CN1790568B - Dielectric ceramic composition, electronic component, and method for manufacturing the same - Google Patents
Dielectric ceramic composition, electronic component, and method for manufacturing the same Download PDFInfo
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- CN1790568B CN1790568B CN 200410095402 CN200410095402A CN1790568B CN 1790568 B CN1790568 B CN 1790568B CN 200410095402 CN200410095402 CN 200410095402 CN 200410095402 A CN200410095402 A CN 200410095402A CN 1790568 B CN1790568 B CN 1790568B
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Abstract
To provide a method for manufacturing a dielectric ceramic composition capable of obtaining the densified dielectric ceramic composition without impairing various electrical characteristics in spite of firing at a low temperature. The method for manufacturing the dielectric ceramic composition having a dielectric oxide expressed by the composition formula: [(Ca<SB>x</SB>Sr<SB>1-x</SB>)O]<SB>m</SB>[(Ti<SB>y</SB>Zr<SB>1-y-x</SB>Hf<SB>z</SB>)O<SB>2</SB>]. wherein symbols x, y, z, and m representing the composition molar ratios in the formula are 0.5<=x<=1.0, 0.01<=y<=0.10, 0<z<=0.20, and 0.90<=m<=1.04, and manganese oxide, aluminum oxide, and sintering assistant, comprises manufacturing the dielectric ceramic composition by using the sintering assistant having a first glass composition whichis composed of SiO<SB>2</SB>as an essential component and further contains MO (M is at least one among Ba, Ca, Sr, and Mg) and a second glass composition which is constituted by including B<SB>2</SB>O<SB>3</SB>, Al<SB>2</SB>O<SB>3</SB>, ZnO, and SiO<SB>2</SB>and has an average grain size of <=1.5 [mu]m.
Description
Technical field
For example the present invention relates to as the dielectric-porcelain composition of the dielectric layer of lamination porcelain capacitor etc. and manufacture method thereof with electronic unit and the manufacture method thereof of this dielectric-porcelain composition as dielectric layer.
Background technology
Constitute an example of electronic unit, promptly the structure of the dielectric-porcelain composition of lamination porcelain capacitor dielectric comprises strong dielectric BaTiO
3, normal dielectric SrTiO
3, CaTiO
3, CaSrZrO
3, CaZrO
3, SrZrO
3, TiO
2, NdTiO
3Etc. various dielectric oxides.
In recent years, developed the dielectric-porcelain composition of reducing resistance.Utilize the dielectric-porcelain composition of this reducing resistance, even be sintering under neutrality～reducing atmosphere in the low oxygen dividing potential drop, also semiconductor transformation not, and can use the material of base metals such as Ni and Cu as internal electrode.
As this kind dielectric-porcelain composition, known have a CaSr-ZrTi-Mn based material (with reference to patent documentation 1), usually, except dielectric oxide as main component, be used for the basis of the sintering aid of acceleration of sintering degree in interpolation, also will for example calcining under the high temperature more than 1300 ℃.
But, if the sintering temperature height then produces following inconvenience.
First, form the material of internal electrode, be the above or temperature range approaching of fusing point of base metal such as Ni with it, its result becomes the main cause that produces following inconvenience: fusing and nodularization can take place in the base metal particle of sintering with the dielectric-porcelain composition while, and the linearity of interior electrode layer can worsen, that is, break in the interior electrode layer.If the linearity of interior electrode layer worsens, the dielectric constant of the capacitor that then obtains reduces, and the result causes capacitance to reduce, and finally can not meet high capacity and thin layerization.
The second, the price height of sintering furnace, and the damage of the sintering furnace that uses is also serious, and the maintenance of sintering furnace and management cost etc. increased along with service time, and simultaneously, porcelain energy needed cost also increases.
Because reason as above, expectation can reduce calcining heat as far as possible.
On the other hand, if calcining heat is low excessively, can not densification when then carrying out porcelain, the dielectric-porcelain composition that can not get having sufficient characteristic.
Therefore, need not damage the densification of dielectric-porcelain composition and can calcine with lower low temperature.
Patent documentation 1 Japanese kokai publication sho 60-131708 communique
Summary of the invention
Even the object of the present invention is to provide a kind of in low temperature (for example 1250 ℃ or following) calcining do not damage various electrology characteristics yet and can obtain the manufacture method of the dielectric-porcelain composition of fine and close dielectric-porcelain composition, the dielectric-porcelain composition that obtains by this method, electronic unit that this dielectric-porcelain composition is obtained as the manufacture method of the electronic unit of the chip capacitor of dielectric layer etc., by this method.
Solve the method for problem
In order to achieve the above object, according to the present invention, provide a kind of manufacture method of dielectric-porcelain composition, described dielectric-porcelain composition is to have with structural formula (Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] dielectric oxide, manganese oxide, the aluminium oxide of expression, the dielectric-porcelain composition of sintering aid, symbol x, the y of the expression constitutive molar ratio in the said structure formula, z, m are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04, it is characterized in that
Use sintering aid to make dielectric-porcelain composition, described sintering aid has:
With SiO
2As main component, also comprise MO (wherein, M is at least a of Ba, Ca, Sr and Mg), first glass composition; With
Its formation comprises B
2O
3, Al
2O
3, ZnO and SiO
2, second glass composition with the following average grain diameter of 1.5 μ m.
According to the present invention, a kind of manufacture method of dielectric-porcelain composition is provided, described medium ceramic composition is to have with structural formula (Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] dielectric oxide, manganese oxide, the aluminium oxide of expression, the dielectric-porcelain composition of sintering aid, symbol x, the y of the expression constitutive molar ratio in the said structure formula, z, m are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04, it is characterized in that, use sintering aid, described sintering aid has:
With SiO
2As main component, also comprise MO (wherein, M is at least a of Ba, Ca, Sr and Mg), first glass composition; With
Its formation comprises B
2O
3, Al
2O
3, ZnO and SiO
2, have following average grain diameter second glass composition of 1.5 μ m,
And have a following step:
Mix the step of raw material before the ready reaction to major general's second glass composition with the initial feed of preparing in order to obtain dielectric oxide;
Make the preceding raw material reaction of off-the-shelf reaction, obtain comprising the step of the dielectric-porcelain composition raw material of reaction raw materials.
Carry out raw materials mixed before the ready reaction during raw material and can be at least the second glass composition in the sintering aid.Preferably the first～the second glass composition in the sintering aid more preferably is sintering aid at least, whole raw materials that optimum is except the dielectric oxide of above-mentioned specific composition.
Be blended at least the second glass composition in the preceding raw material of reaction, be total amount preferably, but also can be its part for final composition.
In the present invention, as " make reaction before the raw material method of reacting ", what can exemplify out has solid phase method (for example calcination method) and a liquid phase method.Described solid phase method is for example BaCO for preparing in order to obtain the main component raw material
3, TiO
2Etc. initial feed, as required,, mix, calcine, pulverize with the common weighing ormal weight of the raw material of auxiliary element, obtain calcining the method for back raw material.As liquid phase method, oxalate method, hydrothermal synthesis method, sol-gel process etc. have been exemplified.The wherein preferred reaction raw materials that obtains by solid phase method that uses.
