# Patent

## Title
Nonreducible dielectric ceramic composition

## Abstract

Disclosed is a nonreducible dielectric composition. Provided is a highly reliable TC based dielectric composition prepared by adding a sintering additive having excellent qualities to a conventional (Ca1-xSrx)m(Zr1-yTiy)O3 based dielectric composition, so that it can be sintered under a reducing atmosphere to be used in formation of a nickel electrode, can be sintered at a temperature of less than 1,300° C., and even more, at a low temperature of 1,250° C., and has a small dielectric loss and a high resistivity. The composition of the present invention includes a nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which has the ranges of 0≦x≦1, 0≦y<0.09, and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, aMnO-bSiO2-dR1O-eR2O2 (a+b+d+e=100, R1 is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and R2 is at least one element of Zr and Ti), which has the ranges of 20≦a≦60, 10≦b≦65, and 0<(d+e)≦65.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a nonreducible dielectric composition to be applied to a laminated ceramic capacitor for temperature compensation, and the like, and more particularly, to a nonreducible dielectric composition having a high insulation resistance and a small dielectric loss, which can be sintered under a reducing atmosphere using an internal electrode containing nickel (Ni).
2. Description of the Related Art
Demand for laminated ceramic capacitors is increasing yearly due to digitalization, miniaturization and high-functionalization of electronic products, and they have been used in a variety of electronic devices such as televisions, computers, video cameras, cellular phones and the like. In recent years, there has been an increased need for a laminated ceramic capacitor having excellent characteristics, that is, a high insulation resistance, a small dielectric loss, and a reduced variation in capacitance upon a variation in temperature.
A conventional laminated ceramic capacitor was manufactured by sintering a high-priced noble metal such as palladium (Pd) or silver-palladium (Ag—Pd) alloy including palladium as an internal electrode, and a BaO—Nd2O3—TiO2— or MgTiO3—CaTiO3—based dielectric composition under an atmosphere of 1,100-1,350° C. However, there have been problems in that due to oxygen vacancies formed when sintered under a reducing atmosphere, the composition exhibits a lowered insulation resistance and a degraded reliability, and thus Ni cannot be employed as an internal electrode.
In order to use nickel as an internal electrode, such a composition must be able to be sintered under a reducing atmosphere. Known up until now has been a CSZT based composition disclosed in Japanese Patent Laid-Open Publication No. 10-335169. The composition consists of a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which meets the conditions: 0≦x≦1, 0≦y≦0.1 and 0.75≦m≦1.04; and a minor component of BCG: 0.5-15 mol %, MnO: 0.2-5 mol %, Al2O3: 0.1-10 mol % (on the basis of the total moles of the main component) and a rare earth element.
The composition disclosed in the above publication has advantages of nonreducibiliy and a reduced variation in capacitance upon a variation in temperature. Furthermore, the composition overcomes a large dielectric loss at high temperature-low frequency condition encountered in lithium glass (Li-glass) based composition. Also, the composition is characterized in that uniform and small grain size can be obtained.
In spite of these advantages, in the above composition, the sintering temperature of dielectric is as high as 1,300° C., and the sintering initiating temperature of dielectric is higher than that of Ni used for an internal electrode. As a result, there is a problem in that cracks, defects or the like are caused by mismatching between the internal electrode and ceramic. This is because the metal of the electrode exhibits a shrinkage rate higher than that of ceramic during the sintering process.
Meanwhile, Japanese Patent Laid-Open Publication No. 63-289709 discloses a composition consisting of a main component, (CaxSr1-x)m(ZryTi1-y)O3 (0.3≦x≦0.5, 0.92≦y≦0.98, and 0.95≦m≦1.08) and a minor component, MnO2(0.01-4.0 wt %) and SiO2(2.0-8.0 wt %), the composition being sinterable under a reducing atmosphere. The dielectric constant of Ca/Sr in the composition is relatively high, below 1.
Nevertheless, the above composition still has a problem in that a dielectric loss at high temperature—low frequency condition is large. Furthermore, the composition involves generation of defects by mismatching between electrode metal and ceramic during a sintering process, because sintering temperature of ceramic is high, up to 1,300° C.
SUMMARY OF THE INVENTION
Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a highly reliable dielectric composition prepared by adding a sintering additives having excellent qualities to a conventional (Ca1-xSrx)m(Zr1-yTiy)O3 based dielectric composition, so that it can be sintered under a reducing atmosphere to be used in formation of a nickel electrode, can be sintered at a temperature of less than 1,300° C., and even more, at a low temperature of 1,250° C., and has a small dielectric loss and a high resistivity.
Another abject of the present invention is to provide a dielectric composition meeting COG/CH characteristics in accordance with the EIA (Electric Industry Association) Standard.
In accordance with one aspect of the present invention, there is provided a nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which has the ranges of 0≦x≦1, 0≦y<0.09, and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, aMnO-bSiO2-cAl2O3 (a+b+c=100), which has the ranges of 20≦a≦60, 10≦b≦65, and 1≦c≦10.
In accordance with another aspect of the present invention, there is provided a nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which has the ranges of 0≦x≦1, 0≦y≦0.09, and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, bSiO2-cAl2O3-dR1O (b+c+d=100, R1 is at least one element selected from the group consisting of Mg, Ca, Sr and Ba), which has the ranges of 10≦b≦65, 0≦c≦10 and 0≦d≦50.
In accordance with still another aspect of the present invention, there is provided a nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which has the ranges of 0≦x≦1, 0≦y<0.09, and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, aMnO-bSiO2-dR1O-eR2O2 (a+b+d+e=100, R1 is one or two elements of Mg, Ca, Sr and Ba, and R2 is at least one of Zr and Ti), which has the ranges of 20≦a≦60, 10≦b≦65, and 0<(d+e)≦65.
Finally, in accordance with yet another aspect of the present invention, there is provided a nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3 which has the ranges of 0≦x≦1, 0≦y<0.09, and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, bSiO2-dR1O-eR2O2 (b+d+e=100, R1 is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and R2 is one of Zr and Ti), which has the ranges of 10≦b≦65, 10≦d≦20, and 10≦e≦60.


DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the nonreducible dielectric composition in accordance with the present invention will be described in detail.
The present invention relates to a nonreducible dielectric composition in which its main component is expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3. In accordance with the present invention, it is required that x, y and m meet the conditions of 0≦x≦1, 0≦y<0.09, and 0.7≦m≦1.05, using conventionally available materials.
The subscript x in the main component is within the range of 0≦x≦1. That is, the composition may contain any mixture of Ca and Sr, or only one element of both of them. The higher the value of x, i.e., the higher the proportion of Sr, the larger the mean grain size of crystals becomes and the more the dielectric constant increases. In order to obtain a smaller sintered grain size, preferred range of x is less than 0.5.
The subscript y in the main component is within the range of 0≦y<0.09. A temperature coefficient of capacitance and a dielectric constant depend on the y value. The higher the value of y, the more negative the temperature coefficient of capacitance becomes and the more the dielectric constant increases. In order to obtain a COG/CH based dielectric composition in accordance with the present invention, the composition range of y is limited to less than 0.09. As a result, a composition can be obtained that meets the requirement of −30 ̃+30 ppm/° C. for a temperature coefficient of capacitance as COG characteristics used for capacitor for thermal compensation or the requirement of −60 ̃+60 ppm/° C. for a temperature coefficient of capacitance as CH characteristics used for capacitor for thermal compensation.
The subscript m of the main component is within the range of 0.7≦m≦1.05. Undesirably, however, if m is less than 0.7, the dielectric loss increases, and if m exceeds 1.05, sintering temperature rises.
A minor component is also included in the dielectric composition of present invention. The minor component is added as a sintering additive selected from sintering additives of four types. In accordance with the present invention, the added amount of sintering additive is preferably 0.5-10 wt % based on the total amount of the main component. Where the amount of the sintering additive is less than 0.5 wt %, sintering property becomes poor. Where the amount exceeds 10 wt %, intrinsic qualities of dielectric become poor, for example, a low dielectric constant, an increased dielectric loss, etc.
The first type sintering additive is a minor component expressed by the general formula, aMnO2-bSiO2-cAl2O3 (a+b+c=100), which has the ranges of 20≦a≦60, 10≦b≦65, and 0<c≦10.
The MnO2 serves as an acceptor and thus absorbs free electrons in oxygen vacancies made when the additive is sintered under a reducing atmosphere, which in turn make it possible to improve nonreducibility. Undesirably, however, if the MnO2 content is less than 20 mol %, the value of resistivity becomes lower, and if the MnO2 content exceeds 60 mol %, solid solution is not good enough for the MnO2 to be deposited, and sintering property becomes poor.
Content of SiO2 is defined as 10-65 mol %. If the content is less than 10 mol %, it has no effect, and if the content exceeds 65 mol %, sintering property is prone to worsen due to viscosity.
The Al2O3 is added to improve water resistance and mechanical strength. Since Al2O3 is deposited without being dissolved when added in excess, it is preferable for Al2O3 to be contained in an amount of less than 10 mol % in the minor component.
