JP2013151380A - Dielectric ceramic composition and ceramic electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition showing excellent reliability, while keeping a high relative dielectric constant, even when especially a dielectric layer is thinned, and to provide a ceramic electronic component to which the dielectric ceramic composition is applied, concerning the dielectric ceramic composition and the ceramic electronic component.SOLUTION: This dielectric ceramic composition contains a main component comprising barium titanate, and contains R1 (R1 is at least one kind or more between Y and Ho) as an accessory component with respect to barium titanate. The dielectric ceramic composition has a core-shell structure and has a shell satisfying an inequality: Ba site substitution amount of R1/Ti site substitution amount of R1>1. Preferably, the dielectric ceramic composition contains both R1 and R2 (R2 is at least one kind or more between Eu, Gd and Tb). More preferably, the thickness of a dielectric layer is ≤1.0 μm. Thus, effects of this invention can be heightened.

Description

  The present invention relates to a dielectric ceramic composition and a ceramic electronic component, and in particular, a dielectric ceramic composition exhibiting good reliability while maintaining a high relative dielectric constant even when the dielectric layer is thinned. And a ceramic electronic component to which the dielectric ceramic composition is applied.

  A multilayer ceramic capacitor as an example of a ceramic electronic component is widely used as a small-sized, high-performance, high-reliability electronic component, and a large number of electric capacitors and electronic devices are used. In recent years, with the miniaturization and high performance of devices, the demand for further miniaturization, high performance, and high reliability of ceramic electronic components has become increasingly severe.

  In response to such demands, the dielectric layers of multilayer ceramic capacitors are being made thinner and multilayered. However, if the particle diameter of the dielectric particles is reduced in order to reduce the thickness of the dielectric layer, there is a problem that a desired characteristic cannot be obtained because the relative permittivity is lowered.

  For example, Patent Document 1 discloses that in a crystal particle made of a perovskite complex oxide containing Ba, Ti, a rare earth element, Mg and Mn as a metal element, the concentration of the rare earth element from the surface of the crystal particle is Mn. Barium titanate with a specific relationship between the ratio of the concentration to the concentration is described. According to Patent Document 1, this perovskite complex oxide is described as having excellent reliability in a high-temperature load test.

  However, the thickness of the dielectric layer of the multilayer ceramic capacitor described in the embodiment of Patent Document 1 is 1 to 3 μm, and if this dielectric layer is further thinned, the reliability in the high temperature load test deteriorates. I understood.

  Patent Document 2 discloses a first phase in which main phase particles are mainly composed of barium titanate and contain a rare earth element, and main phase particles alone or a small amount of rare earth is dissolved in main phase particles. The relationship of the number ratio between the crystal particles and the core-shell crystal particles in which the rare earth is dissolved in the shell portion is described. According to Patent Document 2, high-temperature load characteristics satisfying the EIA standard X5R (85 ° C.) characteristics even when the oxide composed mainly of barium titanate having this structure is thinned to less than 1 μm. It is described that (reliability) can be obtained.

  However, it was found that the multilayer ceramic capacitor described in the embodiment of Patent Document 2 cannot obtain the reliability that satisfies the standard at 105 ° C. required for the EIA standard X6S.

JP2011-132124A JP2011-184279

  The present invention has been made in view of such a situation, and in particular, even when the dielectric layer is thinned, a dielectric ceramic composition exhibiting good reliability while maintaining a high relative dielectric constant, and An object is to provide a ceramic electronic component to which the dielectric ceramic composition is applied.

  A dielectric ceramic composition containing a main component composed of barium titanate and containing R1 (R1 is at least one of Y and Ho) as a subcomponent with respect to the barium titanate, The dielectric ceramic composition has a core-shell structure and has a shell that satisfies the Ba site substitution amount of R1 / Ti site substitution amount of R1> 1.

  Preferably, R2 is contained in addition to R1 (R2 is at least one of Eu, Gd, and Tb).

  In addition, a ceramic electronic component according to the present invention includes a dielectric layer composed of the dielectric ceramic composition described in any one of the above and an electrode. Preferably, the dielectric layer has a thickness of 1.0 μm or less. The ceramic electronic component is not particularly limited.

  In general, it is known that R1 is substituted for both the Ba site and the Ti site. When R1 is substituted for the Ti site, both the relative dielectric constant and the reliability cannot be achieved.

  In the present invention, as described above, the shell satisfying the R1 Ba site substitution amount / R1 Ti site substitution amount> 1 maintains a high dielectric constant even when the layer is thinned. High reliability can be realized.

