CN101031524A - Dielectric porcelain composition and method for production thereof - Google Patents
Dielectric porcelain composition and method for production thereof Download PDFInfo
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- CN101031524A CN101031524A CN200580033116.4A CN200580033116A CN101031524A CN 101031524 A CN101031524 A CN 101031524A CN 200580033116 A CN200580033116 A CN 200580033116A CN 101031524 A CN101031524 A CN 101031524A
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Abstract
A dielectric porcelain composition here contains as main components BaO, Nd 2 O 3 , TiO 2 , MgO and SiO 2 at the given ratios and as subordinate components ZnO, B 2 O 3 and CuO at given ratios, so that it can have a low-temperature sintering capability stable and reliable enough to permit a conductor formed of Ag, an alloy containing Ag as a main component or the like to be used as an internal conductor. It is also possible to obtain a dielectric porcelain composition that has limited resonance frequency changes with temperature changes and a specific dielectric constant lower than that of a BaO-rare earth oxide-TiO 2 base dielectric porcelain composition, and so is suitable for multilayer type device formation.
Description
Technical field
The present invention relates to a kind of dielectric ceramic composition with low-temperature sintering, this character can allow it to adopt Ag or be that the conductors such as alloy of principal constituent are as inner conductor with Ag.
Background technology
In recent years, the development of field of mobile communication such as automobile telephone, mobile telephone is very remarkable.And in these mobile communication, use the high frequency wavestrip that is called so-called quasi-microwave about number 100MHz～number GHz.Therefore, in the electronicss such as the syntonizer that uses in the mobile communication instrument, strainer, electrical condenser, the high frequency characteristic enjoys attention.
In addition, the popularizing of mobile communication in recent years, except the raising of service level, the miniaturization of communication equipment and cheapization also are its important reasons.Therefore, also strong day by day for the requirement of the miniaturization of high-frequency apparatus and cheap.For example resonance with material in order to realize miniaturization, require in frequency of utilization than specific inductivity height, dielectric loss is little and the variation of the temperature profile of resonant frequency is little dielectric ceramic composition.
As the high frequency devices that satisfies above-mentioned requirements, the present known BaO-rare-earth oxide-TiO that has
2The dielectric ceramic composition of class
Present situation is in addition, miniaturization for high-frequency apparatus, the surface encapsulation type parts (SMD:Surface Mount Device) that possess conductors such as electrode or wiring (below, the conductor that possesses electrode or wiring etc. in high-frequency apparatus inside is called " inner conductor ") in inside have become main flow.
Have electrode or wiring in order to be formed on inside, must make conductors such as dielectric ceramic composition and electrode or wiring burn till processing simultaneously.But, because BaO-rare-earth oxide-TiO
2The firing temperature of the dielectric ceramic composition of class is than higher 1300～1400 ℃, and being limited at as the conductive material of electrode that is used in combination with it or wiring etc. can resistant to elevated temperatures palladium (Pd) or platinum noble metals such as (Pt).
But because these noble metals are very expensive, in order to realize the cheap of equipment, expectation can be used as conductors such as low-resistance conductor and cheap Ag, Cu as inner conductor.
In addition, also proposed with BaO-rare-earth oxide-TiO
2Class is in the material of principal constituent, adds B
2O
3Technology Deng minor component, with this, can under than the lower temperature of the fusing point of conductors such as Ag, Cu, burn till dielectric ceramic composition, conductors such as Ag, Cu are burnt till simultaneously as inner conductor become possible (reference example such as TOHKEMY 2001-31468 communique, Japanese kokai publication hei 6-40767 communique).
On the other hand, be the further miniaturization of implement device, also proposed to have the height ratio specific inductivity dielectric ceramic composition, engage with having low dielectric ceramic composition, with the technology (for example with reference to Japanese kokai publication hei 9-139320 communique) of the multi-layered type equipment of the incorporate high characteristic of a plurality of high frequency devices than specific inductivity.
But, in the equipment that forms above-mentioned multilayer type, if the dielectric ceramic composition with height ratio specific inductivity is different with the composition material with low dielectric ceramic composition than specific inductivity, because both contraction behavior and linear expansivitys when burning till are inconsistent, above-mentioned dielectric ceramic composition with height ratio specific inductivity has low dielectric ceramic composition than specific inductivity burning till when engaging with above-mentioned, will produce defective on the junction surface.
Consider from above-mentioned viewpoint, when forming multi-layered type equipment, dielectric ceramic composition with height ratio specific inductivity with have low dielectric ceramic composition than specific inductivity preferably by essentially identical material or similarly material constitute, and possess roughly similarly rerum natura.
But, be applicable to the BaO-rare-earth oxide-TiO of the material of small-sized high frequency devices
2The class dielectric ceramic composition has the high ratio specific inductivity of being put down in writing in the above-mentioned patent documentation 1, even only added minor component, also is difficult to make the low BaO-rare-earth oxide-TiO of ratio specific inductivity that requires in compoundization (multi-layered type equipment)
2The class dielectric ceramic composition.
In addition, in order to make the little high frequency of power consumption multi-layered type equipment, expect a kind of than existing BaO-rare-earth oxide-TiO
2BaO-rare-earth oxide-TiO that the dielectric loss of class dielectric ceramic composition is further improved
2The dielectric ceramic composition of class.
Summary of the invention
In order to solve above-mentioned variety of issue of the prior art, the application's the 1st group of invention, the application's the 2nd group of invention and the application's the 3rd group of invention have been proposed.
[the 1st group of invention]
That is, the purpose of the application's the 1st group of invention is, provides at low temperatures more stable, reliable dielectric ceramic composition of coking property and manufacture method thereof, even if so that contain BaO, rare-earth oxide and TiO
2As principal constituent compositional system, also can use Ag reliably or with Ag as the conductors such as alloy of principal constituent as inner conductor.
Further purpose provides dielectric loss is little, temperature variation causes resonant frequency number and changes little and have than BaO-rare-earth oxide-TiO
2The dielectric ceramic composition and the manufacture method thereof of the ratio specific inductivity that the dielectric ceramic composition of class is lower.
For solving above-mentioned problem, the following formation of dielectric ceramic composition in the 1st group of invention of the present invention: contain composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously, represent that α, the β of the volumetric ratio of each composition in the above-mentioned principal constituent is in the following ranges respectively:
5 (volume %)≤α＜85 (volume %),
15 (volume %)＜β≤95 (volume %), and satisfy the relation of alpha+beta=100 (volume %),
With respect to above-mentioned principal constituent, contain zinc oxide, boron oxide compound, reach copper oxide as minor component, above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, and cCuO when representing, expression with respect to a, the b of the weight ratio of above-mentioned each secondary composition of above-mentioned principal constituent, and c have following relation respectively:
(0.05 weight %)＜a≤17.0 (weight %),
(0.05 weight %)＜b≤17.0 (weight %),
(0.05 weight %)＜c≤14.0 (weight %).
In addition, the 1st group dielectric ceramic composition preferred embodiment is to contain forsterite (2MgOSiO in dielectric ceramic composition
2) crystallization.
In addition, the manufacture method of the 1st group dielectric ceramic composition is, with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, the boracic raw material, and copper-containing raw material burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO,
Use forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
[the 2nd group of invention]
The purpose of the application's the 2nd group of invention is, provides at low temperatures more stable, reliable dielectric ceramic composition of coking property and manufacture method thereof, even if so that contain BaO, rare-earth oxide and TiO
2As principal constituent compositional system, also can use Ag reliably or with Ag as the conductors such as alloy of principal constituent as inner conductor.
Further purpose provide resonant frequency number that a kind of temperature variation causes change little, have than BaO-rare-earth oxide-TiO
2The ratio specific inductivity of the dielectric ceramic composition of class lower and dielectric ceramic composition and manufacture method thereof that improved dielectric loss.
For solving above-mentioned problem, the following formation of dielectric ceramic composition in the 2nd group of invention of the present invention: contain composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously, represent that α, the β of the volumetric ratio of each composition in the above-mentioned principal constituent is in the following ranges respectively:
15 (volume %)≤α＜75 (volume %),
25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %),
With respect to for above-mentioned principal constituent, contain zinc oxide, boron oxide compound, copper oxide and Mn oxide as minor component, above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, when cCuO and dMnO represent, expression has following relation respectively with respect to a, b, c and the d of the weight ratio of the above-mentioned secondary composition of above-mentioned principal constituent:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.01 weight %)≤c≤6.5 (weight %).
In addition, the 2nd group dielectric ceramic composition preferred embodiment is to contain forsterite (2MgOSiO in dielectric ceramic composition
2) crystallization.
It is rerum natura below 50 that the 2nd group dielectric ceramic composition preferably has than specific inductivity.
In addition, the manufacture method of the 2nd group dielectric ceramic composition is, with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, the boracic raw material, and copper-containing raw material burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-MnO class dielectric ceramic composition,
Use forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
[the 3rd group of invention]
The purpose of the application's the 3rd group of invention is, provides at low temperatures more stable, reliable dielectric ceramic composition of coking property and manufacture method thereof, even if so that contain BaO, rare-earth oxide and TiO
2As principal constituent compositional system, also can use Ag reliably or with Ag as the conductors such as alloy of principal constituent as inner conductor.
Further purpose provide resonant frequency number that a kind of temperature variation causes change little, have than BaO-rare-earth oxide-TiO
2The lower dielectric ceramic composition and the manufacture method thereof of ratio specific inductivity of the dielectric ceramic composition of class.
For solving above-mentioned problem, the following formation of dielectric ceramic composition in the 3rd group of invention of the present invention: contain composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously, represent that α, the β of the volumetric ratio of each composition in the above-mentioned principal constituent is in the following ranges respectively:
15 (volume %)≤α＜75 (volume %),
25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %),
With respect to above-mentioned principal constituent, contain zinc oxide, boron oxide compound, copper oxide and alkaline-earth metals oxide as minor component, above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, when cCuO and dRO represent (R is an alkaline-earth metal), expression has following relation respectively with respect to a, b, c and the d of the weight ratio of the above-mentioned secondary composition of above-mentioned principal constituent:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.2 weight %)≤c≤5.0 (weight %).
In addition, the alkaline-earth metal R in the 3rd group the dielectric ceramic composition is preferably selected among Ba, Sr, the Ca at least a kind.
In addition, the 3rd group dielectric ceramic composition preferred embodiment is to contain forsterite (2MgOSiO in dielectric ceramic composition
2) crystallization.
It is rerum natura below 870 ℃ that the 3rd group dielectric ceramic composition preferably has firing temperature.
It is rerum natura below 50 that the 3rd group dielectric ceramic composition preferably has than specific inductivity.
The 3rd group dielectric ceramic composition preferably have than specific inductivity be 20～30, the Qf value is the rerum natura more than the 4000GHz.
In addition, the manufacture method of the 3rd group dielectric ceramic composition is, with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, boracic raw material, and copper-containing raw material and contain the alkaline-earth metal raw material and burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-RO (R is an alkaline-earth metal),
Use forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
Description of drawings
Fig. 1 is the process picture sheet in the manufacture method of dielectric ceramic composition of the present invention the 1st group,
Fig. 2 is the process picture sheet in the manufacture method of dielectric ceramic composition of the present invention the 2nd group,
Fig. 3 is the process picture sheet in the manufacture method of dielectric ceramic composition of the present invention the 3rd group.
Embodiment
Below, embodiments of the present invention are described in detail.
(1) about the explanation of the 1st group of the application invention
Below, the 1st group of preferred forms of inventing implementing the application described.At first, the formation to the 1st group dielectric ceramic composition describes.
[explanation of the 1st group dielectric ceramic composition]
Dielectric ceramic composition of the present invention contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent.
Further, dielectric ceramic composition of the present invention contains zinc oxide, boron oxide compound, reaches copper oxide as minor component with respect to principal constituent with specified amount.
Below, the principal constituent of dielectric ceramic composition of the present invention is formed and minor component is formed and described.At first, the principal constituent composition is described.
(the principal constituent composition is described)
Dielectric ceramic composition of the present invention as mentioned above contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent, represent BaO and Nd respectively
2O
3And TiO
2X, y, the z of molar ratio (mole %) be in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously.
In addition, α, the β that represents the volumetric ratio (volume %) of each composition in the above-mentioned principal constituent respectively is in the following ranges:
5 (volume %)≤α＜85 (volume %),
15 (volume %)＜β≤95 (volume %) are satisfied the relation of alpha+beta=100 (volume %) simultaneously,
Obtain containing of BaO proportional x in the scope of above-mentioned condition, also promptly in the scope of 9 (mole %)≤x≤22 (mole %), preferred range is 10 (mole %)≤x≤19 (mole %), more preferably 14 (mole %)≤x≤19 (mole %).
When this BaO contained proportional less than 9 (mole %), dielectric loss increased, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, when the content of BaO surpassed 22 (mole %), low-temperature sintering was impaired, will produce the tendency that can't form dielectric ceramic composition, further because Qf value reduces the problem of power consumption increase that will the generation high frequency devices greatly.
Obtain Nd
2O
3Contain proportional y in the scope of above-mentioned condition, the also i.e. scope of 9 (mole %)≤y≤29 (mole %), preferred range is 9 (mole %)≤y≤22 (mole %), more preferably 12 (mole %)≤y≤17 (mole %).
This Nd
2O
3When containing proportional less than 9 (mole %), dielectric loss increases, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, Nd
2O
3Content when surpassing 29 (mole %), dielectric loss increases, Qf value will have when producing the tendency that descends, the temperature factor τ f of resonant frequency number also has towards the tendency of negative direction increase.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.
Obtain TiO
2Contain proportional in the scope of above-mentioned condition, the also i.e. scope of 61 (mole %)≤z≤74 (mole %), preferred range is 61.5 (mole %)≤z≤74 (mole %), more preferably 65 (mole %)≤z≤71 (mole %).
This TiO
2When containing proportional less than 61 (mole %), dielectric loss increases, and the Qf value will have when producing the tendency that descends, and the temperature factor τ f of resonant frequency number also has the tendency that increases towards negative direction.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.On the other hand, TiO
2Ratio when surpassing 74 (mole %), low-temperature sintering is impaired, will produce the tendency that can't form dielectric ceramic composition.
In addition, in the composition formula of above-mentioned principal constituent, α, β represent (1) BaO, the Nd of the principal constituent of dielectric ceramic composition of the present invention respectively
2O
3And TiO
2, and (2) MgO and SiO
2Volumetric ratio.
Above-mentioned α, β exist respectively
5 (volume %)≤α＜85 (volume %),
In the scope of 15 (volume %)＜β≤95 (volume %), and satisfy the relation of alpha+beta=100 (volume %) simultaneously, further, α and β preferred range are 15 (volume %)≤α≤75 (volume %), 25 (volume %)≤β≤85 (volume %), preferred scope is 25 (volume %)≤α≤65 (volume %), 35 (volume %)≤β≤75 (volume %), and further preferred range is 35 (volume %)≤α≤55 (volume %), 45 (volume %)≤β≤65 (volume %).
The value of α more than 85 (volume %), the value of β when 15 (volume %) are following, the tendency that produce to increase than DIELECTRIC CONSTANT r of above-mentioned dielectric ceramic composition, the temperature factor τ f of resonant frequency number has the tendency that increases towards positive dirction.Therefore, owing to produce increase than DIELECTRIC CONSTANT r, with BaO-rare-earth oxide-TiO
2The high characterization of the multi-layered type equipment that the class dielectric ceramic composition engages is difficult to realize that because the temperature factor τ f of resonant frequency number increases, temperature causes the easier change of resonant frequency number of high frequency devices.In contrast to this, when the value of the value less than 5 of α (volume %), β surpasses 95 (volume %), the temperature factor τ f of the resonant frequency number of above-mentioned dielectric ceramic composition has the tendency that increases towards negative direction, therefore will produce the problem that the resonant frequency number of the high frequency devices that Yin Wendu causes changes easily.