The second type sintering additive is a minor component expressed by the general formula, bSiO2-cAl2O3-dR1O (b+c+d=100, R1 is at least one element chosen from Mg, Ca, Sr and Ba), which has the ranges of 10≦b≦65, 0<c≦10 and 0≦d≦50.
The third type sintering additive is a minor component expressed by the general formula, aMnO-bSiO2-dR1O-eR2O2 (a+b+d+e=100, R1 is at least one element of Mg, Ca, Sr and Ba, and R2 is at least one element chosen from Zr and Ti), which has the ranges of 20≦a≦60, 10≦b≦65, 0<(d+e)≦65.
Finally, the fourth type sintering additive proposed in the present invention is a minor component expressed by the general formula, bSiO2-dR1O-eR2O2 (b+d+e=100, R1 is at least one element selected from the group consisting of Mg, Ca, Sr and Ba, and R2 is one of element Zr and Ti), which has ranges of 10≦b≦65, 10≦d≦20 and 10≦e≦60.
Metal oxides expressed as R1O or R2O2 may be contained as a part of the minor component to improve properties of the minor component itself such as water resistance, acid resistance, etc. As a metal ion to be used for this purpose, R1 is a least one element selected from the group consisting of Ba, Ca, Sr and Mg, and R2 is a least one element of Ti and Zr. These metal oxides modify the surfaces of glasses or bind to non-bridging oxygen ions, thereby making it possible to improve chemical stability of the minor component. These metal oxides are added to the extent that the sintering property is not lowered and their effects are accomplished, without departing from the ranges of the minor component having a composition of the above sintering additives.
EXAMPLE
Hereinafter, the present invention will be illustrated in detail by way of the non-limiting examples.
In order to prepare (Ca1-xSrx)m(Zr1-yTiy)O3 based nonreducible dielectric composition in the proportions shown in table 1 below, CaCO3, SrCO3, TiO2 and ZrO2 were weighed, and the weighed materials were mixed, then sintered at a temperature of 1,100-1,250° C. for several hours and then pulverized to form a main component.
As for a minor component, MnO2, SiO2, CaCO3, MgCO3, SrCO3, BaCO3, Al2O3, ZrO2 and TiO2 were weighed in the proportions shown in table 2 below, mixed, completely dissolved in a platinum crucible at 1,500° C. and quenched quickly to room temperature to form the component as a glass phase, or alternatively, weighed, mixed, sintered at a temperature of 1,200° C. for several hours, and then pulverized to form the component.
The main component and the minor component were weighed in the proportions shown table 1, PVB or acrylic binder or solvent, plasticizer, etc. were added thereto, and then dispersed with a high-energy mill to form a slurry, which was then transformed into a sheet with a thickness of 10 μm.
An electrode paste using a nickel or a nickel-contained non-metal electrode material as an internal electrode was printed on the transformed sheet and then laminated. The resultant laminate was cut to form green chips, the green chips were baked out in air at 200-300° C. for 12-48 hours, then in nitrogen (N2) atmosphere at 200-600° C. for 0.5-48 hours.
After completion of the baking-out, for avoiding oxydation of an internal electrode, the green chips were sintered under a reducing atmosphere (a partial pressure of oxygen 10−8—10−15 atm) at a sintering temperature of 1,250° C. or below, and then heated under 10−5—10−8 atm of a partial pressure of oxygen in a temperature range of 1,100-800° C. to obtain a sintered body.
The sintered body thus obtained was subjected to polishing. Subsequently, an external electrode was formed of a metal such as Cu. The external electrode was sintered at approximately 700-900° C. and then was plated for avoiding oxydation and soldering.