  Further, the ceramic electronic component is not particularly limited, and examples thereof include a multilayer ceramic capacitor, a piezoelectric element, a chip inductor, a chip varistor, a chip thermistor, a chip resistor, and other surface mount (SMD) chip type electronic components.

FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention. FIG. 2 is a high-resolution STEM-HAADF image (15,000,000 times) of the shell portion. A bright white point indicates a Ba site and a dark white point indicates a Ti site.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

<Multilayer ceramic capacitor 1>
As shown in FIG. 1, a multilayer ceramic capacitor 1 according to an embodiment of the present invention includes a capacitor element body 10 having a configuration in which dielectric layers 2 and internal electrode layers 3 are alternately stacked. The internal electrode layers 3 are laminated so that the respective end faces are alternately exposed on the surfaces of the opposing end portions of the capacitor element body 10. The pair of external electrodes 4 are connected to the exposed end face of the internal electrode layer 3 to constitute a capacitor circuit.

  The shape of the capacitor element body 10 is not particularly limited, but is usually a rectangular parallelepiped as shown in FIG. Moreover, there is no restriction | limiting in particular also in the dimension, What is necessary is just to set it as a suitable dimension according to a use.

<Dielectric layer 2>
The dielectric layer 2 is composed of a dielectric ceramic composition according to this embodiment. The dielectric ceramic composition contains barium titanate as a main component and R1 (R1 is at least one of Y and Ho) as a subcomponent.

  R2 (R2 is at least one of Eu, Gd and Tb) may be contained as a subcomponent.

  Among the ABO3 perovskite dielectric ceramics suitable for multilayer ceramic capacitors, the main phase particles constituting the dielectric ceramics have a so-called “core-shell structure”. The “core shell” is composed of two types of regions: a “shell” having a high concentration of an additive component such as a rare earth and a “core” having a low concentration of the additive component such as a rare earth.

  In this embodiment, the dielectric ceramic composition constituting the dielectric layer is a dielectric ceramic composition containing R1 as a subcomponent, the dielectric ceramic composition having a core-shell structure, and Ba of R1 It has a shell that satisfies the amount of site substitution / Ti site substitution amount of R1> 1.

  In general, it is known that R1 is substituted on both the Ba site and Ti site, and R2 having an ionic radius larger than that of R1 is easily substituted on the Ba site.

  When R2 is contained in the dielectric particles, the reliability can be improved while maintaining a good dielectric constant, but the temperature characteristics of the capacitance tend to deteriorate. In addition, when R2 is used alone, it is difficult to control not only the temperature characteristics of capacitance but also the sintered density and particle size. Therefore, by incorporating R1 into the dielectric particles and maintaining the proper particle size, the temperature characteristics of the capacitance can be improved while maintaining reliability. Such an effect becomes prominent when a shell satisfying R1 Ba site substitution amount / R1 Ti site substitution amount> 1 is satisfied.

  The dielectric ceramic composition according to the present embodiment may further contain other subcomponents according to desired characteristics.

  The thickness of the dielectric layer 2 is not particularly limited, and may be appropriately determined according to desired characteristics, applications, and the like. In the present embodiment, it is preferably 2.0 μm or less per layer. More preferably, it is 1.0 μm or less. In addition, the number of stacked dielectric layers 2 is not particularly limited, and may be determined as appropriate according to the application.

<Internal electrode layer 3>
The conductive material contained in the internal electrode layer 3 is not particularly limited, but a relatively inexpensive base metal can be used when the material constituting the dielectric layer 2 has reduction resistance. As the base metal used as the conductive material, Ni or Ni alloy is preferable. The thickness of the internal electrode layer 3 is not particularly limited, and may be appropriately determined according to the application.

<External electrode 4>
The conductive material contained in the external electrode 4 is not particularly limited, but in the present invention, inexpensive Ni, Cu, and alloys thereof can be used. The thickness of the external electrode 4 may be appropriately determined according to the application and the like, but is usually preferably about 5 to 50 μm.

  The measurement of the rare earth element concentration at the Ba site and Ti site of the shell portion is not particularly limited. For example, a transmission scanning electron microscope (STEM) equipped with an elemental analysis instrument (EDS) and a spherical aberration correction function device (Cs collector) is used. This is done using 10 grains of barium titanate selected as the main component, and 200 points are measured at each site to quantify the amount of R1 Ba site substitution and R1 Ti site substitution. That's fine.

