JP2002029835A - Dielectric porcelain composition, laminated ceramic capacitor using the same and method for manufacturing that capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric porcelain composition, a laminated ceramic capacitor by using the composition and a method for manufacturing the capacitor such that even when the composition is calcined while using a base metal for inner electrodes 3, 4 and a base metal such as Cu is used to form external electrodes 8, 9 by baking, the dielectric layer 2 is not reduced but shows excellent insulation resistance characteristics. SOLUTION: The dielectric porcelain composition is prepared by adding a specified amount of Mg, Dy, Mn, V, Si and Al as sub components to barium titanate as the main component with the Ba/Ti molar ratio controlled to be 1.001 to 1.05. The laminated ceramic capacitor using the above composition and the method for manufacturing the capacitor are also provided.

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, a multilayer ceramic capacitor formed using the same, and a method of manufacturing the same.

[0002]

2. Description of the Related Art FIG. 2 is a cross-sectional view of a conventional multilayer ceramic capacitor formed using a dielectric ceramic composition. In FIG. 2, reference numeral 51 denotes a multilayer ceramic capacitor;
A plurality of internal electrodes 53 and 54 are alternately stacked on a dielectric layer 52 in which a dielectric ceramic composition is formed in a sheet shape to form a laminate 55, and the internal electrodes 53 and 54 are connected to the laminate 5.
5, external electrodes 58 formed on opposing surfaces 56, 57,
59, respectively.

The internal electrodes 53 and 54 and the external electrodes 58 and 59 have been replaced by expensive noble metals with inexpensive base metals such as Ni.

A method of manufacturing a conventional multilayer ceramic capacitor having the above-described structure will be described below.

[0005] First, a dielectric layer 52 and internal electrodes 53 and 54 made of a base metal material such as Ni are alternately stacked in a plurality of stages, and the inactive layers 60 and 61 are stacked on the uppermost stage and the lowermost stage and press-bonded to form a laminate block ( (Not shown). Then, the laminate block is cut into a chip having a predetermined size, and then fired at a predetermined temperature. At this time, firing is performed in a reducing atmosphere such as a nitrogen gas atmosphere in order to prevent the internal electrodes 53 and 54 from being oxidized and deteriorated.

Next, an external electrode paste made of a base metal material is applied to both surfaces 56 and 57 of the laminate 55 where the internal electrodes 53 and 54 are exposed, and the external electrodes 58 and 59 are reduced in a nitrogen gas atmosphere or the like so as not to be oxidized and deteriorated. Perform baking in a neutral atmosphere.

As a dielectric porcelain composition for suppressing the reduction deterioration of the dielectric layer 52, there is one disclosed in JP-A-61-155255.

[0008]

However, the multilayer ceramic capacitor using the dielectric ceramic composition disclosed in Japanese Patent Application Laid-Open No. 61-155255 has a large deterioration in insulation resistance characteristics (IR life characteristics), As the layer becomes thinner, it becomes more difficult to secure reliability, and the rate of change in capacitance is large. In addition, as the external electrode, Cu that easily forms a solid solution with Ni in the internal electrode is selected. When the laminated body is baked in a reducing atmosphere, the dielectric layer is reduced and the insulation resistance is reduced.

Therefore, according to the present invention, even if the internal electrode is baked using a base metal such as Ni and the external electrode is baked using a base metal such as Cu, the dielectric layer is not reduced and has excellent insulation resistance characteristics. An object of the present invention is to provide a dielectric ceramic composition, a multilayer ceramic capacitor using the same, and a method for manufacturing the same.

[0010]

In order to achieve the above object, the present invention has the following arrangement.

[0011] The invention described in claim 1 of the present invention is characterized in that:
For 100 moles of barium titanate, a small amount
At least 0.5 to 5.0 moles of Mg converted to MgO, D
y to Dy_TwoO_Three0.1 to 3.0 mol in terms of
nO_4/30.01 to 0.4 mol in terms of_TwoO_Five
0.01 to 0.26 mol of Si, converted to SiO _Two
The titanic acid was added in an amount of 0.01 to 3.5 mol in terms of
The Ba / Ti molar ratio of barium is 1.001 to 1.05.
Having the composition of a dielectric ceramic composition in the form of moles.
Excess BaO and MnO as basic components_4/3Is a dielectric composition
In particular, MnO_4/3Is in a neutral atmosphere
Or mass firing in a reducing atmosphere
Of the insulation resistance of the ceramic
Suppress variations in the capacitance of capacitors and produce a homogeneous sintered body.
It has the action and effect of forming, MgO, Dy_TwoO_ThreeThe addition of
Satisfactory electricity such as dielectric constant, capacitance temperature characteristic, dielectric tangent
It has the function and effect of obtaining the characteristics,_TwoIs relatively
It promotes sintering of the dielectric composition at low temperature firing,
Obtain a dense sintered body, stabilize insulation resistance and satisfy electrical performance.
Has the effect and effect of adding_TwoO_FiveIs TiO_Twoof
By suppressing the reduction and preventing the deterioration of the insulation resistance, a high insulation resistance
It has the effect of obtaining resistance, and therefore, Ni
Baking using a base metal such as
The dielectric layer is not reduced even when baked using
Thus, a dielectric ceramic composition having excellent insulation resistance characteristics can be obtained.

According to a second aspect of the present invention, there is provided a method according to the first aspect, wherein Al is converted into Al ₂ O ₃ and 0.01 to 3.0 mol is further added to 100 mol of barium titanate. It has the configuration of the described dielectric ceramic composition, whereby a secondary phase precipitated on the surface of the sintered body is suppressed to obtain a homogeneous sintered body.

According to a third aspect of the present invention, in the above composition, Dy and Ho are replaced by Dy / (D
(y + Ho) so that the molar ratio becomes 0.3 to 0.9, the total is 0.1 to ₃ in terms of Dy ₂ O ₃ and Ho ₂ O ₃ , respectively, based on 100 mol of the main component barium titanate. 2. The dielectric porcelain composition according to claim 1, wherein 0 mol is added, whereby the insulation resistance characteristics can be improved even when a laminate in which the dielectric layer is thinned (in particular, 5 μm or less) is mass-fired in a reducing atmosphere. A multilayer ceramic capacitor having a small capacitance temperature change rate can be obtained without loss.

