# Patent

## Title
Dielectric ceramic material and multilayer ceramic capacitor

## Abstract

A dielectric ceramic material comprising the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgO+eRO (wherein coefficients 100, a, b, c, d, and e each represent mols; m represents the molar ratio of (Ba1-xCax) to Ti; and RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3), wherein m, x, a, b, c, d, and e satisfy the relationships: 0.998≦m≦1.030, 0.04≦x≦0.15, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and the dielectric ceramic material has an average grain size of 0.3 μm to 0.7 μm, is used to make reliable multilayer ceramic capacitors including dielectric ceramic layers each having a small thickness of about 1 μm.

## Background
This is a continuation of application Ser. No. PCT/JP2005/008446, filed May 9, 2005.


TECHNICAL FIELD
The present invention relates to dielectric ceramic materials and multilayer ceramic capacitors. The present invention also relates to a dielectric ceramic material capable of constituting a dielectric ceramic layer having a thickness as small as about 1 μm and relates to a multilayer ceramic capacitor that can be produced at low cost.
BACKGROUND ART
It is known that Patent Documents 1, 2, 3, 4, and the like disclose such dielectric ceramic materials.
Patent Documents 1, 2 and 3 each disclose an non-reducible dielectric ceramic composition. Each of the non-reducible dielectric ceramic compositions basically contains 92.0 to 99.4 mol % BaTiO3, 0.3 to 4 mol % Re2O3 (wherein Re represents at least one rare-earth element selected from Tb, Dy, Ho and Er), and 0.3 to 4 mol % Co2O3, which are main components, and contains 0.2 to 4 mol % BaO, 0.2 to 3 mol % MnO, and 0.5 to 5 mol % MgO, which are accessory components.
Each of the non-reducible dielectric ceramic compositions is not converted into a semiconductor even when the compositions are fired at a low oxygen partial pressure and has a dielectric constant εr of 3000 or more and a resistivity ρ of 1011.0 Ωm or more. Furthermore, temperature characteristics of the relative dielectric constant εr is in the range of ±15% at a wide temperature range between −55° C. and +125° C. with reference to a capacitance value at 25° C.
Patent Document 4 discloses a dielectric ceramic composition and a multilayer ceramic capacitor. The dielectric ceramic composition contains barium titanate as a main component and Re (wherein Re represents at least one rare-earth element selected from Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb), Ca, Mg and Si as accessory components. The dielectric ceramic material is represented by the composition: 100BamTiO3+aReO3/2+bCaO+cMgO+dSiO2 (wherein coefficients 100, a, b, c, and d each represent a mols), and satisfy the respective relationships: 0.990≦m≦1.030, 0.5≦a≦6.0, 0.10≦b≦5.00, 0.010≦c≦1.000, and 0.05≦d≦2.00.
The dielectric ceramic composition has a relative dielectric constant εr of 3000 or more, satisfies B characteristics specified by JIS and X7R characteristics specified by EIA, and has a long accelerated life of insulation resistance at high temperatures and high voltages, thus resulting in excellent reliability even when a layer composed of the dielectric ceramic composition has a small thickness.
Patent Document 1: Japanese Unexamined Patent Application Publication No. 5-9066
Patent Document 2: Japanese Unexamined Patent Application Publication No. 5-9067
Patent Document 3: Japanese Unexamined Patent Application Publication No. 5-9068
Patent Document 4: Japanese Unexamined Patent Application Publication No. 2001-39765
DISCLOSURE OF INVENTION
Problems to be Solved by the Invention
In recent years, however, with developments in electronics, rapid progress has been made in the miniaturization of electronic components, and trends toward miniaturization and higher capacities of multilayer ceramic capacitors have become significant. Accordingly, the demand for a high-reliability dielectric ceramic composition having a high dielectric constant, a low change in dielectric constant with temperature, and high insulation performance even when the composition is formed into a thin layer have been growing. However, the known dielectric ceramic compositions have been designed on the premise that the compositions are used under low electric field strength conditions. When used at high electric field strength, disadvantageously, insulation resistance, dielectric strength, and reliability are significantly degraded. Furthermore, the compositions have a relative dielectric constant as low as about 3000, which is insufficient for the demand for miniaturization and higher capacitance. Thus, a ceramic dielectric layer having a smaller thickness requires a lower rated voltage in response to the thickness in the known dielectric ceramic compositions.
In each of the dielectric ceramic compositions disclosed in Patent Documents 1 to 4, it is possible to provide a high-reliability multilayer ceramic capacitor including dielectric ceramic layers each composed of one of the dielectric ceramic compositions. However, when a dielectric ceramic layer has a small thickness of about 1 μm, disadvantageously, it is difficult to ensure the reliability of the multilayer ceramic capacitor.
Furthermore, there is the problem of production costs of the multilayer ceramic capacitor. To reduce the production costs, the amount of electrical energy used for heating in a firing step needs to be minimized. An increase in the number of the multilayer ceramic capacitors fired at the same time results in a reduction in the amount of electrical energy per multilayer ceramic capacitor, thus reducing the production costs. In the case where many multilayer ceramic capacitors are fired at the same time, the temperature inside a firing furnace needs to be controlled so as to be completely uniformized. However, the control cannot be performed in the present circumstances, thus resulting in nonuniformity in capacitance and insulation resistance due to temperature distribution in the firing furnace, causing problems in quality.
It is an object of the present invention to overcome the problems and to provide a high-reliability dielectric ceramic material and a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 5000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X6S characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±22% at temperatures between −25° C. and +105° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (150° C., DC field strength: 6 V/μm), even at a small thickness of a dielectric ceramic layer of about 1 μm, the multilayer ceramic capacitor being capable of being produced at low cost.
Furthermore, it is another object of the present invention to provide a high-reliability dielectric ceramic material and a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 6000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X5R characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±15% at temperatures between −25° C. and +85° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (125° C., DC field strength: 8 V/μm), the multilayer ceramic capacitor being capable of being produced at low cost.
MEAN FOR SOLVING THE PROBLEMS
According to a first aspect of the present invention, there is provided a dielectric ceramic material comprising the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgO+eRO (wherein coefficients 100, a, b, c, d, and e each represent mols; m represents the molar ratio of (Ba1-xCax) to Ti; and RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3), wherein m, x, a, b, c, d and e satisfy the relationships: 0.998≦m≦1.030, 0.04≦x≦0.15, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and the dielectric ceramic material has an average grain size of 0.3 μm to 0.7 μm.
According to a second aspect of the present invention, there is provided a dielectric ceramic material comprising the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgO+eRO (wherein coefficients 100, a, b, c, d, and e each represent mols; m represents the molar ratio of (Ba1-xCax) to Ti; and RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3), wherein m, x, a, b, c, d and e satisfy the relationships: 0.998≦m≦1.030, 0≦x<0.04, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and the dielectric ceramic material has an average grain size of 0.35 μm to 0.65 μm.
According to a third aspect of the present invention, there is provided a multilayer ceramic capacitor comprising a plurality of dielectric ceramic layers, the dielectric ceramic layers being laminated; internal electrodes, each being disposed between dielectric ceramic layers; and external electrodes, each electrically connected to a corresponding one of the internal electrodes, wherein the dielectric ceramic layers are each composed of the dielectric ceramic material according to the first or second aspect.
According to a fourth aspect of the present invention, in the multilayer ceramic capacitor according to the third aspect of the present invention, the internal electrodes are each composed of at least one conductive material selected from among nickel, nickel alloys, copper, and copper alloys.
Advantages
According to the first, third, and fourth aspects of the present invention, it is possible to provide a high-reliability dielectric ceramic material and a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 5000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X6S characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±22% at temperatures between −25° C. and +105° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (150° C., DC field strength: 6 V/μm), even at a small thickness of a dielectric ceramic layer of about 1 μm, the multilayer ceramic capacitor being capable of being produced at low cost.
According to the second, third, and fourth aspects of the present invention, it is possible to provide a high-reliability dielectric ceramic material and a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 6000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X5R characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±15% at temperatures between −25° C. and +85° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (125° C., DC field strength: 8 V/μm), the multilayer ceramic capacitor being capable of being produced at low cost.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to an embodiment of the present invention.



