JP2001135544A - Dielectric porcelain composition and electric component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric porcelain composition, with which a dielectric constant is high, capacity temperature characteristics satisfy the X8R characteristics of EIA standard (within -55 to 150 deg.C and ΔC=±15%) and sintering in a reduced atmosphere is enabled, and an electronic component such as laminate ceramic capacitor using this dielectric porcelain composition. SOLUTION: Concerning the dielectric porcelain composition having a main component containing barium titanate, in the case of observation with an electronic transmission microscope, this composition contains crystal grains having interference stripes more than 30% of the field of observation view.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition having reduction resistance and electronic components such as a multilayer ceramic capacitor using the same.

[0002]

2. Description of the Related Art Multilayer ceramic capacitors as electronic components are widely used as small, large-capacity, high-reliability electronic components, and the number used in one electronic device is large. In recent years, with the miniaturization and high performance of equipment, further miniaturization of multilayer ceramic capacitors,
Demands for higher capacity, lower price, and higher reliability are becoming more and more severe.

In a multilayer ceramic capacitor, usually, a paste for an internal electrode layer and a paste for a dielectric layer are laminated by a sheet method, a printing method, or the like, and the internal electrode layer and the dielectric layer in the laminate are simultaneously fired. Manufactured.

The conductive material of the internal electrode layer is generally Pd
However, since Pd is expensive, relatively inexpensive base metals such as Ni and Ni alloys have been used. When a base metal is used as the conductive material of the internal electrode layer, if the firing is performed in the air, the internal electrode layer is oxidized. Therefore, the simultaneous firing of the dielectric layer and the internal electrode layer must be performed in a reducing atmosphere. is there. But,
When firing in a reducing atmosphere, the dielectric layer is reduced and the specific resistance decreases. For this reason, non-reducing dielectric materials have been developed.

However, a multilayer ceramic capacitor using a non-reducing dielectric material has a remarkable deterioration in IR (insulation resistance) due to application of an electric field, that is, has a short IR life.
There is a problem that reliability is low.

Further, when the dielectric is exposed to a DC electric field, there arises a problem that the relative permittivity εr decreases with time. Further, a capacitor may be used by superimposing a DC voltage. In general, when a DC voltage is applied to a capacitor having a dielectric mainly composed of a ferroelectric substance, there is a problem that the capacitance value is reduced (DC). Bias characteristics). If the dielectric layer is made thinner to reduce the size and capacitance of the chip capacitor, the electric field applied to the dielectric layer when a DC voltage is applied becomes stronger. It becomes extremely large or the DC bias characteristics deteriorate.

Further, the capacitor is required to have good temperature characteristics. In particular, depending on the application, it is required that the temperature characteristics be flat under severe conditions. 2. Description of the Related Art In recent years, multilayer ceramic capacitors have been used in various electronic devices such as an engine electronic control unit (ECU), a crank angle sensor, and an antilock brake system (ABS) module mounted in an engine room of an automobile. Since these electronic devices are for stably performing engine control, drive control, and brake control, they are required to have good circuit temperature stability.

In an environment where these electronic devices are used, it is expected that the temperature drops to about −20 ° C. or less in winter in a cold region, and that the temperature rises to about + 130 ° C. or more in summer after the engine is started. Is done. Recently, there has been a tendency to reduce the number of wire harnesses connecting electronic devices and their controlled devices, and the electronic devices are sometimes installed outside the vehicle, so the environment for the electronic devices is becoming increasingly severe. Therefore, capacitors used in these electronic devices need to have flat temperature characteristics over a wide temperature range.

A capacitor material for temperature compensation having excellent temperature characteristics.
(Sr, Ca) (Ti, Zr) O₃system,
Ca (Ti, Zr) O₃System, Nd₂O₃-2Ti
O₂ System, La₂O₃-2TiO₂System is generally known
But these compositions have very low dielectric constants
(Generally 100 or less), large capacitor
Is virtually impossible to produce.

As a dielectric ceramic composition having a high dielectric constant and a flat capacitance-temperature characteristic, BaTiO ₃ is used as a main component, Nb ₂ O ₅ —Co ₃ O ₄ , MgO—Y, a rare earth element (Dy, Ho, etc.) _), Bi ₂ O 3 -TiO
_{2 and the} like are known. Although the mechanism for flattening the capacitance-temperature characteristics is not necessarily clarified, Japanese Patent Publication No. Hei 7-118431 discloses a
It has been proposed to flatten the capacitance-temperature characteristic by dissolving Mg or a rare earth element in the shell structure. However, the document "Key Engineering Material
s Vols 17-24,157-158 (1999); A study on Capacitanc
e Aging in Ni-Electroded, BaTiO ₃ -Based MLCCs
with X7R Characteristics ''
EIA standard X7R characteristics (-55 to 125 ° C, ΔC = ±
It is reported that a core-shell structure is not essential to satisfy (15% or less).

The temperature characteristics of these dielectric ceramic compositions containing BaTiO ₃ as a main component are as follows. Since the Curie temperature of BaTiO ₃ is around 130 ° C., the R characteristics of the capacitance-temperature characteristics in a higher temperature region (above). ΔC = within ± 15%)
It is very difficult to satisfy. For this reason, BaTiO
_{The 3} series high dielectric constant materials are based on the EIA standard X7R characteristics (-
55-125 ° C., ΔC = ± 15%). Satisfying the X7R characteristic alone cannot be used for electronic devices of automobiles used in the above-mentioned harsh environment. The electronic device requires a dielectric ceramic composition that satisfies the EIA standard X8R characteristic (−55 to 150 ° C., ΔC = ± 15%).

BaTiO₃-Based dielectric porcelain
In order to satisfy X8R characteristics in the composition, BaT
iO₃By replacing Ba in the sample with Bi, Pb, etc.
It is suggested that the Curie temperature be shifted to higher temperatures.
(JP-A-10-25157, 9-40)
465). In addition, BaTiO₃+ CaZrO
₃+ ZnO + Nb₂O₅Choosing the composition of the system
To satisfy the X8R characteristic by
(JP-A-4-295048, JP-A-4-292458)
Gazette, JP-A-4-292459, JP-A-5-10931
9 and 6-243721).

