# Patent

## Title
Dielectric ceramic composition, method of manufacturing the same, and dielectric ceramics and laminated ceramic part using the same

## Abstract

A dielectric ceramic composition having a relative dielectric constant εr of 15-25 allowing formation of a laminated ceramic part having an appropriate size, capable of being sintered at a temperature lower than 800-1000° C. allowing incorporation and lamination of low resistance conductor of Cu or Ag through simultaneous sintering, and having a low dielectric loss tan δ (high Q-value) and a temperature coefficient τf of resonant frequency has an absolute value not larger than 50 ppm/° C. The dielectric ceramic composition contains 3-30 parts by weight of lead-free low melting point glass containing 50 to 75 wt % of ZnO, 5 to 30 wt % of B2O3, 6 to 15 wt % of SiO2, 0.5 to 5 wt % of Al2O3, and 3 to 10 wt % of BaO, based on 100 parts by weight of major component expressed by a general formula of x′Zn2TiO4-(1−x′−y′)ZnTiO3-y′TiO2 where 0.15<x′<0.8 and 0≦y′≦0.2

## Background
This application is a 371 of PCT/JP2004/006735 filed on May 19, 2004, published on Dec. 2, 2004 under publication number WO 2004/103929 A1 which claims priority benefits from Japanese Patent Application Number 2003-142148 filed May 20, 2003 and Japanese Patent Application Number 2003-142149 filed May 20, 2003.
TECHNICAL FIELD
The present invention relates to dielectric ceramics that have a relative dielectric constant of about 15 to 25, and a small absolute value in temperature coefficient τf of resonant frequency, that can be sintered simultaneously with Au, Ag, Cu or the like as a low resistant conductor, and that have less dielectric loss (a large Q-value) suitable for laminated ceramic parts, a composition to obtain the dielectric ceramics, a method of manufacturing the same, and a laminated ceramic part using the same, such as a laminated dielectric condenser, an LC filter, or the like.
In particular, the present invention relates to a dielectric ceramic composition comprising a major component containing Zn2TiO4 and ZnTiO3 and further TiO2 if necessary, and a glass component, a method of manufacturing the same, and dielectric ceramics and a laminated ceramic part using the same, and further relates to a dielectric ceramic composition comprising a major component containing Zn2TiO4, ZnTiO3 and Al2O3 and further TiO2 if necessary, and a glass component, a method of manufacturing the same, and dielectric ceramics and a laminated ceramic part using the same.
BACKGROUND ART
In recent years, a progress of integration of microwave circuits has involved demands for a dielectric resonator having a small size, less dielectric loss (tan δ), and stable dielectric characteristics. There hence has been a growing market of laminated chip parts internally having laminated electrode conductors for dielectric resonator parts. Inner conductors of these laminated chip parts have been using noble metal such as Au, Pt, Pd, or the like. From the view point of cost reduction, however, conductor materials have been replaced with Ag or Cu or alloy containing, as a major component, Ag or Cu, which is relatively cheaper than the conductor materials described above. Particularly, Ag or alloy containing Ag as a major component is strongly demanded, since it has a low resistance to a direct current and therefore is advantageous for improvement in the Q-characteristic of the dielectric resonator, etc. However, Ag or alloy containing Ag as a major component has a low melting point of about 960° C. and necessitates a dielectric material which can be sintered at a temperature lower than the melting point.
In case of forming a dielectric filter with use of a dielectric resonator, characteristics which are requested for a dielectric material are: (1) a small absolute value of the temperature coefficient τf of the resonant frequency of a dielectric material to reduce, as much as possible, characteristic changes caused by temperature changes; and (2) a high Q-value of a dielectric material to reduce insertion loss, as much as possible, as requested for a dielectric filter. Further, with respect to a range near a micro wave used by a cellular phone or the like, the length of a resonator is limited by a relative dielectric constant εr of the dielectric material. Therefore, a high relative dielectric constant εr is requested for downsizing of elements. In this case, the length of the resonator is determined with reference to the wavelength of a used electromagnetic wave. The wavelength λ of the electromagnetic wave propagating through a dielectric material having a relative dielectric constant εr is expressed by λ=λ0/(εr)1/2 wherein the wavelength of the electromagnetic wave propagating through vacuum is λ0.
Accordingly, elements can be downsized more as the dielectric constant of the dielectric material used increases. However, if the element is too small, required processing accuracy is severe. Therefore, actual processing accuracy deteriorates and is easily affected by printing accuracy of electrodes. For some purposes, the relative dielectric constant εr is required to be within a proper range (e.g., about 10 to 40 or more preferably about 15 to 25) so that elements might not be too small.
To satisfy these requirements, known dielectric materials capable of preparing a dielectric member at a temperature not higher than 1000° C. may be a material in which inorganic dielectric particles are dispersed in resin (JP(A)-6-132621), glass ceramics consisting of a composite material of BaO—TiO2—Nd2O3-based ceramics and glass (JP(A)-10-330161, page 3, paragraph [0005] and Table 1), and the like. Also known is a dielectric ceramics which contain TiO2 and ZnO and further contain B2O3-based glass (JP(B)-3103296).
However, the element disclosed in the JP(A)-6-132621 has an allowable temperature limit of about 400° C. and causes a problem that multi-lamination and fine wiring cannot be carried out by simultaneous sintering with Ag or the like used as a wiring conductor.
The glass ceramics material disclosed in JP(A)-10-330161 has a problem as follows. The relative dielectric constant εr of this material is greater than 40 so that the element becomes too small. Consequently, required processing accuracy is so severe that actual processing accuracy deteriorates and is easily affected by printing accuracy of electrodes.
Further, the composition disclosed in the JP(B)-3103296 has a relative dielectric constant εr as high as about 25 to 70, as can be seen from Examples. The temperature coefficient of a dielectric characteristic varies greatly by the composition, so that the absolute value thereof exceeds 700 ppm/° C. in some cases. In order to provide a dielectric part for a high frequency, such a material has been demanded that has a proper relative dielectric constant, a small dependency of the dielectric characteristic on temperature, and a high Q-value.
Further, the dielectric characteristic of dielectric ceramics obtained by sintering a dielectric ceramic composition usually changes or has variants due to changes in sintering temperature and in composition. These changes and variants of the characteristic due to changes in sintering temperature and in composition cause deterioration of the yield in mass production.
DISCLOSURE OF THE INVENTION
An object of the present invention is to provide dielectric ceramics that have a relative dielectric constant of about 10 to 40 or more preferably about 15 to 25 so that laminated ceramic parts and the like can be formed into appropriate sizes, that allows sintering at a temperature of 800 to 1000° C. which enables internal packaging and multi-lamination of a low resistance conductor such as Cu, Ag or the like based on simultaneous sintering, that causes less dielectric loss tan δ (a high Q-value), and that has an absolute value in temperature coefficient τf of resonant frequency of 50 ppm/° C. or less, a dielectric ceramic composition to obtain such dielectric ceramics or particularly a dielectric ceramic composition that causes less characteristic changes and variants caused by changes in sintering temperature and causes less changes in composition at the time of sintering, and a method of manufacturing the same. Another object of the present invention is to provide a laminated ceramic part such as a laminated ceramic condenser or an LC filter that has a dielectric layer made of such dielectric ceramics as described above and an inner electrode containing Cu or Ag as a major component.
(1) First Embodiment of the Present Invention
The present inventors have eagerly made studies to solve the above problems, and have found the following, as a result. That is, if glass containing at least ZnO, B2O3, SiO2, Al2O3, and BaO is added to a mixture containing ZnTiO3 and Zn2TiO4, and further TiO2 if necessary, εr within a range of 15 to 25 and small dielectric loss tan δ (a high Q-value) can be obtained without changing the generation phase ratio between ZnTiO3, Zn2TiO4 and TiO2 even after sintering at 800 to 1000° C. By using glass containing ZnO, dissolution of ZnO components into glass from ZnTiO3 and Zn2TiO4 can be suppressed as much as possible, and therefore, changes in dielectric characteristic caused by changes in the composition can be suppressed. Accordingly, lamination and fine pattern wiring are possible with use of Cu, Ag and the like as wiring conductors.
The present invention relates to a dielectric ceramic composition containing 100 parts by weight of a major component expressed by a general formula of x′Zn2TiO4-(1−x′−y′)ZnTiO3-y′TiO2 where x′ satisfies 0.15<x′<0.8 and y′ satisfies 0≦y′≦0.2; and 3 to 30 parts by weight of lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.
The present invention also relates to dielectric ceramics containing crystalline phases of Zn2TiO4, ZnTiO3 and TiO2 (where the TiO2 phase may be omitted, which applies also to the following cases) and a glass phase, which are obtained by sintering the dielectric ceramic composition.
Further, the present invention relates to a method of manufacturing the dielectric ceramic composition, comprising the steps of mixing powder of raw material of ZnO and powder of raw material of TiO2 and calcining them to obtain ceramic powder containing Zn2TiO4, ZnTiO3 and TiO2 (where the content of TiO2 may be zero); and mixing the ceramic powder with lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.
Further, the present invention relates to a laminated ceramic part comprising plural dielectric layers; an internal electrode formed between the dielectric layers; and an external electrode electrically connected to the internal electrode, wherein the dielectric layers are constituted by dielectric ceramics obtained by sintering the dielectric ceramic composition, and the internal electrode is made of elemental Cu or elemental Ag or alloy material containing Cu or Ag as a major component.
(2) Second Embodiment of the Present Invention
The present inventors also have eagerly made studies to solve the above problems, and have found the following, as a result. That is, if glass containing at least ZnO and B2O3 is added to a mixture containing ZnTiO3, Zn2TiO4 and Al2O3, and further TiO2 if necessary, εr within a preferable range and small dielectric loss tan δ (a high Q-value) can be obtained without changing the generation phase ratio between ZnTiO3, Zn2TiO4, TiO2 and Al2O3 even after sintering at 800 to 1000° C. By using glass containing ZnO, dissolution of ZnO components into glass from ZnTiO3 and Zn2TiO4 can be suppressed as much as possible, and therefore, changes in dielectric characteristic caused by changes in the composition can be suppressed. Accordingly, lamination and fine pattern wiring are possible with use of Cu, Ag and the like as wiring conductors.
The present invention relates to a dielectric ceramic composition containing 100 parts by weight of a major component expressed by a general formula of xZn2TiO4-yZnTiO3-zTiO2-wAl2O3 where x satisfies 0.15<x<1.0, y satisfies 0<y<0.85, z satisfies 0≦z≦0.2, w satisfies 0<w≦0.2, and x+y+z+w=1 is satisfied; and 3 to 30 parts by weight of lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %. In a preferred embodiment of the dielectric ceramic composition of the present invention, x satisfies 0.15<x<0.99, y satisfies 0.05<y<0.85, w satisfies 0.005<w≦0.2.
The present invention also relates to dielectric ceramics containing crystalline phases of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 (where the TiO2 phase may be omitted) and a glass phase, which are obtained by sintering the dielectric ceramic composition.
Further, the present invention relates to a method of manufacturing the dielectric ceramic composition, comprising the steps of mixing powder of raw material of ZnO and powder of raw material of TiO2 and calcining them to obtain ceramic powder containing Zn2TiO4, ZnTiO3 and TiO2 (where the content of TiO2 may be zero); and mixing the ceramic powder with Al2O3 and lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.
Further, the present invention relates to a laminated ceramic part comprising plural dielectric layers; an internal electrode formed between the dielectric layers; and an external electrode electrically connected to the internal electrode, wherein the dielectric layers are constituted by dielectric ceramics obtained by sintering the dielectric ceramic composition, and the internal electrode is made of elemental Cu or elemental Ag or alloy material containing Cu or Ag as a major component.
A dielectric ceramic composition of the present invention comprises a crystalline component containing Zn2TiO4 and ZnTiO3, and TiO2 as an optional component, and a specific glass component. Therefore, sintering is possible at a temperature of 1000° C. or lower. The relative dielectric constant εr of dielectric ceramics obtained by sintering the dielectric ceramic composition can be about 15 to 25. The dielectric loss thereof can be small. The absolute value of the temperature coefficient of resonant frequency thereof can be 50 ppm/° C. or lower. As a result, it is possible to provide a laminated ceramic part which has an internal electrode made of elemental Cu, elemental Ag, or alloy material containing Cu or Ag as a major component.
Another dielectric ceramic composition of the present invention comprises a crystalline component containing Zn2TiO4, ZnTiO3 Al2O3, and TiO2 as an optional component, and a specific glass component. Therefore, sintering is possible at a temperature of 1000° C. or lower. The relative dielectric constant εr of dielectric ceramics obtained by sintering the dielectric ceramic composition can be about 10 to 40, preferably about 15 to 25. The dielectric loss thereof can be small. The absolute value of the temperature coefficient of resonant frequency thereof can be 50 ppm/° C. or lower. Further, it is possible to provide a dielectric ceramic composition in which characteristics as described above are less changed depending on the sintering temperature. As a result, it is possible to provide a laminated ceramic part which has an internal electrode made of elemental Cu, elemental Ag, or alloy material containing Cu or Ag as a major component.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view showing a tri-plate type resonator of a practical form according to the present invention;
FIG. 2 is a schematic cross-sectional view of the resonator of FIG. 1;
FIG. 3 shows an X-ray diffraction pattern of a pellet prepared by sintering dielectric ceramic composition of the present invention in Example 1; and
FIG. 4 shows an X-ray diffraction pattern of a pellet prepared by sintering dielectric ceramic composition of the present invention in Example 15,



