JP2008162826A - Reduction-resistant dielectric ceramic composition, dielectric using it and laminated ceramic capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition manufacturing a laminated ceramic capacitor which has an excellent reduction resistance in firing, an excellent capacity-temperature characteristic and dielectric property after being fired, a high breakdown voltage, and a long high-temperature load acceleration life, and to provide a laminated ceramic capacitor having a high dielectric breakdown voltage and a long high-temperature load acceleration life which is manufactured by using a dielectric obtained by using the dielectric ceramic composition. <P>SOLUTION: The dielectric ceramic composition contains a perovskite-type complex oxide powder containing Ba and Ti and an additive component powder, wherein the specific surface area of the additive component powder is 10-100 times vs. the specific surface area of the perovskite-type complex oxide powder. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dielectric ceramic composition that can be fired in a reducing atmosphere, a dielectric using the dielectric ceramic composition, and a multilayer ceramic capacitor having a dielectric layer made of the dielectric.

  Multilayer ceramic capacitors are used for power supply decoupling and buffering in processors, particularly high power microprocessors. While operating in high power mode, these active electronic components generate large amounts of heat, and even with intensive cooling, the temperature of high power microprocessors in permanent operation can be as high as 70-80 ° C. On the other hand, these multilayer ceramic capacitors may be used at ambient environmental temperatures that drop to about -20 ° C. or lower, for example, in winter in cold regions. Thus, since the multilayer ceramic capacitor is used in a wide temperature range, the temperature characteristic is required to be flat.

  Furthermore, in recent years, in order to enable the use of expensive noble metals such as Pd, Au, and Ag as well as base metals such as Ni for the internal electrodes of the multilayer ceramic capacitor, the dielectric ceramic composition has a reducing atmosphere. It is required that it can be fired in.

In response to these demands, various dielectric ceramic compositions have been developed. For example, in Patent Documents 1 to 3, there is provided a reduction-resistant dielectric ceramic composition in which barium titanate is a main component and subcomponents such as MgO, CaO, BaO, SrO, and Cr ₂ O ₃ are added at a predetermined concentration. Proposed. However, these dielectric ceramic compositions have a low dielectric constant, and further improvements are required particularly in terms of dielectric properties.

  As another method for improving the capacitance-temperature characteristic and the dielectric characteristic, Patent Document 4 discloses a core-shell structure in which a dielectric layer has a core part centered on barium titanate and a shell part on the surface part. Multilayer ceramic capacitors composed of these particles have been proposed.

However, the dielectric ceramic composition and the multilayer ceramic capacitor using the dielectric ceramic composition are not yet sufficient in voltage resistance and need to be further increased.
JP 2000-154057 A JP 2001-192264 A JP 2002-255639 A JP 2004-11951 A

  A dielectric ceramic composition that is excellent in reduction resistance during firing, has excellent capacity-temperature characteristics and dielectric characteristics after firing, and can produce a multilayer ceramic capacitor having a high dielectric breakdown voltage and a long high-temperature load acceleration life. The purpose is to obtain. Another object of the present invention is to obtain a multilayer ceramic capacitor having a high dielectric breakdown voltage and a long high temperature load acceleration life using a dielectric obtained by using this dielectric ceramic composition.

That is, the present invention includes a perovskite complex oxide powder containing Ba and Ti, and an additive component powder, and the specific surface area of the additive component powder is 10 with respect to the specific surface area of the perovskite complex oxide powder. It is a dielectric ceramic composition which is ˜100 times. Preferably, the dielectric ceramic composition is such that the perovskite complex oxide powder is barium titanate. Preferably, the additive component powder includes at least one oxide of an element selected from the group consisting of Y, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, and Yb. It is a composition. More preferably, the additive ceramic powder further includes at least one oxide or carbonate of an element selected from the group consisting of Mn, W, Mo, V, Mg, and Co. is there. More preferably, it is a dielectric ceramic composition in which the additive component powder further contains at least one selected from the group consisting of BaSiO ₃ and CaSiO ₃ .

