# Patent

## Title
Dielectric ceramic and ceramic electronic component

## Abstract

A dielectric ceramic contains a primary constituent represented by general formula (1): a[(SrbCa1−b)TiO3]−(1−a)[Bi2O3.nTiO2] (wherein a and b indicate molar amounts, and n indicates a molar ratio of TiO2 to Bi2O3), and a secondary constituent represented by general formula (2): xMgTiO3+yMnOm+zLn2O3 (wherein x, y, and z indicate weight per 100 parts by weight of the primary constituent, m is 1 to 2, and Ln is at least one of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er), wherein a, b, n, x, y, and z satisfy the expressions 0.88≦a≦0.92, 0.30≦b≦0.50, 1.8≦n≦3.0, 1.0≦x≦3.0, 0.1≦y≦2.0, and 0<z≦3.0. A ceramic electronic component including the dielectric ceramic is also disclosed.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to dielectric ceramics and ceramic electronic components. More particularly, the invention relates to dielectric ceramics with high dielectric constants and ceramic electronic components, such as single-layer capacitors, trimmer capacitors, and monolithic ceramic capacitors, including such dielectric ceramics.
2. Description of the Related Art
As the dielectric ceramic having a high dielectric constant, Japanese Unexamined Patent Application Publication No. 3-97669 discloses a dielectric ceramic containing strontium titanate (SrTiO3), lead titanate (PbTiO3), calcium titanate (CaTiO3), bismuth titanate (Bi2O3), titanium dioxide (TiO2), and tin oxide (SnO2) as primary constituents.
However, the dielectric ceramic described above has a disadvantage from the view of reduction of environmental pollution because is Pb contained in the composition.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a dielectric ceramic which maintains a high dielectric constant and a high Q factor, has excellent linearity in temperature characteristics, and minimizes the rate of change in dielectric constant with temperature, even without containing Pb. It is another object of the present invention to provide a ceramic electronic component including the dielectric ceramic.
The present inventor has carried out thorough research to achieve the objects described above and has obtained the following findings. That is, by using a primary constituent comprising (Sr.Ca)TiO3 and Bi2O3.TiO2, and further a secondary constituent comprising MgTiO3, MnOm, and Ln2O3, and furthermore, by setting molar ratios or specific ranges, and by using, as Ln, a lanthanide selected from the group consisting of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho) and erbium (Er), it is possible to obtain a dielectric constant of 300 or more and a Q factor of 1,000 or more, even if the composition does not contain Pb, and moreover, it is possible to minimize the rate of change in dielectric constant in the ordinary temperature range (−55° C. to 85° C.) (hereinafter referred to as “temperature coefficient”) within −2,000 ppm/° C.
The present invention has been achieved based on the findings described above. In one aspect of the present invention, a dielectric ceramic contains a primary constituent represented by general formula (1):

a[(SrbCa1-b)TiO3]−(1−a)[Bi2O3.nTiO2]

(wherein a and b indicate molar amounts, and n indicates the molar amount of TiO2 relative to Bi2O3), and a secondary constituent represented by general formula (2):

xMg.TiO3−yMnOm−zLn2O3

(wherein x, y, and z indicate weight amounts to 100 parts by weight of the primary constituent, m is 1 to 2, and Ln is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Er), wherein a, b, n, x, y and z satisfy 0.88≦a≦0.92, 0.30≦b≦0.50, 1.8≦n≦3.0, 1.0≦x≦3.0, 0.1 ≦y≦2.0, and 0<z≦3.0.

As a result of further research by the present inventor, it has been found that by adding TiO2 as a material for the secondary constituent so that the molar ratio of the element Ti to the element Ln is about 1.5 or less, the dielectric constant can be further improved without degrading the temperature characteristics.
Accordingly, the secondary constituent further preferably contains TiO2 in the dielectric ceramic of the present invention, and the TiO2 content is determined to satisfy the expression 0<p≦1.5, wherein p is the molar ratio of the element Ti to the element Ln in the secondary constituent.
As a result of still further research by the present inventor, it has been found that by adding silicon dioxide (SiO2) as a material for the secondary constituent at a weight ratio of about 1 or less to 100 parts by weight of the primary constituent, the firing temperature can be decreased without degrading the dielectric characteristics, and the mechanical strength can also be further improved.
Accordingly, the secondary constituent preferably further contains SiO2 in the dielectric ceramic of the present invention, and the SiO2 content is determined to satisfy the expression 0<w≲1 is satisfied, wherein w is the weight ratio of SiO2 to 100 parts by weight of the primary constituent.
In another aspect of the present invention, a ceramic electronic component of the present invention includes a dielectric object made of the dielectric ceramic and electrodes disposed on the surfaces of the object.
The dielectric ceramic of the present invention contains the primary constituent and the secondary constituent, and a, b, n, x, y, and z in general formulae (1) and (2) satisfy 0.88≦a≦0.92, 0.30≦b≦0.50, 1.8≦n≦3.0, 1.0≦x≦3.0, 0.1≦y≦2.0, and 0<z≦3.0. Consequently, even without containing Pb, the dielectric ceramic has a high dielectric constant, a high Q factor, excellent linearity in temperature characteristics, and a low rate of change in dielectric constant with temperature, and has strength sufficient for practical use.
By adding TiO2 as a material for the secondary constituent so that the molar ratio p of the element Ti to the element Ln in the secondary constituent satisfies the expression 0<p≲1.5, it is possible to further improve the dielectric constant without degrading the temperature characteristics.
By adding SiO2 as a material for the secondary constituent so that the weight ratio w of SiO2 to 100 parts by weight of the primary constituent satisfies the expression 0<w≲1, the firing temperature can be decreased, and moreover, the flexural strength can be further improved.
In the ceramic dielectric, the dielectric constant is 300 or more, the Q factor is 1,000 or more, and the temperature coefficient can be decreased to within −2,000 ppm/° C. Consequently, even if the dielectric ceramic object, i.e., the ceramic sintered compact, does not contain Pb, it is possible to easily fabricate ceramic electronic components, such as various ceramic capacitors, which have high quality, high dielectric constants, satisfactory temperature characteristics, and excellent mechanical strength.



BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a front view with a cutaway section of a single-layer capacitor which is a ceramic electronic component fabricated using a dielectric ceramic of the present invention.



DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments of the present invention will now be described below.
FIG. 1 is a front view with a cutaway section of a single-layer capacitor which is a ceramic electronic component fabricated using a dielectric ceramic of the present invention.
The single-layer capacitor includes a ceramic sintered compact 1, electrodes 2 disposed on the surfaces of the ceramic sintered compact 1, a pair of leads 4a and 4b electrically connected to the electrodes 2 with solder joints 3 therebetween, and an outer coating 5 composed of a resin.
In this embodiment, the dielectric ceramic constituting the ceramic sintered compact 1 contains a primary constituent represented by the following general formula (1) and a secondary constituent represented by the following general formula (2).

a[(SrbCa1-b)TiO3]−(1−a)[Bi2O3.nTiO2]  (1)

xMgTiO3−yMnOm−zLn2O3  (2)

In general formula (1), a indicates the molar amount of (SrbCa1-b)TiO3, b indicates the molar amount of Sr, and n indicates the molar ratio of TiO2 to Bi2O3. In general formula (2), x, y and z indicate the weight ratios to 100 parts by weight of the primary constituent, m is 1 to 2, and Ln is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er.
The dielectric ceramic composition (starting material composition) in the dielectric ceramic, is appropriately prepared so that a, b, n, x, y and z satisfy the following expressions (3) to (8), respectively.

0.88≦a≦0.92  (3)

0.30≦b≦0.50  (4)

1.8≦n≦3.0  (5)

1.0≦x≦3.0  (6)

0.1≦y≦2.0  (7)

0<z≦3.0  (8)

