CN102951901A - Dielectric ceramic composition and ceramic electronic component - Google Patents
Dielectric ceramic composition and ceramic electronic component Download PDFInfo
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- CN102951901A CN102951901A CN2011102711714A CN201110271171A CN102951901A CN 102951901 A CN102951901 A CN 102951901A CN 2011102711714 A CN2011102711714 A CN 2011102711714A CN 201110271171 A CN201110271171 A CN 201110271171A CN 102951901 A CN102951901 A CN 102951901A
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Abstract
A dielectric ceramic composition includes a compound having perovskite type crystal structure shown by a general formula ABO3, where A is at least one selected from Ba, Ca and Sr, and B is at least one selected from Ti and Zr. The dielectric ceramic composition includes, as subcomponents, an oxide of RA (Dy, Gd and Tb); an oxide of RB (Ho and Y); an oxide of RC (Yb and Lu); Mg oxide and an oxide including Si in terms of RA2O3, RB2O3, RC2O3, Mg and Si, respectively. Also, when contents of the oxide of RA, RB and RC with respect to 100 moles of the compound are defined as alpha, beta and gamma, respectively, they satisfy relations of 1.2<=alpha/beta<=5.0 and 0.5<=beta]/gamma<=10.0. The dielectric ceramic composition is best used in the dielectric layer thickness of 5.0 microns under electronic parts. If the invention is used, this is can offer even in the case of thin dielectric layer, and can also show good properties of dielectric ceramic composition and electronic parts.
Description
Technical field
The present invention relates to dielectric ceramic composition and this dielectric ceramic composition is used in the ceramic electronic component of dielectric layer, even particularly relate to dielectric layer is done the ceramic electronic component that also can demonstrate the dielectric ceramic composition of good characteristic and use this dielectric ceramic composition in the lamellar situation.
Background technology
As the multi-layer ceramic capacitor of an example of ceramic electronic component, to be used widely as the electronic component of miniaturization, high performance, high reliability, the number that uses in electric installation and electronics is more and more.In recent years, along with miniaturization and the high performance of equipment, more and more stricter to the requirement of the further miniaturization of multi-layer ceramic capacitor, high performance, high reliability.
For such requirement, for example putting down in writing the multi-layer ceramic capacitor with the dielectric ceramics layer that in barium titanate, contains two kinds of rare earth oxides and other metal oxides in the Japanese patent laid-open 10-223471 communique.And put down in writing the situation about having excellent weather resistance in specific inductivity, insulation resistance, temperature profile and the high-temperature load life-span etc. of this multi-layer ceramic capacitor.
But the thickness of the dielectric layer of the multi-layer ceramic capacitor of putting down in writing among the embodiment of Unexamined Patent 10-223471 communique is 8 microns, has the problem that can not improve characteristic in the situation that further makes this dielectric layer slimming.
Summary of the invention
The present invention makes in view of such practical situation, its purpose is, even provide in the situation that makes the dielectric layer slimming, also can demonstrate the dielectric ceramic composition of good characteristic and the ceramic electronic component that this dielectric ceramic composition is used in dielectric layer.
To achieve these goals, dielectric ceramic composition of the present invention is characterized in that,
As principal constituent, contain useful general expression ABO
3The compound with perovskite typed crystalline texture of (A is select among Ba, Ca and the Sr at least a, and B is select from Ti and Zr at least a) expression,
With respect to 100 moles above-claimed cpd, as minor component, contain
Use RA
2O
3Be scaled 0.6～2.5 mole RA oxide compound (RA is select in a group that forms of Dy, Gd and Tb at least a),
Use RB
2O
3Be scaled 0.2～1.0 mole RB oxide compound (that selects in a group that RB is Ho with Y shape becomes is at least a),
Use RC
2O
3Be scaled 0.1～1.0 mole RC oxide compound (RC is select in a group that forms of Yb and Lu at least a),
With Mg be scaled 0.8～2.0 mole the Mg oxide compound,
With Si be scaled 1.2～3.0 moles contain the Si compound,
With respect to 100 moles above-claimed cpd, when the content of the content of above-mentioned RA oxide compound, above-mentioned RB oxide compound and the content of above-mentioned RC oxide compound are designated as respectively α, β, γ, satisfy relational expression 1.2≤α/β≤5.0,0.5≤β/γ≤10.0.
In the present invention, by with the content of each composition in above-mentioned scope, even can access also good dielectric ceramic composition of various characteristics in the situation that makes the dielectric layer slimming.Particularly rare earth element is divided into three groups, by limited proportion that it is contained in above-mentioned scope, to principal constituent (ABO
3) in the solid solution condition of rare earth element control, can make opposite characteristic and deposit.
