Dielectric ceramic composition

Abstract: The present invention relates to a dielectric ceramic composition, comprising from 97.5 to 99.95% by weight of a main component and from 0.05 to 2.5% by weight of a first subsidiary component, and also a dielectric ceramic composition, comprising from 97.0 to 99.94% by weight of a main component, from 0.05 to 2.5% by weight of a first subsidiary component, and from 0.01 to 0.5% by weight of a second subsidiary component. The main component is a mixture represented by formula: {100-(a+b+c+d)}BaTiO₃ + aZnO + b(2Bi₂O₃·3AO₂) + cTa₂O₅ + dRe₂O₃ wherein A represents Zr (first embodiment) or Sn (second embodiment); Re represents at least one selected from the group consisting of La, Pr, Nd, Sm, Dy and Er; and {100-(a+b+c+d)}, a, b, c, and d represent the contents of BaTiO₃, ZnO, (2Bi₂O₃·3AO₂), Ta₂O₅, and Re₂O₃ in terms of molar percent, respectively, provided that a, b, c, and d satisfy the following relationships: 0.5 ≦ a ≦ 4.5 0.5 ≦ b ≦ 4.5 0.5 ≦ c ≦ 4.5 0.5 ≦ d ≦ 5.5 The first subsidiary component is glass mainly comprising SiO₂. The second subsidiary component is at least one selected from the group consisting of oxides of Cr, Mn, Fe, Co, and Ni.

Description: FIELD OF THE INVENTION The present invention relates to a dielectric ceramic composition and more particularly to a dielectric ceramic composition which can be used as a material of laminated ceramic capacitors. BACKGROUND OF THE INVENTION Heretofore, as a dielectric ceramic composition which exhibits a small voltage dependence, a high ceramic strength, and flat dielectric constant-temperature characteristics there has been widely known a ceramic composition mainly composed of BaTiO 3 comprising a bismuth compound and a rare earth element incorporated therein as subsidiary components. Besides the dielectric ceramic composition having the foregoing formulation, a dielectric ceramic composition mainly composed of BaTiO 3 comprising Nb 2 O 5 , rare earth oxides, and oxide of transition metals such as Cr, Mn, Fe, Co and Ni incorporated therein as subsidiary components is reported that it exhibits flat dielectric constant-temperature characteristics irrespective of its dielectric constant as high as not less than 3,000. The temperature characteristics of these dielectric ceramic compositions satisfy X7R characteristics of EIA Standard stipulating that the percent capacitance change from the capacitance at +25°C as reference be within ±15% in the temperature range of from -55°C to +125°C. However, the dielectric ceramic composition mainly composed of BaTiO 3 comprising a bismuth compound incorporated therein exhibits a dielectric constant as low as about 1,000. If the dielectric constant is raised, the capacitance change with temperature becomes large. In addition, when a green composition calcined at an elevated temperature, such a dielectric ceramic composition is subject to evaporation of Bi 2 O 3 , causing the ceramic to be deformed or change in the percent composition, and hence making it impossible to obtain required electrical characteristics or mechanical strength or causing these characteristics to be scattered. The dielectric ceramic composition mainly composed of BaTiO 3 comprising Nb 2 O 5 , rare earth oxides, and oxide of transition metals such as Cr, Mn, Fe, Co and Ni incorporated therein as subsidiary components exhibits a dielectric constant of not less than 3,000 and flat temperature characteristics. However, this dielectric ceramic composition must be fired at a temperature as high as not lower than 1,200°C. In recent years, ceramic capacitors tend to have a smaller size. In particular, laminated ceramic capacitors tend to be composed of thinner dielectric