In the present invention, MgO and the SiO that contains as the part of principal constituent
2Preferably in dielectric ceramic composition, contain with forsterite crystalline form.
In dielectric ceramic composition, whether contain the forsterite crystallization, can confirm by X-ray diffraction device (XRD).
With BaO-Nd
2O
3-TiO
2Compounds is the height ratio specific inductivity that the dielectric ceramic composition of principal constituent has ε r=55～105.On the other hand, the forsterite monomer has the low specific inductivity that compares of ε r=6.8.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can make the ratio specific inductivity of dielectric ceramic composition descend as the principal constituent of the dielectric ceramic composition in the present embodiment.
In addition, with BaO-Nd
2O
3-TiO
2Compounds be the temperature factor τ f of resonant frequency number of the dielectric ceramic composition of principal constituent mostly be on the occasion of.On the other hand, the forsterite monomer has the temperature factor of τ f=-65 (ppm/k) and negative resonant frequency number.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization are as the principal constituent of dielectric ceramic composition, the resonant frequency that makes the temperature factor of positive resonant frequency number and bear is counted temperature factor and is cancelled each other, can be so that the temperature factor of the resonant frequency number of dielectric ceramic composition reaches near zero.Further, by the forsterite crystalline content in the increase and decrease principal constituent, the temperature factor of the resonant frequency number of the dielectric ceramic composition that adjustable abridged edition embodiment relates to.
In addition, with BaO-Nd
2O
3-TiO
2Compounds is about the Qf=2000～8000GHz of dielectric ceramic composition of principal constituent.On the one hand, the monomeric Qf=200000GHz of forsterite, dielectric loss is little.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can obtain the dielectric ceramic composition of low dielectric loss as the principal constituent of dielectric ceramic composition.
The dielectric ceramic composition that present embodiment relates to, for can than main be to burn till under the lower temperature of the fusing point of conductors such as alloy of principal constituent with Ag or with Ag, can constitute by in above-mentioned principal constituent, adding desired minor component.
(minor component is described)
As mentioned above, dielectric ceramic composition of the present invention contains zinc oxide, boron oxide compound, reaches copper oxide as minor component.
Above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, and cCuO when representing, expression with respect to a, the b of the weight ratio of the above-mentioned secondary composition of above-mentioned principal constituent, and c have following relation respectively:
(0.05 weight %)＜a≤17.0 (weight %),
(0.05 weight %)＜b≤17.0 (weight %),
(0.05 weight %)＜c≤14.0 (weight %).
Promptly, obtain with respect to proportionally being scaled 0.05 (weight %)＜a≤17.0 (weight %) containing of the zinc oxide of principal constituent with ZnO, be preferably 0.1 (weight %)≤a≤12.0 (weight %), more preferably 0.5 (weight %)≤a≤9.0 (weight %), more preferably 1.0 (weight %)≤a≤7.0 (weight %).
With respect to proportionally being scaled 0.05 (weight %) when following with ZnO containing of the zinc oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 17.0 (weight %) with ZnO containing of the zinc oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
In addition, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Be scaled 0.05 (weight %)＜b≤17.0 (weight %), be preferably 0.1 (weight %)≤b≤12.0 (weight %), more preferably 0.5 (weight %)≤b≤9.0 (weight %), more preferably 1.0 (weight %)≤b≤7.0 (weight %).
Proportional with respect to containing of the zinc oxide of principal constituent with B
2O
3Be scaled 0.05 (weight %) when following, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Convert when surpassing 17.0 (weight %), dielectric loss increases, and the Qf value has the tendency of decline.
In addition, with respect to proportionally being scaled 0.05 (weight %)＜c≤14.0 (weight %) containing of the copper oxide of principal constituent with CuO, be preferably 0.1 (weight %)≤c≤9.0 (weight %), more preferably 0.5 (weight %)≤c≤6.0 (weight %), more preferably 1.0 (weight %)≤c≤4.0 (weight %).
With respect to proportionally being scaled 0.05 (weight %) when following with CuO containing of the copper oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 14.0 (weight %) with CuO containing of the copper oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
Dielectric ceramic composition among the present invention contains BaO, Nd
2O
3, TiOx, MgO and SiO
2As principal constituent, contain ZnO, B
2O
3, CuO is as minor component, particularly by containing MgO and SiO
2(particularly forsterite crystallization) can make rare-earth oxide-TiO than permittivity ratio BaO-as principal constituent
2The dielectric ceramic composition of class generally lower than specific inductivity.
In addition, the material of the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class is similar, therefore, burns till contraction behavior and linear expansivity and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition unanimity of class.Also promptly, even dielectric ceramic composition of the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages and burns till, and makes multi-layered type equipment, also is difficult for producing on the junction surface defective.Therefore, the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages, and can make the multi-layered type equipment of high characteristic.
Need to prove that dielectric ceramic composition of the present invention also can contain other compound and element in the scope that can bring into play purpose of the present invention and effect.
Dielectric ceramic composition of the present invention as mentioned above must be that the conductors such as alloy of principal constituent are as inner conductor with the Ag of cheapness or with Ag for miniature device is provided with low price.Therefore, require to have can be in dielectric ceramic composition as internal electrode use the fusing point of conductor below burn till low-temperature sintering.In addition, also be affected, so firing temperature is 860 ℃～1000 ℃, is preferably 880 ℃～940 ℃ according to the dielectric characteristics of the different dielectric ceramic compositions of firing temperature.
In addition, the dielectric loss for the dielectric ceramic composition of the key property among the present invention describes as follows.
When applying alternating-current on the ideal dielectric medium, electric current and voltage have the phase differential of 90 degree.But, alternative frequency number increases when becoming high frequency, the orientation of dielectric electropolarization or polar molecule can not be followed the variation of high frequency electric field, and perhaps because electronics or ionic conduct electricity gamma flux density produce phase delay with respect to electric field, electric current and voltage have the phase place beyond 90 degree.Dielectric loss is the phenomenon of the part of above-mentioned high-frequency energy with the form release of heat.The size of dielectric loss is with Q=reciprocal (Q=1/tan δ) expression of the tangent tan δ of the loss angle δ of the difference between the phase differential of the phase differential of the electric current of reality and voltage and ideal electric current and voltage.In the evaluation of the dielectric loss of the dielectric ceramic composition among the present invention, use the value of the long-pending Qf of above-mentioned Q and resonant frequency number.If dielectric loss reduces, it is big that Qf becomes, and if dielectric loss increases, then Qf diminishes.Dielectric loss means the power consumption of high-frequency apparatus, therefore requires the big dielectric ceramic composition of Qf value.Further, during multi-layered type equipment, owing to the reason of high characterization requires to reduce dielectric loss, the Qf value must be more than 3100GHz.Preferably more than 4000GHz, the value of Qf is more preferably more than 4500GHz for the value of Qf.
In addition, one of purpose of the present invention is to make and the BaO-rare-earth oxide-TiO with height ratio specific inductivity
2The formation of the multi-layered type equipment that the dielectric ceramic composition of class engages becomes possibility.Therefore, provide than specific inductivity and be lower than BaO-rare-earth oxide-TiO
2The class dielectric ceramic composition the dielectric ceramic composition of ratio specific inductivity also become problem.There is report to point out BaO-rare-earth oxide-TiO
2The ratio specific inductivity of the dielectric ceramic composition of class is 50～105, the requiring below 50 than DIELECTRIC CONSTANT r of dielectric ceramic composition of the present invention.Further owing to be used for the multi-layered type equipment of high characteristic, than DIELECTRIC CONSTANT r preferably below 40, than DIELECTRIC CONSTANT r more preferably below 30.
In addition, the temperature factor τ f (ppm/K) for as the resonant frequency number of the dielectric ceramic composition of the key property among the present invention carries out following explanation.
The temperature factor τ f (ppm/K) of the resonant frequency number of dielectric ceramic composition calculates by following formula (1).
τ f=[f
T-f
Ref/ f
Ref(T-T
Ref)] * 1000000 (ppm/K) (formula 1)
F herein
TResonant frequency number (kHz) in the expression temperature T, f
RefExpression reference temperature T
RefIn resonant frequency number (kHz).
The size of the absolute value of the temperature factor τ f of resonant frequency number means the size of variable quantity of the resonant frequency number of the dielectric ceramic composition that relative temperature changes.Because high frequency equipment such as electric capacity, dielectric filter must reduce the variation of the resonant frequency number that Yin Wendu produces, therefore require to reduce the absolute value of temperature factor τ f of the resonant frequency number of the dielectric ceramic composition among the present invention.
In addition, when utilizing dielectric ceramic composition among the present invention as dielectric resonator, in order further to reduce the temperature variation of resonant frequency, the temperature factor τ f of resonant frequency number must be in the scope of-45 (ppm/K)～+ 45 (ppm/K).Further, in order to form the multi-layered type equipment of high characteristic, temperature factor τ f requires in the scope of-30 (ppm/K)～+ 30 (ppm/K), preferably in the scope of-20 (ppm/K)～+ 20 (ppm/K), more preferably in the scope of-10 (ppm/K)～+ 10 (ppm/K).
In addition, the evaluation of the low-temperature sintering characteristic of dielectric ceramic composition can be burnt till according to slow reduction firing temperature, whether has carried out sintering and judge on the level of the dielectric medium high frequency characteristic that can measure expectation.In addition, the evaluation of the dielectric characteristics of dielectric ceramic composition can followingly be carried out, the variation of the resonant frequency number that dielectric loss, temperature variation cause (temperature factor of resonant frequency number) and than specific inductivity is estimated according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R).
[explanation of the manufacture method of dielectric ceramic composition]
Below, the manufacture method of the dielectric ceramic composition among the present invention is described.
The manufacture method of dielectric ceramic composition of the present invention is to the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, the boracic raw material, and copper-containing raw material burn till, to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO class dielectric ceramic composition is used forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
Use oxide compound and/or by burning till the compound that becomes oxide compound, as the production of raw material for use of dielectric ceramic composition of the present invention.As becoming the compound of oxide compound example carbonate, nitrate, oxalate, oxyhydroxide, sulfide, organometallic compound etc. are arranged by burning till.
One of embodiment of the manufacture method of the dielectric ceramic composition shown in Fig. 1 among the present invention.
Below, based on Fig. 1 the manufacture method of dielectric ceramic composition of the present invention is described.
At first, prepare for example barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide as the part of raw materials of principal constituent, the specified amount of weighing simultaneously also mixes, and calcines.
Above-mentioned mixing is as composition formula xBaOyNd
2O
3ZTiO
2X, the y of molar ratio and scope that z satisfies the above-mentioned relation composition formula in mix.
The mixing of barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
Raw materials mixed at 100 ℃～200 ℃, preferably 120 ℃～140 ℃ following dryings about 12～36 hour, then calcined thereafter.
Calcining is carried out BaO-Nd for the mixing raw material by barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide
2O
3-TiO
2The synthetic operation of compounds, calcining temperature are 1100 ℃～1500 ℃, preferably carry out 1～24 hour calcining under 1100 ℃～1350 ℃.
With synthetic BaO-Nd
2O
3-TiO
2Compounds is pulverized dry to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain BaO-Nd
2O
3-TiO
2The powder of compounds.
Then, prepare as other raw materials of principal constituent for example magnesium oxide and silicon oxide, the weighing specified amount also mixes, and calcines.The mixing of magnesium oxide and silicon oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
, raw materials mixed at 100 ℃～200 ℃, preferably at 120 ℃～140 ℃ descended about dry 12-36 hour, calcine then thereafter.
Calcining is carried out forsterite crystalline synthetic operation for the mixture by magnesium oxide and silicon oxide, preferably at 1100 ℃～1500 ℃, more preferably carries out 1～24 hour calcining under 1100 ℃～1350 ℃ treatment temp.
By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization be as principal constituent, by forsterite crystalline effect, can reduce dielectric ceramic composition than DIELECTRIC CONSTANT r, the temperature factor that makes the resonant frequency number can reduce dielectric loss near zero.Therefore, in order to increase the additive effect of forsterite, be necessary to reduce the unreacted above-mentioned raw materials that does not synthesize forsterite, it is 2 times of mole number of silicon that the mixing of above-mentioned raw materials preferably makes the mole number of magnesium.
Synthetic forsterite is pulverized after drying to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain forsterite powder.
Can be not by by magnesium raw material, the silicon-containing material synthetic forsterite of containing shown in Figure 1, pulverize the back and obtain forsterite powder, and use commercially available forsterite.That is, also can be with commercially available forsterite, for example using, ball mill by 100 ℃～200 ℃, preferably obtained forsterite powder in dry about 12～36 hours down at 120 ℃～140 ℃ with the grinding mode pulverizing of pure water, ethanol equal solvent.
Below, mix above-mentioned BaO-Nd
2O
3-TiO
2The powder of the powder of compounds, above-mentioned forsterite and for the composition that satisfies above-mentioned minor component in specialized range the zinc oxide of weighing, boron oxide compound, and copper oxide, obtain the raw material mixed powder.
Mixing can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
After mixing end, that raw materials mixed is at 100 ℃～200 ℃, preferably following dry about 12～36 hours at 120 ℃～140 ℃.
Then, the raw material mixed powder is calcined about 1～10 hour under the temperature below the firing temperature, for example 700 ℃～800 ℃ once more.Because this calcining carries out at low temperatures, can forsterite not the fused crystal habit in dielectric ceramic composition, contain forsterite.Then, the raw material mixed powder after the calcining is pulverized and drying.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.Like this by calcining once more and pulverize, can be with principal constituent and minor component homogenizing, can realize the homogenizing of the material of the dielectric ceramic composition in the present embodiment that the back operation makes.
For the powder that obtains as mentioned above, behind the organic binder bonds such as mix polyethylene alcohols, acrylic acid or the like, ethyl cellulose class, be configured as desired shape, this shaping thing is burnt till sintering.Moulding method also can adopt dry pressing methods such as press molding, according to needed shape appropriate selection manufacturing process except wet formings such as plate method or print process.In addition, burn till preferably and for example carrying out under the airborne oxygen atmosphere, firing temperature for the Ag that uses as internal electrode or with below the fusing point of Ag as the conductors such as alloy of principal constituent, for example 860 ℃～1000 ℃, be preferably 880 ℃～940 ℃.
At multi-layered type equipment by the multilayer ceramic substrate manufacturing that a plurality of ceramic layers of the integrated assembly productions of dielectric equipment such as electric capacity, inducer is constituted in inside.Several the dielectric characteristicies green sheet of different stupaliths is mutually prepared in multilayer ceramic substrate such as following manufacturing, and at the conductor of interface configurations formation internal electrode, or the formation through hole is made laminated burning till simultaneously.By the green sheet and the present known common BaO-Nd of usefulness that is shaped with dielectric ceramic composition of the present invention
2O
3-TiO
2The green sheet phase lamination that the class dielectric ceramic composition is shaped can be made the multilayer ceramic substrate that uses dielectric ceramic composition of the present invention.
Below, enumerate specific embodiment, the present invention will be described in detail.
[experimental example 1]
(measuring method of sample making and desired rerum natura)
Make the sample of the various dielectric ceramic compositions shown in the table 1 according to following main points.As mentioned above, the principal constituent composition is defined as α, β, x, y and z especially, and the addition that minor component is formed is defined as a, b and c especially.
The sample No.1 that exemplifies out sample of the present invention about basic manufacture method describes.