Preferably also contain at least a oxide compound of from a group that V, Mo and W form, selecting that useful V, Mo and W are scaled 0.03～0.12 mole as minor component.
Preferably also contain useful Mn as minor component and Cr is scaled 0.10～0.2 mole Mn and/or the oxide compound of Cr.
Therefore dielectric ceramic composition of the present invention can further improve characteristic owing to also contain mentioned component.
Above-mentioned ABO preferably
3Be BaTiO
3Can access so the high dielectric ceramic composition of large capacity and reliability.
Again, ceramic electronic component of the present invention has dielectric layer and the electrode of the dielectric ceramic composition formation of above-mentioned any one record.Preferably the thickness of above-mentioned dielectric layer is below 5.0 microns.As the ceramic electronic product, be not particularly limited, for example can be multi-layer ceramic capacitor, piezoelectric element, chip inductance, chip type voltage dependent resistor, chip type thermistor, chip-resistance, other surface mounting (SMD) chip-type electronic component.
Description of drawings
Fig. 1 is the sectional view of the multi-layer ceramic capacitor of the present invention's one example.
Embodiment
The present invention will be described for the example of the below shown in reference to the accompanying drawings.
Multi-layer ceramic capacitor 1
As shown in Figure 1, as the multi-layer ceramic capacitor 1 of an example of laminated ceramic electronic component, has the capacitor element main body 10 that dielectric layer 2 and interior electrode layer 3 cross laminates consist of.Interior electrode layer 3 laminations alternately expose on the surface of 2 relative ends of capacitor element main body 10 for each end face.Pair of external electrodes 4 is formed at the both ends of capacitor main body 10, is connected in the end face that exposes of the interior electrode layer 3 of alternately configured, consists of capacitor circuit.
Shape to capacitor element main body 10 is not particularly limited, and usually forms as shown in Figure 1 rectangular-shaped.And its size also is not particularly limited, adopt suitable size to get final product according to purposes.
Dielectric layer 2
Dielectric layer 2 is made of the dielectric ceramic composition of this example.The dielectric ceramic composition of this example, as its principal constituent, useful general expression ABO
3The compound of (A is select among Ba, Ca and the Sr at least a, and B is select among Ti and the Zr at least a) expression.Again, to have principal constituent be ABO to this dielectric ceramic composition
3Dielectric particle.
As ABO
3Useful for example { (Ba
(100-x-y)Ca
xSr
y) O}
u(Ti
(100-z)Zr
z)
vO
2The compound of expression.Also have, u, v, x, y, z are any range, but the following stated scope preferably.
In the above-mentioned formula, x is advisable with 0≤x≤10, and more preferably scope is 0≤x≤5.X represents the atomicity of Ca, by making x in above-mentioned scope, and the arbitrarily temperature factor of control capacitance amount and specific inductivity.If x is excessive, then specific inductivity has tendency on the low side.In this example, it is also passable not comprise calcium.
In the above-mentioned formula, y preferably satisfies 0≤y≤10, and more preferably scope is 0≤y≤5.Y represents the atomicity of Sr, is in the above-mentioned scope by making y, and specific inductivity is improved.If y is excessive, then temperature profile has deteriorated tendency.In this example, also can not comprise Sr.
In the above-mentioned formula, z preferably satisfies 0≤z≤30, and more preferably scope is 0≤z≤15.Z represents the atomicity of Zr, is in the above-mentioned scope by making z, and specific inductivity is improved.If z is excessive, then temperature profile has deteriorated tendency.In this example, also can not comprise Zr.
In this example, make ABO
3, particularly be fit to use barium titanate (preferably to use composition formula Ba
uTi
vO
3Expression, u/v satisfies 0.995≤u/v≤1.010).
The dielectric ceramic composition of this example except above-mentioned principal constituent, as minor component, also contains RA oxide compound, RB oxide compound, RC oxide compound, Mg oxide compound, contains the compound of Si.RA, RB and RC are divided into three groups with specific rare earth element.
If the content of RA oxide compound is designated as α, then α is with the ABO with respect to 100 moles
3Use RA
2O
3Be scaled 0.6～2.5 mole and be advisable, preferably 1.2～2.5 moles.If α is excessive, then reduced dielectric constant, or temperature profile has deteriorated tendency.If instead very few, then there is deteriorated tendency in the high-temperature load life-span.RA is select from a group that Dy, Gd, Tb consist of at least a, and RA is that Dy or Gd are then desirable especially.If RA is Gd, when the content of the oxide compound of RA (α) is less, even perhaps α/β described later hour, can fully obtain above-mentioned effect.
