# Patent

## Title
Ceramic powder composition, ceramic material, and multilayer ceramic capacitor fabricated thereby

## Abstract

A ceramic powder composition, a ceramic material and a multi-layer ceramic capacitor fabricated thereby are presented. The ceramic powder composition includes a main component and a glassy component. A content of the glassy component is 0.2 to 2.0 mole % based on the main component. The main component includes (Ba1-xCax)mTiO3+αMgO+βRe2O3+γMnO+δB2O5, where α, β, γ and δ are molar ratio constants, and 0.1≦α≦3.0, 0.05≦β≦3.0, 0.001≦γ≦0.2, and 0.0<δ≦0.1; 0.99≦m≦1.030, and 0.005≦x≦0.015; element Re is selected from a group consisting of yttrium (Y), chromium (Cr), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb); and element B is selected from a group consisting of vanadium (V), niobium (Nb), and tantalum (Ta). The glassy component includes (BayCa1-y)SiO3, where 0<y<1.

## Background
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates to a ceramic powder composition, a ceramic material, and a multi-layer ceramic capacitor fabricated thereby, in particular, to a ceramic powder composition, a ceramic material, and a multi-layer ceramic capacitor fabricated thereby, which meet the X5R temperature range.
2. Related Art
In recent years, as electronic elements develop towards small, chip-based, multi-functional, and high-capacity designs, various integration technologies attract much attention. Similarly, as for capacitors, besides the thin and small and multi-layer design of elements is inevitable, requirements for design of dielectric materials with high capacitance and micro-grain structure become increasingly strict. Therefore, ceramic capacitors also develop in the trend of achieving maximum functions in a minimum volume.
Applications of commercial ceramic capacitors are largely classified into Y5V, X5R, X7R, and X8S specifications, and the specification required by X5R basically refers to a relative capacitance variation of ±15% in a temperature range of −55° C. to 85° C.
SUMMARY OF THE INVENTION
The present invention is directed to a ceramic powder composition, which meets the X5R temperature range.
The present invention is directed to a ceramic material, which meets the X5R temperature range.
The present invention is directed to a multi-layer ceramic capacitor, which meets the X5R temperature range.
The present invention provides a ceramic powder composition, a ceramic material, and a multi-layer ceramic capacitor fabricated thereby. The ceramic powder composition comprises a main component and a glassy component. A content of the glassy component is 0.2-2.0 mole % based on the main component. The main component includes (Ba1-xCax)mTiO3+αMgO+βRe2O3+γMnO+δB2O5, where α, β, γ and δ are molar ratio constants, and 0.1≦α≦3.0, 0.05≦β≦3.0, 0.001≦γ≦0.2, and 0.0<δ≦0.1; 0.99≦m≦1.030, and 0.005≦x≦0.015; element Re is selected from a group consisting of yttrium (Y), chromium (Cr), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb); and element B is selected from a group consisting of vanadium (V), niobium (Nb), and tantalum (Ta). The glassy component comprises (BayCa1-y)SiO3, where 0<y<1.
The present invention further provides a ceramic material, which is formed by sintering the ceramic powder composition.
The present invention further provides a multi-layer ceramic capacitor, which comprises a ceramic dielectric, a plurality of internal electrodes, and at least one external electrode. The ceramic dielectric is formed by sintering the ceramic powder composition. The internal electrodes substantially extend in parallel in the ceramic dielectric, and the external electrode is exposed out of the ceramic dielectric, and is electrically connected to the internal electrodes.
In summary, the present invention provides a ceramic powder composition, a ceramic material, and a multi-layer ceramic capacitor fabricated thereby that meet the X5R temperature range by using a main component in combination with a glassy component.



BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given herein below for illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a relation diagram of a capacitance variation of multi-layer ceramic capacitors and temperature; and
FIG. 2 is a sectional view of a structure of a multi-layer ceramic capacitor.



