JP2002201064A - Dielectric ceramic composition, multilayer ceramic capacitor and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition suitable for a multilayer ceramic capacitor using Ni as an internal electrode, which shows excellent electric properties, and which can be good sintered and is hard to produce cracks even when a lead free solder is used. SOLUTION: The dielectric ceramic composition consists of containing an additive of 2.0-6.0 wt. composed of BaO-Ln2O3-MgO-BaSiO3-MnO-RO3 to a main composition whose formula is BaTiO3 (wherein, Ln is one sort or two sorts of elements chosen from Sc, Y, Nd, Pr or Sm. R is one sort or two sorts of elements chosen from W or Mo.) and the each component which composes the additive is BaO=0-25 mol%, Ln2O3=2-25 mol%, MgO=5-35 mol%, BaSiO3=5-45 mol%, MnO=1-10 mol% and RO3=2-10 mol%, respectively, its average particle size is prepared below 0.3 μm.

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

[0002]

2. Description of the Related Art In response to demands for miniaturization and high performance, multilayer ceramic capacitors (MLCs) have been increasingly miniaturized and multilayered in recent years. Have been made. First, a slurry is prepared by mixing an organic binder, a plasticizer, and an organic solvent with dielectric powder, and a ceramic green sheet is prepared by a doctor blade method or the like. An electrode material to be an internal electrode is applied on the obtained green sheet, a plurality of layers are laminated, thermocompression-bonded, and integrated, and fired at about 1300 ° C. in the air to produce a fired body. It is manufactured by baking an external electrode electrically connected to the internal electrode on the end face of the obtained fired body.

Hitherto, platinum, palladium, and silver have been used as internal electrodes of this multilayer ceramic capacitor because they do not react with a dielectric material even when fired in the air and do not cause an increase in resistance due to oxidation. -Noble metals such as palladium have been used. However, there has been a problem that the production cost is high because the price of precious metals is soaring in recent years, particularly, palladium is expensive.
Therefore, in order to reduce the manufacturing cost, a multilayer capacitor using a base metal Ni having the same characteristics as the above-mentioned noble metal as an internal electrode has been manufactured.

As described above, when Ni is used as an internal electrode, firing in the air and in an oxidizing atmosphere causes a problem that Ni is oxidized and no longer functions as an internal electrode. Required.
However, under this condition, the valence of Ti, which is the main component of the dielectric ceramic, is reduced from tetravalent to trivalent, so that the semiconductor becomes a semiconductor and the average life is sharply reduced. Therefore,
As a countermeasure, MnO, Co ₂ O ₃
And the like to suppress the reduction of Ti,
Oxygen vacancies are reduced by the re-oxidation treatment to prevent a decrease in average life. However, the reoxidation treatment also has a problem in that the influence on the dielectric constant is large and the temperature dependence of the dielectric constant may be adversely affected.

In view of recent environmental problems, the solder generally used for mounting contains lead, which may cause environmental problems. Therefore, the use of lead-less solder is demanded. . Therefore, at present,
The development and commercialization of lead-free solder has been actively carried out, and Sn-
Bi-Ag, Sn-Ag-Cu, Sn-Ag-Bi-G
Lead-less solders such as those based on e-type have begun to be used.

[0006]

By the way, as typified by mobile phones, the necessity of miniaturization, weight reduction, and cost reduction of electronic equipment has been rapidly increasing, and nowadays, multilayer ceramic capacitors are required. However, demands for lower price, higher capacity, higher withstand voltage, higher insulation, and higher reliability are increasing. Among them, as for the cost reduction, as described above, by using the base metal Ni for the internal electrode, the noble metal Pd, A
It has become possible to keep the price lower than using g-Pd.

However, the technique of using base metal Ni for the internal electrode has hitherto been a high-stacked product in which the usage of the internal electrode is large, that is, under a low electric field strength (3 V / μm).
m) or less, and under high electric field strength (3 V / μm or more), the capacitance, withstand voltage,
Problems such as temperature dependency of insulation resistance, DC bias characteristics, and deterioration of reliability frequently occur.

