WO2023080069A1 - 誘電体磁器組成物およびセラミックコンデンサ - Google Patents

誘電体磁器組成物およびセラミックコンデンサ Download PDF

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WO2023080069A1
WO2023080069A1 PCT/JP2022/040331 JP2022040331W WO2023080069A1 WO 2023080069 A1 WO2023080069 A1 WO 2023080069A1 JP 2022040331 W JP2022040331 W JP 2022040331W WO 2023080069 A1 WO2023080069 A1 WO 2023080069A1
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dielectric
ceramic composition
mol
dielectric ceramic
composition
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French (fr)
Japanese (ja)
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智城 村田
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2023557997A priority Critical patent/JP7679887B2/ja
Priority to CN202280073181.3A priority patent/CN118201891A/zh
Publication of WO2023080069A1 publication Critical patent/WO2023080069A1/ja
Priority to US18/646,513 priority patent/US20240294438A1/en
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Definitions

  • the present invention relates to dielectric porcelain compositions and ceramic capacitors.
  • ferroelectric ceramics such as barium titanate (BaTiO 3 ) are generally used as materials for the dielectric portion of ceramic capacitors.
  • dielectric porcelain compositions having various compositions have been proposed as materials for the dielectric portion of ceramic capacitors.
  • a tetragonal tungsten bronze structure with a crystal structure very similar to that of perovskite but with a different polarization structure has been proposed (see Patent Documents 1 and 2, etc.). .
  • Patent Document 1 discloses a compound represented by the general formula ⁇ A 1 ⁇ x (RE) 2x/3 ⁇ y ⁇ D 2 O 5+y and having a tungsten bronze structure, and an oxide of M,
  • A is at least one selected from the group consisting of Ba, Ca, Sr and Mg;
  • D is at least one selected from the group consisting of Nb and Ta;
  • RE is Sc, Y, La, Ce; at least one selected from the group consisting of Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; wherein x and y satisfy the relationship 0 ⁇ x ⁇ 1, y>0;
  • a dielectric ceramic composition is described, wherein M is at least one selected from the group consisting of Al, Si, B and Li.
  • Patent Document 2 discloses a dielectric ceramic composition containing a main component having a tetragonal tungsten bronze structure represented by the general formula A 3 (B1) (B2) 4 O 15 and a subcomponent, A is at least one selected from Ba, Sr, Ca and rare earth elements; B1 and B2 contain Zr and Nb, the subcomponent is at least one selected from Mn, Cu, V, Fe, Co and Si; When the total of B1 and B2 is 100 mol%, the total content of Mn, Cu, V, Fe and Co is 0.5 mol% or more and less than 4 mol%, the Si content is less than 7 mol%, and the Ba content is The content is 9.8 mol% or more and 61.8 mol% or less, the Ca content is less than 51.5 mol%, the Sr content is less than 41.2 mol%, and the rare earth element content is 30.
  • A is at least one selected from Ba, Sr, Ca and rare earth elements
  • B1 and B2 contain Zr and Nb
  • a dielectric porcelain composition is described.
  • Patent Document 3 discloses a dielectric ceramic composition containing oxides of A, R and B and an oxide of Mn, wherein A is at least one selected from the group consisting of K and Na. can be,
  • the R is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc
  • the B is at least one selected from the group consisting of Nb and Ta, the molar ratio of A:R:N:Mn is 2 ⁇ x:1+x/3:5+y:z; wherein x, y and z satisfy -0.3 ⁇ x, 0.6, -0.5 ⁇ y ⁇ 0.5, and 0.001 ⁇ z ⁇ 0.5; Dielectric porcelain composition.
  • Barium titanate which has a perovskite structure, has the drawback that its dielectric constant decreases when a DC voltage is applied (negative bias characteristics) due to its ferroelectricity.
  • the dielectric ceramic compositions described in Patent Documents 1 and 2 which have a tetragonal tungsten bronze structure, suppress the ferroelectricity, thereby reducing the decrease in dielectric constant under direct current voltage. can be done.
  • the dielectric ceramic compositions described in Patent Documents 1 and 2 have not been able to improve the dielectric constant under DC voltage.