TABLE 1











Glass frit
Added Amount


Specimen
X
1-x
Y
1-y
m
(GF) Type
of GF






















Exam. 1
1.0
0.0
0.0
1.0
1.0
A
3.0


Exam. 2
1.0
0.0
0.0
1.0
1.0
B
3.0


Exam. 3
1.0
0.0
0.0
1.0
1.0
C
3.0


Exam. 4
1.0
0.0
0.0
1.0
1.0
D
3.0


Exam. 5
1.0
0.0
0.0
1.0
1.0
E
3.0


Exam. 6
1.0
0.0
0.0
1.0
1.0
F
3.0


Exam. 7
1.0
0.0
0.0
1.0
1.0
H
3.0


Exam. 8
1.0
0.0
0.0
1.0
1.0
I
3.0


Exam. 9
0.0
1.0
0.04
0.96
1.0
H
2.5


Exam. 10
0.7
0.3
0.03
0.97
1.0
A
2.5


Exam. 11
0.7
0.3
0.03
0.97
1.0
C
2.5


Exam. 12
0.7
0.3
0.03
0.97
1.0
F
2.5


Exam. 13
0.7
0.3
0.03
0.97
1.0
H
2.5


Exam. 14
0.7
0.3
0.03
0.97
1.0
I
2.5


Exam. 15
0.7
0.3
0.03
0.97
1.0
H
2.5


Exam. 16
0.7
0.3
0.04
0.96
1.0
H
2.5


Comparative
1.0
0.0
0.0
1.0
1.0
G
3.0


Exam. 1


Comparative
0.0
1.0
0.0
1.0
1.0
B
2.5


Exam. 2


Comparative
0.7
0.3
0.03
0.97
1.0
G
2.5


Exam. 3


Comparative
0.7
0.3
0.09
0.91
1.0
H
2.5


Exam. 4



















TABLE 2









R1
R2
















Specimen
MnO2
SiO2
Al2O3
BaO
MgO
CaO
SrO
TiO2
ZrO2



















A
35.02
56.20
8.78








B
50.00
38.85





11.15


C

50.00
8.29

8.43
33.27



D
22.22
18.52



18.52

40.74


E

63.12



18.44

18.45


F
29.13
49.74
6.86

3.45
10.82



 G*

50.00

25.00


25.00


H
55.24
40.19






4.57


I

42.73
9.02

18.92
29.33





Specimen indicated with an asterisk (*) is that having a sintering additive condition out of the present invention. 






As mentioned above, each specimen prepared in the composition proportions shown in table 1 and table 2, respectively, was tested to measure its characteristics.
The evaluated items were a dielectric constant, a temperature coefficient of capacitance, tan δ and resistivity, which were practiced as the following manner. The dielectric constant was measured on the basis of capacitance at 1 MHz, 25° C., 1 Vrms(AC voltage:1V) and tanδ was also measured at 1 MHz, 25° C., 1 Vrms, which indicates dielectric loss. The temperature coefficient of capacitance (TCC) was determined over −55° C./125° C. on the basis of capacitance at 25° C. and was given by the equation:

TCC(ppm/° C.)=[(CT−C25° C.)/C25° C.]/(T−25° C.) ★106,

where −55° C.≦T≦+125° C.
The resistivity was measured inΩ cm unit at 25° C., after applying a rated voltage of 50V for 60 seconds. The results for each specimen are shown in table 3 below.