Further, when mounting using lead-less solder,
Since the processing temperature is about 20 to 30 ° C. higher than that of ordinary lead-containing solder, there is also a disadvantage that cracks are easily generated. Further, a dielectric material which has been conventionally used to increase the capacity (for example, Japanese Patent Laid-Open No. 6-34273).
5, JP-A-10-255549, JP-A-61-10
No. 1459, Japanese Patent Publication No. 61-14611, etc.), a high dielectric constant can be obtained, but a high electric field strength (3 V
/ Μm or more), the withstand voltage, insulation resistance, and reliability are significantly reduced, and the insulation resistance at high temperatures (150 ° C.) (C
R product).

The present invention has been proposed to solve the above-mentioned problems of the prior art.
Provided is a dielectric ceramic composition which is sinterable, hardly causes cracks even when lead-free solder is used, and has excellent electrical characteristics, and is suitable for a multilayer ceramic capacitor using Ni as an internal electrode. It is in.

[0010] Another object of the present invention is to use such a composition to measure the temperature characteristics of the capacitance as defined by JIS standards.
It is an object of the present invention to provide a highly reliable multilayer ceramic capacitor which satisfies the characteristics and the X7R characteristics defined by the EIA standard, respectively, and further provides an environmentally friendly manufacturing method capable of manufacturing such an excellent multilayer ceramic capacitor. To provide.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, as described in claim 1, as a dielectric material, a dielectric material having a composition formula of BaTiO ₃ is used. the _{composition, BaO-Ln 2 O 3 -MgO} -B
aSiO ₃ —MnO—RO ₃ (where Ln is Sc, Y, N
d, Pr, Sm, and R are one or more elements selected from W and Mo).
It has been found that the above object can be achieved by using a dielectric porcelain composition characterized in that the composition is contained in wt%.

The main component of barium titanate (B
When the above additive is added to aTiO ₃ ), it is preferable that the additive is first calcined at a high temperature of 1100 ° C. or more, homogenized by pulverization, and then added to the base BaTiO ₃ . According to this method, these additives can be selectively deposited uniformly on the grain boundaries after sintering, and the insulation resistance and the reliability can be improved.
Further, since the difference in specific gravity of the additive is small, a more uniform green sheet can be produced.

[0013] Further, as described in claim 2, the BaO
—Ln ₂ O ₃ —MgO—BaSiO ₃ —MnO—RO ₃ (where Ln is Sc, Y, Nd, Pr, Sm, R is W, Mo
Each component constituting the additive consisting of one or more elements selected from BaO = 0 to 20 m
ol%, Ln ₂ O ₃ = _{2 to} 25 mol%, MgO = 5 to 3
5 mol%, BaSiO ₃ = 5-45 mol%, MnO
= 1 to 10 mol%, a RO ₃ = 2 to 10 mol%, average particle size of the additive is desirably 0.3μm or less.

It is more preferable that the base B
It is desirable to mix the above additive having an average particle diameter of 0.3 μm or less with a raw material having an average particle diameter of aTiO ₃ of 0.3 to 0.5 μm. Thereby, since uniform firing is performed during firing, cracks are less likely to occur. Therefore, stable electric characteristics can be obtained in a wide range of the layer thickness of 5 to 40 μm.

Here, the amount of additive and the range of each component are determined for the following reasons. First, BaO-
Ln ₂ O ₃ —MgO—BaSiO ₃ —MnO—RO ₃ (where Ln is Sc, Y, Nd, Pr, Sm, R is W, Mo
From one or more elements selected from the group consisting of 2.0 to 2.0 parts of the base barium titanate.
The reason for adding 〜6.0 wt% is as follows. That is, if the amount of the additive is 2.0 wt% or less, it is difficult to bake at 1250 ° C. or less, a dense sintered body cannot be obtained, and the mechanical strength of the element is weakened. In addition, when soldering leadless solder, cracks are likely to occur. Further, under a high electric field strength (3 V / μm or more), there is almost no effect of improving the withstand voltage and the insulation resistance and reducing the decrease in the capacitance when the DC bias is applied. On the other hand, when the amount of the additive is 6.0 wt% or more, the dielectric constant is lowered.