According to a fourth aspect of the present invention, in place of Dy, the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.1.
9 and Dy ₂ Ho ₃ and Ho ₂ O ₃ , respectively.
In total, 0.1 to 3.0 mol is added to 100 mol of barium titanate as a main component, and Al is added to Al ₂ O _3.
The dielectric magnetic composition according to claim 1, further comprising 0.01 to 3.0 moles added to 100 moles of barium titanate, whereby the dielectric layer is thinned (particularly, Even if a large amount of the laminated body (5 μm or less) is fired in a reducing atmosphere, a uniform rate of change in capacitance with a small change in capacitance temperature without deteriorating the insulation resistance property and suppressing generation of a secondary phase deposited on the surface of the fired body is suppressed. A multilayer ceramic capacitor made of a fired body is obtained.

According to a fifth aspect of the present invention, there is provided a laminate in which dielectric layers and internal electrodes made of a base metal are alternately laminated, and a laminate provided on an exposed end face of the internal electrode of the laminate. An external electrode, wherein the dielectric layer is composed of at least 0.5 to 5.0 moles of Dy in terms of MgO as a subcomponent with respect to 100 moles of barium titanate as a main component.
Is converted to Dy ₂ O ₃ by 0.1 to 3.0 mol, and Mn is Mn.
0.01 to 0.4 mole in terms of O _4/3, in terms of V to V ₂ O _5, in terms 0.01 to 0.26 mol, of Si to SiO ₂ 0.01 to 3 The multilayer ceramic capacitor was formed by adding 0.5 mol, and the molar ratio of Ba / Ti was 1.001 to 1.05 mol.
A highly reliable multilayer ceramic capacitor having excellent insulation properties and a small temperature change rate of capacitance can be obtained.

The invention according to claim 6 of the present invention comprises a dielectric layer in which Al is added to barium titanate in an amount of 0.01 to 3.0 mol in terms of Al ₂ O _3. The multilayer ceramic capacitor according to claim 5, whereby the generation of a secondary phase on the surface of the sintered body is suppressed, and a multilayer ceramic capacitor excellent in mountability is obtained.

According to a seventh aspect of the present invention, Dy and Ho are replaced with Dy ₂ O such that the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.9. ₃ , H
converted to o ₂ O ₃ , the total of which is barium titanate 100
6. The multilayer ceramic capacitor according to claim 5, wherein 0.1 to 3.0 moles are added to the moles, whereby even a thin dielectric layer has excellent insulation resistance characteristics and a temperature change rate of capacitance. And a highly reliable multilayer ceramic capacitor having a small size.

According to the invention of claim 8 of the present invention, the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.1 instead of Dy.
9 and Dy ₂ Ho ₃ and Ho ₂ O ₃ , respectively.
In total, 0.1 to 3.0 mol is added to 100 mol of barium titanate as a main component, and Al is added to Al ₂ O _3.
6. The multilayer ceramic capacitor according to claim 5, wherein 0.01 to 3.0 moles are further added to 100 moles of barium titanate, so that the dielectric resistance is reduced even if the dielectric layer is thinned. It is possible to obtain a multilayer ceramic capacitor made of a homogeneous sintered body having excellent characteristics, excellent reliability with a small rate of temperature change of capacitance, and little generation of a secondary phase on the surface of the sintered body.

According to a ninth aspect of the present invention, there is provided a laminate comprising alternately laminated dielectric layers and internal electrodes formed by using a base metal, and a method of forming a laminate on the exposed end face of the internal electrode layer of the laminate. And an external electrode provided, wherein the dielectric layer is composed of at least 0.5 to 5.0 mol of Mg as MgO as a subcomponent with respect to 100 mol of barium titanate as a main component.
in terms of the y to Dy ₂ O ₃ 0.1~3.0 mole, a Mn M
0.01 to 0.4 mol in terms of nO _4/3 , V is V ₂ O ₅
Converted from 0.01 to 0.26 mol, Si was converted to SiO ₂
A ceramic sheet is formed using a dielectric material having a molar ratio of Ba / Ti of 1.001 to 1.05 mol, which is formed by adding 0.01 to 3.5 mol in terms of. A first step, a second step of forming a laminate in which the ceramic sheets and the internal electrode layers containing a base metal as a main component are alternately laminated, and a third step of firing the laminate, and thereafter, A method for manufacturing a multilayer ceramic capacitor, comprising a fourth step of forming an external electrode on an exposed end face of the internal electrode layer of a multilayer body, whereby the reliability is excellent with an excellent insulation resistance characteristic and a small temperature change rate of capacitance. A multilayer ceramic capacitor having excellent properties can be obtained.

According to a tenth aspect of the present invention, there is provided the method for manufacturing a multilayer ceramic capacitor according to the ninth aspect, wherein the external electrode is formed using a metal containing Cu as a main component. By using the alloy, even when Ni, which is a base metal, is used for the internal electrode, the bonding between the internal electrode and the external electrode becomes firm,
A specified capacitance can be easily obtained, a variation in capacitance value is small, and a multilayer ceramic capacitor excellent in durability against thermal shock and mechanical stress can be obtained.

According to an eleventh aspect of the present invention, there is provided the method for producing a multilayer ceramic capacitor according to the ninth aspect, wherein barium titanate having a specific surface area of ² to 5 m ² / g is used. A multilayer ceramic capacitor having excellent reliability and a small rate of change in capacitance with temperature can be obtained.

According to a twelfth aspect of the present invention, in the X-ray diffraction chart, (2
The peaks of the (00) plane diffraction line and the (002) plane diffraction line are 2
10. The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein barium titanate divided into two is used, whereby crystal grain growth in a firing process is suppressed, a uniform dielectric is obtained, and the dielectric layer is formed into a thin film. Thus, a multilayer ceramic capacitor having a small change rate of the temperature characteristic of the capacitance can be obtained.

According to a thirteenth aspect of the present invention, there is provided
0.5 to 5.0 as Mg (OH) ₂ instead of O
The method for producing a multilayer ceramic capacitor according to claim 9, wherein the dispersibility of MgO in the dielectric can be improved, and the dielectric layer is thinned (particularly, 5 μm or less). Even if a large amount is fired at once in a reducing atmosphere, a uniform composition can be maintained, so that a multilayer ceramic capacitor with good insulation resistance characteristics, small temperature characteristics of capacitance, and stable electric characteristics can be obtained. Can be

According to a fourteenth aspect of the present invention, the first aspect
The Al compound against 100 mol of barium titanate is converted to Al ₂ O ₃ in step a method of manufacturing a multilayer ceramic capacitor according to claim 9, further 0.1 to 3.0 moles additive, thereby In the firing process of the multi-component dielectric ceramic composition, Al ₂ O ₃ acts on sub-components other than the main component to form a uniform component phase, and has an effective action to stabilize sinterability and electrical characteristics. Thus, a multilayer ceramic capacitor having high mechanical strength can be obtained.

