JPH0425006A - Porcelain capacitor and manufacturing method thereof - Google Patents

Abstract

PURPOSE:To contrive to marked improve relative permittivity and to make a porcelain capacitor small-sized and a large capacitance by a method of specifying the composition of a dielectric porcelain composition comprising a dielectric layer of a porcelain capacitor. CONSTITUTION:Additive components with respect to a fundamental component {(Ba1-XCaX)O}K(Ti1-Y-ZZrYRZ)O2-Z/2 are, in an triangular figure in which compositions are shown in mol%, in a range enclosed by six straight lines linking in the following order: a first point A showing a composition of B2O3 1 mol%, SiO2 80mol%, and MO 19mol%; a second point B showing a composition of B2O3 1mol%, SiO2 39mol%, and MO 60mol%; a third point C showing a composition of B2O3 30mol%, SiO2 0mol%, and MO 70mol%; a fourth point D showing a composition of B2O3 90mol%, SiO2 0mol%, and MO 10 mol%; a fifth point E showing a composition of B2O3 90mol%, SiO2 10mol%, and MO 0mol%; and a point F showing a composition of B2O3 20mol%, SiO2 80mol%, and MO 0mol%.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a ceramic capacitor having a single-layer or laminated structure in which a dielectric ceramic layer is sandwiched between at least two internal electrodes, and a method for manufacturing the same. .

[Conventional technology] Multilayer ceramic capacitors are manufactured by printing a conductive paste in a desired pattern on an unsintered porcelain sheet (green sheet) made of dielectric ceramic raw material powder, stacking a plurality of sheets and pressing them together, and placing them in an oxidizing atmosphere. It is manufactured by firing at 1300°C to 1600°C.

By this firing, the unsintered porcelain sheet becomes a dielectric layer, and the conductive paste becomes an internal electrode.

By the way, conventionally, as the conductive paste, one whose main component is a noble metal such as platinum or palladium has been used.

This means that if a conductive paste whose main component is a noble metal such as platinum or palladium is used, the conductive paste will not oxidize even if it is fired at a high temperature of 1300°C to 1600°C in an oxidizing atmosphere. (This is because it can be modified into a desired internal electrode.)

However, since noble metals such as platinum and palladium are expensive, there is a problem in that the cost of multilayer ceramic capacitors is inevitably high.

As a solution to this problem, Japanese Patent Publication No. 60-20851 related to the present applicant ((B
axCaySrz)Olk(T1r+Zr+-n102
A dielectric ceramic composition is disclosed that includes a basic component consisting of Li2O, 5in2, and an additive component consisting of MO (where MO is one or more oxides selected from Bad, CaO, and SrO). ing.

Also, in Japanese Patent Application Laid-open No. 147404/1983, ((Ba
t-++-ycaxsry)O1w(Tut-zZrj
Basic components consisting of Oz, B2O3, SiO2 and L x
A dielectric ceramic composition is disclosed that includes an additive component consisting of 20.

Furthermore, in Japanese Patent Application Laid-open No. 147405/1983, ((Ba
t −x−ycaxsryl ol, (T1. +−
Basic components consisting of zZrzl 02, B2O3 and Si
A dielectric ceramic composition containing an additive component consisting of O□ is disclosed.

Furthermore, in Japanese Patent Application Laid-open No. 147406/1986, ((Ba
t-x-ycaxsrylO)K(Tut-zZrzl
The basic component ゛ consisting of L, B2O3, SiO□ and MO (
However, a dielectric ceramic composition is disclosed in which MO is an additive component consisting of one or more oxides selected from Bad, CaO, and SrO.

The dielectric ceramic compositions disclosed in these publications can be obtained by firing at a relatively low temperature of 1200°C or less in a reducing atmosphere, but the dielectric constant ε is 5000 or more and the resistance is low. The ratio p is 1×10 6 MΩ·cm or more.

[Problems to be Solved by the Invention] Incidentally, in recent years, there has been a remarkable progress toward higher density of electronic circuits, and there is a strong demand for miniaturization of multilayer ceramic capacitors.

For this reason, the dielectric constant ε of the dielectric ceramic composition constituting the dielectric layer of the multilayer ceramic capacitor can be changed from that of the dielectric ceramic composition disclosed in the above-mentioned publications without deteriorating other electrical properties. It has been desired to further increase the dielectric constant ε.