<Method for Manufacturing Multilayer Ceramic Capacitor 1>
In the multilayer ceramic capacitor 1 of this embodiment, a green chip is produced by a normal printing method or a sheet method using a paste, and fired, and then printed or transferred an external electrode, similarly to a conventional multilayer ceramic capacitor. It is manufactured by baking. Hereinafter, the manufacturing method will be specifically described.

  First, a predetermined amount of raw material powder of barium titanate, each oxide and each carbonate as a dielectric material for forming the dielectric layer is prepared, and this is made into a paint to prepare a dielectric layer paste.

  The dielectric layer paste may be an organic paint obtained by kneading a dielectric material and an organic vehicle, or may be a water-based paint.

  As the raw material powder of barium titanate, there are various methods such as those produced by various liquid phase methods (for example, oxalate method, hydrothermal synthesis method, alkoxide method, sol-gel method, etc.) in addition to the so-called solid phase method. Can be used.

An organic vehicle is obtained by dissolving a binder in an organic solvent. A binder is not specifically limited, What is necessary is just to select suitably from normal various binders, such as an ethyl cellulose and polyvinyl butyral. The organic solvent is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, toluene, and the like, depending on the method used, such as a printing method or a sheet method.

Further, when the dielectric layer paste is used as a water-based paint, a water-based vehicle in which a water-soluble binder or a dispersant is dissolved in water and a dielectric material may be kneaded. The water-soluble binder used for the water-based vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, water-soluble acrylic resin, etc. may be used.

The internal electrode layer paste is prepared by kneading a conductive material made of various conductive metals and alloys such as Ni, or various oxides, organometallic compounds, resinates, and the like, which become the conductive material described above after firing, and the above-described organic vehicle. Prepare. The internal electrode layer paste may contain a common material. The common material is not particularly limited, but preferably has the same composition as the main component.

  The external electrode paste may be prepared in the same manner as the internal electrode layer paste described above.

  There is no restriction | limiting in particular in content of the organic vehicle in each above-mentioned paste, For example, what is necessary is just about 1-5 mass% about a normal content, for example, about 10-50 mass% for a solvent. Each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like as necessary. The total content of these is preferably 10% by mass or less.

  When the printing method is used, the dielectric layer paste and the internal electrode layer paste are printed and laminated on a substrate such as PET, cut into a predetermined shape, and then peeled from the substrate to obtain a green chip.

  In the case of using the sheet method, a green sheet is formed using a dielectric layer paste, and after printing the internal electrode layer paste thereon, these are stacked, cut into a predetermined shape, and formed into a green chip. .

  Before firing, the green chip is subjected to binder removal processing. The atmosphere at the time of binder removal is air or a reducing atmosphere.

  After removing the binder, the green chip is fired. In firing, the rate of temperature rise is preferably 200 to 8000 ° C./hour. The holding temperature during firing is preferably 1300 ° C. or less, more preferably 1100 to 1250 ° C., and the holding time is preferably 0.2 to 4 hours. By setting the holding time in such a range, it is possible to prevent the electrodes from being interrupted, to prevent the deterioration of the temperature characteristics of the capacitance, and to prevent the reduction of the dielectric ceramic composition.

  The firing atmosphere is preferably a reducing atmosphere. As the atmosphere gas, for example, a mixed gas of N2 and H2 can be used by humidification.

  In addition, the oxygen partial pressure during firing may be appropriately determined according to the type of the conductive material in the internal electrode layer paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, The oxygen partial pressure is preferably 10-14 to 10-10 MPa.

  After firing in a reducing atmosphere, the capacitor element body is preferably annealed. Annealing is a process for re-oxidizing the dielectric layer, and this can significantly increase the insulation resistance life, thereby improving the high temperature load life.

  The oxygen partial pressure in the annealing atmosphere is preferably 10 −9 to 10 −5 MPa. If the oxygen partial pressure is less than the above range, reoxidation of the dielectric layer is difficult, and if it exceeds the above range, oxidation of the internal electrode layer tends to proceed.

  The holding temperature at the time of annealing is preferably 1100 ° C. or less, particularly preferably 700 to 1100 ° C. When the holding temperature is less than the above range, the dielectric layer is not sufficiently oxidized, so that the insulation resistance (IR) is low and the high temperature load life is likely to be shortened. On the other hand, when the holding temperature exceeds the above range, the internal electrode layer is oxidized and the capacity decreases. In addition, you may comprise annealing only from a temperature rising process and a temperature falling process. That is, the temperature holding time may be zero. In this case, the holding temperature is synonymous with the maximum temperature.