As the Ln component, Sc, Y, Nd,
The reason for using one or more elements selected from Pr and Sm is that they show almost the same properties, and that the same or different elements can be used or used in combination. This is because it was confirmed that an effect was obtained. Further, for the same reason, one or two elements selected from W and Mo are used as the R component.

The reason why the average particle size of the main composition, BaTiO _3, and the additives is limited is that the withstand voltage is 120 V / μm.
This is because excellent MLC as described above can be obtained.

Further, BaO-Ln_TwoO_Three-MgO-Ba
SiO_Three-MnO-RO_Three(However, Ln is Sc, Y, N
d, Pr, Sm, and R are one or more selected from W and Mo.
Are the two or more elements).
With BaO = 0-20 mol%, Ln_TwoO_Three= 2
２５25 mol%, MgO = 5 to 35 mol%, BaSi
O _Three= 5 to 45 mol%, MnO = 1 to 10 mol%,
RO_Three= 2 to 10 mol% for the following reason.
You.

That is, the reason why the amount of BaO is limited to the above range is that if it is outside this range, there is no effect on the improvement of the breakdown voltage, the insulation resistance and the DC bias characteristics. Also, Ln
_The reason that the amount of ₂ O ₃ (Ln is one or more elements selected from Sc, Y, Nd, Pr, and Sm) is limited to the above range is that the dielectric constant is 1000 or less when 25 mol% or more. At the same time, the CR product and the reliability (high temperature load, humidity resistance load, etc.) are reduced. On the other hand, if it is 2 mol% or less, there is no effect on the improvement of the insulation resistance and the reliability is poor.

The reason why the amount of MgO is limited to the above range is as follows.
If the content is 5 mol% or less, the temperature characteristics do not satisfy both the X7R characteristics of the EIA standard and the B characteristics of the JIS standard, and there is no effect of improving the insulation resistance. On the other hand, 35mol
%, The dielectric constant and insulation resistance decrease, and the dielectric loss increases.

The reason why the amount of BaSiO ₃ is limited to the above-mentioned range is that the effect as a sintering aid is hardly observed at 5 mol% or less, while the dielectric constant decreases at 45 mol% or more. That's why.

The reason why the amount of MnO is limited to the above range is as follows.
If the content is 1 mol% or less, it is necessary to convert the semiconductor into a semiconductor.
If it exceeds 1%, the insulation resistance decreases and the capacitance-temperature characteristic becomes EIA.
This is because the standard X7R characteristic is not satisfied.

The amount of RO ₃ (R is one or more elements selected from W and Mo) is limited to the above range. When the amount is less than 2 mol%, the dielectric constant and withstand voltage are also sufficient. This is because not only the value cannot be obtained, but also cracks during firing. On the other hand, when the content is more than 10 mol%, the capacity-temperature characteristic does not satisfy the X7R characteristic of the EIA standard.

Further, as described in claim 3, it has been found that the addition of at least one of CaZrO _{3 and} SrZrO _{3 to} the additive in an amount of 2 to 15 mol% each further improves the insulation resistance characteristics. did.
The reason why the amount of CaZrO ₃ or SrZrO ₃ is limited to the above range is that the sinterability is reduced when the amount is 15 mol% or more, and the effect is not improved when the amount is 2 mol% or less.

As described above, when at least one of CaZrO _{3 and} SrZrO ₃ was added to the additive, a better result was obtained because of the B-site component of BaTiO _{3 as} the main composition. Some of Ti have Zr
Is substituted to change the valence of Ti (+ 4 → +
It is considered that this is because 3) is suppressed. That is,
Overall, it is considered that there is an effect of improving the reduction resistance, and the improvement of the insulation resistance at the time of the reoxidation treatment is increased.