Therefore, the object of the present invention is to
Although it is obtained by firing at a temperature of 200°C or lower, the relative dielectric constant ε of the dielectric ceramic composition constituting the dielectric layer is 7000 or more, and the dielectric loss tan δ is 2.
The object of the present invention is to provide a ceramic capacitor whose electrical characteristics are better than conventional ones, with a resistivity p of 5% or less and a resistivity p of 1×106 MΩ·Cm or more, and a method for manufacturing the same.

[Means for Solving the Problems] A ceramic capacitor according to the present invention includes a dielectric ceramic layer made of a dielectric ceramic composition, and at least two internal electrodes sandwiching the dielectric ceramic layer. In the ceramic capacitor, the dielectric ceramic composition is made of a fired mixture of 100.0 parts by weight of a basic component and 0.2 to 5.0 parts by weight of an additive component, and the basic component is ( (Bat-xcajolh(T1.+-y-zZry
RzlOz-zz2 (However, R is Sc, Y, Gd, D
y, Ho.

One or more elements selected from Er, Yb, Tb, Tm, and Lu; ≦Z≦0.04 1.00≦≦1.04), and the additive components are B2O3, SiO2, and MO (however, MO
is one or more oxides selected from BaO, SrO, Cab, MgO, and ZnO), and the composition range of the B2O3, the SiO2, and the MO is a triangle representing these compositions in mol%. In the figure, the B2O3 is 1 mol%, the SiO□ is 80 mol%,
A first point A in which the MO has a composition of 19 mol%, the B2O3 has a composition of 1 mol%, the SjO□ has a composition of 39 mol%,
a second point B having a composition of 60 mol% of the MO; 30 mol% of the B2O3; 0 mol% of the 5jO2;
a third point C having a composition of 70 mol% of the MO; 90 mol% of the B2O3; 0 mol% of the SiO□;
A fourth dot showing a composition of 10 mol% of the MO, 90 mol% of the 10203 and 10 mol% of the 5in2.
, a fifth point E having a composition in which the MO is 0 mol%, the B2O3 is 20 mol%, and the SiO□ is 80 mol%.
, and the sixth point F where the MO has a composition of 0 mol % are in a region surrounded by six straight lines connecting in this order.

Here, the ratio of the number of Ca atoms in the composition formula of the basic component, that is, the value of X, is set to 0≦X≦0.27 because
If the value of This is because the dielectric constant ε8 is also less than 7,000.

In addition, the ratio of the number of Zr atoms in the composition formula of the basic component, that is, the value of y, is set to 0.05≦y≦0.26 because the value of y is 0.05≦y≦0.26. In this case, it is possible to obtain a sintered body having desired electrical properties, but if it deviates from this range, the dielectric constant ε5 becomes less than 7,000.

In addition, the ratio of the number of atoms of R in the composition formula of the basic component,
In other words, the reason why the value of Z is set to 0.002≦Z≦0.04 is that when the value of Z is 0.002≦2≦0.04, a sintered body having desired electrical characteristics can be obtained. can be done, but 0
．． When it becomes less than 0.002, the dielectric loss tan δ deteriorates significantly, and the resistivity ρ also becomes less than I This is because even if there is, a dense sintered body cannot be obtained.

Note that the R components Sc, Y, Gd, Dy, and Ho.

Er, Yb, Tb, Tm, and Lu work in the same way as the squares, and the same result can be obtained even if one selected from them is used or a count is used.

In the composition formula of the basic component, ((Bat-xCa,)0
), that is, the value of k is set to 1.00≦≦1.04, because if the value of k is 1.00≦≦1.04, the sintered material has the desired electrical characteristics. Although a solid can be obtained, if the resistivity ρ becomes less than 1.00, the resistivity ρ becomes lX
This is because if it is less than 10'MΩ·cm, it is significantly low, and if it exceeds 1.04, a dense sintered body cannot be obtained.

In addition, among the R components in the composition formula of the basic components, T
Although b, Tm and Lu are not listed in Table 1 below, these also have the same effects as the other R components.

In addition, a trace amount of mineralizing agent such as Mn0z (preferably 0.05 to 0.1% by weight) may be added to the basic components within a range that does not impede the purpose of the present invention to improve sinterability. Good too.

Further, other substances may be added as necessary.

Further, as a starting material for obtaining the basic components, oxides other than those shown in the examples, hydroxides, or other compounds may be used.