REFERENCE NUMERALS


    
    
        1 multilayer ceramic capacitor
        2 dielectric ceramic layers
        3A, 3B first and second internal electrodes
        4A, 4B first and second external electrodes
    
    


BEST MODE FOR CARRYING OUT THE INVENTION
An embodiment of the present invention will be described below with reference to FIG. 1. As shown in FIG. 1, for example, a multilayer ceramic capacitor 1 in this embodiment includes a laminate having a plurality of dielectric ceramic layers 2 (five layers in this embodiment), a plurality of first internal electrodes 3A, and a plurality of second internal electrodes 3B, the first and second internal electrodes 3A and 3B being disposed between the dielectric ceramic layers 2; a first external electrode 4A electrically connected to the first internal electrodes 3A; and a second external electrode 4B electrically connected to the second internal electrodes 3B, the first and second external electrodes 4A and 4B being disposed at both ends of the laminate.
As shown in FIG. 1, each first internal electrode 3A extends from one end of a corresponding one of the dielectric ceramic layers 2 (left end in FIG. 1) to the vicinity of the other end thereof (right end). Each second internal electrode 3B extends from the right end of a corresponding one of the dielectric ceramic layers 2 to the vicinity of the left end thereof. The first and second internal electrodes 3A and 3B are each composed of a conductive material. Examples of the conductive material that can be preferably used include a base metal selected from nickel, nickel alloys, copper, and copper alloys. Furthermore, a small amount of a ceramic powder may be incorporated in the conductive material in order to prevent the structural defects in the internal electrodes.
As shown in FIG. 1, the first external electrode 4A is electrically connected to the first internal electrodes 3A in the laminate. The second external electrode 4B is electrically connected to the second internal electrodes 3B in the laminate. Each of the first and second external electrodes 4A and 4B may be composed of any one of the known conductive materials, such as Ag and Cu. Each of the first and second external electrodes 4A and 4B may be appropriately formed by a known process.
Each of the dielectric ceramic layers 2 is composed of dielectric ceramic material (1) or dielectric ceramic material (2).
Dielectric ceramic material (1) according to the present invention has the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgo+eRO (wherein coefficients 100, a, b, c, d, and e each represent a mols; m represents the molar ratio of (Ba1-xCax) to Ti; and RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3), wherein m, x, a, b, c, d, and e satisfy the relationships: 0.998≦m≦1.030, 0.04≦x≦0.15, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and the dielectric ceramic material (1) has an average grain size of 0.3 μm to 0.7 μm.
In dielectric ceramic material (1), (Ba1-xCax)mTiO3 is a component in which Ba ions in barium titanate are partially replaced with Ca ions. At a substitution rate x of Ca ions to Ba ions of less than 0.04 (substitution rate: less than 4%), the mean time to failure in a high-temperature load test is reduced to less than 100 hours. At a substitution rate x exceeding 0.15 (substitution rate: 15%), the relative dielectric constant is reduced to less than 5000, and the rate of change of the dielectric constant with temperature deviates from the range of ±22%. At a ratio of Ba1-xCax to Ti (m=Ba1-xCax/Ti) of less than 0.998, the resistivity is reduced to less than 1010.5 Ωm. At m exceeding 1.030, the relative dielectric constant is reduced to less than 5000, the rate of change of the dielectric constant with temperature deviates from the range of ±22%, the resistivity is reduced to less than 1010.5 Ωm, and the mean time to failure is reduced.
At a molar amount a of MnO of less than 0.01 relative to 100 of (Ba1-xCax)mTiO3, the resistivity is reduced to less than 1010.5 Ωm. At a molar ratio a exceeding 5, the rate of change of the dielectric constant with temperature deviates from the range of ±22%, and the resistivity is reduced to less than 1010.5 Ωm.
At a molar amount b of CuO of less than 0.05, the relative dielectric constant is reduced to less than 5000, and the mean time to failure is reduced to less than 100 hours. Furthermore, MnO particles each having a size of 1 μm or more are segregated to degrade the uniformity in MnO distribution, thus not resulting in a synergistic effect of uniformizing the MnO distribution. At a molar amount b exceeding 5, the rate of change of the dielectric constant with temperature deviates from the range of ±22%.
At a molar amount C of SiO2 of less than 0.2, the relative dielectric constant is reduced to less than 5000, the dielectric loss is increased to more than 10%, the rate of change of the dielectric constant with temperature deviates from the range of ±22%, the resistivity is reduced to less than 1010.5 Ωm, and the mean time to failure is reduced to less than 100 hours. At a molar amount c exceeding 8, the rate of change of the dielectric constant with temperature exceeds 22%, and the mean time to failure is reduced to less than 100 hours.
At a molar amount d of MgO less than 0.05, the grain size is increased, the change in relative dielectric constant when the firing temperature is changed by 60° C. is increased to 1000 or more, thus resulting in nonuniformity in electrical properties due to temperature distribution in firing. At a molar amount d exceeding 3, the relative dielectric constant is reduced to less than 5000.
At a molar amount e of RO less than 0.05, the mean time to failure is reduced to less than 100 hours. At a molar amount exceeding 2.5, the rate of change of the dielectric constant with temperature deviates from the range of ±22%. When a plurality of types of the rare-earth element oxides RO are present, the total of molar amounts of the rare-earth element oxides RO may be defined as d.
At an average grain size of ceramic grains of less than 0.3 μm, the relative dielectric constant is reduced to less than 5000. At an average grain size exceeding 0.7 μm, the dielectric loss exceeds 10%, and the rate of change of the dielectric constant with temperature deviates from the range of ±22%.
On the other hand, the dielectric ceramic material (2) is comprising the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgO+eRO (wherein coefficients 100, a, b, c, d, and e each represent mols; m represents the molar ratio of (Ba1-xCax) to Ti; and RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3), wherein m, x, a, b, c, d and e satisfy the relationships: 0.998≦m≦1.030, 0≦x≦0.04, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and the dielectric ceramic material has an average grain size of 0.35 μm to 0.65 μm.
In dielectric ceramic material (2), (Ba1-xCax)mTiO3 is a component in which Ba ions in barium titanate are partially replaced with Ca ions. At a substitution rate x of Ca ions to Ba ions of 0.04 or more, the relative dielectric constant is reduced to less than 6000. At a ratio of Ba1-xCax to Ti (m=Ba1-xCax/Ti) of less than 0.998, the resistivity is reduced to less than 1010.5 Ωm. At m exceeding 1.030, the relative dielectric constant is reduced to less than 6000, the rate of change of the dielectric constant with temperature deviates from the range of ±15%, and the mean time to failure is reduced.
At a molar amount a of MnO of less than 0.01 relative to 100 of (Ba1-xCax)mTiO3, the resistivity is reduced to less than 1010.5 Ωm. At a molar amount a exceeding 5, the rate of change of the dielectric constant with temperature deviates from the range of ±15%, and the resistivity is reduced to less than 1010.5 Ωm.
At a molar amount b of CuO of less than 0.05, the relative dielectric constant is reduced to less than 6000, and the mean time to failure is reduced to less than 100 hours. Furthermore, MnO particles each having a size of 1 μm or more are segregated to degrade the uniformity in MnO distribution, thus not resulting in a synergistic effect of uniformizing the MnO distribution. At a molar amount b exceeding 5, the rate of change of the dielectric constant with temperature deviates from the range of ±15%.
At a molar amount c of SiO2 of less than 0.2, the relative dielectric constant is reduced to less than 6000, the dielectric loss is increased to more than 10%, the rate of change of the dielectric constant with temperature deviates from the range of ±15%, the resistivity is reduced to less than 1010.5 Ωm, and the mean time to failure is reduced to less than 100 hours. At a molar amount c exceeding 8, the mean time to failure is reduced to less than 100 hours.
At a molar amount d of MgO less than 0.05, the grain size is increased, the change in relative dielectric constant when the firing temperature is changed by 60° C. is increased to 1000 or more, thus resulting in the nonuniformity in electrical properties due to temperature distribution in firing. At a molar amount d exceeding 3, the relative dielectric constant is reduced to less than 6000.
At a molar amount e of RO less than 0.05, the mean time to failure is reduced to less than 100 hours. At a molar amount e exceeding 2.5, the rate of change of the dielectric constant with temperature deviates from the range of ±15%. When a plurality of types of the rare-earth element oxides RO are contained, the total of molar amounts of the rare-earth element oxides RO may be defined as e.
At an average grain size of ceramic grains of less than 0.35 μm, the relative dielectric constant is reduced to less than 6000. At an average grain size exceeding 0.65 μm, the rate of change of the dielectric constant with temperature deviates from the range of ±15%.
A process for producing a material powder used for dielectric ceramic materials (1) and (2) is not particularly limited, and any production process may be employed as long as the compound represented by (Ba1-xCax)mTiO3 can be prepared.
For example, the compound represented by (Ba1-xCax)mTiO3 may be produced by a step of mixing BaCO3, TiO2 and CaCO3 and then a step of reacting the BaCO3, TiO2 and CaCO3 by heat treatment.