However, in any of these composition systems, since Pb, Bi, and Zn, which are easily evaporated and scattered, are used, firing in an oxidizing atmosphere such as in air is a prerequisite. For this reason, there is a problem that an inexpensive base metal such as Ni cannot be used for the internal electrode of the capacitor, and an expensive noble metal such as Pd, Au, or Ag must be used.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a capacitor having a high relative dielectric constant and satisfying the X8R characteristics (-55 to 150 ° C., ΔC = ± 15%) of the EIA standard,
An object of the present invention is to provide a dielectric ceramic composition which can be fired in a reducing atmosphere and an electronic component such as a multilayer ceramic capacitor using the same.

[0015]

Means for Solving the Problems In order to achieve the above object, a dielectric ceramic composition according to a first aspect of the present invention is a dielectric ceramic composition having at least a main component containing barium titanate. When observed with a transmission electron microscope, crystal particles having interference fringes are contained in 30% or more of the observation visual field.

Preferably, the interference fringes are caused by stress.

In order to achieve the above object, a second aspect of the present invention is provided.
The dielectric ceramic composition according to the aspect of the present invention comprises a main component containing barium titanate and a first subcomponent containing an oxide of at least one first element (M1) selected from Mg, Ca, Ba and Si. A dielectric ceramic composition comprising at least a second subcomponent containing an oxide of at least one kind of a second element (R1) selected from Er, Sc, Tm, Yb, and Lu; Ratio of the number of moles of the first element of the first subcomponent to the number of moles of the second element of the subcomponent (M1 / R1)
Is 0 <(M1 / R1) ≦ 2.

Preferably, the ratio of each subcomponent to 100 mol of the main component containing barium titanate is the first subcomponent:
0.1 to 3 mol, second subcomponent: 0.5 to 7 mol (however, the number of moles of the fourth subcomponent is a ratio of R1 alone)
It is.

Preferably, silicon oxide is further included as the third subcomponent, and the content of the third subcomponent is 2 to 10 mol with respect to 100 mol of the main component containing barium titanate.

Preferably, the third subcomponent is (Ba,
Ca) _x SiO _{2 + x} (where x = 0.7-1.
2). In this case, the ratio between Ba and Ca is arbitrary, and only one of them may be contained.

Preferably, V ₄ O is used as the fourth subcomponent.
₅ , MoO ₃ and WO ₃ , wherein the content of the fourth subcomponent is 0.01 to 0.1 with respect to 100 mol of the main component containing barium titanate.
5 moles.

Preferably, the composition further comprises, as a fifth subcomponent, an oxide of R2 (where R2 is at least one selected from Y, Dy, Ho, Tb, Gd and Eu),
The content of the fifth subcomponent is preferably 9 mol or less, more preferably 0.1 mol, per 100 mol of the main component containing barium titanate.
5 to 9 moles (however, the number of moles of the fifth subcomponent is a ratio of R2 alone).

Preferably, the total content of the second sub-component and the fifth sub-component is 10% of the main component containing barium titanate.
13 mol or less, more preferably 10 mol or less with respect to 0 mol (provided that the number of moles of the second subcomponent and the fifth subcomponent is
R1 and R2 alone).

Preferably, MnO is further included as a sixth subcomponent, and the content of the sixth subcomponent is 0.5 mol or less based on 100 mol of the main component containing barium titanate.

Preferably, as barium titanate,
Expressed by a composition formula _{Ba m TiO 2 +} m, m in the composition formula is 0.995 ≦ m ≦ 1.010, Ba and Ti
And 0.995 ≦ Ba / Ti ≦ 1.010.

The electronic component according to the present invention is not particularly limited as long as it has a dielectric layer. For example, a multilayer ceramic having a capacitor element body in which dielectric layers and internal electrode layers are alternately laminated. It is a capacitor element. In the present invention, the dielectric layer is made of any one of the above dielectric ceramic compositions. The conductive material contained in the internal electrode layer is not particularly limited, but is, for example, Ni or a Ni alloy.

[0027]

The present inventors have conducted intensive studies to obtain a dielectric porcelain composition satisfying the X8R characteristic. As a result, when observed by a transmission electron microscope, 30% or more of the observation field has crystal grains having interference fringes. The dielectric porcelain composition constituted by
It has been found that the X8R characteristics are satisfied.

The dielectric porcelain composition according to the present invention has a high relative dielectric constant, a capacity-temperature characteristic satisfying the EIA standard X8R characteristic, can be fired in a reducing atmosphere, and can be used under a DC electric field. The capacitance changes with time are small, and the life of the insulation resistance is long.

Therefore, by using the dielectric ceramic composition of the present invention, it is easy to provide electronic parts such as a multilayer ceramic capacitor having excellent characteristics.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the drawings. FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention, FIG. 2 is a graph showing capacitance-temperature characteristics of the capacitor, FIGS. 3A and 3B are TEM photographs of Samples 3 and 1, respectively. FIG. 4 shows the temperature-DDS of the dielectric ceramic compositions of Samples 3 and 1.
5 is a graph showing a C curve, and FIG. 5 is BaTiO ₃ + MgO +
R ₂ O ₃ (R = Gd, Tb, Dy, Y, Ho, E
at least one selected from r, Sc, Tm, Yb and Lu) + MnO + V ₂ O ₅ + (BaCa) SiO
It is a figure which shows the X-ray-diffraction (XRD) chart of the (002) and (200) crystal plane of ₃ system.

As shown in FIG. 1, a multilayer ceramic capacitor 1 according to one embodiment of the present invention has a dielectric layer 2 and an internal electrode layer 3.
And the capacitor element body 10 having a configuration in which the capacitor element bodies are alternately stacked. At both ends of the capacitor element body 10, a pair of external electrodes 4 are formed which are electrically connected to the internal electrode layers 3 alternately arranged inside the element body 10. The shape of the capacitor element body 10 is not particularly limited, but is generally a rectangular parallelepiped. The size is not particularly limited, and may be an appropriate size depending on the application.
~ 5.6 mm) x (0.3 to 5.0 mm) x (0.3 to
(1.9 mm).

The internal electrode layers 3 are laminated so that each end face is alternately exposed on the surfaces of two opposing ends of the capacitor element body 10. The pair of external electrodes 4 are formed at both ends of the capacitor element body 10 and connected to the exposed end faces of the alternately arranged internal electrode layers 3 to form a capacitor circuit.