When the dielectric ceramic has such a composition, it is possible to easily fabricate a single-layer capacitor in which a high dielectric constant of 300 or more and a Q factor of 1,000 or more are maintained, and the temperature coefficient based on the capacitance at 20° C. in the temperature range of −55° C. to 85° C. can be decreased to within −2,000 ppm/° C., which has excellent linearity in temperature characteristics, and moreover which has mechanical strength sufficient for practical use.
The reasons for the limitations will be described in detail below.
(1) Molar Amount a
If the molar amount a of (SrbCa1−b)TiO3 is less than 0.88, the molar amount (1−a) of Bi2O3.nTiO2 exceeds 0.12. In such a case, the Q factor is less than 1,000 since the molar quantity of Bi2O3 is excessive, and hence it is not possible to obtain a dielectric ceramic composition with a high Q factor. On the other hand, if the molar amount a exceeds 0.92, the molar quantity of Bi2O3.nTiO2 is less than 0.08, and the temperature coefficient negatively deviates from −2,000 ppm/° C., thus degrading the temperature characteristics.
Therefore, the composition is prepared in this embodiment so that the molar amount a satisfies the expression 0.88≦a≦0.92.
(2) Molar Amount b
If the molar amount b of Sr is less than 0.30, the molar quantity of CaTiO3 becomes excessive. Consequently, the dielectric constant decreases to less than 300, and hence it is not possible to obtain a dielectric ceramic with a high dielectric constant. On the other hand, if the molar ratio b exceeds 0.50, since the molar quantity of SrTiO3 becomes excessive, the Q factor decreases to less than 1,000, and hence it is not possible to obtain a dielectric ceramic with a high Q factor.
Therefore, the composition in this embodiment is prepared so that the molar ratio b satisfies the expression 0.30≦b≦0.50.
(3) Molar Ratio n
If the molar ratio n of TiO2 to Bi2O3 is less than 1.8, the molar content of TiO2 becomes excessively low. Consequently, the dielectric constant decreases to less than 300, and hence it is not possible to obtain a dielectric ceramic with a high dielectric constant. On the other hand, if the molar ratio n exceeds 3.0, the molar quantity of TiO2 increases excessively. Consequently, the Q factor decreases to less than 1,000, and hence it is not possible to obtain a dielectric ceramic with a high Q factor.
Therefore, the composition in this embodiment is prepared so that the molar ratio n satisfies the expression 1.8≦n≦3.0.
(4) Weight Ratio x
If the weight x of MgTiO3 to 100 parts by weight of the primary constituent represented by general formula (1) is less than 1.0, the temperature coefficient negatively deviates from −2,000 ppm/° C., thus degrading the temperature characteristics. On the other hand, if the weight ratio x exceeds 3.0, the dielectric constant decreases to less than 300, and hence it is not possible to obtain a dielectric ceramic with a high dielectric constant.
Therefore, the composition is prepared in this embodiment so that the weight x satisfies the expression 1.0≦x≦3.0.
(5) Weight y
If the weight y of MnOm (wherein m is 1 to 2) to 100 parts by weight of the primary constituent represented by general formula (1) is less than 0.1, the temperature coefficient negatively deviates from −2,000 ppm/° C., thus degrading the temperature characteristics. On the other hand, if the weight y exceeds 2.0, the dielectric constant decreases to less than 300, and hence it is not possible to obtain a dielectric ceramic with a high dielectric constant.
Therefore, the composition in this embodiment is prepared so that the weight ratio y satisfies the expression 0.1≦y≦2.0.
(6) Weight Ratio z
By adding Ln2O3, as a material for the secondary constituent, to the primary constituent represented by general formula (1), the temperature characteristics and the flexural strength can be improved. If the weight z to 100 parts by weight of the principal constituent exceeds 3.0, the dielectric constant decreases to less than 300, and hence it is not possible to obtain a dielectric ceramic with a high dielectric constant.
Therefore, the composition is prepared in this embodiment so that the weight ratio z satisfies the expression 0<z≦3.0.
(7) Ln
By limiting Ln to specific elements selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er in the lanthanoide series, and by adding the specific elements in the form of Ln2O3 so that the weight z to 100 parts by weight of the principal constituent satisfies the expression 0<z≦3.0, it is possible to obtain a dielectric ceramic with excellent dielectric characteristics in which the dielectric constant is 300 or more, the Q factor is 1,000 or more, and the temperature coefficient can be minimized to within −2,000 ppm/° C., and moreover, with excellent mechanical strength in which the flexural strength is 130 MPa or more.
When an element other than the specific elements described above, for example, Yb or Y, is added, at least one of the dielectric constant and the Q factor is decreased, and it is not possible to obtain a dielectric ceramic having a desired high dielectric constant and high quality factor.
Therefore, the specific lanthanide is added in this embodiment, as a material for the secondary constituent, to the dielectric ceramic.
Next, a method for fabricating the single-layer capacitor will be described.
First, the dielectric ceramic is prepared.
That is, SrCO3, CaCO3, Bi2O3, TiO2, MgTiO3, MnCO3 and Ln2O3 (wherein Ln is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er) are weighed so that the primary constituent and the secondary constituent represented by general formulae (1) and (2) satisfy the expressions (3) to (8), and the weighed materials are mixed. The resultant mixture is placed into a pot together with grinding media, such as zirconia, and wet mixing and pulverization are performed for a predetermined period of time. The pulverized mixture is subjected to evaporation drying and then placed in a sagger composed of zirconia, and calcination is performed at 900 to 1,000° C. for about 2 hours. A raw dielectric ceramic powder is thereby prepared.
Next, the raw dielectric ceramic powder together with a binder, such as polyvinyl alcohol, is placed into a pot, and wet mixing is performed for a predetermined period of time. The resultant mixture is dehydrated and dried, and particle size regulation is performed. The mixture is formed into a predetermined disk by application of pressure to prepare a ceramic green compact. The ceramic green compact is then fired at 1,180 to 1,280° C. for 2 hours to produce a dielectric ceramic, i.e., a ceramic sintered compact 1.
A conductive paste containing Ag or the like as a primary constituent is applied to both surfaces of the dielectric ceramic sintered compact 1, followed by baking to form electrodes 2.
The electrodes 2 and leads 4a and 4b are connected to each other with solder joints 3 therebetween, and an outer coating 5 is formed by resin molding. A single-layer capacitor is thereby fabricated.
Since the primary constituent and the secondary constituent represented by general formulae (1) and (2) in the dielectric ceramic in this embodiment satisfy the expressions (3) to (8), it is possible to easily fabricate a Pb-free single-layer capacitor which has a high dielectric constant, a high quality factor, and excellent temperature characteristics, and which has strength sufficient for practical use.
It is to be understood that the present invention is not limited to the embodiment described above.
For example, it is possible to improve the dielectric constant by approximately 5% to 10% without degrading the temperature characteristics by incorporating TiO2 into the secondary constituent.
However, the TiO2 content must be adjusted so that the molar ratio p of the element Ti to the element Ln (=Ti/Ln) is about 1.5 or less. The reason for this is that, there is a possibility that the dielectric constant may be decreased if the molar ratio p exceeds about 1.5.
Preferably, a secondary constituent represented by the following general formula (9), instead of general formula (2), together with the primary constituent is incorporated into the dielectric ceramic.

xMgTiO3−yMnOm(wherein m=1 to 2)−zLn2O3−wSiO2  (9)

Herein, w is the weight of SiO2 to 100 parts by weight of the primary constituent, and the expression 0<w≦1.0 is satisfied.