It is considered that the form of CaZrO ₃ and SrZrO ₃ can be more stably present at the grain boundary than the case where CaZrO ₃ and SrZrO ₃ are added alone, that is, as CaO + ZrO ₂ , so that the insulation resistance can be improved. In addition, since the addition of a simple substance makes it easy for Zr to be substituted for the Ti site,
This is presumably because grain growth is likely to occur, making it difficult to obtain a core-shell structure unique to X7R characteristics.

As a method of adding the above-mentioned additive to barium titanate which is a main component, first, a specific component (eg, MgO or MnO) is reacted with BaTiO ₃ at a high temperature, and then the remaining component is added. May be used.

By setting the dielectric porcelain composition within the above composition range, X7R characteristics of EIA standard and B of JIS standard can be obtained at a firing temperature of 1100 to 1250 ° C. in a reducing atmosphere.
A dielectric material having characteristics can be easily obtained.

Further, when the device is used at a high electric field strength (5 V / μm) while maintaining the dielectric constant at 1500 to 2500, the product of the capacitance and the insulation resistance (CR product) is 4 at 25 ° C.
000-6000 Ω · F, 500 Ω · F or more at 150 ° C., and withstand voltage is extremely high, 120 V / μm or more, 5 V / μ.
A dielectric material having a capacitance reduction rate of 40% or less when m is applied, and an MLC using the same can be manufactured.

According to a fourth aspect of the present invention, there is provided a method of manufacturing a multilayer ceramic capacitor by alternately laminating an internal electrode and a dielectric to form a laminated body and firing the laminated body. A composition selected from the dielectric porcelain composition described in claim 3 is used as a dielectric. According to this method, claims 1 to
By using the composition described in No. 3, sintering can be performed favorably without generating cracks, so that cracks due to soldering can be prevented, so that its electrical characteristics can be improved.

According to a fifth aspect of the present invention, in the method according to the fourth aspect, the laminate is fired under the condition that the sintered particles of the dielectric ceramic composition have a particle size of 0.2 to 0.5 μm. And heat-treated. According to this method, the ML having excellent withstand voltage, insulation resistance and DC bias characteristics is provided.
C can be obtained.

A multilayer ceramic capacitor according to a sixth aspect is manufactured by the method according to the fifth aspect. That is, by using the manufacturing method described in claim 5, it is possible to obtain a high-performance and highly reliable multilayer ceramic capacitor having excellent electric characteristics. In particular, the present invention is suitable for a wide range of multilayer ceramic capacitors having a dielectric layer of 5 to 40 μm.

As described above, a more preferable range for the method of manufacturing the multilayer ceramic capacitor according to the present invention is as follows. That is, the base BaTiO
₃ , using a raw material having an average particle size of 0.3 to 0.5 μm,
As an additive _{BaO-Ln 2 O 3 -MgO-} BaSiO 3
—MnO—RO ₃ (where Ln is Sc, Y, Nd, P
r, Sm, and R are one or more elements selected from W and Mo).
ol%, Ln ₂ O ₃ = _{2 to} 25 mol%, MgO = 5 to 3
5 mol%, BaSiO ₃ = 5-45 mol%, MnO
= 1 to 10 mol%, a RO ₃ = 2 to 10 mol%, the oxide component and the average particle diameter of 0.3μm or less, further, at least one of CaZrO ₃ or SrZrO _3, respectively 2~15mol % Of the oxide component added to the base BaTiO ₃ in the range of 2.0 to 6.0.
The dielectric material to which wt% is added is fired at 1150 to 1250 ° C., and the average particle diameter after firing is set to 0.2 to 0.5 μm.