If the content of RB oxide compound is designated as β, then β is with the ABO with respect to 100 moles
3Use RB
2O
3Be scaled 0.2～1.0 mole and be advisable, preferably 0.2～0.6 mole.If β is excessive, there is deteriorated tendency in then reduced dielectric constant, or the high-temperature load life-span.If instead very few, then temperature profile has deteriorated tendency.RB is select from a group of Ho and Y formation at least a, and RA is that Ho is then desirable especially.
If the content of the oxide compound of RC is designated as γ, then γ is with the ABO with respect to 100 moles
3Use RC
2O
3Be scaled 0.1～1.0 mole and be advisable, preferably 0.1～0.6 mole.If γ is excessive, there is deteriorated tendency in then reduced dielectric constant, or the high-temperature load life-span.Otherwise if very few, then temperature profile has deteriorated tendency.RC is elect from a group of Yb and Lu formation at least a, and RC is that Yb is then desirable especially.
Again, α, β and γ satisfy 1.2≤α/β≤5.0, and the relation of 0.5≤β/γ≤10.0.
Particularly, be in the situation of Dy at RA, " α/β " satisfies the relation of 3.0≤α/β≤4.25 and is advisable.Again, " β/γ " is advisable with the relation that satisfies 0.5≤β/γ≤6.0.More preferably satisfy the relation of 3.0≤α/β≤4.25 and 0.5≤β/γ≤6.0.In the situation that can not satisfy above-mentioned relation, temperature profile and high-temperature load life-span have and are difficult to hold concurrently excellent tendency.
Further, the pass of " β/γ " is 0.5≤β/γ≤2.0, satisfies the relation of 0.5≤β/γ≤1.0 and is advisable.More preferably satisfy the relation of 0.5≤β/γ≤0.95.Have like this temperature profile and high-temperature load life-span to take into account (and depositing), RB amount capable of reducing using reduces the advantages such as cost.
Again, RA is in the situation of Gd, and " α/β " is advisable with the relation that satisfies 1.4≤α/β≤3.0.Again, " β/γ " is advisable with the relation that satisfies 0.5≤β/γ≤6.0.More preferably satisfy the relation of 1.4≤α/β≤3.0 and 0.5≤β/γ≤6.0.Satisfying in the situation of above-mentioned relation, having temperature profile and high-temperature load life-span to take into account (and depositing), can reduce the advantages such as RA usage quantity, reduction cost.
Further, the pass of " β/γ " is 0.5≤β/γ≤2.0, satisfies the relation of 0.5≤β/γ＜1.0 and is advisable.More preferably satisfy the relation of 0.5≤β/γ≤0.95.Have like this temperature profile and high-temperature load life-span to take into account, RB amount capable of reducing using reduces the advantages such as cost.
In this example, at ABO
3In the dielectric particle for principal constituent, the metallic element of solid solution minor component, for example RA, RB and RC.Also have, dielectric particle can have so-called nucleocapsid (コ ア シ エ Le) structure, also can have complete solid solution structure.
In this example, the effective ionic radius value with specific rare earth element during according to 6 coordination is divided into 3 groups (RA, RB, RC).Rare earth element is replaced ABO usually
3A side, solid solution is in ABO
3At this moment, the difference of the effective ionic radius of the effective ionic radius of rare earth element and A side's atom is little, replaces easily (solid solution) A side, and its poor large having is difficult to replace the tendency of (solid solution) A side.
In this example, be equivalent to RA with the poor little element of the ionic radius of A side's atom, the element that difference is large is equivalent to RC.RA and RC are at ABO
3In the solid solution degree different.RA tends to be solid-solubilized in fully easily ABO
3In, RC solid solution is in ABO
3Periphery.Tend to form easily so-called nucleocapsid structure.Consequently, although RA has improved the life-span of dielectric ceramic composition, temperature profile has deteriorated tendency.On the other hand, although RC can make the temperature profile of dielectric ceramic composition good, there is deteriorated tendency in the life-span.
Therefore consider content and ratio by control RA and RC, by means of the interpolation of RC, suppress RA at ABO
3In excessively solid solution, seeks temperature profile and life-span and take into account, but such consideration is inadequate.
Therefore in this example, the rare earth element (RB) of the effective ionic radius of the centre by it being contained have RA and RC is controlled the solid solution condition of 3 kinds of rare earth elements, takes into account temperature profile and life-span.And the ratio by making RA, RB, RC content (α, β, β) separately can take into account temperature profile and life-span in above-mentioned scope, and can improve other characteristics (specific inductivity, CR long-pending etc.).
The content of the oxide compound of Mg is with the ABO with respect to 100 moles
3Be scaled 0.8～2.0 mole with each element and be advisable, more preferably 1.3～2.0 moles.If the content of above-mentioned oxide compound is too much, then there is deteriorated tendency in the high-temperature load life-span, if instead very few, particle overgrowth then, temperature profile has deteriorated tendency.