Preferred above-mentioned second glass composition also comprises Na
2O.
Preferred above-mentioned second glass composition comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, the ZnO of 10～60 weight %, the Na of 0～15 weight %
2The SiO of O and 5～35 weight %
2
Preferred use following such sintering aid, described sintering aid has for 100 moles dielectric oxide and is 0.5～15 mole first glass composition and is second glass composition of 0.1～10 weight % for 100 weight % dielectric oxides.
The preferred dielectric-porcelain composition with sintering aid of making has following such sintering aid, comprises with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] dielectric oxide, the manganese oxide of expression, first glass composition and second glass composition of aluminium oxide, symbol x, the y of the expression constitutive molar ratio in the said structure formula, z, m are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤020,0.90≤m≤1.04
For 100 moles of dielectric oxides, contain and be converted into MnO and be 0.2～5 mole manganese oxide, be converted into Al
2O
3Be 0.1～10 mole aluminium oxide, 0.5～15 mole first glass composition,
With respect to 100 weight % dielectric oxides, contain second glass composition of 0.1～10 weight %.
Preferred dielectric-porcelain composition also contains vanadium oxide, for 100 moles of dielectric oxides, is converted into V
2O
5Be 0～2.5 mole (except 0 mole).
Preferred dielectric-porcelain composition also contains the oxide of rare earth element, and it is scaled 0.02～1.5 mole with respect to 100 moles of dielectric oxides by rare earth element.
Preferred dielectric-porcelain composition also contains at least a oxide among Nb, Mo, Ta, W and the Mg, for 100 moles of dielectric oxides, is scaled 0.02～1.5 mole by this Nb, Mo, Ta, W and Mg.
Preferably in 1250 ℃ or following calcining heat, make dielectric-porcelain composition.
In the present invention, according to best mode, provide a kind of manufacture method of dielectric-porcelain composition, described dielectric-porcelain composition is to make to have with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] at least a oxide in dielectric oxide, manganese oxide, aluminium oxide, the vanadium oxide of expression, oxide, Nb, Mo, Ta, W and the Mg of rare earth element and the dielectric-porcelain composition of sintering aid, symbol x, the y of the expression constitutive molar ratio in the said structure formula, z, m are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤020,0.90≤m≤1.04
For 100 moles of dielectric oxides, contain: manganese oxide, being converted into MnO is 0.2～5 mole; Aluminium oxide is converted into Al
2O
3It is 0.1～10 mole; Vanadium oxide is converted into V
2O
5Be 0～2.5 mole (except 0 mole); The oxide of rare earth element is scaled 0.02～1.5 mole by rare earth element; At least a oxide among Nb, Mo, Ta, W and the Mg is scaled 0.02～1.5 mole by this Nb, Mo, Ta, W and Mg, it is characterized in that, uses sintering aid, and described sintering aid has:
With SiO
2As main component, also comprise first glass composition of MO (wherein, M is at least a of Ba, Ca, Sr and Mg), be 0.5～15 mole for 100 moles of dielectric oxides;
Its formation comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, the ZnO of 10～60 weight %, the Na of 0～15 weight %
2The SiO of O and 5～35 weight %
2, have the following average grain diameter of 1.5 μ m, with respect to 100 weight % dielectric oxides, be second glass composition of 0.1～10 weight %,
And have a following step:
Mix the step of raw material before the ready reaction to major general's second glass composition with the initial feed of preparing in order to obtain dielectric oxide;
Make the preceding raw material reaction of ready reaction, obtain comprising the step of the dielectric-porcelain composition raw material of reaction raw materials;
The dielectric-porcelain composition raw material that sintering obtains in 1250 ℃ of calcining heats or following temperature is made the step of dielectric-porcelain composition.
The insulating particles of the dielectric-porcelain composition that formation is obtained by above-mentioned any method has the average crystalline particle diameter below the 0.8 μ m.By for example, compiling method etc. are calculated this average crystalline particle diameter.
The present inventor finds, the sintering aid that comprises second glass composition by use, control constitutes the average crystalline material footpath of the insulating particles of the dielectric-porcelain composition that obtains, its result can improve the capacitance of the electronic unit of the lamination porcelain capacitor that uses this dielectric-porcelain composition manufacturing etc.
That is, according to the present invention, provide a kind of dielectric-porcelain composition, it has the insulating particles that possesses the average crystalline particle diameter below the 0.8 μ m that is obtained by above-mentioned any method.
According to the present invention, a kind of manufacture method of electronic unit is provided, manufacturing has the dielectric layer that is made of dielectric-porcelain composition and with the electronic unit of base metal as the interior electrode layer of main component, it is characterized in that, makes described dielectric-porcelain composition by above-mentioned any method.
According to the present invention, a kind of electronic unit is provided, have dielectric layer that constitutes by dielectric-porcelain composition and the electronic unit that comprises the interior electrode layer of base metal, it is characterized in that dielectric-porcelain composition is above-mentioned each described dielectric-porcelain composition.
As electronic unit, no particular determination, but illustration has lamination porcelain capacitor, laminated piezoelectric device, other mounted on surface (SMD) chip type electronic unit.
The effect of invention
The present inventor finds, by except previously used sintering aid, using specific glass composition as sintering aid, even for example calcining in 1250 ℃ or the following low temperature, the linearity of internal electrode is worsened, do not damage various electrology characteristics, and can obtain fine and close dielectric-porcelain composition and electronic unit.Its result has realized the thin layerization of dielectric layer and the high capacity of electronic unit.
Control constitutes the insulating particles of the dielectric-porcelain composition that is obtained by this method imperceptibly, makes the average crystalline particle diameter below 0.8 μ m.The present inventor thinks that the miniaturization of the average crystalline particle diameter of such insulating particles helps high capacity.
Promptly, according to the present invention, though provide a kind of in low temperature calcining do not damage various electrology characteristics yet and can obtain the manufacture method of the dielectric-porcelain composition of fine and close dielectric-porcelain composition, the dielectric-porcelain composition that obtains by this method, electronic unit that this dielectric-porcelain composition is obtained as the manufacture method of the electronic units such as chip capacitor of dielectric layer, by this method.
Brief Description Of Drawings
Fig. 1 is the profile of the lamination porcelain capacitor that relates to of an embodiment of the invention.
Embodiment
Below, based on the explanation of the execution mode shown in accompanying drawing the present invention.
As shown in Figure 1, the lamination porcelain capacitor 1 that relates to of an embodiment of the invention has alternately repeatedly the dielectric layer 2 of lamination and the capacitor element main body 10 that interior electrode layer 3 constitutes.Formed pair of external electrodes 4 at the both ends of this capacitor element main body 10, this outer electrode respectively with interior electrode layer 3 conductings in the inside alternate configurations of element unit body 10.The shape of capacitor element main body 10 does not have particular determination, but is generally rectangular-shaped.In addition, its size does not have particular determination yet, and normally (0.4～5.6mm) * (0.2～5.0mm) * (0.2～1.9mm).
