KR20080060187A - Sintering aid, sintered bode and ceramic condenser - Google Patents

Abstract

A sintering aid is provided to produce a dense sintered material without deteriorating characteristics of the sintered material even when a dielectric layer material is fired at low temperature. A sintering aid includes a first component of a silicon compound, a second component comprising at least one of a boron compound and an aluminum compound, and a third component comprising at least one selected from a barium compound, a zinc compound, and a calcium compound. When a molar ratio of the first component is X, a molar ratio of the second component is Y, and a molar ratio of the third component is Z, a composition(X,Y,Z) formed by the molar ratios of the first, second, and third components satisfies the boundary surrounded by a point A(X, Y, Z)=(0.21, 0.37, 0.42), a point B(X, Y, Z)=(0.364, 0.192, 0.444), a point C(X, Y, Z)=(0.47, 0.174, 0.356), a point D(X, Y, Z)=(0.618, 0.182, 0.20), a point E(X, Y, Z)=(0.618, 0.228, 0.154), and a point F(X, Y, Z)=(0.261, 0.375, 0.364) of a triangle comprising a point(X, Y, Z)=(1, 0, 0), a point(X, Y, Z)=(0, 1, 0), and a point(X, Y, Z)=(0, 0, 1) as the three apices of the triangle.

Description

Sintering aids, sintered bodies and ceramic capacitors {SINTERING AID, SINTERED BODE AND CERAMIC CONDENSER}

The present invention relates to a sintering aid, a sintered body to which the sintering aid is added, and a ceramic capacitor using the sintered body as a dielectric layer.

Conventionally, barium titanate is widely used as a material for dielectric layers in multilayer ceramic capacitors, but this kind of powder is difficult to sinter as it is, and then fired after adding a sintering aid that promotes sintering (for example, Japanese Patent Laid-Open No. 2002-). 338332, Japanese Patent Laid-Open No. 2002-338333).

Recently, with the miniaturization and high density of electronic circuits, there is a strong demand for miniaturization of ceramic capacitors. In order to increase the size and capacity of ceramic capacitors, internal electrode layers and dielectric layers have been made thinner and more stacked. However, when the thickness of the inner electrode proceeds, in particular, when the inexpensive Ni or Ni alloy is used as the material of the inner electrode, the inner electrode may be broken or delamination due to the spherical shrinkage of Ni. ) Tends to occur, and there is a problem in that the capacity decreases. In order to prevent this, there is a method of lowering the firing temperature, but if the firing temperature is low, there is a problem in that the sintered body cannot be obtained, a compact sintered body cannot be obtained, or the electrical characteristics are lowered.

The present invention provides a sintering aid, a sintered body and a ceramic capacitor capable of obtaining densified crystals without impairing properties even when fired at a low temperature.

According to one embodiment of the present invention, a second component containing at least one of a first component made of a silicon (Si) compound, a boron (B) compound, and an aluminum (Al) compound, a barium (Ba) compound, and zinc (Zn) ) A sintering aid comprising a third component comprising at least one of a compound and a calcium (Ca) compound, wherein X is the molar ratio of the first component, Y is the molar ratio of the second component, and Z is the molar ratio of the third component. In this case, the composition ratio (X, Y, Z) based on the molar ratio of these first components, the second components, and the third components is the point (X, Y, Z) = (1, 0, 0), the point (X, Y). , Z) = (0, 1, 0) and point (X, Y, Z) = (0, 0, 1) triangle point A (X, Y, Z) = (0.21, 0.37, 0.42), point B (X, Y, Z) = (0.364, 0.192, 0.444), point C (X, Y, Z) = (0.47, 0.174, 0.356), point D (X, Y, Z) = (0.618, 0.182, 0.20) and point E (X, Y, Z) = (0.618, 0.228, 0.154) and point F (X, Y, Z) = satisfies the range surrounded by (0.261, 0.375, 0.364) Provided is a sintering aid, characterized in that do.

According to another aspect of the present invention, there is provided a sintered compact, which is produced by adding and sintering the sintering aid to a raw material containing barium titanate as a main component.

Furthermore, according to another aspect of the present invention, there is provided a ceramic capacitor, comprising a plurality of electrodes and a dielectric layer provided between the electrodes and made of the sintered body.

