electronic unit described in claim 12 or 13, wherein above-mentioned dielectric layer thickness are 3 μ m or following.
15, the electronic unit described in claim 12 or 13, wherein the average grain diameter of above-mentioned ceramic particle is 0.3 μ m or following.
16, the electronic unit described in claim 12 or 13 is characterized in that, in above-mentioned dielectric layer, contains magnesium oxide as accessory ingredient, and with respect to the 100mol barium titanate calcium, the content of magnesium oxide is 0～2mol (wherein not comprising 0).
17, the electricity described in claim 12 or 13 is characterized in that in parts, in above-mentioned dielectric layer, contains Mn oxide and/or chromated oxide as accessory ingredient, with respect to the 100mol barium titanate calcium, is converted into MnO and Cr
2O
3, the total amount of Mn oxide and chromated oxide is 0～0.5mol (wherein not comprising 0).
18, the electronic unit described in claim 12 or 13 is characterized in that, in above-mentioned dielectric layer, contains rare-earth oxide as accessory ingredient, and with respect to the 100mol barium titanate calcium, the content of rare-earth oxide is 0～4mol (wherein not comprising 0 and 4).
19, the electronic unit described in claim 12 or 13, it is characterized in that, in above-mentioned dielectric layer, contain barium oxide, tungsten oxide, tantalum pentoxide and/or niobium oxide as accessory ingredient, with respect to the 100mol barium titanate calcium, the total amount of barium oxide, tungsten oxide, tantalum pentoxide and niobium oxide is 0～0.5mol (wherein not comprising 0).
20, the electronic unit described in claim 12 or 13 is characterized in that, in above-mentioned dielectric layer, contains glass ingredient, and with respect to the 100mol barium titanate calcium, the content of glass ingredient is 0.5～12mol.
21, the electronic unit described in claim 12 or 13, it is to have the multilayer ceramic capacitor that mutual lamination has above-mentioned dielectric layer and interior electrode layer element body mutually.
22, described electronic unit described in claim 21, wherein above-mentioned interior electrode layer are principal component with the base metal.
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|---|---|---|---|---|
| CN102019754A (en) * | 2009-09-15 | 2011-04-20 | 精工爱普生株式会社 | Liquid ejecting head, liquid ejecting apparatus, and piezoelectric element |
| CN114582628A (en) * | 2019-02-13 | 2022-06-03 | 三星电机株式会社 | Multilayer Ceramic Capacitors |
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| JP2009044017A (en) | 2007-08-09 | 2009-02-26 | Taiyo Yuden Co Ltd | Multilayer ceramic capacitor and method of manufacturing multilayer ceramic capacitor |
| JP2010040798A (en) | 2008-08-06 | 2010-02-18 | Murata Mfg Co Ltd | Stacked ceramic capacitor |
| JP5159682B2 (en) * | 2009-03-26 | 2013-03-06 | 京セラ株式会社 | Multilayer ceramic capacitor |
| JP2012129508A (en) | 2010-11-22 | 2012-07-05 | Tdk Corp | Laminated ceramic electronic component |
| JP6781544B2 (en) * | 2015-12-28 | 2020-11-04 | Tdk株式会社 | Ceramic electronic components |
| KR101905143B1 (en) * | 2017-05-11 | 2018-10-08 | 한국과학기술원 | Nonferroelectric dielectric materials and method thereof |
| KR102483896B1 (en) * | 2017-12-19 | 2022-12-30 | 삼성전자주식회사 | Ceramic dielectric and method of manufacturing the same and ceramic electronic component and electronic device |
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|---|---|---|---|---|
| CN102019754A (en) * | 2009-09-15 | 2011-04-20 | 精工爱普生株式会社 | Liquid ejecting head, liquid ejecting apparatus, and piezoelectric element |
| CN114582628A (en) * | 2019-02-13 | 2022-06-03 | 三星电机株式会社 | Multilayer Ceramic Capacitors |
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