[0033]Dielectric layer The dielectric layer 2 contains the dielectric ceramic composition of the present invention.
The dielectric porcelain composition of the present invention comprises barium titanate (preferably).
Or the composition formula Ba_m TiO_{2 + m}Where m is
0.995 ≦ m ≦ 1.010, and the ratio of Ba to Ti
Is 0.995 ≦ Ba / Ti ≦ 1.010)
It has at least the main components and is observed with a transmission electron microscope.
In this case, the crystal particles having interference fringes are reduced to 30% or less of the observation field.
Above, preferably 50% or more.

If the content of the crystal particles having interference fringes is less than 30% of the visual field observed by the transmission electron microscope, X8
The R characteristics cannot be satisfied.

Although the cause of the observation of the interference fringes is not necessarily clear, since the additive partially reacted and diffused,
This is considered to be a stress interference fringe generated due to, for example, distortion or stress.

The average crystal grain size of the dielectric ceramic composition of the present invention is not particularly limited, and may be appropriately determined, for example, in the range of 0.1 to 3 μm according to the thickness of the dielectric layer. The capacitance-temperature characteristics tend to be worse as the dielectric layer is thinner, and worse as the average crystal grain size is smaller. For this reason, the dielectric ceramic composition of the present invention is particularly effective when the average crystal grain size needs to be reduced, specifically, when the average crystal grain size is 0.1 to 0.5 μm. is there. In addition, if the average crystal grain size is reduced, the IR life is prolonged, and the change with time in the capacity under a DC electric field is reduced, and from this point, the average crystal grain size is preferably small as described above. .

The Curie temperature (phase transition temperature from ferroelectric to paraelectric) of the dielectric porcelain composition of the present invention can be changed by selecting the composition, but in order to satisfy the X8R characteristic. Is preferably 120 ° C. or higher, more preferably 123 ° C. or higher. The Curie temperature is
It can be measured by DSC (differential scanning calorimetry) or the like.

The thickness of the dielectric layer composed of the dielectric ceramic composition of the present invention is usually 40 μm or less per layer.
In particular, it is 30 μm or less. The lower limit of the thickness is usually 2 μm
It is about. The dielectric ceramic composition of the present invention is effective for improving the capacitance-temperature characteristics of a multilayer ceramic capacitor having such a thin dielectric layer. The number of stacked dielectric layers is usually about 2 to 300.

The multilayer ceramic capacitor using the dielectric ceramic composition of the present invention has a temperature of 80.degree.
It is suitable for use as an electronic component for equipment used in an environment of 0 ° C. In such a temperature range, the temperature characteristic of the capacitance satisfies the R characteristic of the EIA standard.
The X8R characteristics are also satisfied. In addition, the EIAJ standard B characteristic [capacity change rate within ± 10% at −25 to 85 ° C. (reference temperature 20 ° C.)] and the EIA standard X7R characteristic (−55 to 125
° C, ΔC = within ± 15%) at the same time.

In the case of a multilayer ceramic capacitor, the dielectric layer usually has a thickness of 0.02 V / μm or more, particularly 0.2 V / μm or more.
Above, more than 0.5V / μm, generally 5V / μm
An AC electric field of less than about and a DC electric field of 5 V / μm or less are superimposed on the AC electric field. Even when such an electric field is applied, the temperature characteristics of the capacitance are extremely stable.

In the dielectric porcelain composition of the present invention, an example of a composition under the condition where interference fringes are observed when observed with a transmission electron microscope is shown below.

That is, such a composition comprises titanic acid
Barium (preferably, the composition formula Ba _mTiO_{2 + m}
Where m is 0.995 ≦ m ≦ 1.010, and B
The ratio of a to Ti is 0.995 ≦ Ba / Ti ≦ 1.010
And Mg, Ca, Ba and Si
Acid of at least one first element (M1) selected from
A first sub-component containing an oxide, Er, Sc, Tm, Yb and
And at least one second element (R
1) having at least a second subcomponent containing an oxide of
The amount of the first subcomponent with respect to the number of moles of the second element of the second subcomponent is
The ratio (M1 / R1) of the number of moles of the first element is 0 <(M1 /
R1) ≦ 2, preferably 0.1 ≦ (M1 / R1) ≦ 1
is there.

Preferably, the ratio of each subcomponent to 100 mol of the main component containing barium titanate is the first subcomponent:
0.1 to 3 mol (preferably 0.5 to 2.5 mol) and the second subcomponent: 0.5 to 7 mol (preferably 0.5 to 5 mol).

The ratio of the second subcomponent is not the molar ratio of R1 oxide but the molar ratio of R1 alone. That is,
For example, when an oxide of Yb is used as the second subcomponent, the fact that the ratio of the second subcomponent is 1 mol means that Yb ₂ O ₃
Is not 1 mol, but the ratio of Yb is 1 mol.

In the present specification, each oxide constituting the main component and each subcomponent is represented by a stoichiometric composition. However, the oxidation state of each oxide may deviate from the stoichiometric composition. Good. However, the above ratio of each subcomponent is determined by converting the amount of metal contained in the oxide constituting each subcomponent to an oxide having the above stoichiometric composition.

The reasons for limiting the contents of the respective subcomponents are as follows. First subcomponents (Mg, Ca, Ba and S
If the content of at least one oxide of the first element (M1) selected from i) is too small, the rate of change in capacitance with temperature will increase. On the other hand, if the content is too large, the sinterability deteriorates. Note that the constituent ratio of each oxide in the first subcomponent is arbitrary.

The second sub-component (Er, Sc, Tm, Yb, and Lu, at least one second element (R
The oxide 1) has an effect of shifting the Curie temperature to a higher temperature side and an effect of flattening the capacity-temperature characteristic. If the content of the second subcomponent is too small, such an effect becomes insufficient, and the capacity-temperature characteristics deteriorate. on the other hand,
If the content is too large, sinterability tends to deteriorate. Among the second subcomponents, a Yb oxide is preferable because it has a high property improving effect and is inexpensive.

By adjusting the ratio of the first sub-component to the second sub-component within the above range, it is possible to obtain a composition in which the above-mentioned interference fringes are observed, and to flatten the capacity-temperature characteristic (X8R characteristic). , CR product and sinterability can also be improved.