wherein reference numeral 1 denotes a dielectric layer, 2 an internal electrode, and 3 an external electrode.
BEST MODE FOR CARRYING OUT THE INVENTION
(1) First Embodiment of the Present Invention
A dielectric ceramic composition according to the first embodiment of the present invention will now be described specifically.
The composition according to the present invention is a dielectric ceramic composition which contains a major component containing Zn2TiO4 and ZnTiO3, and TiO2 as an optional component, and a glass component. The major component is expressed by a general formula of x′Zn2TiO4-(1−x′−y′)ZnTiO3-y′TiO2 where x′ is within a range of 0.15<x′<0.8 and y′ is within a range of 0≦y′≦0.2. The glass component is lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %. The dielectric ceramic composition of the present invention contains the glass component of 3 to 30 parts by weight relative to the main component of 100 parts by weight.
In the composition described above, x′ should preferably be greater than 0.15 and smaller than 0.8. Where x′ is 0.15 or less or 0.8 or more, the absolute value of τf undesirably exceeds 50 ppm/° C.
In addition, in the above composition, y′ should preferably be within a range of 0 to 0.2. Since TiO2 is contained, the specific dielectric constant tends to increase slightly. However, in the composition having y′ of 0.2 or less, the effects which the present invention aims at can be obtained. If y′ is greater than 0.2, τf exceeds +50 ppm/° C. undesirably.
In the dielectric ceramic composition of the present invention, the amount of the glass component should preferably be within a range of 3 to 30 parts by weight with respect to 100 parts by weight of the major component which constitutes ceramic base material. In case where the amount of the glass component is less than 3 parts by weight, the sintering temperature is equal to or higher than the melting point of Ag or Cu or alloy containing Ag or Cu as a major component. Therefore, electrodes made of these materials cannot be used undesirably. If the amount of the glass component exceeds 30 parts by weight, there is a tendency that excellent sintering cannot be performed due to elution of glass.
Zn2TiO4 used in the present invention can be obtained by mixing zinc oxide ZnO and titanium oxide TiO2 at a molar ratio of 2:1 and calcining the obtained mixture. ZnTiO3 can be obtained by mixing zinc oxide ZnO and titanium oxide TiO2 at a molar ratio of 1:1 and calcining the obtained mixture. As raw materials of Zn2TiO4 and ZnTiO3, it is possible to use nitrate, carbonate, hydroxide, chloride, organic metal compounds, and the like which contain Zn and/or Ti to form oxide at the time of calcination, in addition to TiO2 and ZnO.
The dielectric ceramic composition is characterized by containing a predetermined amount of particular glass. The glass used in the present invention contains ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %. These oxide components are mixed at a predetermined ratio and are melted, cooled, and vitrified.
The composition of the glass used in the present invention will now be described in the following. ZnO has a tendency that at a rate lower than 50 wt %, the softening point of glass is so high that excellent sintering cannot be performed, and at a rate higher than 75 wt %, vitrification is difficult at a desired temperature. B2O3 has a tendency that at a rate lower than 5 wt %, the softening point of glass is so high that excellent sintering cannot be performed, and at a rate higher than 30 wt %, excellent sintering cannot be performed due to elution of glass. SiO2 has a tendency that at a rate lower than 6 wt % or higher than 15 wt %, the softening point of glass is so high that excellent sintering cannot be performed. Al2O3 has a tendency that at a rate lower than 0.5 wt %, chemical durability of the dielectric ceramics obtained degrades, and at a rate higher than 5 wt %, vitrification is difficult at a desired temperature. BaO has a tendency that at a rate lower than 3 wt % or higher than 10 wt %, vitrification is difficult at a desired temperature. If glass contains a component of Pb or Bi, the Q-value of the dielectric ceramic composition tends to decrease. Since glass does not contain Pb according to the dielectric ceramic composition of the present invention, environmental pollution by Pb is not caused.
According to the present invention, with respect to 100 parts by weight of a major component expressed by a general formula of x′Zn2TiO4-(1−x′−y′)ZnTiO3-y′TiO2 where x′ is within a range of 0.15<x′<0.8 and y′ is within a range of 0≦y′≦0.2, 3 to 30 parts by weight of lead-free low-melting glass is contained, the lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %. Accordingly, sintering can be achieved at a lower temperature of 800 to 1000° C. By sintering the dielectric ceramic composition as described above, the dielectric ceramics according to the present invention can be obtained. The dielectric ceramics of the present invention are characterized by a relative dielectric constant εr of about 15 to 25, a large unloaded Q-value, and an absolute value of 50 ppm/° C. or less which is the absolute value of the temperature coefficient τf of the resonant frequency. The composition of the dielectric ceramics is substantially the same as that of the raw materials of the dielectric ceramic composition, and comprising crystalline phases of Zn2TiO4, ZnTiO3 and TiO2 and a glass phase. According to the dielectric ceramic composition of the present invention, it is possible to perform low-temperature sintering to obtain dielectric ceramics having characteristics as described above.
In the present invention, grains of Zn2TiO4 and ZnTiO3, and TiO2 as an optional component, and glass grains are pulverized individually and mixed before sintering. Alternatively, grains of respective raw materials are mixed with each other and then pulverized before sintering. The average grain diameter of these raw materials before sintering should be preferably 2.0 μm or less, more preferably 1.0 μm or less, in order to obtain improved dispersiveness, a high no-loaded Q-value and a stable relative dielectric constant εr. If the average grain diameter is too small, handling may be difficult in some cases. Hence, the average grain diameter should also preferably be 0.05 μm or more.
Next, a method of manufacturing the dielectric ceramic composition and dielectric ceramics of the present invention will be described. Powder of row material of ZnO and powder of row material of TiO2 are mixed and calcined, to obtain ceramic powder containing Zn2TiO4 and ZnTiO3, and TiO2 as an optional component. This ceramic powder is mixed with lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5.5 wt %, and BaO at 3 to 10 wt %. Thus, the dielectric ceramic composition is obtained. Ceramic powder of each of Zn2TiO4, ZnTiO3 and TiO2 may be prepared individually. Alternatively, the ratio between raw materials of ZnO and TiO2 may be adjusted to directly obtain powder containing Zn2TiO4, ZnTiO3 and TiO2 in a mixed state.
The method of individually preparing powder of each of Zn2TiO4 and ZnTiO3 to obtain the dielectric ceramic composition of the present invention will further be described. At first, zinc oxide and titanium oxide at a molar ratio of 2:1 are weighed, and are blended together with a solvent such as water, alcohol, or the like. Subsequently, water, alcohol, or the like is removed from the resultant, which is then subjected to calcination at a temperature of 900 to 1200° C. in an oxygen-contained atmosphere (e.g., in an air atmosphere) for about 1 to 5 hours. Calcined powder thus obtained consists of Zn2TiO4. Next, titanium oxide and zinc oxide at a molar ratio of 1:1 are weighed. ZnTiO3 is prepared in the same preparation method as Zn2TiO4. A predetermined amount of major component containing Zn2TiO4, ZnTiO3 and TiO2 is weighed. Further, lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt % is weighed to satisfy a predetermined ratio to the major component. The glass and the major component are blended together with a solvent such as water, alcohol, or the like. Subsequently, the water, alcohol, or the like is removed and thereafter pulverized to prepare the dielectric ceramic composition intended, which is raw material powder for the dielectric ceramics.
The dielectric ceramic composition of the present invention is sintered to form a pellet of dielectric ceramics, and the dielectric characteristic thereof is measured. More specifically, an organic binder such as polyvinyl alcohol is mixed with the raw material powder for dielectric ceramics to be homogenized. Drying and pulverizing are carried out, and thereafter, the resultant is pressed into a pellet form (under a pressure of about 100 to 1000 Kg/cm2). The obtained formation is sintered at 800 to 1000° C. in an oxygen-contained gas atmosphere like air, thereby to obtain dielectric ceramics in which phases of Zn2TiO4, ZnTiO3 and TiO2 and a glass phase coexist.