By incorporating SiO2 so that the weight w is about 1 or less, it is possible to decrease the firing temperature without adversely affecting the dielectric characteristics since SiO2 functions as a sintering aid.
Moreover, by incorporating SiO2 at a weight w of about 1 or less as a material for the secondary constituent into the dielectric ceramic, the mechanical strength can be further improved. Such an improvement in mechanical strength is particularly useful for trimmer capacitors. When a trimmer capacitor is fabricated, the surface of the dielectric unit is polished to decrease the thickness, and then assembly is performed by mechanical caulking. In such a case, defects, such as cracks and chips, easily occur if the mechanical strength, i.e., flexural strength, of the dielectric unit is low. Therefore, preferably, the flexural strength is improved in the range in which the dielectric characteristics, etc., are not impaired.
From such a viewpoint, SiO2 is preferably incorporated into the dielectric ceramic as a material for the secondary constituent at a weight w of about 1 or less, and by incorporating SiO2, the flexural strength can be further improved, and a ceramic electronic component with excellent strength can be fabricated.
In the embodiment described above, carbonates, such as SrCO3 and CaCO3, and TiO2 are used as materials for the primary constituent. Titanate compounds, such as SrTiO3 and CaTiO3, may also be used as materials for the primary constituent to form the dielectric ceramic.
Additionally, the same advantageous effects as those in the embodiment described above are obtained with respect to other various types of ceramic electronic components, such as monolithic ceramic capacitors.
The present invention will now be described based on the specific examples.
EXAMPLE 1
In each of Samples 1 to 26, as materials for the primary constituent, SrCO3, CaCO3, Bi2O3, and TiO2 were first weighed so that a was 0.87 to 0.93, b was 0.25 to 0.55, and n was 1.50 to 3.20. Furthermore, MgTiO3, MnCO3, and La2O3 as materials for the secondary constituent, were weighed so that x was 0.50 to 5.00, y was 0.00 to 3.00, and z was 0.00 to 4.00. The materials for the primary constituent and the materials for the secondary constituent were mixed. The resultant mixture was placed into a polyethylene pot together with zirconia balls (grinding media), and wet mixing and pulverization were performed for 16 hours. The pulverized mixture was subjected to evaporation drying and then placed in a sagger composed of zirconia, and calcination was performed at 950° C. for 2 hours. A calcine (i.e., raw dielectric ceramic powder) was thereby prepared.
Next, the calcine together with polyvinyl alcohol (binder) was placed into a polyethylene pot, and wet mixing was performed for 16 hours to prepare a mixture.
The mixture was dehydrated and dried, and particle size regulation was performed. The mixture was formed into a disk with a diameter of 12 mm and a thickness of 1.2 mm by application of pressure to prepare a ceramic green compact. The ceramic green compact was then fired at 1,230 to 1,260° C. for 2 hours to produce a ceramic sintered compact (i.e., dielectric ceramic). Next, an Ag paste was applied to both surfaces of the ceramic sintered compact, followed by baking to form electrodes. Single-layer capacitors of Samples 1 to 26 were thereby fabricated.
Table 1 shows the compositions for the individual samples.