DETAILED DESCRIPTION OF THE INVENTION
The ceramic powder composition of the present invention is described below with reference to related drawings. For ease of understanding, the same members are used to refer to the same parts in the embodiments.
The ceramic powder composition of the present invention is formed by combining and sintering a main component and a glassy component at a particular ratio. A content of the glassy component is 0.2-2.0 mole % based on the main component, in other words, when a fraction of the main component is 1 mole, a fraction of the glassy component may be ranged from 0.002 to 0.02 mole. A ceramic powder composition meeting the X5R temperature range can be obtained by sintering the main component and the glassy component at the fractions above.
The main component includes (Ba1-xCax)mTiO3+αMgO+βRe2O3+γMnO+δB2O5, where α, β, γ, and δ are molar ratio constants, and 0.1≦α≦3.0, 0.05≦β≦3.0, 0.001≦γ≦0.2, and 0.0<δ≦0.1; 0.99≦m≦1.030, and 0.005≦x≦0.015; element Re is selected from a group consisting of yttrium (Y), chromium (Cr), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb); and element B is selected from a group consisting of vanadium (V), niobium (Nb), and tantalum (Ta).
The glassy component is (BayCa1-y)SiO3 (referred to as BCG hereinafter), where 0<y<1, and a numerical value range of y is essentially 0.3≦y≦0.6, and the glassy component BCG is a material comprising BaO, CaO and SiO2.
The main component and the glassy component are combined at the above fractions and sintered at a sintering temperature in a range of 1190 to 1300° C., to form a ceramic material, for use in a multi-layer ceramic capacitor device.
Hereinafter, the present invention is described with reference to Examples 1 to 4, in which the glassy component in Examples 1 to 4 is exemplified with the material BCG; however, the present invention is not limited to the following examples.
EXAMPLE 1
Example 1 is an embodiment in which values X and m in (Ba1-xCax)mTiO3 in the main component are changed. Referring to Table 1, mixing ratios of MgO, Y2O3, MnO, V2O5, and Cr2O3 in the main component and the glassy component (BCG) are respectively fixed, in which fixed addition mole percentages of MgO, Y2O3, MnO, V2O5, Cr2O3 and BCG are respectively 2.3, 0.13, 0.007, 0.024, 1.74, and 1.87, and values X and m are changed in ranges 0.01≦x≦0.06 and 0.9948≦m≦0.9988.
Table 2 shows characteristic behaviors of ceramic materials obtained by sintering 9 groups (A1-A9) of raw materials shown in Table 1 at 1235° C. It can be known from Table 2 that the characteristic behaviors of the ceramic powder based composition of Groups A1-A9 all meet the X5R specification.