[0034]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention. [1. Manufacturing process] [1-1. Preparation of Dielectric Slurry] As a dielectric base material, BaTiO ₃ having an average particle diameter of 0.3 μm was used.
The BaTiO ₃ used was obtained by hydrothermal growth. In addition, when preparing an oxide component as an additive, first, BaO, Ln ₂ O ₃ (Ln = Sc, Y, N
d, Pr, one or more elements of Sm), Mg
O, BaSiO ₃ , MnO, RO ₃ (R = one or two or more elements of Mo), CaZrO ₃ , SrZrO ₃
Were weighed in predetermined amounts according to the compositions shown in Table 1, respectively. Then, these are put into an aluminum crucible, and 115
Calcination was performed at 0 ° C. for 4 hours. Next, the obtained calcined powder is pulverized using a fine pulverizer such as a jet mill or an attritor mill to have an average particle size of 0.2 to 0.5 μm.
m oxide powder was obtained. Note that part or all of the oxide powder may be vitrified depending on manufacturing conditions, but there is no great difference in characteristics obtained if the composition is uniform.

From the dielectric base material and the oxide powder obtained as described above, as shown in Table 1, a plurality of dielectric raw materials having different mixing ratios of the respective materials were produced. That is, a solvent obtained by mixing water, ethyl alcohol, and a dispersant at a ratio of 80: 19: 1 was added to 1000 g of each dielectric material.
Then, the mixture was dispersed using a homogenizer. This mixture is dispersed for 20 hours using a ball mill or an attrition mill, which is a well-known dispersion method, and then a solution containing an aqueous emulsion, an acrylic resin, and a plasticizer is added. A dielectric slurry was prepared (Examples 1 to 28). The viscosity of each of these slurries was adjusted to about 200 cps.

[Table 1]

[1-2. Production of Green Chip] Using the dielectric slurry obtained as described above, a green sheet having a thickness of 20 μm is formed on a PET film by a doctor blade device, and an internal electrode is formed on the green sheet. The paste was printed with a thickness of 2 μm.
The paste for the internal electrode has an average particle size of 0.5 μm.
m, 100 parts by weight of Ni particles, 40 parts by weight of an organic vehicle (8 parts by weight of ethyl cellulose resin dissolved in 92 parts by weight of butyl carbitol), and 10 parts by weight of butyl carbitol were kneaded by a three-roll mill. The paste was used.

Next, the sheet is peeled off from the PET film.
1 ton / cm at 80 ° C ^TwoUsing the hydrostatic pressure of
A green chip was obtained by pressure bonding. Number of layers is 100
And Next, this green chip is cut into a predetermined size.
Mounted on a metal plate setter, debinding and firing
And annealing are performed continuously under the following conditions.
A sensor element was manufactured. It should be noted that the binder removal process, firing and
Conditions for annealing and annealing are as follows. Also, each
A wetter was used for humidifying these atmosphere gases. (Binder removal treatment) Heating rate: 20 ° C / hour Holding temperature: 300 ° C Temperature holding time: 8 hours Atmospheric gas: in air (firing) Heating rate: 300 ° C / hour Holding temperature: 1200 ° C and 1250 ° C Temperature holding Time: 2 hours Cooling rate: 200 ° C./hour Atmosphere gas: Humidified N_TwoAnd H_TwoMixed gas with oxygen partial pressure: 1 × 10^-11atm (annealing) Holding temperature: 750 ° C Temperature holding time: 4 hours Heating / cooling rate: 300 ° C / hour Atmospheric gas: air Oxygen partial pressure: 2 × 10^-1atm

[1-3. Barrel treatment and external electrode formation]
After polishing the end face of the obtained capacitor element by barrel processing, 100 parts by weight of Cu particles having an average particle size of 0.5 μm and an organic vehicle (8 parts by weight of ethyl cellulose resin dissolved in 92 parts by weight of butyl carbitol) 35 Parts by weight and 7 parts by weight of butyl carbitol are kneaded, and the paste for an external electrode is transferred to the end face.
_By firing at 850 ° C. for 5 minutes in _two atmospheres to form external electrodes, a multilayer ceramic capacitor having a configuration as shown in FIG. 1 was obtained. In the figure, 1 is a dielectric layer, 2
Is an internal electrode, and 3 is an external electrode.