Next, the addition amount of the additive component was set to 0.2 to 5.0 parts by weight relative to 100 parts by weight of the basic component. A sintered body with desired electrical properties can be obtained by firing at a temperature of 125% by weight.
Even at 0°C, a dense sintered body cannot be obtained, and if it exceeds 5.0 parts by weight, the dielectric constant is 8. , is 7
This is because it is less than 000.

In the triangular diagram showing the composition of B2O3, 5in2, and MO in mol%, the composition of the additive component was set within the range surrounded by the six straight lines connecting the points A-F in this order. If the composition is within this range, a sintered body with desired electrical properties can be obtained, but if the composition of the additive components is outside this range, a dense sintered body cannot be obtained. Because you can't.

Note that the MO components are Bad, SrO, and Cab.

Either one of MgO and ZnO may be used, or an appropriate ratio may be used.

Next, the method for manufacturing a porcelain capacitor according to the present invention includes the steps of preparing a mixture of unsintered porcelain powder made of the basic components and additive components, and forming an unsintered porcelain sheet of the mixture. a step of forming a laminate in which the unsintered porcelain sheet is sandwiched between two or more conductive paste films; a step of heat treating the laminate in a non-oxidizing atmosphere; and a step of heat-treating the laminate in a non-oxidizing atmosphere. The method includes a step of heat-treating the laminate in an oxidizing atmosphere.

Here, the non-oxidizing atmosphere may be not only a reducing atmosphere such as H2 or CO, but also a neutral atmosphere such as N2 or Ar.

Further, the temperature of the heat treatment in a non-oxidizing atmosphere can be varied in consideration of the electrode material. When nickel is used as the internal electrode, heat treatment can be performed in the range of 1050° C. to 1200° C. with almost no agglomeration of the nickel particles.

Further, the temperature of the heat treatment in an oxidizing atmosphere may be lower than the sintering temperature, and is preferably in the range of 500 to 1000°C. The temperature to be set needs to be changed in various ways, taking into account the oxidation of the electrode material (nickel, etc.) and the oxidation of the dielectric ceramic layer. Although the temperature of this heat treatment was set to 600° C. in the examples described later, it is not limited to this temperature.

Note that the present invention is of course applicable to general single-layer ceramic capacitors other than multilayer ceramic capacitors.

[Example] First, the case of sample No. 1 in Table 1 will be explained.

Weighed each of the compounds of blade formulation 1, put these compounds into a pot mill together with a plurality of alumina balls and water at 2.5°C, and stirred and mixed for 15 hours to obtain a mixture. Ta.

Here, the weight (g) of each compound in Formulation 1 is a value calculated so that the compositional formula of the basic components is as follows.

Next, the mixture was placed in a stainless steel pot and dried at 150°C for 4 hours using a hot air dryer, and the dried mixture was coarsely ground. It was calcined at 1200° C. for 2 hours to obtain a powder having the basic components represented by the composition formula (1).

11 In addition, each of the compounds of Formulation 2 was weighed, and these compounds were placed in a polyethylene pot with a plurality of alumina balls and 3
00m and C alcohol and stirred and mixed for 10 hours to obtain a mixture.

Here, the weight (g) of each compound in Formulation 2 is: B2O3 is 1 mol%, Si Oa is 80 mol%, MO is 19 mol% 1Bao (3.8 mol%) + Ca0 (9.5 mol%)
+Mg0 (5.7 mol%)).

In addition, the proportions of Bad, CaO, and MgO in MO are 20 mol% for BaO, 50 mol% for CaO, and 50 mol% for MgO.
gO is 30 mol%.

Next, the mixture was calcined in the air at a temperature of about 1000°C for 2 hours, put into an alumina pot together with a plurality of alumina balls and water at 300m°C, pulverized for 15 hours, and then heated to 150°C for 4 hours. It was dried for a period of time to obtain a powder of the additive component having the above composition.

Preparation of slurry Next, 100 parts by weight (1000 g) of the basic ingredients,
Put 2 parts by weight (20 g) of the above additive components into a ball mill, and further add 15% by weight of an organic binder and 50% by weight of water based on the total weight of these basic components and additive components, and mix these. and pulverized to obtain a slurry that would serve as a raw material for a dielectric ceramic composition.

Here, the organic binder used was an aqueous solution of acrylic acid ester polymer glycerin and condensed phosphate.