At first, use the BaCO of the raw material of principal constituent
3, Nd (OH)
3And TiO
2, weighing makes as the BaO-Nd after the calcining
2O
3-TiO
2The BaO of compounds, Nd
2O
3And TiO
2X, the y of molar ratio and the principal constituent of the sample No.1 that z satisfies following table 1 form the standard shown in the hurdle.That is, weighing makes x=18.5 (mole %), y=15.4 (mole %) and z=66.1 (mole %).
Adding pure water in the raw material of weighing, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.This exsiccant powder is calcined in air (1200 ℃, 4 hours).BaO-Nd after calcining
2O
3-TiO
2It is 25% that compounds adding pure water makes slurry concentration, carries out 16 hours case of wet attrition in ball mill, descends dry 24 hours at 120 ℃ then, makes BaO-Nd
2O
3-TiO
2Type compound powder.
Then, use is as MgO, the SiO of other raw material of principal constituent
2, weighing makes that the mole number of magnesium is 2 times of mole number of silicon, adding pure water, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.
This exsiccant powder is calcined in air (1200 ℃, 3 hours).Adding pure water in the forsterite after calcining, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down, make forsterite powder.
Then, preparation is as ZnO, the B of minor component raw material
2O
3, and CuO.
At first, with the above-mentioned BaO-Nd that pulverizes
2O
3-TiO
2The blending ratio of the powder of the above-mentioned forsterite after the powder of compounds and the pulverizing cooperates shown in following table 1, simultaneously for principal constituent, cooperates aZnO, bB
2O
3, and the represented minor component ratio of cCuO with the standard shown in the hurdle of the minor component addition of the sample No.1 that satisfies table 1, obtain the raw material mixed powder.Also be, weighing makes α=5 (volume %), β=95 (volume %), a=6.0 (weight %), b=4.5 (weight %) and c=3.0 (weight %), it is 25% that the adding pure water makes slurry concentration, in ball mill, carry out 16 hours case of wet attrition, obtained the raw material mixed powder down in dry 24 hours at 120 ℃ then.
Above-mentioned this exsiccant powder that obtains is calcined (750 ℃, 2 hours) once more in air, obtain calcined powder.
Adding pure water in the calcined powder that obtains, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.In the powder that this is pulverized once more, add polyvinyl alcohol water solution and carry out granulation as tackiness agent, be configured as the cylindric of diameter 12mm * height 6mm, in the temperature shown in the hurdle of the firing temperature of the sample No.1 of table 1, promptly burn till under 900 ℃ and obtained dielectric ceramic composition in 1 hour.
The little test sample No.1 that certainly makes of cylinder of diameter 10mm * high 5mm is made on the surface of the dielectric ceramic composition that cutting so obtains.
For the dielectric ceramic composition of sample No.1, measure according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R) than the temperature factor τ f of DIELECTRIC CONSTANT r, Qf value, resonant frequency number.Be 13.5GHz to measure frequency number during mensuration, in addition, the resonant frequency number is measured in-40 ℃～85 ℃ temperature range, calculates the temperature factor τ f of resonant frequency number according to the calculating formula of above-mentioned formula (1).
Therefore the mensuration that can realize above-mentioned each rerum natura of sample No.1 as shown in table 1 can be learnt and carry out sufficient sintering under 900 ℃ low temperature.Need to prove, the measurement result of each rerum natura, as shown in table 1 is temperature factor τ f=-44 (ppm/K) than DIELECTRIC CONSTANT r=9.3, Qf=7782 (GHz), resonant frequency number.
According to the manufacture method of above-mentioned sample No.1, make the various samples shown in the table 1.Obtaining (the sample that has the record of " can not measure " in the table 1 of low sintering while that can carry out which kind of degree, be illustrated under the level that to measure dielectric medium high frequency characteristic not sintering), simultaneously for sintering sample, (scope of measuring frequency number is 5.7～13.5GHz), reach the temperature factor τ f of resonant frequency number to obtain ε r, Qf value.
The result represents in following table 1.Need to prove that the sample that has * is represented comparative example.
Table 1 (1)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | ||||||||
| α | β | x | y | z | a | b | c | εr | Q·f(GHz) | τf(ppm/k) | ||
| 1 | 5 | 95 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 9.3 | 7782 | -44 |
| 2 | 15 | 85 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 10.2 | 7515 | -38 |
| 3 | 25 | 75 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 13.3 | 6754 | -29 |
| 4 | 35 | 65 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 17.0 | 6219 | -20 |
| 5 | 45 | 55 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 21.1 | 5622 | -9 |
| 6 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 26.6 | 5124 | 1 |
| 7 | 65 | 35 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 37.0 | 4887 | 16 |
| 8 | 75 | 25 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 48.3 | 4670 | 33 |
| * 9 (comparisons) | 85 | 15 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 900 | 55.1 | 4529 | 46 |
| 10 | 55 | 45 | 18.5 | 15.4 | 66.1 | 2.0 | 1.5 | 1.0 | 950 | 28.4 | 4519 | 24 |
| 11 | 55 | 45 | 18.5 | 15.4 | 66.1 | 2.0 | 1.5 | 1.0 | 1000 | 29.4 | 3852 | 23 |
| 12 | 55 | 45 | 18.5 | 15.4 | 66.1 | 4.0 | 3.0 | 2.0 | 900 | 27.4 | 4439 | 9 |
| 13 | 55 | 45 | 18.5 | 15.4 | 66.1 | 4.0 | 3.0 | 2.0 | 950 | 28.2 | 3759 | 8 |
| 14 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 950 | 27.2 | 4111 | -1 |
| 15 | 55 | 45 | 18.5 | 15.4 | 66.1 | 8.0 | 6.0 | 4.0 | 900 | 25.6 | 5776 | -5 |
| 16 | 55 | 45 | 18.5 | 15.4 | 66.1 | 8.0 | 6.0 | 4.0 | 950 | 26.0 | 4532 | -5 |
| 17 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 850 | Can not measure | ||
| 18 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 880 | 25.4 | 5044 | 2 |
| 19 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 910 | 26.9 | 4982 | 0 |
Table 1 (2)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | ||||||||
| α | β | x | y | z | a | b | c | εr | Q·f(GHz) | τf(ppm/k) | ||
| 20 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 940 | 27.4 | 4520 | -1 |
| 21 | 65 | 35 | 16.7 | 9.7 | 73.6 | 4.0 | 3.0 | 2.0 | 900 | 28.9 | 4400 | 9 |
| 22 | 70 | 30 | 16.7 | 9.7 | 73.6 | 4.0 | 3.0 | 2.0 | 900 | 32.2 | 4262 | 13 |
| 23 | 75 | 25 | 16.7 | 9.7 | 73.6 | 4.0 | 3.0 | 2.0 | 900 | 35.0 | 4178 | 15 |
| 24 | 60 | 40 | 16.7 | 12.7 | 70.6 | 4.0 | 3.0 | 2.0 | 900 | 27.4 | 5257 | 2 |
| 25 | 65 | 35 | 16.7 | 12.7 | 70.6 | 4.0 | 3.0 | 2.0 | 900 | 30.5 | 5128 | 7 |
| 26 | 70 | 30 | 16.7 | 12.7 | 70.6 | 4.0 | 3.0 | 2.0 | 900 | 33.4 | 5040 | 11 |
| 27 | 65 | 35 | 16.7 | 21.7 | 61.6 | 4.0 | 3.0 | 2.0 | 900 | 30.0 | 6113 | 14 |
| 28 | 70 | 30 | 16.7 | 21.7 | 61.6 | 4.0 | 3.0 | 2.0 | 900 | 33.1 | 5951 | 18 |
| 29 | 75 | 25 | 16.7 | 21.7 | 61.6 | 4.0 | 3.0 | 2.0 | 900 | 35.8 | 5095 | 21 |
| * 30 (comparisons) | 55 | 45 | 6.7 | 26.7 | 66.6 | 6.0 | 4.5 | 3.0 | 900 | 19.2 | 3003 | -23 |
| 31 | 55 | 45 | 9.0 | 24.4 | 66.6 | 6.0 | 4.5 | 3.0 | 900 | 20.3 | 4015 | -38 |
| 32 | 55 | 45 | 11.7 | 21.7 | 66.6 | 6.0 | 4.5 | 3.0 | 900 | 21.5 | 4052 | -37 |
| 33 | 55 | 45 | 16.7 | 16.7 | 66.6 | 6.0 | 4.5 | 3.0 | 900 | 25.6 | 6311 | -36 |
| 34 | 55 | 45 | 22.0 | 11.4 | 66.6 | 6.0 | 4.5 | 3.0 | 900 | 28.2 | 4085 | -30 |
| * 35 (comparisons) | 55 | 45 | 23.7 | 12.7 | 63.6 | 6.0 | 4.5 | 3.0 | 900 | Can not measure | ||
| * 36 (comparisons) | 55 | 45 | 18.7 | 7.7 | 73.6 | 6.0 | 4.5 | 3.0 | 900 | 29.7 | 2937 | 17 |
| 37 | 55 | 45 | 17.0 | 9.0 | 74.0 | 6.0 | 4.5 | 3.0 | 900 | 28.9 | 4096 | 6 |
| 38 | 55 | 45 | 16.7 | 15.7 | 67.6 | 6.0 | 4.5 | 3.0 | 900 | 26.2 | 6448 | -11 |
| 39 | 55 | 45 | 16.7 | 18.7 | 64.6 | 6.0 | 4.5 | 3.0 | 900 | 24.0 | 5625 | -26 |
Table 1 (3)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | ||||||||
| α | β | x | y | z | a | b | c | εr | Q·f(GHz) | τf(ppm/k) | ||
| 40 | 55 | 45 | 9.4 | 29.0 | 61.6 | 6.0 | 4.5 | 3.0 | 900 | 20.5 | 4195 | -40 |
| * 41 (comparisons) | 55 | 45 | 16.7 | 30.7 | 52.6 | 6.0 | 4.5 | 3.0 | 900 | 17.6 | 2864 | -40 |
| * 42 (comparisons) | 55 | 45 | 16.7 | 26.7 | 56.6 | 6.0 | 4.5 | 3.0 | 900 | 17.8 | 3020 | -38 |
| 43 | 55 | 45 | 16.5 | 21.5 | 62.0 | 6.0 | 4.5 | 3.0 | 900 | 20.0 | 5266 | -33 |
| 44 | 55 | 45 | 18.5 | 11.7 | 69.6 | 6.0 | 4.5 | 3.0 | 900 | 24.9 | 7109 | 4 |
| * 45 (comparisons) | 55 | 45 | 11.7 | 11.7 | 76.6 | 6.0 | 4.5 | 3.0 | 900 | Can not measure | ||
| * 46 (comparisons) | 55 | 45 | 18.5 | 15.4 | 66.1 | 0 | 0 | 0 | 900 | Can not measure | ||
| * 47 (comparisons) | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.05 | 4.5 | 3.0 | 900 | Can not measure | ||
| 48 | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.1 | 4.5 | 3.0 | 900 | 23.8 | 4824 | 7 |
| 49 | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.5 | 4.5 | 3.0 | 900 | 24.9 | 4986 | 6 |
| 50 | 55 | 45 | 18.5 | 15.4 | 66.1 | 3.0 | 4.5 | 3.0 | 900 | 27.1 | 5058 | 5 |
| 51 | 55 | 45 | 18.5 | 15.4 | 66.1 | 9.0 | 4.5 | 3.0 | 900 | 26.2 | 4875 | -2 |
| 52 | 55 | 45 | 18.5 | 15.4 | 66.1 | 12.0 | 4.5 | 3.0 | 900 | 25.5 | 4125 | -5 |
| 53 | 55 | 45 | 18.5 | 15.4 | 66.1 | 16.0 | 4.5 | 3.0 | 900 | 24.7 | 3754 | -8 |
| * 54 (comparisons) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.05 | 3.0 | 900 | Can not measure | ||
| 55 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.1 | 3.0 | 900 | 24.6 | 4700 | 6 |
| 56 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.5 | 3.0 | 900 | 25.0 | 4776 | 5 |
| 57 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 3.0 | 3.0 | 900 | 27.0 | 5305 | 3 |
| 58 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 9.0 | 3.0 | 900 | 22.1 | 4631 | -1 |
| 59 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 12.0 | 3.0 | 900 | 20.3 | 4022 | -2 |
Table 1 (4)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | ||||||||
| α | β | x | y | z | a | b | c | εr | Q·f(GHz) | τf(ppm/k) | ||
| 60 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 16.0 | 3.0 | 900 | 17.4 | 3479 | -4 |
| * 61 (comparisons) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.05 | 900 | Can not measure | ||
| 62 | 55 | 45 | 18.5 | 15.4 | 661 | 6.0 | 4.5 | 0.1 | 900 | 25.8 | 4922 | 4 |
| 63 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.5 | 900 | 25.9 | 5003 | 3 |
| 64 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 1.5 | 900 | 27.0 | 5245 | 2 |
| 65 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 6.0 | 900 | 26.0 | 4827 | -6 |
| 66 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 9.0 | 900 | 25.5 | 4068 | -11 |
| 67 | 55 | 45 | 18.5 | 15.4 | 66.1 | 60 | 4.5 | 12.0 | 900 | 25.0 | 3190 | -15 |
Sample No.1～No.9 for a change α and beta ratio makes the example of dielectric ceramic composition., about the ratio of α and β how any ratio can be made down for 900 ℃ at firing temperature, be that the conductors such as alloy of principal constituent use as conductor with Ag or with Ag no matter.But when decent product No.1 the same ground α diminished, the temperature factor τ f of the resonant frequency number of dielectric ceramic composition increased towards negative direction, will produce the tendency that increases with respect to the variation of the resonant frequency number of the temperature variation of high frequency devices.
On the other hand, as the sample No.9 in the comparative example, with α be that 85 (volume %) are above, β is the following ratio of 15 (volume %) when making because the ratio specific inductivity of dielectric ceramic composition surpasses 50, though with BaO-rare-earth oxide-TiO
2The manufacturing that the dielectric ceramic composition of class engages the multi-layered type equipment of high characteristic becomes difficult.Further, the temperature factor τ f of resonant frequency number increases towards positive dirction, and the tendency of increase is arranged with respect to the variation of the resonant frequency number of the temperature variation of high frequency devices.
As sample No.1～No.8 of embodiment, when α and β made in invention scope, if α increases, β diminished, then Qf value decline, and τ f passes towards positive dirction, has the tendency of increase than DIELECTRIC CONSTANT r.Opposite, if α reduces, β increases, and then the Qf value rises, and τ f passes towards negative direction, has the tendency that reduces than DIELECTRIC CONSTANT r.That is, by changing the ratio of α and β within the scope of the invention, can obtain to have be fit to practical than DIELECTRIC CONSTANT r, Qf value, reach the dielectric ceramic composition of the temperature factor τ f of resonant frequency number.
Sample No.10～No.16 is embodiment, is that ratio, all amounts of increase and decrease minor component that does not change between each minor component that adds in dielectric ceramic composition added the example of making dielectric composition.If increase all amounts of minor component, the temperature factor τ f of resonant frequency number has the tendency of passing towards negative direction.
Sample No.17～No.20 is embodiment, is to change the example that firing temperature is made dielectric ceramic composition.Sample No.17 is the example that burns till under 850 ℃, but firing temperature is a not sintering of low temperature so dielectric ceramic composition.Sample No.18～No.20 burns till under 880 ℃～940 ℃ of firing temperatures, follows increasing of firing temperature, has electric dielectric loss to lose and increases the tendency that the Qf value diminishes.
Sample No.21～No.41 is for a change as the BaO-Nd of one of principal constituent
2O
3-TiO
2The BaO of compounds, Nd
2O
3And TiO
2X, the y of mol ratio and the value of z to make the example of dielectric ceramic composition.