According to a fifteenth aspect of the present invention, there is provided
The compound is added after calcination of another dielectric material.
A method for manufacturing a multilayer ceramic capacitor according to
As a result, a multilayer ceramic capacitor having better temperature characteristics of capacitance can be obtained.

[0026] The invention according to claim 16 of the present invention provides a method according to Dy.
In place of Dy and Ho, the moles of Dy / (Dy + Ho)
Dy so that the ratio becomes 0.3 to 0.9, respectively._TwoO_Three,
Ho _TwoO_ThreeConverted to a total of 10 barium titanate
10. The method according to claim 9, wherein 0.1 to 3.0 mol is added to 0 mol.
It is a method for manufacturing the multilayer ceramic capacitor described in
Capacitance without reducing the life characteristics even when the conductor layer is thinned
Of multilayer ceramic capacitor with excellent temperature characteristics
It is.

According to a seventeenth aspect of the present invention, Dy
And the molar ratio of Dy / (Dy + Ho) is 0.3 to
0.9 and Dy ₂ Ho ₃ , respectively.
A total of 0.1 to 3.0 mol is added to 100 mol of barium titanate as a main component in terms of ₂ O ₃ , and Al is added to Al.
10. The method for producing a multilayer ceramic capacitor according to claim 9, wherein 0.01 to 3.0 mol is further added to 100 mol of barium titanate in terms of ₂ O ₃ , whereby the dielectric layer is formed into a thin film. Thus, a multilayer ceramic capacitor having excellent temperature characteristics of capacitance without deterioration of life characteristics and excellent strength with less generation of secondary phase on the surface of the sintered body can be obtained.

[0028] The invention according to claim 18 of the present invention provides a Dy
_{In place} of each single component of ₂ O ₃ , SiO ₂ and Al ₂ O ₃ , Dy _{2
O 3 · SiO 2, Dy 2} O 3 · Al 2 a O ₃ mixture was thereby been premixed form of a combined total 0.1 to 3.0 manufacturing method of a multilayer ceramic capacitor according to claim 9 moles added Thus, a multilayer ceramic capacitor having good capacitance temperature characteristics can be obtained without impairing the life characteristics even when the effective layer is made thin.

[0029] The invention described in claim 19 of the present invention provides a method for producing
_TwoO_Three, Ho_TwoO_Three, SiO_Two, Al_TwoO _ThreeFor each single component
And Dy each_TwoO_Three・ SiO_Two, Dy_TwoO_Three・ Al_TwoO
_Three, Ho_TwoO_Three・ SiO_Two, Ho_TwoO_Three・ Al_TwoO_ThreeIn the form of
Combine the pre-mixed mixture and Dy and Ho
When the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.9.
10. The method according to claim 9, wherein 0.1 to 3.0 moles are added so as to be added.
This is a method of manufacturing a multilayer ceramic capacitor.
Even if the dielectric layer is thinned, the life characteristics will not be impaired.
Layered ceramic with good temperature characteristics of capacitance.
A capacitor is obtained.

According to a twentieth aspect of the present invention, the third aspect
The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein a step of re-oxidizing the dielectric layer is provided between the third step and the fourth step, or a step of lowering the temperature of the step. Has high insulation resistance characteristics,
A highly reliable multilayer ceramic capacitor can be obtained.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1) Hereinafter, the first embodiment of the present invention will be described with reference to FIGS.
The invention described in Item 20 will be described.

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

In FIG. 1, reference numeral 1 denotes a multilayer ceramic capacitor, in which internal electrodes 3 and 4 made of a base metal mainly composed of Ni are alternately stacked on a dielectric layer 2 formed of a dielectric ceramic composition in a sheet shape. Together, a laminated body 5 is formed, and external electrodes 8 and 9 made of a base metal containing Cu as a main component are formed on opposing surfaces 6 and 7 of the laminated body 5 and connected to the internal electrodes 3 and 4, respectively. A nickel plating layer 10 is formed on the surfaces of the external electrodes 8 and 9, and a solder plating layer 11 is formed on the surface of the nickel plating layer 10.

The manufacturing method of the multilayer ceramic capacitor 1 configured as described above will be described below.

As a first step, a method for producing a ceramic sheet from starting materials will be described.

First, each starting material was made of BaTiO ₃ 100
With respect to the mole, BaC is selected so that the composition shown in (Table 1) is obtained.
O ₃ , Dy ₂ O ₃ , MgO, MnO _4/3 , BaO · SiO ₂
V ₂ O ₅ is weighed, and wet mixed and pulverized for 17 hours with a ball mill using yttria partially stabilized zirconia balls as a medium, and then dried.

[0037]

[Table 1]

Next, the dehydrated and dried mixed material was crushed, passed through a 32-mesh sieve, put into an alumina crucible, and kept at a temperature of 1100 ° C. for 2 hours and calcined. This calcination is performed at a temperature at which the carbonate is decomposed and the main component barium titanate and the subcomponents are in a state of being appropriately reacted. At this time, if the calcination temperature is too high, the obtained multilayer ceramic capacitor is obtained. Care must be taken because the temperature change rate of the capacitance may become too large.

Next, as in the case of mixing the calcined raw materials, the mixture is wet-pulverized by a ball mill so that the average particle size becomes 1.0 μm or less, then dehydrated and dried, and passed through a 32 mesh sieve to produce a dielectric material. did.

A polyvinyl butyral resin as a binder, n-butyl acetate as a solvent, and dibutyl phthalate as a plasticizer were added to the prepared dielectric material, and mixed with a yttria partially stabilized zirconia ball in a ball mill for 72 hours to prepare a slurry.

Using the obtained slurry, a ceramic green sheet (hereinafter, referred to as a green sheet) to be the dielectric layer 2 shown in FIG. 1 was formed on a polyester film using a doctor blade. This green sheet was produced by setting the thickness to be 14 μm after firing.

