JP2013001625A - Dielectric composition and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric composition which can be used at a higher temperature and has a higher dielectric constant, and a method for manufacturing the same.SOLUTION: The dielectric composition has a composition represented by the general formula: M(1)M(2)M(3)M(4)ON, wherein M(1) element is at least one element selected from Y, La, Ce, Pr, Nd and Gd; M(2) element is at least one element selected from Mg, Ca, Sr and Ba; M(3) element is at least one element selected from Ti and Zr; M(4) element is at least one element selected from V, Nb and Ta; and O element and N element are oxygen and nitrogen, respectively.

Description

  The present invention relates to a dielectric composition mainly composed of an inorganic compound and a method for producing the same. More specifically, the present invention relates to a high-temperature dielectric composition that has a high relative dielectric constant and can be used under higher temperature conditions than before, and a method for producing the same.

In recent years, global attention has been gathered on the global warming problem, and there is a strong demand for reduction of CO ₂ emissions or improvement of energy efficiency through the spread of electric vehicles, hybrid cars, next-generation power transmission networks, etc. . For these, a power module having a high junction temperature is generally used. Therefore, an electronic device disposed around the power module is required to have a high operating temperature.

Dielectrics are widely used in capacitors, thermistors, filters, resonators, antennas, oscillators, etc., but barium titanate, a typical dielectric, has an upper temperature range of 125 ° C due to the Curie point. It is. However, the junction temperature of the power module is expected to reach 200 ° C., and development of a dielectric composition that can be used even under high temperature conditions replacing barium titanate is strongly desired.
In addition, when considering in-vehicle applications such as electric vehicles and hybrid cars, electronic devices are required to be smaller and lighter as well as general in-vehicle components. Barium titanate, which is a typical dielectric, is a dielectric having a high relative dielectric constant of about 1000 to 2000. However, due to the demand for reduction in size and weight of electronic devices at present, dielectric materials (dielectric compositions) There is a strong demand for higher dielectric constants.

As an attempt to extend the upper limit of the operating temperature range of barium titanate, a method in which a part of the Ba site is replaced with Ca and Dy ₂ O ₃ and MgO are added has been studied (see Non-Patent Document 1 below). . According to this method, a rapid change in the relative dielectric constant in the vicinity of the Curie point is suppressed, but at the same time, there is a problem that the relative dielectric constant decreases in a usable temperature range below the Curie point.

Nitride and oxynitride generally have a higher thermal phase transition point than oxides because they have higher covalent bonding than oxides. Since the Curie point of barium titanate is caused by the phase transition, it is presumed that the dielectric material containing nitrogen has a high Curie point.
A wide variety of compounds are known as nitrides and oxynitrides (nitrides, oxynitride perovskite compounds) having a perovskite structure that is the same crystal structure as barium titanate. Patent Document 1 discloses a synthesis method and dielectric characteristics of various nitrides and oxynitrides having a perovskite structure, and in addition, in a temperature range of 90 to 370 K (−183 to 97 ° C.). It is described that there is no change in the dielectric constant. However, details regarding the dielectric properties are not described, and the dielectric properties of nitride and oxynitride perovskite compounds are not clear.

Non-Patent Document 2 discloses that various types of oxynitrides having a perovskite structure, BaTaO ₂ N and SrTaO ₂ N, exhibit dielectric properties and have a relative dielectric constant of about 4900 and 2900, respectively. ing. However, the relative permittivity described in Non-Patent Document 2 is not sufficient to meet the current demand for smaller and lighter electronic devices.

US Pat. No. 4,734,390

Noriyuki Kubotera et al. Ceramics 45 (2010) 453-457. Young-Il Kim, et. al. Chem. Mater. , 16 (2004) 1267-1276. Teruki Motohashi, et. al. , Mater. Res. Bull. , 44 (2009) 1899-1905.

  The present invention is intended to solve the above-mentioned problems, has no Curie point between room temperature and 200 ° C., and has a higher relative dielectric constant than the conventionally known oxynitride perovskite compounds. It is an object of the present invention to provide a dielectric composition having the above and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a compound having a specific chemical composition does not have a Curie point between room temperature and 200 ° C., and is a conventionally known oxynitriding process. It has been found that it has a relative dielectric constant higher than that of a physical perovskite type compound, and the present invention shown below has been completed.

[1] General formula: M (1) _1-x M (2) _x M (3) _1-y M (4) _y O _{2 + xy} N _{1-x + y}
A dielectric composition characterized by having a composition represented by:
However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb, and Ta, and O element and N The elements are oxygen and nitrogen, and 0 <x <1 and 0 ≦ y ≦ 1.
[2] The dielectric composition as described in [1] above, wherein 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9.
[3] The above-mentioned [2], wherein the M (1) element is at least one selected from La, Ce, Pr, and Nd, and the M (2) element is at least one selected from Sr and Ba. The dielectric composition according to 1.
[4] The dielectric according to [3] above, wherein the M (1) element is La, the M (2) element is Ba, the M (3) element is Ti, and the M (4) element is Ta. Composition.