The material powder of the dielectric ceramic material may be produced by a step of mixing the compound represented by (Ba1-xCax)mTiO3 and additional components, i.e., oxides of each Mn, Cu, Si and Mg, and RO (wherein RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3).
Furthermore, examples of the production process of the compound represented by (Ba1-xCax)mTiO3 include hydrothermal synthesis, hydrolysis, and wet synthesis such as a sol-gel method.
The additional components, i.e., the oxides of each Mn, Cu, Si and Mg, and RO (wherein RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3) are not limited to powdery oxides, as long as the dielectric ceramic material according to the present invention can be produced. A solution of an alkoxide, an organometallic compound, or a carbonate may be used. There is no deterioration of the characteristics obtained by using these materials.
Such material powders are fired to produce the dielectric ceramic materials (1) and (2).
The dielectric ceramic material (1) needs to have an average grain size of 0.3 to 0.7 μm. The dielectric ceramic material (2) needs to have an average grain size of 0.35 to 0.65 μm. When the dielectric ceramic material of the present invention is used in a multilayer ceramic capacitor including layers each having a thickness of about 1 μm, the particle size of the material powder is preferably adjusted to about 0.1 to about 0.2 μm, since the particles grow during firing so as to have a predetermined grain size of the ceramic material.
To appropriately control the increase in grain size in such a manner that an intended grain size of the ceramic material is achieved, firing conditions, such as a firing temperature and a firing time, may be controlled. In dielectric ceramic materials (1) and (2) of the present invention, in particular, the presence of CuO accelerates the increase in grain size. The presence of MgO suppresses the increase in grain size. Thus, the incorporation of 0.05 to 5 mol of CuO and 0.05 to 3.0 mol of MgO relative to 100 mol of (Ba1-xCax)mTiO3 results in the dielectric ceramic materials (1) and (2) each having a stable grain size, thereby stabilizing electrical properties.
Therefore, the dielectric constant and insulation resistance are stabilized even when temperature maldistribution occurs during firing, thus suppressing the occurrence of the nonuniformity in quality. Furthermore, many multilayer ceramic capacitors can be produced at a time, thus reducing the production costs.
The use of dielectric ceramic materials (1) and (2) can provides a high-reliability multilayer ceramic capacitor including dielectric ceramic layers even having a small thickness of about 1 μm.
The use of dielectric ceramic material (1) results in a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 5000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X6S characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±22% at temperatures between −25° C. and +105° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (150° C., DC field strength: 6 V/μm), even at a small thickness of a dielectric ceramic layer of about 1 μm. Hence, even a reduction in the thickness of the dielectric ceramic layer to about 1 μm does not require reducing the rated voltage, thus leading to a multilayer ceramic capacitor that achieves further miniaturization and higher capacitance. Furthermore, many stable multilayer ceramic capacitors having satisfactory quality can be produced at a time even when temperature distribution occurs during firing, thus reducing the production costs.
The use of dielectric ceramic material (2) results in a high-reliability dielectric ceramic material and a high-reliability multilayer ceramic capacitor having a high relative dielectric constant εr of 6000 or more, a low dielectric loss (tan δ) of 10.0% or less, temperature characteristics of the dielectric constant satisfying X5R characteristics (the rate of capacitance change with reference to a capacitance at 25° C. is in the range of ±15% at temperatures between −25° C. and +85° C.), a high resistivity ρ of 1010.5 Ωm or more, and a mean time to failure of 100 hours or more in an accelerated reliability test (125° C., DC field strength: 8 V/μm). Hence, even a reduction in the thickness of the dielectric ceramic layer to about 1 μm does not require reducing the rated voltage in the same way as in the case of dielectric ceramic material (1), thus leading to a multilayer ceramic capacitor that achieves further miniaturization and higher capacitance. Furthermore, many stable multilayer ceramic capacitors having satisfactory quality can be produced at low cost.
The multilayer ceramic capacitor according to this embodiment may be fired in a reducing atmosphere; hence, the internal electrodes may be each composed of a base metal, such as nickel, a nickel alloy, copper, or a copper alloy.
EXAMPLES
The present invention will be described below on the basis of specific examples.
Example 1
In this example, after the preparation of material powders of dielectric ceramic material (1), multilayer ceramic capacitors were produced with the material powders. First, high-purity TiO2, BaCO3 and CaCO3, which were starting materials, were prepared. These starting materials were weighed in a manner such that the Ti, Ba and Ca were contained in amounts represented by samples A to N shown in Table 1, wet-mixed, pulverized, and dried to prepare mixed powders. The mixed powders were heated at 950° C. or more for 2 hours to prepare (Ba,Ca)TiO3 powders represented by samples A to N having compositions and average grain sizes Ra shown in Table 1, the material powders each having an average particle size of 0.1 to 0.2 μm. A MgO powder, a CuO powder, a MnCO3 powder, a SiO2 powder and an RO powder (wherein RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2C3 and Lu2O3) were prepared as other material powders. In Table 1, samples A to D marked with asterisks “*” indicate that x and m were outside the range of the present invention.
Subsequently, the powders were weighed in a manner such that compositions shown in Tables 2 and 3 were achieved, and then mixed to obtain mixtures represented by sample Nos. 1 to 95. A polyvinyl butyral binder and an organic solvent such as ethanol were added to each mixture, and the resulting mixtures were wet-mixed with ball mills to prepare ceramic slurries. Each of the resulting ceramic slurries was formed into a sheet by a doctor blade method to obtain a rectangular ceramic green sheet having a thickness of 1.4 μm. Next, a conductive paste principally composed of nickel (Ni) was applied onto each of the resulting ceramic green sheets by printing to provide a conductive paste film to be converted into an internal electrode. One end of the conductive paste film is disposed at a first end of the ceramic green sheet, and the other end of the conductive paste film was disposed away from a second end of the ceramic green sheet. In Table 2, asterisk-marked sample Nos. 1 to 19 were samples in which any one of x, m, a, b, c, d and e was outside the range of the present invention.
Next, a plurality of the ceramic green sheets that were the same type were stacked in a manner such that the first end, in which the conductive paste films were disposed, and the second end were alternately disposed. The resulting stack was interposed between ceramic green sheets each having no conducting paste film and then was subjected to press bonding to obtain a laminate. Each of the resulting laminates was heated to 350° C. in an N2 atmosphere to decompose the binder and then fired for 2 hours in a reducing atmosphere containing a H2 gas, a N2 gas, and a H2O gas and having an oxygen partial pressure of 10−9 to 10−12 MPa at the temperature shown in Tables 2 and 3.
A silver paste containing a B2O3—SiO2—BaO-based glass frit was applied to both ends of each of the fired laminates and then baked at 600° C. in an N2 atmosphere to form external electrodes electrically connected to the internal electrodes. Thereby, laminated ceramic capacitors including the dielectric ceramic material (1) of the present invention were produced.
The outer dimensions of each of the resulting multilayer ceramic capacitors (sample Nos. 1 to 95) were 5.0 mm in width, 5.7 mm in length, and 2.4 mm in thickness. The dielectric ceramic layers disposed between the internal electrodes each had a thickness of 1.0 μm. The number of effective dielectric ceramic layers was five layers. The area of each of the opposite electrodes was 16.3×10−6 m2 per layer.
Next, the electrical properties of the multilayer ceramic capacitors of sample Nos. 1 to 95 were measured. Capacitance C and dielectric loss (tan δ) were measured with an automatic bridge measurement according to JIS 5102. Dielectric constant εr was calculated from the resulting capacitance C. Tables 4 and 5 show the results.
To measure insulation resistance R, an insulation resistance tester was used. That is, 4 V DC was applied for 1 minute, and the insulation resistance R was measured at +25° C., and then the resistivity ρ was calculated. Tables 4 and 5 show the results as log ρ.
With respect to the rate of change of capacitance C with temperature, the rate of change ΔC/C25° C. in the range of −25° C. to +105° C. with reference to a capacitance C at 25° C. was determined. Tables 4 and 5 show the results as the rate of change of the dielectric constant with temperature.
With respect to a high-temperature load test, 6 V DC was applied to 12 specimens of each sample at 150° C., and the change in insulation resistance R with time was measured. In the high temperature load test, a state in which the insulation resistance R of each sample reached 105Ω or less was defined as failure. After the measurement of the time required for reaching failure, the meantime to failure was determined. Tables 4 and 5 show the results.
With respect to the average grain size, after the break of each fired sample, the resulting samples were exposed for 5 minutes to the same oxygen partial pressure as that during firing at a temperature 100° C. lower than the firing temperature. Electron micrographs of the resulting samples were taken. Then, the size of 200 grains of the ceramic material were measured per sample. The mean value thereof was defined as an average grain size.