Next, as a second step, an internal electrode paste containing Ni as a main component is printed on the surface of the green sheet by a screen, and after drying, the green sheet on which the Ni internal electrode paste is printed is removed. After stacking 10 sheets and thermocompression bonding to form a green laminate, 3.3 mm
It was cut into a laminated green chip (hereinafter referred to as a green chip) shape of × 1.7 mm.

Next, as a third step, the green chips are mixed with zirconia bedding powder and placed in an alumina sheath to remove organic substances in an atmosphere in which nickel is not excessively oxidized. Next, in a reducing atmosphere in which nickel formed by mixing carbon dioxide or water vapor with nitrogen and hydrogen is not excessively oxidized and the dielectric layer 2 can be sintered, the maximum temperature 122
The laminate 5 is held at 0 to 1340 ° C. for 2 hours to perform sintering.
Then, at a temperature of 800 to 1200 ° C. for 1 hour, nitrogen,
After reconstituting the dielectric layer 2 reduced in the firing step in a reducing atmosphere in an atmosphere in which nickel is not excessively oxidized, the structure is formed by using carbon dioxide gas or steam for hydrogen, and then cooled to room temperature and sintered. The body was made.

As the optimum firing temperature for each composition, the temperature at which the density of the sintered body of each dielectric layer 2 was maximized was used.

Next, as a fourth step, after the surface and the end face of the sintered body are polished by a barrel polishing machine, the sintered body is sintered so as to be electrically connected to the internal electrodes 3 and 4 exposed on the end face of the sintered body. An external electrode paste containing Cu (copper) as a main component is applied to the facing end surfaces 6 and 7 of the body, and nitrogen and oxygen are mixed to form an atmosphere in which Cu (copper) is not excessively oxidized.
In this atmosphere, baking was performed at 850 ° C. for 15 minutes to form external electrodes 8 and 9.

Next, a nickel plating layer 10 was formed on the surfaces of the external electrodes 8 and 9 by electrolytic plating, and a solder plating layer 11 was further formed on the surface of the nickel plating layer 10 as shown in FIG.
Has been completed.

The obtained multilayer ceramic capacitor 1 is
20 ° C. (room temperature), dielectric constant at a frequency of 1 KHz, variation in dielectric loss tangent (tan δ), and −55 to + 125 ° C.
The rate of change with respect to the capacitance at 20 ° C. during the measurement was measured, and the results are shown in (Table 2). The insulation resistance (IR) when a DC voltage of 25 V was applied at room temperature, and the 125 ° C. At a temperature, the insulation resistance after continuously applying a voltage of 200 V DC for 250 hours was measured.
Those degraded to ⁷ Ω or less were counted as defective, and the results are shown in (Table 2). As is clear from (Table 2),
The dielectric composition according to the present invention has good initial dielectric constant and dielectric tangent (tan δ) variations, insulation resistance, capacitance temperature change rate, and insulation resistance after an accelerated life test.

[0048]

[Table 2]

Here, if the addition of MgO is less than 0.5 mol, the sintering becomes insufficient, and if it exceeds 5 mol, the capacitance temperature change rate of the multilayer ceramic capacitor becomes large, and the capacitance changes with time. Becomes larger. If Dy ₂ O ₃ is less than 0.1 mol, the rate of change in capacitance with temperature increases, and the rate of change in capacitance with time and tan δ increase. If it exceeds 3 mol, the dielectric constant drops to 2000 or less, which is practical. No longer. Therefore, it is preferable that Dy is added in an amount of 0.1 to 3.0 mol in terms of Dy ₂ O _{3 based} on 100 mol of barium titanate. In addition, by using Dy ₂ O ₃ having a specific surface area of 7 to 15 m ² / g, the dispersibility is improved, and the effect is more remarkable.

Further, the addition of MnO _4/3 can prevent the reduction of TiO _{2. Even if} the laminate is fired in a large amount in a neutral atmosphere or a reducing atmosphere, the insulation resistance can be prevented from deteriorating and the static electricity can be prevented. There is an effect that variation in capacity can be suppressed and a homogeneous sintered body can be obtained.

However, if the addition amount is less than 0.01 mol, the sintered body is partially converted into a semiconductor, and the variation in capacitance is large, and the insulation resistance value is reduced. As a result, the insulation resistance value in the accelerated life test is reduced. Degrades significantly. On the other hand, if it exceeds 0.4 mol, the rate of change in capacitance with temperature and the rate of change with time will be large, and the deterioration of insulation resistance will also be large. Therefore, it is effective to add 0.01 to 0.4 mol of Mn in terms of MnO _4/3 with _respect to 100 mol of barium titanate.

The addition of V ₂ O ₅ has the effect of suppressing the reduction of TiO ₂ , increasing the insulation resistance and preventing the insulation resistance from deteriorating. However, when the added amount of V ₂ O ₅ is 0.
If it exceeds 26 moles, the rate of change in capacitance with temperature increases, and the insulation resistance deteriorates. Also, 0.01
If the amount is less than the mole, the insulation resistance is low, and the composition deteriorates in an accelerated test. Therefore, the addition amount of V ₂ O ₅ is from 0.01 to 0.26 mol is valid for 100 moles of barium titanate.

Further, the addition of SiO ₂ promotes sintering of the dielectric layer 2 in firing at a relatively low temperature, and increases the capacitance,
This has the effect of reducing the variation in insulation resistance.

However, if the addition amount is less than 0.01 mol, a sufficient sintered body cannot be obtained, and the capacitance and insulation resistance vary, which is not practical. In addition, 3.5
If the molar ratio is exceeded, the sinterability is improved, but the dielectric constant is reduced, and the temperature change rate of the capacitance is increased, which is not practical. Therefore, SiO ₂ is added in an amount of 0.0 with respect to 100 mol of barium titanate.
1-3.5 moles are effective.

In the first embodiment, SiO ₂ is
The amount of barium carbonate, which is added in the form of BaO.SiO ₂ .Al ₂ O ₃ glass, and the amount of excess BaO contained in barium titanate (0 in the first embodiment) is added separately from the glass. Together, the molar ratio of Ba / Ti is 1.001.
１．０1.05.

In the first embodiment, the metal is added in the form of glass. However, it may be added in the form of a calcined compound, a Si compound, or an Al compound.

(Embodiment 2) Hereinafter, a second embodiment of the present invention will be described with reference to FIGS.

The manufacturing method of the multilayer ceramic capacitor according to the second embodiment is basically the same as that of the first embodiment, and therefore, detailed description is omitted, and the characteristic portions will be described here.