  Further, the present invention is a dielectric obtained by using a dielectric ceramic composition, having a core-shell structure, wherein the core portion is a perovskite complex oxide, and the shell portion is an additive component.

  The present invention is also a multilayer ceramic capacitor having a dielectric layer made of a dielectric.

The present invention also relates to a method for producing a dielectric ceramic composition, wherein the specific surface area of the additive component powder is 10 to 100 times the specific surface area of the perovskite type composite oxide powder. It is a manufacturing method of a dielectric ceramic composition including a step of mixing a composite oxide powder and an additive component powder. Preferably, in the method for producing a dielectric ceramic composition, the perovskite complex oxide powder is barium titanate. Preferably, the additive component powder contains at least one oxide of an oxide of an element selected from the group consisting of Y, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, and Yb. It is a manufacturing method of a dielectric ceramic composition. More preferably, the additive ceramic powder further includes at least one oxide or carbonate of an element selected from the group consisting of Mn, W, Mo, V, Mg and Co. It is a manufacturing method. More preferably, it is a method for producing a dielectric ceramic composition, wherein the additive component powder further includes at least one selected from the group consisting of BaSiO ₃ and CaSiO ₃ .

  According to the present invention, it is possible to manufacture a monolithic ceramic capacitor that has excellent resistance to temperature during firing, has excellent capacity-temperature characteristics and dielectric characteristics after firing, and has a high dielectric breakdown voltage and a long high temperature load accelerated life. A dielectric ceramic composition can be obtained. In addition, according to the present invention, a multilayer ceramic capacitor having a high dielectric breakdown voltage and a long high temperature load acceleration life can be obtained using a dielectric obtained by using this dielectric ceramic composition.

  The dielectric ceramic composition of the present invention is a dielectric having a core / shell structure, wherein the core is a perovskite complex oxide containing Ba and Ti, and the shell is an additive component. It can be used as a raw material for By adopting the core-shell structure, a dielectric having an excellent capacitance with temperature characteristics can be obtained.

  The characteristic of the dielectric ceramic composition of the present invention is that it contains an additive component having a large specific surface area compared to the specific surface area (BET) of the perovskite type complex oxide powder. Specifically, the specific surface area of the additive component powder is 10 to 100 times the specific surface area of the perovskite complex oxide powder. However, considering the handling of fine powders, the specific surface area ratio is preferably 10 to 50 times. By setting it as such a specific surface area, the dielectric material with which voltage tolerance was improved can be obtained.

  In the present invention, the specific surface area (BET) means the surface area of the powder of unit mass, and is a known method, for example, Japanese Industrial Standard R1626 “Method for measuring specific surface area by gas adsorption BET method of fine ceramic powder. Can be measured.

In the dielectric ceramic composition of the present invention, the perovskite complex oxide powder containing Ba and Ti is preferably barium titanate (generally BaTiO ₃ ). Note that the barium titanate used in the dielectric ceramic composition of the present invention does not necessarily contain Ba and Ti at a ratio of 1: 1. When expressed barium titanate and _{[Ba x Ti (2-x)] O 3,} it is preferable x is in the range of 0.990 to 1.010. Further, when x is in the range of 0.990 or more and 0.995 or less, the capacitance change due to temperature of the multilayer ceramic capacitor having the dielectric layer obtained by firing this dielectric ceramic composition is further increased. This is more preferable because it is suppressed and the lifetime is further increased. Moreover, when barium titanate is described as (BaO) _m · TiO ₂ , m is preferably in the range of 0.990 or more and 1.010 or less. When m is in the range of 0.990 or more and 0.995 or less, the capacitance change due to the temperature of the multilayer ceramic capacitor having the dielectric layer obtained by firing this dielectric ceramic composition is further suppressed. In addition, since the lifetime is further increased, it is more preferable. The specific surface area of the perovskite complex oxide powder is preferably in the range of 3 to 5 m ² / g. This perovskite type complex oxide powder can become a core part of a core-shell structure in a dielectric after firing the dielectric ceramic composition.