[5] A step of heating any of the following raw materials [1] to [3] to produce an intermediate compound of any of the following [4] to [6], and the intermediate compound in a reducing atmosphere The method for producing a dielectric composition as described in any one of [1] to [4] above, further comprising a step of heating in.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[6] The method for producing a dielectric composition as described in [5] above, wherein at least one of the compounds is an oxide.
[7] The production of the dielectric composition as described in any one of [1] to [4] above, which includes a step of heating any of the following raw materials [1] to [3] Method.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the compounds).
[8] The method for producing a dielectric composition as described in [7] above, wherein at least one of the compounds is an oxide.
[9] The production of the dielectric composition as described in any one of [1] to [4] above, which includes a step of heating any of the following raw materials [1] to [3] Method.
[1] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material comprising one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element and M (4) element are included in at least one of the above compounds).
[10] The method for producing a dielectric composition as described in [9] above, wherein at least one of the compounds is an oxide.

  According to the above configuration, it is possible to provide a dielectric composition that does not have a Curie point between room temperature and 200 ° C. and has a higher relative dielectric constant than a conventionally known oxynitride perovskite compound. it can. That is, it is possible to provide a dielectric composition that has a high relative dielectric constant and can be used as a dielectric even under higher temperature conditions than before.

Hereinafter, the dielectric composition according to the present embodiment will be described in detail.
The dielectric composition of the present embodiment is
General formula: M (1) _1-x M (2) _x M (3) _1-y M (4) _y O _{2 + xy} N _{1-x + y}
It is characterized by comprising the composition shown by.
However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb, and Ta, and O element and N Elements are oxygen and nitrogen.
In addition, you may contain another element in the dielectric composition of this invention in the range which does not impair the effect of this invention. Moreover, you may contain the other element inevitably introduced in a manufacturing process.
In the present embodiment, the values of x and y are in the range of 0 <x <1, 0 ≦ y ≦ 1.
Hereinafter, the reasons for limiting each element and the numerical range of the above x and y will be described in detail.

The M (1) element is preferably at least one selected from La, Ce, Pr, and Nd. The M (2) element is preferably at least one selected from Sr and Ba.
In the dielectric composition having the composition represented by the above general formula, each of the M (1) and M (2) elements is selected from one or more selected from La, Ce, Pr, and Nd, and Sr and Ba. When it is one or more, a dielectric composition having no Curie point between room temperature and 200 ° C. and having a higher relative dielectric constant than a conventionally known oxynitride perovskite compound can be obtained. .
The most preferred M (1), M (2), M (3) and M (4) elements are La, Ba, Ti and Ta, respectively. When the elements M (1), M (2), M (3), and M (4) are La, Ba, Ti, and Ta, respectively, they do not have a Curie point between room temperature and 200 ° C. A dielectric composition having a dielectric constant sufficiently higher than that of known oxynitride perovskite compounds can be obtained.

In the present embodiment, the values of x and y are in the range of 0 <x <1, 0 ≦ y ≦ 1. It is preferable that 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9. A conventionally known oxynitride having no Curie point between room temperature and 200 ° C. when the values of x and y are in the range of 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9 A dielectric composition having a higher relative dielectric constant than the perovskite type compound can be obtained.
More preferable values of x and y are 0 <x ≦ 0.4 and 0 ≦ y ≦ 0.5. A conventionally known oxynitride having no Curie point between room temperature and 200 ° C. when the values of x and y are in the range of 0 <x ≦ 0.4 and 0 ≦ y ≦ 0.5 A dielectric composition having a dielectric constant sufficiently higher than that of the perovskite type compound can be obtained.
Further preferable values of x and y are 0.05 <x ≦ 0.2 and 0.05 ≦ y ≦ 0.15. When the values of x and y are in the range of 0.05 <x ≦ 0.2, 0.15 ≦ y ≦ 0.15, there is no Curie point between room temperature and 200 ° C., and it is conventionally known It is possible to obtain a dielectric composition having a dielectric constant sufficiently higher than that of the oxynitride-based perovskite compound.
The reason why the value of the dielectric constant changes depending on the values of x and y is not clear, but the crystal structure is changed by the change in nitrogen content due to the solid solution of elements having different ionic radii or the solution of elements having different oxidation numbers. It can be considered that moderate distortion is generated, and as a result, dielectric polarization is likely to occur.