First, BaTiO ₃ shown in (Table 3) was prepared, and then BaC was added to 100 moles of BaTiO _3.
O ₃ 0.2 mol, MgO 2.5 mol, 1.0 mol Dy ₂ O _3, the MnO _4/3 0.2 mole, V ₂ O ₅ 0.1
5 mol and 2.1 mol of a BaO.SiO ₂ compound are weighed, pure water is added to these starting materials, and the mixture is wet-mixed and pulverized for 17 hours by a ball mill using partially stabilized zirconia balls as a medium, and then dried. At this time, the same additives as in Embodiment 1 were used.

[0060]

[Table 3]

Next, Embodiment 1 is performed using this mixed material.
The multilayer ceramic capacitor shown in FIG.

Next, the dielectric constant, dielectric loss tangent (tan δ), and −55 calculated from the capacitance of this multilayer ceramic capacitor at 20 ° C. (room temperature) and a frequency of 1 KHz.
The rate of change of the capacitance between 20 ° C. and + 125 ° C. was measured, and the results are shown in (Table 4). The initial insulation resistance (IR) and the insulation resistance after continuous application of a voltage of 200 V DC for 250 hours at 125 ° C. as an accelerated life test were measured, and the insulation resistance IR was 1 × 10 ⁷ Ω. In the following, those that deteriorated were counted as defectives and are shown in Table 4.

[0063]

[Table 4]

As can be seen from Table 4, the dielectric composition according to the present invention has a high initial dielectric constant of 2000 or more, a small variation in capacitance of ± 5% or less, and a change in capacitance. The rate is as small as ± 15% or less, the insulation resistance is as high as 1 × 10 ¹² Ω, and no deterioration is observed. In contrast, the molar ratio of BaO / TiO _{2 in} BaTiO ₃ is 1.0
If it is smaller than 00, sufficient insulation resistance cannot be obtained, and the rate of change in capacitance is large, which is not preferable.

Further, if the specific surface area is smaller than 2 m ² / g, a sufficient sintered body cannot be obtained, and if it exceeds 5 m ² / g, the dielectric constant decreases and the temperature change rate increases. Therefore, the specific surface area of barium titanate is effectively in the range of ² to 5 m ² / g.

When the peak of the (002) plane and the peak of the (200) plane at an X-ray diffraction angle 2θ of 40 to 50 ° are not separated, the rate of change in capacitance with temperature is large, which is not practical. Therefore, when the X-ray diffraction angle 2θ is 40 to 50 °, (0
Barium titanate in which the peaks of the (02) plane and the (200) plane are separated is effective.

Third Embodiment The third embodiment of the present invention will be described below with reference to the third embodiment.

Since the multilayer ceramic capacitor of the third embodiment and the method of manufacturing the same are basically the same as those of the first embodiment, a detailed description thereof will be omitted, and only the characteristic portions will be described. .

First, the dielectric composition of the present invention is made of BaTiO.
₃ 100 mol 0.2 mol of BaCO ₃ to, MgO 2.5 mol, and the MnO ₂ was added 0.2 mole, BaO · SiO ₂ type compound 2.1 mol. Further, the amounts of Dy ₂ O ₃ and Ho ₂ O ₃ shown in (Table 5) are weighed respectively. At this time, BaTiO ₃ adjusted in the same manner as in Embodiment 1 was used.

[0070]

[Table 5]

Next, after preparing the material powder under the same conditions as in the first embodiment, the thickness of the dielectric layer 2 was set to 3 μm after firing.

Thereafter, the electrical characteristics of the obtained multilayer ceramic capacitor were evaluated in the same manner as in the first embodiment. However,
The voltage applied in the accelerated life test was 64V. The results are shown in (Table 6).

[0073]

[Table 6]

As shown in Table 6, Dy / (Dy + H
o) Dy ₂ O ₃ and H so that the molar ratio is 0.3 to 0.9.
By adding 0.1 to 3.0 mol of o ₂ O ₃ in total,
Even when the thickness of the dielectric is reduced to 5 μm or less, a multilayer ceramic capacitor having high insulation resistance without deterioration of insulation resistance and a small rate of temperature change of capacitance can be obtained.

That is, although Dy has the effect of preventing the insulation resistance from deteriorating, when the dielectric layer 2 is made thinner, the temperature characteristic of the capacitance tends to deteriorate. However, by adding Ho to the dielectric porcelain composition, it has the effect of improving the temperature characteristics, and by adding both Dy and Ho,
Even if the dielectric layer 2 is made thin, a multilayer ceramic capacitor having good temperature characteristics of capacitance and high insulation resistance can be obtained.

At this time, if the Dy / (Dy + Ho) molar ratio is less than 0.3, the deterioration of the life characteristics is accelerated, and
If it exceeds, the temperature change rate of the capacitance increases, which is not practically preferable.

If the total amount of Dy ₂ O ₃ and Ho ₂ O ₃ is less than 0.1 mol, the rate of change of capacitance with temperature increases, and the rate of change of capacitance with time and tan δ also increase. If it exceeds 3 moles, the dielectric constant drops to 2000 or less,
Not practically preferable.

Therefore, the total added amount of Dy ₂ O ₃ and Ho ₂ O ₃ is 0.1 to 3.0 with respect to 100 mol of barium titanate.
It is effective to add it in molar.

The specific surface area of each of Dy ₂ O ₃ and Ho ₂ O ₃ is 7 to 15 m ² / g, and the use of spherical and few agglomerated particles improves dispersibility. Become noticeable.

(Embodiment 4) Hereinafter, a fourth embodiment of the present invention will be described with reference to FIGS.

The manufacturing method of the monolithic ceramic capacitor according to the fourth embodiment is basically the same as that of the first embodiment. Therefore, detailed description is omitted, and the characteristic portions will be described here.

First, the dielectric composition of the present invention is made of BaTiO.
_Three MnO per 100 moles_Two0.2 mol, MgO
Add 2.5 mol, Dy_TwoO_Three・ Al_TwoO_Three, Dy_TwoO_Three・ S
iO _TwoMixture, and Ho_TwoO_Three・ Al_TwoO_Three, Ho_TwoO_Three・
SiO_TwoWas added in the amounts shown in (Table 7) and (Table 8).
Further, the Ba / Ti molar ratio is set to be 1.03.
To BaCO_ThreeAnd the total amount of Si is 2.1 mol.
Dy_TwoO _Three・ SiO_TwoOr Dy_Two
O_Three・ SiO_TwoAnd Ho_TwoO_Three・ SiO_TwoTogether,
Less than 2.1 moles of SiO_TwoAs correction added
Was. Similarly, Al is also 2.1 mol in total.
If less than 2.1 mol, Al_TwoO_ThreeAs supplement
Positive addition.