TABLE 1









a(SrbCa1−b)TiO3 −




(1−a)[Bi2O3.nTiO2]
xMgTiO3 + yMnOm + zLa2O3















Sample
a
b
n
x
y
z



















 1*
0.87
0.45
2.00
1.00
0.20
1.50



 2
0.90
0.45
2.00
2.00
0.20
2.00



 3*
0.93
0.45
2.00
2.00
1.00
3.00



 4*
0.91
0.25
2.00
1.50
0.80
1.00



 5
0.88
0.35
2.00
2.00
1.50
3.00



 6
0.92
0.50
2.00
2.50
0.50
1.50



 7
0.89
0.40
3.00
1.00
0.20
2.00



 8*
0.90
0.55
2.00
1.00
0.80
2.50



 9*
0.92
0.45
1.50
2.00
1.20
1.00



10
0.92
0.30
1.80
1.50
0.30
2.00



11
0.88
0.50
2.00
2.50
1.80
2.00



12
0.90
0.40
2.50
1.00
2.00
3.00



13
0.91
0.45
3.00
2.00
0.30
1.00



14*
0.92
0.40
3.20
2.00
0.50
2.50



15*
0.92
0.40
2.25
0.50
1.00
1.50



16
0.90
0.35
2.00
2.00
0.20
2.00



17*
0.89
0.45
2.00
4.00
0.50
1.00



18*
0.92
0.40
2.00
5.00
0.30
1.00



19*
0.92
0.35
3.00
1.50
0.00
2.00



20
0.91
0.50
3.00
2.50
0.20
1.50



21*
0.90
0.45
2.00
1.00
2.10
3.00



22*
0.92
0.35
2.00
1.50
3.00
1.00



23*
0.91
0.30
2.00
2.00
0.30
0.00



24
0.92
0.45
2.00
2.00
0.80
0.10



25
0.92
0.40
3.00
2.50
1.50
0.50



26*
0.89
0.45
2.00
2.00
0.20
4.00







*Out of the ranges of the present invention 






Next, the dielectric constant ε and the Q factor were measured at a temperature of 20° C., a frequency of 1 MHz and a voltage of 1 V with respect to the single-layer capacitor of each of Samples 1 to 26. The rate of change in dielectric constant ε based on the capacitance at 20° C. in the temperature range of −55° C. to 85° C. was measured, and the maximum rate of change was calculated as the temperature coefficient.
With respect to each of Samples 1 to 26, a ceramic plate (25 mm by 6 mm; 1 mm thick) was obtained by firing. The ceramic plate was placed on two supports 20 mm apart, and a load was applied at the center at a rate of 0.5 mm/sec to measure the flexural strength, and the mechanical strength was thereby evaluated.
Table 2 shows the results thereof.












TABLE 2








Temperature
Firing
Flexural



Dielectric
Q factor
coefficient
Temperature
strength


Sample
constant ∈ (−)
(−)
(ppm/° C.)
(° C.)
(MPa)




















 1*
380
500
−1100
1230
150


 2
360
1050
−1400
1240
140


 3*
330
2320
−2400
1250
130


 4*
280
3500
−1350
1240
150


 5
350
1500
−1200
1230
150


 6
330
1200
−1850
1250
140


 7
360
1300
−1400
1230
140


 8*
380
850
−1800
1240
140


 9*
260
1500
−1900
1260
140


10
310
3000
−1850
1250
150


11
380
1050
−1200
1230
140


12
360
1800
−1500
1240
140


13
350
1800
−1700
1240
130


14*
320
900
−1800
1250
140


15*
310
1500
−2200
1260
140


16
320
2500
−1400
1240
140


17*
290
1500
−1350
1240
140


18*
250
1200
−1600
1250
140


19*
310
3500
−2100
1240
150


20
330
1200
−1900
1250
140


21*
290
1100
−1800
1240
140


22*
230
4000
−1200
1250
140


23*
300
3300
−2100
1240
130


24
350
1100
−1600
1240
140


25
310
1100
−1700
1240
140


26*
285
1100
−1200
1230
140





*Out of the ranges of the present invention 






As is evident from Tables 1 and 2, since a is too small with respect to Sample 1 at 0.87, the Q factor is small at 500. With respect to Sample 3, a is too large at 0.93, and the temperature coefficient is −2,400 ppm/° C. with a large negative deviation, and thus temperature characteristics are degraded.
With respect to Sample 4, since b is too small at 0.25, the dielectric constant is small at 280. With respect to Sample 8, since b is too large at 0.55, the Q factor is small at 850.
With respect to Sample 9, since n is too small at 1.50, the dielectric constant is small at 260. With respect to Sample 14, since n is too large at 3.20, the Q factor is small at 900.
With respect to Sample 15, since x is too small at 0.50, the temperature coefficient is −2,200 ppm/° C. with a large negative deviation, and thus temperature characteristics are degraded. With respect to Samples 17 and 18, since the x values are too large at 4.00 and 5.00, the dielectric constants are low at 290 and 250, respectively.
With respect to Sample 19, the temperature coefficient is −2,100 ppm/° C. with a large negative deviation since MnOm is not incorporated in the secondary constituent, and thus temperature characteristics are degraded. With respect to Samples 21 and 22, since the y amounts are too large at 2.10 and 3.00, the dielectric constants are low at 290 and 230, respectively.
With respect to Sample 23, the temperature coefficient is −2,100 ppm/° C. with a large negative deviation since La2O3 is not incorporated in the secondary constituent, and thus temperature characteristics are degraded. With respect to Sample 26, since z is too large at 4.00, the dielectric constant is low at 285.
In contrast, as seen with respect to each of Samples 2, 5 to 7, 10 to 13, 16, 20, 24, and 25, since all of the molar values a, b and n, and the weight values x, y and z are set so as to be in the ranges of the present invention, the dielectric constant is 300 or more, the Q factor is 1,000 or more, and moreover, the temperature coefficient is decreased to within −2,000 ppm/° C., and thus temperature characteristics with excellent linearity is exhibited.
Moreover, the flexural strength is 130 MPa or more, and thus the mechanical strength is sufficient for practical use.
EXAMPLE 2
The materials for the primary constituent and the materials for the secondary constituent were selected as in Sample 2 (shown in Table 1), and TiO2 was weighed so that the molar ratio p of the element Ti to the element La (=Ti/La) was 0.5 to 1.8, and a single-layer capacitor for each of Samples 31 to 34 was fabricated as in EXAMPLE 1.