ceramic layers having a thickness of from 5 to 15 µm for miniaturization and larger capacitance. A dielectric ceramic composition having a small voltage dependence is thus desired. However, since the foregoing dielectric ceramic composition having a high dielectric constant exhibits a large voltage dependence, its thickness cannot be reduced as required by the recent market, making it impossible to prepare a small-sized large capacitance laminated ceramic capacitor. Further, since the foregoing dielectric ceramic composition exhibits a low ceramic mechanical strength, it may be destroyed during using. SUMMARY OF THE INVENTION An object of the present invention is to provide a dielectric ceramic composition which can be sintered at a temperature of not higher than 1,160°C, exhibits a percent capacitance change of from -15% to +15% with temperature from the capacitance at +25°C in a wide temperature range of from -55°C to +125°C and a high ceramic mechanical strength, can be operated at a relatively high rated voltage even if the thickness of the dielectric ceramic layers is as low as 5 to 15 µm, and shows a small percent capacitance change with temperature at an applied voltage of 50% of the rated voltage in accordance with the specification of RB characteristics of JIS C6429. Other objects and effects of the present invention will be apparent from the following description. The present invention relates to a dielectric ceramic composition, comprising from 97.5 to 99.95% by weight of a main component and from 0.05 to 2.5% by weight of a first subsidiary component. The present invention also relates to a dielectric ceramic composition, comprising from 97.0 to 99.94% by weight of a main component, from 0.05 to 2.5% by weight of a first subsidiary component, and from 0.01 to 0.5% by weight of a second subsidiary component. The main component is a mixture represented by formula: {100-(a+b+c+d)}BaTiO 3 + aZnO + b(2Bi 2 O 3 ·3AO 2 ) + cTa 2 O 5 + dRe 2 O 3 wherein A represents Zr or Sn; Re represents at least one selected from the group consisting of La, Pr, Nd, Sm, Dy and Er; and {100-(a+b+c+d)}, a, b, c, and d represent the contents of BaTiO 3 , ZnO, (2Bi 2 O 3 ·3AO 2 ), Ta 2 O 5 , and Re 2 O 3 in terms of molar percent, respectively, provided that a, b, c, and d satisfy the following relationships: 0.5 ≤ a ≤ 4.5 0.5 ≤ b ≤ 4.5 0.5 ≤ c ≤ 4.5 0.5 ≤ d ≤ 5.5 The first subsidiary component is glass mainly comprising SiO 2 . The second subsidiary component is at least one selected from the group consisting of oxides of Cr, Mn, Fe, Co, and Ni. The dielectric ceramic composition according to the present invention can be sintered at a temperature as low as not higher than 1,160°C and shows a small percent capacitance change with temperature (bias TC) when a direct current is applied. Therefore, the thickness of the dielectric ceramic can be reduced to from 5 to 15 µm. As a result, a laminated ceramic capacitor having a smaller size and a higher capacitance can be provided. Further, since the dielectric ceramic composition according to the present invention has a high ceramic mechanical strength, it is insusceptible to damage such as cracking or chipping during using when incorporated in laminated ceramic capacitors. Thus, any accident such as fire damage due to short circuit and heat generation can be prevented. Moreover, the dielectric ceramic composition according to the present invention shows a percent capacitance change as small as from -15% to +15% with temperature from the capacitance at +25°C as a reference in a wide temperature range of from -55°C to +125°C and hence is thermally stable. This shows that the dielectric ceramic composition according to the present invention finds wide application as dielectric ceramic for industrial use or consumer use. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to preferred embodiments thereof, but the invention is not construed as being limited thereto. A process for the preparation of the main component of the dielectric ceramic composition will be first described. Commercially available industrial materials of BaTiO 3 , ZnO, Bi 2 O 3 , ZrO 2 or SnO 2 , Ta 2 O 5 and Re 2 O 3 (in which Re represents La, Pr, Nd, Sm, Dy or Er) were used as starting materials. These starting materials were each measured out such that ceramic compositions set forth in Tables 1 and 5 were obtained. These starting materials were wet-ground in admixture over 16 hours by means of a ball mill, and then evaporated to dryness to obtain powder mixtures. The powder mixtures were each then charged into a zirconia crucible. The powder mixtures were each calcined at a temperature of 1,000°C in a natural atmosphere over 2 hours, and then coarsely ground to obtain 200-mesh sieve fractions as powdered starting materials of main component of dielectric ceramic composition. A process for the preparation of a first subsidiary component of the dielectric ceramic composition will be next described. In the present example, as the first subsidiary component which lowers the sintering temperature to not higher than 1,160°C, an oxide glass represented by 8BaO-6SrO-6CaO-30Li 2 O-50SiO 2 (by mole) was used. Commercially available industrial materials of BaCO 3 , SrCO 3 , CaCO 3 , Li 2 O and SiO 2 were used as starting materials. These starting materials were each measured out such that the foregoing compositions were obtained. These starting materials were wet-ground in admixture over 16 hours by means of a ball mill, and then evaporated to dryness to obtain powder mixtures. The powder mixtures were each put into an alumina crucible where it was then allowed to stand at a temperature of 1,300°C over 1 hour. The molten powder was then quenched rapidly so that it was vitrified. The material thus vitrified was then ground to obtain 200-mesh sieve fractions as powdered starting materials of first subsidiary component of dielectric ceramic composition. The powdered starting materials of first subsidiary component were each added to the powdered starting material of the main component in a weight proportion set forth in Tables 1 and 5. Commercially available industrial materials of Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Co 2 O 3 and NiO were used as the second subsidiary component. These second subsidiary components were each added to a composition composed of 93.0BaTiO 3 + 1.5ZnO + 1.5(2Bi 2 O 3 ·3ZrO 2 ) + 2.0Ta 2 O 5 + 2.0Nd 2 O 3 (by mole) (for Sample Nos. 21 to 30) or 93.0BaTiO 3 + 1.5ZnO + 1.5(2Bi 2 O 3 ·3SnO 2 ) + 2.0Ta 2 O 5 + 2.0Nd 2 O 3 (by mole) (for Sample Nos. 21' to 30') comprising 1.0% by weight of the foregoing first subsidiary component incorporated therein in such an amount that ceramic compositions set forth in Tables 2 and 6 were obtained. To the mixture were then added a polyvinyl butyral binder and an organic solvent such as toluene and ethyl alcohol. These materials were then mixed in a wet process by means of a ball mill over 16 hours. The mixture was then formed into a sheet by doctor blade coating method to obtain a green sheet. The thickness of the green sheet thus obtained was 19 µm. An internal electrode pattern was then printed on the green sheet with a paste made of a 70/30 (in terms of weight percent) mixture of Ag and Pd. These green sheets were then laminated in 6 layers. The laminate was then subjected to hot contact bonding with dummy sheets. Formed samples having a length