In the dielectric porcelain composition of the present invention, if necessary, the third subcomponent containing silicon oxide may be contained in an amount of 2 to 10 mol (more preferably 2 to 5 mol) per 100 mol of the main component containing barium titanate. Mol).
The third subcomponent is (Ba, Ca) _x SiO
_{2 + x} (where x = 0.7 to 1.2) is preferable. In this case, Ba and C
The ratio with a is arbitrary, and may contain only one. If the content of the third subcomponent (silicon oxide) is too small, the capacitance-temperature characteristics are deteriorated, and the IR (insulation resistance) tends to decrease. On the other hand, if the content is too large, the IR life tends to be insufficient and the dielectric constant tends to sharply decrease. [(Ba, Ca) _x SiO _{2 + x} ] as a more preferred embodiment of the third subcomponent
Although BaO and CaO in it are also contained in the first subcomponent,
Since (Ba, Ca) _x SiO _{2 + x} , which is a composite oxide, has a low melting point and good reactivity with the main component, it is preferable to add BaO and / or CaO as the composite oxide in the present invention. _{X in} (Ba, Ca) xSiO2 _{+ x} as a preferable embodiment of the third subcomponent is preferably 0.7 to 1.2, and more preferably 0.8 to 1.1. If x is too small, that is, if there is too much SiO ₂ , the main component BaTiO ₃
And the dielectric properties are degraded. On the other hand, if x is too large, the melting point becomes high and the sinterability deteriorates, which is not preferable. The ratio between Ba and Ca is arbitrary, and may contain only one of them.

In the dielectric ceramic composition of the present invention, if necessary, the fourth subcomponent containing at least one selected from V ₂ O ₅ , MoO ₃ and WO ₃ may contain a main component containing barium titanate. 0.01 to 0.5 per 100 mol
Mole (more preferably 0.1 to 0.4 mole). Fourth subcomponent (V ₂ O ₅ , Mo
O ₃ and WO ₃ ) show an effect of flattening the capacitance-temperature characteristics at the Curie temperature or higher and an effect of improving the IR life. If the content of the fourth subcomponent is too small, such an effect tends to be insufficient. On the other hand, if the content is too large, the IR tends to decrease significantly. In addition,
The constituent ratio of each oxide in the third subcomponent is arbitrary.

In the dielectric porcelain composition of the present invention, if necessary, R2 oxide (where R2 is at least one selected from Y, Dy, Ho, Tb, Gd and Eu) may be used as a fifth subcomponent. Is 9 mol or less (more preferably 0.5 mol
To 9 mol). The fifth subcomponent (R2 oxide) has an effect of improving IR and IR life, and has little adverse effect on the capacity-temperature characteristics. However, when the content of the R2 oxide is too large, the sinterability tends to deteriorate. Among the fifth subcomponents, a Y oxide is preferable because it has a high property improving effect and is inexpensive.

The total content of the second subcomponent and the fifth subcomponent is preferably 13 mol or less, more preferably 10 mol or less with respect to 100 mol of the main component containing barium titanate (provided that the second subcomponent is not more than 10 mol). And the number of moles of the fifth subcomponent is the ratio of R1 and R2 alone). This is for maintaining good sinterability.

Further, the dielectric ceramic composition of the present invention may contain MnO as a sixth subcomponent. The sixth subcomponent has the effect of promoting sintering, the effect of increasing IR, and the effect of improving IR life. In order to sufficiently obtain such an effect, it is preferable that the ratio of the sixth subcomponent to 100 mol of the main component containing barium titanate is 0.01 mol or more. However, if the content of the sixth subcomponent is too large, the capacity-temperature characteristics are adversely affected.
Preferably, it is 0.5 mol or less.

In the dielectric porcelain composition of the present invention,
In addition to the above oxides, Al₂O₃ May be included
No. Al₂O₃Has a large effect on the capacitance-temperature characteristics
And has the effect of improving sinterability, IR and IR life.
You. Where Al₂O₃Too high content of sintering
Deteriorates and the IR decreases, so that Al₂O₃Is good
More preferably, 100 moles of the main component containing barium titanate
1 mole or less, more preferably, dielectric ceramic composition
1 mol or less of the whole product.

At least one of Sr, Zr and Sn is composed of Ba in the main component of the perovskite structure.
Alternatively, when Ti is substituted, the Curie temperature shifts to a lower temperature side, so that the capacity-temperature characteristics at 125 ° C. or higher deteriorate. Therefore, BaTiO ₃ containing these elements is used.
It is preferable not to use [for example, (Ba, Sr) TiO ₃ ] as a main component. However, there is no particular problem as long as it is contained as an impurity (about 0.1 mol% or less of the whole dielectric ceramic composition).

By satisfying such conditions, interference fringes appear, the capacitance-temperature characteristics are improved, and the X8R characteristics can be satisfied.

The dielectric porcelain composition containing the crystal grains in which the interference fringes are observed in a predetermined amount or more can satisfy the above composition conditions. The above characteristics (30% or more of crystal grains having interference fringes) can be satisfied by appropriately controlling the conditions.

[0058] Without being limited internal electrode layer conductive material included in the internal electrode layer 3 in particular, since the material constituting the dielectric layer 2 has reduction resistance, a base metal can be used. As the base metal used as the conductive material, Ni or a Ni alloy is preferable. The Ni alloy is selected from Mn, Cr, Co and Al.
An alloy of at least one kind of element and Ni is preferable.
The content is preferably at least 95% by weight. In addition,
Various trace components such as P are contained in Ni or Ni alloy in an amount of 0.1%.
It may be contained up to about 1% by weight. The thickness of the internal electrode layer may be appropriately determined according to the application and the like.
It is preferably about 5 to 5 μm, particularly about 0.5 to 2.5 μm.

[0059] A conductive material included in the external electrode external electrode 4 is not particularly limited,
In the present invention, inexpensive Ni, Cu and their alloys can be used. The thickness of the external electrode may be appropriately determined according to the use or the like, but is usually preferably about 10 to 50 μm.

Manufacturing Method of Multilayer Ceramic Capacitor A multilayer ceramic capacitor using the dielectric ceramic composition of the present invention can be produced in the same manner as a conventional multilayer ceramic capacitor.
A green chip is produced by a normal printing method or a sheet method using a paste, fired, and then external electrodes are printed or transferred and fired. Less than,
The manufacturing method will be specifically described.

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

As the dielectric material, the above-mentioned oxides, mixtures thereof, and composite oxides can be used. In addition, various compounds that become the above-mentioned oxides and composite oxides by firing, such as carbonates and oxalates, can be used. Acid salts, nitrates, hydroxides,
They can be appropriately selected from organometallic compounds and the like, and used by mixing. The content of each compound in the dielectric raw material may be determined so that the composition of the dielectric ceramic composition described above after firing is obtained.