TABLE 3









a(SrbCa1−b)TiO3 −




(1−a)[Bi2O3.nTiO2]
xMgTiO3 + yMnOm + zLa2O3














Sample
a
b
n
x
y
z
p

















31
0.90
0.45
2.00
2.00
0.20
2.00
0.50


32
0.90
0.45
2.00
2.00
0.20
2.00
1.00


33
0.90
0.45
2.00
2.00
0.20
2.00
1.50


34
0.90
0.45
2.00
2.00
0.20
2.00
1.80









Next, the dielectric constant, the Q factor, the temperature coefficient, and the flexural strength were measured as in EXAMPLE 1 with respect to the single-layer capacitor of each of Samples 31 to 34.
Table 4 shows the results thereof.












TABLE 4








Temperature
Firing
Flexural



Dielectric
Q factor
coefficient
Temperature
strength


Sample
constant ∈ (−)
(−)
(ppm/° C.)
(° C.)
(MPa)




















31
365
1200
−1400
1240
140


32
380
1000
−1400
1240
140


33
360
1100
−1350
1240
140


34
350
1300
−1350
1240
130









As is evident from Tables 3 and 4, TiO2 is incorporated so that the molar ratio p is 0.50 in Sample 31, and TiO2 is incorporated so that the molar ratio p is 1.00 in Sample 32. Consequently, the dielectric constants are improved to 365 and 380, respectively, compared to Sample 2 (dielectric constant: 360) in which TiO2 is not incorporated.
In Sample 33, TiO2 is incorporated so that the molar ratio p is 1.50, and the dielectric constant was the same as that of Sample 2.
Although TiO2 is added as a material for the secondary constituent with respect to Sample 34, since the molar ratio p is large at 1.80 and the molar quantity of TiO2 is too large, the dielectric constant is 350, which is lower than the dielectric constant in Sample 2 in which TiO2 is not added.
As is evident from the results described above, adding TiO2 so that the molar ratio p satisfies the expression 0<p≲1.5 results in an improvement in dielectric constant compared to a case in which TiO2 is not added.
EXAMPLE 3
Various single-layer capacitors were fabricated with different additive elements in Ln2O3 in general formula (2), n, and p, and various characteristics were evaluated as in EXAMPLE 1.
That is, as materials for the primary constituent, SrCO3, CaCO3, Bi2O3, and TiO2 were weighed so that a was 0.92, b was 0.50, and n was 2.00. Furthermore, as materials for the secondary constituent, MgTiO3, MnCO3, and Ln2O3 (wherein Ln was Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho or Er) were weighed so that the weight x was 2.00, the weight y was 0.20, and the weight z was 2.00. Each of Samples 41 to 49 was prepared as in Example 1. Additionally, ceramic sintered compacts were obtained at a firing temperature of 1,250° C. in Samples 41 to 49.
In addition to the materials for the primary constituent and the materials for secondary constituent described above (wherein Ln was Ce, Gd, or Er), TiO2, as a material for the secondary constituent, was weighed so that the molar ratio p of the element Ti to the element Ln (=Ti/Ln) was 1.00, and each of Samples 50 to 52 was prepared as in EXAMPLE 1. Additionally, ceramic sintered compacts were obtained at a firing temperature of 1,240° C. in Samples 50 to 52.
A single-layer capacitor of Sample 53 was fabricated as in Samples 41 to 49 except that ytterbium (Yb) was used as Ln. A single-layer capacitor of Sample 54 was also fabricated as in Samples 41 to 49 except that yttrium (Y) was used as Ln.
Furthermore, single-layer capacitors of Samples 55 to 63 were fabricated as in Samples 41 to 49 by using the lanthanides of the present invention as Ln and by setting z at 4.00. Additionally, in Samples 55 to 63, ceramic sintered compacts were obtained at firing temperatures of 1,220 to 1,250° C.
Table 5 shows the compositions for Samples 41 to 63.