According to the present invention, there is provided a sintering aid, a sintered body and a ceramic capacitor capable of obtaining densified crystals without compromising properties even when sintered at low temperature.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

The sintering aid according to the embodiment of the present invention is a first component of a silicon (Si) compound (for example, SiO ₂ ), a boron (B) compound (for example, B ₂ O ₃ ), and an aluminum (Al) compound (for example For example, a second component comprising at least one of Al ₂ O ₃ ) and a barium (Ba) compound (eg, BaCO ₃ ), a zinc (Zn) compound (eg, ZnO) and a calcium (Ca) compound (for example, CaCO ₃₎ has a third component comprising at least one of.

When the molar ratio of the first component is X, the molar ratio of the second component is Y, and the molar ratio of the third component is Z, the composition ratio (X, Y, Z) by the molar ratio of these first component, the second component, and the third component ) Points (X, Y, Z) = (1, 0, 0), points (X, Y, Z) = (0, 1, 0) and points (X, Y, Z) = (0, 0, Point A (X, Y, Z) = (0.21, 0.37, 0.42), Point B (X, Y, Z) = (0.364, 0.192, 0.444), Point C ( X, Y, Z) = (0.47, 0.174, 0.356), point D (X, Y, Z) = (0.618, 0.182, 0.20) and point E (X, Y, Z) = (0.618, 0.228, 0.154) And points F (X, Y, Z) = (0.261, 0.375, 0.364) are satisfied.

The present inventors started samples A-M of thirteen sintering aids which varied the composition ratio (molar ratio) of the said 1st-3rd component. Table 1 shows the composition ratio (molar ratio) of the 1st-3rd components of each sample A-M.

Molar ratio of each component BaO ZnO SiO ₂ B ₂ O ₃ Al ₂ O ₃ CaO First component Second component Third component Sample A 0.24 0.18 0.21 0.37 0.21 0.37 0.42 Sample B 0.127 0.163 0.364 0.146 0.046 0.153 0.364 0.192 0.444 Sample C 0.158 0.198 0.47 0.174 0.47 0.174 0.356 Sample D 0.093 0.018 0.618 0.154 0.028 0.089 0.618 0.182 0.2 Sample E 0.047 0.018 0.618 0.2 0.028 0.089 0.618 0.228 0.154 Sample F 0.128 0.096 0.261 0.337 0.038 0.14 0.261 0.375 0.364 Sample G 0.13 0.125 0.31 0.24 0.045 0.15 0.31 0.285 0.405 Sample H 0.19 0.16 0.365 0.2 0.045 0.04 0.365 0.245 0.39 Sample I 0.1 0.16 0.4 0.2 0.04 0.1 0.4 0.24 0.36 Sample J 0.105 0.16 0.45 0.2 0.045 0.04 0.45 0.245 0.305 Sample K 0.16 0.18 0.204 0.176 0.048 0.223 0.204 0.224 0.573 Sample L 0.153 0.106 0.416 0.056 0.046 0.223 0.416 0.102 0.482 Sample M 0.104 0.018 0.624 0.104 0.035 0.116 0.624 0.139 0.237

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of Sample A is represented by the points A (X, Y, Z) = (0.21, 0.37, 0.42) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of Sample B is represented by the points B (X, Y, Z) = (0.364, 0.192, 0.444) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample C is represented by the point C (X, Y, Z) = (0.47, 0.174, 0.356) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample D is represented by the point D (X, Y, Z) = (0.618, 0.182, 0.20) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of Sample E is represented by the point E (X, Y, Z) = (0.618, 0.228, 0.154) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample F is represented by the points F (X, Y, Z) = (0.261, 0.375, 0.364) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample G is represented by the points G (X, Y, Z) = (0.31, 0.285, 0.405) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample H is represented by the points H (X, Y, Z) = (0.365, 0.245, 0.39) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample I is represented by the point I (X, Y, Z) = (0.4, 0.24, 0.36) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample J is set to the point J (X, Y, Z) = (0.45, 0.245, 0.305) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample K is set to the point K (X, Y, Z) = (0.204, 0.224, 0.573) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample L is represented by the points L (X, Y, Z) = (0.416, 0.102, 0.482) of the triangle of FIG. appear.

The composition ratio (X, Y, Z) by the molar ratio of the first component, the second component, and the third component of the sample M is represented by the points M (X, Y, Z) = (0.624, 0.139, 0.237) of the triangle of FIG. appear.

Each sample A to M of the sintering aid is prepared according to the steps shown in FIG.

First, in step S1, dry mixing is performed by combining the respective component compounds based on the composition ratios shown in Table 1 to obtain a powder. Alternatively, each component compound is combined to be wet mixed and pulverized to form a slurry, and the slurry is dehydrated and dried to prepare a powder.