  The additive component powder contained in the dielectric ceramic composition of the present invention is not particularly limited as long as it can form a dielectric after sintering. Hereinafter, the additive component powder will be described by being divided into three types: the main component powder, the subcomponent powder, and other additive component powders. In addition, it is not always necessary that the additive component powder includes all of these three types. These additive component powders can become the shell portion of the core-shell structure in the dielectric after firing the dielectric ceramic composition.

  The dielectric ceramic composition of the present invention is preferably an element selected from the group consisting of Y, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm and Yb as the main component powder of the additive component powder. Including at least one kind of oxide. Further, preferably, the main component powder of the additive component powder includes at least one oxide of an element selected from the group consisting of Y and Yb.

The content of Y ₂ O _{3 in} the dielectric ceramic composition is preferably 0.6 to 1.2 parts by weight with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Preferably it is 0.6-0.9 weight part. When Y ₂ O ₃ is in this range, the change in capacitance due to the temperature of the multilayer ceramic capacitor having the dielectric material obtained by firing the dielectric ceramic composition as a dielectric layer is suppressed, the dielectric constant is sufficiently high, and the lifetime is also long. long.

The content of Yb ₂ O _{3 in} the dielectric ceramic composition is preferably 0.18 to 0.5 parts by weight with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Preferably it is 0.2-0.4 weight part. When Yb ₂ O _{3 in} this dielectric ceramic composition is in this range, the capacitance change due to temperature of the multilayer ceramic capacitor having a dielectric layer obtained by firing this dielectric ceramic composition is suppressed, The dielectric constant is sufficiently high and the lifetime is long.

  The dielectric ceramic composition of the present invention is at least one oxide or carbonate of an element selected from the group consisting of Mg, W, Mn, Mo, V and Co as a subcomponent powder of the additive component powder, It is preferable to include. More preferably, the subcomponent powder of the additive component powder further includes at least one oxide or carbonate of an element selected from the group consisting of Mg, W, Mn, and Mo.

  The dielectric ceramic composition of the present invention is preferably 0.6 to 1.5 parts by weight, more preferably 0.6 to 1.5 parts by weight of MgO with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Contains 1.2 parts by weight. When MgO in this dielectric ceramic composition is in this range, the capacitance change due to temperature of the multilayer ceramic capacitor having a dielectric layer obtained by firing this dielectric ceramic composition is suppressed, and the dielectric breakdown voltage is reduced. Is sufficiently high, the dielectric constant is sufficiently high, and the lifetime is long.

In the dielectric ceramic composition of the present invention, WO ₃ is preferably 0.02 to 0.2 parts by weight, more preferably 0.02 parts per 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Contains 0.1 part by weight. When WO ₃ is in this range, the CR product (product of capacitance and insulation resistance) of a multilayer ceramic capacitor having a dielectric layer obtained by firing this dielectric ceramic composition is large, and the dielectric breakdown voltage Is sufficiently high and has a long service life.

The dielectric ceramic composition of the present invention is preferably 0.1 to 0.4 parts by weight, more preferably 0.2 parts by weight of MnCO ₃ with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Contains 0.4 parts by weight. When MnCO ₃ is in this range, the capacitance change due to temperature of the multilayer ceramic capacitor having a dielectric layer formed by the dielectric ceramic composition is suppressed, the CR product is large, the dielectric constant is sufficiently high, and the lifetime Also long.