The number of sets of "1" is carved into 4 pieces.Next, the slurry is put into a vacuum defoaming machine and degassed,
This defoamed slurry is applied onto a polyester film to a predetermined thickness using a reverse coater, and this applied slurry is coated with this polyester film in one coat.
It was dried by heating at 00'C to obtain a long unsintered m-lid sheet with a thickness of about 25 gm. Then, this long unsintered porcelain sheet was cut to obtain a 10 cm square unsintered porcelain sheet.

The average particle size of the electric paste is 1. ! 10g of 5um nickel powder,
0.9g of ethylcellulose to 9.1g of butylcarpitol
A conductive paste for internal electrodes was obtained by putting the mixture in a stirrer and stirring for 10 hours.

Then, five patterns (length 14 mm, width 7 mm) made of this conductive paste were placed on one side of the unsintered porcelain sheet.
0 pieces, formed by screen printing method and dried.

Next, two of the unsintered porcelain sheets were laminated with the side on which the pattern made of conductive paste was formed facing upward. During this lamination, the patterns made of conductive paste were shifted by about half in the longitudinal direction between the upper and lower adjacent unsintered porcelain sheets.

Then, four unsintered porcelain sheets each having a thickness of 60 μm were laminated on the upper and lower surfaces of the laminated product as described above to obtain a laminate.

Then, at a temperature of about 50°C, a load of about 40 tons was applied from the thickness direction to this laminate to press the unsintered porcelain sheets that make up the laminate together. I let it happen. Then, this laminate was cut into a grid shape to obtain 50 laminate chips.

Layer Chip FiringNext, this laminate chip was placed in a furnace capable of atmosphere firing, the inside of the furnace was made into an atmospheric atmosphere, and the layered chip was heated at a rate of 100°C/h for 6 hours.
The temperature was raised to 00°C to burn off the organic binder in the unsintered porcelain sheet.

After that, the atmosphere inside the furnace is changed from atmospheric to reducing atmosphere (H
2 (2 volume%) + N2f98 volume%)), the temperature in the furnace was raised from 600 °C to 1160 °C at a rate of 100 °C/h, the temperature of 1160 °C was maintained for 3 hours, and then 100 °C The temperature was lowered at a rate of ℃/h, the atmosphere inside the furnace was changed to an atmospheric atmosphere (oxidizing atmosphere), and the temperature of 600℃ was lowered to 3
The sample was held for 0 minutes to perform oxidation treatment, and then cooled to room temperature to obtain a laminated sintered chip.

11! Then, among the opposing sides of this laminated sintered chip,
A pair of external electrodes is formed on the side surface where the ends of the internal electrodes are exposed, and a negative dielectric ceramic layer 12 is formed as shown in FIG.
'12.12 and a pair of external electrodes 16.16 at the end of the laminated sintered chip 15 consisting of two layers of internal electrodes 14.14.
A multilayer ceramic capacitor 10 was obtained.

Here, the external electrode 16 includes zinc, glass frit, and vehicle on the side surface.
After drying, this conductive paste is baked in the atmosphere at a temperature of 550'C for 15 minutes to form a zinc electrode layer 18. Further, on this zinc electrode layer 18, an electroless A copper layer 20 is formed by plating method, and Pb-3n is further formed on this copper layer 20 by electroplating method.
It was formed by providing a solder layer 22.

Note that the dielectric ceramic layer 12 of this multilayer ceramic capacitor 10
The thickness of the electrode is 0.02 mm, and the opposing area of the pair of internal electrodes 14.14 is 5 mm x 5 mm = 25 mm2. Further, the composition of the dielectric ceramic layer 12 after sintering is substantially the same as the composition of the mixture of basic components and additive components before sintering.

Measurement of electrical... Next, the electrical characteristics of the multilayer ceramic capacitor 10 are measured,
When the average values were determined, as shown in Table 1, the relative dielectric constant ε was 5200, the tan δ was 1.2%, and the resistivity ρ was 2.78×10'MΩ·cm.

Note that the electrical characteristics were measured in the following manner.

FA) Relative permittivity ε5 is temperature 20°C1 frequency 1, k
Hz, voltage (effective value) 1. The capacitance was measured under OV conditions, and this measured value was combined with the opposing area (25 mm2) of the pair of internal electrodes 14.14 and the thickness (0, 02mm).

(1 dielectric loss tan δ (%) is the relative dielectric constant ε
, was measured under the same conditions as in the case of measurement.