The prepared powder is placed in a crucible made of (Pt-Rh), for example, and dissolved in the atmosphere at 1,200 to 1,700 ° C for 3 to 4 hours (step S2). ). This glass was pulverized (step S5) to prepare respective samples A to M of the sintering aid.

The above-described raw material containing barium titanate (BaTiO ₃ ) as a main component and barium carbonate (BaCO ₃ ), dysprosium oxide (Dy ₂ O ₃ ), magnesium oxide (MgO), and manganese oxide (Mn ₃ O ₄ ) as a main component. It is produced by adding a sintering aid having a composition that satisfies the range surrounded by the triangles A, B and C shown in Fig. 1 and firing them in a reducing component atmosphere, for example.

By adding a sintering aid having a composition ratio that satisfies the range surrounded by the triangles A, B, C, D, E and F shown in FIG. The sintered body can be sintered even at the firing temperature of), and the compact and compact electrical properties can be obtained. In addition, it is possible to reduce the production cost of the sintering furnace at low temperature.

3 is a schematic sectional view illustrating a cross-sectional structure of the ceramic capacitor according to the present embodiment.

The ceramic capacitor is fired by adding a sintering aid having a composition ratio that satisfies the range surrounded by the points A, B, C, D, E and F of the triangle shown in FIG. 1 described above between the opposing internal electrodes 2. It has a structure provided with a dielectric layer (1) comprising a. This is obtained by forming the internal electrodes 2 on one side of the green sheet in which the sintered body is formed in the form of a sheet, laminating a plurality of them and firing them. Moreover, the external electrodes 3 and 4 connected to the edge part of the internal electrode 2 are provided in the side surface of this laminated body.

As the material of the internal electrodes 2 and the external electrodes 3, 4, metals such as Cu, Ni, W, Mo, or alloys thereof, In-Ga, Ag, Ag-10Pd alloys, or the like, or carbon, graphite, carbon and graphite Mixtures thereof and the like can be used.

The internal electrode 2 is a powder made of the main material, for example, a predetermined amount of an organic binder, a dispersant, an organic solvent, a reducing agent, etc. is added, and then mixed and kneaded to obtain a dielectric paste having a predetermined viscosity. It is formed by printing the surface to have a predetermined pattern and firing it in a reducing atmosphere. As the internal electrode 2, Ni or Ni alloy, which is relatively inexpensive, is preferable.

Moreover, Cu is preferable as the external electrodes 3 and 4 because it is low in resistance and inexpensive. The external electrodes 3 and 4 are formed on the outer surface of the laminate of the internal electrode 2 and the dielectric layer 1 by applying a coating method or the like.

According to the ceramic capacitor according to the present embodiment, low-temperature firing of 1,050 ° C. or lower is possible, and therefore, spherical shrinkage of Ni can be suppressed even when Ni and Ni alloys are used for the internal electrode 2, thereby resulting in positive Structural defects such as breaks and delaminations can be prevented. As a result, the capacity decrease of the capacitor can be suppressed. In addition, when using Ni or Ni alloy which is a nonmetal which is simply oxidized in air, the internal electrode 2 needs to be fired in a reducing component so that the Ni or Ni alloy is not oxidized, but in this case, the present embodiment described above The sintered compact obtained by adding the sintering aid according to the present invention has excellent reduction resistance and can suppress the reduction of the dielectric layer 1 using the sintered compact. As a result, the dielectric constant of the dielectric layer 1 can be increased and the capacity of the ceramic capacitor can be increased.

Next, an example of the manufacturing method of the ceramic capacitor which concerns on this embodiment is demonstrated.

First, for example, BaCO ₃ and TiO ₂ are combined as a raw material of the main component BaTiO ₃ of the dielectric layer.

Next, the compound of the main component is put into a ball mill, water is added, wet and mixed for about 20 minutes, and pulverized to obtain a slurry. Then, the slurry was dehydrated and dried, temporarily burned at 1,000 ° C. or higher, and then pulverized to adjust the particles so that the average particle diameter was less than 0.3 μm. The average particle diameter was obtained by observing the powder with a scanning electron microscope and measuring the particle diameter of 100 particles.

Next, a powder of BaCO ₃ , Dy ₂ O ₃ , MgO, Mn ₃ O ₄ , and the powder of the above-mentioned sintering aid are placed in a ball mill with respect to the main component in a toluene ethanol mixed solvent, a polyvinylbutylal binder, a plasticizer, The mixture was mixed together until a proper viscosity was prepared, and a green sheet was manufactured by the doctor blade method.