  • the dielectric ceramic composition described in Patent Document 3, which has a tetragonal tungsten bronze structure can improve the relative dielectric constant under a DC voltage, but it can expand the application of ceramic capacitors and improve electrical characteristics. In view of this, further improvement in the relative permittivity under DC voltage is required.
  • Non-Patent Document 1 discloses that a substance having such a composition exhibits a low dielectric constant and a low resistivity. Since the substance described in Non-Patent Document 1 has a low resistivity, it is considered difficult to use it as a dielectric under DC voltage, and furthermore, it is not suitable for use as a material for the dielectric portion of a ceramic capacitor.
  • An object of the present invention is to provide a novel dielectric porcelain composition that has a high dielectric constant, a small dielectric loss, an increase in the dielectric constant under a DC voltage, and a high maximum rate of increase. It is in.
  • a further object of the present invention is to provide a ceramic capacitor comprising such a dielectric porcelain composition.
  • the oxide (I) has a tetragonal tungsten bronze structure, said A comprises K and Ba;
  • the R is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc,
  • the B is at least one selected from the group consisting of Nb and Ta,
  • the amount of the substance of B is 4.75 mol or more and 5.25 mol or less with respect to 2 mol of A,
  • X is at least one selected from the group consisting of Mn, Cu, Fe, Co, Ni, V and Si.
  • a novel dielectric porcelain composition which has a high dielectric constant, a small dielectric loss, an increase in the dielectric constant under a DC voltage, and a large maximum rate of increase.
  • a ceramic capacitor comprising such a dielectric porcelain composition.
  • FIG. 1 shows a schematic cross-sectional view of a ceramic capacitor in one embodiment of the present invention
  • FIG. (a) shows a graph of relative permittivity ⁇ ' versus electric field strength E for samples Nos. 1 to 3
  • (b) shows a graph of dielectric loss tan ⁇ with respect to electric field intensity E for samples of sample numbers 1 to 3;
  • the dielectric porcelain composition of the present embodiment (which may also be simply referred to as “(ferro)dielectric ceramic”) contains A, R and B oxides (I).
  • the oxide (I) has a tetragonal tungsten bronze structure, said A comprises K and Ba;
  • the R is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc,
  • the B is at least one selected from the group consisting of Nb and Ta,
  • the amount of substance of B is 4.75 mol or more and 5.25 mol or less with respect to 2 mol of A,
  • the total molar fraction of A, R and B in all metal elements contained in the dielectric ceramic composition is 0.975 or more.
  • the dielectric ceramic composition containing the oxide (I) of A, R, and B A, R, and B are defined, and the relationship between the amounts of A and B and the dielectric ceramic composition
  • A, R, and B are defined, and the relationship between the amounts of A and B and the dielectric ceramic composition
  • the “tetragonal tungsten bronze structure” described in this specification is a crystal structure represented by the general formula A 6 B 10 O 30 (thus also represented by A 3 B 5 O 15 ) (for example Non-Patent Document 1), which is characterized by having a tetragonal crystal structure in a certain temperature range, but is not limited to a tetragonal crystal structure in other temperature ranges, and is accompanied by displacement of each atomic position. It can have other crystal structures including cubic, orthorhombic, and monoclinic.
  • the tetragonal tungsten bronze type structure it is possible to introduce various site defects such as A site and B site, interstitial sites, and site substitution solid solutions. It is called a tetragonal tungsten bronze type.
  • the dielectric ceramic composition contains oxides (I) of A, R and B, the amounts of A, R and B, and the total amount of metal elements contained in the dielectric ceramic composition are arbitrary. can be confirmed and determined by appropriate elemental analysis of A, R and B mole fractions can be identified and determined. It can be confirmed by X-ray diffraction (XRD) analysis or the like that oxide (I) has a tetragonal tungsten bronze structure.
  • XRD X-ray diffraction
  • metal elements include metalloid elements such as B, Si, Ge, As, Sb, and Te in addition to elements that are usually classified as metals.
  • Oxides of A, R and B typically have the general formula K 2-2x Ba 2x (A1) y R ⁇ (1-2x/3) B 5+z O 15+ ⁇ (Wherein, R and B are as described above, A1 is an element other than K and Ba among the elements corresponding to A, x, y and z are 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.5, -0.25 ⁇ z ⁇ 0.25.) can be represented by Without limiting this embodiment, in this case B can be located on the B site of the tetragonal tungsten bronze type structure and K, Ba and A1 are located on the A site of the tetragonal tungsten bronze type structure.