Next, a method for producing a dielectric composition according to this embodiment will be described.
The manufacturing method of the dielectric composition of the present embodiment is as described above.
General formula: M (1) _1-x M (2) _x M (3) _1-y M (4) _y O _{2 + xy} N _{1-x + y}
(However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb and Ta, and O and N Are oxygen and nitrogen.) In order to obtain a dielectric composition having the composition represented by (1) to [3], any one of the following [1] to [3] is heated, and the following [4] to [6] And a step of heating the intermediate compound in a reducing atmosphere.
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
The intermediate compound is obtained by a mixed powder obtained by mechanically mixing the raw materials (synthetic raw materials) as shown in the above [1] to [3], or by a method of mixing via a liquid phase. It can be obtained by calcining the raw material mixture.

  It is preferable that at least one of the compounds described in the above [1] to [3] used as a raw material for synthesis of the dielectric composition of the present invention is an oxide. In addition to oxides, compounds that form oxides by heating, or complex compounds containing the above elements may be used.

Examples of the method for mixing the raw materials for synthesis include a method of mechanically mixing powdery raw materials for synthesis (raw material powder) and a method of mixing via a liquid phase.
When mixing mechanically, it can be mixed by a dry mill that does not use a solvent, but it is generally preferable to mix with a solvent by a wet mill to form a mixed slurry. When the wet mill method using a solvent is used, this mixed slurry is evaporated to dryness, whereby a microscopically uniform mixed powder can be obtained in a short time.
In addition, as a kind of mill, a ball mill, a vibration mill, an attrition mill or the like can be used, but a ball mill is suitable from the viewpoint of equipment cost. In addition, examples of the solvent used for mixing in the wet mill include ethanol, methanol, isopropanol, hexane, acetone, water, and the like. Is preferred.

Moreover, the ratio of the raw material powder and the solvent is determined by the viscosity of the obtained mixed slurry. A preferred mixed slurry has a viscosity of 50 to 500 cps. If the viscosity of the mixed slurry is less than 50 cps, the amount of energy required for drying the mixed slurry increases, which is not preferable. On the other hand, when the viscosity of the mixed slurry exceeds 500 cps, it takes a long time to obtain a uniform mixed powder, which is not preferable.
The obtained mixed slurry may be left in a dryer or the like to evaporate the solvent. However, using a spray dryer, the solvent was removed in a shorter time without worrying about re-separation of the raw material powder. A mixed powder can be obtained. Moreover, since the mixed powder obtained using the spray dryer has a granular form of several tens to several hundreds of μm, it is excellent in fluidity and easy to handle.

Moreover, the case where a raw material powder is mixed through a liquid phase to make a raw material mixture is described.
The raw material mixture used for the synthesis of the dielectric composition of the present invention can also be obtained by a method via a liquid phase, such as a coprecipitation method, a metal alkoxide method, or a gelation method (see Non-Patent Document 3). When a raw material mixture obtained by a liquid phase method is used for synthesis of a dielectric composition, a desired dielectric composition is obtained by firing in a shorter time than when raw material powders are mechanically mixed. Can do.

  The dielectric composition of the present invention is synthesized by calcining a mixed powder obtained by mechanical mixing of raw material powders as described above, or a raw material mixture obtained by a method via a liquid phase. In addition to the intermediate compound, a mixture of intermediate compounds or a mixture of intermediate compound and raw material powder can be used. As the mixing method in this case, the same method as the above-described raw material powder mixing method can be used.

Moreover, it is preferable that at least one of the compounds described in [4] to [6] constituting the intermediate compound is an oxide. In the case where the elements M (1), M (2), M (3) and M (4) are La, Ba, Ti and Ta, respectively,
La ₂ Ti ₂ O ₇ , LaTiO ₃ , La ₂ TiO ₅ , La ₄ Ti ₃ O ₁₂ , La _1.33 Ti ₈ O ₁₆ , La ₅ Ti ₄ O ₁₅ , La ₉ Ti ₇ O ₂₇ , La ₄ Ti ₉ O ₂₄ , La ₅ Ti ₅ O ₁₇ , La ₂ Ti ₃ O ₉ , Ba ₂ Ti ₆ O ₁₃ , BaTi ₂ O ₅ , Ba ₂ TiO ₄ , BaTi ₆ O ₁₃ , BaTiO ₃ , Ba ₂ Ti _5.5 O ₁₃ , BaTi ₈ O ₁₆ , Ba ₆ Ti ₁₇ O ₄₀ , BaTi ₅ O ₁₁ , BaTi ₄ O ₉ , Ba ₂ Ti ₉ O ₂₀ , Ba ₂ Ti ₁₃ O ₂₂ , Ba ₄ Ti ₁₂ O ₂₇ , Ba ₄ Ti ₁₃ O ₃₀
BaLa ₄ Ti ₄ O ₁₅ , BaLa ₂ Ti ₃ O ₁₀ , Ba ₂ La ₄ Ti ₅ O ₁₈ , Ba _3.99 La _8.94 Ti ₁₈ O ₅₄ , Ba _0.998 La _2.235 Ti _4.5 O _{13 .5}
LaTaO ₄ , La ₃ TaO ₇ , LaTa ₇ O ₁₉ , LaTa ₃ O ₉ , Ba ₅ Ta ₄ O ₁₅ , BaTa ₂ O ₆ , Ba ₂ Ta ₁₅ O ₃₂ , Ba ₃ Ta ₅ O ₁₅ , Ba ₄ Ta ₂ O ₉
La ₃ Ti _1.92 Ta _1.08 O ₁₁ , La ₆ Ti _3.84 Ta _2.16 O ₂₂
Etc. can be exemplified.