TABLE 5









a(SrbCa1 − b)TiO3 −




(1 − a)[Bi2O3.nTiO2]
xMgTiO3 + yMnOm + zLn2O3















Sample
a
b
n
x
y
z
Ln
p


















41
0.92
0.50
2.00
2.00
0.20
2.00
Ce
0.00


42
0.92
0.50
2.00
2.00
0.20
2.00
Pr
0.00


43
0.92
0.50
2.00
2.00
0.20
2.00
Nd
0.00


44
0.92
0.50
2.00
2.00
0.20
2.00
Sm
0.00


45
0.92
0.50
2.00
2.00
0.20
2.00
Eu
0.00


46
0.92
0.50
2.00
2.00
0.20
2.00
Gd
0.00


47
0.92
0.50
2.00
2.00
0.20
2.00
Dy
0.00


48
0.92
0.50
2.00
2.00
0.20
2.00
Ho
0.00


49
0.92
0.50
2.00
2.00
0.20
2.00
Er
0.00


50
0.92
0.50
2.00
2.00
0.20
2.00
Ce
1.00


51
0.92
0.50
2.00
2.00
0.20
2.00
Gd
1.00


52
0.92
0.50
2.00
2.00
0.20
2.00
Er
1.00


53*
0.92
0.50
2.00
2.00
0.20
2.00
Yb
0.00


54*
0.92
0.50
2.00
2.00
0.20
2.00
Y
0.00


55*
0.92
0.50
2.00
2.00
0.20
4.00
Ce
0.00


56*
0.92
0.50
2.00
2.00
0.20
4.00
Pr
0.00


57*
0.92
0.50
2.00
2.00
0.20
4.00
Nd
0.00


58*
0.92
0.50
2.00
2.00
0.20
4.00
Sm
0.00


59*
0.92
0.50
2.00
2.00
0.20
4.00
Eu
0.00


60*
0.92
0.50
2.00
2.00
0.20
4.00
Gd
0.00


61*
0.92
0.50
2.00
2.00
0.20
4.00
Dy
0.00


62*
0.92
0.50
2.00
2.00
0.20
4.00
Ho
0.00


63*
0.92
0.50
2.00
2.00
0.20
4.00
Er
0.00





*Out of the ranges of the present invention 






Next, the dielectric constant, the Q factor, the temperature coefficient, and the flexural strength were measured as in EXAMPLE 1.
Table 6 shows the results thereof.












TABLE 6








Temperature
Firing
Flexural



Dielectric
Q factor
coefficient
Temperature
strength


Sample
constant ∈ (−)
(−)
(ppm/° C.)
(° C.)
(MPa)




















41
350
1360
−1600
1250
140


42
350
1100
−1650
1250
140


43
350
1100
−1600
1250
140


44
350
1250
−1700
1250
140


45
350
1250
−1650
1250
140


46
350
1250
−1600
1250
140


47
330
1270
−1600
1250
140


48
340
1200
−1650
1250
140


49
340
1130
−1700
1250
140


50
370
1000
−1350
1240
140


51
360
1100
−1300
1240
140


52
350
1100
−1200
1240
140


53*
360
900
−1800
1250
140


54*
290
1370
−1600
1250
140


55*
280
2100
−1100
1220
150


56*
280
2100
−1050
1220
150


57*
290
2000
−1300
1250
150


58*
280
2100
−1350
1250
150


59*
270
2000
−1050
1220
150


60*
280
2200
−1400
1250
150


61*
260
2000
−950
1220
150


62*
280
2300
−1450
1250
150


63*
270
2000
−1500
1250
150





*Out of the ranges of the present invention 






As is evident from Tables 5 and 6, since Yb, which is out of the range of the present invention, is added in Sample 53, the Q factor is small at 900. In Sample 54, since Y, which is out of the range of the present invention, is added, the dielectric constant is low at 290, and it is not possible to obtain a ceramic electronic component with a high dielectric constant.
Although lanthanides of the present invention are added in Samples 55 to 63, since the Ln2O3 content is high at a weight z of 4.0, the dielectric constant is low at 260 to 290, and it is not possible to obtain a ceramic electronic component with a high dielectric constant.
In contrast, since Ce, Pr, Nd, Sm, Eu, Dy, Ho, or Er is used as Ln, and since the weight ratio z is set to be 2.00, the dielectric constant is 300 or more, the Q factor is 1,000 or more, and the temperature coefficient can be controlled within −2,000 ppm/° C. in Samples 41 to 52.
In particular, since TiO2 in Samples 50 to 52 is added so that molar ratio p (=Ti/Ln) is 1.00, it is possible to obtain a dielectric ceramic with a higher dielectric constant compared to Samples 41, 46, and 49 in which TiO2 is not incorporated.
EXAMPLE 4
SiO2 was further added as a material for the secondary constituent, and the advantageous effect of SiO2 was confirmed.
In addition to the composition of Sample 2 (shown in Table 1), SiO2 was added so that the weight w to 100 parts by weight of the primary constituent was 0.50, and a single-layer capacitor of Sample 71 was fabricated as in EXAMPLE 1.
Furthermore, TiO2 was added as a material for the secondary constituent so that the molar ratio p was 1.00 in addition to the materials for the primary constituent and the materials for the secondary constituent of Sample 71, and a single-layer capacitor of Sample 72 was fabricated as in EXAMPLE 1.
Next, SiO2 was added in the composition of Sample 5 (shown in Table 1) so that the weight w to 100 parts by weight of the primary constituent was 1.00, and a single-layer capacitor of Sample 73 was fabricated as in EXAMPLE 1.
Furthermore, TiO2 was added as a material for the secondary constituent in the materials for the primary constituent and the materials for the secondary constituent of Sample 73 so that the molar ratio p was 1.00, and a single-layer capacitor of Sample 74 was fabricated as in EXAMPLE 1.
Table 7 shows the compositions of Samples 71 to 74.