  As other annealing conditions, the temperature holding time is preferably 0 to 30 hours, and the temperature drop rate is preferably 50 to 500 ° C./hour. In addition, as the annealing atmosphere gas, for example, humidified N 2 gas or the like is preferably used.

  In the above-described binder removal processing, firing and annealing, for example, a wetter or the like may be used to wet the N2 gas, mixed gas, or the like. In this case, the water temperature is preferably about 5 to 75 ° C.

  The binder removal treatment, firing and annealing may be performed continuously or independently.

  The capacitor element main body obtained as described above is subjected to end face polishing, for example, by barrel polishing or sand blasting, and the external electrode paste is applied and fired to form the external electrode 4. Then, if necessary, a coating layer is formed on the surface of the external electrode 4 by plating or the like.

  The multilayer ceramic capacitor of this embodiment manufactured in this way is mounted on a printed circuit board or the like by soldering or the like and used for various electronic devices.

  As mentioned above, although embodiment of this invention has been described, this invention is not limited to the embodiment mentioned above at all, and can be variously modified within the range which does not deviate from the summary of this invention.

  In the above-described embodiment, the multilayer ceramic capacitor is exemplified as the ceramic electronic component according to the present invention. However, the ceramic electronic component according to the present invention is not limited to the multilayer ceramic capacitor, and any electronic component having the above configuration may be used. good.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.

<Experimental example 1>
First, Ba0.997Y0.003TiO3 powder obtained by substituting a part of Ba of main component barium titanate with subcomponent Y, and using MgCO3, MnCO3, V2O5, Tb2O3.5, and SiO2 as raw materials of other subcomponents. , Each prepared.

MgCO3, MnCO3 and CaCO3 will be contained in the dielectric ceramic composition as MgO, MnO and CaO after firing.

  Next, a mixture of barium titanate and subcomponent materials weighed in a predetermined amount: 100 parts by mass, polyvinyl butyral resin: 10 parts by mass, dioctyl phthalate (DOP) as a plasticizer: 5 parts by mass, and as a solvent Alcohol: 100 parts by mass was mixed with a ball mill to obtain a paste, and a dielectric layer paste was obtained.

  In addition to the above, Ni powder: 44.6 parts by mass, terpineol: 52 parts by mass, ethyl cellulose: 3 parts by mass, and benzotriazole: 0.4 parts by mass are kneaded by three rolls, and slurry To prepare an internal electrode layer paste.

  Then, a 1.0 μm green sheet was formed on the PET film using the dielectric layer paste prepared above. Next, the electrode layer was printed in a predetermined pattern using the internal electrode layer paste thereon, and then the sheet was peeled off from the PET film to produce a green sheet having the electrode layer. Next, a plurality of green sheets having electrode layers were laminated and pressure-bonded to obtain a green laminated body, and the green laminated body was cut into a predetermined size to obtain a green chip.

  Next, the obtained green chip was subjected to binder removal processing, firing and annealing under the following conditions to obtain an element body as a sintered body.

    The binder removal treatment conditions were temperature rising rate: 25 ° C./hour, holding temperature: 260 ° C., temperature holding time: 8 hours, and atmosphere: in the air.

  The firing conditions were a temperature increase rate of 600 ° C./hour, a holding temperature of 1100 to 1250 ° C., and a holding time of 2 hours. The temperature decreasing rate was the same as the temperature increasing rate. The atmosphere gas was a humidified N2 + H2 mixed gas, and the oxygen partial pressure was 10-12 MPa.

  The annealing conditions were as follows: temperature rising rate: 200 ° C./hour, holding temperature: 1000-1100 ° C., temperature holding time: 2 hours, temperature falling rate: 200 ° C./hour, atmospheric gas: humidified N 2 gas (oxygen partial pressure: 10− 7 MPa).

    A wetter was used for humidifying the atmospheric gas during firing and annealing.

  Next, after polishing the end face of the obtained element body by sand blasting, In—Ga was applied as an external electrode to obtain a multilayer ceramic capacitor sample shown in FIG. 1. The size of the obtained multilayer ceramic capacitor sample was 2.0 mm × 1.25 mm × 0.4 mm, the thickness of the dielectric layer was 0.9 μm, and the thickness of the internal electrode layer was about 1.0 μm. The number of dielectric layers sandwiched between the internal electrode layers was four.