  The above-mentioned intermediate compound can be obtained by heating (calcining) a mixed powder or a raw material mixture, which is an oxide or a compound that forms an oxide by heating, in air. In consideration of the reactivity of the nitriding process described later, the heating temperature (temporary firing temperature) is preferably 1400 ° C. or lower. When the pre-baking temperature exceeds 1400 ° C., the particle size of the generated intermediate compound becomes large, which is not preferable because the reactivity in the nitriding treatment process is lowered.

  The above-described oxide group is merely an example of an intermediate compound, and La, Ba, Ti, and Ta constituting the above-described oxide group are represented by M (1), M (2), M (3) and M (4) element (M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, Gd, and M (2) element is Mg, Ca, Sr, One or more elements selected from Ba, M (3) element is one or more elements selected from Ti, Zr, and M (4) element is one or more elements selected from V, Nb, Ta In the case of (element), the same effect can be obtained. The same effect can be obtained by using a double oxide composed of the above-described oxide, M (1) element oxide, and M (2) element oxide.

In addition, the dielectric composition according to the present embodiment can also be manufactured by heating (baking) the above-described raw material (synthetic raw material) in a reducing atmosphere.
That is, the method for manufacturing a dielectric composition according to this embodiment may include a step of heating any of the following raw materials [7] to [9] in a reducing atmosphere.
[7] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[8] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[9] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
As described above, the dielectric composition according to this embodiment can be manufactured by a method in which the raw material is directly reduced and nitrided without generating the intermediate compound as described above.

In addition, the dielectric composition according to the present embodiment can be produced by using the above-described intermediate compound as a starting material and heating (baking) the starting material in a reducing atmosphere.
That is, the method for manufacturing a dielectric composition according to this embodiment may include a step of heating any of the following raw materials (intermediate compounds) [10] to [12] in a reducing atmosphere.
[10] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[11] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[12] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)

  When the above raw material mixture, mixed powder, intermediate compound or mixture containing the intermediate compound is fired in a reducing atmosphere (nitriding treatment step), it is preferably fired in a state where the bulk density is maintained at 40% or less. The bulk density is the volume filling rate of the powder, and is a value obtained by dividing the ratio of mass to volume when filling a certain container by the theoretical density of the compound. Firing while maintaining the bulk density at 40% or less is achieved by firing the raw material mixture, mixed powder, intermediate compound or mixture containing the intermediate compound with a free space around the raw material mixture, mixing This is because the reactivity of the powder, the intermediate compound or the mixture containing the intermediate compound and the atmospheric gas is improved.

The firing temperature when firing in a reducing atmosphere is in the temperature range of 800 to 1500 ° C. Although a desired dielectric composition is obtained by this, a preferable temperature range is 800-1200 degreeC. If the firing temperature is lower than 800 ° C., it takes a long time to obtain a desired dielectric composition, and if it is higher than 1500 ° C., thermal decomposition starts on the surface of the dielectric composition, which is not preferable.
The firing time is about 1 to 20 hours, but repeated firing may be performed in order to obtain a more uniform dielectric composition. In the case of repeatedly firing, it is preferable to improve uniformity by crushing and mixing the first fired product before the second and subsequent firings.
The firing atmosphere is a reducing atmosphere. In addition, the atmosphere in which at least one selected from nitrogen and ammonia and hydrogen as necessary is added is preferable. Most preferred is in an ammonia atmosphere. The atmosphere gas may be in a state where it is filled in a firing furnace, but it is preferable to perform the firing in an atmosphere gas flow. The gas flow rate is usually 10 ml / min or more.

Further, alumina, calcia, magnesia, graphite or boron nitride can be used as the material for the container filled with the intermediate compound or the mixture containing the intermediate compound.
At the start of firing, it is necessary to temporarily reduce the pressure in a reduced pressure or vacuum state and exhaust the residual air in the furnace to the outside of the furnace, or purge the residual air in the furnace using the atmospheric gas to be used. In the latter case, since it takes a long time to remove residual air, it is preferable to use a reduced pressure or vacuum state.