Sample No.30～No.35 is BaO-Nd for a change
2O
3-TiO
2The example that the BaO content of compounds is made.Too less than outside the invention scope time, dielectric loss increases the content of BaO as the sample No.30 of comparative example, and the Qf value reduces.On the other hand, when the content of BaO too surpasses outside the invention scope as the sample No.35 of comparative example, BaO-Nd
2O
3-TiO
2Compounds can't burn till.When the content of BaO is in the invention scope as the sample No.31～No.34 of comparative example, can make dielectric ceramic composition with superperformance.
Sample No.21～No.29 and No.36～No.41 are increase and decrease BaO-Nd
2O
3-TiO
2The Nd of compounds
2O
3The example that content is made.Nd as the sample No.41 of comparative example
2O
3Content when too surpassing outside the invention scope, dielectric loss increases, Qf value reduces, the temperature factor τ f of resonant frequency number increases towards negative direction, for the change increase of the resonant frequency number of temperature.On the other hand, Nd as the sample No.36 of comparative example
2O
3Content when too being less than outside the invention scope, dielectric loss increases, the Qf value reduces.Nd
2O
3Content when being in the invention scope, can make dielectric ceramic composition with superperformance.
Sample No.42～No.45 is BaO-Nd for a change
2O
3-TiO
2The TiO of compounds
2The example that content is made.TiO
2Content when reducing, the Qf value has the tendency that reduces, TiO as the sample No.42 of comparative example
2Content when too being less than outside the invention scope, dielectric loss increases, the Qf value reduces.On the other hand, TiO as the sample No.45 of comparative example
2Content when too surpassing outside the invention scope, BaO-Nd
2O
3-TiO
2Compounds can't burn till.TiO
2Content when being in the invention scope, can make dielectric ceramic composition with superperformance.
Sample No.46～No.67 is the example of the content manufacturing dielectric ceramic composition of minor component for a change.The sample No.46 of comparative example is not for containing minor component fully to make the example of dielectric ceramic composition.Just can't not make dielectric ceramic composition with easy fired if do not contain minor component.
Sample No.47～No.53 makes the example of dielectric ceramic composition for the content of the ZnO of increase and decrease minor component.Too less than outside the invention scope time, dielectric ceramic composition can't low-temperature sintering for the content of ZnO.On the other hand, when the content of ZnO too surpassed outside the invention scope, dielectric loss increased, and the Qf value reduces.When the content of ZnO is in the invention scope, can make dielectric ceramic composition with superperformance.
Sample No.54～No.60 is the B of increase and decrease minor component
2O
3Content is to make the example of dielectric ceramic composition.B
2O
3Content too less than outside the invention scope time, dielectric ceramic composition can't low-temperature sintering.On the other hand, B
2O
3Content when too surpassing outside the invention scope, dielectric loss increases, the Qf value reduces.B
2O
3Content when being in the invention scope, can make dielectric ceramic composition with superperformance.
Sample No.61～No.67 for the content of the CuO of increase and decrease minor component to make the example of dielectric ceramic composition.Too less than outside the invention scope time, dielectric ceramic composition can't low-temperature sintering for the content of CuO.On the other hand, when the content of CuO too surpassed outside the invention scope, dielectric loss increased, and the Qf value reduces.When the content of CuO is in the invention scope, can make dielectric ceramic composition with superperformance.
As described above, dielectric ceramic composition of the present invention contains BaO, the Nd as principal constituent within the scope of the invention
2O
3, TiO
2, MgO and SiO
2, and scope of the present invention contains ZnO, B as the minor component of above-mentioned dielectric ceramic composition
2O
3And CuO, can obtain following dielectric ceramic composition, it can be the low-temperature sintering of the conductors such as alloy of principal constituent as its inner conductor with Ag or with Ag that this dielectric ceramic composition has, dielectric loss reduces, and the variation of the resonant frequency number that produces because of temperature variation reduces and can have than BaO-rare-earth oxide-TiO
2The ratio specific inductivity that the ratio specific inductivity of the dielectric ceramic composition of class is lower.
(2) the 2nd group of invention to the application describes
Below, the 2nd group of preferred forms of inventing implementing the application described.At first, the formation to the 2nd group dielectric ceramic composition describes.
[explanation of the 2nd group dielectric ceramic composition]
Dielectric ceramic composition of the present invention contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent.
Further, dielectric ceramic composition of the present invention with specified amount with respect to principal constituent contain zinc oxide, boron oxide compound, and copper oxide and Mn oxide as minor component.
Below, the principal constituent of dielectric ceramic composition of the present invention is formed and minor component is formed and described.At first, the principal constituent composition is described.
(the principal constituent composition is described)
Dielectric ceramic composition of the present invention as mentioned above contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent, represent BaO and Nd respectively
2O
3And TiO
2X, y, the z of molar ratio (mole %) be in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously.
In addition, α, the β that represents the volumetric ratio (volume %) of each composition in the above-mentioned principal constituent respectively is in the following ranges:
15 (volume %)≤α≤75 (volume %),
25 (volume %)≤β≤85 (volume %) are satisfied the relation of alpha+beta=100 (volume %) simultaneously.
Obtain containing of BaO proportional x in the scope of above-mentioned condition, the also i.e. scope of 9 (mole %)≤x≤22 (mole %), preferred range is 10 (mole %)≤x≤19 (mole %), more preferably 14 (mole %)≤x≤19 (mole %).
When this BaO contained proportional less than 9 (mole %), dielectric loss increased, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, when the content of BaO surpassed 22 (mole %), low-temperature sintering was impaired, will produce the tendency that can't form dielectric ceramic composition, further because Qf value reduces the problem of power consumption increase that will the generation high frequency devices greatly.
Obtain Nd
2O
3Contain proportional y in the scope of above-mentioned condition, the also i.e. scope of 9 (mole %)≤y≤29 (mole %), preferred range is 9 (mole %)≤y≤22 (mole %), more preferably 12 (mole %)≤y≤17 (mole %).
This Nd
2O
3When containing proportional less than 9 (mole %), dielectric loss increases, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, Nd
2O
3Content when surpassing 29 (mole %), Qf value will have when producing the tendency that descends, the temperature factor τ f of resonant frequency number also has towards the tendency of negative direction increase.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.
Obtain TiO
2Contain proportional in the scope of above-mentioned condition, the also i.e. scope of 61 (mole %)≤z≤74 (mole %), preferred range is 61.5 (mole %)≤z≤74 (mole %), more preferably 65 (mole %)≤z≤71 (mole %).
This TiO
2When containing proportional less than 61 (mole %), dielectric loss increases, and the Qf value will have when producing the tendency that descends, and the temperature factor τ f of resonant frequency number also has the tendency that increases towards negative direction.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.On the other hand, TiO
2Ratio when surpassing 74 (mole %), low-temperature sintering is impaired, will produce the tendency that can't form dielectric ceramic composition.
In addition, in the composition formula of above-mentioned principal constituent, α, β represent (1) BaO, the Nd of the principal constituent of dielectric ceramic composition of the present invention respectively
2O
3And TiO
2, and (2) MgO and SiO
2Volumetric ratio.
Above-mentioned α, β exist respectively
15 (volume %)≤α≤75 (volume %),
In the scope of 25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %) simultaneously, further, α and β preferred range are 25 (volume %)≤α≤65 (volume %), 35 (volume %)≤β≤75 (volume %), and preferred scope is 35 (volume %)≤α≤55 (volume %), 45 (volume %)≤β≤65 (volume %).
When the value of α surpasses the value less than 25 (volume %) of 75 (volume %), β, the tendency than DIELECTRIC CONSTANT r generation increase of above-mentioned dielectric ceramic composition, the temperature factor τ f of resonant frequency number has the tendency that increases towards positive dirction simultaneously.Therefore, owing to produce increase than DIELECTRIC CONSTANT r, with BaO-rare-earth oxide-TiO
2The high characterization of the multi-layered type equipment that the class dielectric ceramic composition engages is difficult to realize, because the temperature factor τ f of resonant frequency number increases the also easier change of the resonant frequency number of the high frequency devices that Yin Wendu causes.In contrast, when the value of the value less than 15 of α (volume %), β surpasses 85 (volume %), the temperature factor τ f of the resonant frequency number of above-mentioned dielectric ceramic composition has the tendency that increases towards negative direction, therefore will produce the problem that the resonant frequency number of the high frequency devices that Yin Wendu causes changes easily.
In the present invention, MgO and the SiO that contains as the part of principal constituent
2Preferably in dielectric ceramic composition, contain with forsterite crystalline form.
In dielectric ceramic composition, whether contain the forsterite crystallization, can confirm by X-ray diffraction device (XRD).
With BaO-Nd
2O
3-TiO
2Compounds is the height ratio specific inductivity that the dielectric ceramic composition of principal constituent has ε r=55～105.On the other hand, the forsterite monomer has the low ratio specific inductivity of ε r=6.8.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can make the ratio specific inductivity of dielectric ceramic composition descend as the principal constituent of the dielectric ceramic composition in the present embodiment.
In addition, with BaO-Nd
2O
3-TiO
2Compounds be the temperature factor τ f of resonant frequency number of the dielectric ceramic composition of principal constituent mostly be on the occasion of.On the other hand, the forsterite monomer has the temperature factor of τ f=-65 (ppm/k) and negative resonant frequency number.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization are as the principal constituent of dielectric ceramic composition, the resonant frequency that makes the temperature factor of positive resonant frequency number and bear is counted temperature factor and is cancelled each other, can be so that the temperature factor of the resonant frequency number of dielectric ceramic composition reaches near zero.Further, by the forsterite crystalline content in the increase and decrease principal constituent, the temperature factor of the resonant frequency number of the dielectric ceramic composition in the adjustable abridged edition embodiment.
In addition, with BaO-Nd
2O
3-TiO
2Compounds is about the Qf=2000～8000GHz of dielectric ceramic composition of principal constituent.On the one hand, the monomeric Qf=200000GHz of forsterite, dielectric loss is little.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can obtain the dielectric ceramic composition of low dielectric loss as the principal constituent of dielectric ceramic composition.
The dielectric ceramic composition that present embodiment relates to, for can than main be to burn till under the lower temperature of the fusing point of conductors such as alloy of principal constituent with Ag or with Ag, can constitute by in above-mentioned principal constituent, adding desired minor component.
(minor component is described)
As mentioned above, dielectric ceramic composition of the present invention contains zinc oxide, boron oxide compound, copper oxide, reaches Mn oxide as minor component.
Above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, and cCuO and dMnO when representing, expression has following relation respectively with respect to a, b, c and the d of the weight ratio (weight %) of the above-mentioned secondary composition of above-mentioned principal constituent:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.01 weight %)≤d≤6.5 (weight %).
That is, obtain, be preferably 0.5 (weight %)≤a≤9.0 (weight %), more preferably 1.0 (weight %)≤a≤7.0 (weight %) with respect to proportionally being scaled 0.1 (weight %)≤a≤12.0 (weight %) containing of the zinc oxide of principal constituent with ZnO.
Proportional during with ZnO conversion less than 0.1 (weight %) with respect to containing of the zinc oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 12.0 (weight %) with ZnO containing of the zinc oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
In addition, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Be scaled 0.1 (weight %)≤b≤12.0 (weight %), be preferably 0.5 (weight %)≤b≤9.0 (weight %), more preferably 1.0 (weight %)≤b≤7.0 (weight %).
Proportional with respect to containing of the zinc oxide of principal constituent with B
2O
3During conversion less than 0.1 (weight %), the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Convert when surpassing 12.0 (weight %), dielectric loss increases, and the Qf value has the tendency of decline.
In addition, with respect to proportionally being scaled 0.1 (weight %)≤c≤9.0 (weight %) containing of the copper oxide of principal constituent, be preferably 0.5 (weight %)≤c≤6.0 (weight %), more preferably 1.0 (weight %)≤c≤4.0 (weight %) with CuO.
Proportional when converting less than 0.1 (weight %) with CuO with respect to containing of the copper oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 9.0 (weight %) with CuO containing of the copper oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
For reducing dielectric loss, except adding above-mentioned minor component, also further add Mn oxide among the present invention.That is, the Mn oxide of interpolation converts with MnO, is 0.01 (weight %)≤d≤6.5 (weight %) with respect to principal constituent, is preferably 0.1 (weight %)≤d≤6.0 (weight %), more preferably 0.5 (weight %)≤d≤3.0 (weight %).
With respect to proportionally converting less than 0.01 (weight %) when following containing of the Mn oxide of principal constituent, can't obtain to reduce the effect of dielectric loss with MnO.On the other hand, with respect to proportionally converting when surpassing 6.5 (weight %) containing of the copper oxide of principal constituent, produce the problem that dielectric loss increases with MnO.
Dielectric ceramic composition among the present invention contains BaO, Nd
2O
3, TiO
2, MgO and SiO
2As principal constituent, contain ZnO, B
2O
3, CuO and MnO be as minor component, particularly by containing MgO and SiO
2(particularly forsterite crystallization) can make rare-earth oxide-TiO than permittivity ratio BaO-as principal constituent
2The dielectric ceramic composition of class generally lower than specific inductivity.In addition, having can be the low-temperature sintering that the conductors such as alloy of principal constituent burn till simultaneously with Ag or with Ag, and reduces the variation of the resonant frequency number that causes because of temperature variation.
In addition, be minor component by containing MnO, can also improve BaO-rare-earth oxide-TiO
2The dielectric loss of the dielectric ceramic composition of class.
In addition, the material of the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class is similar, therefore, burns till contraction behavior and linear expansivity and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition unanimity of class.Also promptly, even dielectric ceramic composition of the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages and burns till, and makes multi-layered type equipment, also is difficult for producing on the junction surface defective.Therefore, the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages, and can make the multi-layered type equipment of high characteristic.In addition, the dielectric ceramic composition among the present invention can also contain other compound and element in the scope of purpose of the present invention and action effect.
Dielectric ceramic composition of the present invention as mentioned above is in order to provide miniature device with low price, and the conductors such as alloy that must be principal constituent with the Ag of cheapness or with Ag are as inner conductor.Therefore, require to have can be in dielectric ceramic composition as internal electrode use the fusing point of conductor below burn till low-temperature sintering.In addition, also be affected, so firing temperature is 800 ℃～950 ℃, is preferably 850 ℃～900 ℃ according to the dielectric characteristics of the different dielectric ceramic compositions of firing temperature.
In addition, the dielectric loss for the dielectric ceramic composition of the key property among the present invention describes as follows.
When applying alternating-current on the ideal dielectric medium, electric current and voltage have the phase differential of 90 degree.But, alternative frequency number increases when becoming high frequency, the orientation of dielectric electropolarization or polar molecule can not be followed the variation of high frequency electric field, and perhaps because electronics or ionic conduct electricity gamma flux density produce phase delay with respect to electric field, electric current and voltage have the phase place beyond 90 degree.Dielectric loss is the phenomenon of the part of above-mentioned high-frequency energy with the form release of heat.The size of dielectric loss is with Q=reciprocal (Q=1/tan δ) expression of the tangent tan δ of the loss angle δ of the difference between the phase differential of the phase phase differential of the electric current that shows and voltage and ideal electric current and voltage.In the evaluation of the dielectric loss of the dielectric ceramic composition among the present invention, use the value of the long-pending Qf of above-mentioned Q and resonant frequency number.If dielectric loss reduces, it is big that Qf becomes, and if dielectric loss increases, then Qf diminishes.Dielectric loss means the power consumption of high-frequency apparatus, therefore requires the big dielectric ceramic composition of Qf value.Further, during multi-layered type equipment, owing to the reason of high characterization requires to reduce dielectric loss, the Qf value is particularly preferably in more than the 4500GHz.The value of Qf is more preferably more than 5000GHz.