  • R can be located at the A site of the tetragonal tungsten bronze type structure (with A substituted by R and R in solid solution).
  • the molar ratio in the dielectric ceramic composition can be determined based on the amount of A (the sum of K, Ba and A1 corresponds to "2+y").
  • the amount of oxygen O (molarized) “15+ ⁇ ” is difficult to identify by analysis, and ⁇ can take any value depending on the oxidation state and defect state of the substance, but the value of ⁇ is the value of the present invention. It does not affect the effect.
  • ⁇ may satisfy ⁇ 5 ⁇ 7.5.
  • ⁇ can take any value depending on the type of A1 and the ratio of K, Ba and A1.
  • ⁇ may satisfy 0.8 ⁇ 1.2, and may further satisfy 0.9 ⁇ 1.1.
  • A includes K and Ba.
  • the dielectric loss can be reduced while maintaining the dielectric constant, the dielectric constant can be increased under direct current, and the maximum rate of increase can be increased.
  • K and Ba which have similar ionic radii and different valences, a tetragonal tungsten bronze structure can be obtained while moderately suppressing ferroelectricity. It is considered that the polarization structure is modulated (the polarization network is modulated) and a large effect is obtained.
  • the molar fraction (or atomic ratio) of K in A may be, for example, 0.1 or more, further 0.2 or more, and may be, for example, 0.95 or less.
  • the molar fraction (or atomic ratio) of Ba in A may be, for example, 0.05 or more, and may be, for example, 0.9 or less, or even 0.8 or less.
  • the total molar fraction (or total atomic ratio) of K and Ba in A can be, for example, 0.8 or more, further 0.9 or more, particularly 0.94 or more, and can be 1 or less.
  • A may further contain alkali metal elements such as Na and alkaline earth metal elements such as Sr.
  • the molar fraction (or atomic ratio) of A in all the metal elements contained in the oxide (I) can be, for example, 0.2 or more, further 0.23 or more, especially 0.25 or more, for example 0 .3 or less, or even 0.28 or less.
  • R is a rare earth element and at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc .
  • R includes La and Pr.
  • the dielectric constant can be increased under a DC voltage, and the maximum rate of increase can be increased.
  • the present invention is not bound by any theory, it is believed that by combining La and Pr, which have large ionic radii, the polarization structure is appropriately adjusted (the polarization network is modulated), and a greater effect can be obtained. .
  • the total molar fraction (or total atomic ratio) of La and Pr in R can be selected as appropriate, and can be, for example, 0.25 or more, further 0.333 or more, and for example, 1 or less. obtain.
  • R may be La and Pr only, or may contain at least one other element in addition to La and Pr.
  • the substance amount of R may be, for example, 0.4 mol or more, further 0.466 mol or more, and may be, for example, 0.967 mol or less with respect to 2 mol of A.
  • B is at least one selected from the group consisting of Nb and Ta, and preferably contains Nb.
  • the molar fraction (or atomic ratio) of Nb in B can be, for example, 0.8 or more, or even 0.9 or more, and can be 1 or less.
  • the amount of substance of B is 4.75 mol or more and 5.25 mol or less with respect to 2 mol of A.
  • the dielectric loss can be reduced while maintaining the dielectric constant, the dielectric constant can be increased under direct current, and the maximum rate of increase can be increased.
  • the ratio of A to B is within a certain range, so that the heterophase segregation is suppressed and the tetragonal tungsten bronze structure is maintained, and the tetragonal tungsten bronze structure is It is considered that the polarization structure of is modulated (the polarization network is modulated), and a large effect can be obtained.
  • the total molar fraction (or total atomic ratio) of A, R and B in all the metal elements contained in the ceramic composition is 0.975 or more, for example 0.980 or more, or more preferably 0.980 or more. It can be 985 or greater, 1 or less, and can be 0.997 or less.
  • the high molar fractions of A, R, and B contained in the ceramic composition, and the presence of the oxide (I) as a main component, facilitates the appropriate adjustment of the polarization structure (the polarization network is easily modulated). ), it is considered that a large effect can be obtained.
  • the dielectric ceramic composition may further contain X oxide (II).