  When producing a sintered body of the dielectric composition of the present invention, a small amount of sintering aid can be used. Examples of the sintering aid include alkali metals, alkaline earth metals, silicon, bismuth, boron oxides, fluorides, and the like. Generally, the addition amount of the sintering aid is about 0.1 to 10% by weight.

Moreover, it is also possible to produce a laminated sintered body by using the dielectric composition according to the present invention.
When producing this laminated sintered body, a sintering aid, a binder, a solvent and other additives are added to the dielectric composition powder of the present invention and kneaded to form a ceramic slurry. As the binder, polyvinyl butyral resin, polyvinyl alcohol, acrylic acid polymer, or the like can be used. As the solvent, ethanol, isopropyl alcohol, water, or the like can be used.
The obtained ceramic slurry is applied to a long base film such as a PET film in the form of a sheet using an application machine such as a doctor blade or a roll coater to obtain a ceramic green sheet.

When a multilayer ceramic capacitor is manufactured, a conductive paste is applied to the ceramic green sheet by screen printing or the like to form an internal electrode metal layer. As the conductive paste used for forming the internal electrode metal layer, a metal powder such as Pt, Pd, Ag, Cu, or Ni dispersed in a binder is used.
The ceramic green sheets on which the internal electrode metal layer is formed are punched into a predetermined shape, and these are stacked and pressure-bonded to obtain a ceramic laminate. This laminate is cut and divided to obtain laminate chips. The laminate chip is heated, debindered, and then fired.
An external electrode is formed by baking a conductive paste on the fired multilayer chip to obtain a multilayer ceramic capacitor. Alternatively, a conductive paste may be applied to an unsintered multilayer chip and baked simultaneously with the firing of the ceramic dielectric layer.

The dielectric composition of the present invention can be used as a circuit board material having a function as a capacitor by producing a composite in which a dielectric composition powder and a resin are mixed.
The resin in this case may be either thermoplastic or thermosetting resin, but is preferably a thermosetting resin from the viewpoint of solder heat resistance. As the thermoplastic resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyetherimide resin, liquid crystal polymer resin, polystyrene resin, polyethylene resin, fluorine resin, or the like can be used. Moreover, in thermosetting resin, resin generally used for the insulating layer of a printed wiring board, such as an epoxy resin, a phenol resin, a polyimide resin, an acrylic resin, a cyanate resin, a benzocyclobutene resin, can be used. In particular, an epoxy resin is preferable from the viewpoint of thermosetting shrinkage and viscosity. The epoxy resin is a resin obtained by combining a prepolymer containing two or more epoxy groups (oxirane rings) in a molecular structure and a curing agent. Moreover, conventionally used curing agents such as a phenol novolak resin, a bisphenol A type novolak resin, an aminotriazine compound, and a naphthol compound can be used as the curing agent.

As a method for dispersing the dielectric composition powder in the resin when producing the composite, conventional methods such as ultrasonic dispersion, three rolls, CLEARMIX, homogenizer, media disperser, and rotation / revolution mixer may be used. However, from the viewpoint of controlling the dispersion state, it is preferable to use one selected from three rolls, a media disperser, and a rotation / revolution mixer.
As a method for uniformly dispersing the dielectric composition powder in the resin, modification of the surface of the dielectric composition powder, addition of a dispersant, addition of a solvent, and the like are performed. As a modification of the surface of the dielectric composition powder, rosin treatment, acid treatment, basic treatment, etc., as a dispersant, nonionic, cationic, anionic surfactant, wetting agent such as polyvalent carboxylic acid, Examples thereof include amphoteric substances and resins having highly sterically hindered substituents.

As described above, a dielectric composition powder and a resin, and a paste solution composed of a solvent, a dispersant, etc., as appropriate, are applied onto a substrate using a spinner, screen printing, blade coater, die coater, etc. After that, the circuit board material can be obtained by removing the solvent or thermosetting using a heating device such as a hot plate or an oven.
The substrate can be selected from an organic substrate, an inorganic substrate, and a substrate in which circuit constituent materials are arranged.
In addition to being used for the production of a built-in capacitor on a printed wiring board, the above composite can be applied to many electronic components and devices such as an interlayer insulating film, a frequency filter, a radio antenna, and an electromagnetic shield of a multilayer board.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