of 5.5 mm, a width of 4.5 mm and a thickness of 1 mm were cut out from the laminates thus contact-bonded. The formed samples were each then fired at a temperature set forth in Tables 3, 4, 7 and 8 to obtain sintered samples. The thickness of the dielectric materials thus sintered was 13 µm. A silver electrode was printed on the edge of the sintered samples to obtain samples (laminated capacitors) to be measured. These samples were measured for dielectric constant (ε), dielectric loss ( tanδ ), TC and bias TC at room temperature. The dielectric constant (ε) and dielectric loss ( tanδ ) were measured at a temperature of 25°C, 1 kHz and 1 Vrms. For the measurement of TC, the absolute value of the maximum percent capacitance change with temperature between -55°C and +125°C from the capacitance at 25°C as a reference, i.e., maximum percent capacitance change (¦ΔC/C¦ max ) was determined. For the measurement of bias TC, the capacitance was determined while a direct current voltage of 25 V being applied in the foregoing temperature range, and the maximum capacitance change (ΔC maxB ) from the capacitance at 25°C and an applied voltage of 0 V as a reference was determined. Further, the ceramic bending strength was measured by three-point bending test. Starting materials having formulation set forth in Tables 1, 2, 5 and 6 were press-formed into formed articles having a length of 35 mm, a width of 7 mm and a thickness of 1.2 mm. These formed articles were each then fired at temperatures set forth in Tables 3 and 4 over 2 hours to obtain strip ceramics. Thereafter, 20 samples having different compositions were each then measured for bending strength. These measurements were averaged to determine the bending strength of each composition. The results of these tests on the compositions in Tables 1, 2, 5 and 6 are set forth in Tables 3, 4, 7 and 8, respectively. In Tables 1 to 8, samples indicated with an asterisk are outside the scope of the present invention. Sample No. Amount of ceramic composition (wt%) Amount of second subsidary component (wt%) Cr Mn Fe Co Ni 21 99.99 0 0.01 0 0 0 22 99.85 0.05 0.05 0.05 0 0 23 99.95 0 0 0 0.05 0 24 99.9 0.05 0 0 0 0.05 25 99.85 0 0.1 0 0 0.05 26 99.65 0.05 0.2 0.05 0.05 0 27 99.6 0 0.3 0 0 0.1 28 99.55 0 0.3 0 0.1 0.05 29 99.5 0.1 0.3 0 0.1 0 * 30 99.45 0 0.35 0.05 0.1 0.05 Note: "Amount of ceramic composition" represents the total amount of the main component and the first subsidary component. Sample No. Firing temperature (°C) Electric property Mechanical property ε tanδ (%) TC (%) Bias TC (%) Bending strength (kg/cm 2 ) |ΔC/C| max ΔC maxB 1 1150 2010 1.6 7.4 -33.2 2060 2 1110 1790 1.5 7.2 -30.9 2310 3 1110 1800 1.5 14.1 -31.0 2160 4 1160 2000 1.8 12.0 -34.0 1800 5 1130 1760 1.7 7.4 -32.1 2210 6 1090 1370 1.0 13.9 -28.0 2200 7 1110 1590 1.1 14.6 -33.1 2090 8 1110 1620 1.5 12.0 -32.3 2120 * 9 1160 1690 2.2 17.2 -33.8 1490 * 10 1130 2210 1.4 22.1 -42.7 2030 * 11 1130 1710 1.8 23.2 -36.1 1470 * 12 1110 970 1.1 14.8 -28.3 2250 * 13 1110 1820 1.4 22.7 -31.0 2280 * 14 1150 1510 1.1 16.5 -33.1 1990 * 15 1150 1920 1.3 22.0 -41.2 2000 * 16 1130 1600 1.8 18.4 -44.5 2110 * 17 Not sintered at 1,160°C 18 1160 1680 1.3 13.1 -36.0 1620 19 1090 1380 1.0 7.3 -33.5 2140 * 20 1090 940 1.1 13.9 -35.8 2090 Sample No. Firing temperature (°C) Electric property Mechanical property ε tanδ (%) TC (%) bias TC (%) Bending strength (kg/cm 2 ) |ΔC/C| max ΔC maxB 21 1130 1920 1.6 7.4 -33.4 2040 22 1130 1830 1.8 7.3 -33.6 2020 23 1130 1940 1.5 7.4 -34.2 1970 24 1130 1890 1.7 7.3 -32.8 2030 25 1130 1870 1.6 7.3 -33.4 2040 26 1130 1880 2.0 7.3 -33.8 1960 27 1130 1860 2.0 7.3 -32.3 1950 28 1130 1900 2.1 7.4 -35.6 1980 29 1130 1890 2.2 7.3 -33.2 1960 * 30 1130 1870 