Interior electrode layer 3 is laminated on the surface of opposed two ends that each end face alternately is exposed to capacitor element main body 10.Form pair of external electrodes 4 at the both ends of capacitor element main body 10, is connected the formation capacitor circuit with the end face that exposes of the interior electrode layer 3 of alternate configurations.
Dielectric layer 2 contains the dielectric-porcelain composition of being made by method of the present invention.The dielectric-porcelain composition that the method that is related to by an embodiment of the invention obtains has at least a oxide among oxide, Nb, Mo, Ta, W and the Mg of dielectric oxide, manganese oxide, aluminium oxide, vanadium oxide, rare earth element.And, comprise 17 kinds of elements that constitute by Sc, Y and lanthanide series etc. in the rare earth element.
Dielectric oxide structural formula (Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] expression.Symbol x, the y of the expression constitutive molar ratio in this formula, z, m are 0.5≤x≤1.0 (preferred 0.6≤x≤0.9), 0.01≤y≤0.10 (preferred 0.02≤y≤0.07), 0＜z≤0.20 (preferred 0＜z≤0.10), 0.90≤m≤1.04 (preferred 1.005≤m≤1.025).
The amount of at least a oxide among the oxide of manganese oxide, aluminium oxide, vanadium oxide, rare earth element, Nb, Mo, Ta, W and the Mg is as follows.
For 100 moles of dielectric oxides, contain:
Manganese oxide, being converted into MnO is 0.2～5 mole, preferably 0.2～3 mole;
Aluminium oxide is converted into Al
2O
3Be 0.1～10 mole, preferably 0.1～5 mole;
Vanadium oxide is converted into V
2O
5Be 0～2.5 mole (except 0 mole), preferably 0.5～2.5 mole;
The oxide of rare earth element is scaled 0.02～1.5 mole by rare earth element, preferably 0.10～1.0 mole;
At least a oxide among Nb, Mo, Ta, W and the Mg is scaled 0.02～1.5 mole by this Nb, Mo, Ta, W and Mg, preferably 0.10～1.0 mole.
The dielectric-porcelain composition that the method that is related to by an embodiment of the invention obtains contains sintering aid.Be described in detail later on.
Can suitably determine each condition such as the lamination number of dielectric layer 2 and thickness according to purpose and purposes, but in the present embodiment, the thickness of dielectric layer 2 preferably below the 3 μ m, is more preferably and is thinned to below the 1 μ m below 5 μ m.In addition, dielectric layer 2 is made of with crystal boundary mutually crystal grain.In the present embodiment, the average crystalline particle diameter of the crystal grain of dielectric layer 2 (insulating particles) preferably below 0.8 μ m, is more preferably fine below 0.5 μ m.Because the average crystalline particle diameter is through miniaturization, easily corresponding to the thin layerization of product, its result can realize high capacity.Crystal boundary mutually usually with the oxide that constitutes the oxide of the oxide of the raw material of dielectric substance or internal electrode material, the raw material that adds in addition, be blended into the other raw material in the step as impurity as composition, and constitute by the glass or the nature of glass usually.
The electric conducting material that is included in the interior electrode layer 3 does not have particular determination, but for the constituent material of dielectric layer 2 has reducing resistance, can use cheap base metal.As the base metal as electric conducting material, preferably Ni or Ni alloy.As the Ni alloy, the alloy of the element of more than one that from Mn, Cr, Co and Al, select and Ni preferably, the Ni amount in the alloy is preferably more than 95 weight %.And, also can comprise various micro constitutents such as 0.1 weight % following P, Fe, Mg in Ni or the Ni alloy.The thickness of interior electrode layer can be according to suitably decision such as purposes, but 0.5～5 μ m normally, preferred especially 1～2.5 μ m.
The electric conducting material that is included in the outer electrode 4 does not have particular determination, but uses Cu and Cu alloy or Ni and Ni alloy etc. usually.And, also can use Ag and Ag-Pd alloy etc.And, use cheap Ni, Cu and their alloy in the present embodiment.The thickness of outer electrode can be according to suitably decision such as purposes, but usually preferred about 10～50 μ m.
Lamination porcelain capacitor 1 that the manufacture method of the dielectric-porcelain composition that use the present invention relates to is made and existing lamination porcelain electrical condenser are similarly, utilization has used the common print process of paste and thin-layer method to make living thin slice, behind its sintering, printing or duplicate outer electrode after sintering and making.Below, describe particularly about manufacture method.
Make dielectric layer at first, respectively with paste, internal electrode paste and outer electrode paste.
When the manufacturing dielectric layer is used paste, at first, prepare to be included in dielectric-porcelain composition raw material wherein.In the dielectric-porcelain composition raw material, comprise principal component raw material and auxiliary element raw material.
As the main component raw material, use the dielectric oxide of above-mentioned composition.
As the auxiliary element raw material, use the compound and the sintering aid that become at least a oxide among Nb, Mo, Ta, W and the Mg behind at least a oxide among compound, Nb, Mo, Ta, W and the Mg that becomes the oxide of rare earth element behind the oxide of the compound that becomes vanadium oxide behind compound, vanadium oxide and/or the sintering that becomes aluminium oxide behind compound, aluminium oxide and/or the sintering that becomes manganese oxide behind manganese oxide and/or the sintering, rare earth element and/or the sintering and/or the sintering.
In the present invention, use specific sintering aid.This sintering aid contains first glass composition and second glass composition.
First glass composition is the composition of the sintering degree when being used for acceleration of sintering.
First glass composition is with SiO
2As main component, also comprise MO (wherein, M is at least a of Ba, Ca, Sr and Mg).Preferably with SiO
2As main component, also comprise among BaO and the CaO one or both.
This first glass composition mainly plays sintering aid, but also has the effect of the disqualification rate of the initial insulation resistance (IR) when improving thin layer dielectric layer 2.More preferably this first glass composition comprises with composition formula { (Ba
w, Ca
1-w) O}
vSiO
2The composite oxides (below be also referred to as BCG) of expression.Because composite oxides { (Ba
w, Ca
1-w) O}
vSiO
2Fusing point low, so reactive good for the main component raw material.At composition formula { (Ba as optimal way
w, Ca
1-w) O}
vSiO
2In, the symbol v of the expression constitutive molar ratio in this composition formula is 0.5≤v≤4.0 preferably, are more preferably 0.55≤v≤3.0.If v is too small, i.e. SiO
2Too much, just, dielectric characteristic is worsened with the main component reaction.On the other hand, if v is excessive, then fusing point uprises, and the sintering degree is worsened, and is therefore bad.And the symbol w of the constitutive molar ratio of expression Ba and Ca is (0≤w≤1) arbitrarily, also can only contain a side, but preferred 0.5≤w≤1.
The fusing point of first glass composition is preferably at 1150 ℃ or following, more preferably 900～1100 ℃.Fusing point just hangs down sintering in low temperature easily.
The amount of first glass composition is 0.5～15 mole for 100 moles of dielectric oxides, preferably 0.5～10 mole, and more preferably 0.5～5 mole.By a small amount of interpolation first glass composition, can reduce the generation of initial IR disqualification rate effectively, otherwise but if too much, then electric medium constant reduces, and might can not guarantee enough electric capacity.