<Example 1>
First, an intermediate compound was synthesized using barium carbonate powder, lanthanum oxide powder and titanium oxide powder as raw materials for synthesis of the dielectric composition.
Specifically, in the general formula in the present invention, barium carbonate powder, lanthanum oxide powder, and titanium oxide powder are expressed in the form of a dielectric composition having a composition in which x is a value shown in Table 1 and y = 0. The mixture was weighed at a ratio shown in 1 and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1100 ° C. for 2 hours to synthesize an intermediate compound. did. The obtained intermediate compound was crushed in a menor mortar and the product phase was identified by a powder X-ray diffractometer. As a result, it was found that the intermediate compound was composed of La ₂ Ti ₂ O ₇ , BaTiO ₃ and a small amount of La ₂ O ₃ . .
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1100 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition _{was La 0.9 Ba 0.1 TiO 2 N 0.9} .
The dielectric constant was measured by using a sample obtained by molding the obtained dielectric composition powder into a disk shape having a diameter of about 10 mm and a thickness of about 1 mm at a pressure of 10 MPa, and further performing CIP molding at a pressure of 200 MPa. It was. After measuring the density of the molded body of the sample, a conductive paste was applied, and the capacitance was measured at 300 K and 100 kHz in a vacuum. The specific permittivity was corrected from the obtained capacitance value using the Lichtnecker logarithmic mixing rule in accordance with the method described in Japanese Patent No. 3246001. The relative dielectric constant in the case of Example 1 was 11000. The relative dielectric constants of Examples 2 to 11 are shown in Table 1 as relative values when the relative dielectric constant of Example 1 is 100.
Next, a sample of the obtained dielectric composition was loaded into a cooling / heating device, and the change in relative dielectric constant was examined in a temperature range from −130 ° C. to 800 ° C. in a vacuum. In the relative dielectric constant, no significant change corresponding to the Curie-Weiss effect of barium titanate, that is, a change indicating a phase transition from a ferroelectric to a paraelectric, is not observed. It was found that it can be used in a wide temperature range.

<Example 2>
In Example 2, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was La _0.95 Ba _0.05 TiO _2.05 N _0.95 . The relative dielectric constant was 85.2, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 2 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 3>
In Example 3, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.925 Ba 0.075 TiO 2.075 N 0.925} . The relative dielectric constant was 93.3, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 3 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 4>
In Example 4, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder, and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was La _0.91 Ba _0.09 TiO _2.09 N _0.91 . The relative dielectric constant was 98.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 4 has the same crystal structure as the dielectric composition of Example 1 and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 5>
In Example 5, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.89 Ba 0.11 TiO 2.11 N 0.89} . The relative dielectric constant was 98.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 5 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 6>
In Example 6, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.875 Ba 0.125 TiO 2.125 N 0.875} . The relative dielectric constant was 94.2, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 6 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 7>
In Example 7, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.85 Ba 0.15 TiO 2.15 N 0.85} . The relative dielectric constant was 88.8, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 7 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 8>
In Example 8, a dielectric composition was produced in the same manner as in Example 1 except that the barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.8 Ba 0.2 TiO 2.2 N 0.8} . The relative dielectric constant was 83.9, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 8 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 9>
In Example 9, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.7 Ba 0.3 TiO 2.3 N 0.7} . The relative dielectric constant was 82.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 9 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 10>
In Example 10, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.6 Ba 0.4 TiO 2.4 N 0.6} . The relative dielectric constant was 79.9, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 10 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 11>
In Example 11, a dielectric composition was produced in the same manner as in Example 1 except that barium carbonate powder, lanthanum oxide powder and titanium oxide powder were used in the proportions shown in Table 1. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _1, it was found to consist of _{La 2 Ti 2 O 7, BaTiO} 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.5 Ba 0.5 TiO 2.5 N 0.5} . The relative dielectric constant was 71.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 11 has the same crystal structure as the dielectric composition of Example 1, and the components of the composition are the same as those of Example 1, the dielectric composition of Example 1 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 12>
Intermediate compounds were synthesized using barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder as raw materials for synthesis of the dielectric composition.
Specifically, in the general formula in the present invention, barium carbonate powder, lanthanum oxide powder, and titanium oxide powder are used so that the dielectric composition has a composition in which x = 0.1 and y is a value shown in Table 2. The mixture was weighed at the ratio shown in Table 2 and uniformly mixed with a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1300 ° C. for 2 hours to synthesize an intermediate compound. did. In addition, when the obtained intermediate compound was crushed with a menor mortar and the generated phase was identified by a powder X-ray diffractometer, it was composed of La ₂ Ti ₂ O ₇ , LaTaO ₄ , BaTiO ₃ and a small amount of La ₂ O _3. I understood.
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1200 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition _{was La 0.9 Ba 0.1 Ti 0.95 Ta 0.05} O 2.05 N 0.95.
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constants of Examples 12 to 22 are shown in Table 2 as relative values when the relative dielectric constant of Example 1 is 100.
Next, a sample of the obtained dielectric composition was loaded into a cooling / heating device, and the change in relative dielectric constant was examined in a temperature range from −130 ° C. to 800 ° C. in a vacuum. As in Example 1, there was no significant change in the dielectric constant corresponding to the Curie-Weiss effect of barium titanate, and the dielectric composition of the present invention can be used in a wide temperature range. I understood.