TABLE 1










Particle size



Sample
x
m
of material









*A 
0.037
1.005
0.12



*B 
0.160
1.005
0.13



*C 
0.080
0.995
0.12



*D 
0.100
1.032
0.14



E
0.050
1.002
0.15



F
0.040
1.002
0.11



G
0.058
1.011
0.16



H
0.070
1.004
0.13



I
0.100
1.007
0.12



J
0.125
1.020
0.14



K
0.150
1.005
0.11



L
0.050
0.998
0.13



M
0.050
1.015
0.12



N
0.050
1.030
0.12




























TABLE 2






Rare-









Firing



earth
Powder








temperature


Sample
element
used
x
m
a
b
c
d
e
Ra
[° C.]







*No. 1
Sm
A
0.037
1.005
0.150
0.60
2.40
0.80
0.40
0.38
1200


*No. 2
Sm
B
0.160
1.005
0.150
0.60
2.40
0.80
0.40
0.38
1200


*No 3
Sm
C
0.080
0.995
0.150
0.60
2.40
0.80
0.40
0.41
1200


*No. 4
Sm
D
0.100
1.032
0.150
0.60
2.40
0.80
0.40
0.47
1200


*No. 5
Sm
E
0.050
1.002
0.007
0.60
2.40
0.80
0.40
0.38
1200


*No. 6
Sm
E
0.050
1.002
5.200
0.60
2.40
0.80
0.40
0.70
1200


*No. 7
Sm
E
0.050
1.002
0.150
0.04
2.40
0.80
0.40
0.25
1150


*No. 8
Sm
E
0.050
1.002
0.150
5.10
2.40
0.80
0.40
0.89
1300


*No. 9
Sm
E
0.050
1.002
0.150
0.60
0.15
0.80
0.40
0.58
1200


*No. 10
Sm
E
0.050
1.002
0.150
0.60
8.10
0.80
0.40
0.53
1200


*No. 11
Sm
E
0.050
1.002
0.150
0.60
2.40
0.00
0.40
0.75
1170


*No. 12
Sm
E
0.050
1.002
0.150
0.60
2.40
0.00
0.40
0.88
1200


*No. 13
Sm
E
0.050
1.002
0.150
0.60
2.40
0.00
0.40
1.04
1230


*No. 14
Sm
E
0.050
1.002
0.150
0.60
2.40
0.04
0.40
0.73
1170


*No. 15
Sm
E
0.050
1.002
0.150
0.60
2.40
0.04
0.40
0.89
1200


*No. 16
Sm
E
0.050
1.002
0.150
0.60
2.40
0.04
0.40
1.04
1230


*No. 17
Sm
E
0.050
1.002
0.150
0.60
2.40
3.20
0.40
0.26
1200


*No. 18
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
0.04
0.48
1200


*No. 19
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
2.70
0.49
1200


 No. 20
Sm
F
0.040
1.002
0.150
0.60
2.40
0.80
0.40
0.44
1200


 No. 21
Sm
G
0.058
1.011
0.150
0.60
2.40
0.80
0.40
0.56
1200


 No. 22
Sm
H
0.070
1.004
0.150
0.60
2.40
0.80
0.40
0.45
1200


 No. 23
Sm
I
0.100
1.007
0.150
0.60
2.40
0.80
0.40
0.55
1200


 No. 24
Sm
K
0.125
1.020
0.150
0.60
2.40
0.80
0.40
0.47
1200


 No. 25
Sm
L
0.150
1.005
0.150
0.60
2.40
0.80
0.40
0.33
1200


 No. 26
Sm
L
0.050
0.998
0.150
0.60
2.40
0.80
0.40
0.56
1200


 No. 27
Sm
M
0.050
1.015
0.150
0.60
2.40
0.80
0.40
0.47
1200


 No. 28
Sm
N
0.050
1.030
0.150
0.60
2.40
0.80
0.40
0.43
1200


 No. 29
Sm
E
0.050
1.002
0.010
0.60
2.40
0.80
0.40
0.61
1200


 No. 30
Sm
E
0.050
1.002
0.100
0.60
2.40
0.80
0.40
0.55
1200


 No. 31
Sm
E
0.050
1.002
0.400
0.60
2.40
0.80
0.40
0.55
1200


 No. 32
Sm
E
0.050
1.002
0.700
0.60
2.40
0.80
0.40
0.58
1200


 No. 33
Sm
E
0.050
1.002
1.000
0.60
2.40
0.80
0.40
0.51
1175


 No. 34
Sm
E
0.050
1.002
2.000
0.60
2.40
0.80
0.40
0.41
1175


 No. 35
Sm
E
0.050
1.002
3.500
0.60
2.40
0.80
0.40
0.40
1150


 No. 36
Sm
E
0.050
1.002
5.000
0.60
2.40
0.80
0.40
0.39
1150


 No. 37
Sm
E
0.050
1.002
0.150
0.05
2.40
0.80
0.40
0.45
1200


 No. 38
Sm
E
0.050
1.002
0.150
0.15
2.40
0.80
0.40
0.42
1200


 No. 39
Sm
E
0.050
1.002
0.150
0.90
2.40
0.80
0.40
0.52
1200


 No. 40
Sm
E
0.050
1.002
0.150
1.20
2.40
0.80
0.40
0.52
1200


 No. 41
Sm
E
0.050
1.002
0.150
3.00
2.40
0.80
0.40
0.42
1200


 No. 42
Sm
E
0.050
1.002
0.150
5.00
2.40
0.80
0.40
0.54
1200


 No. 43
Sm
E
0.050
1.002
0.150
0.60
0.20
0.80
0.40
0.54
1225


 No. 44
Sm
E
0.050
1.002
0.150
0.60
0.60
0.80
0.40
0.42
1225


 No. 45
Sm
E
0.050
1.002
0.150
0.60
1.00
0.80
0.40
0.56
1200


 No. 46
Sm
E
0.050
1.002
0.150
0.60
4.50
0.80
0.40
0.41
1200


 No. 47
Sm
E
0.050
1.002
0.150
0.60
6.50
0.80
0.40
0.53
1150


 No. 48
Sm
E
0.050
1.002
0.150
0.60
8.00
0.80
0.40
0.59
1150


 No. 49
Sm
E
0.050
1.002
0.150
0.60
2.40
0.05
0.40
0.62
1200


 No. 50
Sm
E
0.050
1.002
0.150
0.60
2.40
0.15
0.40
0.38
1170



























TABLE 3






Rare-









Firing



earth
Powder








temperature


Sample
element
used
x
m
a
b
c
d
e
Ra
[° C.]







No. 51
Sm
E
0.050
1.002
0.150
0.60
2.40
0.15
0.40
0.46
1200


No. 52
Sm
E
0.050
1.002
0.150
0.60
2.40
0.15
0.40
0.54
1230


No. 53
Sm
E
0.050
1.002
0.150
0.60
2.40
0.40
0.40
0.48
1180


No. 54
Sm
E
0.050
1.002
0.150
0.60
2.40
1.00
0.40
0.43
1170


No. 55
Sm
E
0.050
1.002
0.150
0.60
2.40
1.00
0.40
0.56
1200


No. 56
Sm
E
0.050
1.002
0.150
0.60
2.40
1.00
0.40
0.62
1230


No. 57
Sm
E
0.050
1.002
0.150
0.60
2.40
1.70
0.40
0.52
1200


No. 58
Sm
E
0.050
1.002
0.150
0.60
2.40
2.60
0.40
0.43
1200


No. 59
Sm
E
0.050
1.002
0.150
0.60
2.40
3.00
0.40
0.47
1150


No. 60
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
0.05
0.45
1200


No. 61
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
0.20
0.30
1200


No. 62
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
0.90
0.38
1200


No. 63
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
1.20
0.46
1200


No. 64
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
1.80
0.49
1200


No. 65
Sm
E
0.050
1.002
0.150
0.60
2.40
0.80
2.50
0.57
1200


No. 66
Y
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.56
1200


No. 67
Y
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.38
1200


No. 68
La
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.40
1200


No. 69
La
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.66
1200


No. 70
Ce
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.59
1200


No. 71
Ce
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.40
1200


No. 72
Nd
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.59
1200


No. 73
Nd
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.46
1225


No. 74
Eu
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.47
1200


No. 75
Eu
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.48
1200


No. 76
Gd
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.50
1200


No. 77
Gd
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.65
1200


No. 78
Tb
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.34
1200


No. 79
Tb
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.41
1200


No. 80
Dy
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.42
1200


No. 81
Dy
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.47
1200


No. 82
Ho
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.36
1200


No. 83
Ho
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.55
1200


No. 84
Er
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.47
1200


No. 85
Er
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.50
1200


No. 86
Tm
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.43
1200


No. 87
Tm
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.49
1200


No. 88
Yb
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.51
1200


No. 89
Yb
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.37
1200


No. 90
Lu
E
0.050
1.002
0.150
0.60
2.40
0.80
0.40
0.38
1200


No. 91
Lu
E
0.050
1.002
0.150
0.60
2.40
0.80
1.50
0.39
1200


No. 92
Sm + Dy
E
0.050
1.002
0.150
0.60
2.40
0.80
0.60
0.59
1200



(0.3 each)


No. 93
Sm + Dy
E
0.050
1.002
0.150
0.60
2.40
0.80
1.40
0.52
1200



(0.7 each)


No. 94
Gd + Yb
E
0.050
1.002
0.150
0.60
2.40
0.80
0.60
0.54
1200



(0.3 each)


No. 95
Gd + Yb
E
0.050
1.002
0.150
0.60
2.40
0.80
1.40
0.46
1200



(0.7 each)





















TABLE 4








Rate of change
Resis-




Relative

of dielectric
tivity
Mean time



dielectric
tan δ
constant with
Log ρ
to failure


Sample
constant εr
[%]
temperature [%]
ρ: Ωm
[hour]




















*No. 1
5270
8.1
−22.5
10.9
10


*No. 2
4520
7.9
−23.2
11.0
30


*No 3
5380
7.7
−22.1
9.2
Unmeasurable


*No. 4
4820
10.5
−23.5
7.9
Unmeasurable


*No. 5
5290
7.9
−21.3
8.5
Unmeasurable


*No. 6
5940
10.7
−22.5
9.2
30


*No. 7
4870
7.2
−21.0
11.0
5


*No. 8
7450
13.2
−29.2
10.7
140


*No. 9
4120
13.2
−24.2
9.3
25


*No. 10
5650
8.7
−23.2
10.7
20


*No. 11
6210
11.4
−23.5
11.0
140


*No. 12
6810
12.1
−23.7
11.1
130


*No. 13
7540
13.5
−24.3
11.3
140


*No. 14
6350
11.2
−24.2
11.1
120


*No. 15
6940
12.2
−24.1
11.1
150


*No. 16
7520
13.3
−24.1
11.1
120


*No. 17
4630
6.6
−20.1
11.1
120


*No. 18
5200
8.2
−20.4
11.1
Unmeasurable


*No. 19
5500
8.1
−24.3
11.2
190


 No. 20
5420
7.9
−20.0
11.3
170


 No. 21
5560
8.7
−21.0
10.7
170


 No. 22
5360
8.4
−20.7
11.1
130


 No. 23
5690
8.7
−21.1
10.7
160


 No. 24
5480
8.6
−20.5
10.7
150


 No. 25
5220
7.3
−19.6
11.3
160


 No. 26
5650
8.7
−20.8
10.8
160


 No. 27
5440
8.6
−19.7
10.9
150


 No. 28
5360
8.3
−19.8
10.8
105


 No. 29
5650
8.9
−20.5
10.9
140


 No. 30
5690
8.7
−20.4
11.2
130


 No. 31
5560
9.0
−20.3
10.6
160


 No. 32
5690
9.0
−21.4
10.8
170


 No. 33
5610
8.5
−20.4
11.0
170


 No. 34
5280
8.3
−20.5
10.6
170


 No. 35
5260
7.8
−20.3
10.9
120


 No. 36
5280
8.1
−19.4
11.1
170


 No. 37
5470
8.0
−20.3
11.4
150


 No. 38
5410
7.7
−19.6
10.8
150


 No. 39
5630
8.4
−20.5
11.3
160


 No. 40
5530
8.8
−20.8
11.4
160


 No. 41
5310
7.7
−20.8
10.7
150


 No. 42
5680
8.8
−20.8
11.0
120


 No. 43
5660
8.4
−20.9
11.3
130


 No. 44
5330
7.8
−19.6
11.0
150


 No. 45
5530
8.4
−21.2
10.9
180


 No. 46
5270
8.2
−19.9
11.3
150


 No. 47
5530
8.5
−20.2
11.0
130


 No. 48
5750
8.8
−20.9
10.6
180


 No. 49
5720
8.8
−20.9
11.0
110


 No. 50
5240
9.0
−20.2
10.7
170





















TABLE 5








Rate of change
Resis-




Relative

of dielectric
tivity
Mean time



dielectric
tan δ
constant with
Log ρ
to failure


Sample
constant εr
[%]
temperature [%]
ρ: Ωm
[hour]