The dielectric ceramic composition of the present invention is preferably 0.02 to 0.2 parts by weight, more preferably 0.05 parts by weight of MoO ₃ with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Contains 0.15 parts by weight. When MoO ₃ is in this range, the capacitance change due to temperature of the multilayer ceramic capacitor having a dielectric layer formed by the dielectric ceramic composition is suppressed, the CR product is large, the dielectric breakdown voltage is sufficiently high, and Long life.

In the dielectric ceramic composition of the present invention, the additive component powder preferably further includes at least one selected from the group consisting of BaSiO ₃ and CaSiO ₃ as the other additive component powder. These powders also have a function as a sintering aid.

The dielectric ceramic composition of the present invention is preferably 0.6 to 2 parts by weight, more preferably 0.8 to 0.8 parts by weight of BaSiO ₃ with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. Contains 1.5 parts by weight. When BaSiO ₃ is in this range, the capacitance change due to temperature is suppressed after firing, the dielectric constant is sufficiently high, and the lifetime is long.

The dielectric ceramic composition of the present invention is preferably 0.4 to 1.5 parts by weight, more preferably 0.5 parts by weight of CaSiO ₃ with respect to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. -1.0 part by weight included. When CaSiO _{3 in} this dielectric ceramic composition is in this range, the capacitance change due to temperature of the multilayer ceramic capacitor having a dielectric layer obtained by firing this dielectric ceramic composition is suppressed, and the dielectric constant Is sufficiently high and has a long life.

  In the dielectric ceramic composition of the present invention, the total weight of the additive component powder is preferably 1 to 6 parts by weight with respect to 100 parts by weight of the perovskite complex oxide powder. Further, the total is more preferably 3 to 4 parts by weight.

In addition, a preferable exemplary composition of the additive component powder contained in the dielectric ceramic composition of the present invention is such that Yb ₂ O ₃ is added in an amount of 0.1% to 100 parts by weight of the perovskite complex oxide powder containing Ba and Ti. 18-0.5 parts by weight, MgO 0.6-1.5 parts by weight, CaSiO ₃ 0.4-1.5 parts by weight, WO ₃ 0.02-0.2 parts by weight, MnCO ₃ 0 0.1 to 0.4 parts by weight, and MoO ₃ is 0.02 to 0.2 parts by weight.

  The dielectric ceramic composition of the present invention may contain other trace amounts of oxides and impurities as long as the characteristics of the multilayer ceramic capacitor of the present invention are not affected.

  By firing the dielectric ceramic composition of the present invention, the core portion is a perovskite type complex oxide containing Ba and Ti, and the dielectric has a core-shell structure having a shell portion as an additive component on the surface thereof. The body can be formed. The dielectric may be a dielectric layer of a multilayer ceramic capacitor.

  The dielectric ceramic composition of the present invention and the method for producing a dielectric using the same will be described below by taking a method for producing a multilayer ceramic capacitor as an example.

  First, a dielectric ceramic composition is obtained by mixing a perovskite complex oxide powder containing Ba and Ti and an additive component powder. In this mixing, the dielectric ceramic composition of the present invention is such that the specific surface area of the additive component powder is 10 to 100 times, preferably 10 to 50 times the specific surface area of the perovskite complex oxide powder. This is a feature of the manufacturing method. In this case, the perovskite complex oxide powder is preferably barium titanate. The additive component powder preferably contains the oxide or carbonate already exemplified.

  The specific surface area can be set to a predetermined value by pulverizing the perovskite type complex oxide powder and the additive component powder for a predetermined time using a ball mill or a medium stirring mill. In addition, since the grinding efficiency is high, it is preferable to use a bead mill. Since the specific surface area after pulverization is approximately proportional to the pulverization time, pulverization is performed until a desired specific surface area is obtained. The diameter of the beads used for grinding by the bead mill is preferably 0.1 mm to 2.0 mm. The peripheral speed of the bead mill rotor is preferably 7 to 12 m / s. This is because if the peripheral speed is lower than this value, the crushing ability is inferior, and if it is higher than this value, problems such as unstable operation of the apparatus occur.