Contain the Si compound and mainly contain effect as sintering aid.Contain the content of Si compound with the ABO with respect to 100 moles
3Be scaled 1.2～3.0 moles with Si and be advisable, 1.2～1.9 moles then better, also has, and as containing the Si compound, also can be the composite oxides etc. that contain Si, but preferably not contain displacement ABO
3The element (for example Ca, Ba) of A side, independent SiO
2Then better.Because if comprise the element of replacing A side, then as the ABO of principal constituent
3The A/B ratio might change.
The dielectric ceramic composition of this example as minor component, preferably also comprises at least a oxide compound selected and the oxide compound of Mn and/or Cr from a group that V, Mo and W consist of.
The content of at least a oxide compound of selecting from a group of V, Mo and W composition is with the ABO with respect to 100 moles
3, be scaled 0.03～0.12 mole with V, Mo and W and be advisable, more preferably 0.07～0.12 mole.If the content of above-mentioned oxide compound is too much, then insulation resistance (CR is long-pending) has the tendency of decline, if instead very few, low tendency of high-temperature load life-span is arranged then.In this example, V preferably.
The content of the oxide compound of Mn and/or Cr is with the ABO with respect to 100 moles
3, be scaled 0.10～0.2 mole with Mn and/or Cr and be advisable, more preferably 0.15～0.2 mole.If the content of Mn and/or Cr oxide compound is too much, then temperature profile has deteriorated tendency, if instead very few, then insulation resistance has the tendency of decline.In this example, Mn preferably.
The crystallization particle diameter of the dielectric particle that comprises in the dielectric ceramic composition of this example is not particularly limited, but in order to adapt to the thin layer requirement of dielectric layer, preferably 0.15～0.30 micron.The dielectric ceramic composition of this example can also contain other compositions according to desirable characteristic.
The thickness of dielectric layer 2 is for the requirement corresponding to the dielectric layer slimming, and every one deck is preferably below 5.0 microns.
The lamination number of dielectric layer 2 is not particularly limited, and is then more desirable more than 50 layers to be advisable more than 20 layers, particularly desirably more than 100 layers.The upper limit of lamination number is not particularly limited, and for example can be about 2000 layers.
Interior electrode layer 3
The electro-conductive material that contains in the interior electrode layer 3 is not particularly limited, and has reducing resistance owing to consist of the material of dielectric layer 2, base metal that therefore can the usage comparison cheapness.The base metal that uses as electro-conductive material is nickel or nickelalloy preferably.More than one elements of preferably selecting among Mn, Cr, Co and the Al as nickelalloy and the alloy of nickel, nickel content is preferably more than 95 % by weight in the alloy.Also have, also can contain the following various trace ingredientss such as P of 0.1 % by weight in nickel or the nickelalloy.The thickness of interior electrode layer 3 can suitably determine according to purposes etc., preferably 0.1～3 micron usually, and particularly about 0.2～2.0 micron.
Outer electrode 4
The electro-conductive material that comprises in the outer electrode 4 is not particularly limited, and can adopt cheap Ni, Cu or their alloy in this example.The thickness of outer electrode 4 gets final product according to suitable decisions such as purposes, usually preferably about 10～50 microns.
The manufacture method of multi-layer ceramic capacitor 1
The multi-layer ceramic capacitor 1 of this example, the same with existing multi-layer ceramic capacitor, utilize the common printing process or the slice method that use cream to make living chip, after it is burnt till, then printing or duplicating outer electrode burn till, and make described electrical condenser with this.The below is specifically described manufacture method.
At first prepare dielectric medium raw material (dielectric ceramic composition powder), with its coating, modulation forms the cream (dielectric layer cream) that dielectric layer is used.
As the dielectric medium raw material, at first prepare ABO
3Raw material and the raw material of the oxide compound of R.These raw materials can adopt the oxide compound of mentioned component or its mixture, composite oxides.Again can from by burn till the various compounds that form above-mentioned oxide compound or composite oxides, such as suitably selecting carbonate, oxalate, nitrate, oxyhydroxide, the organometallic compound etc., mix and use.
ABO
3Raw material, be except adopting so-called solid phase method, the raw material that the various manufacture method such as raw material that can adopt various liquid phase methods (such as oxalate method, hydrothermal synthesis method, alkoxide (Alkoxide) method, colloidal solution gel method etc.) to make are made.
The decision of the content of the various compounds in the dielectric medium raw material is as long as determine as forming the composition of above-mentioned dielectric ceramic composition after burning till.Under the state before the coating, the particle diameter of dielectric medium raw material is about 0.1～1 micron of median size normally.