No. 51
5490
8.7
−20.5
10.9
160


No. 52
5720
8.7
−20.0
11.0
170


No. 53
5410
8.2
−20.0
11.0
120


No. 54
5440
8.3
−20.1
11.1
180


No. 55
5680
8.2
−20.5
11.0
140


No. 56
5900
8.6
−19.9
10.8
170


No. 57
5470
8.3
−20.3
10.7
180


No. 58
5430
8.3
−20.6
10.7
140


No. 59
5460
8.6
−20.2
11.2
140


No. 60
5490
8.3
−20.8
11.4
120


No. 61
5200
7.6
−20.1
11.1
110


No. 62
5170
7.8
−19.6
11.0
140


No. 63
5450
8.2
−20.6
11.2
110


No. 64
5440
8.5
−20.4
10.7
140


No. 65
5630
8.5
−20.5
10.9
170


No. 66
5670
8.6
−20.3
11.0
150


No. 67
5190
7.8
−19.6
11.1
180


No. 68
5400
7.9
−20.0
10.7
160


No. 69
5850
9.6
−21.4
11.3
150


No. 70
5720
9.0
−20.3
10.8
160


No. 71
5340
8.0
−20.3
10.8
120


No. 72
5750
8.8
−21.0
11.3
120


No. 73
5330
8.0
−19.7
10.7
110


No. 74
5520
8.1
−19.8
11.2
160


No. 75
5500
8.3
−20.0
11.0
160


No. 76
5440
8.7
−20.4
10.8
120


No. 77
5740
9.1
−21.7
10.6
170


No. 78
5190
7.7
−19.8
10.8
150


No. 79
5370
7.6
−19.5
10.9
170


No. 80
5340
7.9
−20.1
11.0
180


No. 81
5450
8.4
−20.1
10.8
150


No. 82
5160
7.8
−20.2
11.2
130


No. 83
5610
9.0
−20.7
10.9
110


No. 84
5500
8.3
−20.2
11.1
130


No. 85
5530
8.5
−20.0
10.7
110


No. 86
5330
7.9
−19.8
10.9
160


No. 87
5450
8.5
−20.6
10.8
140


No. 88
5620
8.5
−21.1
11.4
130


No. 89
5340
7.7
−20.2
11.0
180


No. 90
5350
7.7
−20.0
10.9
120


No. 91
5200
7.6
−20.3
11.4
110


No. 92
5750
9.1
−20.8
11.0
140


No. 93
5570
8.9
−20.9
11.3
160


No. 94
5670
8.6
−20.1
11.4
110


No. 95
5390
8.0
−20.1
11.2
140









As is clear from the measurement results shown in Tables 4 and 5, all of the multilayer ceramic capacitors sample Nos. 20 to 95, each including dielectric ceramic material (1) having a composition within the range of the present invention was found to be a high-reliability multilayer ceramic capacitor having a mean time to failure of 100 hours or more in the high-temperature load test, a high dielectric constant εr of 5000 or more, a small dielectric loss (tan δ) of 10% or less, a rate of change of the dielectric constant with temperature meeting the X6S characteristics (within ±22%), and a high resistivity p of 1010.5 Ωm (log ρ=10.5) or more, in spite of the fact that the thickness of the dielectric ceramic layer was reduced to about 1 μm.
It was found that in the case where the molar ratio d of MgO was in the range of 0.05≦d≦3.0 relative to 100 of (Ba,Ca)TiO3, even when each of sample Nos. 54 to 56 having the same composition was fired at a firing temperature range between 1170° C. and 1230° C., a difference in temperature of 60° C., the change in relative dielectric constant εr was small to achieve stable quality without the nonuniformity in electrical properties.
Furthermore, as is clear from the case of sample Nos. 66 to 69, in the case where the molar amount e, which was the total of the molar amounts of two rare-earth element oxides, was in the range of 0.05≦e≦2.5 relative to 100 of (Ba,Ca)TiO3, it was possible to obtain the multilayer ceramic capacitors having satisfactory electrical properties in the same way as in other sample Nos. 20 to 91 each containing a single type of rare-earth element oxide, even when the dielectric ceramic layers each have a small thickness of about 1 μm.
In contrast, as is clear from the measurement results of sample Nos. 1 to 19 shown in Table 4, it was found that if any one of the content of the oxides was outside the range of the present invention, the resulting multilayer ceramic capacitors had degraded electrical properties even if each of the contents of the other oxides was within the range of the present invention, as described below.
In the case of sample No. 1 using sample A in which Ba ions in (Ba1-xCax)mTiO3 were partially replaced with Ca ions and the substitution rate x of Ca ions was less than 0.04, the mean time to failure in the high-temperature load test was as short as 10 hours. In the case of sample No. 2 using sample B in which the substitution rate x exceeded 0.15, the relative dielectric constant εr was 4520, which was less than 5000, the rate of change of the dielectric constant with temperature was −23.2%, which was outside the range of ±22%, and mean time to failure was as short as 30 hours.
In the case of sample No. 3 using sample C in which the ratio m, i.e., Ba1-xCax/Ti, was less than 0.998, the resistivity p was 109.2 Ωm, which was less than 1010.5 Ωm. The mean time to failure was too short to be measured. In the case of sample No. 4 using sample D in which the ratio m exceeded 1.030, the relative dielectric constant εr was 4820, which was less than 5000. The dielectric loss (tan δ) was 10.5%, which exceeded 10%. The resistivity ρ was 107.9 Ωm, which was less than 1010.5 Ωm. The mean time to failure was too short to be measured.
In the case of sample No. 5 in which the molar ratio a of MnO was less than 0.01 relative to 100 of (Ba1-xCax)mTiO3, the resistivity ρ was 108.5 Ωm, which was less than 1010.5 Ωm. The mean time to failure was too short to be measured. In the case of sample No. 6 in which the molar ratio a exceeded 5, the rate of change of the dielectric constant with temperature was −22.5%, which was outside of the range of ±22%. The resistivity p was 109.2 Ωm, which was less than 1010.5 Ωm. The mean time to failure was as short as 30 hours.
In the case of sample No. 7 in which the molar ratio b of CuO was less than 0.05, the relative dielectric constant εr was 4870, which was less than 5000. The mean time to failure was as short as 5 hours. Furthermore, MnO particles each having a size of 1 μm or more are segregated to degrade the uniformity in MnO distribution. In the case of sample No. 8 in which the molar ratio b exceeded 5, the rate of change of the dielectric constant with temperature was −29.2%, which was outside the range of ±22%.
In the case of sample No. 9 in which the molar ratio c of SiO2 was less than 0.2, the relative dielectric constant εr was 4120, which was less than 5000. The dielectric loss (tan δ) was 13.2%, which exceeded 10%. The rate of change of the dielectric constant with temperature was −24.2%, which was outside the range of ±22%. The resistivity ρ was 109.3 Ωm, which was less than 1010.5 Ωm. The mean time to failure was as short as 25 hours. In the case of sample No. 10 in which the molar ratio c exceeded 8, the rate of change of the dielectric constant with temperature was −23.2%, which was outside the range of ±22%. The mean time to failure was as short as 20 hours.
In cases of sample Nos. 11 to 16 in which the molar ratios d were each less than 0.05, each average grain size exceeded 0.7 μm (see Table 2). When the firing temperature was changed from 1170° C. to 1230° C., a difference in temperature of 60° C., the change in relative dielectric constant εr was 1000 or more to cause the nonuniformity in electrical properties. In the case of sample No. 17 in which the molar ratio d exceeded 3, the grain size was 0.26 μm, which was less than 0.3 μm. The relative dielectric constant εr was 4630, which was less than 5000.
In the case of sample No. 18 in which the molar ratio e of RO was less than 0.05, the mean time to failure was too short to be measured. In the case of sample No. 19 in which the molar ratio d exceeded 2.5, the rate of change of the dielectric constant with temperature was −24.3%, which was outside the range of ±22%.
In cases of sample Nos. 7 and 17 in which the average grain sizes were each less than 0.3 μm, each relative dielectric constant εr was as small as less than 5000. In cases of sample Nos. 8 and 11 to 16 in which the average grain sizes each exceeded 0.7 μm, each rate of change of the dielectric constant with temperature exceeded ±22%.
Example 2
In this example, after the preparation of material powders of dielectric ceramic material (2), multilayer ceramic capacitors were produced with the material powders. First, high-purity TiO2, BaCO3 and CaCO3, which were starting materials, were prepared. These starting materials were weighed in a manner such that Ti, Ba and Ca were contained in amounts represented by samples A′ to K′ shown in Table 6, wet-mixed, pulverized, and dried to prepare mixed powders. The mixed powders were heated at 950° C. or more for 2 hours to prepare BaTiO3 or (Ba,Ca)TiO3 powders represented by samples A′ to K′ having compositions shown in Table 6, the material powders each having an average particle size of 0.1 to 0.2 μm. A MgO powder, a CuO powder, a MnCO3 powder, a SiO2 powder and an RO powder (wherein RO represents at least one rare-earth element oxide selected from Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3) were prepared as other material powders. In Table 6, samples A′, B′, and C′ with asterisks “*” indicate that x and m were outside the range of the present invention.
Subsequently, the powders were weighed in a manner such that compositions shown in Tables 7 and 8 were achieved, and then mixed to obtain mixtures represented by sample Nos. 101 to 192. A polyvinyl butyral binder and an organic solvent such as ethanol were added to each mixture, and the resulting mixtures were wet-mixed with ball mills to prepare ceramic slurries. Each of the resulting ceramic slurries was formed into a sheet by a doctor blade method to obtain a rectangular ceramic green sheet having a thickness of 1.4 μm. Next, a conductive paste principally composed of nickel (Ni) was applied onto each of the resulting ceramic green sheets by printing to provide a conductive paste film to be an internal electrode. One end of the conductive paste film is disposed at a first end of the ceramic green sheet, and the other end of the conductive paste film was disposed away from a second end of the ceramic green sheet. In Table 7, asterisk-marked sample Nos. 101 to 118 were samples in which any one of x, m, a, b, c, d, and e was outside the range of the present invention.
Next, a plurality of the ceramic green sheets that were the same type were stacked in a manner such that the first end, in which the conductive paste films were disposed, and the second end were alternately disposed. The resulting stack was interposed between ceramic green sheets each having no conducting paste film and then was subjected to press bonding to obtain a laminate. Each of the resulting laminates was heated to 350° C. in an N2 atmosphere to decompose the binder and then fired for 2 hours in a reducing atmosphere containing a H2 gas, a N2 gas, and a H2O gas and having an oxygen partial pressure of 10−9 to 10−12 MPa at a temperature shown in Tables 7 and 8.
A silver paste containing a B2O3—SiO2—BaO-based glass frit was applied to both ends of each of the fired laminates and then baked at 600° C. in an N2 atmosphere to form external electrodes electrically connected to the internal electrodes. Thereby, laminated ceramic capacitors including the dielectric ceramic material (2) of the present invention were produced.
The outer dimensions of each of the resulting multilayer ceramic capacitors (sample Nos. 101 to 192) were 5.0 mm in width, 5.7 mm in length, and 2.4 mm in thickness, similar to EXAMPLE 1. The dielectric ceramic layers each disposed between the internal electrodes each had a thickness of 1.0 μm. The number of effective dielectric ceramic layers was five layers. The area of each of the opposite electrodes was 16.3×10−6 m2 per layer.
Next, the electrical properties of the multilayer ceramic capacitors of sample Nos. 101 to 192 were measured. The relative dielectric constant εr and the dielectric loss (tan δ) were measured in the same methods as in EXAMPLE 1. Tables 9 and 10 show the results.
To measure insulation resistance R, an insulation resistance tester was used. That is, 4 V DC was applied for 1 minute, and the insulation resistance R was measured at +25° C., and then the resistivity ρ was calculated. Tables 9 and 10 show the results as log ρ.
With respect to the rate of change of capacitance C with temperature, the rate of change ΔC/C25° C. in the range of −25° C. to +85° C. with reference to a capacitance at 25° C. was determined. Tables 9 and 10 show the results as the rate of change of the dielectric constant with temperature.
With respect to a high-temperature load test, 8 V DC was applied at 125° C. to 12 specimens of each sample, and a change in insulation resistance R with time was measured. In the high-temperature load test, a state in which the insulation resistance R of each sample reached 105Ω or less was defined as failure. After measurement of the time required for reaching failure, the mean time to failure was determined. Tables 9 and 10 show the results.
The average grain size was measured by the same method as in EXAMPLE 1.