The dielectric material usually has an average particle size of 0.1 to 3
Used as a powder of about μm.

The organic vehicle is obtained by dissolving a binder in an organic solvent. The binder used for the organic vehicle is not particularly limited, and may be appropriately selected from various ordinary binders such as ethyl cellulose and polyvinyl butyral. In addition, the organic solvent to be used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, and toluene according to a method to be used such as a printing method and a sheet method.

In the case where the paste for the dielectric layer is an aqueous paint, an aqueous vehicle in which a water-soluble binder or dispersant is dissolved in water may be kneaded with a dielectric material. The water-soluble binder used for the aqueous vehicle is not particularly limited, and for example, polyvinyl alcohol, cellulose, a water-soluble acrylic resin, or the like may be used.

The internal electrode layer paste is prepared by mixing the above-mentioned organic vehicle with the above-mentioned conductive material made of various dielectric metals or alloys, or various kinds of oxides, organometallic compounds, resinates, etc. which become the above-mentioned conductive material after firing. It is prepared by kneading. The external electrode paste may be prepared in the same manner as the internal electrode layer paste described above.

The content of the organic vehicle in each of the above-mentioned pastes is not particularly limited, and may be a usual content, for example, about 1 to 5% by weight of a binder and about 10 to 50% by weight of a solvent. Further, each paste may contain additives selected from various dispersants, plasticizers, dielectrics, insulators, and the like, as necessary. Their total content is 1
The content is preferably 0% by weight or less.

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

When a sheet method is used, a green sheet is formed by using a dielectric layer paste, and an internal electrode layer paste is printed thereon, and these are laminated to form a green chip.

Before firing, the green chip is subjected to a binder removal treatment. The binder removal treatment may be performed under ordinary conditions. However, when a base metal such as Ni or a Ni alloy is used as the conductive material of the internal electrode layer, the temperature is preferably increased at a rate of 5 to 300 ° C./hour in an air atmosphere. , More preferably 10 to 10
0 ° C./hour, the holding temperature is preferably 180 to 400 ° C.,
More preferably, the temperature is maintained at 200 to 300 ° C., and the temperature holding time is preferably 0.5 to 24 hours, more preferably 5 to 20 hours.

The atmosphere at the time of firing the green chip 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 a Ni alloy is used as the conductive material, the firing atmosphere may be changed. Oxygen partial pressure is 10 ⁻⁸ to 1
Preferably, the pressure is ^0-12 atm. If the oxygen partial pressure is less than the above range, the conductive material of the internal electrode layer may abnormally sinter and be interrupted. If the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.

The holding temperature during firing is preferably 1
100-1400 ° C, more preferably 1200-136
0 ° C, more preferably 1200 to 1320 ° C.
If the holding temperature is less than the above range, the densification becomes insufficient, and if the holding temperature exceeds the above range, the electrode is interrupted due to abnormal sintering of the internal electrode layer, the deterioration of the capacitance temperature characteristic due to the diffusion of the internal electrode layer constituent material, the dielectric Reduction of the body porcelain composition is likely to occur.

Other firing conditions include a heating rate of preferably 50 to 500 ° C./hour, more preferably 20 to 500 ° C./hour.
0 to 300 ° C./hour, the temperature holding time is preferably 0.5
-8 hours, more preferably 1-3 hours, the cooling rate is preferably 50-500 ° C./hour, more preferably 200-500 ° C./hour.
300 ° C./hour. The firing atmosphere is preferably a reducing atmosphere. As the atmosphere gas, for example, a mixed gas of N ₂ and H ₂ is preferably used after being humidified.

When firing in a reducing atmosphere, the capacitor element body is preferably annealed. Annealing is a process for re-oxidizing the dielectric layer, which can significantly increase the IR life, thereby improving reliability.

The oxygen partial pressure in the annealing atmosphere is 10 ⁻⁶
It is preferable that the pressure be ^equal to or higher than the atmospheric pressure, particularly, 10 ⁻⁵ to 10 ⁻⁴ atm. When the oxygen partial pressure is less than the above range, it is difficult to reoxidize the dielectric layer, and when the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.

The holding temperature at the time of annealing is preferably 1100 ° C. or less, particularly preferably 500 to 1100 ° C. If the holding temperature is lower than the above range, the oxidation of the dielectric layer becomes insufficient, so that the IR is low and the IR life tends to be short. On the other hand, when the holding temperature exceeds the above-mentioned range, not only the internal electrode layer is oxidized and the capacity is reduced, but also the internal electrode layer reacts with the dielectric substrate, so that the capacity-temperature characteristic deteriorates and I
A reduction in R and a reduction in IR life are likely to occur. Note that the annealing may include only the temperature increasing process and the temperature decreasing process. That is, the temperature holding time may be set to 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 20 hours, more preferably 6 to 20 hours.
For 10 hours, the cooling rate is preferably 50 to 500 ° C./hour, more preferably 100 to 300 ° C./hour. It is preferable to use, for example, humidified N ₂ gas or the like as an atmosphere gas for annealing.

In the above-mentioned binder removal processing, firing and annealing, for example, a wetter or the like may be used to humidify the N ₂ gas or the mixed gas. in this case,
The water temperature is preferably about 5 to 75C.

The binder removal treatment, firing and annealing are as follows.
It may be performed continuously or independently. When these are continuously performed, after removing the binder, the atmosphere is changed without cooling, and then the temperature is raised to the holding temperature at the time of firing, firing is performed, and then cooling is performed, and the temperature reaches the holding temperature of annealing. It is preferable to perform the annealing while changing the atmosphere. On the other hand, when performing these independently, at the time of firing, after raising the temperature under N ₂ gas atmosphere with N ₂ gas or wet to the holding temperature of the binder removal processing, further continuing the heating to change the atmosphere After cooling to the holding temperature at the time of annealing, it is preferable to change to an N ₂ gas or humidified N ₂ gas atmosphere again and continue cooling. In annealing, N ₂
After the temperature is raised to the holding temperature in the gas atmosphere, the atmosphere may be changed, or the entire annealing process may be performed in a humidified N ₂ gas atmosphere.