[2. Test Result] Subsequently, characteristics were compared based on the difference in dielectric composition as follows. Also,
The size of each sample manufactured as described above is 5.
7 × 5.0 × 2.3 mm, the effective dielectric layer has a thickness of 15 μm × 100 layers, and the internal electrode layer has a thickness of about 1.2 μm.
Met.

The composition of the dielectric layer of each sample is as shown in Table 1 above.
8 is a composition according to the present invention, and Reference Examples 1 to 8 are compositions outside the scope of the present invention. That is, Reference Example 1 is a sample composed of a dielectric composition to which no oxide component is added, and Reference Examples 2 to 8 are dielectric compositions in which the compositions marked with * are outside the scope of the present invention. This is a sample consisting of

Then, for each of the plurality of samples having the dielectric compositions shown in Table 1, an appearance inspection such as the number of cracks after mounting when using lead-less solder was performed, and the dielectric constant and the temperature characteristics of the capacitance were measured. , Dielectric loss, withstand voltage, insulation resistance, and the like, the results shown in Table 2 below were obtained. The details of the inspection and measurement in this case are as follows.

(Inspection of appearance) The number of solder cracks was determined by using 20 samples for each composition, immersing in solder bath at 280 ° C, observing cracks generated in the element with an optical microscope, The rate was determined. (Temperature Characteristics of Capacitance) The temperature characteristics of capacitance are as follows.
It was examined whether the characteristics were satisfied. Specifically, the capacitance was measured at a measurement voltage of 1 V at −55 to 125 ° C. with an LCR meter, and the capacitance change rate was within ± 15% (reference temperature 2
(5 ° C.). Also, -25 to 85
The capacitance was measured at a measurement voltage of 1 V at 0 ° C., and it was checked whether or not the rate of change of the capacitance was within ± 10% (reference temperature: 20 ° C.). ○: when both are satisfied, ×: when not satisfied
And

(Relative Dielectric Constant εs and Dielectric Loss) The capacitance at 20 ° C. was measured, and the relative dielectric constant was measured from the electrode area and the thickness of the dielectric. The dielectric constant and dielectric loss are 1 vrm
s, the value at 1.0 kHz was used. (Withstand voltage) A voltage at which a current was applied to the MLC element by 10 mA or more was defined as a withstand voltage. The number of measurements was 5 for each composition, and the average was determined.

(Capacitance resistance product under high electric field strength) The element was left in a constant temperature bath at 25 ° C. and 150 ° C., and after 10 minutes, the 1 minute value of the capacitance and the insulation resistance when 5 V was applied per 1 μm of the dielectric thickness was calculated. The product was measured, and the product was defined as CR (5 V / μm). (DC bias characteristics) First, 1 kHz, 1 Vrms A
After measuring the capacitance when the C voltage is applied, DC 75
The capacitance when V and 1 kHz and 1 Vrms AC voltage were applied simultaneously was measured. From the obtained measurement values, the rate of decrease in capacitance was calculated.

[Table 2]

As is clear from Table 2, the characteristics of the samples having the dielectric composition according to the present invention (Examples 1 to 28) are all the same as those of the sample having the dielectric composition outside the scope of the present invention (Reference Example). It is much better than 1-8). That is, as is clear from the characteristics of Examples 1 to 28, when the dielectric composition according to the present invention is used, no crack occurs even when immersed in a 280 ° C. solder bath. Further, it is possible to manufacture an MLC having excellent withstand voltage. In addition, the obtained ML
C was 25 ° C. and 1 ° C. even under high electric field strength (5 V / μm).
The insulation resistance is extremely high at 50 ° C., and the rate of decrease in capacitance when DC bias is applied is small.