TABLE 1







Sample
(Ba1−x Cax)mTiO3















No.
X
MgO
Y2O3
MnO
V2O5
Cr2O3
BCG
m





A1
0.01
2.3
0.13
0.007
0.024
1.74
1.87
0.9988


A2
0.01
2.3
0.13
0.007
0.024
1.74
1.87
0.9968


A3
0.01
2.3
0.13
0.007
0.024
1.74
1.87
0.9948


A4
0.03
2.3
0.13
0.007
0.024
1.74
1.87
0.9988


A5
0.03
2.3
0.13
0.007
0.024
1.74
1.87
0.9968


A6
0.03
2.3
0.13
0.007
0.024
1.74
1.87
0.9948


A7
0.06
2.3
0.13
0.007
0.024
1.74
1.87
0.9988


A8
0.06
2.3
0.13
0.007
0.024
1.74
1.87
0.9968


A9
0.06
2.3
0.13
0.007
0.024
1.74
1.87
0.9948




















TABLE 2









X5R


Sample
Dielectric Constant
DF (%)
Db
Characteristics



















A1
3054.6
0.91
5.794
OK


A2
3044.7
0.85
5.806
OK


A3
2896.9
0.87
5.818
OK


A4
2639.4
1.04
5.808
OK


A5
2473.7
1.42
5.799
OK


A6
2287.1
1.25
5.779
OK


A7
2174.67
1.65
5.727
OK


A8
2279.9
1.55
5.737
OK


A9
2418.82
1.76
5.718
OK









EXAMPLE 2
Example 2 is an embodiment in which the content of the glassy component (BCG) and the sintering temperature are changed. Referring to Table 3, the content of the main component is fixed to be (Ba0.09Ca0.01)0.9968TiO3 (BC1T)+0.75 mol % MgO+1.42 mol % Y2O3+0.0667 mol % MnO+0.074 mol % V2O5+1.14 mol % Cr2O3, and the content of the glassy component (BCG) is changed in a range of 0.48 to 1.27 mole %.
Table 4 shows characteristic behaviors of ceramic materials obtained by sintering 4 groups (B1-B4) of raw materials shown in Table 3 at different sintering temperatures of 1190° C., 1205° C., 1220° C., and 1235° C. It can be known from Table 4 that sintered densities are all higher than 5.6 g/cm3, a maximal dielectric constant is up to 3550, and the characteristic behaviors all meets the X5R specification.








TABLE 3








δBCG















No.
BC1T
MgO
Y2O3
MnO
V2O5
Cr2O3
BCG
A/B





B1
100
0.75
1.42
0.0667
0.074
1.14
0.48
0.9968


B2
100
0.75
1.42
0.0667
0.074
1.14
0.64
0.9968


B3
100
0.75
1.42
0.0667
0.074
1.14
0.79
0.9968


B4
100
0.75
1.42
0.0667
0.074
1.14
1.27
0.9968





















TABLE 4






S/T
Dielectric


X5R


Sample
temp. (C.)
Constant
DF (%)
Db
Characteristics







B1
1235
3292
1.14
5.72
OK



1220
3360
1.14
5.71
OK



1205
3510
1.27
5.75
OK



1190
3549
2.11
5.68
OK


B2
1235
3318
1.11
5.73
OK



1220
3398
1.52
5.72
OK



1205
3338
1.27
5.72
OK



1190
3353
1.66
5.68
OK


B3
1235
3439
1.47
5.76
OK



1220
3466
1.06
5.74
OK



1205
3463
1.19
5.81
OK



1190
3535
1.35
5.71
OK


B4
1235
3187
1.00
5.83
OK



1220
3278
0.99
5.76
OK



1205
3278
1.05
5.85
OK



1190
3350
1.44
5.73
OK









EXAMPLE 3
Example 3 is an embodiment in which amounts of MgO and Y2O3 in the main component are changed. Referring to Table 5, the content of the main component is fixed to be (Ba0.98Ca0.02)0.9968TiO3 (BC2T)+αMgO+βY2O3+0.0667 mol % MnO+0.074 mol % V2O5+1.14 mol % Cr2O3, where 0.1≦α≦3.0, 0.05≦β≦3.0, and the content of the glassy component (BCG) is 0.79 mole %.
Table 6 shows characteristic behaviors of ceramic materials obtained by sintering 7 groups (C1-C7) of raw materials shown in Table 5 at a sintering temperature of 1220° C. It can be known from Table 7 that the ceramic powder based compositions of Groups C1-C7 all have a sintered density higher than 5.6 g/cm3, and when the amounts of αMgO and βY2O3 are 0.1≦α≦3.0 and 0.05≦β≦3.0 mole %, the characteristic behaviors all meets the X5R specification.








TABLE 5







Sample
αMgO + βY2O3















No.
BC2T
MgO
Y2O3
MnO
V2O5
Cr2O3
BCG
A/B


















C1
100
0.05
1.42
0.0667
0.074
1.14
0.79
0.9968


C2
100
1.5
1.42
0.0667
0.074
1.14
0.79
0.9968


C3
100
2.25
1.42
0.0667
0.074
1.14
0.79
0.9968


C4
100
3.25
1.42
0.0667
0.074
1.14
0.79
0.9968


C5
100
1.5
0.62
0.0667
0.074
1.14
0.79
0.9968


C6
100
1.5
2.22
0.0667
0.074
1.14
0.79
0.9968


C7
100
1.5
3.02
0.0667
0.074
1.14
0.79
0.9968


















TABLE 6









MLCC, TCC (%)



at (° C.)