In addition, one of purpose of the present invention is to make and the BaO-rare-earth oxide-TiO with height ratio specific inductivity
2The formation of the multi-layered type equipment that the dielectric ceramic composition of class engages becomes possibility.Therefore, provide than BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of the ratio specific inductivity that the ratio specific inductivity of the dielectric ceramic composition of class is lower also becomes problem.There is report to point out BaO-rare-earth oxide-TiO
2The ratio specific inductivity of the dielectric ceramic composition of class is 50～105, the requiring below 50 than DIELECTRIC CONSTANT r of dielectric ceramic composition of the present invention.Further, owing to be used for the multi-layered type equipment of high characteristic, preferably below 40, more preferably below 30, be more preferably 20～30 especially than DIELECTRIC CONSTANT r than DIELECTRIC CONSTANT r.
In addition, the temperature factor τ f (ppm/K) for as the resonant frequency number of the dielectric ceramic composition of the key property among the present invention carries out following explanation.
The temperature factor τ f (ppm/K) of the resonant frequency number of dielectric ceramic composition calculates by following formula (1).
τ f=[f
T-f
Ref/ f
Ref(T-T
Ref)] * 1000000 (ppm/K) (formula 1)
F herein
TResonant frequency number (kHz) in the expression temperature T, f
RefExpression reference temperature T
RefIn resonant frequency number (kHz).
The size of the absolute value of the temperature factor τ f of resonant frequency number means the size of variable quantity of the resonant frequency number of the dielectric ceramic composition that relative temperature changes.Because high frequency equipment such as electric capacity, dielectric filter must reduce the variation of the resonant frequency number that Yin Wendu produces, therefore require to reduce the absolute value of temperature factor τ f of the resonant frequency number of the dielectric ceramic composition among the present invention.
In addition, when utilizing dielectric ceramic composition among the present invention as dielectric resonator, in order further to reduce the temperature variation of resonant frequency, the temperature factor τ f of resonant frequency number must be in the scope of-40 (ppm/K)～+ 40 (ppm/K).Further, in order to form the multi-layered type equipment of high characteristic, temperature factor τ f requires in the scope of-25 (ppm/K)～+ 25 (ppm/K), more preferably in the scope of-10 (ppm/K)～+ 10 (ppm/K).
In addition, the evaluation of the low-temperature sintering characteristic of dielectric ceramic composition can be burnt till according to slow reduction firing temperature, whether has carried out sintering and judge on the level of the dielectric medium high frequency characteristic that can measure expectation.
In addition, the evaluation of the dielectric characteristics of dielectric ceramic composition can followingly be carried out, the variation of the resonant frequency number that dielectric loss, temperature variation cause (temperature factor of resonant frequency number) and than specific inductivity is estimated according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R).
[explanation of the manufacture method of dielectric ceramic composition]
Below, the manufacture method of the dielectric ceramic composition among the present invention is described.
The manufacture method of dielectric ceramic composition of the present invention is to the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, the boracic raw material, and copper-containing raw material burn till, to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-MnO class dielectric ceramic composition is used forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
Use oxide compound and/or by burning till the compound that becomes oxide compound, as the production of raw material for use of dielectric ceramic composition of the present invention.As becoming the compound of oxide compound example carbonate, nitrate, oxalate, oxyhydroxide, sulfide, organometallic compound etc. are arranged by burning till.
One of embodiment of the manufacture method of the dielectric ceramic composition shown in Fig. 2 among the present invention.
Below, based on Fig. 2 the manufacture method of dielectric ceramic composition of the present invention is described.
At first, prepare for example barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide as the part of raw materials of principal constituent, the specified amount of weighing simultaneously also mixes, and calcines.
Above-mentioned mixing is at composition formula xBaOyNd
2O
3ZTiO
2X, the y of molar ratio and scope that z satisfies the above-mentioned relation composition formula in mix.
The mixing of barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
Raw materials mixed at 100 ℃～200 ℃, preferably 120 ℃～140 ℃ following dryings about 12～36 hour, then calcined thereafter.
Calcining is carried out BaO-Nd for the mixing raw material by barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide
2O
3-TiO
2The synthetic operation of compounds, calcining temperature are 1100 ℃～1500 ℃, preferably carry out 1～24 hour calcining under 1100 ℃～1350 ℃.
With synthetic BaO-Nd
2O
3-TiO
2Compounds is pulverized dry to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain BaO-Nd
2O
3-TiO
2The powder of compounds.
Then, prepare as other raw materials of principal constituent for example magnesium oxide and silicon oxide, the weighing specified amount also mixes, and calcines.The mixing of magnesium oxide and silicon oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
Raw materials mixed at 100 ℃～200 ℃, preferably 120 ℃～140 ℃ following dryings about 12～36 hour, then calcined thereafter.
Calcining is carried out forsterite crystalline synthetic operation for the mixture by magnesium oxide and silicon oxide, preferably at 1100 ℃～1500 ℃, more preferably carries out 1～24 hour calcining under 1100 ℃～1350 ℃ treatment temp.
By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization be as principal constituent, by forsterite crystalline effect, can reduce dielectric ceramic composition than DIELECTRIC CONSTANT r, the temperature factor that makes the resonant frequency number can reduce dielectric loss near zero.Therefore, in order to increase the additive effect of forsterite, be necessary to reduce the unreacted above-mentioned raw materials that does not synthesize forsterite, it is 2 times of mole number of silicon that the mixing of above-mentioned raw materials preferably makes the mole number of magnesium.
Synthetic forsterite is pulverized after drying to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain forsterite powder.
Can be not by by magnesium raw material, the silicon-containing material synthetic forsterite of containing shown in Figure 2, pulverize the back and obtain forsterite powder, and use commercially available forsterite.That is, also can be with commercially available forsterite, for example using, ball mill by 100 ℃～200 ℃, preferably obtained forsterite powder in dry about 12～36 hours down at 120 ℃～140 ℃ with the grinding mode pulverizing of pure water, ethanol equal solvent.
Below, mix above-mentioned BaO-Nd
2O
3-TiO
2The powder of the powder of compounds and above-mentioned forsterite and for the composition that satisfies above-mentioned minor component in specialized range the zinc oxide of weighing, boron oxide compound, and copper oxide and manganous carbonate, obtain the raw material mixed powder.
Mixing can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
After mixing end, that raw materials mixed is at 100 ℃～200 ℃, preferably following dry about 12～36 hours at 120 ℃～140 ℃.
Then, the raw material mixed powder is calcined about 1～10 hour under the temperature below the firing temperature, for example 700 ℃～800 ℃ once more.Because this calcining carries out at low temperatures, can forsterite not the fused crystal habit in dielectric ceramic composition, contain forsterite.Then, the raw material mixed powder after the calcining is pulverized and drying.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.Like this by calcining once more and pulverize, can be with principal constituent and minor component homogenizing, can realize the homogenizing of the material of the dielectric ceramic composition in the present embodiment that the back operation makes.
For the powder that obtains as mentioned above, behind the organic binder bonds such as mix polyethylene alcohols, acrylic acid or the like, ethyl cellulose class, be configured as desired shape, this shaping thing is burnt till sintering.Moulding method also can adopt dry pressing methods such as press molding, according to needed shape appropriate selection manufacturing process except wet formings such as plate (SHEET) method or print process.In addition, burn till preferably and for example carrying out under the airborne oxygen atmosphere, require firing temperature be the Ag that uses as internal electrode or with below the fusing point of Ag as the conductors such as alloy of principal constituent, for example 800 ℃～950 ℃, be preferably 850 ℃～900 ℃.
At multi-layered type equipment by the multilayer ceramic substrate manufacturing that a plurality of ceramic layers of the integrated assembly productions of dielectric equipment such as electric capacity, inducer is constituted in inside.Several the dielectric characteristicies green sheet of different stupaliths is mutually prepared in multilayer ceramic substrate such as following manufacturing, and at the conductor of interface configurations formation internal electrode, or the formation through hole is made laminated burning till simultaneously.By the green sheet and present known common BaO-rare-earth oxide-TiO that is shaped with dielectric ceramic composition of the present invention
2The green sheet phase lamination that the dielectric ceramic composition of class is shaped can be made the multilayer ceramic substrate that uses dielectric ceramic composition of the present invention.
Below, enumerate specific embodiment, the present invention will be described in detail.
[experimental example 2-1]
(manufacturing of sample and the measuring method of desirable rerum natura)
Make the sample of the various dielectric ceramic compositions shown in the table 2 according to following main points.As mentioned above, the principal constituent composition is defined as α, β, x, y and z especially, and the addition that minor component is formed is defined as a, b, c and d especially.
The sample No.2-3 that exemplifies out sample of the present invention about basic manufacture method describes.
At first, use the BaCO of the raw material of principal constituent
3, Nd (OH)
3And TiO
2, weighing makes as the BaO-Nd after the calcining
2O
3-TiO
2The BaO of compounds, Nd
2O
3And TiO
2X, the y of molar ratio and the principal constituent of the sample No.2-3 that z satisfies following table 2 form the standard shown in the hurdle.That is, weighing makes x=18.5 (mole %), y=15.4 (mole %) and z=66.1 (mole %).
Adding pure water in the raw material of weighing, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.This exsiccant powder is calcined in air (1200 ℃, 4 hours).BaO-Nd after calcining
2O
3-TiO
2It is 25% that compounds adding pure water makes slurry concentration, carries out 16 hours case of wet attrition in ball mill, descends dry 24 hours at 120 ℃ then, makes BaO-Nd
2O
3-TiO
2Type compound powder.
Then, use is as MgO, the SiO of other raw material of principal constituent
2, weighing makes that the mole number of magnesium is 2 times of mole number of silicon, adding pure water, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.
This exsiccant powder is calcined in air (1200 ℃, 3 hours).Adding pure water in the forsterite after calcining, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down, make forsterite powder.
Then, preparation is as ZnO, the B of minor component raw material
2O
3, CuO and MnCO
3
At first, with the above-mentioned BaO-Nd that pulverizes
2O
3-TiO
2The blending ratio of the powder of the above-mentioned forsterite after the powder of compounds and the pulverizing cooperates shown in following table 2, simultaneously for principal constituent, cooperates aZnO, bB
2O
3, the represented minor component ratio of cCuO and dMnO is with the standard shown in the hurdle of the minor component addition of the sample No.2-3 that satisfies table 2, obtains the raw material mixed powder.Also be, weighing makes α=55 (volume %), β=45 (volume %), a=6.0 (weight %), b=4.5 (weight %) and c=3.0 (weight %) and d=0.1 (weight %), it is 25% that the adding pure water makes slurry concentration, in ball mill, carry out 16 hours case of wet attrition, obtained the raw material mixed powder down in dry 24 hours at 120 ℃ then.
Above-mentioned this exsiccant powder that obtains is calcined (750 ℃, 2 hours) once more in air, obtain calcined powder.
Adding pure water in the calcined powder that obtains, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.In the powder that this is pulverized once more, add polyvinyl alcohol water solution and carry out granulation as tackiness agent, be configured as the cylindric of diameter 12mm * height 6mm, in the temperature shown in the hurdle of the firing temperature of the sample No.2-3 of table 2, promptly burn till under 880 ℃ and obtained dielectric ceramic composition in 1 hour.
The surface of the dielectric ceramic composition that cutting so obtains is made the cylinder fritter of diameter 10mm * high 5mm and is made test sample No.2-3.
For the dielectric ceramic composition of sample No.2-3, than DIELECTRIC CONSTANT r, Qf value, and the temperature factor τ f of resonant frequency number measure according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R).Be 8.2GHz to measure frequency number during mensuration, in addition, the resonant frequency number is measured in-40 ℃～85 ℃ temperature range, calculates the temperature factor τ f of resonant frequency number according to the calculating formula of above-mentioned formula (1).
Therefore the mensuration that can realize above-mentioned each rerum natura of sample No.2-3 as shown in table 1 can be learnt and carry out sufficient sintering under 880 ℃ low temperature.Need to prove, the measurement result of each rerum natura, as shown in table 2 is temperature factor τ f=3 (ppm/K) than DIELECTRIC CONSTANT r=25.4, Qf=5420 (GHz), resonant frequency number.
According to the manufacture method of above-mentioned sample No.2-3, make the various samples shown in the table 2.Simultaneously for sintering sample, (scope of measuring frequency number is 7.8～9.3GHz), reach the temperature factor τ f of resonant frequency number to obtain ε r, Qf value.
The result represents in following table 2.
Need to prove that the sample that has " * " in the table 2 is not represented " comparative example ", and represent " reference example "." reference example " is equivalent to above-mentioned the 1st group of invention that the application's inventors finish.
Table 2 (1)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d | εr | Q·f(GHz) | τf(ppm/k) | ||
| *2-1 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | - | 880 | 25.4 | 5044 | 2 |
| *2-2 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | - | 900 | 26.6 | 5124 | 1 |
| 2-3 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.1 | 880 | 25.4 | 5420 | 3 |
| 2-4 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.1 | 900 | 26.5 | 5272 | 3 |
| 2-5 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.5 | 880 | 25.3 | 5748 | 4 |
| 2-6 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.5 | 900 | 26.3 | 5513 | 4 |
| 2-7 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.0 | 880 | 25.2 | 6012 | 5 |
| 2-8 | 55 | 45 | 18.5 | 15.4 | 66.1 | 60 | 4.5 | 3.0 | 1.0 | 900 | 26.1 | 5735 | 5 |
| 2-9 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.5 | 880 | 25.1 | 5992 | 5 |
| 2-10 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.5 | 900 | 26.0 | 5811 | 5 |
| 2-11 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.0 | 880 | 25.0 | 5946 | 5 |
| 2-12 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.0 | 900 | 25.9 | 5752 | 5 |
| 2-13 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 3.0 | 880 | 24.9 | 5876 | 4 |
| 2-14 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 3.0 | 900 | 25.8 | 5701 | 4 |
| 2-15 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 4.5 | 880 | 24.4 | 5368 | 3 |
| 2-16 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 4.5 | 900 | 25.5 | 5197 | 3 |
| 2-17 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 6.0 | 880 | 23.9 | 5096 | 1 |
| 2-18 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 6.0 | 900 | 25.0 | 4915 | 0 |
| *2-19 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 7.5 | 880 | 23.3 | 4587 | -4 |
| *2-20 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 7.5 | 900 | 24.2 | 4394 | -4 |
Table 2 (2)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | Y | z | a | b | c | d | εr | Q·f(GHz) | τf(ppm/k) | ||
| 2-21 | 55 | 45 | 9.0 | 24.4 | 66.6 | 6.0 | 4.5 | 3.0 | 1.5 | 900 | 20.2 | 4451 | -37 |
| *2-22 | 55 | 45 | 9.0 | 24.4 | 66.6 | 6.0 | 4.5 | 3.0 | - | 900 | 20.3 | 4015 | -38 |
| 2-23 | 55 | 45 | 22.0 | 11.4 | 66.6 | 6.0 | 4.5 | 3.0 | 1.5 | 900 | 27.8 | 4500 | -28 |
| *2-24 | 55 | 45 | 22.0 | 11.4 | 66.6 | 6.0 | 4.5 | 3.0 | - | 900 | 28.2 | 4085 | -30 |
| 2-25 | 55 | 45 | 17.0 | 9.0 | 74.0 | 6.0 | 4.5 | 3.0 | 1.5 | 900 | 28.6 | 4509 | 7 |
| *2-26 | 55 | 45 | 17.0 | 9.0 | 74.0 | 6.0 | 4.5 | 3.0 | - | 900 | 28.9 | 4096 | 6 |
| 2-27 | 55 | 45 | 9.4 | 29.0 | 61.6 | 6.0 | 4.5 | 3.0 | 1.5 | 900 | 20.3 | 4597 | -39 |
| *2-28 | 55 | 45 | 9.4 | 29.0 | 61.6 | 6.0 | 4.5 | 3.0 | - | 900 | 20.5 | 4195 | -40 |
| 2-29 | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.1 | 4.5 | 3.0 | 1.5 | 900 | 23.5 | 5147 | 8 |
| *2-30 | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.1 | 4.5 | 3.0 | - | 900 | 23.8 | 4824 | 7 |
| 2-31 | 55 | 45 | 18.5 | 15.4 | 66.1 | 120 | 4.5 | 3.0 | 1.5 | 900 | 25.1 | 4486 | -3 |
| *2-32 | 55 | 45 | 18.5 | 15.4 | 66.1 | 12.0 | 4.5 | 3.0 | - | 900 | 25.5 | 4125 | -5 |
| 2-33 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.1 | 3.0 | 1.5 | 900 | 24.3 | 4921 | 7 |
| *2-34 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.1 | 3.0 | - | 900 | 24.6 | 4700 | 6 |
| 2-35 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 12.0 | 3.0 | 1.5 | 900 | 20.0 | 4440 | 1 |
| *2-36 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 12.0 | 3.0 | - | 900 | 20.3 | 4022 | -2 |
| 2-37 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.1 | 1.5 | 900 | 25.3 | 5401 | 6 |
| *2-38 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.1 | - | 900 | 25.8 | 4922 | 4 |
| 2-39 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 9.0 | 1.5 | 900 | 25.1 | 4574 | -9 |
| *2-40 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 9.0 | - | 900 | 25.5 | 4068 | -11 |
Result as shown in table 2 effect of the present invention as can be known.That is, dielectric ceramic composition of the present invention contains BaO, Nd as principal constituent with the ratio of regulation
2O
3, TiO
2, MgO and SiO
2As principal constituent, contain ZnO, B as the minor component of above-mentioned dielectric ceramic composition with the ratio of regulation
2O
3And CuO, further contain MnO as above-mentioned minor component, can make Ag or be that the conductors such as alloy of principal constituent use reliably as its inner conductor with Ag, can make the coking property under the low temperature more stable and actual.Further, the variation of the resonant frequency number that produces because of temperature variation is reduced, have than BaO-rare-earth oxide-TiO
2The ratio specific inductivity that the ratio specific inductivity of the dielectric ceramic composition of class is lower, and improve dielectric loss.