TABLE 7









a[(SrbCa1 − b)TiO3] −
xMgTiO3 + yMnOm + zLa2O3 +



(1 − a)[Bi2O3.nTiO2]
wSiO2















Sam-










ple
a
b
n
x
y
z
w
p


















71
0.90
0.45
2.00
2.00
0.20
2.00
0.50
0.00


72
0.90
0.45
2.00
2.00
0.20
2.00
0.50
1.00


73
0.88
0.35
2.00
2.00
1.50
3.00
1.00
0.00


74
0.88
0.35
2.00
2.00
1.50
3.00
1.00
1.00









Next, the dielectric constant, the Q factor, the temperature coefficient, and the flexural strength were measured as in EXAMPLE 1.
Table 8 shows the results thereof.












TABLE 8








Temperature
Firing
Flexural



Dielectric
Q factor
coefficient
Temperature
strength


Sample
constant ∈ (−)
(−)
(ppm/° C.)
(° C.)
(MPa)




















71
355
1200
−1500
1230
160


72
390
1000
−1600
1220
150


73
330
1800
−1350
1210
160


74
350
1600
−1400
1200
160









As is evident from Tables 7 and 8, with Sample 71 in which the firing temperature is 1,230° C. and the flexural strength is 160 MPa, it is possible to decrease the firing temperature and to improve the flexural strength compared to Sample 2 (firing temperature: 1,240° C.; flexural strength: 140 MPa) in which SiO2 is not incorporated.
With respect to Sample 73, in which the firing temperature is 1,210° C. and the flexural strength is 160 MPa, it is possible to decrease the firing temperature and to improve the flexural strength compared to Sample 5 (firing temperature: 1,230° C.; flexural strength: 150 MPa) in which SiO2 is not incorporated.
(?) In Sample 72, in which TiO2 is added so that the molar ratio p is 1.00, the dielectric constant is improved to 390 compared to Sample 71 (dielectric constant: 355) in which TiO2 is not incorporated.
Since TiO2 is added so that the molar ratio p is 1.00 with respect to Sample 74, the dielectric constant is improved to 350 compared to Sample 73 (dielectric constant: 330) in which TiO2 is not incorporated.

## Claims

1. A dielectric ceramic comprising:
a primary constituent represented by general formula (1): 


a[(SrbCa1-b)TiO3]−(1−a)[Bi2O3.nTiO2]



(wherein a and b indicate molar amounts, and n indicates a molar ratio of TiO2 to Bi2O3); and
a secondary constituent represented by general formula (2): 


xMgTiO3−yMnOm−zLn2O3 



(wherein x, y, and z indicate weight amounts per 100 parts by weight of the primary constituent, m is 1 to 2, and Ln is at least one element selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho and Er), and
wherein a, b, n, x, y, and z satisfy the expressions 


0.88≦a≦0.92, 



0.3≦b≦0.5, 



1.8≦n≦3, 



1≦x≦3, 



0.1≦y≦2, and 



0<z≦3.

2. A dielectric ceramic according to claim 1, wherein the secondary constituent further comprises TiO2, and the TiO2 content is such as to satisfy the expression 0<p≦1.5, wherein p is the molar ratio of the element Ti to the element Ln in the secondary constituent.

3. A dielectric ceramic according to claim 2, wherein p is 0.5 to 1.5.

4. A dielectric ceramic according to claim 3, wherein the secondary constituent further comprises SiO2, and the SiO2 content is such as to satisfy the expression 0<w≦1, wherein w is the weight of SiO2 per 100 parts by weight of the primary constituent.

5. A dielectric ceramic according to claim 4, wherein w is 0.5 to 1.

6. A dielectric ceramic according to claim 5, wherein Ln is La.

7. A dielectric ceramic according to claim 6, wherein b is 0.45 to 0.5, x is 1 to 2.5, y is 0.2 to 2 and z is 0.2 to 2.

8. A dielectric ceramic according to claim 1, wherein the secondary constituent further comprises SiO2, and the SiO2 content is such as to satisfy the expression 0<w≦1, wherein w is the weight of SiO2 per 100 parts by weight of the primary constituent.

9. A dielectric ceramic according to claim 8, wherein w is 0.5 to 1.

10. A dielectric ceramic according to claim 1, wherein Ln is La.

11. A dielectric ceramic according to claim 1, wherein b is 0.45 to 0.5, x is 1 to 2.5, y is 0.2 to 2 and z is 0.2 to 2.

12. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 10; and 
electrodes disposed on the surfaces of the object.

13. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 8; and 
electrodes disposed on the surfaces of the object.

14. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 7; and 
electrodes disposed on the surfaces of the object.

15. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 6; and 
electrodes disposed on the surfaces of the object.

16. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 5; and 
electrodes disposed on the surfaces of the object.

17. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 4; and 
electrodes disposed on the surfaces of the object.

18. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 3; and 
electrodes disposed on the surfaces of the object.

19. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 2; and 
electrodes disposed on the surfaces of the object.

20. A ceramic electronic component comprising:
an object comprising a dielectric ceramic according to claim 1; and 
electrodes disposed on the surfaces of the object.