Sample
Dielectric Constant
DF (%)
Db
−50
85















C1
5.74
3166
53.4
2.41
−15.4


C2
5.76
3321
58.9
1.21
−12.2


C3
5.69
3070
60.3
1.21
−9.1


C4
5.42
2950
63.9
1.07
−7.5


C5
5.72
3145
59.2
1.32
−9.7


C6
5.81
3190
58.7
1.17
−13.9


C7
5.79
3041
58.7
1.18
−17.8









EXAMPLE 4
Example 4 is an embodiment in which amounts of MnO and V2O5 in the main component are changed. Referring to Table 7, the contents of the main component is fixed to be (Ba0.98Ca0.02)0.9968TiO3+0.75 MgO+1.42 Y2O3+γ mol % MnO+δ mol % V2O5+1.14 mol % Cr2O3, where 0.001≦γ≦0.2, and 0.0<δ≦0.1, and the content of the glassy component (BCG) is 0.79 mole %.
Table 8 shows characteristic behaviors of ceramic materials obtained by sintering 5 groups (D1-D5) of raw materials shown in Table 7 at 1220° C. It can be known from Table 8 that the ceramic powder based compositions of Groups D1-D5 all have a sintered density higher than 5.6 g/cm3, and when the amounts of γMnO+δV2O5 are 0.001≦γ≦0.2 and 0.0≦δ≦0.1 mole %, the characteristic behaviors all meets the X5R specification.








TABLE 7







Sample
γMnO + δV2O5















No.
BC2T
MgO
Y2O3
MnO
V2O5
Cr2O3
BCG
A/B


















D1
100
0.75
1.42
0.005
0.074
1.14
0.79
0.9968


D2
100
0.75
1.42
0.0667
0.074
1.14
0.79
0.9968


D3
100
0.75
1.42
0.25
0.074
1.14
0.79
0.9968


D4
100
0.75
1.42
0.0667
0.01
1.14
0.79
0.9968


D5
100
0.75
1.42
0.0667
0.15
1.14
0.79
0.9968


















TABLE 8









MLCC, TCC (%)



at (° C.)












Sample
Dielectric Constant
DF (%)
Db
−50
85





D1
5.75
3398
55.4
1.87
−13.7


D2
5.74
3466
55.8
2.03
−13.8


D3
5.69
3296
54.9
2.98
−15.7


D4
5.69
3189
59.6
2.10
−13.9


D5
5.81
3415
54.1
2.32
−14.8









EXAMPLE 5
Experiments were conducted with Sample A2 in Example 1 and Sample B4 in Example 2, to observe a relation between the capacitance variation and the temperature. FIG. 1 is a relation diagram of the capacitance variation of multi-layer ceramic capacitors of Samples A2 and B4. It can be known from FIG. 1 that the multi-layer ceramic capacitors of Groups A2 and B4 have a capacitance variation meeting the X5R temperature range, that is, has a relative capacitance variation of ±15% in a temperature range of −55° C. to 85° C.
The ceramic powder composition of the present invention is mainly used in a multi-layer ceramic capacitor device. FIG. 2 is a sectional view of a structure of a multi-layer ceramic capacitor. As shown in FIG. 4, a multi-layer ceramic capacitor 1 comprises a ceramic capacitor body 110 and an external electrode 120. The ceramic capacitor body 110 comprises a plurality of dielectric ceramic layers 112 and a plurality of internal electrodes 111 formed along surfaces of the dielectric ceramic layers, and the external electrode 120 is formed out of the ceramic capacitor body 110, and is electrically connected to a part of the internal electrodes 111. The internal electrodes 111 may be nickel electrodes.
It should be particularly noted that the dielectric ceramic layers 112 of the multi-layer ceramic capacitor 1 are formed by sintering the ceramic powder composition of the present invention at a sintering temperature of 1190-1300° C. After sintering, it can be known from experimental results that the multi-layer ceramic capacitor formed by the dielectric ceramic layers 112 formed by sintering the ceramic powder composition of the present invention has a capacitance variation meeting the X5R temperature range, that is, has a relative capacitance variation of ±15% in a temperature range of −55° C. to 85° C. Thus, a multi-layer ceramic capacitor meeting the X5R temperature range is provided.
In summary, the present invention provides a ceramic powder composition, a ceramic material, and a multi-layer ceramic capacitor fabricated thereby that meet the X5R temperature range by combining a main component with a glassy component.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims.