Next, after screen printing the internal electrodes in a predetermined shape using a dielectric paste made of Ni powder on each green sheet, a plurality of green sheets printed with the conductive paste were laminated, thermocompression-bonded and integrated to prepare a laminate.

The laminate was heated in air to remove the organic binder, calcined for 2 hours in a reducing atmosphere at 1,100 ° C, and then reoxidized for 2 hours in an N ₂ gas atmosphere at 1,000 ° C. The external electrode was heated to the edge surface portion of the laminate to prepare the structure illustrated in FIG. 3.

The present inventors evaluated and evaluated the relative dielectric constant (epsilon), dielectric loss (tan-delta), specific resistance, capacity change rate, and density with respect to the sintered compact obtained by adding the samples A-M of the sintering aid mentioned above. The results are shown in Tables 2 and 3.

evaluation Sintering aid Firing temperature (℃) Relative permittivity ε Dielectric loss tanδ (%) Density (g / cm 3) Resistivity (Ωcm) Kinds weight% NG A 1.0 1011 Insufficient plasticity 5.53 A 1.0 1020 1700 0.81 5.79 1.0E + 13 A 1.0 1029 1752 0.87 5.80 1.0E + 13 A 1.0 1037 1810 0.89 5.85 1.7E + 13 A 1.0 1049 1883 0.90 5.89 1.5E-13 NG B 1.0 1016 Insufficient plasticity 5.28 B 1.0 1029 2030 1.02 5.72 1.1E + 13 B 1.0 1033 2086 1.29 5.78 2.4E + 13 B 1.0 1041 2096 1.06 5.81 1.2E + 13 B 1.0 1049 2185 1.23 5.83 8.0E + 13 NG C 0.6 1011 Insufficient plasticity 5.33 C 0.6 1024 1853 1.01 5.76 2.0E + 13 C 0.6 1033 1898 1.12 5.81 2.9E + 13 C 0.6 1049 1890 1.08 5.83 3.7E + 13

NG C 0.80.8 1033 Insufficient Firing 5.69 C 0.8 1049 1857 1.11 5.84 3.5E + 13 NG D 0.6 1011 Insufficient plasticity 5.56 D 0.6 1025 1826 1.29 5.70 1.0E + 13 D 0.6 1033 1864 1.38 5.74 9.8E + 12 D 0.6 1049 1851 1.36 5.74 1.0E + 13 NG D 0.8 1033 Insufficient Firing 5.58 D 0.8 1049 1803 1.30 5.78 1.3E + 13 NG E 0.6 1016 Insufficient plasticity 5.55 E 0.6 1029 1793 1.40 5.72 5.6E + 12 E 0.6 1033 1805 1.42 5.74 7.3E + 12 E 0.6 1049 1800 1.47 5.75 9.2E + 12 NG E 0.4 1033 Insufficient plasticity 5.46 E 0.4 1049 1734 1.29 5.79 1.4E + 13

evaluation Sintering aid Firing temperature (℃) Relative permittivity ε Dielectric loss t anδ (%) Density (g / cm 3) Resistivity (Ωcm) Kinds weight% NG F 1.0 1007 Insufficient plasticity 5.68 F 1.0 1016 1720 0.73 5.78 9.4E + 12 F 1.0 1025 1788 0.84 5.83 1.1E + 13 F 1.0 1033 1838 0.83 5.84 1.7E + 13 F 1.0 1041 1907 0.88 5.89 2.1E + 13 NG G 1.0 1003 Insufficient plasticity 5.50 G 1.0 1011 1982 1.11 5.71 1.9E + 13 G 1.0 1020 2019 1.06 5.76 2.0E + 13 G 1.0 1033 2039 1.00 5.85 2.4E + 13 G 1.0 1041 2095 0.99 5.89 2.2E + 13 G 1.0 1049 2091 1.02 5.87 2.4E + 13 NG H 1.0 1003 Insufficient plasticity 5.58 H 1.0 1011 1600 1.18 5.70 1.0E + 13 H 1.0 1016 1640 1.11 5.73 1.6E + 13 H 1.0 1025 1736 1.26 5.78 1.7E + 13 H 1.0 1029 1743 1.02 5.80 1.8E + 13 H 1.0 1037 1885 1.27 5.85 1.5E + 13 H 1.0 1049 2022 1.27 5.90 1.1E + 13 NG I 1.0 997 Insufficient plasticity 5.64 I 1.0 1007 1724 1.07 5.72 1.5E + 13 I 1.0 1016 1759 1.16 5.73 1.4E + 13 I 1.0 1033 1883 1.21 5.75 1.5E + 13 I 1.0 1049 1945 1.27 5.77 1.3E + 13 NG J 1.0 1016 Insufficient plasticity 5.62 J 1.0 1025 1853 1.19 5.72 1.6E + 13 J 1.0 1033 1905 1.27 5.73 1.5E + 13 J 1.0 1049 1949 1.37 5.74 1.1E + 13 NG K 1.0 1049 Insufficient plasticity 5.67 NG L 1.0 1049 Insufficient plasticity 5.69 NG M 1.0 1049 Insufficient plasticity 5.59