  • the form in which the oxide of X (II) exists in the dielectric ceramic composition is not particularly limited. may be dissolved in the oxide of X (I). That is, at least part of the elements (constituent elements) contained in the oxide (II) of X may replace at least part of the elements (constituent elements) contained in the oxide (I), Elements (constituent elements) contained in the oxide (II) may intervene between the elements (constituent elements) contained in the oxide (I).
  • X is preferably at least one selected from the group consisting of Mn, Cu, Fe, Co, Ni, V and Si, and at least one selected from the group consisting of Mn, Si, Fe and Cu. Preferably.
  • the amount of substance of X may be, for example, 0.18 mol or less, further 0.15 mol or less, especially 0.1 mol or less, for example 0 mol or more, further 0.025 mol or more, relative to 2 mol of A. obtain.
  • the total molar fraction (or total atomic ratio) of A, R, B and X in all the metal elements contained in the dielectric ceramic composition is, for example, 0.8 or more, further 0.9 or more, especially 0 .95 or greater and may be 1 or less.
  • the dielectric ceramic composition of the present embodiment contains oxides of A, R and B (I), optionally further containing oxides of X (II), and typically substantially oxides ( I), or these oxides (I) and (II).
  • the dielectric porcelain composition of this embodiment may contain other trace substances, such as trace elements that may be unavoidably mixed.
  • the dielectric composition of the present embodiment may optionally be any suitable material depending on the application desired for the dielectric magnetic composition. other tertiary ingredients (in relatively minor amounts relative to the essential ingredients).
  • the dielectric porcelain composition of this embodiment can be manufactured by any appropriate method, and can be manufactured, for example, as follows.
  • the dielectric ceramic composition of the present embodiment may be obtained by obtaining a main component composition consisting of oxides of A, R and B, and optionally introducing an oxide of X as an auxiliary component.
  • Such base compositions can be prepared by any suitable method, which may be a solid phase method, a wet method or a gas phase method.
  • the solid phase method uses at least one selected from the group consisting of oxides, hydroxides, carbonates and other compounds of each element as element sources for A, R and B, and powders of such element sources is calcined to obtain oxides of A, R and B by solid phase reaction, and the main component composition can be in the form of calcined raw material powder.
  • the wet method includes a coprecipitation method, a hydrothermal method, an oxalic acid method, and the like.
  • the vapor phase method includes, for example, a method using high-frequency plasma.
  • the base composition may have a tetragonal tungsten bronze type structure consisting of oxides of A, R and B, which means that oxidation of A, R and B in the final dielectric porcelain composition It is not essential to this embodiment, as long as a tetragonal tungsten bronze type structure consisting of crystalline materials is obtained.
  • Introduction of the oxide of X into the main component composition can be carried out by any suitable method.
  • the element source of X at least one selected from the group consisting of oxides, hydroxides, carbonates and other compounds of X is used, and the powder of the element source of X is added to the main component composition.
  • a dielectric ceramic composition into which an oxide of X is introduced may be obtained by adding X and subjecting the resulting X mixed material composition to a heat treatment.
  • the elemental sources of A, R, B and X to be used can be weighed according to the molar ratios desired for the finally obtained dielectric ceramic composition.
  • a tetragonal tungsten bronze type consisting of oxides of A, R and B It is believed that it does not substantially affect the structure.
  • the dielectric porcelain composition of this embodiment has a high dielectric constant.
  • the relative dielectric constant ⁇ (-) is, for example, 280 or more, or even 330 It may be above, especially above 380, for example below 1,200, further below 800, especially below 700.
  • the dielectric loss may be for example less than 1%, even 0.8% or less, especially 0.7% or less.
  • the dielectric porcelain composition of this embodiment can be suitably used as a material for the dielectric portion of a ceramic capacitor.
  • the dielectric ceramic composition of the present embodiment has an increased dielectric constant under a DC voltage (positive bias characteristic), and the maximum rate of increase is large.
  • the dielectric constant initially increases and shows a peak (maximum value) at a certain voltage value. After that, it decreases at higher voltage values.
  • the dielectric ceramic composition of this embodiment has a large rate of increase ⁇ DC from the relative permittivity ⁇ ( ⁇ ) to the peak relative permittivity ⁇ DC ( ⁇ ) when no voltage is applied.