Dielectric layer can be dielectric medium raw material and the mixed uniformly organic coating of organic carrier (vehicle) with cream, also can be aqueous coating.
So-called organic carrier is that caking agent is dissolved in material in the organic solvent.The caking agent that is used in organic carrier is not particularly limited, and can suitably select to get final product from the common various caking agents such as ethyl cellulose, Vinyl Acetate Copolymer butyral (Poly vinyl butyral).The organic solvent that uses also is not particularly limited, and suitably selects to get final product from the various organic solvents such as terpinol, diethylene glycol monobutyl ether, acetone, toluene according to using method such as print process or slice methods.
Again, dielectric layer adopts with cream in the situation of aqueous coating, the water system carrier (vehicle) that makes water soluble adhesive and dispersion agent etc. be dissolved in water is evenly mixed getting final product with the dielectric medium raw material.The water soluble adhesive that is used in the water system carrier is not particularly limited, and can adopt such as polyvinyl alcohol, Mierocrystalline cellulose, water soluble acrylic resin etc.
Interior electrode layer cream is the electro-conductive material that above-mentioned various conductive metal or alloy are consisted of or the mixture (レ ジ ネ one ト) that burns till various oxide compounds, organometallic compound, organometallic compound and the caking agent of the above-mentioned electro-conductive material of rear formation etc. with the even hybrid modulation formation of above-mentioned organic carrier.With in the cream, also can contain inhibitor at interior electrode layer again.Be not particularly limited as inhibitor, but preferably with principal constituent by identical forming.
Outer electrode gets final product with the same modulation of cream with above-mentioned interior electrode layer with cream.
Organic carrier content in above-mentioned each cream is not particularly limited, and content, gets final product about solvent 10～50 % by weight about caking agent 1～5 % by weight for for example usually.In each cream, also can contain the additive of selecting in various dispersion agents, softening agent, dielectric medium, the isolator etc. as required.The total content of these additives is preferably in below 10 % by weight.
Use in the situation of print process, with dielectric layer with cream and interior electrode layer with the cream printing, be stacked on the substrate such as PET, be cut to after the regulation shape, strip down as the life chip from substrate.
Again, with in the situation of slice method, form raw cook with dielectric layer with cream, print interior electrode layer cream thereon, form after the internal electrode pattern, with its lamination as the life chip.
Before burning till, implement to take off the caking agent processing to giving birth to chip.As taking off the caking agent condition, preferably heat-up rate is 5～300 ℃/hour, preferably 180～400 ℃ of holding temperatures, soaking time preferably 0.5～24 hour.Atmosphere around when taking off caking agent again, adopts air or reducing atmosphere.
Burn till giving birth to chip after taking off caking agent.When burning till, preferably 100～500 ℃/hour of heat-up rates.Holding temperature when burning till is to be advisable below 1300 ℃, and preferably 1150～1280 ℃, its soaking time was advisable with 5～8 hours, and 2～3 hours then better.If holding temperature is less than above-mentioned scope institute temp. displaying function, then densification is abundant not, if surpass this scope, the unusual sintering of interior electrode layer then, can cause lead rupture or owing to the diffusion of interior electrode layer constituent material causes the electrical capacity temperature profile deteriorated, the reduction of dielectric ceramic composition occur easily again.
Surrounding atmosphere during sintering is reducing atmosphere preferably, and the gas as surrounding atmosphere uses can use the mixed gas humidification of for example nitrogen and hydrogen.
Again, the oxygen partial pressure when burning till suitably determines get final product according to the kind of interior electrode layer with the electro-conductive material in the cream, but in the situation of the base metals such as electro-conductive material employing nickel or nickelalloy, the oxygen partial pressure in the surrounding atmosphere when burning till preferably 10
-14～10
-10MPa.Oxygen partial pressure is during less than the numerical value of above-mentioned scope, and the electro-conductive material abnormal sintering of interior electrode layer has the situation of fracture.Again, if oxygen partial pressure surpasses the numerical value of above-mentioned scope, then interior electrode layer has the tendency of oxidation.Preferably 50～500 ℃/hour of cooling rates.
After in reducing atmosphere, burning till, preferably the capacitor element main body is annealed.Annealing is the processing that dielectric layer is used in oxidation, can make like this IR life-span (life-span of insulation resistance) significant prolongation, therefore can improve reliability.
Oxygen partial pressure in the Annealing Protection atmosphere preferably 10
-9～10
-5MPa.Oxygen partial pressure is during less than the numerical value of above-mentioned scope dictates, and reoxidizing of dielectric layer had any problem, in case surpass above-mentioned scope, then has interior electrode layer to continue the tendency of oxidation.