2.7 12.0 -32.5 1990 Sample No. Amount of ceramic composition (wt%) Amount of second subsidary component (wt%) Cr Mn Fe Co Ni 21' 99.99 0 0.01 0 0 0 22' 99.85 0.05 0.05 0.05 0 0 23' 99.95 0 0 0 0.05 0 24' 99.9 0.05 0 0 0 0.05 25' 99.85 0 0.1 0 0 0.05 26' 99.65 0.05 0.2 0.05 0.05 0 27' 99.6 0 0.3 0 0 0.1 28' 99.55 0 0.3 0 0.1 0.05 29' 99.5 0.1 0.3 0 0.1 0 * 30' 99.45 0 0.35 0.05 0.1 0.05 Note: "Amount of ceramic composition" represents the total amount of the main component and the first subsidary component. Sample No. Firing temperature (°C) Electric property Mechanical property ε tanδ (%) TC (%) bias TC (%) Bending strength (kg/cm 2 ) |ΔC/C| max ΔC maxB 1' 1150 2000 1.5 7.4 -33.4 2050 2' 1100 1800 1.5 7.4 -31.1 2300 3' 1110 1790 1.6 14.3 -30.9 2170 4' 1160 2010 1.8 12.5 -34.1 1820 5' 1140 1770 1.7 7.2 -32.5 2230 6' 1100 1390 1.1 13.8 -28.3 2210 7' 1100 1600 1.2 14.3 -33.0 2100 8' 1110 1610 1.6 12.2 -31.8 2110 * 9' 1160 1700 2.1 17.8 -33.6 1510 * 10' 1120 2200 1.3 22.0 -42.5 2010 * 11' 1130 1720 1.8 23.2 -36.0 1480 * 12' 1100 980 1.1 14.9 -28.4 2250 * 13' 1100 1830 1.3 22.9 -30.7 2270 * 14' 1150 1520 1.2 17.0 -33.0 1990 * 15' 1150 1910 1.4 22.1 -41.2 2000 * 16' 1130 1610 1.7 19.1 -44.5 2090 * 17' Not sintered at 1,160°C 18' 1160 1670 1.3 13.5 -36.0 1640 19' 1080 1380 1.1 7.5 -33.8 2090 * 20' 1080 940 1.1 13.9 -35.4 2070 Sample No. Firing temperature (°C) Electric property Mechanical property ε tanδ (%) TC (%) bias TC (%) Bending strength (kg/cm 2 ) |ΔC/C| max ΔC maxB 21' 1130 1930 1.5 7.4 -34.0 2040 22' 1130 1840 1.7 7.3 -33.5 2010 23' 1130 1940 1.6 7.4 -34.3 1990 24' 1130 1990 1.7 7.4 -33.0 2020 25' 1130 1870 1.5 7.3 -33.5 2040 26' 1130 1870 1.9 7.3 -33.9 1960 27' 1130 1860 2.0 7.3 -32.3 1970 28' 1130 1900 2.0 7.4 -35.6 1970 29' 1130 1890 2.1 7.3 -33.3 1960 * 30' 1130 1880 2.8 12.1 -33.0 1980 The reason why the range of the amount of main component, first subsidiary component and second subsidiary component are limited herein will be described hereinafter. First, the reason why the range of the main component is limited herein will be described hereinafter. As demonstrated by Sample Nos. 9 and 9' in Tables 1 and 5, when the value a ,i.e., the amount of ZnO falls below 0.5 mol%, TC disadvantageously exceeds 15% and the bending strength disadvantageously falls below 1,500 kg/cm 2 . On the other hand, as demonstrated by Sample Nos. 10 and 10', when the value a exceeds 4.5 mol%, bias TC disadvantageously falls below -40% and TC exceeds 15%. As demonstrated by Sample Nos. 11 and 11' in Tables 1 and 5, when the value b , i.e., the amount of 2Bi 2 O 3 ·3ZrO 2 or 2Bi 2 O 3 ·3SnO 2 falls below 0.5 mol%, TC disadvantageously exceeds 15% and the bending strength disadvantageously falls below 1,500 kg/cm 2 . On the other hand, as demonstrated by Sample Nos. 12 and 12', when the value b exceeds 4.5 mol%, ε disadvantageously falls below 1,000. As demonstrated by Sample Nos. 13 and 13' in Table 1 and 5, when the value c , i.e., the amount of Ta 2 O 5 falls below 0.5 mol% or as demonstrated by Sample Nos. 14 and 14' in Tables 1 and 5, when the value c exceeds 4.5 mol%, TC disadvantageously exceeds 15%. As demonstrated by Sample Nos. 15 and 15' in Tables 1 and 5, when the value d , i.e., the amount of Re 2 O 3 falls below 0.5 mol%, or as demonstrated by Sample Nos. 16 and 16' in Tables 1 and 5, when the value d exceeds 5.5 mol%, TC disadvantageously exceeds 15% and bias TC disadvantageously falls below -40%. The reason why the range of the first subsidiary component is limited herein will be described hereinafter. As demonstrated by Sample Nos. 17 and 17' in Tables 1 and 5, when the added amount of the first subsidiary component falls below 0.05% by weight, the sintering