The dielectric ceramic composition of the present invention according to the first embodiment is processed into an appropriate shape and an appropriate size upon necessity, or sheet forming based on a doctor blade method or the like and lamination of sheets and electrodes are carried out with use of the dielectric ceramic composition. Thus, the dielectric ceramic composition can be used as a material for constituting various kinds of laminated ceramic parts. Laminated ceramic parts may be a laminated ceramic condenser, LC filter, dielectric resonator, dielectric substrate, or the like.
The laminated ceramic part according to the first embodiment of the present invention has plural dielectric layers, an internal electrode formed between the dielectric layers, and an external electrode electrically connected to the internal electrode. The dielectric layer is constituted of dielectric ceramic obtained by sintering the dielectric ceramic composition according to the first embodiment of the present invention. The internal electrode is made of elemental Cu or elemental Ag, or an alloy material containing Cu or Ag as a major component. The laminated ceramic part according to the present invention can be obtained by simultaneously sintering the dielectric layers consisting of the dielectric ceramics and elemental Cu, elemental Ag or an alloy material containing Cu or Ag as a major component.
A practical form of the laminated ceramic part of the present invention according to the first embodiment may be a tri-plate type resonator shown in FIGS. 1 and 2. FIG. 1 is a schematic perspective view showing the tri-plate type resonator of the practical form according to the present invention. FIG. 2 is a schematic cross-sectional view thereof. As shown in FIGS. 1 and 2, the tri-plate type resonator is a laminated ceramic part having a plurality of dielectric layers 1, an internal electrode 2 formed between the dielectric layers, and an external electrode 3 electrically connected to the internal electrode. The tri-plate type resonator is obtained by laminating the plurality of dielectric layers 1 with the internal electrode 2 disposed at a central portion. The internal electrode 2 is formed so as to pass through the resonator from a first face A to a second face B opposing the first face A. Only the first face A is an open face. The external electrode 3 is formed on five faces of the resonator exclusive of the first face A. The internal electrode 2 and the external electrode 3 are connected to each other on the second face B. The material of the internal electrode 2 contains Cu or Ag, or an alloy material containing Cu or Ag as a major component. Since the dielectric ceramic composition according to the present invention can be sintered at a low temperature, these materials for the internal electrode can be used.
(2) Second Embodiment of the Present Invention
A dielectric ceramic composition according to the second embodiment of the present invention will now be described in details hereinafter.
The composition according to the present invention is a dielectric ceramic composition which contains a major component containing Zn2TiO4, ZnTiO3 and Al2O3, and TiO2 as an optional component, and a glass component. The major component is expressed by a general formula of xZn2TiO4-yZnTiO3-zTiO2-wAl2O3 where x is within a range of 0.15<x<1.0, y is within a range of 0<y<0.85, z is within a range of 0≦z≦0.2, w is within a range of 0<w≦0.2, and x+y+z+w=1 is satisfied. Zn2TiO4, ZnTiO3, TiO2 and Al2O3 each has a crystalline form. On the other side, the glass component may be glass containing ZnO at 50 to 75 wt % and B2O3 at 5 to 30 wt %. The dielectric ceramic composition of the present invention contains 3 to 30 parts by weight of the glass component with respect to 100 parts by weight of the major component.
In the composition described above, the molar fraction x of Zn2TiO4 should preferably be within a range of greater than 0.15 and smaller than 1.0, particularly greater than 0.15 and smaller than 0.99. If x is 0.15 or less or x is 1.0, the absolute value of τf exceeds 50 ppm/° C. undesirably.
Also in the composition described above, the molar fraction y of ZnTiO3 should preferably be within a range of greater than 0 and smaller than 0.85, particularly greater than 0.005 and smaller than 0.85. If y is 0 or y is 0.85 or more, the absolute value of τf exceeds 50 ppm/° C. undesirably.
Also in the composition described above, the molar fraction z of TiO2 should preferably be within a range of 0 to 0.2. Since TiO2 is contained, the dielectric constant tends to increase slightly. However, the advantages which the present invention aims at can be attained in any composition that has z of 0.2 or less. If z is greater than 0.2, τf exceeds +50 ppm/° C. undesirably.
Also in the composition described above, the molar fraction w of Al2O3 should preferably be greater than 0 and not greater than 0.2, particularly greater than 0.005 and not greater than 0.2. If w is 0, changes in the dielectric characteristic which are caused by changes in the sintering temperature become greater, and therefore, the range of the sintering temperature narrows undesirably. If w is greater than 0.2, the sintering temperature becomes equal to or higher than a temperature of the melting point of Ag or Cu or alloy containing Ag or Cu as a major component. This undesirably prevents use of the electrodes of such materials which is an object of the present invention.
Also in the dielectric ceramic composition of the present invention, the amount of the glass component should preferably be within a range of 3 to 30 parts by weight with respect to 100 parts by weight of the major component which constitutes ceramic base material. In case where the amount of the glass component is less than 3 parts by weight, the sintering temperature is equal to or higher than the melting point of Ag or Cu or alloy containing Ag or Cu as a major component. Therefore, electrodes of these materials cannot be used, undesirably. If the amount of the glass component exceeds 30 parts by weight, there is a tendency that excellent sintering cannot be performed due to elution of glass.
Zn2TiO4 used in the present invention can be obtained by mixing zinc oxide ZnO and titanium oxide TiO2 at a molar ratio of 2:1 and calcining the obtained mixture. ZnTiO3 can be obtained by mixing zinc oxide ZnO and titanium oxide TiO2 at a molar ratio of 1:1 and calcining the obtained mixture. As raw materials of Zn2TiO4 and ZnTiO3, it is possible to use nitrate, carbonate, hydroxide, chloride, organic metal compounds, and the like which contain Zn and/or Ti to form oxide at the time of calcination, in addition to TiO2 and ZnO.
The glass used in the present invention should preferably be glass containing ZnO at 50 to 75 wt %. Since a ZnO component is contained in the glass, the ZnO component of Zn2TiO4 and ZnTiO3 constituting the major component can be inhibited from shifting to a glass phase. Therefore, changes in the dielectric characteristic caused by changes in the composition during sintering can be reduced. In addition, if the glass contains B2O3 at 5 to 30 wt %, the low-temperature sintering easily proceeds desirably. A particularly preferred glass component contains ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %. In case of a dielectric ceramic composition in which the glass component is mixed with the major component described above, the relative dielectric constant εr can be within a preferable range of about 15 to 25. Used as the glass to be mixed is glass which is obtained by melting, cooling and vitrificating respective oxide components as described above mixed at a predetermined ratio. The composition of the glass used in the present invention will now be described in the following. ZnO has a tendency that at a rate lower than 50 wt %, the softening point of glass is so high that excellent sintering cannot be performed, and at a rate higher than 75 wt %, vitrification is difficult at a desired temperature. B2O3 has a tendency that at a rate lower than 5 wt %, the softening point of glass is so high that excellent sintering cannot be performed, and at a rate higher than 30 wt %, excellent sintering cannot be performed due to elution of glass. SiO2 has a tendency that at a rate lower than 6 wt % or higher than 15 wt %, the softening point of glass is so high that excellent sintering cannot be performed. Al2O3 has a tendency that at a rate lower than 0.5 wt %, chemical durability of the dielectric ceramics obtained degrades, and at a rate higher than 5 wt %, vitrification is difficult at a desired temperature. BaO has a tendency that at a rate lower than 3 wt % or higher than 10 wt %, vitrification is difficult at a desired temperature. If glass contains a component of Pb or Bi, the Q-value of the dielectric ceramic composition tends to decrease. Since glass does not contain Pb according to the dielectric ceramic composition of the present invention, environmental pollution by Pb is not caused.