Second glass composition is in order the time to improve the composition of the reactivity (for example false burn reactive) of each stock yard as calcining at the sintering precedent.Its result has the advantage of the sintering after can carrying out in lower temperature.
Second glass composition comprises B at least
2O
3, Al
2O
3, ZnO and SiO
2, preferably also comprise Na
2O.
The ratio of these oxides in second glass composition is:
B
2O
3, 10～35 weight %, preferably 15～30 weight %;
Al
2O
3, 5～25 weight %, preferably 10～20 weight %;
ZnO, 10～60 weight %, preferably 20～45 weight %;
SiO
2, 5～35 weight %, preferably 10～20 weight %.
Comprising Na
2Na under the situation of O
2The ratio of O is 0～15 weight % (not comprising 0 weight %), preferably 0.001～2 weight %.
The second glass composition average grain diameter is below 1.5 μ m, preferably below 1 μ m.If average grain diameter is excessive, then the dispersiveness of second glass composition reduces, and hinders uniform sintering.
In the scope of purpose of the present invention, also can in second glass composition, contain the oxide except above-mentioned oxide.
The fusing point of second glass composition is preferably at 650 ℃ or following, more preferably 580～650 ℃.Fusing point just hangs down sintering in low temperature easily.
The amount of second glass composition is 0.1～10 weight % with respect to 100 weight % dielectric oxides, preferably 0.1～3 weight %.If the addition of second glass composition is very few, the trend of the sintering deficiency that becomes in the low temperature is then arranged, then inhomogeneous if too much because of the average crystalline particle diameter of the separation insulating particles of second glass composition, the trend of temperature characterisitic deterioration is arranged.
In the present embodiment, when utilizing solid phase method and liquid phase method etc. to make the main component raw material, under rated condition, make and mix the mixture reaction that obtains, obtain dielectric-porcelain composition raw material (preceding interpolation), described mixture mixes second glass composition (the first～the second glass composition in the sintering aid preferably at least, more preferably be sintering aid (comprising first glass composition and second glass composition) at least, most preferably comprise whole auxiliary element raw material of sintering aid).
Below, adopt when making the main component raw material by solid phase method (for example calcination method), mix whole auxiliary element raw materials and the situation that obtains dielectric-porcelain composition is that example describes.
At first, with as the initial feed of the dielectric oxide of main component raw material (SrCO for example
3, CaCO
3, TiO
2, ZrO
2, HfO
2Deng) common weighing ormal weight, for example MnCO
3, Al
2O
3, V
2O
5, Y
2O
3Deng auxiliary element raw material, first glass composition, second glass composition, in addition, if need, also other auxiliary element raw material of weighing mixes their and dry, prepares raw material before the final calcining of forming.
Then, calcine the preceding pulvis of off-the-shelf calcining.Calcination condition does not have particular determination, but can carry out according to the following condition that illustrates.Particularly in the present embodiment, owing to before calcining, comprise second glass composition in the raw material, therefore,, also can promote calcination reaction fully even, preferably calcine in 900～1100 ℃ the low temperature at for example 1100 ℃ or following.As the programming rate of other calcination conditions, preferably 50～400 ℃/hour, be more preferably 100～300 ℃/hour.Preferably 0.5～6 hour retention time of calcining heat, more preferably 1～3 hour.Processing atmosphere can be any in the air, in the nitrogen and in the reducing atmosphere.And, also can repeatedly calcine.
Then, the calcined powder after utilizing aluminium oxide roller etc. to calcining is organized after the pulverizing, and carries out drying, obtains dielectric-porcelain composition raw material (powder).
Then, with this dielectric-porcelain composition raw material coatingization, adjust the dielectric layer paste.The organic system coating of dielectric layer after with paste dielectric-porcelain composition raw material that can be mixing and organic vehicle also can be the coating of water system.
As the dielectric-porcelain composition raw material, can use above-mentioned oxide and its mixture, composite oxides, but in addition, after also can from all cpds that forms above-mentioned oxide and composite oxides by sintering such as carbonate, oxalates, nitrate, hydroxide, organo-metallic compound etc., suitably selecting, mix the back and use.Can decide the amount of each compound in the dielectric-porcelain composition raw material like this, making becomes the composition of above-mentioned dielectric-porcelain composition behind the sintering.
Under the state before coatingization, the particle diameter of dielectric-porcelain composition powder is average grain diameter 0.1～3 μ m normally.
Organic vehicle is that binding agent is dissolved in material in the organic solvent.The binding agent that is used for organic vehicle does not have particular determination, can suitably select from various common binding agents such as ethyl cellulose, polyvinyl butyral resin.In addition, the organic solvent of use does not have particular determination yet, can suitably select from various organic solvents such as terpinol, DEGMBE, acetone, toluene according to the method for utilizations such as print process and thin-layer method.
In that dielectric layer is used under the situation of paste as aqueous coating, the water system medium that water miscible binding agent and dispersant etc. are dissolved in the water can be mixed with the dielectric raw material.Being used for the vectorial water-soluble binder of water system does not have particular determination, for example uses polyvinyl alcohol, cellulose, water soluble acrylic resin etc.
Constitute various oxides, organo-metallic compound, resinate of above-mentioned electric conducting material etc. behind electric conducting material that will constitute by various conductive metal and alloy or the sintering, carry out mixingly, be modulated into internal electrode paste with above-mentioned organic vehicle.
Outer electrode is also similarly modulated with this internal electrode paste with paste.
Using under the situation of print process, dielectric layer be printed on the substrate of polyethylene terephthalate etc. with the paste lamination with paste and interior electrode layer, cut into the regulation shape after, from strippable substrate, the one-tenth thin slice of making a living.To this, under the situation of using thin-layer method, use dielectric layer to form living substrate with paste, print in the above after the internal electrode paste, it is laminated into the thin slice of making a living.
Then, before sintering, implement to take off adhesive treatment to giving birth to thin slice.Taking off adhesive treatment can carry out under usual conditions, but in the electric conducting material of interior electrode layer, use under the situation of base metals such as Ni and Ni alloy, preferably at programming rate: 5～300 ℃/hour, particularly 10～100 ℃/hour, retening temperature: 180～400 ℃, particularly 200～300 ℃, temperature hold-time: 0.5～24 hour, particularly 5～20 hours, atmosphere: carry out under the airborne condition.
Can be according to the kind of the electric conducting material in the internal electrode paste, the atmosphere when suitably the thin slice sintering is given birth in decision, but using under the situations of base metal as electric conducting material such as Ni and Ni alloy, the oxygen partial pressure in the sintering atmosphere preferably is made as 10
-7～10
-3Pa.If the not enough above-mentioned scope of oxygen partial pressure, will cause the unusual sintering of electric conducting material of interior electrode layer and break.In addition, if oxygen partial pressure surpasses above-mentioned scope, the trend of interior electrode layer oxidation is just arranged.