(3) the 3rd group of invention to the application describes
Below, the 3rd group of preferred forms of inventing implementing the application described.At first, the formation to the 3rd group dielectric ceramic composition describes.
[explanation of the 3rd group dielectric ceramic composition]
Dielectric ceramic composition of the present invention contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent.
Further, dielectric ceramic composition of the present invention with specified amount with respect to principal constituent contain zinc oxide, boron oxide compound, and copper oxide and alkaline-earth oxides class as minor component.
Below, the principal constituent of dielectric ceramic composition of the present invention is formed and minor component is formed and described.At first, the principal constituent composition is described.
(the principal constituent composition is described)
Dielectric ceramic composition of the present invention as mentioned above contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented principal constituent, represent BaO and Nd respectively
2O
3And TiO
2X, y, the z of molar ratio (mole %) be in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %) satisfy the relation of x+y+z=100 (mole %) simultaneously.
In addition, α, the β that represents the volumetric ratio (volume %) of each composition in the above-mentioned principal constituent respectively is in the following ranges:
15 (volume %)≤α≤75 (volume %),
25 (volume %)≤β≤85 (volume %) are satisfied the relation of alpha+beta=100 (volume %) simultaneously,
Obtain containing of BaO proportional x in the scope of above-mentioned condition, the also i.e. scope of 9 (mole %)≤x≤22 (mole %), preferred range is 10 (mole %)≤x≤19 (mole %), more preferably 14 (mole %)≤x≤19 (mole %).
When this BaO contained proportional less than 9 (mole %), dielectric loss increased, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, when the content of BaO surpassed 22 (mole %), low-temperature sintering was impaired, will produce the tendency that can't form dielectric ceramic composition, further because Qf value reduces the problem of power consumption increase that will the generation high frequency devices greatly.
Obtain Nd
2O
3Contain proportional y in the scope of above-mentioned condition, the also i.e. scope of 9 (mole %)≤y≤29 (mole %), preferred range is 9 (mole %)≤y≤22 (mole %), more preferably 12 (mole %)≤y≤17 (mole %).
This Nd
2O
3When containing proportional less than 9 (mole %), dielectric loss increases, and the Qf value will have the tendency of the decline of producing, and the power consumption of high-frequency apparatus increases.On the other hand, Nd
2O
3Content when surpassing 29 (mole %), Qf value will have when producing the tendency that descends, the temperature factor τ f of resonant frequency number also has towards the tendency of negative direction increase.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.
Obtain TiO
2Contain proportional in the scope of above-mentioned condition, the also i.e. scope of 61 (mole %)≤z≤74 (mole %), preferred range is 61.5 (mole %)≤z≤74 (mole %), more preferably 65 (mole %)≤z≤71 (mole %).
This TiO
2When containing proportional less than 61 (mole %), dielectric loss increases, and the Qf value will have when producing the tendency that descends, and the temperature factor τ f of resonant frequency number also has the tendency that increases towards negative direction.Therefore, the power consumption of high frequency devices increases, the also easier change of resonant frequency number of the high frequency devices that is caused by temperature.On the other hand, TiO
2Ratio when surpassing 74 (mole %), low-temperature sintering is impaired, will produce the tendency that can't form dielectric ceramic composition.
In addition, in the composition formula of above-mentioned principal constituent, α, β represent (1) BaO, the Nd of the principal constituent of dielectric ceramic composition of the present invention respectively
2O
3And TiO
2, and (2) MgO and SiO
2Volumetric ratio.
Above-mentioned α, β exist respectively
15 (volume %)≤α≤75 (volume %),
In the scope of 25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %) simultaneously, further, α and β preferred range are 25 (volume %)≤α≤65 (volume %), 35 (volume %)≤β≤75 (volume %), and preferred scope is 35 (volume %)≤α≤55 (volume %), 45 (volume %)≤β≤65 (volume %).
The value of α more than 75 (volume %), during the value less than 25 of β (volume %), the tendency that produce to increase than DIELECTRIC CONSTANT r of above-mentioned dielectric ceramic composition, the temperature factor τ f of resonant frequency number has the tendency that increases towards positive dirction simultaneously.Therefore, owing to produce increase than DIELECTRIC CONSTANT r, with BaO-rare-earth oxide-TiO
2The high characterization of the multi-layered type equipment that the class dielectric ceramic composition engages is difficult to realize, because the temperature factor τ f of resonant frequency number increases the also easier change of the resonant frequency number of the high frequency devices that Yin Wendu causes.In contrast, when the value of the value less than 15 of α (volume %), β surpasses 85 (volume %), the temperature factor τ f of the resonant frequency number of above-mentioned dielectric ceramic composition has the tendency that increases towards negative direction, therefore will produce the problem that the resonant frequency number of the high frequency devices that Yin Wendu causes changes easily.
In the present invention, MgO and the SiO that contains as the part of principal constituent
2Preferably in dielectric ceramic composition, contain with forsterite crystalline form.
In dielectric ceramic composition, whether contain the forsterite crystallization, can confirm by X-ray diffraction device (XRD).
With BaO-Nd
2O
3-TiO
2Compounds is the height ratio specific inductivity that the dielectric ceramic composition of principal constituent has ε r=55～105.On the other hand, the forsterite monomer has the low ratio specific inductivity of ε r=6.8.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can make the ratio specific inductivity of dielectric ceramic composition descend as the principal constituent of the dielectric ceramic composition in the present embodiment.
In addition, with BaO-Nd
2O
3-TiO
2Compounds be the temperature factor τ f of resonant frequency number of the dielectric ceramic composition of principal constituent mostly be on the occasion of.On the other hand, the forsterite monomer has the temperature factor of τ f=-65 (ppm/k) and negative resonant frequency number.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization are as the principal constituent of dielectric ceramic composition, the resonant frequency that makes the temperature factor of positive resonant frequency number and bear is counted temperature factor and is cancelled each other, can be so that the temperature factor of the resonant frequency number of dielectric ceramic composition reaches near zero.Further, by the forsterite crystalline content in the increase and decrease principal constituent, the temperature factor of the resonant frequency number of the dielectric ceramic composition in the adjustable abridged edition embodiment.
In addition, with BaO-Nd
2O
3-TiO
2Compounds is about the Qf=2000～8000GHz of dielectric ceramic composition of principal constituent.On the one hand, the monomeric Qf=200000GHz of forsterite, dielectric loss is little.By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization can obtain the dielectric ceramic composition of low dielectric loss as the principal constituent of dielectric ceramic composition.
The dielectric ceramic composition that present embodiment relates to, for can than main be to burn till under the lower temperature of the fusing point of conductors such as alloy of principal constituent with Ag or with Ag, can constitute by in above-mentioned principal constituent, adding desired minor component.
(minor component is described)
As mentioned above, dielectric ceramic composition of the present invention contain zinc oxide, boron oxide compound, and copper oxide and alkaline-earth metal as minor component.
Above-mentioned minor component is separately with aZnO, bB simultaneously
2O
3, and during cCuO and dRO (R is an alkaline-earth metal) expression, expression with respect to a, the b of the weight ratio of the above-mentioned secondary composition of above-mentioned principal constituent, and c have following relation respectively:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.2 weight %)≤d≤5.0 (weight %).
That is, obtain, be preferably 0.5 (weight %)≤a≤9.0 (weight %), more preferably 1.0 (weight %)≤a≤7.0 (weight %) with respect to proportionally being scaled 0.1 (weight %)≤a≤12.0 (weight %) containing of the zinc oxide of principal constituent with ZnO.
Proportional when converting less than 0.1 (weight %) with ZnO with respect to containing of the zinc oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 12.0 (weight %) with ZnO containing of the zinc oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
In addition, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Be scaled 0.1 (weight %)≤b≤12.0 (weight %), be preferably 0.5 (weight %)≤b≤9.0 (weight %), more preferably 1.0 (weight %)≤b≤7.0 (weight %).
Proportional with respect to containing of the zinc oxide of principal constituent with B
2O
3Conversion is during less than 0.1 (weight %), and the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, proportional with respect to containing of the boron oxide compound of principal constituent with B
2O
3Convert when surpassing 12.0 (weight %), dielectric loss increases, and the Qf value has the tendency of decline.
In addition,, be preferably 0.5 (weight %)≤c≤6.0 (weight %), further be preferably 1.0 (weight %)≤c≤4.0 (weight %) with respect to proportionally being scaled 0.1 (weight %)≤c≤9.0 (weight %) containing of the copper oxide of principal constituent with CuO.
Proportional when converting less than 0.1 (weight %) with CuO with respect to containing of the copper oxide of principal constituent, the low-temperature sintering effect of dielectric ceramic composition will produce inadequate tendency.On the other hand, with respect to proportionally converting when surpassing 9.0 (weight %) with CuO containing of the copper oxide of principal constituent, dielectric loss increases, and the Qf value has the tendency of decline.
In the present invention, for the low-temperature sintering effect that further improves dielectric ceramic composition (can in the effect of lower sintering temperature), also further in above-mentioned minor component, add alkaline-earth metals oxide.Promptly, with respect to proportionally being scaled 0.2 (weight %)≤d≤5.0 (weight %) containing of the alkaline-earth metals oxide of principal constituent with RO (R is an alkaline-earth metal), be preferably 0.5 (weight %)≤d≤3.5 (weight %), further be preferably 1.0 (weight %)≤d≤3.0 (weight %).
R as alkaline-earth metal can enumerate Ba, Sr, Ca as preferred example.Also can mix them uses more than 2 kinds.
Proportional when converting less than 0.2 (weight %) with respect to containing of the alkaline-earth oxides class of principal constituent with RO (R is an alkaline-earth metal), can't expect to obtain further low-temperature sintering effect.On the other hand, with respect to proportionally converting when surpassing 5.0 (weight %) with RO containing of the alkaline-earth metals oxide of principal constituent, though can obtain the effect of low-temperature sintering, dielectric loss increases, and the Qf value has the tendency of decline.
Need to prove, when using Ba, with respect to proportionally converting preferably in the scope of 0.5 (weight %)≤d≤3.5 (weight %) containing of the alkaline-earth metals oxide of principal constituent with BaO as alkaline-earth metal R.In addition, when using Sr, with respect to proportionally converting preferably in the scope of 0.4 (weight %)≤d≤2.5 (weight %) containing of the alkaline-earth metals oxide of principal constituent with SrO as alkaline-earth metal R.When using Ca, with respect to proportionally converting preferably in the scope of 0.2 (weight %)≤d≤1.5 (weight %) containing of the alkaline-earth metals oxide of principal constituent with CaO as alkaline-earth metal R.
Dielectric ceramic composition among the present invention contains BaO, Nd
2O
3, TiO
2, MgO and SiO
2As principal constituent, contain ZnO, B
2O
3, CuO and RO (R is an alkaline-earth metal) be as minor component, particularly by containing MgO and SiO
2(particularly forsterite crystallization) can make rare-earth oxide-TiO than permittivity ratio BaO-as principal constituent
2The dielectric ceramic composition of class generally lower than specific inductivity.
And by containing RO (R is an alkaline-earth metal) as minor component, can realization and Ag or burn till simultaneously as the conductors such as alloy of principal constituent with Ag, further improve low-temperature sintering.
In addition, the material of the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class is similar, therefore, burns till contraction behavior and linear expansivity and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition unanimity of class.Also promptly, even dielectric ceramic composition of the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages and burns till, and makes multi-layered type equipment, also is difficult for producing on the junction surface defective.Therefore, the dielectric ceramic composition among the present invention and BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of class engages, and can make the multi-layered type equipment of high characteristic.
Need to prove that dielectric ceramic composition of the present invention also can contain other compound and element in the scope that can bring into play purpose of the present invention and effect.Particularly, dielectric loss can be suppressed at less degree by containing Mn oxide with respect to principal constituent.
Dielectric ceramic composition of the present invention as mentioned above must be that the conductors such as alloy of principal constituent are as inner conductor with the Ag of cheapness or with Ag for miniature device is provided with low price.Therefore, require to have can be in dielectric ceramic composition as internal electrode use the fusing point of conductor below burn till low-temperature sintering.In addition, be affected, so firing temperature is 800 ℃～950 ℃, is preferably 850 ℃～900 ℃ according to the dielectric characteristics of the different dielectric ceramic compositions of firing temperature.
In addition, the dielectric loss for the dielectric ceramic composition of the key property among the present invention describes as follows.
When applying alternating-current on the ideal dielectric medium, electric current and voltage have the phase differential of 90 degree.But, alternative frequency number increases when becoming high frequency, the orientation of dielectric electropolarization or polar molecule can not be followed the variation of high frequency electric field, and perhaps because electronics or ionic conduct electricity gamma flux density produce phase delay with respect to electric field, electric current and voltage have the phase place beyond 90 degree.Dielectric loss is the phenomenon of the part of above-mentioned high-frequency energy with the form release of heat.The size of dielectric loss is with Q=reciprocal (Q=1/tan δ) expression of the tangent tan δ of the loss angle δ of the difference between the phase differential of the phase phase differential of the electric current that shows and voltage and ideal electric current and voltage.In the evaluation of the dielectric loss of the dielectric ceramic composition among the present invention, use the value of the long-pending Qf of above-mentioned Q and resonant frequency number.If dielectric loss reduces, it is big that Qf becomes, and if dielectric loss increases, then Qf diminishes.Dielectric loss means the power consumption of high-frequency apparatus, therefore requires the big dielectric ceramic composition of Qf value.Further, during multi-layered type equipment, owing to the reason of high characterization requires to reduce dielectric loss, preferably more than 4000GHz, the value of Qf is more preferably more than 4500GHz for the value of Qf.