According to the present invention, with respect to 100 parts by weight of a major component expressed by a general formula of xZn2TiO4-yZnTiO3-zTiO2-wAl2O3 where x satisfies 0.15<x<1.0, y satisfies 0<y<0.85, z satisfies 0≦z≦0.2, w satisfies 0<w≦0.2, and x+y+z+w=1 is satisfied, 3 to 30 parts by weight of a glass component containing ZnO and B2O3 is contained. Accordingly, sintering can be achieved at a lower temperature of 800 to 1000° C. By sintering the dielectric ceramic composition as described above, the dielectric ceramics according to the present invention can be obtained. The dielectric ceramics of the present invention is characterized by a relative dielectric constant εr of 10 to 40, preferably about 15 to 25, a large no-loaded Q-value, and an absolute value of 50 ppm/° C. or less which is the absolute value of the temperature coefficient τf of the resonant frequency. The composition of the dielectric ceramics is substantially the same as that of the raw materials of the dielectric ceramic composition, and comprising crystalline phases of Zn2TiO4, ZnTiO3, TiO2 and Al2O3, and a glass phase. According to the dielectric ceramic composition of the present invention, it is possible to perform low-temperature sintering to obtain dielectric ceramics having characteristics as described above.
The dielectric ceramic composition of the present invention is expressed as a mixture of Zn2TiO4, ZnTiO3, TiO2, Al2O3 and the glass described above before sintering. Even if this mixture is further mixed with additives such as a solvent, organic material, and the like added in a preparation process, the mixed resultant is a dielectric ceramic composition intended by the present invention. The mixture of the ceramic composition according to the present invention causes less changes in compositions of the crystalline phases and glass phase even after sintering. Therefore, dielectric ceramics obtained by sintering the mixture is dielectric ceramics constituted by the dielectric ceramic composition of the present invention.
In the present invention, grains of Zn2TiO4, ZnTiO3, TiO2 and Al2O3, and glass grains are pulverized individually and mixed before sintering. Alternatively, grains of respective raw materials are mixed with each other and then pulverized before sintering. The average grain diameter of these raw materials before sintering should be preferably 2.0 μm or less, more preferably 1.0 μm or less, in order to obtain improved dispersiveness, a high no-loaded Q-value and a stable relative dielectric constant εr. If the average grain diameter is too small, handling may be difficult in some cases. Hence, the average grain diameter should also preferably be 0.05 μm or more.
Next, a method of manufacturing the dielectric ceramic composition and dielectric ceramics of the present invention will be described. Powder of each of Zn2TiO4, ZnTiO3 and TiO2 constituting part of the major component may be prepared individually. Alternatively, with the ratio between raw materials of ZnO and TiO2 adjusted, calcination may be carried out, to obtain directly mixed powder of Zn2TiO4, ZnTiO3 and TiO2. In order to obtain mixed powder of Zn2TiO4, ZnTiO3 and TiO2 by performing one calcination step, powder of raw materials of ZnO and TiO2 may be mixed at a preset ratio and calcined. A resultant may be mixed with a predetermined amount of Al2O3, and then can be used as the major component of the dielectric ceramic composition of the present invention. To obtain the dielectric ceramic composition of the present invention, 100 parts by weight of the major component may be mixed with 3 to 30 parts by weight of a glass component containing ZnO at 50 to 75 wt % and B2O3 at 5 to 30 wt %.
In a preferable method of manufacturing the dielectric ceramic composition, powder of raw material of ZnO and powder of raw material of TiO2 are mixed and calcined to obtain ceramic powder containing Zn2TiO4, ZnTiO3 and TiO2. This ceramic powder is mixed with a predetermined amount of lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.
In case of preparing individually ceramic powder of each of Zn2TiO4 and ZnTiO3, titanium oxide (TiO2) and zinc oxide (ZnO) may be mixed at molar ratios of 2:1 and 1:1 respectively for Zn2TiO4 and ZnTiO3 and then calcined. Predetermined amounts of obtained Zn2TiO4, ZnTiO3, TiO2 and Al2O3 are weighed and mixed, and then, the resultant can be used as the major component of the dielectric ceramic composition of the present invention.
The method of individually preparing powder of each of Zn2TiO4 and ZnTiO3 to obtain the dielectric ceramic composition of the present invention will now be described in further details. At first, titanium oxide (TiO2) and zinc oxide (ZnO) at a molar ratio of 2:1 are weighed, and are blended together with a solvent such as water, alcohol, or the like. Subsequently, water, alcohol, or the like is removed from the resultant. Thereafter, the resultant is pulverized and subjected to calcination at a temperature of 900 to 1200° C. in an oxygen-contained atmosphere (e.g., in an air atmosphere) for about 1 to 5 hours. Calcined powder thus obtained consists of Zn2TiO4. Next, titanium oxide and zinc oxide at a molar ratio of 1:1 are weighed. ZnTiO3 is prepared in the same preparation method as Zn2TiO4. Zn2TiO4, ZnTiO3, and further TiO2 and Al2O3, and the glass at a predetermined ratio are weighed, and are blended together with a solvent such as water, alcohol, or the like. Subsequently, water, alcohol, or the like is removed, and thereafter, the resultant is pulverized to prepare the dielectric ceramic composition intented, which is powder of raw material for the dielectric ceramics.
The dielectric ceramic composition of the present invention is sintered to form a pellet of dielectric ceramics, and the dielectric characteristic thereof is measured. More specifically, an organic binder such as polyvinyl alcohol is mixed with the raw material powder for dielectric ceramics to be homogenized. Drying and pulverizing are carried out, and thereafter, the resultant is pressed to have a pellet form (under a pressure of about 100 to 1000 Kg/cm2). The obtained formation is sintered at 800 to 1000° C. in an oxygen-contained gas atmosphere like air, thereby to obtain dielectric ceramics in which phases of Zn2TiO4, ZnTiO3, TiO2 and Al2O3, and a glass phase coexist.
The dielectric ceramic composition according to the second embodiment can be used as material for various laminated ceramic parts like in the first embodiment.
The laminated ceramic part of the present invention according to the second embodiment are obtained in the same manner as that of the first embodiment except that the dielectric layers are made of dielectric ceramics obtained by sintering the dielectric ceramic composition of the present invention according to the second embodiment.
EXAMPLES
Examples of the present invention and relevant comparative examples thereof will now be described.
Example 1
Example Belonging to the First Embodiment of the Present Invention
0.33 mole of titanium oxide (TiO2) and 0.66 mole of zinc oxide (ZnO) together with ethanol were put in a ball mill and blended for 12 hours. After removing the solvent from the solution, the resultant was pulverized and calcined in an air atmosphere at 1000° C. to obtain calcined powder of Zn2TiO4. Next, 0.5 mole of TiO2 and 0.5 mole of ZnO were blended in the same manner as described above and were calcined to obtain calcined powder of ZnTiO3. The calcined powders of Zn2TiO4 and ZnTiO3 thus obtained, and TiO2 were mixed at a ratio shown in Table 1, to prepare a base material (major component). To 100 parts by weight of this base material, 10 parts by weight of glass powder consisting of ZnO at 63.5 wt %, SiO2 at 8 wt %, Al2O3 at 1.5 wt %, BaO at 7 wt %, and B2O3 at 20 wt % was added, and the resultant was put in a ball mill and was blended for 24 hours. After removing the solvent from the solution, the resultant was pulverized till the average grain diameter became 1 μm. To the pulverized resultant was added an appropriate amount of a polyvinyl alcohol solution, followed by drying. Thereafter, the resultant was shaped into a pellet having a diameter of 12 mm and a thickness of 4 mm and the pellet obtained was sintered in an air atmosphere at 900° C. for 2 hours. FIG. 3 shows an X-ray diffraction pattern of the sintered pellet prepared. As can be seen from FIG. 3, phases of Zn2TiO4, ZnTiO3 and TiO2 coexist in the sintered pellet of the dielectric ceramic composition according to the present invention.
The dielectric ceramics thus obtained was processed into a size having a diameter of 7 mm and a thickness of 3 mm. Thereafter, the no-loaded Q-value at the resonant frequency of 7 to 11 GHz, the relative dielectric constant εr and the temperature coefficient τf of resonant frequency were measured, according to a dielectric resonance method. Table 2 shows the results.