TABLE 6










Particle size



Sample
x
m
of material









*A′ 
0.042
1.003
0.12



*B′ 
0.020
0.996
0.13



*C′ 
0.010
1.031
0.11



D′
0.000
1.001
0.14



E′
0.005
1.001
0.15



F′
0.010
1.011
0.13



G′
0.020
1.004
0.13



H′
0.039
1.007
0.14



I′
0.000
0.998
0.12



J′
0.000
1.017
0.14



K′
0.000
1.030
0.13




























TABLE 7






Rare-









Firing



earth
Powder








temperature


Sample
element
used
x
m
a
b
c
d
e
Ra
[° C.]


























*No. 101 
Gd
A′
0.042
1.003
0.200
0.50
1.50
1.00
0.60
0.49
1220


*No. 102 
Gd
B′
0.020
0.996
0.200
0.50
1.50
1.00
0.60
0.42
1220


*No. 103 
Gd
C′
0.010
1.031
0.200
0.50
1.50
1.00
0.60
0.57
1220


*No. 104 
Gd
D′
0.000
1.001
0.008
0.50
1.50
1.00
0.60
0.41
1220


*No. 105 
Gd
D′
0.000
1.001
5.100
0.50
1.50
1.00
0.60
0.43
1220


*No. 106 
Gd
D′
0.000
1.001
0.200
0.045
1.50
1.00
0.60
0.28
1180


*No. 107 
Gd
D′
0.000
1.001
0.200
5.20
1.50
1.00
0.60
0.78
1260


*No. 108 
Gd
D′
0.000
1.001
0.200
0.50
0.18
1.00
0.60
0.59
1220


*No. 109 
Gd
D′
0.000
1.001
0.200
0.50
8.20
1.00
0.60
0.46
1220


*No. 110 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.00
0.60
0.72
1170


*No. 111 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.00
0.60
0.79
1200


*No. 112 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.00
0.60
0.93
1230


*No. 113 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.04
0.60
0.73
1190


*No. 114 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.04
0.60
0.81
1220


*No. 115 
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.04
0.60
0.92
1250


*No. 116 
Gd
D′
0.000
1.001
0.200
0.50
1.50
3.10
0.60
0.27
1220


*No. 117 
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.03
0.49
1220


*No. 118 
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
2.60
0.43
1220


No. 119
Gd
E′
0.005
1.001
0.200
0.50
1.50
1.00
0.60
0.60
1220


No. 120
Gd
F′
0.010
1.011
0.200
0.50
1.50
1.00
0.60
0.53
1220


No. 121
Gd
G′
0.020
1.004
0.200
0.50
1.50
1.00
0.60
0.38
1220


No. 122
Gd
H′
0.039
1.007
0.200
0.50
1.50
1.00
0.60
0.46
1220


No. 123
Gd
I′
0.000
0.998
0.200
0.50
1.50
1.00
0.60
0.48
1220


No. 124
Gd
J′
0.000
1.017
0.200
0.50
1.50
1.00
0.60
0.60
1220


No. 125
Gd
K′
0.000
1.030
0.200
0.50
1.50
1.00
0.60
0.54
1220


No. 126
Gd
D′
0.000
1.001
0.010
0.50
1.50
1.00
0.60
0.54
1220


No. 127
Gd
D′
0.000
1.001
0.030
0.50
1.50
1.00
0.60
0.49
1220


No. 128
Gd
D′
0.000
1.001
0.100
0.50
1.50
1.00
0.60
0.55
1220


No. 129
Gd
D′
0.000
1.001
0.400
0.50
1.50
1.00
0.60
0.45
1220


No. 130
Gd
D′
0.000
1.001
0.700
0.50
1.50
1.00
0.60
0.35
1190


No. 131
Gd
D′
0.000
1.001
1.500
0.50
1.50
1.00
0.60
0.57
1190


No. 132
Gd
D′
0.000
1.001
3.600
0.50
1.50
1.00
0.60
0.41
1180


No. 133
Gd
D′
0.000
1.001
5.000
0.50
1.50
1.00
0.60
0.55
1170


No. 134
Gd
D′
0.000
1.001
0.200
0.05
1.50
1.00
0.60
0.50
1220


No. 135
Gd
D′
0.000
1.001
0.200
0.20
1.50
1.00
0.60
0.42
1220


No. 136
Gd
D′
0.000
1.001
0.200
0.80
1.50
1.00
0.60
0.57
1220


No. 137
Gd
D′
0.000
1.001
0.200
1.30
1.50
1.00
0.60
0.36
1220


No. 138
Gd
D′
0.000
1.001
0.200
3.20
1.50
1.00
0.60
0.43
1220


No. 139
Gd
D′
0.000
1.001
0.200
5.00
1.50
1.00
0.60
0.58
1220


No. 140
Gd
D′
0.000
1.001
0.200
0.50
0.20
1.00
0.60
0.48
1240


No. 141
Gd
D′
0.000
1.001
0.200
0.50
0.50
1.00
0.60
0.43
1220


No. 142
Gd
D′
0.000
1.001
0.200
0.50
1.20
1.00
0.60
0.52
1220


No. 143
Gd
D′
0.000
1.001
0.200
0.50
2.70
1.00
0.60
0.36
1220


No. 144
Gd
D′
0.000
1.001
0.200
0.50
5.80
1.00
0.60
0.44
1170


No. 145
Gd
D′
0.000
1.001
0.200
0.50
8.00
1.00
0.60
0.49
1170


No. 146
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.05
0.60
0.37
1220


No. 147
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.20
0.60
0.39
1180


No. 148
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.20
0.60
0.48
1210


No. 149
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.20
0.60
0.55
1240


No. 150
Gd
D′
0.000
1.001
0.200
0.50
1.50
0.50
0.60
0.53
1200



























TABLE 8






Rare-









Firing



earth
Powder








temperature


Sample
element
used
x
m
a
b
c
d
e
Ra
[° C.]