Holding temperature during annealing to be to be advisable below 1100 ℃, particularly 1000～1100 ℃ then even more ideal.Holding temperature is during less than the described numerical value of above-mentioned scope, and the oxidation of dielectric layer is insufficient, so IR is low, and the IR life-span shortens easily.On the other hand, if holding temperature surpasses above-mentioned scope, then interior electrode layer generation oxidation, not only electrical capacity descends, and interior electrode layer reacts with base of dielectric, and the electrical capacity temperature profile is deteriorated, IR decline, the IR life-span, low situation occured easily.Also have, annealing also can only consist of with temperature-rise period and temperature-fall period.That is to say, can soaking time be 0 also.In this case, holding temperature is exactly top temperature.
Annealing conditions in addition, soaking time was advisable with 0～20 hour, and 2～4 hours are then more desirable, and cooling rate is advisable with 50～500 ℃/hour, and 100～300 ℃/hour are then more desirable.Again, the protective atmosphere of annealing preferably uses nitrogen such as humidification etc.
Above-mentioned taking off during caking agent processes, burns till and anneal is in order to give the humidifications such as nitrogen or mixed gas, as long as use such as humidifier etc.In this case, water temperature is preferably about 5～75 ℃.
Take off caking agent and process, burn till and anneal and to carry out continuously, also can independently carry out.
To the capacitor element main body that obtains as mentioned above, utilize methods such as cylinder grinding or sandblast that end face is ground, then be coated with outer electrode to burn till again with cream, form outer electrode 4.And as required externally the surface of electrode 4 utilize the method formation coatings such as platings.
The multi-layer ceramic capacitor of this example of making like this utilizes the method such as soldering to be installed on tellite etc., is used in various electronicss etc.
More than example of the present invention is illustrated, but the present invention to above-mentioned example without any restriction, in the scope that does not break away from main idea of the present invention, various changes can be arranged.
For example, in above-mentioned example, as ceramic electronic component of the present invention, illustration multi-layer ceramic capacitor, but as such ceramic electronic component, be not limited to multi-layer ceramic capacitor, so long as have the electronic component of said structure, also can be other parts.
Example
Further the present invention will be described according to specific embodiment for the below, but the invention is not restricted to these embodiment.
Embodiment 1
At first, as ABO
3Raw material powder prepared BaTiO
3Powder as the RA oxide raw material, has been prepared Dy
2O
3Powder; As the raw material of RB oxide compound, prepared Ho
2O
3Powder; As the RC oxide raw material, prepared Yb
2O
3Powder.As the raw material of Mg oxide compound, prepared MgCO again,
3Powder; As the Mn oxide raw material, prepared the MnO powder; As the raw material of V oxide compound, prepared V
2O
5Powder; Prepared SiO as sintering aid
2Powder.
Then according to each raw material powder of the above-mentioned preparation of quantity weighing shown in the table 1, carry out 10 hours wet mixing, pulverizing, oven dry with ball mill, obtain the dielectric medium raw material.Also have, for No. 7 and No. 8 samples, as the raw material of RA oxide compound, prepare Tb
4O
7Powder (No. 7 samples) and Gd
2O
3Powder (No. 8 samples).For No. 12 samples, as the raw material of RB oxide compound, prepare Y
2O
3Powder.For No. 16 samples, as the raw material of RC oxide compound, prepare Lu
2O
3Powder.Again, MgCO
3After burning till, be contained in the dielectric ceramic composition as MgO.
Then, with the dielectric medium raw material of 100 weight parts that obtain, Vinyl Acetate Copolymer butyral (the Poly vinyl butyral) resin of 10 weight parts, the DOP (Di-Octyl Phthalate as softening agent of 5 weight parts; Dioctyl phthalate), the ethanol as solvent of 100 weight parts mixes with ball mill, forms paste, obtains dielectric layer cream.
Again the Ni particle of 44.6 weight parts, the terpinol of 52 weight parts, the ethyl cellulose of 3 weight parts, the benzotriazole (Benzotriazole) of 0.4 weight part are mixed the formation paste with three rollers, make interior electrode layer cream.
Then form raw cook with cream at the PET film with the dielectric layer of making as mentioned above, can after oven dry, obtain the raw cook of 4.5 microns of thickness.After then using interior electrode layer with cream electrode layer to be printed with the pattern of stipulating, peel raw cook from the PET film thereon, be manufactured with the raw cook of electrode layer.Then, will have the multi-disc raw chip laminating of electrode layer, and form by crimping and give birth to (green) multilayer body, should give birth to multilayer body and be cut to specified dimension, to obtain giving birth to chip.
Then, the living chip that obtains is taken off caking agent under the following conditions process, burn till and anneal, obtain the multi-layered ceramic sintered body.