The end of the capacitor element body obtained as described above is polished by, for example, barrel polishing or sand blasting, and the external electrode paste is printed or transferred and baked to form the external electrode 4. The firing condition of the external electrode paste is preferably, for example, about 600 minutes to about 800 ° C. for about 10 minutes to about 1 hour in a humidified mixed gas of N ₂ and H ₂ . 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 the present invention thus manufactured is mounted on a printed circuit board by soldering or the like,
Used for various electronic devices.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments at all, and it goes without saying that the present invention can be implemented in various modes without departing from the gist of the present invention. It is.

For example, in the above-described embodiment, the multilayer ceramic capacitor is exemplified as the electronic component according to the present invention. However, the electronic component according to the present invention is not limited to the multilayer ceramic capacitor, but may be a dielectric ceramic composition having the above composition. Any material may be used as long as it has a dielectric layer made of a material.

[0083]

Next, the present invention will be described in more detail by way of examples which embody the embodiments of the present invention. However, the present invention is not limited to only these examples.

Example 1 A main component raw material and a subcomponent raw material each having a particle size of 0.1 to 1 μm were prepared. Carbonate was used as a raw material for MgO and MnO, and oxides were used for other raw materials. The raw material of the second subcomponent is (Ba _0.6 Ca _0.4 ) SiO
₃ was used. Note that (Ba _0.6 Ca _0.4 ) S
iO ₃ is composed of BaCO ₃ , CaCO ₃ and SiO
₂ was wet-mixed with a ball mill for 16 hours, dried,
It was manufactured by firing at 1150 ° C. in the air and further wet grinding with a ball mill for 100 hours.

The main component, BaTiO _3, is composed of B
aCO ₃ and TiO ₂ are each weighed, wet-mixed using a ball mill for about 16 hours, dried, fired in air at a temperature of 1100 ° C. and wet-pulverized for about 16 hours by a ball mill to produce Similar characteristics were obtained by using the obtained material. In addition, the main component Ba
Similar characteristics were obtained by using TiO ₃ produced by hydrothermal synthesis powder, oxalate method or the like.

These raw materials were blended such that the composition after firing was as shown in Table 1 below with respect to 100 mol of BaTiO _{3 as} the main component, and the mixture was mixed by a ball mill.
The mixture was wet-mixed and dried to obtain a dielectric material. Then
100 parts by weight of the obtained dielectric material after drying, 4.8 parts by weight of acrylic resin, 40 parts by weight of methylene chloride, 20 parts by weight of ethyl acetate, 6 parts by weight of mineral spirit,
4 parts by weight of acetone were mixed with a ball mill to form a paste, thereby obtaining a dielectric layer paste.

Next, N having an average particle size of 0.2 to 0.8 μm
100 parts by weight of i-particles, 40 parts by weight of an organic vehicle (8 parts by weight of ethyl cellulose dissolved in 92 parts by weight of butyl carbitol), and 10 parts by weight of butyl carbitol are kneaded with a three-roll mill to form a paste. An electrode layer paste was obtained.

Next, Cu particles 1 having an average particle size of 0.5 μm
00 parts by weight and an organic vehicle (ethyl cellulose resin 8
35 parts by weight of butyl carbitol dissolved in 92 parts by weight of butyl carbitol) and 7 parts by weight of butyl carbitol were kneaded into a paste to obtain a paste for an external electrode.

Next, a 15 μm-thick green sheet was formed on a PET film using the above-mentioned dielectric layer paste, and after the internal electrode layer paste was printed thereon, the green sheet was peeled off from the PET film. . Next, these green sheets and protective green sheets (without printing the internal electrode layer paste) are laminated,
Crimping was performed to obtain a green chip. The number of stacked sheets having internal electrodes was four.

Next, the green chip is cut into a predetermined size, and a binder removal process, firing and annealing are performed.
A laminated ceramic fired body was obtained.

The binder removal treatment was performed under the conditions of a heating time of 15 ° C./hour, a holding temperature of 280 ° C., a holding time of 8 hours, and an air atmosphere.

The firing is performed at a temperature rising rate of 200 ° C./hour, a holding temperature of 1280 ° C., a holding time of 2 hours, a cooling rate of 300 ° C./hour, a humidified N ₂ + H ₂ mixed gas atmosphere (oxygen partial pressure is 10 ⁻⁹ atm). Was performed under the following conditions.

Annealing was performed at a holding temperature of 900 ° C., a temperature holding time of 9 hours, a cooling rate of 300 ° C./hour, and humidified N _2.
The ^test was performed under a gas atmosphere (oxygen partial pressure was 10 ⁻⁵ atm). Note that a wetter with a water temperature of 35 ° C. was used for humidifying the atmosphere gas during firing and annealing.

Next, after polishing the end face of the laminated ceramic fired body by sand blasting, the external electrode paste was transferred to the end face, and fired at 800 ° C. for 10 minutes in a humidified N ₂ + H ₂ atmosphere. To form
A sample of the multilayer ceramic capacitor having the configuration shown in FIG. 1 was obtained.

The size of each sample thus obtained was 3.2 mm × 1.6 mm × 0.6 mm, the number of dielectric layers sandwiched between the internal electrode layers was 4, and its thickness was 10
μm, and the thickness of the internal electrode layer was 1.5 μm.

In addition to the capacitor sample, a disk-shaped sample was also prepared. This disc-shaped sample has the same composition as the dielectric layer of each capacitor sample and the same sintering conditions, and is obtained by coating an In-Ga electrode having a diameter of 5 mm on both surfaces of the sample.

Each sample was evaluated for the following characteristics.

Specific dielectric constant (εr), dielectric loss (tan δ) The capacitance and ta of a disk-shaped sample were measured at 25 ° C. under the conditions of 1 kHz and 1 Vrms by an LCR meter.
nδ was measured. Then, the relative dielectric constant was calculated from the capacitance, the electrode dimensions, and the thickness of the sample. The results are shown in each table.

Insulation Resistance (IR) The specific resistance at 25 ° C. of the disc-shaped sample was measured. The specific resistance was measured by an insulation resistance meter (R8340A (50 V-1 minute value) manufactured by Advantest Corporation). The results are shown in each table.