  With respect to the obtained multilayer ceramic capacitor sample, the relative permittivity, dielectric loss, capacitance temperature characteristics, MTTF, and measurement of the R1 Ba site substitution amount and R1 Ti site substitution amount in the shell of the crystal grains were respectively measured. The method was as follows.

<Relative permittivity ε>
The relative dielectric constant ε is measured for a multilayer ceramic capacitor sample at a reference temperature of 25 ° C. with a digital LCR meter (YHP 4274A) under the conditions of a frequency of 1 kHz and an input signal level (measurement voltage) of 1.0 Vrms. Calculated from the capacitance (no unit). It is preferable that the relative dielectric constant is high, and in this example, 1500 or more was considered good. The results are shown in Table 1.

<Dielectric loss (tan δ)>
Dielectric loss (tan δ) is measured with a digital LCR meter (YHP 4274A) at a reference temperature of 25 ° C. and a frequency of 1 kHz and an input signal level (measurement voltage) of 1.0 Vrms with respect to a multilayer ceramic capacitor sample. did. The dielectric loss is preferably as low as possible. In this example, 5.0% or less was considered good. The results are shown in Table 1.

<Temperature characteristics of capacitance (TC105)>
The capacitance at −55 to 105 ° C. was measured for the multilayer ceramic capacitor sample, the capacitance change rate ΔC was calculated, and it was evaluated whether the E5 standard X5R characteristic or B characteristic was satisfied. That is, it was evaluated whether the rate of change ΔC at 105 ° C. was within ± 22%. The results are shown in Table 1.

<High temperature load life (MTTF)>
The multilayer ceramic capacitor sample was maintained at 180 ° C. in a DC voltage application state under an electric field of 20 V / μm, and the life time h was measured to evaluate the high temperature load life. In this example, the time from the start of application until the insulation resistance drops by an order of magnitude was defined as the lifetime. In this example, the above evaluation was performed on 20 multilayer ceramic capacitor samples, and the average value was defined as the high temperature load life. The evaluation criteria was good for 3 hours or more. The results are shown in Table 1.

<Substitution site and substitution amount of R1>
The rare earth element concentrations of the Ba site and Ti site of the shell portion were examined using a transmission scanning electron microscope (STEM) equipped with an elemental analyzer (EDS) and a spherical aberration correction function device (Cs collector). As a sample, a laminated ceramic capacitor was cut out in a plane perpendicular to the dielectric layer, and a thin piece produced by FIB processing was used as a TEM sample.

Further, the amorphous layer on the surface of the TEM sample was removed using a low acceleration Ar ion polishing apparatus immediately before observation.

  For such a sample, the orientation of the TEM sample is adjusted so that the <100> direction of the crystal particles mainly composed of barium titanate and the incident direction of the STEM electron beam are parallel, and a high-resolution STEM-HAADF image is obtained. The shell part was observed. The result is shown in FIG.

  Elemental analysis was performed using an EDS apparatus, and the rare earth element concentrations of the Ba site and Ti site of the shell portion were examined. Elemental analysis is performed using 10 arbitrarily selected crystal grains mainly composed of barium titanate, and 200 points are measured at each site, and the obtained spectrum of 200 points is added up at each site. And quantified. The results are shown in Table 1.

<Experimental example 2>
First, BaTiO3 powder was prepared as a main component material, and Y2O3 was prepared as a subcomponent material.

  Next, the BaTiO3 powder prepared above and the raw material of the accessory component are wet-ground for 20 hours with a ball mill and dried to increase the Ba site substitution amount of Y to 1100 ° C. Heat treatment was performed in 2 hours.

  MgCO3, MnCO3, V2O5, Tb2O3.5, and SiO2 were prepared as raw materials for subcomponents other than Y2O3 in the powder thus obtained.

  From pasting to chipping, the same conditions as in Experimental Example 1 were prepared, and the same evaluation was performed. The results are shown in Table 1.

  In Experimental Example 2, even when R1: Ho2O3, R2: Gd2O3 and Eu2O3 were used as subcomponents, they were produced under the same conditions as in Experimental Example 1 and evaluated in the same manner. Table 1 shows the combinations of the subcomponents and the evaluation results.

<Experimental example 3>
First, BaTiO3 powder was prepared as a main component material, and MgCO3, MnCO3, V2O5, Tb2O3.5 and SiO2 were prepared as subcomponent materials.