  (1) The dielectric ceramic composition of the present invention is printed or applied on a substrate. In some cases, the dielectric ceramic composition of the present invention is a conventional component, for example, a solvent such as ethanol, toluene, propanol or water, a binder such as polyvinyl butyral, ethyl cellulose or polyvinyl alcohol (PVA), or a plasticizer such as phthalate ester. And may be used as a paste by mixing. The thickness of printing or coating is determined so that the multilayer ceramic capacitor obtains a desired capacitance. Generally, the thickness of the dielectric layer after firing is about 1 to 10 μm. The printing or coating method is not particularly limited, and can be performed by a screen printing method, a transfer method, a doctor blade method, or the like.

  (2) Next, the dielectric ceramic composition layer printed or applied in step (1) is dried. Drying is usually carried out by heating at a temperature of 80 to 100 ° C. for 5 to 10 minutes.

  (3) An internal electrode paste is printed or applied to the formed dielectric ceramic composition layer. As the internal electrode paste, a paste containing a base metal such as nickel can be preferably used. For example, a paste obtained by kneading nickel powder, an organic vehicle (for example, 8 parts by weight of ethyl cellulose dissolved in 92 parts by weight of terpineol) and terpineol can be used as the internal electrode paste. The printing or coating method is not particularly limited. The thickness to be printed is usually such that the thickness of the internal electrode after firing is 0.8 to 1.2 μm.

  (4) Next, the internal electrode paste layer printed in step (3) is dried. Drying is usually carried out by heating at 80 to 100 ° C. for 5 to 10 minutes.

  (5) Next, the above-described steps (1) to (4) are repeated until a desired number of laminations is obtained, thereby obtaining an unfired laminate. For example, in the case of a laminated body of about 160 layers, the thickness of the chip laminated ceramic capacitor is about 0.5 mm.

(6) The unfired laminate thus obtained is removed from the base material and cut using a blade or the like to produce a laminate block. The final chip multilayer ceramic capacitor is cut to a size such that, for example, width = 0.5 mm and length = 1.0 mm. Thereafter, the obtained laminated block is heated to 500 ° C. in an atmosphere where H ₂ : N ₂ is in a volume ratio of 1:99 to burn the binder. Thereafter, the oxygen partial pressure is 10 ⁻⁹ to 10 ⁻¹² MPa, and in a reducing atmosphere composed of H ₂ , N ₂ and H ₂ O, the temperature is 1100 to 1300 ° C., preferably 1170 to 1250 ° C. for 1 hour and a half. Bake for ½ hours. By this firing, a core-shell structure is formed in which the core portion is a perovskite type complex oxide containing Ba and Ti, and a shell portion which is an additive component is formed on the surface thereof. The dielectric ceramic composition layer and the internal electrode paste layer become a dielectric layer and an internal electrode, respectively, to obtain a multilayer ceramic capacitor.

After the firing, it is preferable to perform a reoxidation treatment in an N ₂ atmosphere at a temperature of 950 to 1100 ° C., preferably 1000 to 1050 ° C. for 1 hour and a half to 2 hours, if necessary.

  (7) A conductive paste for external electrodes is applied to the fired monolithic ceramic capacitor, and then separately fired in a neutral atmosphere at a temperature of 900 ° C. for about 5 minutes to 15 minutes. An electrode can be formed into a chip multilayer ceramic capacitor.

  When a dielectric obtained using the dielectric ceramic composition of the present invention is used, it is possible to obtain a multilayer ceramic capacitor having excellent capacitance-temperature characteristics and dielectric characteristics, as well as a high breakdown voltage and a long high temperature load acceleration life. it can. In addition, since the dielectric ceramic composition of the present invention can be fired in a reducing atmosphere, a multilayer ceramic capacitor using a dielectric obtained by using this dielectric ceramic composition is less expensive than a conventional noble metal. Base metals can be used. As a result, significant cost reduction of the multilayer ceramic capacitor can be expected.