<Example 13>
In Example 13, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.925 Ta 0.075} O 2.025 N 0.975. The relative dielectric constant was 130.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 13 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 14>
In Example 14, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.91 Ta 0.09} O 2.01 N 0.99. The relative dielectric constant was 129.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 14 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 15>
In Example 15, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder, and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.9 Ta 0.1} O 2 N. The relative dielectric constant was 127.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 15 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 16>
In Example 16, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.89 Ta 0.11} O 1.99 N 1.01. The relative dielectric constant was 125.1, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 16 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 17>
In Example 17, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.875 Ta 0.125} O 1.975 N 1.025. The relative dielectric constant was 122.6, assuming that the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 17 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 18>
In Example 18, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.85 Ta 0.15} O 1.95 N 1.05. The relative dielectric constant was 121.3, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 18 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 19>
In Example 19, a dielectric composition was produced in the same manner as in Example 12, except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.8 Ta 0.2} O 1.9 N 1.1. The relative dielectric constant was 117.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 19 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 20>
In Example 20, a dielectric composition was produced in the same manner as in Example 12 except that the barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.7 Ta 0.3} O 1.8 N 1.2. The relative dielectric constant was 109.5, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 20 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 21>
In Example 21, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.6 Ta 0.4} O 1.7 N 1.3. The relative dielectric constant was 103.4, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 21 has the same crystal structure as that of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Example 22>
In Example 22, a dielectric composition was produced in the same manner as in Example 12 except that barium carbonate powder, lanthanum oxide powder, titanium oxide powder and tantalum oxide powder were used in the proportions shown in Table 2. Incidentally, was identified product phase of the resulting intermediate compound was synthesized in analogy to Example _12, it was found to consist of _{La 2 Ti 2 O 7, LaTaO} 4, BaTiO 3 and a small amount of _La 2 _{O 3.}
The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. Further, the composition was _{La 0.9 Ba 0.1 Ti 0.5 Ta 0.5} O 1.6 N 1.4. The relative dielectric constant was 101.0, where the relative dielectric constant of Example 1 was 100.
Since the dielectric composition of Example 22 has the same crystal structure as the dielectric composition of Example 12, and the components of the composition are the same as those of Example 12, the dielectric composition of Example 12 is the same. Like body compositions, it is believed that they can be used as ferroelectrics over a wide temperature range.

<Comparative Example 1>
An oxynitride having a composition in which x and y in the general formula in the present invention were set to x = 0 and y = 0 was synthesized.
First, an intermediate compound was synthesized using lanthanum oxide powder and titanium oxide powder. Specifically, lanthanum oxide powder and titanium oxide powder were weighed in the proportions shown in Table 3, and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry is evaporated to dryness to obtain a mixed powder, and then the powder obtained by pulverizing the mixed powder is placed in an alumina container and baked in air at 1100 ° C. for 2 hours to synthesize an intermediate compound. did. In addition, when the obtained intermediate compound was crushed with a menor mortar and the generated phase was identified by a powder X-ray diffractometer, it was found to be composed of La ₂ Ti ₂ O ₇ and a small amount of La ₂ O ₃ .
Next, the obtained intermediate compound was placed in an alumina boat and baked at 1100 ° C. for 6 hours in an ammonia stream to produce a dielectric composition. The obtained dielectric composition was dark red to reddish brown. The crystal structure of the obtained dielectric composition was confirmed to be a perovskite phase containing nitrogen by powder X-ray diffraction. The composition was LaTiO ₂ N.
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constant of Comparative Example 1 is shown in Table 3 as relative values when the relative dielectric constant of Example 1 is 100.

<Comparative example 2>
An oxide having a composition in which x and y in the general formula in the present invention are x = 1 and y = 0 was synthesized.
Barium titanate was synthesized using barium oxide powder and titanium oxide powder. Specifically, barium oxide powder and titanium oxide powder were weighed in the proportions shown in Table 3, and uniformly mixed by a wet ball mill using ethanol as a solvent to obtain a mixed slurry. Next, the obtained slurry was evaporated to dryness to obtain a mixed powder, which was then placed in an alumina container and baked in air at 1100 ° C. for 2 hours. The obtained product was crushed with a menor mortar, and the product phase was identified by a powder X-ray diffractometer. As a result, it was found to be composed of BaTiO ₃ .
Subsequently, the relative dielectric constant was measured in the same manner as in Examples 1-11. The relative dielectric constant of Comparative Example 2 is shown in Table 3 as relative values when the relative dielectric constant of Example 1 is 100.