TABLE 1













Post-



Base material composition

Amount of
Amount of
pulverization



(Molar fraction)
Glass composition
base material
glass
Average grain















Zn2TiO4
ZnTiO3
TiO2
(wt %)
(part
(part by
diameter





















x′
1 − x′ − y′
y′
SiO2
Al2O3
ZnO
BaO
B2O3
Bi2O3
PbO
by weight)
weight)
(μm)

























Example
1
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



2
0.40
0.59
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



3
0.75
0.24
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



4
0.22
0.78
0.00
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



5
0.20
0.70
0.10
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



6
0.18
0.62
0.20
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



7
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
2



8
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
0.5



9
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
0.1



10
0.22
0.77
0.01
6.0
1.5
71.0
3.5
18.0
0.0
0.0
100
10
1



11
0.22
0.77
0.01
8.0
5.0
50.0
10.0
27.0
0.0
0.0
100
10
1



12
0.22
0.77
0.01
10.0
5.0
50.0
5.0
30.0
0.0
0.0
100
10
1



13
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
5
1



14
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
25
1


Comp.
1
0.10
0.86
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1


Example
2
0.85
0.14
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



3
0.16
0.54
0.30
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



4
0.11
0.39
0.50
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
10
1



5
0.22
0.77
0.01
8.0
1.5
18.5
7.0
20.0
45.0
0.0
100
10
1



6
0.22
0.77
0.01
8.0
1.5
20.5
7.0
20.0
0.0
43.0
100
10
1



7
0.22
0.77
0.01
20.0
0.5
75.0
2.5
2.0
0.0
0.0
100
10
1



8
0.22
0.77
0.01
17.0
7.0
42.0
1.0
33.0
0.0
0.0
100
10
1



9
0.22
0.77
0.01
10.0
5.0
33.0
2.0
50.0
0.0
0.0
100
10
1



10
0.22
0.77
0.01
4.0
1.6
66.3
7.3
20.9
0.0
0.0
100
10
1



11
0.22
0.77
0.01
18.0
1.3
56.6
6.2
17.8
0.0
0.0
100
10
1



12
0.22
0.77
0.01
8.1
0.1
64.4
7.1
20.3
0.0
0.0
100
10
1



13
0.22
0.77
0.01
7.6
7.0
60.0
6.6
18.9
0.0
0.0
100
10
1



14
0.22
0.77
0.01
11.4
2.1
48.0
10.0
28.5
0.0
0.0
100
10
1



15
0.22
0.77
0.01
4.4
0.8
80.0
3.8
11.0
0.0
0.0
100
10
1



16
0.22
0.77
0.01
8.4
1.6
66.9
2.0
21.1
0.0
0.0
100
10
1



17
0.22
0.77
0.01
7.6
1.4
60.1
12.0
18.9
0.0
0.0
100
10
1



18
0.22
0.77
0.01
9.6
1.8
76.2
8.4
4.0
0.0
0.0
100
10
1



19
0.22
0.77
0.01
6.5
1.2
51.6
5.7
35.0
0.0
0.0
100
10
1



20
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
2
1



21
0.22
0.77
0.01
8.0
1.5
63.5
7.0
20.0
0.0
0.0
100
40
1





















TABLE 2








Q × f
τ f
Sintering temp.