(C) Resistivity ρ (MO・am) is measured after applying DC 100V for 1 minute at a temperature of 20°C.
The resistance value was measured between 6.16 and calculated based on the measured value and the dimensions.

Above, sample No. 31 was described, but samples No. 2 to
Regarding Sample No. 83, the compositions of the basic components and additive components were changed as shown in the left column of Table 1, and the firing temperature in the reducing atmosphere was changed as shown in the right column of Table 1.
, 1 and all (multilayer ceramic capacitors are made using the same method,
Electrical properties were measured using the same method. Sample No. 2-8
The electrical characteristics of Sample No. 3 were as shown in the right column of Table 1.

In Table 1, the column 1-x shows the ratio of the number of Ba atoms in the composition formula of the basic component, and the column X shows the ratio of the number of Ca atoms in the composition formula of the basic component. The -z column shows the ratio of the number of Ti atoms in the composition formula of the basic component, the y column shows the ratio of the number of Zr atoms in the composition formula of the basic component, and the Z column shows the ratio of the number of Zr atoms in the composition formula of the basic component. The ratio of the number of atoms of R is shown in the column k in the composition formula of the basic component (
The percentage of (Ba, -xcaxlo) is shown.

Also, Sc, Y, Gd, Dy, and Ho in the Z column.

Er and Yb indicate the content of R in the composition formula of the basic component, each column of these elements shows the ratio of the number of atoms of these elements, and the total column shows the atoms of these elements. The total value (Z value) of the number ratio is shown.

In addition, the amount added in the column of content of added components is shown in parts by weight based on 100 parts by weight of the basic component, and the column of content of MO shows Ba
d, SrO, Cab, MgO.

The proportion of ZnO is shown in mole %.

As is clear from Table 1, according to the samples according to the present invention, when fired at 1200°C or less in a non-oxidizing atmosphere, the relative dielectric constant ε8 is 7000 or more, the dielectric loss tan δ is 2.5% or less, It is possible to obtain a ceramic capacitor equipped with a dielectric ceramic composition having electrical characteristics such that the resistivity ρ is 1×10 6 MΩ·cm or more.

On the other hand, No, 11-13, 20, 25° 26.3
1,37,43,44,48,49゜53.63,68
, 69, 73, 74, 78° 79 and 83, it was not possible to obtain a ceramic capacitor having the desired electrical characteristics.

Therefore, these samples No. are outside the scope of the present invention. Next, the reason for limiting the composition range of the dielectric ceramic composition used in the ceramic capacitor according to the present invention will be explained.

First, the ratio of the number of Ca atoms in the composition formula of the basic component, ie, the value of X, will be explained.

The value of X, as shown in sample Nos. 36 and 42, is 0.
In the case of sample No. 27, a sintered body having desired electrical properties can be obtained.

37 and 43, in the case of 0.30, the firing temperature is as high as 1250°C, and the dielectric constant ε5 is also 7000°C.
less than Therefore, the upper limit of the value of X is 0.27.

Further, Ca has the effect of flattening the temperature characteristics and improving the resistivity p, but even if the value of X is zero, a sintered body with desired electrical characteristics can be obtained. Therefore, X
The lower bound of the value of is zero.

Next, the ratio of the number of Zr atoms in the composition formula of the basic component, that is, the value of y, will be explained.

As shown in sample Nos. 45 and 50, the value of y is 0.
In the case of sample No. 05, a sintered body having desired electrical properties can be obtained.

44 and 49, in the case of 0.03, the dielectric constant ε5 is less than 7000.

Therefore, the lower limit of the value of y is 0.05.

On the other hand, the value of y is as shown in samples No. 47 and 52,
In the case of 0.26, a sintered body with desired electrical properties can be obtained, but as shown in sample Nos. 48 and 53,
In the case of 0929, the dielectric constant is 8. , is less than 7000. Therefore, the upper limit of the value of y is 0.26.

Next, the ratio of the number of atoms of R in the composition formula of the basic component,
That is, the value of Z will be explained.

As shown in sample Nos. 64 and 70, the value of Z is 0.
In the case of sample No. 002, a sintered body having desired electrical properties can be obtained.

63 and 69, in the case of 0.001, the dielectric loss tan δ deteriorates significantly and the resistivity p also]XIO
'MΩ・cm. Therefore, the lower limit of the value of Z is 0.
It is 002.