The condition of taking off the caking agent processing is heat-up rate: 25 ℃/hour, holding temperature: 260 ℃, soaking time: 8 hours.Surrounding atmosphere is air.
Firing condition is heat-up rate: 200 ℃/hour, holding temperature: 1240 ℃, soaking time: 2 hours.Cooling rate is 200 ℃/hour.Also have, protective atmosphere adopts the nitrogen of humidification and the mixed gas of hydrogen, and oxygen partial pressure is 10
-12MPa.
Annealing conditions is heat-up rate: 200 ℃/hour, holding temperature: 1000 ℃, soaking time: 2 hours, cooling rate are the nitrogen (oxygen partial pressure 10 that 200 ℃/hour, protective atmosphere adopt humidification
-7MPa).
Burn till and the humidification of the protective atmosphere when annealing uses humidifier.
Then, after the end face of the multi-layered ceramic sintered body that obtains ground with blasting method, Cu was as outer electrode in coating, obtains the sample of multi-layer ceramic capacitor shown in Figure 1.The electrical condenser sample that obtains is of a size of 3.2mm * 1.6mm * 0.6mm, and the thickness of dielectric layer is 3.0 microns, and the thickness of interior electrode layer is 1.1 microns, and the number of the dielectric layer that is clipped by interior electrode layer is 4 layers.
To the electrical condenser sample that obtains, utilize respectively that following method measures that its specific inductivity, CR are long-pending, electrical condenser temperature profile and high-temperature load life-span (HALT).
DIELECTRIC CONSTANT ε
DIELECTRIC CONSTANT ε is to the electrical condenser sample, under 25 ℃ of reference temperatures, with digital LCR meter (the 4274A type that YHP Co., Ltd. makes), under the condition of 1kHz frequency, incoming signal level (test voltage) 1.0Vrms, measure and draw electrical capacity, (without the unit) that then calculates according to electrical capacity.Specific inductivity is higher unreasonablely to be thought, in the present embodiment, is good more than 1500.The results are shown in table 1.
CR is long-pending
To the electrical condenser sample, under 20 ℃ temperature, the volts DS that the electrical condenser sample is applied the 10V/ micron is measured its insulation resistance IR after 1 minute with insulating-resistance meter (R8340A that the ア of Amada Co., Ltd. De バ Application テ ス ト makes).CR is long-pending by asking the electrical capacity C (the μ F of unit) that measures as mentioned above and the product of insulation resistance IR (the M Ω of unit) to obtain.In the present embodiment preferably more than 500.The results are shown in table 1.
The temperature profile of electrical capacity
To the electrical condenser sample, measure electrical capacity-55～125 ℃ temperature ranges, calculate the velocity of variation Δ C of electrical capacity, the X7R characteristic that whether satisfies the EIA standard is estimated.That is to say that the velocity of variation Δ C that estimates in the said temperature scope is whether in ± 15%.The results are shown in table 1.
The high-temperature load life-span
To the electrical condenser sample, under 195 ℃ temperature, the electric field that remains on 48V/ μ m applies the state of volts DS, measures life time, with this high-temperature load life-span is estimated.In the present embodiment, will it be the life-span from beginning to be applied to the timing definition that insulation resistance descends till the order of magnitude.And in the present embodiment, 20 electrical condenser samples are carried out above-mentioned evaluation, with its mean value as the high-temperature load life-span.In the present embodiment, take more than 3 hours as good.The results are shown in table 1.
Again, in table 1, be that sample marking below 1300 ℃ is " well " with firing temperature, be " bad " with firing temperature than 1300 ℃ of high sample markings.
According to table 1, confirm under the content and ratio situation within the scope of the invention thereof of Mg compound, RA oxide compound, RB oxide compound, RC oxide compound and Si oxide compound, satisfy the X7R characteristic, the good high-temperature load life-span that obtains simultaneously, and obtain high-k.Confirm again RA, RB, RC, also can access identical effect in the situation of the element beyond employing Dy, Ho, the Yb.
Embodiment 2
Except the quantity shown in the content employing table 2 of each composition, make in the same manner as in Example 1 the sample of multi-layer ceramic capacitor, carry out in the same manner as in Example 1 evaluating characteristics.The results are shown in table 2.Also have, to No. 47 samples, as the raw material of RA oxide compound, prepare Tb
4O
7Powder as the raw material of RB oxide compound, is prepared Y
2O
3Powder.To No. 48 samples, as the raw material of RB oxide compound, prepare Y
2O
3Powder.