  Hereinafter, the present invention will be described with reference to examples and comparative examples. The present invention is not limited by these examples. In Examples and Comparative Examples, “parts” is expressed by parts by weight unless otherwise specified.

In Examples and Comparative Examples, using a BaTiO ₃ powder as perovskite-type composite oxide powder, with respect to 100 parts by weight of the _powder, Y 2 _{O 3} 0.8 parts by weight, 1 part by weight of BaSiO _3, the MnCO ₃ An additive component powder comprising 0.3 part by weight, 0.9 part by weight of MgO, 0.1 part by weight of WO ₃ and 0.1 part by weight of MoO ₃ was used. Although the compositions of the additive component powders in the examples and comparative examples are the same, different specific surface areas were used. The specific surface areas of Examples 1 and 2 and Comparative Example 1 are shown in Table 1.

In order to set the specific surface area to a predetermined value, the perovskite complex oxide powder and additive component powder were pulverized using a medium stirring mill (bead mill). Specifically, the pulverization by the bead mill was performed using zirconia beads having a diameter of 0.3 mm at a peripheral speed of 10 m / s of the rotor of the bead mill. In addition, when this grinding condition is used, the specific surface area is increased in proportion to the grinding time, such as a specific surface area of 50 m ² / g for a grinding time of 7 minutes and a specific surface area of 100 m ² / g for a grinding time of 14 minutes. I was able to.

  Then, these were wet mixed and pulverized by adding ethanol and toluene with a ball mill. Thereafter, a polyvinyl butyral binder and butyl benzyl phthalate were further added and mixed to prepare a paste. This paste was formed into a sheet by the doctor blade method and then dried to obtain a green sheet having a thickness of 2.3 μm. Then, a nickel electrode paste was screen-printed on the green sheet, dried and laminated so as to be opposed to each other, and integrated by thermocompression bonding. The nickel electrode paste is composed of 40 parts by weight of an organic vehicle (8 parts by weight of ethyl cellulose dissolved in 92 parts by weight of terpineol) and 10 parts by weight of terpineol with respect to 100 parts by weight of nickel particles having an average particle diameter of 0.2 μm. This was kneaded using a three-roll mill to form a paste.

Individual laminated blocks for capacitors were cut out from the laminated body integrated by thermocompression bonding with a blade. The laminated block thus obtained was heated to 500 ° C. in an atmosphere having a volume ratio of H ₂ : N ₂ of 1:99 to burn the binder, and then an oxygen partial pressure of 10 ⁻⁹ to 10 ⁻¹² MPa. Baked at a temperature of 1200 ° C. for 2 hours in a reducing atmosphere consisting of H ₂ , N ₂ and H ₂ O. Thereafter, re-oxidation treatment was performed in an N ₂ atmosphere at 1000 ° C. for 2 hours to obtain a multilayer ceramic capacitor.

A copper electrode paste was applied to the surface of the obtained multilayer ceramic capacitor and baked in a neutral atmosphere (nitrogen atmosphere) at a temperature of 900 ° C. for 10 minutes to form an external electrode to obtain a chip multilayer ceramic capacitor. The dimensions of the chip multilayer ceramic capacitors produced in this example and comparative example are as follows.
Appearance dimensions: Width = 0.5mm, Length = 1.0mm, Thickness = 0.5mm
Dielectric thickness: t = 1.7 μm
Effective number of layers: N = 163