No. 151
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.20
0.60
0.45
1190


No. 152
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.20
0.60
0.51
1220


No. 153
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.20
0.60
0.55
1250


No. 154
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.90
0.60
0.48
1220


No. 155
Gd
D′
0.000
1.001
0.200
0.50
1.50
2.50
0.60
0.50
1220


No. 156
Gd
D′
0.000
1.001
0.200
0.50
1.50
3.00
0.60
0.48
1170


No. 157
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.05
0.42
1220


No. 158
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.25
0.54
1220


No. 159
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.70
0.55
1220


No. 160
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.00
0.47
1220


No. 161
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.52
1220


No. 162
Gd
D′
0.000
1.001
0.200
0.50
1.50
1.00
2.50
0.48
1220


No. 163
Y
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.49
1220


No. 164
Y
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.55
1220


No. 165
La
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.50
1220


No. 166
La
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.40
1220


No. 167
Ce
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.51
1220


No. 168
Ce
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.48
1220


No. 169
Nd
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.41
1220


No. 170
Nd
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.47
1245


No. 171
Eu
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.57
1220


No. 172
Eu
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.59
1220


No. 173
Sm
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.50
1220


No. 174
Sm
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.59
1220


No. 175
Tb
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.58
1220


No. 176
Tb
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.38
1220


No. 177
Dy
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.52
1220


No. 178
Dy
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.48
1220


No. 179
Ho
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.43
1220


No. 180
Ho
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.59
1220


No. 181
Er
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.51
1220


No. 182
Er
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.39
1220


No. 183
Tm
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.44
1220


No. 184
Tm
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.60
1220


No. 185
Yb
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.57
1220


No. 186
Yb
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.50
1220


No. 187
Lu
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.57
1220


No. 188
Lu
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.38
1220


No. 189
Gd + Ho
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.46
1220



(0.3 each)


No. 190
Gd + Ho
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.40
1220



(0.85 each)


No. 191
Dy + Lu
D′
0.000
1.001
0.200
0.50
1.50
1.00
0.60
0.47
1220



(0.3 each)


No. 192
Dy + Lu
D′
0.000
1.001
0.200
0.50
1.50
1.00
1.70
0.37
1220



(0.85 each)





















TABLE 9








Rate of change
Resis-




Relative

of dielectric
tivity
Mean time



dielectric
tan δ
constant with
Log ρ
to failure


Sample
constant εr
[%]
temperature [%]
ρ: Ωm
[hour]




















*No. 101 
5420
7.7
−13.1
11.2
140


*No. 102 
6340
7.3
−13.3
9.2
Un-







measurable


*No. 103 
3960
8.9
−16.3
11.2
Un-







measurable


*No. 104 
6590
7.6
−13.4
9.9
Un-







measurable


*No. 105 
6530
6.8
−15.6
10.2
120


*No. 106 
5420
6.3
−12.8
11.1
20


*No. 107 
6300
6.8
−16.2
10.7
140


*No. 108 
3900
12.1
−17.1
9.4
15


*No. 109 
6820
7.7
−12.9
10.2
40


*No. 110 
7040
8.2
−14.5
10.8
120


*No. 111 
7590
9.5
−15.2
10.7
140


*No. 112 
8300
10.8
−15.7
11.0
130


*No. 113 
7420
8.3
−15.2
11.0
140


*No. 114 
8030
9.5
−15.7
11.1
120


*No. 115 
8540
10.2
−16.2
11.2
150


*No. 116 
5210
6.8
−12.6
10.9
110


*No. 117 
6810
8.5
−13.1
11.2
Un-







measurable


*No. 118 
6500
7.3
−16.2
11.2
120


No. 119
7350
8.7
−13.9
10.9
140


No. 120
7170
8.5
−13.6
10.8
140


No. 121
6430
6.4
−12.9
10.8
120


No. 122
6560
8.2
−12.9
11.1
130


No. 123
6810
7.9
−13.4
10.8
150


No. 124
7490
9.8
−14.4
10.8
110


No. 125
7110
8.0
−14.3
11.2
140


No. 126
7190
9.1
−13.4
11.0
130


No. 127
6880
8.1
−13.2
10.8
130


No. 128
7200
8.5
−13.7
11.0
170


No. 129
6600
7.2
−13.5
10.8
110


No. 130
6310
6.1
−12.6
11.3
140


No. 131
7270
9.6
−13.6
11.2
160


No. 132
6390
7.3
−12.8
10.8
140


No. 133
7180
8.9
−14.3
11.2
150


No. 134
6790
7.8
−13.1
10.8
150


No. 135
6460
7.3
−13.5
11.1
130


No. 136
7320
9.2
−13.7
10.8
140


No. 137
6270
6.4
−12.8
11.2
140


No. 138
6640
8.0
−13.3
11.0
180


No. 139
7280
9.5
−14.7
11.2
180


No. 140
6690
7.7
−13.1
10.9
160


No. 141
6630
8.1
−13.6
11.2
160


No. 142
6970
9.1
−13.7
11.0
140


No. 143
6290
6.5
−12.5
10.8
130


No. 144
6700
8.2
−12.8
11.3
150


No. 145
6750
8.9
−13.0
10.9
130


No. 146
6210
7.1
−13.0
11.2
120


No. 147
6300
7.3
−14.1
11.2
160


No. 148
6480
8.4
−12.9
10.8
130


No. 149
6900
9.2
−14.2
10.7
120


No. 150
7170
9.1
−13.9
11.2
170





















TABLE 10








Rate of change
Resis-




Relative

of dielectric
tivity
Mean time



dielectric
tan δ
constant with
Log ρ
to failure


Sample
constant εr
[%]
temperature [%]
ρ: Ωm
[hour]