ε r
(GHz)
(ppm/° C.)
° C.





















Example
1
20.0
10000
0
900



2
19.3
10000
−5
900



3
18.0
9000
−43
900



4
19.8
10000
−3
900



5
22.1
12000
15
900



6
24.5
13000
30
900



7
20.0
10000
0
900



8
19.0
8000
10
900



9
17.5
6000
30
900



10
19.5
13000
−20
900



11
18.0
12000
−5
900



12
16.0
8000
−20
900



13
22.0
13000
10
900



14
18.0
7500
−10
900


Comp.
1
23.5
12000
55
900


Example
2
17.2
7000
−55
900



3
26.0
13000
53
900



4
42.0
14000
80
900



5
24.0
1000
−60
900



6
25.0
2000
−70
900











7

Not sintered at 1000° C. or lower



8

Glass was eluted at 800° C. or higher



9

Glass was eluted at 800° C. or higher



10

Not sintered at 1000° C. or lower



11

Not sintered at 1000° C. or lower



12

Melted in 4 wt % sulfuric acid solution



13

Not sintered at 1000° C. or lower



14

Not sintered at 1000° C. or lower



15

Not sintered at 1000° C. or lower



16

Not sintered at 1000° C. or lower



17

Not sintered at 1000° C. or lower



18

Not sintered at 1000° C. or lower



19

Glass was eluted at 800° C. or higher



20

Not sintered at 1000° C. or lower



21

Glass was eluted at 900° C. or higher









To 100 g of the mixture of the base material and the glass, 9 g of polyvinyl butyral as a binder, 6 g of dibutylphthalate as a plasticizer, and 60 g of toluene and 30 g of isopropyl alcohol both as a solvent were added to prepare a green sheet having a thickness of 100 μm, according to the doctor blade method. Then, 22 layers of the green sheets were laminated by the thermo compression bonding of applying a pressure of 200 kg/cm2 at a temperature of 65° C. At this time, a layer having been printed with Ag as an internal electrode was positioned such that it was provided at the center in the thickness direction. After sintering the obtained laminate at 900° C. for 2 hours, an external electrode was formed to prepare a tri-plate type resonator. The resonator had a size of 4.9 mm in width, 1.7 mm in height, and 8.4 mm in length.
The obtained tri-plate type resonator was evaluated on the no-loaded Q-value at a resonant frequency of 2 GHz. As a result, the no-loaded Q-value of the tri-plate type resonator was 210. Thus, it was possible to obtain a tri-plate type resonator having an excellent characteristic by using the dielectric ceramic composition according to the present invention.
Examples 2 and 3
Examples Belonging to the First Embodiment
Influence of x′
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1, and were evaluated on various characteristics in the same method as in the example 1. The results thereof are shown in Table 2.
Examples 4 to 6
Examples Belonging to the First Embodiment
Influence of y′
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1, and were evaluated on various characteristics in the same method as in the example 1. The results thereof are shown in Table 2.
Examples 7 to 9
Examples Belonging to the First Embodiment
Influence of the Grain Diameter
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1, and the resultant was pulverized until the grain diameter thereof became the average grain diameters shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1, and were evaluated on various characteristics in the same method as in the example 1. The results thereof are shown in Table 2.
Examples 10 to 12
Examples Belonging to the First Embodiment
Influence of the Glass Composition
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass of various compositions at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1, and were evaluated on various characteristics in the same method as in the example 1. The results thereof are shown in Table 2.
Examples 13 and 14
Examples Belonging to the First Embodiment
Influence of the Glass Amount
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1, and were evaluated on various characteristics in the same method as in the example 1. The results thereof are shown in Table 2.
Comparative Examples 1 and 2
Influence of x′
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1. However, when the molar ratio x′ of Zn2TiO4 was smaller than 0.15, the temperature coefficient τf of resonant frequency was greater than +50 ppm/° C. When x′ was greater than 0.8, the temperature coefficient τf of resonant frequency was smaller than −50 ppm/° C. The results thereof are shown in Table 2.
Comparative Examples 3 and 4
Influence of y′
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1. However, when the molar ratio y′ of TiO2 was greater than 0.2, the temperature coefficient τf of resonant frequency was greater than +50 ppm/° C. The results thereof are shown in Table 2.
Comparative Examples 5 to 19
Influence of the Glass Composition
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass of various compositions at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1. However, when glass compositions which are out of the range of the glass compositions adopted in the present invention were used, the Q-value was lowered, and the temperature coefficient τf of resonant frequency was smaller than −50 ppm/° C. (Comparative Examples 5 and 6), glass was melted by a sulfuric acid solution (Comparative Example 12), or the pellets could not be sintered at 1000° C. or lower, or glass was eluted at 800° C. or higher (Comparative Examples 7 to 11 or 13 to 19). The results thereof are shown in Table 2.
Comparative Examples 20 and 21
Influence of the Glass Amount
In the same manner as in the example 1 described above, mixtures of Zn2TiO4, ZnTiO3 and TiO2 mixed at ratios shown in Table 1 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 1. Then, sintered pellets were prepared under the same conditions as in the example 1. However, when the glass amount was smaller than 3 parts by weight, sintering could not be achieved at 1000° C. or lower. When the glass amount is greater than 30 parts by weight, glass was eluted at 900° C. or higher, and reacted with a setter. The results thereof are shown in Table 2.
Example 15
Example Belonging to the Second Embodiment of the Present Invention
0.33 mole of titanium oxide (TiO2) and 0.66 mole of zinc oxide (ZnO) together with ethanol were put in a ball mill and blended for 12 hours. After removing the solvent from the solution, the resultant was pulverized and calcined in an air atmosphere at 1000° C. to obtain calcined powder of Zn2TiO4. Next, 0.5 mole of TiO2 and 0.5 mole of ZnO were blended in the same manner as described above and were calcined to obtain calcined powder of ZnTiO3. The calcined powders of Zn2TiO4 and ZnTiO3 thus obtained, and TiO2 and Al2O3 were mixed at a ratio shown in Table 3, to prepare a base material (major component). To 100 parts by weight of this base material, 10 parts by weight of glass powder consisting of ZnO at 63.5 wt %, SiO2 at 8 wt %, Al2O3 at 1.5 wt %, BaO at 7 wt %, and B2O3 at 20 wt % was added, and the resultant was put in a ball mill and was blended for 24 hours. After removing the solvent from the solution, the resultant was pulverized till the average grain diameter became 1 μm. To the pulverized resultant was added an appropriate amount of a polyvinyl alcohol solution, followed by drying. Thereafter, the resultant was shaped into a pellet having a diameter of 12 mm and a thickness of 4 mm and the pellet obtained was sintered in an air atmosphere at 850° C. for 2 hours (Example 15a). FIG. 4 shows an X-ray diffraction pattern of the sintered pellet prepared. As can be seen from FIG. 4, phases of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 coexist in the sintered pellet of the dielectric ceramic composition according to the present invention. Another pellet obtained in the same manner was sintered in the same manner at 950° C. for 2 hours (Example 15b).
The dielectric ceramics thus obtained was processed into a size having a diameter of 7 mm and a thickness of 3 mm. Thereafter, the no-loaded Q-value at the resonant frequency of 7 to 11 GHz, the relative dielectric constant εr and the temperature coefficient τf of resonant frequency were measured, according to a dielectric resonance method. Table 4 shows the results.