The evaluation sample was produced as follows. A green sheet containing barium titanate as a main component and BaCO ₃ , Dy ₂ O ₃ , MgO, Mn ₃ O ₄ as the main components and the above-mentioned samples A to M as a sintering aid was cut at an angle of 1 cm and the thickness was 1 (mm). ) To be stacked. Next, this is molded at a pressure of 1000 (kg / cm 3). Subsequently, calcining was carried out at 300 ° C. for 10 hours in order to incinerate the resin component, and then calcined at a reducing atmosphere for 2 hours in the reducing atmosphere of the mixed gas of N ₂ , H ₂ and H ₂ O at the firing temperatures shown in Table 2. . Then, it stabilized at 1000 degreeC in nitrogen gas, and the reoxidation process was performed for 2 hours.

In each evaluation sample, the ratio of barium titanate (Ba / Ti) as a main component is 0.998 to 1.003. Ba element addition amount is 1.0 mol%, Dy element addition amount is 0.9 mol%, Mg element addition amount is 1.1 mol%, and Mn element addition amount is 0.2 mol% with respect to this main component. The addition amount (weight part) with respect to the main component of each sample A-M of a sintering aid was changed variously as Table 2.

Density (g / cm <3>) was measured using the Archimedes method.

The electrical characteristics of each species were measured after In-Ga was applied to both ends of the evaluation sample to form a condenser structure.

The relative permittivity? Was measured using an LCR meter under the condition of frequency 1 (kW) and voltage 1.0 (?), And was calculated from the capacitance, the thickness of the dielectric layer, and the electrode area obtained by the measurement.

Dielectric loss tan δ (%) was measured using an LCR meter under the same conditions as the relative dielectric constant.

Specific resistance (kV / cm) was measured by applying the voltage of direct current 250 ((nu)) for 1 minute on 25 degreeC conditions.

When the density did not satisfy at least one of 5.7 (g / cm 3) or more, relative permittivity of 1600 or more, and dielectric loss of 3.0 (%) or less, desired characteristics were not obtained and the evaluation result was "NG".

According to Table 2, if the sintering aid of the composition ratio that satisfies the range surrounded by the points A, B, C, D, E and F of the triangle shown in Fig. 1 is appropriately set by the point amount for the main component (barium titanate), The result was that a sintered compact and a condenser having a high density and satisfactory electrical characteristics can be obtained at a low temperature baking of 1050 캜 or lower.

Moreover, the present inventors performed various evaluations about the sample which laminated | stacked the dielectric layer and the electrode.

Sintering aid Firing temperature (℃) Relative permittivity ε Dielectric loss tanδ Insulation resistance logR (Ω) Capacity change rate of -55 ℃ (%) Capacity change rate of 88 ℃ (%) Kinds Parts by weight A 1.0 1037 2570 5.5 10.2 -3.9 -14.6 B 1.0 1041 2934 6.4 10.1 -3.5 -0.1 C 0.6 1033 2771 6.5 10.1 -3.4 -6.6 D 0.6 1049 2710 5.5 10.1 -3.5 -7.8 E 0.6 1049 2628 6.6 10.4 -3.5 -8.6 F 1.0 1045 2783 6.2 10.1 0.6 -5.6 G 1.0 1041 2891 5.6 10.3 -4.9 -4.7 H 1.0 1037 2740 5.8 10.2 -2.9 -3.6 I 1.0 1049 2700 6.1 10.1 -3.0 -6.1 J 1.0 1049 2730 6.3 10.2 -3.2 -7.2

The thickness of each dielectric layer was 5 mu m and the effective dielectric layer was 10 layers. In addition, the inner (facing) electrode area per layer was set to 0.91 (mm 2).