According to table 2, confirm content and the ratio (No. 31～40a sample) in extraneous situation of the present invention thereof of Mg compound, RA oxide compound, RB oxide compound, RC oxide compound and Si oxide compound, specific inductivity, X7R characteristic and high-temperature load have more than one deteriorated in the life-span, and only contain at rare earth element (RA, RB and RC) in the situation of one or both (No. 41～No. 48 samples), X7R characteristic and high-temperature load life-span can not be taken into account simultaneously.In addition, can find out, even the content of Mg oxide compound, RA oxide compound, RB oxide compound, RC oxide compound and Si oxide compound within the scope of the invention, its ratio is (No. 49 samples) in extraneous situation of the present invention, and for example deteriorated situation of high-temperature load life-span can occur.
Embodiment 3
Except the content that changes V oxide compound and Mn oxide compound, make in the same manner as in Example 1 the sample of multi-layer ceramic capacitor, carry out in the same manner as in Example 1 evaluating characteristics.The results are shown in table 3.
According to table 3, confirm the content (61,65,66 and No. 70 samples) in desirable extraneous situation of the present invention of V oxide compound and Mn oxide compound, CR is long-pending, X7R characteristic and a certain item of high-temperature load in the life-span have deteriorated tendency.
Embodiment 4
Except the thickness (layer thickness) of the dielectric layer of No. 2, No. 47 and No. 48 samples is the thickness shown in the table 4, make in the same manner as in Example 1 the sample of multi-layer ceramic capacitor, carry out in the same manner as in Example 1 evaluating characteristics.The results are shown in table 4.
Table 4
"
*" represent comparative example of the present invention
Confirm according to table 4, even make in the situation of dielectric layer thin layer of No. 2 samples, also not only can obtain the good high-temperature load life-span, and can when satisfying the X7R characteristic, also obtain large specific inductivity.
By contrast, also confirm in the situation of the dielectric layer thin layer that makes No. 47 samples, not only can not satisfy the X7R characteristic, and also there is deteriorated tendency in the high-temperature load life-span.And in the situation of the dielectric layer thin layer that makes No. 48 samples, although the X7R characteristic is met, the high-temperature load life-span is extremely deteriorated.
Claims (6)
1. a dielectric ceramic composition is characterized in that,
As principal constituent, contain useful general expression ABO
3The compound with perovskite typed crystalline texture of expression, and (A is select among Ba, Ca and the Sr at least a, B be from Ti and Zr select at least a)
With respect to 100 moles above-claimed cpd, as minor component, contain
Use RA
2O
3Convert, 0.6～2.5 mole RA oxide compound, RA be select in a group that forms of Dy, Gd and Td at least a,
Use RB
2O
3Convert, select in a group that 0.2～1.0 mole RB oxide compound, RB are Ho with Y shape becomes at least a,
Use RC
2O
3Be scaled 0.1～1.0 mole RC oxide compound, RC be select in a group that forms of Yb and Lu at least a,
With Mg be scaled 0.8～2.0 mole the Mg oxide compound,
With Si be scaled 1.2～3.0 moles contain the Si compound;
With respect to 100 moles above-claimed cpd, when the content of the content of above-mentioned RA oxide compound, above-mentioned RB oxide compound and the content of above-mentioned RC oxide compound are designated as respectively α, β, γ, satisfy relational expression 1.2≤α/β≤5.0,0.5≤β/γ≤10.0.
2. dielectric ceramic composition according to claim 1 is characterized in that, as minor component, also contains be scaled 0.03～0.12 mole at least a oxide compound of selecting with V, Mo, W from a group that V, Mo, W form.
3. dielectric ceramic composition according to claim 1 and 2 is characterized in that, as minor component, also contains with Mn and Cr and is scaled 0.10～0.2 mole Mn and/or the oxide compound of Cr.
4. dielectric ceramic composition according to claim 1 and 2 is characterized in that, described ABO
3Be BaTiO
3
5. a ceramic electronic component is characterized in that, has dielectric layer and the electrode of the dielectric ceramic composition formation of claim 1 record, and the thickness of described dielectric layer is below 5.0 microns.
6. ceramic electronic component according to claim 5 is characterized in that,
As minor component, also contain and be scaled 0.03～0.12 mole at least a oxide compound of from a group that V, Mo, W form, selecting with V, Mo, W,
Contain with Mn and Cr and be scaled 0.10～0.2 mole Mn and/or the oxide compound of Cr.
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| CN108569897A (en) * | 2017-03-09 | 2018-09-25 | Tdk株式会社 | Piezoelectric composition and piezoelectric element |
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| JP6451293B2 (en) * | 2014-12-17 | 2019-01-16 | Tdk株式会社 | Multilayer ceramic capacitor |
| KR102222606B1 (en) * | 2015-12-29 | 2021-03-05 | 삼성전기주식회사 | Dielectric composition and multilayer ceramic capacitor comprising the same |
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