  • the positive bias peak value ⁇ DC (%) may be, for example, greater than 23%, further 25% or more, particularly 30% or more.
  • the peak electric field intensity E DC may be, for example, 4 MV/m or more, or even 5 MV/m or more, and may be, for example, 20 MV/m or less, or even 15 MV/m or less.
  • the dielectric porcelain composition of this embodiment can be suitably used as a material for the dielectric portion of a ceramic capacitor for applications where a high DC voltage is applied. can be effectively reduced.
  • the ceramic capacitor of this embodiment includes two electrodes and a dielectric portion located between the two electrodes, and the dielectric portion is formed from the dielectric porcelain composition described above.
  • a ceramic capacitor needs at least two electrodes, and two or three or more electrodes are provided with a dielectric portion positioned between them.
  • the electrodes may include an internal electrode that exists inside the dielectric portion and an external electrode that exists outside the dielectric portion and is (at least electrically) connected to a predetermined internal electrode.
  • the electrode material is not particularly limited, and any appropriate conductive material can be used.
  • the ceramic capacitor of this embodiment can be, for example, the multilayer ceramic capacitor 10 shown in FIG.
  • a multilayer ceramic capacitor 10 includes a dielectric portion 1 made of a dielectric porcelain composition, internal electrodes 3 and 5 embedded in the dielectric portion 1 and alternately arranged, and connected to the internal electrodes 3 and 5, respectively. and external electrodes 7 and 9 .
  • three internal electrodes 3 and 5 are schematically shown, but the number of internal electrodes can be appropriately selected according to the specifications of the capacitor.
  • the ceramic capacitor of this embodiment can be manufactured by any appropriate method.
  • the ceramic capacitor of the present embodiment may be manufactured by using, as the ceramic raw material, the X mixed raw material composition described above with respect to the method for manufacturing the dielectric ceramic composition. It is not limited to this.
  • the ceramic capacitor of this embodiment can exhibit the same effect as the dielectric ceramic composition of this embodiment described above, has a high dielectric constant, and improves the dielectric constant under a DC voltage.
  • a dielectric magnetic composition comprising oxides of A, R and B and optionally an oxide of X (having a tetragonal tungsten bronze type structure consisting of oxides of A, R and B) was prepared by the following procedure. , optionally further comprising an oxide of X), wherein the molar ratios of A, R, B and X are varied as shown in Sample Nos. 1-37 in Tables 1-2.
  • a porcelain composition was obtained. More specifically, it comprises two electrodes and a dielectric portion located between the two electrodes, the dielectric portion comprising dielectrics having different molar ratios of A, R, B and X as described above.
  • a ceramic capacitor formed from the body ceramic composition was produced.
  • those corresponding to the comparative examples of the present invention are marked with a symbol "*", and the others correspond to the examples of the present invention.
  • PSZ partially stabilized zirconia
  • the slurry thus obtained is dried, sized, and then calcined in the atmosphere at 1,000 to 1,200° C. to obtain a main component composition from the oxides of A, R, and B.
  • a calcined raw material powder having a tetragonal tungsten bronze type structure was synthesized.
  • MnCO 3 , SiO 2 , Fe 2 O 3 , and CuO are used as the element source of X in this calcined raw material powder, and the molar ratio of X to each element of A, R, and B shown in Tables 1 and 2 is adjusted to Correspondingly, these elemental sources were weighed and added to obtain the X mixed raw material composition.
  • a polyvinyl butyral-based binder, a plasticizer, ethanol and toluene were added to this X mixed raw material composition, and wet-mixed together with PSZ balls by a ball mill to prepare a ceramic slurry for sheet molding.
  • This sheet-forming ceramic slurry was formed into a sheet with a thickness of 20 ⁇ m by a doctor blade method to obtain a rectangular ceramic green sheet.
  • a conductive paste containing Pt powder as a conductive component was screen-printed in a predetermined pattern on the ceramic green sheets to form precursor layers of internal electrodes.
  • the ceramic green sheets printed with a conductive paste (precursor layers of internal electrodes) containing Pt powder as a conductive component were arranged so that the sides where the conductive paste reached the sheet ends (extracted to the outside) were alternately arranged.
  • a laminate was obtained by laminating a predetermined number of sheets on the .