<Example 23>
A sintering aid having a composition of B ₂ O ₃ ; 63 mol%, SiO ₂ ; 3 mol%, Li ₂ O; 34 mol% was added to the dielectric composition powder used in Example 1 in an amount of 5 mol%. Molding was performed using a small amount of polyvinyl alcohol as an agent (binder), and the binder was removed at 400 ° C. Thereafter, sintering was performed at 1000 ° C. in a nitrogen atmosphere. The obtained sintered body had a porosity of 0.1% or less.

<Example 24>
Dicyclopentadiene-based HP7200 (manufactured by Dainippon Ink Industries, Ltd.) as the main component of the epoxy resin; 20 parts by weight; phenol novolac TD-2131 (manufactured by Dainippon Ink Industries, Ltd.) as the curing agent; 8 parts by weight Then, 0.28 parts by weight of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) as a curing accelerator; 30.5 parts by weight of solvent γ-butyrolactone; 30.5 parts by weight were mixed to prepare an epoxy resin solution. To this resin solution, 215 parts by weight of the dielectric composition powder used in Example 1 was mixed as an inorganic filler to prepare a composite (resin composition). At this time, when the total amount of the inorganic filler and the resin was 100% by volume, the content of the inorganic filler was 65% by volume.
Next, after kneading this resin composition using three rolls, it was applied to a 300 μm thick aluminum substrate using a die coater and dried in an oven at 80 ° C. for 20 minutes to remove the solvent. Then, the resin was cured at 170 ° C. for 1 hour to obtain a dielectric composition as a circuit board material having a thickness of 10 μm.
Next, an aluminum electrode was formed on this dielectric composition by vapor deposition, and the relative dielectric constant was measured in accordance with JIS K6911. As a result, the relative dielectric constant was 650.

  Since the dielectric composition of the present invention does not have a Curie point between room temperature and 200 ° C., and has a higher relative dielectric constant than a conventionally known oxynitride perovskite compound, Suitable for the electronic device to be arranged. In the future, it can be expected that the present invention will be greatly utilized and greatly contribute to industrial development.

Claims (10)

General formula: M (1) _1-x M (2) _x M (3) _1-y M (4) _y O _{2 + xy} N _{1-x + y}
A dielectric composition comprising:
However, the M (1) element is one or more elements selected from Y, La, Ce, Pr, Nd, and Gd, and the M (2) element is one or more elements selected from Mg, Ca, Sr, and Ba. M (3) element is one or more elements selected from Ti and Zr, M (4) element is one or more elements selected from V, Nb and Ta, and O and N are Oxygen and nitrogen, 0 <x <1 and 0 ≦ y ≦ 1. The dielectric composition according to claim 1, wherein 0 <x ≦ 0.9 and 0 ≦ y ≦ 0.9. The M (1) element is at least one selected from La, Ce, Pr, and Nd, and the M (2) element is at least one selected from Sr and Ba. Dielectric composition. The dielectric composition according to claim 3, wherein the M (1) element is La, the M (2) element is Ba, the M (3) element is Ti, and the M (4) element is Ta. Heating the raw material of any of the following [1] to [3] to produce an intermediate compound of any of the following [4] to [6], and heating the intermediate compound in a reducing atmosphere The method for producing a dielectric composition according to any one of claims 1 to 4, further comprising:
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds),
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds),
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)
[4] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (provided that M (1) element, M (2 ) Element and M (3) element are included in at least one of the above compounds)
[5] Intermediate compound containing one or more compounds containing M (1) element and / or M (2) element and M (4) element (provided that M (1) element, M (2 ) Element and M (4) element are included in at least one of the above compounds)
[6] Intermediate compound comprising one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)   The method for producing a dielectric composition according to claim 5, wherein at least one of the compounds is an oxide. The method for producing a dielectric composition according to any one of claims 1 to 4, further comprising a step of heating the raw material according to any one of [1] to [3] below in a reducing atmosphere. .
[1] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (3) element (provided that M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds),
[2] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element and M (4) element (provided that M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds),
[3] A raw material containing one or more compounds containing one or more of M (1) element, M (2) element, M (3) element and M (4) element (provided that M (1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)   The method for producing a dielectric composition according to claim 5, wherein at least one of the compounds is an oxide. The method for producing a dielectric composition according to any one of claims 1 to 4, further comprising a step of heating the raw material according to any one of [1] to [3] below in a reducing atmosphere. .
[1] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element (however, M (1) element, M (2) Element and M (3) element are included in at least one of the above compounds)
[2] A raw material comprising one or more compounds containing M (1) element and / or M (2) element and M (4) element (however, M (1) element, M (2) Element and M (4) element are included in at least one of the above compounds)
[3] A raw material containing one or more compounds containing M (1) element and / or M (2) element and M (3) element and / or M (4) element (provided that M ( 1) Element, M (2) element, M (3) element, and M (4) element are included in at least one of the above compounds)   The method for producing a dielectric composition according to claim 7, wherein at least one of the compounds is an oxide.