In addition, one of purpose of the present invention is to make and the BaO-rare-earth oxide-TiO with height ratio specific inductivity
2The formation of the multi-layered type equipment that the dielectric ceramic composition of class engages becomes possibility.Therefore, provide than BaO-rare-earth oxide-TiO
2The dielectric ceramic composition of the ratio specific inductivity that the ratio specific inductivity of the dielectric ceramic composition of class is lower also becomes problem.There is report to point out BaO-rare-earth oxide-TiO
2The ratio specific inductivity of the dielectric ceramic composition of class is 50～105, the requiring below 50 than DIELECTRIC CONSTANT r of dielectric ceramic composition of the present invention.Further, owing to be used for the multi-layered type equipment of high characteristic, preferably below 40, more preferably below 30, be more preferably 20～30 especially than DIELECTRIC CONSTANT r than DIELECTRIC CONSTANT r.
In addition, the temperature factor τ f (ppm/K) for as the resonant frequency number of the dielectric ceramic composition of the key property among the present invention carries out following explanation.
The temperature factor τ f (ppm/K) of the resonant frequency number of dielectric ceramic composition calculates by following formula (1).
τ f=[f
T-f
Ref/ f
Ref(T-T
Ref)] * 1000000 (ppm/K) (formula 1)
F herein
TResonant frequency number (kHz) in the expression temperature T, f
RefExpression reference temperature T
RefIn resonant frequency number (kHz).
The size of the absolute value of the temperature factor τ f of resonant frequency number means the size of variable quantity of the resonant frequency number of the dielectric ceramic composition that relative temperature changes.Because high frequency equipment such as electric capacity, dielectric filter must reduce the variation of the resonant frequency number that Yin Wendu produces, therefore require to reduce the absolute value of temperature factor τ f of the resonant frequency number of the dielectric ceramic composition among the present invention.
In addition, when utilizing dielectric ceramic composition among the present invention as dielectric resonator, in order further to reduce the temperature variation of resonant frequency, the temperature factor τ f of resonant frequency number must be in the scope of-40 (ppm/K)～+ 40 (ppm/K).Further, in order to form the multi-layered type equipment of high characteristic, temperature factor τ f is preferably in the scope of-25 (ppm/K)～+ 25 (ppm/K), more preferably in the scope of-10 (ppm/K)～+ 10 (ppm/K).
In addition, the evaluation of the low-temperature sintering characteristic of dielectric ceramic composition can be burnt till according to slow reduction firing temperature, whether has carried out sintering and judge on the level of the dielectric medium high frequency characteristic that can measure expectation.In addition, the evaluation of the dielectric characteristics of dielectric ceramic composition can followingly be carried out, the variation of the resonant frequency number that dielectric loss, temperature variation cause (temperature factor of resonant frequency number) and than specific inductivity is estimated according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R).
[explanation of the manufacture method of dielectric ceramic composition]
Below, the manufacture method of the dielectric ceramic composition among the present invention is described.
The manufacture method of dielectric ceramic composition of the present invention is to the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, boracic raw material, copper-containing raw material and contain the alkaline-earth metal raw material and burn till, to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-RO (R is an alkaline-earth metal) class dielectric ceramic composition is used forsterite (2MgOSiO
2) powder is as above-mentioned magnesium raw material and the above-mentioned silicon-containing material of containing.
Use oxide compound and/or by burning till the compound that becomes oxide compound, as the production of raw material for use of dielectric ceramic composition of the present invention.As becoming the compound of oxide compound example carbonate, nitrate, oxalate, oxyhydroxide, sulfide, organometallic compound etc. are arranged by burning till.
One of embodiment of the manufacture method of the dielectric ceramic composition shown in Fig. 3 among the present invention.
Below, based on Fig. 3 the manufacture method of dielectric ceramic composition of the present invention is described.
At first, prepare for example barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide as the part of raw materials of principal constituent, the specified amount of weighing simultaneously also mixes, and calcines.
Above-mentioned mixing is at composition formula xBaOyNd
2O
3ZTiO
2X, the y of molar ratio and scope that z satisfies the above-mentioned relation composition formula in mix.
The mixing of barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
Raw materials mixed at 100 ℃～200 ℃, preferably 120 ℃～140 ℃ following dryings about 12～36 hour, then calcined thereafter.
Calcining is carried out BaO-Nd for the mixing raw material by barium carbonate, neodymium hydroxide Neodymium trihydroxide and titanium oxide
2O
3-TiO
2The synthetic operation of compounds, calcining temperature are 1100 ℃～1500 ℃, preferably carry out 1～24 hour calcining under 1100 ℃～1350 ℃.
With synthetic BaO-Nd
2O
3-TiO
2Compounds is pulverized dry to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain BaO-Nd
2O
3-TiO
2The powder of compounds.
Then, prepare as other raw materials of principal constituent for example magnesium oxide and silicon oxide, the weighing specified amount also mixes, and calcines.The mixing of magnesium oxide and silicon oxide can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
Raw materials mixed at 100 ℃～200 ℃, preferably 120 ℃～140 ℃ following dryings about 12～36 hour, then calcined thereafter.
Calcining is carried out forsterite crystalline synthetic operation for the mixture by magnesium oxide and silicon oxide, preferably at 1100 ℃～1500 ℃, more preferably carries out 1～24 hour calcining under 1100 ℃～1350 ℃ treatment temp.
By containing BaO-Nd
2O
3-TiO
2Compounds and forsterite crystallization be as principal constituent, by forsterite crystalline effect, can reduce dielectric ceramic composition than DIELECTRIC CONSTANT r, the temperature factor that makes the resonant frequency number can reduce dielectric loss near zero.Therefore, in order to increase the additive effect of forsterite, be necessary to reduce the unreacted above-mentioned raw materials that does not synthesize forsterite, it is 2 times of mole number of silicon that the mixing of above-mentioned raw materials preferably makes the mole number of magnesium.
Synthetic forsterite is pulverized after drying to make powder.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.
The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.By as mentioned above, can obtain forsterite powder.
Can be not by by magnesium raw material, the silicon-containing material synthetic forsterite of containing shown in Figure 3, pulverize the back and obtain forsterite powder, and use commercially available forsterite.That is, also can be with commercially available forsterite, for example using, ball mill by 100 ℃～200 ℃, preferably obtained forsterite powder in dry about 12～36 hours down at 120 ℃～140 ℃ with the grinding mode pulverizing of pure water, ethanol equal solvent.
Below, mix above-mentioned BaO-Nd
2O
3-TiO
2The powder of the powder of compounds and above-mentioned forsterite and for the composition that satisfies above-mentioned minor component in specialized range the zinc oxide of weighing, boron oxide compound, copper oxide and alkaline earth metals carbonate, obtain the raw material mixed powder.
Mixing can be adopted hybrid modes such as dry type mixing, wet mixing, and for example using, ball mill carries out with the hybrid mode of pure water, ethanol equal solvent.Mixing time is to get final product about 4～24 times.
After mixing end, that raw materials mixed is at 100 ℃～200 ℃, preferably following dry about 12～36 hours at 120 ℃～140 ℃.
Then, the raw material mixed powder is calcined about 1～10 hour under the temperature below the firing temperature, for example 700 ℃～800 ℃ once more.Because this calcining carries out at low temperatures, can forsterite not the fused crystal habit in dielectric ceramic composition, contain forsterite.Then, the raw material mixed powder after the calcining is pulverized and drying.Pulverize and to be grinding modes such as dry type pulverizing, case of wet attrition, use ball mill for example to carry out with the grinding mode of pure water, ethanol equal solvent.The pulverizing time is to get final product about 4～24 times.The drying of the powder of pulverizing preferably got final product in drying under 120 ℃～140 ℃ the treatment temp at 100 ℃～200 ℃ in about 12～36 hours.Like this by calcining once more and pulverize, can be with principal constituent and minor component homogenizing, can realize the homogenizing of the material of the dielectric ceramic composition in the present embodiment that the back operation makes.
For the powder that obtains as mentioned above, behind the organic binder bonds such as mix polyethylene alcohols, acrylic acid or the like, ethyl cellulose class, be configured as desired shape, this shaping thing is burnt till sintering.Moulding method also can adopt dry pressing methods such as press molding, according to needed shape appropriate selection manufacturing process except wet formings such as plate (SHEET) method or print process.In addition, burn till preferably and for example carrying out under the airborne oxygen atmosphere, firing temperature for the Ag that uses as internal electrode or with below the fusing point of Ag as the conductors such as alloy of principal constituent, for example 800 ℃～950 ℃, be preferably 850 ℃～900 ℃.
At multi-layered type equipment by the multilayer ceramic substrate manufacturing that a plurality of ceramic layers of the integrated assembly productions of dielectric equipment such as electric capacity, inducer is constituted in inside.Several the dielectric characteristicies green sheet of different stupaliths is mutually prepared in multilayer ceramic substrate such as following manufacturing, and at the conductor of interface configurations formation internal electrode, or the formation through hole is made laminated burning till simultaneously.By the green sheet and present known common BaO-Nd that is shaped with dielectric ceramic composition of the present invention
2O
3-TiO
2The green sheet phase lamination that the class dielectric ceramic composition is shaped can be made the multilayer ceramic substrate that uses dielectric ceramic composition of the present invention.
Below, enumerate specific embodiment, the present invention will be described in detail.
[experimental example 3-1]
(manufacturing of sample and the measuring method of desirable rerum natura)
Make the sample of the various dielectric ceramic compositions shown in the table 3 according to following main points.As mentioned above, the principal constituent composition is defined as α, β, x, y and z especially, and the addition that minor component is formed is defined as a, b, c and d or R especially.
The sample No.3-8 that exemplifies out sample of the present invention about basic manufacture method describes.
At first, use the BaCO of the raw material of principal constituent
3, Nd (OH)
3And TiO
2, weighing makes as the BaO-Nd after the calcining
2O
3-TiO
2The BaO of compounds, Nd
2O
3And TiO
2X, the y of molar ratio and the principal constituent of the sample No.3-8 that z satisfies following table 3 form the standard shown in the hurdle.That is, weighing makes x=18.5 (mole %), y=15.4 (mole %) and z=66.1 (mole %).
Adding pure water in the raw material of weighing, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.This exsiccant powder is calcined in air (1200 ℃, 4 hours).BaO-Nd after calcining
2O
3-TiO
2It is 25% that compounds adding pure water makes slurry concentration, carries out 16 hours case of wet attrition in ball mill, descends dry 24 hours at 120 ℃ then, makes BaO-Nd
2O
3-TiO
2Type compound powder.
Then, use is as MgO, the SiO of other raw material of principal constituent
2, weighing makes that the mole number of magnesium is 2 times of mole number of silicon, adding pure water, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.
This exsiccant powder is calcined in air (1200 ℃, 3 hours).Adding pure water in the forsterite after calcining, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down, make forsterite powder.
Then, preparation is as ZnO, the B of minor component raw material
2O
3, CuO and BaCO
3
At first, with the above-mentioned BaO-Nd that pulverizes
2O
3-TiO
2The blending ratio of the powder of the above-mentioned forsterite after the powder of compounds and the pulverizing cooperates shown in following table 2, simultaneously for principal constituent, cooperates aZnO, bB
2O
3, the represented minor component ratio of cCuO and dBaO is with the standard shown in the hurdle of the minor component addition of the sample No.3-8 that satisfies table 3, obtains the raw material mixed powder.Also be, weighing makes α=55 (volume %), β=45 (volume %), a=6.0 (weight %), b=4.5 (weight %) and c=3.0 (weight %) and d=0.69 (weight %), it is 25% that the adding pure water makes slurry concentration, in ball mill, carry out 16 hours case of wet attrition, obtained the raw material mixed powder down in dry 24 hours at 120 ℃ then.
Above-mentioned this exsiccant powder that obtains is calcined (750 ℃, 2 hours) once more in air, obtain calcined powder.
Adding pure water in the calcined powder that obtains, to make slurry concentration be 25%, carries out 16 hours case of wet attrition in ball mill, then 120 ℃ dry 24 hours down.In the powder that this is pulverized once more, add polyvinyl alcohol water solution and carry out granulation as tackiness agent, be configured as the cylindric of diameter 12mm * height 6mm, in the temperature shown in the hurdle of the firing temperature of the sample No.3-8 of table 1, promptly burn till under 870 ℃ and obtained dielectric ceramic composition in 1 hour.
The surface of the dielectric ceramic composition that cutting so obtains is made the cylinder fritter of diameter 10mm * high 5mm and is made test sample No.3-8.
For the dielectric ceramic composition of sample No.3-8, than DIELECTRIC CONSTANT r, Qf value, and the temperature factor τ f of resonant frequency number measure according to Japanese Industrial Standards' " マ イ Network ロ ripple with Off ア イ Application セ ラ ミ Star ク ス Lure Electricity characteristic Try test method " (1,627 1996 years of JIS R).Be 8.2GHz to measure frequency number during mensuration, in addition, the resonant frequency number is measured in-40 ℃～85 ℃ temperature range, calculates the temperature factor τ f of resonant frequency number according to the calculating formula of above-mentioned formula (1).
Sample No.3-8 is as shown in table 3, can carry out the mensuration of above-mentioned each rerum natura as can be known, has carried out sufficient sintering under 870 ℃ low temperature.Need to prove, the measurement result of each rerum natura, as shown in table 3 is temperature factor τ f=-2 (ppm/K) than DIELECTRIC CONSTANT r=25.2, Qf=4957 (GHz), resonant frequency number.
According to the manufacture method of above-mentioned sample No.3-8, make the various samples shown in the table 3.In the sample group of definite composition scope, obtain the low-temperature sintering (having the sample of the record of " can not measure " to represent in the table 3) that in whole firing temperature (850～910 ℃) scope, can carry out which kind of degree not at the horizontal sintering that can carry out dielectric medium high frequency characteristic measurement, simultaneously for sintering sample, (scope of measuring frequency number is 7.6～8.2GHz), reach the temperature factor τ f of resonant frequency number to obtain ε r, Qf value.
The result represents in following table 3.Need to prove that the sample that has " * " in the table 3 is not represented " comparative example ", and represent " reference example "." reference example " is equivalent to above-mentioned the 1st group of invention that the application's inventors finish.
In addition, the sample that has the mark of " * * " in the table 3 is represented " comparative example ".