  • a conductive paste containing Pt powder as a conductive component is applied to both end surfaces where the conductive paste (precursor layer of the internal electrode) of the laminate is exposed to form a precursor of the external electrode, It was degreased by heating at 500° C. in the air. By holding this degreased laminate at 1,300 to 1,450° C. for 120 minutes in the atmosphere, the ceramic containing oxides of the elements shown in Tables 1 and 2 is densified, and the conductive paste is removed from the inside. Electrodes and external electrodes were formed.
  • a multilayer ceramic capacitor 10 was fabricated including external electrodes 7 and 9 connected to , and 5, respectively.
  • the obtained multilayer ceramic capacitor had external dimensions of 2.7 mm in width, 3.6 mm in length and 0.56 mm in thickness, and the total number of internal electrodes was two.
  • the layer thickness was 48 ⁇ m
  • the thickness of each internal electrode was 1 ⁇ m
  • the counter electrode area of adjacent internal electrodes was 3.2 mm 2 .
  • the capacitance and dielectric loss tan ⁇ of the manufactured multilayer ceramic capacitors of sample numbers 1 to 37 were measured at room temperature under the conditions of a measurement frequency of 1 kHz and a measurement voltage of 1 Vrms without applying a DC voltage. It was measured. A dielectric constant ⁇ ( ⁇ ) was calculated from the capacitance. When the dielectric loss tan ⁇ was less than 10%, the insulation was good and judged as G. When the dielectric loss tan ⁇ was 10% or more, the insulation was judged as poor and judged as NG.
  • dielectric loss is generally a value that indicates the dielectric properties of a material. becomes larger. Since the value of dielectric loss tan ⁇ derived from the dielectric properties of the dielectric magnetic composition of the present embodiment is generally less than 10%, when the value of dielectric loss tan ⁇ is 10% or more, this is regarded as the contribution of leakage current. It was determined that the insulation was defective. In the case of poor insulation, it was not possible to measure capacitance under a DC voltage, which will be described below.
  • a DC voltage is applied while changing the voltage value from 0 V to 770 V under the conditions of a measurement frequency of 1 kHz and a measurement voltage of 1 Vrms at room temperature, and the capacitance at each voltage is measured.
  • a dielectric constant was calculated.
  • the relative permittivity monotonically decreased under a DC voltage (negative bias characteristics), and in some of the samples, the relative permittivity increased as the voltage was increased (positive bias characteristics). All of the samples exhibiting positive bias characteristics had a peak (maximum value) in relative permittivity at a certain voltage value, and the relative permittivity turned to decrease at a voltage value higher than that.
  • the electric field strength at which the relative permittivity changes from increasing to decreasing is defined as the peak electric field strength E DC
  • the relative permittivity at the peak electric field strength E DC is defined as the peak relative permittivity ⁇ DC .
  • sample numbers 1 to 37 that correspond to the examples of the present invention have an overall judgment of "G” or "G+”. It had a high dielectric constant ⁇ , a small dielectric loss tan ⁇ , and a high positive bias peak value ⁇ DC (that is, the dielectric constant increased under DC voltage, and the maximum rate of increase was large. rice field). From this, it can be said that good insulation and positive bias characteristics are compatible. Further, as shown in sample numbers 1 to 6, 8 to 17, 30, 31, 33 to 36, A consists of K and Ba, and the total molar fraction of La and Pr in R is 0.333 or more.
  • sample number 29 when the substance amount of B is less than 4.75 mol with respect to 2 mol of A, the ferroelectricity is strongly exhibited, so the dielectric constant decreases monotonically under a DC voltage. and did not exhibit positive bias characteristics.
  • sample number 32 when the substance amount of B exceeds 5.5 mol with respect to 2 mol of A, heterophase segregation (segregation of a crystal phase without a tetragonal tungsten type structure) occurs, resulting in insulation. sexuality worsened.
  • sample number 37 when the total mole fraction of A, R and B in all the metal elements contained in the dielectric ceramic composition is less than 0.975, slight impurity segregation occurs. insulation deteriorated.
  • the dielectric porcelain composition of the present invention can be suitably used as a material for the dielectric portion of ceramic capacitors, but is not limited to this.
  • the ceramic capacitor of the present invention can be used in a wide variety of applications where a DC voltage is applied, but is not limited to this.

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