In the densification that can give birth to thin slice fully, and do not produce unusual sintering electrode because of interior electrode layer break, because of the diffusion temperature characteristic of capacitance of interior electrode layer constituent material worsen or the scope of the reduction of dielectric-porcelain composition in, the retening temperature when suitably determining sintering.This be because, if sintering temperature is too low, it is not fine and close then to give birth to thin slice, if sintering temperature is too high, then produce internal electrode break (linear deterioration), because the diffusion of electric conducting material and temperature characteristic of capacitance worsens, or dielectric reduction.
In the past, the thin thin slice of giving birth to of life that comprises the CaSr-ZrTi-Mn based material for densification fully, need calcine more than 1300 ℃, but in the present embodiment, but owing to contain the sintering aid of above-mentioned low temperature calcination, therefore, even comprise the living thin slice of CaSr-ZrTi-Mn based material, also can be at preferred 1250 ℃ or following, more preferably in 1230 ℃ or following low temperature, calcine.Like this, the damage of sintering furnace can be prevented, maintenance and management cost or cost of energy can be suppressed effectively, and, can prevent troubles such as crackle and electric medium constant reduction.And the lower limit of calcining heat preferably is about 950 ℃, more preferably from about is 1000 ℃.
As calcination condition in addition, preferably programming rate is made as 50～500 ℃/hour, more preferably 200～300 ℃/hour, temperature hold-time was made as 0.5～8 hour, more preferably 1～3 hour, cooling rate is made as 50～500 ℃/hour, more preferably 200～300 ℃/hour.In addition, calcination atmosphere preferably is made as reducing atmosphere, as the gas in the atmosphere, for example preferably with N
2And H
2The mist humidification after use.
Carry out under the calcining situation in reducing atmosphere, preferably the sintered body behind the sintering (capacitor element main body) is implemented annealing.Annealing is in order to reoxidize the processing of dielectric layer, by like this, because like this can the phenomenal growth IR life-span, so the reliability raising.
Oxygen partial pressure in the annealing atmosphere is preferably 1 * 10
-4More than the Pa, be preferably 1 * 10 especially
-4～10Pa.If the not enough above-mentioned scope of oxygen partial pressure, reoxidizing of dielectric layer is just difficult, if surpass above-mentioned scope, the trend of interior electrode layer oxidation is just arranged.
Retening temperature during annealing is preferably at 1200 ℃ or following, preferred especially 500～1200 ℃.Because if keep the not enough above-mentioned scope of temperature, the oxidation of dielectric layer is just insufficient, therefore, the IR step-down, in addition, the IR life-span just shortens easily.On the other hand, if retening temperature surpasses above-mentioned scope, then not only after the internal electrode oxidation electric capacity reduce, and internal electrode and dielectric reaction just are easy to generate that temperature characteristic of capacitance worsens, IR reduction, IR life-span reduce.And annealing steps also can only be made of temperature-rise period and temperature-fall period.That is, also temperature hold-time can be made as zero.Under this situation, retening temperature is equivalent to maximum temperature.
As annealing conditions in addition, preferably temperature hold-time is made as 0～20 hour, more preferably 2～10 hours, cooling rate is made as 50～500 ℃/hour, more preferably 100～300 ℃/hour.In addition, as the gas in the atmosphere of annealing, for example preferably use the N behind the humidification
2Gas etc.
Above-mentioned taking off in adhesive treatment, sintering and the annealing, humidification N
2Gas and mist etc. can use for example humidifier etc.Under this situation, preferably 5～75 ℃ of water temperatures.
Taking off adhesive treatment, sintering and annealing can carry out continuously, also can independently carry out.Under the situation of carrying out continuously, do not cool off after preferably taking off adhesive treatment, and change atmosphere, the retening temperature when then being warmed up to sintering and carry out sintering, cooling then when having reached the maintenance temperature of annealing, changes atmosphere and anneals.On the other hand, under the situation of independently carrying out, preferably when sintering, at N
2The N of gas or humidification
2Be warmed up under the gas atmosphere after the retening temperature when taking off adhesive treatment, further continued after the change atmosphere to heat up, preferably after the retening temperature when being cooled to annealing, changed over N once more
2The N of gas or humidification
2Gas atmosphere is proceeded cooling.In addition, can be when annealing, at N
2Change atmosphere after being warmed up to retening temperature under the gas atmosphere, also the whole process of annealing all can be made as the N of humidification
2Gas atmosphere.
To the capacitor sintered body that obtains as mentioned above, utilize for example enforcement such as barreling and sanding machine end surface grinding, printing or duplicating outer electrode paste form outer electrode 4 behind the sintering.Outer electrode is with the sintering condition of paste, for example preferably carries out about 10 minutes B～1 hour in the mist of nitrogen behind humidification and hydrogen in 600～800 ℃.Then, as required, by forming cover layer (laying) on the surface of electroplate waiting electrode 4 externally.
Utilize soldering etc., the porcelain capacitor of the present embodiment made like this is installed on the printed circuit board (PCB), and is used for various electronic equipments etc.
More than be illustrated about embodiments of the present invention, but the present invention is not limited to above-mentioned execution mode, can do various distortion in the scope that does not break away from purport of the present invention.
For example, the dielectric-porcelain composition that is obtained by the method that the present invention relates to not only is used in lamination porcelain capacitor, also can be used in other the electronic unit that forms dielectric layer.
Embodiment
Below, enumerating more specifically, embodiment illustrates the present invention in further detail.But the present invention not only is defined in these embodiment.
Embodiment 1
The modulation of dielectric raw material
At first, as the initial feed that is used to prepare the main component raw material, prepared the SrCO of average grain diameter 0.4 μ m
3, CaCO
3, TiO
2, ZrO
2And HfO
2
Then, by finally consisting of [Ca
0.7Sr
0.3] O] [((Ti
0.05Zr
0.9Hf
0.05) O
2] atomic ratio, ready each initial feed of weighing.
Then, add up to 100 moles for each initial feed after the weighing have added 1 mole MnCO
3, 0.5 mole Al
2O
3, 3 moles (Ba
0.6Ca
0.4) SiO
3(BCG) as first glass composition.In addition, for the total 100 weight % of each initial feed after the weighing, the B-Al-Zn-Si that has added specified weight % be frit as second glass composition, obtain calcining preceding pulvis after the interpolation.
Then, calcined the preceding pulvis of the calcining that obtains.Calcination condition is as follows.Programming rate: 200 ℃/hour, retening temperature: 1100 ℃, temperature hold-time: 2 hours, atmosphere: in the air.
Then, become the calcining pulvis after pulverizing the material that calcining obtains with the aluminium oxide roller, obtained the dielectric raw material (dielectric-porcelain composition raw material (pulvis)) that constitutes by this calcining pulvis.
In the present embodiment, as shown in table 1, making each test portion change B-Al-Zn-Si is the average grain diameter and the addition of frit.In addition, be frit as B-Al-Tn-Si, use B by 25 weight %
2O
3, the ZnO of 25 weight %, the SiO of 25 weight %
2, 15 weight % Al
2O
3, 10 weight % Na
2O constitutes, has the material of 600 ℃ softening point.