TABLE 3













Post-



Base material composition

Amount of
Amount of
pulverization



(molar fraction)
Glass composition
base material
glass
Average grain
















Zn2TiO4
ZnTiO3
TiO2
Al2O3
(wt %)
(part by
(part by
diameter




















x
y
z
w
SiO2
Al2O3
ZnO
BaO
B2O3
weight)
weight)
(μm)
























Example
15a, b
0.22
0.76
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



16a, b
0.40
0.58
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



17a, b
0.80
0.18
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



18a, b
0.97
0.01
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



19a, b
0.22
0.77
0.00
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



20a, b
0.20
0.69
0.10
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



21a, b
0.18
0.61
0.20
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



22a, b
0.22
0.75
0.01
0.02
8.0
1.5
63.5
7.0
20.0
100
10
1



23a, b
0.21
0.73
0.01
0.05
8.0
1.5
63.5
7.0
20.0
100
10
1



24a, b
0.19
0.65
0.01
0.15
8.0
1.5
63.5
7.0
20.0
100
10
1



25a, b
0.22
0.76
0.01
0.01
7.0
3.0
75.0
10.0
5.0
100
10
1



26a, b
0.22
0.76
0.01
0.01
6.0
1.5
72.0
2.5
18.0
100
10
1



27a, b
0.22
0.76
0.01
0.01
8.0
5.0
50.0
10.0
27.0
100
10
1



28a, b
0.22
0.76
0.01
0.01
10.0
5.0
50.0
5.0
30.0
100
10
1



29a, b
0.22
0.76
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
5
1



30a, b
0.22
0.76
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
25
1


Comp.
22a, b
0.10
0.88
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1


Example
23a, b
0.98
0.00
0.01
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



24a, b
0.15
0.54
0.30
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



25a, b
0.11
0.38
0.50
0.01
8.0
1.5
63.5
7.0
20.0
100
10
1



26a, b, c
0.22
0.77
0.01
0
8.0
1.5
63.5
7.0
20.0
100
10
1



27
0.16
0.58
0.01
0.25
8.0
1.5
63.5
7.0
20.0
100
10
1



28
0.22
0.76
0.01
0.01
20.0
0.5
75.0
2.5
2.0
100
10
1



29
0.22
0.76
0.01
0.01
17.0
7.0
42.0
1.0
33.0
100
10
1



30
0.22
0.76
0.01
0.01
10.0
5.0
33.0
2.0
50.0
100
10
1



31
0.22
0.76
0.01
0.01
25.0
1.5
45.0
8.5
20.0
100
10
1



32
0.22
0.76
0.01
0.01
6.0
1.5
80.0
7.5
5.0
100
10
1



33
0.22
0.76
0.01
0.01
4.0
1.6
66.3
7.3
20.9
100
10
1



34
0.22
0.76
0.01
0.01
18.0
1.3
56.6
6.2
17.8
100
10
1



35
0.22
0.76
0.01
0.01
8.1
0.1
64.4
7.1
20.3
100
10
1



36
0.22
0.76
0.01
0.01
7.6
7.0
60.0
6.6
18.9
100
10
1



37
0.22
0.76
0.01
0.01
11.4
2.1
48.0
10.0
28.5
100
10
1



38
0.22
0.76
0.01
0.01
4.4
0.8
80.0
3.8
11.0
100
10
1



39
0.22
0.76
0.01
0.01
8.4
1.6
66.9
2.0
21.1
100
10
1



40
0.22
0.76
0.01
0.01
7.6
1.4
60.1
12.0
18.9
100
10
1



41
0.22
0.76
0.01
0.01
9.6
1.8
76.2
8.4
4.0
100
10
1



42
0.22
0.76
0.01
0.01
6.5
1.2
51.6
5.7
35.0
100
10
1



43
0.22
0.76
0.01
0.01
6.0
1.5
80.0
7.5
5.0
100
2
1



44
0.22
0.76
0.01
0.01
6.0
1.5
80.0
7.5
5.0
100
40
1





















TABLE 4








Q × f
τ f
Sintering temp.



ε r
(GHz)
(ppm/° C.)
° C.





