On the other hand, when the value of 2 is 0.04, as shown in sample Nos. 67 and 72, a sintered body having desired electrical properties can be obtained; Thus, in the case of 0.06, a dense sintered body cannot be obtained even if the firing temperature is 1250°C. Therefore,
The limit of the value of Z is 0.04.

Note that the R components Sc, Y, Dy, Ho, and Er.

Yb works in the same way as f, and the same result can be obtained even if one selected from these or a plurality of them are used.

Next, the ratio of ((Bat-xcaj 01), that is, the value of k in the composition formula of the basic component will be explained.

As shown in sample Nos. 75 and 80, the value of k is 1.
In the case of sample No. 00, a sintered body having desired electrical properties can be obtained.

As shown in 74 and 79, in the case of 0.99, the resistivity p is significantly low (less than 1×10'MΩ·cm).

Therefore, the lower limit of the value of k is 1.00.

On the other hand, when the value of k is 1.04, as shown in sample Nos. 77 and 82, a sintered body with desired electrical characteristics can be obtained;

As shown in Nos. 78 and 83, in the case of 1.05, a dense sintered body cannot be obtained.

Therefore, the upper limit of the value of k is 1.04.

Next, the amounts of the additive components to be added will be explained.

When the amount of the additive component is 0.2 parts by weight relative to 100 parts by weight of the basic component, as shown in Sample Nos. 21 and 27, the desired electrical properties can be obtained by firing at 1190 to 1200°C. However, sample No.
, 20 and 26, if the amount of the additive component is zero, a dense sintered body cannot be obtained even if the firing temperature is 1250°C. Therefore, the lower limit of the additive component is 0.2 part by weight per 100 parts by weight of the basic component.

On the other hand, when the amount of the additive component added is 5 parts by weight relative to 100 parts by weight of the basic component, as shown in Sample Nos. 24 and 30, a sintered body having desired electrical properties can be obtained. However, as shown in samples No. 25 and 31, when the amount of the additive component is 7 parts by weight relative to 100 parts by weight of the basic component, the dielectric constant ε8 becomes less than 7000.

Therefore, the upper limit of the amount of the additive component added is 5 parts by weight per 100 parts by weight of the basic component.

Next, a preferred composition range of the additive components will be explained.

The preferred composition range of the additive components is 8203-3 in Figure 2.
It can be determined based on a triangular diagram showing the composition ratio of iO□-MO.

The first point A in the diagonal diagram shows the composition of sample No. 1 with 1 mol% of B2O3, 80 mol% of 5i02, and 19 mol% of MO, and the second point B shows the composition of sample No. 1 with B2O3 of 1 mol%. 1 mol%, SiO□ is 39 mol%, and MO is 60 mol%.
mol%, 5jO2 is 0 mol%, MO is 70 mol%, and the fourth mark shows that sample No. 4 has a composition of 90 mol%
mol%, 5in2 shows a composition of 0 mol%, MO shows a composition of 10 mol%, and the fifth point E is sample No. 5 with a composition of 90% B2O3.
mol%, 5in2 shows a composition of 10 mol%, MO shows a composition of 0 mol%, and the sixth point F has a composition in which B2O3 of sample No. 6 is 20 mol%.
The composition is 80 mol% for 5in2 and 0 mol% for MO.

The added components of the sample belonging to the composition range of the present invention are within the range surrounded by six straight lines connecting points 1 to 6 in this order in the triangular diagram shown in FIG.

If the composition of the additive components is within this range, a sintered body having desired electrical properties can be obtained. On the other hand, if the composition of the additive components is outside the range specified in the present invention, as in Samples Nos. 11 to 13, a dense sintered body cannot be obtained.

In addition, MO acid components such as Bad, SrO, and Cab as shown in Sample Nos. 14 to 18.

It may be either one of MgO or ZnO, or it may be in an appropriate ratio as shown in other samples.

[Effects of the Invention] According to the present invention, since the composition of the dielectric ceramic composition constituting the dielectric layer of the ceramic capacitor is configured as described above, it can be fired at 1200°C or lower in a non-oxidizing atmosphere. Despite the fact that the relative dielectric constant ε3 is 7000 ~
20100, and therefore,
It has become possible to make ceramic capacitors smaller and larger in capacity.