Table 3 (1)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d(R) | εr | Q·f(GHz) | τf(ppm/k) | ||
| *3-1 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | -- | 850 | Can not measure | ||
| *3-2 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | -- | 870 | Can not measure | ||
| *3-3 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | -- | 880 | 25.4 | 5044 | 2 |
| *3-4 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | -- | 890 | 25.9 | 4998 | 1 |
| *3-5 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | -- | 910 | 26.9 | 4982 | 0 |
| 3-6 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.69(Ba) | 850 | Can not measure | ||
| 3-7 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.69(Ba) | 860 | Can not measure | ||
| 3-8 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.69(Ba) | 870 | 25.2 | 4957 | -2 |
| 3-9 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.69(Ba) | 890 | 27.0 | 4901 | -2 |
| 3-10 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.69(Ba) | 910 | 27.7 | 4843 | -3 |
| 3-11 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.72(Ba) | 850 | Can not measure | ||
| 3-12 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.72(Ba) | 860 | 25.9 | 4551 | -4 |
| 3-13 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.72(Ba) | 870 | 27.2 | 4847 | -5 |
| 3-14 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.72(Ba) | 890 | 28.0 | 4794 | -5 |
| 3-15 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.72(Ba) | 910 | 28.3 | 4708 | -5 |
| 3-16 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 3.44(Ba) | 850 | 27.9 | 4398 | -6 |
| 3-17 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 45 | 3.0 | 3.44(Ba) | 860 | 28.2 | 4528 | -6 |
| 3-18 | 55 | 45 | 18.5 | 15.4 | 66.1 | 60 | 4.5 | 3.0 | 3.44(Ba) | 870 | 28.3 | 4485 | -7 |
| 3-19 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 3.44(Ba) | 890 | 28.4 | 4467 | -7 |
| 3-20 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 3.44(Ba) | 910 | 28.5 | 4422 | -8 |
| * 3-21 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 5.16(Ba) | 850 | 28.6 | 3776 | -11 |
| * 3-22 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 5.16(Ba) | 860 | 28.7 | 3744 | -11 |
Table 3 (2)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d(R) | εr | Q·f(GHz) | τf(ppm/k) | ||
| 3-23 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.47(Sr) | 850 | Can not measure | ||
| 3-24 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.47(Sr) | 860 | Can not measure | ||
| 3-25 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.47(Sr) | 870 | 25.5 | 4812 | 2 |
| 3-26 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.47(Sr) | 890 | 27.3 | 4877 | 2 |
| 3-27 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.47(Sr) | 910 | 27.8 | 4820 | 2 |
| 3-28 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.16(Sr) | 850 | Can not measure | ||
| 3-29 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.16(Sr) | 860 | 27.0 | 4628 | 6 |
| 3-30 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.16(Sr) | 870 | 28.1 | 4773 | 5 |
| 3-31 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.16(Sr) | 890 | 28.6 | 4711 | 5 |
| 3-32 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.16(Sr) | 910 | 28.9 | 4650 | 5 |
| 3-33 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.33(Sr) | 850 | 28.5 | 4199 | 9 |
| 3-34 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.33(Sr) | 860 | 29.0 | 4393 | 9 |
| 3-35 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.33(Sr) | 870 | 29.2 | 4423 | 8 |
| 3-36 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.33(Sr) | 890 | 29.3 | 4376 | 8 |
| 3-37 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 2.33(Sr) | 910 | 29.4 | 4389 | 8 |
| 3-38 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.25(Ca) | 850 | Can not measure | ||
| 3-39 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.25(Ca) | 860 | Can not measure | ||
| 3-40 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.25(Ca) | 870 | 26.6 | 4800 | 1 |
| 3-41 | 55 | 45 | 18.5 | 15.4 | 66.1 | 60 | 4.5 | 3.0 | 0.25(Ca) | 890 | 28.3 | 4834 | 1 |
| 3-42 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.25(Ca) | 910 | 28.8 | 4795 | 1 |
Table 3 (3)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d(R) | εr | Q·f(GHz) | τf(ppm/k) | ||
| 3-43 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 850 | Can not measure | ||
| 3-44 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 860 | 28.0 | 4577 | 4 |
| 3-45 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 29.2 | 4698 | 3 |
| 3-46 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 890 | 29.4 | 4642 | 3 |
| 3-47 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 910 | 29.5 | 4605 | 3 |
| 3-48 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.26(Ca) | 850 | 29.0 | 4123 | 10 |
| 3-49 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.26(Ca) | 860 | 29.5 | 4251 | 10 |
| 3-50 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.26(Ca) | 870 | 29.6 | 4247 | 9 |
| 3-51 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.26(Ca) | 890 | 29.7 | 4258 | 9 |
| 3-52 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 1.26(Ca) | 910 | 29.7 | 4271 | 9 |
Result by table 3 can clear and definite effect of the present invention.Promptly, firing temperature with sample No.*3-3 (reference example) is judged as benchmark value for 880 ℃, by contain alkaline-earth metals oxide with specified amount, can be that firing temperature drops to 870 ℃ (sample No.3-8), 860 ℃ (sample No.3-12), 850 ℃ (sample No.3-16), 870 ℃ (sample No.3-25), 860 ℃ (sample No.3-29), 850 ℃ (sample No.3-33), 870 ℃ (sample No.3-40), 860 ℃ (sample No.3-44), 850 ℃ (sample No.3-48) among the present invention as minor component.
In addition, sample No.*3-21 (comparative example) and sample No.*3-22 (comparative example), though can make firing temperature drop to 850 ℃ or 860 ℃, the addition of alkaline-earth metals oxide is too much, Qf value no show 4000GHz produces the big problem of dielectric loss.
[experimental example 3-2]
Below, according to making the sample of the described various dielectric ceramic compositions of subordinate's table 4 with the same manufacture method of above-mentioned experimental example 3-1.
In table 4, defined α, β, x, y and the z of principal constituent composition and represented a, the b of the addition of minor component composition, the value of c to make various changes special, these are changed the influence that above-mentioned parameter is produced investigate experiment.Need to prove that use Ca as alkaline-earth metal R, it contains proportional d and is decided to be 0.63 weight %.
The result represents in following table 4.Need to prove, in the table 4 expression firing temperature (℃) value be 870 ℃ without exception.And the sample that has " * * " in the table 4 is represented " comparative example ".
Table 4 (1)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d(R) | εr | Q·f(GHz) | τf(ppm/k) | ||
| * 3-53 (comparison) | 5 | 95 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 9.9 | 7428 | -41 |
| 3-54 | 15 | 85 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 10.9 | 7159 | -35 |
| 3-55 | 25 | 75 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 14.3 | 6488 | -27 |
| 3-56 | 35 | 65 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 18.3 | 5961 | -18 |
| 3-57 | 45 | 55 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 22.5 | 5408 | -7 |
| 3-58 | 65 | 35 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 38.8 | 4644 | 17 |
| 3-59 | 75 | 25 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 49.8 | 4474 | 35 |
| * 3-60 (comparison) | 85 | 15 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 57.6 | 4316 | 47 |
| * 3-61 (comparison) | 55 | 45 | 6.7 | 26.7 | 66.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 21.1 | 2998 | -21 |
| 3-62 | 55 | 45 | 11.7 | 21.7 | 66.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 23.7 | 4010 | -35 |
| 3-63 | 55 | 45 | 16.7 | 16.7 | 66.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 27.9 | 6082 | -33 |
| * 3-64 (comparison) | 55 | 45 | 23.7 | 12.7 | 63.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | Can not measure | ||
| * 3-65 (comparison) | 55 | 45 | 18.7 | 7.7 | 73.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 31.7 | 2856 | 18 |
| 3-66 | 55 | 45 | 16.7 | 15.7 | 67.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 28.3 | 6172 | -9 |
| 3-67 | 55 | 45 | 16.7 | 18.7 | 64.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 25.4 | 5342 | -24 |
| * 3-68 (comparison) | 55 | 45 | 16.7 | 30.7 | 52.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 19.4 | 2753 | -37 |
| * 3-69 (comparison) | 55 | 45 | 16.7 | 26.7 | 56.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 19.5 | 2982 | -35 |
| 3-70 | 55 | 45 | 16.5 | 21.5 | 62.0 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 21.3 | 5025 | -31 |
| 3-71 | 55 | 45 | 18.7 | 11.7 | 69.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 27.0 | 6838 | 5 |
| * 3-72 (comparison) | 55 | 45 | 11.7 | 11.7 | 76.6 | 6.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | Can not measure | ||
Table 4 (2)
| Sample No. | Principal constituent is formed | The minor component addition | Firing temperature (℃) | Dielectric medium high frequency characteristic | |||||||||
| α | β | x | y | z | a | b | c | d(R) | εr | Q·f(GHz) | τf(ppm/k) | ||
| * 3-73 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.05 | 4.5 | 3.0 | 0.63(Ca) | 870 | Can not measure | ||
| 3-74 | 55 | 45 | 18.5 | 15.4 | 66.1 | 0.5 | 4.5 | 3.0 | 0.63(Ca) | 870 | 27.4 | 4812 | 8 |
| 3-75 | 55 | 45 | 18.5 | 15.4 | 66.1 | 3.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 29.3 | 4887 | 6 |
| 3-76 | 55 | 45 | 18.5 | 15.4 | 66.1 | 9.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 28.5 | 4752 | 0 |
| * 3-77 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 16.0 | 4.5 | 3.0 | 0.63(Ca) | 870 | 27.0 | 3604 | -6 |
| * 3-78 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.05 | 3.0 | 0.63(Ca) | 870 | Can not measure | ||
| 3-79 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 0.5 | 3.0 | 0.63(Ca) | 870 | 27.3 | 4597 | 7 |
| 3-80 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 3.0 | 3.0 | 0.63(Ca) | 870 | 29.3 | 4763 | 5 |
| 3-81 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 9.0 | 3.0 | 0.63(Ca) | 870 | 24.2 | 4522 | 1 |
| * 3-82 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 16.0 | 3.0 | 0.63(Ca) | 870 | 19.5 | 3370 | -2 |
| * 3-83 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.05 | 0.63(Ca) | 870 | Can not measure | ||
| 3-84 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 0.5 | 0.63(Ca) | 870 | 28.3 | 4848 | 5 |
| 3-85 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 1.5 | 0.63(Ca) | 870 | 29.2 | 5068 | 3 |
| 3-86 | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 6.0 | 0.63(Ca) | 870 | 28.2 | 4671 | -4 |
| * 3-87 (comparison) | 55 | 45 | 18.5 | 15.4 | 66.1 | 6.0 | 4.5 | 12.0 | 0.63(Ca) | 870 | 27.4 | 3055 | -13 |
Result by above-mentioned table 3 and table 4 can clear and definite effect of the present invention.
In addition, can clear and definite effect of the present invention by above-mentioned each result of experiment.That is, the present invention contains BaO, Nd by the ratio with regulation
2O
3, TiO
2, MgO and SiO
2As the principal constituent of dielectric ceramic composition, contain ZnO, B with the ratio of stipulating
2O
3And CuO is as the minor component of above-mentioned dielectric ceramic composition, further contain alkaline-earth metals oxide RO (R: alkaline-earth metal) as above-mentioned minor component, can obtain the more stable and reliable product of coking property at low temperatures, with use Ag reliably or with Ag as the conductors such as alloy of principal constituent as inner conductor.Further, can also obtain the variation of the resonant frequency number that temperature variation causes little, have than BaO-rare-earth oxide-TiO
2The ratio specific inductivity of class dielectric ceramic composition lower than dielectric constant dielectric ceramic composition, and provide suitable dielectric ceramic composition for forming multi-layered type equipment.
Industrial applicability
Dielectric ceramic composition of the present invention can be used in the field of various electronic equipment industries widely.
Claims (15)
1. dielectric ceramic composition is characterized by, and contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %), and satisfy the relation of x+y+z=100 (mole %), represent that α, the β of the volumetric ratio of each composition in the described principal constituent is in the following ranges respectively:
5 (volume %)≤α＜85 (volume %),
15 (volume %)＜β≤95 (volume %), and satisfy the relation of alpha+beta=100 (volume %), with respect to described principal constituent, contain zinc oxide, boron oxide compound, and copper oxide as minor component, described minor component is separately with aZnO, bB simultaneously
2O
3, and cCuO when representing, expression with respect to a, the b of the weight ratio of the described secondary composition of described principal constituent, and c have following relation respectively:
(0.05 weight %)＜a≤17.0 (weight %),
(0.05 weight %)＜b≤17.0 (weight %),
(0.05 weight %)＜c≤14.0 (weight %).
2. the described dielectric ceramic composition of claim 1, it contains forsterite (2MgOSiO
2) crystallization.
3. the described dielectric ceramic composition of claim 1, it has than specific inductivity is rerum natura below 50.
4. the manufacture method of dielectric ceramic composition is with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, the boracic raw material, and copper-containing raw material burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO class dielectric ceramic composition is characterized by and uses forsterite (2MgOSiO
2) powder is as described magnesium raw material and the described silicon-containing material of containing.
5. dielectric ceramic composition is characterized by, and contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %), and satisfy the relation of x+y+z=100 (mole %), represent that α, the β of the volumetric ratio of each composition in the described principal constituent is in the following ranges respectively:
15 (volume %)≤α＜75 (volume %),
25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %), with respect to described principal constituent, containing zinc oxide, boron oxide compound, copper oxide and Mn oxide as minor component, these minor components are separately with aZnO, bB simultaneously
2O
3, when cCuO and dMnO represent, expression has following relation respectively with respect to a, b, c and the d of the weight ratio of the described secondary composition of described principal constituent:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.01 weight %)≤d≤6.5 (weight %).
6. the described dielectric ceramic composition of claim 5, it contains forsterite (2MgOSiO
2) crystallization.
7. the described dielectric ceramic composition of claim 5, it has than specific inductivity is rerum natura below 50.
8. the manufacture method of dielectric ceramic composition is with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, boracic raw material, copper-containing raw material and contain the manganese raw material and burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-MnO class dielectric ceramic composition is characterized by and uses forsterite (2MgOSiO
2) powder is as described magnesium raw material and the described silicon-containing material of containing.
9. dielectric ceramic composition is characterized by, and contains composition formula { α (xBaOyNd
2O
3ZTiO
2)+β (2MgOSiO
2) represented composition is principal constituent, expression BaO and Nd
2O
3And TiO
2X, y, the z of molar ratio be in respectively in the following scope:
9 (mole %)≤x≤22 (mole %),
9 (mole %)≤y≤29 (mole %),
61 (moles %)≤z≤74 (mole %), and satisfy the relation of x+y+z=100 (mole %), represent that α, the β of the volumetric ratio of each composition in the described principal constituent is in the following ranges respectively:
15 (volume %)≤α＜75 (volume %),
25 (volume %)≤β≤85 (volume %), and satisfy the relation of alpha+beta=100 (volume %), with respect to described principal constituent, contain zinc oxide, boron oxide compound, copper oxide and alkaline-earth metals oxide as minor component, these minor components are separately with aZnO, bB simultaneously
2O
3, cCuO and dRO (R represents alkaline-earth metal) expression, expression has following relation respectively with respect to a, b, c and the d of the weight ratio of the described secondary composition of described principal constituent:
(0.1 weight %)≤a≤12.0 (weight %),
(0.1 weight %)≤b≤12.0 (weight %),
(0.1 weight %)≤c≤9.0 (weight %),
(0.2 weight %)≤d≤5.0 (weight %).
10. the described dielectric ceramic composition of claim 9, described alkaline-earth metals oxide is at least a kind that is selected among Ba, Sr, the Ca.
11. the described dielectric ceramic composition of claim 9, it contains forsterite (2MgOSiO
2) crystallization.
12. the described dielectric ceramic composition of claim 9 has firing temperature and is the rerum natura below 870 ℃.
13. the described dielectric ceramic composition of claim 9, it has than specific inductivity is rerum natura below 50.
14. the described dielectric ceramic composition of claim 9, its have than specific inductivity be 20～30, the Qf value is the rerum natura more than the 4000GHz.
15. the manufacture method of dielectric ceramic composition is with the baric raw material, contain neodymium raw material, titaniferous materials, contain magnesium raw material, silicon-containing material, contain the zinc raw material, boracic raw material, copper-containing raw material and contain the alkaline-earth metal raw material and burn till to make BaO-Nd
2O
3-TiO
2-MgO-SiO
2-ZnO-B
2O
3The method of-CuO-RO (R is an alkaline-earth metal) class dielectric ceramic composition is characterized by and uses forsterite (2MgOSiO
2) powder is as described magnesium raw material and the described silicon-containing material of containing.
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| CN101844918A (en) * | 2009-03-25 | 2010-09-29 | Tdk株式会社 | Dielectric ceramic composition and the electronic unit that uses it |
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