Example
15a
20.0
10000
0
850



15b
20.0
10000
0
950



16a
19.3
10000
−5
850



16b
19.3
10000
−5
950



17a
17.7
9000
−30
850



17b
17.7
9000
−30
950



18a
17.0
9000
−50
850



18b
17.0
9000
−50
950



19a
20.0
10000
−1
850



19b
20.0
10000
−1
950



20a
22.1
12000
15
850



20b
22.1
12000
15
950



21a
24.5
13000
30
850



21b
24.5
13000
30
950



22a
20.0
10000
0
850



22b
20.0
10000
0
950



23a
19.0
8000
10
850



23b
19.0
8000
10
950



24a
17.5
6000
30
850



24b
17.5
6000
30
950



25a
18.5
13000
−15
850



25b
18.5
13000
−15
950



26a
19.5
13000
−20
850



26b
19.5
13000
−20
950



27a
18.0
12000
−5
850



27b
18.0
12000
−5
950



28a
16.0
8000
−20
850



28b
16.0
8000
−20
950



29a
22.0
13000
10
850



29b
22.0
13000
10
950



30a
18.0
7500
−10
850



30b
18.0
7500
−10
950


Comp.
22a
23.5
12000
55
850


Example
22b
23.5
12000
55
950



23a
16.5
6000
−60
850



23b
16.5
6000
−60
950



24a
26.0
13000
53
850



24b
26.0
13000
53
950



25a
42.0
14000
80
850



25b
42.0
14000
80
950



26a
20.0
10000
−54
850



26b
20.0
10000
0
900



26c
20.0
10000
20
950










27
Not sintered at 1000° C. or lower



28
Not sintered at 1000° C. or lower



29
Glass was eluted at 800° C. or lower



30
Glass was eluted at 800° C. or lower



31
Not sintered at 1000° C. or lower



32
Not sintered at 1000° C. or lower



33
Not sintered at 1000° C. or lower



34
Not sintered at 1000° C. or lower



35
Melted in 4 wt. % sulfuric acid solution



36
Not sintered at 1000° C. or lower



37
Not sintered at 1000° C. or lower



38
Not sintered at 1000° C. or lower



39
Not sintered at 1000° C. or lower



40
Not sintered at 1000° C. or lower



41
Not sintered at 1000° C. or lower



42
Glass was eluted at 800° C. or higher



43
Not sintered at 1000° C. or lower



44
Glass was eluted at 900° C. or higher









To 100 g of the mixture of the base material and the glass, 9 g of polyvinyl butyral as a binder, 6 g of dibutylphthalate as a plasticizer, and 60 g of toluene and 30 g of isopropyl alcohol both as a solvent were added to prepare a green sheet having a thickness of 100 μm, according to the doctor blade method. Then, 22 layers of the green sheets were laminated by the thermo compression bonding of applying a pressure of 200 kg/cm2 at a temperature of 65° C. At this time, a layer having been printed with Ag as an internal electrode was positioned such that it was provided at the center in the thickness direction. After sintering the obtained laminate at 900° C. for 2 hours, an external electrode was formed to prepare a tri-plate type resonator. The resonator had a size of 4.9 mm in width, 1.7 mm in height, and 8.4 mm in length.
The obtained tri-plate type resonator was evaluated on the no-loaded Q-value at a resonant frequency of 2 GHz. As a result, the no-loaded Q-value of the tri-plate type resonator was 210. Thus, it was possible to obtain a tri-plate type resonator having an excellent characteristic by using the dielectric ceramic composition according to the present invention.
Examples 16 to 18
Examples Belonging to the Second Embodiment
Influence of x and y
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15, and were evaluated on various characteristics in the same method as in the example 15. The results thereof are shown in Table 4.
Examples 19 to 21
Examples Belonging to the Second Embodiment
Influence of z
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15, and were evaluated on various characteristics in the same method as in the example 15. The results thereof are shown in Table 4.
Examples 22 to 24
Examples Belonging to the Second Embodiment
Influence of w
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15, and were evaluated on various characteristics in the same method as in the example 15. The results thereof are shown in Table 4. It can be seen that the dielectric ceramic composition of the present invention containing Al2O3 as in these examples provides stable characteristics of appropriate relative dielectric constant, less dielectric loss (a high Q-value) and less variation of temperature coefficient τf of resonant frequency when sintered in a wide range of the sintering temperature of 850 to 950° C.
Examples 25 to 28
Examples Belonging to the Second Embodiment
Influence of the Glass Composition
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass of various compositions at the ratio also shown in Table 3, and the resultant was pulverized until the grain diameter thereof became the average grain diameters shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15, and were evaluated on various characteristics in the same method as in the example 15. The results thereof are shown in Table 4.
Examples 29 and 30
Examples Belonging to the Second Embodiment
Influence of the Glass Amount
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15, and were evaluated on various characteristics in the same method as in the example 15. The results thereof are shown in Table 4.
Comparative Examples 22 and 23
Influence of x and y
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15. However, when the molar ratio x of Zn2TiO4 was equal to or smaller than 0.15 or the molar ratio y of ZnTiO3 was equal to or greater than 0.85, the temperature coefficient τf of resonant frequency was greater than +50 ppm/° C. When y was equal to 0, the temperature coefficient τf of resonant frequency was smaller than −50 ppm/° C. The results thereof are shown in Table 4.
Comparative Examples 24 and 25
Influence of z
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15. However, when the molar ratio z of TiO2 was greater than 0.2, the temperature coefficient τf of resonant frequency was greater than +50 ppm/° C. The results thereof are shown in Table 4.
Comparative Examples 26 and 27
Influence of w
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions (sintering temperature of 900° C. was additionally conducted) as in the example 15. However, when the molar ratio w of Al2O3 was equal to 0, the absolute value of the temperature coefficient τf of resonant frequency was greater than 50 ppm/° C. in case of sintering temperature of 850° C., and the temperature coefficient τf of resonant frequency was unstably and greatly varied in a range of sintering temperature of 850 to 950° C. When w was equal to or higher than 0.2, the sintering temperature was equal to or higher than 1000° C. The results thereof are shown in Table 4.
Comparative Examples 28 to 42
Influence of the Glass Composition
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass of various compositions at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15. However, when glass compositions which are out of the range of the glass compositions adopted in the present invention were used, glass was melted by a sulfuric acid solution (Comparative Example 35), or the pellets could not be sintered at 1000° C. or lower, or glass was eluted at 800° C. or higher (Comparative Examples 28 to 34 or 36 to 42. The results thereof are shown in Table 4.
Comparative Examples 43 and 44
Influence of the Glass Amount
In the same manner as in the example 15 described above, mixtures of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 mixed at ratios shown in Table 3 were used as base materials. These base materials were mixed with glass at the ratio also shown in Table 3. Then, sintered pellets were prepared under the same conditions as in the example 15. However, when the glass amount was smaller than 3 parts by weight, sintering could not be achieved at 1000° C. or lower. When the glass amount is greater than 30 parts by weight, glass was eluted at 900° C., and reacted with a setter. The results thereof are shown in Table 4.
INDUSTRIAL APPLICABILITY
The dielectric ceramic composition of the present invention enables sintering at a temperature equal to or lower than the melting point of Ag or Cu or alloy containing, as a major component, Ag or Cu, which has been difficult in conventional techniques. Therefore, according to the dielectric ceramic composition of the present invention, such a metal can be used as material of the internal conductor in internal packaging and multi-lamination thereof when manufacturing electronic parts. The dielectric ceramics obtained by sintering the dielectric ceramic composition of the present invention have a relative dielectric constant of about 10 to 40, preferably about 15 to 25, less dielectric loss tan δ (a high Q-value) and an absolute value in temperature coefficient τf of resonant frequency of 50 ppm/° C. or less. According to the present invention, there are provided a dielectric ceramic composition and manufacturing method for obtaining such dielectric ceramics, especially the dielectric ceramic composition and manufacturing method which cause less characteristic changes and variants caused by changes in sintering temperature and causes less changes in composition at the time of sintering. Furthermore, according to the present invention, there is provided a laminated ceramic part such as a laminated ceramic condenser or an LC filter that has a dielectric layer made of such a dielectric ceramic composition as described above and an inner electrode containing Ag or Cu or alloy containing, as a major component, Ag or Cu.

## Claims

1. A dielectric ceramic composition containing:
100 parts by weight of a major component expressed by a general formula of x′Zn2TiO4-(1−x′−y′)ZnTiO3-y′TiO2 where x′ satisfies 0.15<x′<0.8 and y′ satisfies 0≦y′≦0.2; and
3 to 30 parts by weight of lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.

2. Dielectric ceramics containing crystalline phases of Zn2TiO4, ZnTiO3 and TiO2 (where the TiO2 phase may be omitted) and a glass phase, which are obtained by sintering the dielectric ceramic composition as claimed in claim 1.

3. A method of manufacturing the dielectric ceramic composition as claimed in claim 1, comprising the steps of:
mixing powder of raw material of ZnO and powder of raw material of TiO2 and calcining them to obtain ceramic powder containing Zn2TiO4, ZnTiO3 and TiO2 (where the content of TiO2 may be zero); and
mixing the ceramic powder with lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.

4. A laminated ceramic part comprising:
plural dielectric layers;
an internal electrode formed between the dielectric layers; and
an external electrode electrically connected to the internal electrode,
wherein the dielectric layers are constituted by dielectric ceramics obtained by sintering the dielectric ceramic composition as claimed in claim 1, and the internal electrode is made of elemental Cu or elemental Ag or alloy material containing Cu or Ag as a major component.

5. A dielectric ceramic composition containing:
100 parts by weight of a major component expressed by a general formula of xZn2TiO4-yZnTiO3-zTiO2-wAl2O3 where x satisfies 0.15<x<1.0, y satisfies 0<y<0.85, z satisfies 0≦z≦0.2, w satisfies 0<w≦0.2, and x+y+z+w=1 is satisfied; and
3 to 30 parts by weight of lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.

6. Dielectric ceramics containing crystalline phases of Zn2TiO4, ZnTiO3, TiO2 and Al2O3 (where the TiO2 phase may be omitted) and a glass phase, which are obtained by sintering the dielectric ceramic composition as claimed in claim 5.

7. A method of manufacturing the dielectric ceramic composition as claimed in claim 5, comprising the steps of:
mixing powder of raw material of ZnO and powder of raw material of TiO2 and calcining them to obtain ceramic powder containing Zn2TiO4, ZnTiO3 and TiO2 (where the content of TiO2 may be zero); and
mixing the ceramic powder with Al2O3 and lead-free low-melting glass containing ZnO at 50 to 75 wt %, B2O3 at 5 to 30 wt %, SiO2 at 6 to 15 wt %, Al2O3 at 0.5 to 5 wt %, and BaO at 3 to 10 wt %.

8. A laminated ceramic part comprising:
plural dielectric layers;
an internal electrode formed between the dielectric layers; and
an external electrode electrically connected to the internal electrode,
wherein the dielectric layers are constituted by dielectric ceramics obtained by sintering the dielectric ceramic composition as claimed in claim 5, and the internal electrode is made of elemental Cu or elemental Ag or alloy material containing Cu or Ag as a major component.