## Claims

1. A ceramic powder composition, comprising
a main component, comprising (Ba1-xCax)mTiO3+αMgO+βRe2O3+γMnO+δB2O5, wherein α, β, γ and δ are molar ratio constants, and 0.1≦α≦3.0, 0.05≦β≦3.0, 0.001≦γ≦0.2, and 0.0<δ≦0.1; 0.99≦m≦1.030, and 0.005≦x≦0.015; element Re is selected from a group consisting of yttrium (Y), chromium (Cr), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb); and element B is selected from a group consisting of vanadium (V), niobium (Nb), and tantalum (Ta); and
a glassy component, having a content of 0.2-2.0 mole % based on the main component, and comprising (BayCa1-y)SiO3, wherein 0<y<1.

2. The ceramic powder composition according to claim 1, wherein a numerical value range of y is essentially 0.3≦y≦0.6.

3. The ceramic powder composition according to claim 1, wherein the element B is essentially vanadium (V).

4. The ceramic powder composition according to claim 1, wherein the element Re is essentially yttrium (Y) or chromium (Cr).

5. A ceramic material, formed by sintering the ceramic powder composition according to claim 1.

6. The ceramic material according to claim 5, wherein a sintering temperature for the ceramic material is 1190-1300° C.

7. A multi-layer ceramic capacitor, comprising:
a ceramic dielectric, formed by sintering a dielectric ceramic composition comprising:
a main component, comprising (Ba1-xCax)mTiO3+αMgO+βRe2O3+γMnO+δB2O5, wherein α, β, γ and δ are molar ratio constants, and 0.1≦α≦3.0, 0.05≦β≦3.0, 0.001≦γ≦0.2, and 0.0<δ≦0.1; 0.99≦m≦1.030, and 0.005≦x≦0.015; element Re is selected from a group consisting of yttrium (Y), chromium (Cr), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb); and element B is selected from a group consisting of vanadium (V), niobium (Nb), and tantalum (Ta); and
a glassy component, having a content of 0.2-2.0 mole % based on the main component, and comprising (BayCa1-y)SiO3, wherein 0<y<1;
a plurality of internal electrodes, substantially extending in parallel in the ceramic dielectric; and
at least one external electrode, exposed out of the ceramic dielectric, and electrically connected to the internal electrodes.

8. The multi-layer ceramic capacitor according to claim 7, wherein the multi-layer ceramic capacitor has a capacitance variation meeting the X5R temperature range, that is, has a relative capacitance variation of ±15% in a temperature range of −55° C. to 85° C.

9. The multi-layer ceramic capacitor according to claim 7, wherein the internal electrodes are nickel electrodes.

10. The multi-layer ceramic capacitor according to claim 7, wherein a numerical value range of y is essentially 0.3≦y≦0.6.

11. The multi-layer ceramic capacitor according to claim 7, wherein the element B is essentially vanadium (V).

12. The multi-layer ceramic capacitor according to claim 7, the element Re is essentially yttrium (Y) or chromium (Cr).

13. The multi-layer ceramic capacitor according to claim 7, wherein a sintering temperature for the ceramic material is 1190-1300° C.