And, by by ball mill with BaCO
3, CaCO
3And SiO
2Wet mixed 16 hours, dry back in 1000～1300 ℃ in air sintering, by ball mill case of wet attrition 100 hours, just made (Ba again
0.6Ca
0.4) SiO
3
Then, use the dielectric raw material that obtains, each test portion is made following disk shaped samples and capacitor sample.
The making of disk shaped samples
At first, the polyvinyl alcohol that the medium raw material that obtains is added 0.6 weight % is mixed into graininess as binding agent with binding agent and dielectric raw material.Then, the granular dielectric raw material of this of weighing 0.3g is used 1.3ton/cm
2Exert pressure, obtained the discoid compact of diameter 1mm, thickness 0.7mm.
Then, the discoid compact that obtains is implemented to take off adhesive treatment, sintering and annealing, obtained the discoid sintered body of the about 10mm of diameter, the about 0.5mm of thickness.Under the condition of 200 ℃/hour of heating-up times, 400 ℃ of temperature of maintenance, retention time 2 hours, air atmosphere, take off adhesive treatment.In addition, in 200 ℃/hour of programming rates, retening temperature: with reference to the N behind table 1, retention time 2 hours, 200 ℃/hour of cooling rates, the humidification
2+ H
2Mixed-gas atmosphere (oxygen partial pressure 10
-12Pa) carry out sintering under the condition.N behind 1100 ℃ of retening temperatures, temperature hold-time 2 hours, 200 ℃/hour of cooling rates, humidification
2Gas atmosphere (oxygen partial pressure 10
-2Pa) anneal under the condition.And the humidification of the atmosphere gas when sintering and annealing uses humidifier.
Then,, just form the electrode of Φ 6mm, made disk shaped samples by at the coated on both sides In-Ga of the discoid sintered body that obtains alloy.
The making of capacitor sample
With ball mill dielectric raw material 100 weight portions that obtain, allyl resin 4.8 weight portions, carrene 40 weight portions, ethyl acetate 20 weight portions, mineral turpentine 6 weight portions, acetone 4 weight portions are mixed, obtained the dielectric layer paste after making pasty state.
By Ni particle 100 weight portions, organic vehicle (in DEGMBE 92 weight portions, having dissolved ethyl cellulose 8 weight portions) 40 weight portions, DEGMBE 10 weight portions of three mixing average grain diameter 0.1～0.8 μ m of roll, obtained the interior electrode layer paste after making pasty state.
Cu particle 100 weight portions of mixing average grain diameter 0.5 μ m, organic vehicle (having dissolved ethyl cellulose 8 weight portions in DEGMBE 92 weight portions) 35 weight portions and DEGMBE 7 weight portions have obtained the outer electrode paste after making pasty state.
Then, use above-mentioned dielectric layer paste, on the PET film, form the living substrate of thickness 7 μ m, on it the printing interior electrode layer with paste after, peel off living substrate from the PET film.
Then, these living substrates of lamination and protection have obtained living thin slice with living substrate (not printing the living substrate of interior electrode layer with paste) after the pressure welding.The lamination number of the substrate with internal electrode is made as 5 layers.
Then, will give birth to cutting sheet and become given size, take off adhesive treatment, sintering and annealing (all the condition when making above-mentioned disk shaped samples is identical), obtain lamination porcelain sintered body.
Then, ground by sanding machine after the end face of lamination porcelain sintered body, on end face, duplicated outer electrode paste, the N behind humidification
2+ H
2In the atmosphere, sintering is 10 minutes in 800 ℃, forms outer electrode, has obtained the sample of the lamination porcelain capacitor of the structure shown in Fig. 1.The size of each sample that obtains like this is 3.2mm * 1.6mm * 0.6mm, and the quantity that is clipped in the dielectric layer in the interior electrode layer is 4, and its thickness is 4.9 μ m, and the thickness of interior electrode layer is 0.2 μ m.
The evaluation of disk shaped samples and capacitor sample
Disk shaped samples that use obtains and capacitor sample carry out the evaluating characteristics of porcelain characteristic (sintered density), electrology characteristic (insulation resistance IR).In addition, measured the average crystalline particle diameter of insulating particles.In result shown in the table 1.
The following porcelain characteristic (sintered density) of having estimated.Size and quality according to disk shaped samples are calculated, and sintered density is 4.5g/cm preferably
3And, use disk shaped samples to count n=10, obtained the value of sintered density from the mean value of the value measured.
The following electrology characteristic (insulation resistance IR) of having estimated.For capacitor sample, use insulating-resistance meter (ア De バ Application テ ス ト corporate system R8340A), capacitor sample has been measured the DC50V insulation resistance IR (unit is Ω) afterwards that in 25 ℃, has added 60 seconds.Insulation resistance IR is preferably 1 * 10
11More than the Ω.And, use capacitor sample to count n=10, obtained the value of insulation resistance IR from the mean value of the value measured.Result shown in the table 1.
The compiling method of the SEM photo of capacitor sample has been used in utilization, has calculated the average crystalline particle diameter that constitutes the insulating particles (particle) of dielectric layer.In the present embodiment, the shape of insulating particles is assumed to be sphere, calculates particle diameter easily.Specifically, at first, use the SEM photo of the fine structure that shows dielectric layer, on this SEM photo, draw arbitrary line, obtain and the quantity that is present in the adjacent insulating particles of this line crystal boundary each other staggered (intersection point).Then, according to the number of hits PL of the number of hits calculating of trying to achieve with the crystal boundary of per unit length.Then, use the value of the PL that obtains, calculation code length L 3.Obtain code length L3 with 1/PL.Then, with on duty 1.5 of the L3 that obtains be L3 * 1.5, calculated the average crystalline particle diameter of insulating particles.And if the visual field of the SEM photo of usefulness is 23 μ m * 30 μ m, each sample uses 5～6 photos, calculates particle diameter separately, and these mean values are made as the average crystalline particle diameter.Result shown in the table 1.
And, in the table 1, in the numerical value of insulation resistance IR, " m*10
n" be expression " m * 10
n".
Table 1
Following as can be understood from Table 1 item.As test portion 1, as sintering aid,, then in 1250 ℃ or following low temperature, under the situation of sintering, can not get enough sintered densities if do not comprise second glass composition, insulation resistance reduces."-" on the insulation resistance hurdle of test portion 1 expression sintered density is crossed low and can not densification, can not measure insulation resistance.
As test portion 2～3, in order under the state that does not comprise second glass composition, to obtain enough sintered densities, under sintering temperature rises the situation that has surpassed 1250 ℃, insulation resistance disappears, but the linear deterioration of internal electrode, and, the average crystalline particle diameter of insulating particles is excessive, so can not thin layerization, its result can not high capacity.
As test portion 8, if the addition of second glass composition is too much, then in low temperature under the situation of sintering, obtained enough sintered densities, insulation resistance also disappears, but because the average crystalline particle diameter of insulating particles is excessive, so can not thin layerization, its result can not high capacity.
As test portion 10,, then in low temperature, under the situation of sintering, can not obtain enough sintered densities if the average grain diameter of second glass composition that uses is excessive."-" in the hurdle of the insulation resistance of test portion 10 is identical with the situation of test portion 1.