[3. Other Embodiments] It should be noted that the present invention is not limited to the above-described embodiments, and various other modifications can be made within the scope of the present invention. For example, the specific composition of the dielectric ceramic composition can be appropriately selected within the scope of the present invention. Similarly, the composition of the electrode metal, the composition of the binder, and the like can be appropriately selected. Furthermore, specific manufacturing steps and conditions of each step can be appropriately selected. For example, the temperature conditions, the temperature rising / falling rate conditions, the atmosphere gas conditions, and the like in the binder removal processing, firing, and annealing can be appropriately selected.

[0047]

As described above, according to the present invention,
For multilayer ceramic capacitors that can be sintered well, hardly cause cracks when soldering leadless solder, show excellent withstand voltage and DC bias characteristics, and have a high capacitance-resistance product under high electric field strength (5 V / μm). As a result, a dielectric ceramic composition suitable for the present invention can be provided.

Further, using such a composition, EIA
It is possible to provide a high-performance and highly reliable multilayer ceramic capacitor capable of satisfying the standard X7R characteristic and the JIS standard B characteristic. Further, it is possible to provide a manufacturing method which is capable of manufacturing such an excellent multilayer ceramic capacitor and has excellent environmental properties.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a configuration of a multilayer ceramic capacitor according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Dielectric layer 2 ... Internal electrode 3 ... External electrode

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kiyoji Handa 1-17-1 Higashi-Ome, Ome-shi, Tokyo F-term in Nippon Chemi-Con Corporation 4G031 AA03 AA04 AA05 AA06 AA07 AA08 AA11 AA12 AA17 AA18 AA19 AA30 BA09 CA04 GA03 5E001 AB03 AC09 AE02 AE03 AE04 AH00 AH09 AJ01 AJ02 5G303 AA01 AB02 AB20 BA12 CA01 CB03 CB06 CB17 CB18 CB22 CB32 CB35 CB37 CB40 CB41 DA05 DA07

Claims (6)

[Claims]
1. 1. A to the main composition formula consists of _{BaTiO 3, BaO-Ln 2 O} 3 -MgO-BaSiO 3 -
   MnO—RO ₃ (where Ln is Sc, Y, Nd, Pr,
   Sm, R is one or two or more elements selected from W and Mo) in an amount of 2.0 to 6.0 wt%.
2. 2. The BaO-Ln ₂ O ₃ -MgO-BaS
   iO ₃ —MnO—RO ₃ (where Ln is Sc, Y, Nd,
   Pr, Sm, and R are one or two selected from W and Mo.
   The components constituting the additive consisting of at least one kind of element are BaO = 0 to 20 mol% and Ln ₂ O ₃ = 2 to 25, respectively.
   mol%, MgO = 5 to 35 mol%, BaSiO ₃ =
   5 to 45 mol%, MnO = 1 to 10 mol%, RO ₃
   2. The dielectric ceramic composition according to claim 1, wherein the average particle diameter of the additive is 0.3 μm or less.
3. 3. The method according to claim 1, wherein the additive is CaZrO ₃ or SrZ.
   at least one of rO ₃ is 2-15
   3. The method according to claim 1, wherein mol% is added.
   A dielectric porcelain composition as described in the above.
4. 4. A method of manufacturing a multilayer ceramic capacitor by forming a laminate by alternately laminating Ni internal electrodes and dielectrics, and firing the laminate to produce a multilayer ceramic capacitor. A method for producing a multilayer ceramic capacitor, comprising using a composition selected from the above dielectric ceramic compositions as a dielectric.
5. 5. The multilayer ceramic capacitor according to claim 4, wherein the multilayer body is fired and heat-treated under the condition that the sintered particles of the dielectric ceramic composition have a particle size of 0.2 to 0.5 μm. Manufacturing method.
6. 6. A multilayer ceramic capacitor manufactured by the method according to claim 5.