[0083]

[Table 7]

[0084]

[Table 8]

Next, after a material powder was produced under the same conditions as in the first embodiment, the laminated ceramic capacitor was manufactured in the same manner as in the first embodiment except that the thickness of the dielectric layer 2 was 3 μm after firing. Produced.

Thereafter, the multilayer ceramic capacitor obtained in the same manner as in the first embodiment was evaluated. However, the voltage applied in the accelerated life test was 64V. The results at that time are shown in (Table 9) and (Table 10).

[0087]

[Table 9]

[0088]

[Table 10]

As shown in (Table 9) and (Table 10), Dy
_TwoO_Three・ Al_TwoO_Three, Dy_TwoO_Three・ SiO _TwoCombine the mixture
The thickness of the dielectric by adding 0.1 to 3.0 moles.
High insulation resistance and insulation resistance even when the thickness is reduced to 5 μm or less.
Multilayer ceramic with low temperature change rate of capacitance without deterioration
A mic capacitor is obtained.

Further, the molar ratio of Dy / (Dy + Ho) is 0.1.
Dy to be 3 to 0.9_TwoO_Three・ SiO_Two, Dy_TwoO_Three
・ Al_TwoO_Three, Ho_TwoO_Three・ SiO_Two, Ho_TwoO_Three・ Al
_TwoO_Three, Ho _TwoO_Three0.1 to 3.0 moles in total
By doing so, even if the thickness of the dielectric is reduced to 5 μm or less,
Compared to the case of adding each alone, the capacity-temperature characteristics
Improve and maintain high insulation resistance, reliable multilayer ceramic
A mic capacitor is obtained.

The reason is that Dy ₂ O ₃ .SiO ₂ , Dy ₂ O
₃ · Al ₂ O ₃ , Ho ₂ O ₃ · SiO ₂ , Ho ₂ O ₃ · Al ₂ O ₃
The reason for this is that the particle shape can be made very small, the dispersibility in the dielectric material is improved, and the sintered state becomes more uniform.

However, Dy ₂ O ₃ .SiO ₂ , Dy ₂
O ₃ · Al ₂ O ₃ , Ho ₂ O ₃ · SiO ₂ , Ho ₂ O ₃ · Al ₂
O ₃ was added to (Dy ₂ O ₃ .Si
O ₂ , Dy ₂ O ₃ .Al ₂ O ₃ ) or (Dy ₂ O ₃ .Si
O ₂ , Dy ₂ O ₃ .Al ₂ O ₃ ) and (Ho ₂ O ₃ .SiO ₂ , H
o ₂ O ₃ .Al ₂ O ₃ ) When the total amount is less than 0.1 mol, the temperature change rate of the capacitance increases, and the temporal change rate and tan δ of the capacitance increase. It is lowered to 2000 or less and is not practical.

Therefore, (Dy ₂ O ₃ .SiO ₂ , Dy ₂ O ₃
・ Al ₂ O ₃ ) or (Dy ₂ O ₃ .SiO ₂ , Dy ₂ O ₃
· Al ₂ O ₃ ) and (Ho ₂ O ₃ · SiO ₂ , Ho ₂ O ₃ · Al ₂
O ₃ ) It is effective to add 0.1 to 3.0 mol of the combined amount to 100 mol of barium titanate.
Furthermore, when these Dy mixture and Ho mixture are added together, if the addition ratio is Dy / (Dy + Ho) molar ratio less than 0.3, the deterioration of the life characteristics is accelerated,
If it exceeds 0.9, the temperature change rate of the capacitance becomes large, which is not practical.

Therefore, (Dy ₂ O ₃ .SiO ₂ , Dy ₂ O ₃
· Al ₂ O ₃ ) and (Ho ₂ O ₃ · SiO ₂ , Ho ₂ O ₃ · Al ₂
When O ₃ ) is added, the addition ratio is Dy / (D
(y + Ho) It is effective to add such that the molar ratio is in the range of 0.3 to 0.9. Note that Dy ₂ O ₃ .Si
O ₂ , Dy ₂ O ₃ .Al ₂ O ₃ , Ho ₂ O ₃ .SiO ₂ , Ho ₂
Both O ₃ and Al ₂ O ₃ have a specific surface area of 10 to 40 m ² / g, and the effect becomes more remarkable by using fine particles having good dispersibility.

(Embodiment 5) Hereinafter, a fifth embodiment of the present invention will be described with reference to Embodiment 5.

The manufacturing method of the multilayer ceramic capacitor according to the fifth embodiment has basically the same configuration as that of the first embodiment, and therefore detailed description is omitted, and the characteristic portions will be described here.

[0097] First, with respect to 100 mol of barium titanate, BaCO ₃ 0.2 mol of MnO _4/3 0.2 mol,
2.1 mol of BaO · SiO ₂ type glass, Dy ₂ O _3, H
1 mol of Dy ₂ O ₃ and Ho ₂ O ₃ was added to o ₂ O _{3 so} that the molar ratio of Dy / (Dy + Ho) became 0.75, and Mg (OH) synthesized by a gas phase method was further added. ₂ ) was added in the amounts shown in (Table 11).

[0098]

[Table 11]

Next, a multilayer ceramic capacitor 1 was manufactured under the same conditions as in Embodiment 1 except that the thickness of the dielectric layer 2 was 3 μm.

Thereafter, the multilayer ceramic capacitor obtained in the same manner as in the first embodiment was evaluated. However, the voltage applied in the accelerated life test was 64V. The results at that time are shown in (Table 12).

[0101]

[Table 12]

As shown in Table 12, by using Mg (OH) ₂ as the Mg compound, the capacitance-temperature characteristics are further improved as compared with the case using MgO, and the effect of preventing the deterioration of the insulation resistance is also obtained. There is. The reason is that Mg (OH) ₂ synthesized by a gas phase method has a spherical particle shape and is hard to form an aggregate, so that the dispersibility in the dielectric is improved.

Therefore, even when the thickness of the dielectric layer 2 is reduced to 5 μm or less, a multilayer ceramic capacitor having a high insulation resistance without deterioration of the insulation resistance and a small temperature change rate of the capacitance can be obtained.