The dielectric layer was produced by the following method as in the evaluation test described above with reference to Table 2. As a main component, barium titanate was used as a _secondary component, and BaCO ₃ , Dy ₂ O ₃ , MgO, Mn ₃ O ₄ , and a slurry containing a sintering aid of the kind shown in Table 4 were applied to the PET film by the doctor blade method. Molded green sheets were molded. Ni paste, an internal electrode, was printed on the green sheet. These were laminated | stacked in 10 layers and thermocompression-bonded to make the laminated body. Next, this laminated body was processed so that it might become width 2.0mm, length 3.8mm, and thickness 0.6mm. Next, it was heated for 10 hours at 300 ° C. in the air to incinerate the organic binder (resin component). Thereafter, the mixture was calcined for 2 hours at the firing temperature shown in Table 4 in a reducing atmosphere of a mixed gas of N ₂ and H ₂ H ₂ O. Next, it was stabilized at 1000 degreeC in nitrogen gas atmosphere, and the reoxidation process was performed for 2 hours. Thereafter, a conductive paste made of Cu is applied to the outer surface of the sintered laminate (cutting surface at the opposite position), and heated at 650 ° C. in an N ₂ gas atmosphere to be electrically connected to the internal electrode as shown in FIG. 3. The formed external electrode was formed to create a multilayer ceramic capacitor. The ratio (Ba / Ti) of barium titanate as a main component in each sample was 0.998. For this main component, the amount of Ba element added is 1.0 mol part in terms of Ba of Ba compound, the amount of Dy element added is 0.9 mol part in Dy of Dy compound, the amount of Mg element is 1.1 mol part in Mg of Mg compound, and the amount of Mn element added is It is 0.2 mol part in terms of Mn of Mn compound. The addition amount (weight part) with respect to the main component of each sample of a sintering aid is as showing in Table 4. As a method of measuring various characteristics, the relative permittivity ε is measured by using an LCR meter under the condition of frequency 1 (㎑) and voltage 1.0 (ν), and calculated from capacitance, thickness of dielectric layer and internal electrode area obtained by this measurement. did. The dielectric loss tanδ (%) was measured using an LCR meter under the same conditions as the relative dielectric constant. The capacitance change rate was measured using an LCR meter under conditions of a frequency of 1 (Hz) and a voltage of 1.0 (ν) at temperatures of -55 ° C to 85 ° C in each laminated ceramic capacitor.

The laminated body obtained using the sintering aid which concerns on this embodiment mentioned above from the result of Table 4 is the X5R specification of EIA (Electronic Industries Association) (capacity change rate of (-55 degreeC to 85 degreeC (25 degreeC reference | standard) plus minus 15%)). It was confirmed that it is suitable for.

BRIEF DESCRIPTION OF THE DRAWINGS It is a triangle which shows the composition range of the 1st-3rd component contained in the sintering aid which concerns on embodiment of this invention.

2 is a flow chart of a sintering aid manufacturing method according to the embodiment of the present invention.

3 is a schematic sectional view illustrating a cross-sectional structure of a ceramic capacitor according to an embodiment of the present invention.

<Code Description of Main Parts of Drawing>

1: dielectric layer

2: internal electrode

3: external electrode

Claims (4)

Among the second component comprising at least one of a first component of a silicon (Si) compound, a boron (B) compound, and an aluminum (Al) compound, and a barium (Ba) compound, a zinc (Zn) compound, and a calcium (Ca) compound. A sintering aid comprising a third component comprising at least one, When the molar ratio of the first component is X, the molar ratio of the second component is Y and the molar ratio of the third component is Z, the composition ratio (X, Y) by the molar ratio of these first components, the second component, and the third component , Z) points (X, Y, Z) = (1, 0, 0), points (X, Y, Z) = (0, 1, 0) and points (X, Y, Z) = (0, Points A (X, Y, Z) = (0.21, 0.37, 0.42), Point B (X, Y, Z) = (0.364, 0.192, 0.444), Point C (X, Y, Z) = (0.47, 0.174, 0.356), point D (X, Y, Z) = (0.618, 0.182, 0.20) and point E (X, Y, Z) = (0.618, 0.228, 0.154 ) And point F (X, Y, Z) = (0.261, 0.375, 0.364) in the range surrounded by the sintering aid. A sintered compact prepared by adding and sintering the sintering agent according to claim 1 to a raw material containing barium titanate as a main component. A plurality of electrodes, A ceramic capacitor, provided between the electrodes, comprising a dielectric layer made of the sintered body according to claim 2. The method of claim 3, The electrode is a ceramic capacitor, characterized in that it comprises Ni or Ni alloy.

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