TABLE 3









TCC (ppm/° C.)

Grain
















Sintering
Dielectric
Tanδ


Character-
Resistivity
size


Specimen
Temp. (° C.)
Constant
(%)
125° C.
−55° C.
istic
(Ω cm)
(μm)


















Exam. 1
1,250
27.59
0.04
39.6
40.3
CH
>E15
1.6


Exam. 2
1,250
28.98
0.02
−12.2
−23.5
COG
>E15
2.0


Exam. 3
1,300
28.59
0.03
−3.0
−8.8
COG
>E15
1.4


Exam. 4
1,250
28.50
0.03
−12.1
−22.3
COG
>E15
1.8


Exam. 5
1,300
26
0.05
−18.5
−37.3
CH
>E15
1.6


Exam. 6
1,230
28.37
0.03
25.6
20.8
COG
>E15
1.5


Exam. 7
1,200
27.88
0.03
42.9
41.5
CH
>E15
1.3


Exam. 8
1,250
28.66
0.03
1.7
−1.1
COG
>E15
1.5


Exam. 9
1,250
33.33
0.05
22
−25
COG
>E15
1.5


Exam. 10
1,230
31.39
0.04
23.5
27.5
COG
>E15
1.3


Exam. 11
1,300
31.74
0.04
4.8
−13.3
COG
>E15
1.4


Exam. 12
1,200
32.01
0.04
7.1
4.0
COG
>E15
1.5


Exam. 13
1,200
33.13
0.04
35.6
20.1
CH
>E15
1.3


Exam. 14
1,300
31.73
0.04
2.9
−10.3
COG
>E15
1.3


Exam. 15
1,200
32.1
0.03
35
27
CH
>E15
1.3


Exam. 16
1,200
33.4
0.03
−9.2
−9.6
COG
>E15
1.3


Comp.
1,300
21.25
0.06
12.3
10.9
COG
>E15
0.7


Exam. 1


Comp.
1,300
30.14
0.05
134
162
—
>E15
2.5


Exam. 2


Comp.
1,230
35.81
0.04
−33.6
−85.3
—
>E15
1.4


Exam. 3


Comp.
1,200
38.4
0.04
−147
−180
PH
>E15
1.5


Exam. 4









As can be seen from the above table 3, examples of the present invention had a small dielectric loss(tan δ) and a high resistivity, could be sintered under a reducing atmosphere to be used in formation of a nickel electrode and could be sintered at temperature of less than 1,300° C., and even more, at a low temperature of 1,250° C. In particular, the examples of the present invention provided a dielectric composition meeting COG/CH characteristics (±30 ppm/° C., ±60 ppm/° C.) in accordance with the EIA Standard.
On the other hand, comparative examples (1-4) out of the composition range of the present invention had excessively high resistivities and did not meet COG/CH characteristics.
As apparent from the above description, the present invention provides a composition capable of being sintered at temperature of less than 1,300° C., and even more, at a low temperature of 1,250° C., as well as being sintered under a reducing atmosphere to be used in formation of a nickel electrode. As a result, mismatching between a nickel electrode and ceramic during the sintering process can be prevented. Further, the dielectric composition can provide a TC based electric composition having a small dielectric loss and a high resistivity.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

## Claims

1. A nonreducible dielectric composition comprising a main component expressed by the general formula, (Ca1-xSrx)m(Zr1-yTiy)O3, which has the ranges of 0≦x≦1, 0≦y≦0.09 and 0.7≦m≦1.05; and 0.5-10 wt % of a minor component expressed by the general formula, aMnO-bSiO2-eZrO2(a+b+e=100), which has the ranges of 20≦a≦60, 10≦b≦65 and 0≦e≦65.

2. A multi-layered ceramic capacitor comprising:
a plurality of sheets of dielectric composition according to claim 1; and 
a plurality of electrodes on each of the plurality of sheets, 
wherein the sheets and the electrodes are alternatively laminated.