Various characteristics were measured for each sample of the example. The measurement method is as follows.
Capacitance (C), dielectric loss (dielectric loss tangent; tan δ): Measured by an automatic bridge at 1 KHz and 0.5 Vrms using a capacitance meter (model number 4278A, manufactured by Hewlett-Packard Company).
Insulation resistance (R): Measure the resistance value after applying 6.3V to the multilayer ceramic capacitor for 1 minute with a high insulation resistance measuring device (model number DSM-8541 Digital Super Megohmmeter manufactured by TOA). Insulation resistance (R).
Capacitance temperature change rate: The maximum value of the change rate in the temperature range from −55 ° C. to 85 ° C. was shown based on the capacitance at 25 ° C. In addition, since the absolute value of the capacity | capacitance temperature change rate in 85 degreeC was the largest about all the samples, the change rate in 85 degreeC was described in Table 2.
High temperature load accelerated life test (HALT): Five samples were placed in a 105 ° C. constant temperature bath, a DC voltage of 25 V was applied, and the insulation resistance was measured under a DC electric field. The time from the start of voltage application until the insulation resistance became 1 × 10 ⁶ Ω or less was defined as the lifetime of the sample.
Dielectric breakdown voltage (VB): A DC voltage was applied to the sample at a step-up speed of 10 V / sec, the voltage when a leakage current of 5 mA was observed was measured, and this voltage was taken as the dielectric breakdown voltage (VB). In Examples and Comparative Examples, measurement was performed using samples having the same thickness.

  Table 2 and FIGS. 1 to 5 show the measurement results of Examples 1 and 2 and Comparative Example 1. As these results show, in the examples of the present invention, despite the firing in a reducing atmosphere, not only the excellent capacitance-temperature characteristics and dielectric characteristics after firing, but also high breakdown voltage and long high temperature load A multilayer ceramic capacitor having an accelerated life could be obtained.

3 is a result of a capacity-temperature characteristic test of Example 1. FIG. It is a high temperature load accelerated life test result of Example 1. It is a capacity-temperature characteristic test result of Example 2. It is a high temperature load accelerated life test result of Example 2. It is a capacity-temperature characteristic test result of the comparative example 1. It is a high temperature load accelerated life test result of the comparative example 1.

Claims (12)

A perovskite complex oxide powder containing Ba and Ti;
And additive component powder,
A dielectric ceramic composition, wherein the specific surface area of the additive component powder is 10 to 100 times the specific surface area of the perovskite complex oxide powder.   The dielectric ceramic composition according to claim 1, wherein the perovskite complex oxide powder is barium titanate.   The dielectric material according to claim 1 or 2, wherein the additive component powder contains at least one oxide of an element selected from the group consisting of Y, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, and Yb. Body porcelain composition.   The dielectric ceramic composition according to claim 3, wherein the additive component powder further contains at least one oxide or carbonate of an element selected from the group consisting of Mn, W, Mo, V, Mg, and Co. The dielectric ceramic composition according to claim 3 or 4, wherein the additive component powder further contains at least one selected from the group consisting of BaSiO ₃ and CaSiO ₃ .   It is obtained using the dielectric ceramic composition according to any one of claims 1 to 5, has a core-shell structure, the core part is a perovskite complex oxide, and the shell part is an additive component. Dielectric.   A multilayer ceramic capacitor having a dielectric layer made of the dielectric according to claim 6.   A method for producing a dielectric ceramic composition, wherein the specific surface area of the additive component powder is 10 to 100 times the specific surface area of the perovskite type composite oxide powder, A method for producing a dielectric ceramic composition, comprising a step of mixing additive component powder.   The method for producing a dielectric ceramic composition according to claim 8, wherein the perovskite complex oxide powder is barium titanate.   The additive component powder contains at least one oxide of an oxide of an element selected from the group consisting of Y, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, and Yb. A method for producing the dielectric ceramic composition as described.   11. The production of a dielectric ceramic composition according to claim 10, wherein the additive component powder further contains at least one oxide or carbonate of an element selected from the group consisting of Mn, W, Mo, V, Mg, and Co. Method. The method for producing a dielectric ceramic composition according to claim 10 or 11, wherein the additive component powder further contains at least one selected from the group consisting of BaSiO ₃ and CaSiO ₃ .