However, like MgO, Mg (O
H) If the amount of ₂ added is less than 0.5 mol per 100 mol of barium titanate, sintering will not be performed. If it exceeds 5.0 mol, the rate of change in capacitance with temperature increases.
Therefore, the range of 0.5 to 5.0 mol is effective.

(Embodiment 6) Hereinafter, the present invention will be described with reference to Embodiments 6, 4, 6, 8, 14, and 1.
The inventions described in 5, 17 will be described.

The dielectric ceramic composition of the sixth embodiment and a method for manufacturing a multilayer ceramic capacitor using the same are as follows.
Since the configuration is basically the same as that of the second embodiment, a detailed description will be omitted, and a characteristic portion will be described here.

First, the flash of titanate used in the second embodiment was used.
Per 100 moles of BaCO _Three0.2 mol, M
2.5 mol of gO, Dy_TwoO_Three1.0 mol, MnO_TwoTo
0.2 mol, BaO.SiO_Two2.1 mol of compound
And the same BaTiO_ThreeAgainst BaCO_ThreeTo
0.2 mol, 2.5 mol of MgO, MnO_Two0.2 m
, BaO ・ SiO_Two2.1 mol of a compound based on Dy_TwoO_Three
And Ho_TwoO_ThreeIs expressed as Dy / (Dy + Ho).
Dy so that it becomes 0.45_TwoO_ThreeAnd Ho_TwoO_ThreeTogether
1.5 mol in total, and further pulverized after calcination (Table
13) The amount of Al shown in 13) _TwoO_ThreeIs added to each composition
Was.

[0108]

[Table 13]

Next, a multilayer ceramic capacitor was manufactured in the same manner as in the first embodiment. Then, the first embodiment
Evaluate the obtained multilayer ceramic capacitor in the same way as
The results are shown in (Table 14).

[0110]

[Table 14]

The dielectric porcelain composition of the present invention is liable to generate a secondary phase. When the secondary phase is formed, the mechanical strength of the multilayer ceramic capacitor may be deteriorated. However, as shown in (Table 14), Al ₂ O ₃
Is added, the formation of the secondary phase can be suppressed, and the mechanical strength can be improved without deteriorating the characteristics.

When the addition amount of Al ₂ O ₃ exceeds 3.0 mol, the temperature change rate of the capacitance and the dielectric loss increase,
If the amount is less than 0.1 mol, the effect of addition is not remarkably exhibited.

Note that this Al ₂ O ₃ was added after calcining other starting materials. Like other starting materials, they may be added first, but if added after calcination, the temperature characteristics of capacitance can be further improved.

From the above results, the BaTiO of the present invention was_ThreeTo
The main component, which contains BaO, MgO, Dy_TwoO_Three, MnO
_Two, SiO_Two, V_TwoO_Five, Reducing atmosphere by adding
In mass firing with air, prevent dielectric reduction and prevent insulation
Improves anti-performance and also improves Al _TwoO_ThreeBy adding
Multi-layer ceramic with suppressed generation of sub-components on the surface of sintered body
Capacitors are obtained, and Dy_TwoO_ThreePart of Ho
_TwoO_ThreeOr Dy _TwoO_Three・ SiO_Two, Dy_TwoO_Three・ Al_Two
O_Three, Ho_TwoO_Three・ SiO_Two, Ho_TwoO_Three・ Al_TwoO_ThreeReplace with
Or MgO to Mg (OH)_TwoBy replacing
In addition, multilayer ceramics with excellent capacitance temperature characteristics and insulation resistance
A capacitor is obtained.

[0115]

As described above, according to the present invention, even when the internal electrode is baked using a base metal such as Ni and the external electrode is baked using a base metal such as Cu, the dielectric layer is not reduced, and the excellent performance is obtained. A dielectric ceramic composition having insulation resistance characteristics, a multilayer ceramic capacitor using the same, and a method of manufacturing the same are obtained.

Even when a dielectric layer having a thickness of 5 μm or less is formed, the insulation resistance is high, the variation in capacitance is small, and the temperature characteristics are good and the reliability with a small rate of change over time is excellent. A multilayer ceramic capacitor is obtained.

It should be noted that the present invention also has excellent electrical characteristics when the external electrodes of the multilayer ceramic capacitor are formed using a noble metal such as silver.

[Brief description of 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 cross-sectional view of a conventional multilayer ceramic capacitor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multilayer ceramic capacitor 2 Dielectric layer 3,4 Internal electrode 5 Laminated body 6,7 Opposite both sides 8,9 External electrode 10 Nickel plating layer 11 Solder plating layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01G 4/12 364 H01G 4/30 301C 5G303 4/30 301 301E H05K 3/46 T H05K 3/46 H B28B 11/00 Z (72) Inventor Keiji Kobayashi 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Kurumitsu 1006 Okadoma Kazuma Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. 4G031 AA03 AA06 AA07 AA11 AA13 AA19 AA29 AA30 BA09 GA02 4G055 AA08 AC09 BA22 BA29 5E001 AB03 AC09 AE02 AE03 AE04 AJ01 AJ02 AJ03 5E082 AA01 AB03 BC35 EE04 EE11 GG23 GG01 GG23 5E346 AA12 AA13 AA15 AA33 AA36 CC17 CC21 CC32 CC37 DD13 DD24 EE24 EE27 EE29 GG04 GG08 GG14 GG2 4 GG26 GG28 HH08 5G303 AA01 AB01 AB06 AB11 BA12 CA01 CB01 CB03 CB17 CB18 CB30 CB35 CB36 CB41 CB43

Claims (20)