Now that it has become possible to make ceramic capacitors smaller and larger in capacity, it is possible to reduce the cost of ceramic capacitors by using conductive paste of base metals such as nickel to form internal electrodes. Became.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention, and FIG. 2 is a triangular diagram showing the composition range of additive components. 12... Dielectric ceramic layer 14... Internal electrode 15
...Laminated sintered chip 16...External electrode 18...
・Zinc electrode layer 20...Copper layer 22 ・P b
-S n Handa layer agent Patent attorney Kubo 1) Akira Hou

Claims (1)

[Claims] 1. A ceramic capacitor comprising a dielectric ceramic layer made of a dielectric ceramic composition and at least two or more internal electrodes sandwiching the dielectric ceramic layer, wherein the dielectric ceramic composition contains 100.0 parts by weight. and 0.2 to 5.0 parts by weight of additive components, and the basic components are {(Ba_1_−_xCa_x)O}_k(Ti_1_
-_y_-_zZr_yR_z)O_2_-_z_/_
2 (However, R is Sc, Y, Gd, Dy, Ho, Er,
One or two selected from Yb, Tb, Tm and Lu
The elements x, y, z, k satisfy the following: 0≦x≦0.27 0.05≦y≦0.26 0.002≦z≦0.04 1.00≦k≦1.04 the additive components are B_2O_3, SiO_2, and MO (where MO is one or more oxides selected from BaO, SrO, CaO, MgO, and ZnO), and the B_2O_3 and the In a triangular diagram in which the composition range of SiO_2 and the MO is expressed in mol%, a first point indicates a composition in which the B_2O_3 is 1 mol%, the SiO_2 is 80 mol%, and the MO is 19 mol%. A, a second point B having a composition of 1 mol% of B_2O_3, 39 mol% of SiO_2, and 60 mol% of MO; 30 mol% of B_2O_3, 0 mol% of SiO_2, and 0 mol% of MO; A third point C has a composition of 70 mol% of the B_2O_3, a fourth point D has a composition of 90 mol% of the B_2O_3, 0 mol% of the SiO_2, and 10 mol% of the MO; Mol%, the SiO_2 is 10
a fifth point E showing a composition in which the MO is 0 mol %; the B_2O_3 is 20 mol % and the SiO_2 is 80 mol %;
mol %, and the MO is located within a region surrounded by six straight lines connecting in this order a sixth point F showing a composition of 0 mol %. 2. A step of preparing a mixture made of unsintered porcelain powder, a step of forming an unsintered porcelain sheet made of the mixture, and a lamination in which the unsintered porcelain sheet is sandwiched between at least two or more conductive paste films. a step of forming a product; a step of heat treating the laminate in a non-oxidizing atmosphere;
and heat treating the heat-treated laminate in an oxidizing atmosphere, wherein the mixture of the unsintered porcelain powder contains 100.0 parts by weight of the basic component and 0.2 to 5 parts by weight. The basic component is {(Ba_1_−_xCa_x)O}_k(Ti_1_
-_y_-_zZr_yR_z)O_2_-_z_/_
2 (However, R is Sc, Y, Gd, Dy, Ho, Er,
One or two selected from Yb, Tb, Tm and Lu
The elements x, y, z, k satisfy the following: 0≦x≦0.27 0.05≦y≦0.26 0.002≦z≦0.04 1.00≦k≦1.04 the additive components are B_2O_3, SiO_2, and MO (where MO is one or more oxides selected from BaO, SrO, CaO, MgO, and ZnO), and the B_2O_3 and the In a triangular diagram in which the composition range of SiO_2 and the MO is expressed in mol%, a first point indicates a composition in which the B_2O_3 is 1 mol%, the SiO_2 is 80 mol%, and the MO is 19 mol%. A, a second point B having a composition of 1 mol% of B_2O_3, 39 mol% of SiO_2, and 60 mol% of MO; 30 mol% of B_2O_3, 0 mol% of SiO_2, and 0 mol% of MO; A third point C has a composition of 70 mol% of the B_2O_3, a fourth point D has a composition of 90 mol% of the B_2O_3, 0 mol% of the SiO_2, and 10 mol% of the MO; Mol%, the SiO_2 is 10
a fifth point E showing a composition in which the MO is 0 mol %; the B_2O_3 is 20 mol % and the SiO_2 is 80 mol %;
A method for manufacturing a ceramic capacitor, characterized in that the MO is located within an area surrounded by six straight lines connecting in this order the sixth point F showing a composition of 0 mol %.