No. 151
7020
7.8
−13.8
10.7
110


No. 152
7240
8.8
−13.9
10.9
170


No. 153
7490
9.0
−13.9
10.8
110


No. 154
6850
7.8
−13.7
11.1
180


No. 155
7040
8.4
−14.1
10.8
120


No. 156
6690
8.2
−13.9
10.7
150


No. 157
6660
7.8
−12.6
10.8
170


No. 158
7050
9.0
−14.1
11.2
110


No. 159
7260
8.6
−13.9
11.2
110


No. 160
6660
8.6
−13.3
10.7
150


No. 161
6780
8.6
−13.4
10.8
120


No. 162
6910
8.0
−13.9
10.9
170


No. 163
6880
8.0
−13.6
11.3
170


No. 164
7290
8.6
−14.5
10.7
110


No. 165
6830
8.2
−13.8
11.1
110


No. 166
6450
6.7
−13.3
10.9
170


No. 167
6850
9.0
−13.3
10.8
130


No. 168
6850
7.9
−13.1
11.3
120


No. 169
6510
7.3
−13.1
10.9
130


No. 170
6600
7.9
−13.0
10.9
110


No. 171
7240
8.9
−14.1
10.9
150


No. 172
7400
9.1
−14.4
11.1
110


No. 173
7020
8.9
−13.3
10.7
120


No. 174
7200
9.1
−13.9
10.9
150


No. 175
7200
9.6
−13.6
11.0
160


No. 176
6460
7.7
−12.8
11.2
130


No. 177
6900
8.8
−14.1
11.0
160


No. 178
6810
7.9
−13.6
11.0
160


No. 179
6450
7.1
−13.1
11.2
130


No. 180
7220
9.3
−14.6
11.1
110


No. 181
7080
7.6
−14.2
11.3
110


No. 182
6410
6.7
−12.9
11.1
160


No. 183
6730
8.0
−13.0
10.9
110


No. 184
7500
9.7
−14.0
11.2
170


No. 185
7240
9.5
−14.4
11.3
180


No. 186
7020
8.5
−13.9
10.8
150


No. 187
7220
8.8
−13.6
11.2
160


No. 188
6250
7.4
−13.2
11.2
120


No. 189
6590
8.2
−12.9
11.0
150


No. 190
6320
7.0
−12.5
10.9
120


No. 191
6620
7.9
−13.3
11.2
150


No. 192
6290
6.3
−12.9
10.8
180









As is clear from the measurement results shown in Tables 9 and 10, all of the multilayer ceramic capacitors sample Nos. 119 to 192, each including dielectric ceramic material (2) having a composition within the range of the present invention, was found to be a high-reliability, high-dielectric multilayer ceramic capacitor having a mean time to failure of 100 hours or more in the high-temperature load test, a high dielectric constant εr of 6000 or more, a small dielectric loss (tan δ) of 10% or less, a rate of change of the dielectric constant with temperature meeting the X5R characteristics (within ±15%), and a high resistivity p of 1010.5 Ωm (log ρ=10.5) or more, in spite of the fact that the thickness of the dielectric ceramic layer was reduced to about 1 μm.
It was found that in the case where the molar ratio d of MgO was in the range of 0.05≦d≦3.0 relative to 100 of (Ba,Ca)TiO3, even when each of sample Nos. 147 to 149 having the same composition was fired at a firing temperature range between 1180° C. and 1240° C., a difference in temperature of 60° C., the change in relative dielectric constant εr was small to achieve stable quality without the nonuniformity in electrical properties.
Furthermore, as is clear from the case of sample Nos. 189 to 192, in the case where the molar ratio d, which was the total of the molar ratios of two rare-earth element oxides, was in the range of 0.05≦e≦2.5 relative to 100 of (Ba,Ca)TiO3, it was possible to obtain the multilayer ceramic capacitors having satisfactory electrical properties in the same way as in other sample Nos. 119 to 188 each containing a single type of rare-earth element oxide, even when the dielectric ceramic layers each have a small thickness of about 1 μm.
In contrast, as is clear from the measurement results shown in Table 9, it was found that if any one of contents of the oxides was outside the range of the present invention, the resulting multilayer ceramic capacitors had degraded electrical properties even if each of the contents of the other oxides was within the range of the present invention, as described below.
In the case of sample No. 101 using sample A′ in which Ba ions in (Ba1-xCax)mTiO3 were partially replaced with Ca ions and the substitution rate x of Ca ions was 0.04 or more, the relative dielectric constant εr was 5420, which was less than 6000.
In the case of sample No. 102 using sample B′ in which the ratio m, i.e., Ba1-xCax/Ti, was less than 0.998, the resistivity ρ was 109.2 Ωm, which was less than 1010.5 Ωm. The mean time to failure was too short to be measured. In the case of sample No. 103 using sample C′ in which the ratio m exceeded 1.030, the relative dielectric constant εr was 3960, which was significantly lower than 6000. The rate of change of the dielectric constant with temperature was −16.3%, which was outside the range of ±15%. The mean time to failure was too short to be measured.
In the case of sample No. 104 in which the molar ratio a of MnO was less than 0.01 relative to 100 of (Ba1-xCax)mTiO3, the resistivity ρ was 109.9 Ωm, which was less than 1010.5 Ωm. In the case of sample No. 105 in which the molar ratio a exceeded 5, the rate of change of the dielectric constant with temperature was −15.6%, which was outside the range of ±15%. The resistivity ρ was 1010.2 Ωm, which was less than 1010.5 Ωm.
In the case of sample No. 106 in which the molar amount b of CuO was less than 0.05, the relative dielectric constant εr was 5420, which was less than 6000. The mean time to failure was as short as 20 hours. In the case of sample No. 107 in which the molar amount b exceeded 5, the rate of change of the dielectric constant with temperature was −16.2%, which was outside the range of ±15%.
In the case of sample No. 108 in which the molar amount c of SiO2 was less than 0.2, the relative dielectric constant εr was 3900, which was less than 6000. The dielectric loss (tan δ) was 12.1%, which exceeded 10%. The rate of change of the dielectric constant with temperature was −17.1%, which was outside the range of ±15%. The Re ρ was 109.4 Ωm, which was less than 1010.5 Ωm. The mean time to failure was as short as 15 hours. In the case of sample No. 109 in which the molar amount c exceeded 8, the mean time to failure was as short as 40 hours.
In cases of sample Nos. 110 to 115 in which the molar amounts d were each less than 0.05, each average grain size exceeded 0.65 μm. When the firing temperature was changed from 1170° C. to 1230° C., a difference in temperature of 60° C., the change in relative dielectric constant εr was 1000 or more to cause the nonuniformity in electrical properties. In the case of sample No. 17 in which the molar amount d exceeded 3, the average grain size was as small as 0.27 μm. The relative dielectric constant εr was 5210, which was less than 6000.
In the case of sample No. 117 in which the molar amount e of RO was less than 0.05, the mean time to failure was too short to be measured. In the case of sample No. 118 in which the molar amount d exceeded 2.5, the rate of change of the dielectric constant with temperature was −16.2%, which was outside the range of ±15%.
The present invention is not limited to the above-described examples. Many widely different embodiments of the invention may be made without departing from the spirit thereof. For example, at least one element selected from a plurality of rare-earth elements is used. However, when a plurality of types of the rare-earth elements were used, the total amount d of the plurality of types of oxides thereof may satisfy the relationship: 0.05≦d≦2.5.
INDUSTRIAL APPLICABILITY
The present invention can be applied to a multilayer ceramic capacitor for a circuit board used in an electronic device or the like.

## Claims

1. A dielectric ceramic material comprising the composition: 100(Ba1-xCax)mTiO3+aMnO+bCuO+cSiO2+dMgO+eRO, wherein coefficients 100, a, b, c, d, and e each represent mols; m represents the molar ratio of (Ba1-x—Cax) to Ti; and RO represents at least one rare-earth element oxide selected from the group consisting of Y2O3, La2O3, 2CeO2, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3 and Lu2O3, wherein m, x, a, b, c, d, and e satisfy the relationships: 0.998≦m≦1.030, 0≦x≦0.15, 0.01≦a≦5, 0.05≦b≦5, 0.2≦c≦8, 0.05≦d≦3.0, and 0.05≦e≦2.5, and wherein the dielectric ceramic material has an average grain size of 0.3 μm to 0.7 μm.

2. A dielectric ceramic material according to claim 1, wherein RO is a single member of said group.

3. A dielectric ceramic material according to claim 1, wherein RO is at least two members of said group.

4. A dielectric ceramic material according to claim 1, wherein 0.04≦x≦0.15.

5. A dielectric ceramic material according to claim 4, wherein RO is a single member of said group.

6. A dielectric ceramic material according to claim 4, wherein RO is at least two members of said group.

7. A dielectric ceramic material according to claim 4, wherein RO comprises Sm2O3 or Gd2O3, 1.002≦m≦1.02, 0.05≦x≦0.125, 0.15≦a≦3.5, 0.15≦b≦3, 0.6≦c≦6.5, 0.15≦d≦1, and 0.25≦e≦1.7, and wherein the dielectric ceramic material has an average grain size of 0.39 μm to 0.62 μm.

8. A dielectric ceramic material according to claim 2, wherein 0≦x<0.04 and the dielectric ceramic material has an average grain size of 0.35 μm to 0.65 μm.

9. A dielectric ceramic material according to claim 8, wherein RO is a single member of said group.

10. A dielectric ceramic material according to claim 8, wherein RO is at least two members of said group.

11. A dielectric ceramic material according to claim 4, wherein RO comprises Sm2O3 or Gd2O3, 1.002≦m≦1.02, 0≦x≦0.125, 0.15≦a≦3.5, 0.15≦b≦3, 0.6≦c≦6.5, 0.15≦d≦1, and 0.25≦e≦1.7, and wherein the dielectric ceramic material has an average grain size of 0.39 μm to 0.62 μm.

12. A multilayer ceramic capacitor comprising a plurality of superposed dielectric ceramic layers; a pair of internal electrodes, each being disposed between a pair of dielectric ceramic layers; and a pair of external electrodes, each electrically connected to a different one of the internal electrodes, wherein the dielectric ceramic layers comprise the dielectric ceramic material according to claim 11.

13. A multilayer ceramic capacitor comprising a plurality of superposed dielectric ceramic layers; a pair of internal electrodes, each being disposed between a pair of dielectric ceramic layers; and a pair of external electrodes, each electrically connected to a different one of the internal electrodes, wherein the dielectric ceramic layers comprise the dielectric ceramic material according to claim 8.

14. The multilayer ceramic capacitor according to claim 13, wherein the internal electrodes comprise at least one conductive material selected from the group consisting of nickel, nickel alloy, copper, and copper alloy.

15. A multilayer ceramic capacitor comprising a plurality of superposed dielectric ceramic layers; a pair of internal electrodes, each being disposed between a pair of dielectric ceramic layers; and a pair of external electrodes, each electrically connected to a different one of the internal electrodes, wherein the dielectric ceramic layers comprise the dielectric ceramic material according to claim 7.

16. A multilayer ceramic capacitor comprising a plurality of superposed dielectric ceramic layers; a pair of internal electrodes, each being disposed between a pair of dielectric ceramic layers; and a pair of external electrodes, each electrically connected to a different one of the internal electrodes, wherein the dielectric ceramic layers comprise the dielectric ceramic material according to claim 4.

17. The multilayer ceramic capacitor according to claim 16, wherein the internal electrodes comprise at least one conductive material selected from the group consisting of nickel, nickel alloy, copper, and copper alloy.

18. A multilayer ceramic capacitor comprising a plurality of superposed dielectric ceramic layers; a pair of internal electrodes, each being disposed between a pair of dielectric ceramic layers; and a pair of external electrodes, each electrically connected to a different one of the internal electrodes, wherein the dielectric ceramic layers comprise the dielectric ceramic material according to claim 1.

19. The multilayer ceramic capacitor according to claim 18, wherein the internal electrodes comprise at least one conductive material selected from the group consisting of nickel, nickel alloy, copper, and copper alloy.