To this, as test portion 4～7,9,11,12, by adding second glass composition that has suitable average grain diameter in right amount, in low temperature under the situation of sintering, also obtain enough sintered densities, the also miniaturization of average crystalline particle diameter of insulating particles, and obtain enough insulation resistances.
Embodiment 2
As B-Al-Zn-Si is frit, does not comprise Na except using
2O is by the B of 25 weight %
2O
3, the ZnO of 25 weight %, the SiO of 25 weight %
2, 25 weight % Al
2O
3Constitute and have outside 650 ℃ the softening point, with the test portion 6 of embodiment 1 similarly, make disk shaped samples and capacitor sample, similarly carried out estimating (test portion 13).Result shown in the table 2.
Table 2
As shown in table 2, can think, as second glass composition, use not comprise Na
2The B-Al-Zn-Si of O is a frit, also with the situation of test portion 6 similarly, sintering in low temperature, sintered density also reduces significantly, the average crystalline particle diameter of insulating particles is also suitable, obtains good insulation performance resistance.
Embodiment 3
As B-Al-Zn-Si is frit, except using the B by 35 weight %
2O
3, the ZnO of 10 weight %, the SiO of 35 weight %
2, 5 weight % Al
2O
3, 5 weight % Na
2O constitutes and has outside 610 ℃ the softening point, with the test portion 6 of embodiment 1 similarly, make disk shaped samples and capacitor sample, similarly estimate.Its result has obtained same result.And present embodiment is the example under the situation of composition in optimum range of the present invention of frit.
Reference example 1
As B-Al-Zn-Si is frit, except using the B by 10 weight %
2O
3, the ZnO of 70 weight %, the SiO of 2 weight %
2, 5 weight % Al
2O
3, 13 weight % Na
2O constitutes and has outside 630 ℃ the softening point, with the test portion 6 of embodiment 1 similarly, make disk shaped samples and capacitor sample, similarly estimate.Its result can determine that the sintering degree has the trend of deterioration.And present embodiment is that the composition of frit breaks away from the example under the situation of optimum range of the present invention.
Claims (20)
1. the manufacture method of a dielectric ceramic composition, described ceramic composition have with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] expression dielectric oxide, manganese oxide, aluminium oxide, sintering aid, symbol x, y, z, the m of expression constitutive molar ratio are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04 in the said structure formula, it is characterized in that, use following sintering aid to make dielectric ceramic composition in this method, described sintering aid has:
With SiO
2As main component, and contain first glass composition of MO, wherein, M is at least a among Ba, Ca, Sr and the Mg; With
Its formation comprises B
2O
3, Al
2O
3, ZnO and SiO
2, second glass composition with the following average grain diameter of 1.5 μ m.
2. the manufacture method of dielectric ceramic composition as claimed in claim 1 is characterized in that, above-mentioned second glass composition also comprises Na
2O.
3. the manufacture method of dielectric ceramic composition as claimed in claim 1 is characterized in that, above-mentioned second glass composition comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, the ZnO of 10～60 weight % and the SiO of 5～35 weight %
2
4. the manufacture method of dielectric ceramic composition as claimed in claim 2 is characterized in that, above-mentioned second glass composition comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, ZnO, 0～15 weight % of 10～60 weight % but Na except the 0 weight %
2The SiO of O and 5～35 weight %
2
5. the manufacture method of dielectric ceramic composition as claimed in claim 1 or 2 is characterized in that, uses following sintering aid, and described sintering aid has:
First glass composition that dielectric oxide with respect to 100 moles is 0.5～15 mole;
Second glass composition with respect to dielectric oxide 0.1～10 weight % of 100 weight %.
6. the manufacture method of a dielectric ceramic composition, described ceramic composition have with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] expression dielectric oxide, manganese oxide, aluminium oxide, sintering aid, symbol x, y, z, the m of expression constitutive molar ratio are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04 in the said structure formula, it is characterized in that, this method is used sintering aid and is comprised the steps that described sintering aid has:
With SiO
2As main component, and contain MO, wherein, M is the first at least a glass composition among Ba, Ca, Sr and the Mg; With and constitute and to comprise B
2O
3, Al
2O
3, ZnO and SiO
2, second glass composition with the following average grain diameter of 1.5 μ m,
Described step is:
Mix the step of raw material before the ready reaction to major general's second glass composition with the initial feed of preparing in order to obtain dielectric oxide;
Adopt solid reaction process to make the preceding raw material reaction of off-the-shelf reaction, obtain comprising the step of the dielectric ceramic composition raw material of the raw material that has reacted.
7. as the manufacture method of claim 1,2, each described dielectric ceramic composition of 6, described ceramic composition has with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] expression dielectric oxide, manganese oxide, aluminium oxide, contain the sintering aid of first glass composition and second glass composition, symbol x, y, z, the m of expression constitutive molar ratio are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04 in the said structure formula
And described ceramic composition contains with respect to 100 moles of dielectric oxides, and to be converted into MnO be 0.2～5 mole manganese oxide, be converted into Al
2O
3Being 0.1～10 mole aluminium oxide, the dielectric oxide of amount with respect to 100 moles of first glass composition, is 0.5～15 mole,
And described ceramic composition also contains the dielectric oxide with respect to 100 weight %, second glass composition of 0.1～10 weight %.
8. the manufacture method of dielectric ceramic composition as claimed in claim 7, wherein said dielectric ceramic composition also contains vanadium oxide, and its dielectric oxide with respect to 100 moles is converted into V
2O
5Be 0～2.5 mole, but except 0 mole.
9. the manufacture method of dielectric ceramic composition as claimed in claim 7, wherein said dielectric ceramic composition also contains the oxide of rare earth element, and its dielectric oxide with respect to 100 moles is scaled 0.02～1.5 mole by rare earth element.
10. the manufacture method of dielectric ceramic composition as claimed in claim 7, dielectric ceramic composition wherein also contains at least a oxide among Nb, Mo, Ta, W and the Mg, it is scaled 0.02～1.5 mole with respect to 100 moles of dielectric oxides by Nb, Mo, Ta, W and Mg.
11. as the manufacture method of claim 1,2, each described dielectric ceramic composition of 6, dielectric ceramic composition wherein is sintering in 900-1250 ℃ sintering temperature.