[Claims] At least 0.5 to 5.0 mol of Mg as a sub-component and 0.1 to 0.1 mol of Dy as Dy ₂ O ₃ as subcomponents relative to 100 mol of barium titanate as a main component.
~ 3.0 mol, Mn converted to MnO _4/3 , 0.01 ~
0.4 mol, V is converted to V ₂ O ₅ and 0.01 to 0.26
A dielectric porcelain composition wherein 0.01 to 3.5 moles of Si, in terms of SiO _2, are added, and the Ba / Ti mole ratio of the barium titanate is 1.001 to 1.05 mole. 2. The dielectric ceramic composition according to claim 1, wherein Al is converted to Al ₂ O ₃ and 0.01 to 3.0 mol is further added to 100 mol of barium titanate. 3. A total of Dy and Ho in which the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.9 instead of Dy, converted into Dy ₂ O ₃ and Ho ₂ O ₃ , respectively. The dielectric porcelain composition according to claim 1, wherein 0.1 to 3.0 mol is added to 100 mol of barium titanate as a main component. 4. A method in which Dy and Ho having a molar ratio of Dy / (Dy + Ho) of 0.3 to 0.9 are converted to Dy ₂ O ₃ and Ho ₂ O ₃ , respectively, in place of Dy. The component is added in an amount of 0.1 to 3.0 mol based on 100 mol of barium titanate, and Al is converted to Al ₂ O _{3. Further} , 0.01 to 3.0 mol is added to 100 mol of barium titanate. The dielectric magnetic composition according to claim 1, which is added. 5. A laminate comprising: a laminate in which dielectric layers and internal electrodes made of a base metal are alternately laminated; and an external electrode provided on an exposed end face of the internal electrode of the laminate. The layer is composed of at least 0.5 to 5.0 mol of Mg as MgO and 0.1 mol of Dy as Dy ₂ O ₃ as sub-components with respect to 100 mol of barium titanate as a main component.
~ 3.0 mol, Mn converted to MnO _4/3 , 0.01 ~
0.4 mol, V is converted to V ₂ O ₅ and 0.01 to 0.2
It is formed by adding 6 mol and 0.01 to 3.5 mol of Si in terms of SiO ₂ , and the molar ratio of Ba / Ti of the main component barium titanate is 1.001 to 1.05 mol. And multilayer ceramic capacitors. 6. The barium titanate further comprises A
in terms of l to Al ₂ O _3, the laminated ceramic capacitor according to claim 5 consisting of 0.01 to 3.0 mol per mol of the dielectric layer. 7. Dy and Ho are replaced by Dy / Ho instead of Dy.
Dy ₂ O ₃ and Ho ₂ O ₃ , respectively, so that the molar ratio of (Dy + Ho) is 0.3 to 0.9, and the total is 0.1 to 3 based on 100 mol of the main component barium titanate. .0
The multilayer ceramic capacitor according to claim 5, which is added in a molar amount. 8. The total of Dy and Ho in which the molar ratio of Dy / (Dy + Ho) is 0.3 to 0.9 instead of Dy, converted to Dy ₂ O ₃ and Ho ₂ O ₃ , respectively. The component is added in an amount of 0.1 to 3.0 mol based on 100 mol of barium titanate, and Al is converted to Al ₂ O _{3. Further} , 0.01 to 3.0 mol is added to 100 mol of barium titanate. The multilayer ceramic capacitor according to claim 5, wherein the capacitor is added. 9. A method for manufacturing a capacitor in which an external electrode is provided on an exposed end face of an internal electrode of a laminate obtained by alternately laminating dielectric layers and internal electrodes manufactured using a base metal, wherein a ceramic sheet is manufactured. A first step, a second step of forming a laminate in which the ceramic sheets and the internal electrodes containing a base metal as a main component are alternately laminated, and a third step of firing the laminate, and then the lamination A fourth step of forming an external electrode on an exposed end face of the internal electrode of the body, wherein the dielectric layer comprises barium titanate 1 as a main component.
At least Mg is added as MgO
0.01 to 0.4 mole of 0.5 to 5.0 mol in terms, from 0.1 to 3.0 mol in terms of Dy to Dy ₂ O _3, and Mn in terms of MnO _4/3 to , V converted to V ₂ O ₅ ,
1 to 0.26 mol, 0.01 of Si converted to SiO ₂
To 3.5 mol, and the main component barium titanate has a Ba / Ti molar ratio of 1.001 to
A method for manufacturing a multilayer ceramic capacitor using 1.05 mol of a dielectric material. 10. The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein the external electrodes are formed using a metal containing Cu as a main component. 11. The method for producing a multilayer ceramic capacitor according to claim 9, wherein barium titanate having a specific surface area of ² to 5 m ² / g is used. 12. In the X-ray diffraction chart, a diffraction angle of 2
Diffraction line of (200) plane at θ 45 ° and (002)
The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein barium titanate having a surface diffraction line peak divided into two is used. 13. The method for producing a multilayer ceramic capacitor according to claim 9, wherein 0.5 to 5.0 mol of Mg (OH) ₂ is added instead of MgO. 14. The multilayer ceramic capacitor according to claim 9, wherein the Al compound is converted to Al ₂ O ₃ in the first step, and 0.1 to 3.0 mol is further added to 100 mol of barium titanate. Production method. 15. The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein the Al compound is added after calcining another dielectric material. 16. Dy and Ho are replaced by Dy / Ho instead of Dy.
Dy ₂ O ₃ and Ho ₂ O ₃ , respectively, so that the molar ratio of (Dy + Ho) is 0.3 to 0.9, and the total is 0.1 to 3 based on 100 mol of the main component barium titanate. .0
The method for producing a multilayer ceramic capacitor according to claim 9, wherein a molar amount is added. 17. Dy / (Dy + Ho) instead of Dy
Are converted into Dy ₂ O ₃ and Ho ₂ O ₃ , respectively, in a total of 0.1 to 3.0 mol per 100 mol of barium titanate. 0 mole added, and in terms of Al to Al ₂ O _3, the method of production of a multilayer ceramic capacitor according to claim 9, with respect to 100 moles of barium titanate, and further 0.01 to 3.0 mol per mol. 18. Dy ₂ O _3, instead of the single components of _{SiO 2, Al 2 O 3,} Dy 2 O 3 · SiO 2, Dy 2 O 3 · Al 2
The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein a total of 0.1 to 3.0 mol of a mixture previously mixed in the form of O ₃ is added. 19. Dy ₂ O ₃ , Ho ₂ O ₃ , SiO ₂ , Al ₂
Instead of the single components of _{O 3, Dy 2 O 3 ·} SiO 2, Dy 2
O ₃ · Al ₂ O ₃ , Ho ₂ O ₃ · SiO ₂ , Ho ₂ O ₃ · Al ₂
In the form of O ₃ combined premixed mixture, and Dy and Ho molar ratio of Dy / (Dy + Ho) is 0.1 to 3.0 mol added to a 0.3 to 0.9 A method for manufacturing the multilayer ceramic capacitor according to claim 9. 20. The method for manufacturing a multilayer ceramic capacitor according to claim 9, wherein a step of reoxidizing the dielectric layer is provided between the third step and the temperature decreasing step of the third step or between the third step and the fourth step.