Temperature Characteristics of Capacitance The capacitance of the capacitor sample was measured in a temperature range of -55 to 160 ° C., and it was examined whether the X8R characteristic was satisfied. In addition, a sample containing Yb (sample 3) was selected as an example of the present invention, and a sample containing Y (sample 1) was selected as a comparative example.
FIG. 2 shows the capacity-temperature characteristics at -160 ° C. FIG.
, A rectangular range satisfying the X7R characteristic (the inner rectangle in FIG. 2) and a rectangular range satisfying the X8R characteristic (the outer rectangle in FIG. 2) are also described. In addition, LCR was used for measurement.
The measurement voltage was 1 V using a meter (HP4284A).

TEM (Transmission Electron Microsco
Observation of dielectric structure by pe) In this example, an observation sample was prepared by the following procedure. In particular, care was taken so that the observation sample was not affected by the processing.

First, the capacitor sample was polished to about 100 μm with a diamond saw and sandpaper. Next, the sample surface was buffed using a solution in which diamond powder of 1 μm or less was suspended. Then, about 20 μm using a dip grinder
Was polished to a thickness of, and further polished by ion milling to produce an observation sample. During processing by ion milling, the sample stage was cooled using liquid nitrogen to prevent the temperature of the sample from rising.

Next, the obtained observation sample was fixed to a sample holder of a TEM (JEM-2000FXII manufactured by JEOL Ltd.), and the tissue of the observation sample set was subjected to an acceleration voltage of 20 μm.
0kV, observed under the conditions of magnification 20,000 to 50,000,
It was examined whether crystal grains having interference fringes were contained in 30% or more of the observation visual field. Those satisfying the condition are indicated by “○”, and those not satisfying the condition are indicated by “×”.

FIG. 3A shows a TEM photograph of Sample 3 which is a typical composition of this example. From this, it can be seen that crystal grains having stress interference fringes are contained in 55%, which is 30% or more of the observation visual field (the entire area of the photograph). For comparison, the TEM for Sample 1 was
The photograph is shown in FIG. 3 (B), but no crystal particles containing stress interference fringes were observed.

The value of the interference fringes was determined by dividing (dividing) the total area of the partial areas where the interference fringes were observed by the area of the entire observation visual field. The discrimination between the stress interference fringes and the interference fringes based on the sample thickness was confirmed by changing the inclination angle. The domain was determined by varying the tilt angle of the sample and confirming disappearance of the domain. In addition,
The inclination angle of the sample was changed at ± 5 degrees.

10 V / μm at 200 ° C. for a sample of an IR life capacitor under a DC electric field.
The acceleration test was performed under an electric field of m, and the time until the insulation resistance became 1 MΩ or less was defined as the life time, and is shown in each table.

Measurement by DSC The endothermic peaks of the disc-shaped samples (samples 1 and 3) were measured by DSC (differential scanning calorimetry) to determine the Curie temperature. FIG. 4 shows a temperature-DDSC curve of the sample. From this, it was also confirmed that the sample of the example exhibited a shift in Curie temperature to a higher temperature side and an improvement in temperature characteristics as compared with the sample of the comparative example.

[0108]

[Table 1]

In the above table, in the numerical value of the insulation resistance (IR), “mE + n” means “m × 10 ^{+ n} ”.

From the results shown in the above table, when the molar ratio (Mg / Y) between Mg in the first subcomponent and Y in the second subcomponent is within a predetermined range, stress interference fringes are observed. The crystal grains accounted for 30% or more of the observation visual field, and it was found that the samples of the present example satisfied the X8R characteristics, had sufficiently high relative permittivity and insulation resistance, and had no problem with dielectric loss. . In addition, the sample of this example satisfied not only the X8R characteristic but also the B characteristic of the EIAJ standard and the X7R characteristic of the EIA standard described above.

Also, by containing the second subcomponent,
It was confirmed that a sufficient IR life was obtained. Under this condition, if the lifetime is 1 hour or more, it can be said that the IR lifetime is sufficient.

A sample was prepared separately, and the structure was observed with a scanning electron microscope and the density of the sample was measured. As a result, when the content of the second subcomponent became 10 mol or more, the firing temperature range was 1280 ° C. It was also confirmed that the sinterability was insufficient. If the sinterability is insufficient, characteristics such as dielectric loss, relative dielectric constant, and IR life will be reduced, and moisture resistance and strength will also be insufficient. Although it is possible to improve the sinterability by further raising the firing temperature, firing at a high temperature exceeding 1320 ° C. may cause interruption of the internal electrode layer and reduction of the dielectric ceramic composition. It will be easier.

Example 2 A disc-shaped sample of this example was prepared in the same manner as in Sample No. 3 of Example 1 except that 4.26 mol of Yb, Tm, Lu, Sc, and Er were added as second subcomponents. Samples were prepared (Samples 3-1 and 6-9). Further, as a second subcomponent, nothing is added, or Y, La, Ce, P
A disc-shaped sample according to a comparative example was prepared in the same manner as in Sample No. 3 of Example 1 except that 4.26 mol of r, Nd, Sm, Eu, Gd, Tb, Dy or Ho was added (Sample 10-21). For these disc-shaped samples,
The same measurement as in Example 1 was performed. Table 2 shows the results.

[0114]

[Table 2]

From the results shown in Table 2, nothing was added as the second subcomponent, or Y, La, Ce, Pr, N
As compared to the sample according to the comparative example to which d, Sm, Eu, Gd, Tb, Dy or Ho was added, in the sample containing Yb, Tm, Lu, Sc or Er as the second subcomponent, the stress interference fringe was reduced. The observed crystal particles are 3
0% or more, and it was confirmed that the samples of the present example satisfied the X8R characteristic similarly to Example 1.

Example 3 Y ₂ O ₃ as a fifth subcomponent was further added,
Samples were prepared in the same manner as in Sample No. 3 of Example 1 except that 4.26 mol of the subcomponent was added (Sample Nos. 22 to 22).
24), the same measurement as in Example 1 was performed. Table 3 shows the results. Sample 1 is also shown for reference. The firing temperature was 1320 ° C.

[0117]

[Table 3]

From the results shown in Table 3, it was confirmed that the IR life was improved by adding the Y oxide (fifth subcomponent) in addition to the Yb oxide (second subcomponent).
It was also confirmed that the addition of Y oxide did not adversely affect other characteristics.