12. the manufacture method of a dielectric ceramic composition, described ceramic composition have with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] at least a oxide, sintering aid in dielectric oxide, manganese oxide, aluminium oxide, the vanadium oxide of expression, oxide, Nb, Mo, Ta, W and the Mg of rare earth element, symbol x, y, z, the m of expression constitutive molar ratio are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04 in the said structure formula
Wherein with respect to 100 moles of dielectric oxides, contain that to be converted into MnO be 0.2～5 mole manganese oxide; Be converted into Al
2O
3It is 0.1～10 mole aluminium oxide; Be converted into V
2O
5Be 0～2.5 mole vanadium oxide, but except 0 mole; Be converted into the oxide that rare earth element is 0.02～1.5 mole a rare earth element; Be scaled at least a oxide among 0.02～1.5 mole Nb, Mo, Ta, W and the Mg by this Nb, Mo, Ta, W and Mg,
Described sintering aid has:
With SiO
2As main component, and contain MO, wherein, M is the first at least a glass composition among Ba, Ca, Sr and the Mg; It is 0.5～15 mole with respect to 100 moles of dielectric oxides; With
Its formation comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, the ZnO of 10～60 weight %, the Na of 0～15 weight %
2The SiO of O and 5～35 weight %
2, second glass composition with the following average grain diameter of 1.5 μ m, it is 0.1～10 weight % with respect to 100 weight % dielectric oxides,
This method also comprises the steps:
Mix the step of raw material before the ready reaction to major general's second glass composition with the initial feed of preparing in order to obtain dielectric oxide;
Adopt solid reaction process to make the preceding raw material reaction of off-the-shelf reaction, obtain comprising the step of the dielectric ceramic composition raw material of the raw material that has reacted;
The dielectric ceramic composition raw material that sintering obtains in sintering temperature 900-1250 ℃ temperature, the step of manufacturing dielectric ceramic composition.
13. a dielectric ceramic composition, described ceramic composition have with structural formula [(Ca
xSr
1-x) O]
m[(Ti
yZr
1-y-zHf
z) O
2] at least a oxide, sintering aid in dielectric oxide, manganese oxide, aluminium oxide, the vanadium oxide of expression, oxide, Nb, Mo, Ta, W and the Mg of rare earth element, symbol x, y, z, the m of expression constitutive molar ratio are 0.5≤x≤1.0,0.01≤y≤0.10,0＜z≤0.20,0.90≤m≤1.04 in the said structure formula
Wherein, contain with respect to 100 moles of dielectric oxides
Be converted into MnO and be 0.2～5 mole manganese oxide;
Be converted into Al
2O
3It is 0.1～10 mole aluminium oxide;
Be converted into V
2O
5Be 0～2.5 mole vanadium oxide, but except 0 mole;
Be converted into the oxide that rare earth element is 0.02～1.5 mole a rare earth element;
Be scaled at least a oxide among 0.02～1.5 mole Nb, Mo, Ta, W and the Mg by this Nb, Mo, Ta, W and Mg,
Described dielectric ceramic composition utilizes sintering aid manufacturing, and described sintering aid has:
With SiO
2As main component, and contain MO, wherein, M is the first at least a glass composition among Ba, Ca, Sr and the Mg; With
Its formation comprises B
2O
3, Al
2O
3, ZnO and SiO
2Second glass composition, average grain diameter is 1.5 μ m before the sintering of described second glass composition,
The average grain diameter of the insulating particles of the dielectric layer behind the formation sintering is below the 0.8 μ m.
14. dielectric ceramic composition as claimed in claim 13, wherein, above-mentioned second glass composition also comprises Na
2O.
15. dielectric ceramic composition as claimed in claim 13, wherein, above-mentioned second glass composition comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, the ZnO of 10～60 weight % and the SiO of 5～35 weight %
2
16. dielectric ceramic composition as claimed in claim 14, wherein, above-mentioned second glass composition comprises the B of 10～35 weight %
2O
3, 5～25 weight % Al
2O
3, ZnO, 0～15 weight % of 10～60 weight % but Na except the 0 weight %
2The SiO of O and 5～35 weight %
2
17. dielectric ceramic composition as claimed in claim 13, wherein, described dielectric ceramic composition uses following sintering aid, and described sintering aid has:
With respect to 100 moles dielectric oxide, 0.5～15 mole first glass composition;
Second glass composition with respect to dielectric oxide 0.1～10 weight % of 100 weight %.
18. dielectric ceramic composition as claimed in claim 13, wherein said dielectric ceramic composition are sintering in 900-1250 ℃ sintering temperature.
19. the manufacture method of an electronic unit, described electronic unit is to have the dielectric layer that is made of dielectric ceramic composition and with the electronic unit of base metal as the interior electrode layer of main component, it is characterized in that described dielectric ceramic composition is the dielectric ceramic composition of being made by claim 1,2, any one method of 6.
20. an electronic unit, described electronic unit have the dielectric layer that is made of dielectric ceramic composition and comprise the interior electrode layer of base metal, wherein, described dielectric ceramic composition is the described dielectric ceramic composition of claim 13.
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| US7923395B2 (en) | 2005-04-07 | 2011-04-12 | Kemet Electronics Corporation | C0G multi-layered ceramic capacitor |
| JP4809036B2 (en) * | 2005-10-27 | 2011-11-02 | 京セラ株式会社 | Multilayer ceramic capacitor and manufacturing method thereof |
| JP4678022B2 (en) * | 2007-11-26 | 2011-04-27 | Ｔｄｋ株式会社 | Method for producing dielectric ceramic composition |
| JP2010040798A (en) * | 2008-08-06 | 2010-02-18 | Murata Mfg Co Ltd | Stacked ceramic capacitor |
| JP5532505B2 (en) * | 2009-07-23 | 2014-06-25 | 日本電気硝子株式会社 | Glass film for condenser |
| JP6076331B2 (en) * | 2012-03-19 | 2017-02-08 | 株式会社村田製作所 | Ceramic electronic components |
| JP7196484B2 (en) * | 2018-09-13 | 2022-12-27 | Tdk株式会社 | Dielectric compositions and electronic components |
| JP7099212B2 (en) * | 2018-09-13 | 2022-07-12 | Tdk株式会社 | Dielectric compositions and electronic components |
| CN113457668B (en) * | 2020-03-31 | 2023-08-08 | 中国石油化工股份有限公司 | High specific heat capacity matrix material and preparation method and application thereof |
| US12051545B2 (en) | 2021-08-02 | 2024-07-30 | Taiyo Yuden Co., Ltd. | Ceramic electronic device including dielectric layer containing perovskite compound with yttria-stabilized zirconia, and manufacturing method of same |
| CN115340376B (en) * | 2022-06-28 | 2023-08-08 | 清华大学深圳国际研究生院 | Ceramic substrate for LTCC and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317459A (en) * | 2000-04-07 | 2001-10-17 | 株式会社村田制作所 | Non-reducing dielectric ceramic, and single-block ceramic capacitor using such ceramic |
| CN1359874A (en) * | 2000-12-20 | 2002-07-24 | 松下电器产业株式会社 | Dielectric ceramic composition and dielectric device |
-
2003
- 2003-12-18 JP JP2003420609A patent/JP4267438B2/en not_active Expired - Lifetime
-
2004
- 2004-12-03 TW TW93137351A patent/TW200529261A/en unknown
- 2004-12-17 CN CN 200410095402 patent/CN1790568B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317459A (en) * | 2000-04-07 | 2001-10-17 | 株式会社村田制作所 | Non-reducing dielectric ceramic, and single-block ceramic capacitor using such ceramic |
| CN1359874A (en) * | 2000-12-20 | 2002-07-24 | 松下电器产业株式会社 | Dielectric ceramic composition and dielectric device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005179105A (en) | 2005-07-07 |
| TW200529261A (en) | 2005-09-01 |
| TWI326092B (en) | 2010-06-11 |
| CN1790568A (en) | 2006-06-21 |
| JP4267438B2 (en) | 2009-05-27 |
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