  In addition, since the amount of substitution of the Ba site of Y is larger than the amount of substitution of the Ti site of Y, Y2TiO5 in which Y is easily substituted at the Ba site than Y2O3 was prepared.

  The addition amount of each subcomponent was set to the amount shown in Table 1.

  A similar evaluation was performed under the same conditions as in Experimental Example 1 except that the main component material was changed to BaTiO3. The results are shown in Table 1.

  In Experimental Example 3, when the subcomponent Y2TiO5 was changed to Y2Ti2O7, it was produced under the same conditions as in Experimental Example 1 except that the main component material was changed to BaTiO3, and the same evaluation was performed. The results are shown in Table 1.

<Experimental example 4>
First, BaTiO3 powder was prepared as a main component material, and MgCO3, MnCO3, V2O5, Tb2O3.5, Y2O3, and SiO2 were prepared as subcomponent materials.

  The sample was prepared under the same conditions as in Experimental Example 1 except that the main component material was changed to BaTiO3.

  At this time, in Experimental Example 4, a sample having a dielectric layer thickness of 0.9 μm and a sample having a thickness of 3.0 μm were prepared.

  For the evaluation, the same evaluation as in Experimental Example 1 was performed. The results are shown in Table 1.

<Experimental example 5>
A sample was prepared by the same method as Patent Document 2 so that the number of dielectric layers was 4, and the thickness of the dielectric layers was 0.9 μm.

  In—Ga was used for the external electrode.

  For the evaluation, the same evaluation as in Experimental Example 1 was performed. The results are shown in Table 1.

Sample No. 1-8
From Table 1, it was confirmed that when a shell satisfying R1 Ba site substitution amount / R1 Ti site substitution amount> 1 was satisfied, good reliability could be realized while maintaining a high relative dielectric constant. Also, good temperature characteristics could be realized.

Sample No. 3
From Table 1, even when R1 is replaced with Y and Ho has a shell in which the Ba site substitution amount of R1 is larger than the Ti site substitution amount, high reliability is maintained while maintaining a high relative dielectric constant. It was confirmed that can be realized.

Sample No. 4, 5
From Table 1, even when R1 is Y and R2 is Gd or Eu, if the shell satisfies R1 Ba site substitution amount / R1 Ti site substitution amount> 1, the relative dielectric constant is increased. It was confirmed that good reliability could be realized while maintaining.

Sample No. 6
According to Table 1, even when R1 is Y and R2 is not contained, the dielectric constant is increased when the shell satisfies R1 Ba site substitution amount / R1 Ti site substitution amount> 1. It was confirmed that good reliability could be realized while maintaining.

Sample No. 1, 2, 7, 8
From Table 1, it can be confirmed that, for example, when R1 is Y, a shell satisfying R1 Ba site substitution amount / R1 Ti site substitution amount> 1 is formed in any of the methods of Experimental Examples 1-3. It was.

Sample No. 9, 10
From Table 1, good reliability was obtained when the dielectric layer was 3.0 μm, but good reliability was not obtained when the dielectric layer was 0.9 μm. From the above, in the case of having a shell that does not satisfy R1 Ba site substitution amount / R1 Ti site substitution amount> 1, it is possible to realize good reliability in a sample having a dielectric layer of 1.0 μm or less. could not.

Sample No. 11
From Table 1, when the shell does not satisfy R1 Ba site substitution amount / R1 Ti site substitution amount> 1, good reliability could not be realized. In addition, good capacitance temperature characteristics were not obtained.

DESCRIPTION OF SYMBOLS 1 ... Multilayer ceramic capacitor 2 ... Dielectric layer 3 ... Internal electrode layer 4 ... External electrode 10 ... Capacitor element main body 5 ... Bright white point: Ba site 6 ... Dark white point: Ti site

Claims (4)

1.   A dielectric ceramic composition comprising a main component composed of barium titanate, and containing R1 (R1 is at least one of Y and Ho) as a subcomponent with respect to the barium titanate, The dielectric ceramic composition has a core-shell structure and has a shell satisfying the Ba site substitution amount of R1 / Ti site substitution amount of R1> 1.
2.   The dielectric ceramic composition according to claim 1, comprising R1 and R2 (R2 is at least one of Eu, Gd, and Tb).
3.   The dielectric ceramic composition according to claim 1, wherein the dielectric layer has a thickness of 1.0 μm or less.
4.   The ceramic electronic component which has a dielectric material layer comprised from the dielectric material ceramic composition in any one of Claims 1-3, and an electrode.