Example 4 Sc, Er, Tm, Yb, and Lu were used as the second subcomponents.
A disk-shaped sample of this example was produced in the same manner as in Sample No. 3 of Example 1, except that the addition was made in molar. Also, the second
Gd, Tb, Dy, Y outside the scope of the present invention as subcomponents
Alternatively, a disc-shaped sample according to a comparative example was prepared in the same manner as in Sample No. 3 of Example 1 except that 4 mol of Ho was added. FIG. 5 shows the results of X-ray diffraction (XRD) measurement of the (002) and (200) crystal planes of these disc-shaped samples. Looking at this, as the second subcomponent, E
(200) and (00) by adding at least one selected from r, Sc, Tm, Yb and Lu.
2) It was confirmed that the peak position of the crystal plane was widened. This is considered to indicate that the ac axis ratio is large, that is, the crystal axis of BaTiO ₃ is distorted. In other words, these (at least one selected from Er, Sc, Tm, Yb, and Lu) form a solid solution on a part of the BaTiO ₃ surface, so that Ba is formed.
The TiO ₃ crystal is distorted. For this reason, BaTiO
_It is considered that strain and stress are generated inside the crystal of No. ₃ and interference fringes are observed during TEM observation.

The disc samples of this example were used to evaluate whether or not the X8R characteristics were satisfied in the same manner as in Example 1. As a result, all of them satisfied the X8R characteristics.

Since BaTiO ₃ is a ferroelectric substance, it is considered that the Curie temperature and the capacitance temperature characteristic change due to the strain stress.

Example 5 Sc, Er, Tm, Yb, and Lu were 2
A sample of this example was prepared in the same manner as in Sample No. 3 of Example 1 (see Table 1) except that 4 mol or 4.26 mol was added. Further, a sample according to a comparative example was prepared in the same manner as in Sample No. 3 of Example 1, except that 2 mol or 4.26 mol of Y out of the range of the present invention was added as the second subcomponent.

These samples were heat treated at 150 ° C. for 1 hour.
And left at room temperature (25 ° C.) for 24 hours with no load
After that, measured voltage 1kHz, 1Vr by LCR meter
Initial capacity C in ms₀Was measured. Next, one dielectric layer
DC electric field of 6.3V per hour at 40 ° C for 100 hours
After that, it was left at room temperature (25 ° C.) with no load. Release
24 hours and 111 hours after the start of the₀Measurement
Measure the capacity under the same conditions as when_oFrom
Of change ΔC₁And the capacitance change rate ΔC₁ / C₀
Was calculated.

As a result, as compared with the sample according to the comparative example which contains Y and satisfies the X7R characteristic, the sample according to the present embodiment has the same capacity as that of the sample according to the comparative example in the change with time in the capacity under a DC electric field. It was confirmed that the size was small and the reliability was sufficiently high.

[0125]

As described above, according to the present invention, the dielectric constant is high, and the capacitance-temperature characteristic is X8 of EIA standard.
Satisfies R characteristics (−55 to 150 ° C., ΔC = ± 15% or less), can be fired in a reducing atmosphere, has a small capacity change with time under a DC electric field, and has a long life of insulation resistance. It is possible to provide a dielectric ceramic composition that can be lengthened.

Electronic components such as multilayer ceramic capacitors having a dielectric layer composed of the dielectric ceramic composition can operate stably in various devices used under severe environments such as automobile electronic devices. Because
Significantly improve the reliability of applied equipment.

[Brief description of the drawings]

FIG. 1 is a sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.

FIG. 2 is a graph showing capacitance-temperature characteristics of a capacitor.

FIG. 3A is a TEM photograph of Sample 3, FIG.
(B) is a TEM photograph of Sample 1.

FIG. 4 is a graph showing the temperature-DDSC curves of the dielectric ceramic compositions of Sample 3 and Sample 1.

FIG. 5 is a diagram showing BaTiO ₃ + MgO + R ₂ O
₃ (R = Gd, Tb, Dy, Y, Ho, Er, Sc,
At least one selected from Tm, Yb, and Lu) + M
nO + V ₂ O ₅ + (BaCa) SiO ₃ based (0
It is a figure which shows the X-ray-diffraction (XRD) chart of a (02) and (200) crystal plane.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 multilayer ceramic capacitor 10 capacitor element body 2 dielectric layer 3 internal electrode layer 4 external electrode

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Yoshihiro Terada 1-13-1, Nihonbashi, Chuo-ku, Tokyo Inside TDK Corporation (72) Inventor Akiko Nagai 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK In-house F term (reference) 4G031 AA03 AA04 AA06 AA07 AA11 AA30 BA09 BA26 CA03 5E001 AB03 AC03 AC09 AD03 AE00 AE02 AE03 AE04 AF06 AH01 AH05 AH09 AJ01 AJ02 5G303 AA01 AB06 AB11 AB20 BA12 CA01 CB03 CB03 CB03 CB03

Claims (4)

[Claims] 1. A dielectric ceramic composition having a main component containing barium titanate, wherein the dielectric ceramic composition contains, when observed by a transmission electron microscope, crystal grains having interference fringes of 30% or more of an observation field. Composition. 2. A main component containing barium titanate; a first subcomponent containing an oxide of at least one first element (M1) selected from Mg, Ca, Ba and Si; and Er, Sc, A dielectric ceramic composition comprising at least a second subcomponent including an oxide of at least one type of second element (R1) selected from Tm, Yb, and Lu, wherein the second element of the second subcomponent is The ratio of the number of moles of the first element of the first subcomponent to the number of moles of (M1 / R1) is 0 <(M1
/ R1) dielectric ceramic composition satisfying ≦ 2. 3. An electronic component having a dielectric layer, wherein the dielectric layer is made of a dielectric porcelain composition having a main component containing barium titanate, wherein the dielectric porcelain composition comprises: An electronic component containing, when observed with a transmission electron microscope, crystal grains having interference fringes of 30% or more of the observation field. 4. An electronic component having a dielectric layer, wherein the dielectric layer is composed of a dielectric porcelain composition having a main component containing barium titanate, wherein the dielectric porcelain composition comprises: A main component containing barium titanate; a first subcomponent containing an oxide of at least one first element (M1) selected from Mg, Ca, Ba and Si; Er, Sc, Tm, Yb and Lu And at least one second subcomponent containing an oxide of a second element (R1) selected from the group consisting of: a first element of the first subcomponent with respect to a mole number of the second element of the second subcomponent. The ratio of the number of moles (M1 / R1) is 0 <(M1
/ R1) ≦ 2 electronic components.