temperature disadvantageously exceeds 1,160°C. On the other hand, as demonstrated by Sample Nos. 20 and 20', when the added amount of the first subsidiary component exceeds 2.5% by weight, ε disadvantageously falls below 1,000. The reason why the range of the second subsidiary component is limited herein will be described hereinafter. As demonstrated by Sample Nos. 30 and 30' in Tables 2 and 6, when the added amount of the second subsidiary component exceeds 0.5% by weight, tanδ disadvantageously exceeds 2.5%. In the foregoing examples, as the first subsidiary component a BaO-SrO-CaO-Li 2 O-SiO 2 oxide glass was used. The sintering aid as the first subsidiary component which lowers the calcining temperature to not higher than 1,160°C is not limited to such an oxide glass. For example, a boron-containing oxide glass such as BaO-Li 2 O-B 2 O 3 -SiO 2 glass may be used. Alternatively, a glass including monoxide components such as SiO 2 -B 4 C glass may be used. In the foregoing examples, a first subsidiary component was previously blended in a predetermined mixing ratio. It was heat-treated and melted at an elevated temperature, ground, and then vitrified. The first subsidiary component was then added to the main component of the ceramic composition. However, other methods for blending the main component and the first subsidiary component may be used. For example, a starting material which has been modified by blending these components in a predetermined mixing ratio and then heating the blend such that it is not molten, e.g., solid solution such as Bi 4 Zr 3 O 12 may be added. Alternatively, the various constituting elements of the first subsidiary component may be separately added to the main component in the form of proper compound such as metal alkoxide. In the foregoing examples, the second subsidiary component was previously added in the form of oxide. However, in the stage of preparation of starting material, the second subsidiary component may be used in a form that can become an oxide in the stage of calcination or calcining, such as carbonate of various elements. While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the claims.

Claims: A dielectric ceramic composition, comprising from 97.5 to 99.95% by weight of a main component and from 0.05 to 2.5% by weight of a first subsidiary component, said main component being a mixture represented by formula: {100-(a+b+c+d)}BaTiO 3 + aZnO + b(2Bi 2 O 3 ·3AO 2 ) + cTa 2 O 5 + dRe 2 O 3 wherein A represents Zr or Sn; Re represents at least one selected from the group consisting of La, Pr, Nd, Sm, Dy and Er; and {100-(a+b+c+d)}, a, b, c, and d represent the ontents of BaTiO 3 , ZnO, (2Bi 2 O 3 ·3AO 2 ), Ta 2 O 5 , and Re 2 O 3 in terms of molar percent, respectively, provided that a, b, c, and d satisfy the following relationships: 0.5 ≤ a ≤ 4.5 0.5 ≤ b ≤ 4.5 0.5 ≤ c ≤ 4.5 0.5 ≤ d ≤ 5.5 said first subsidiary component being glass mainly comprising SiO 2 . A dielectric ceramic composition, comprising from 97.0 to 99.94% by weight of a main component, from 0.05 to 2.5% by weight of a first subsidiary component, and from 0.01 to 0.5% by weight of a second subsidiary component, said main component being a mixture represented by formula: {100-(a+b+c+d)}BaTiO 3 + aZnO + b(2Bi 2 O 3 ·3AO 2 ) + cTa 2 O 5 + dRe 2 O 3 wherein A represents Zr or Sn; Re represents at least one selected from the group consisting of La, Pr, Nd, Sm, Dy and Er; and {100-(a+b+c+d)}, a, b, c, and d represent the contents of BaTiO 3 , ZnO, (2Bi 2 O 3 ·3AO 2 ), Ta 2 O 5 , and Re 2 O 3 in terms of molar percent, respectively, provided that a, b, c, and d satisfy the following relationships: 0.5 ≤ a ≤ 4.5 0.5 ≤ b ≤ 4.5 0.5 ≤ c ≤ 4.5 0.5 ≤ d ≤ 5.5 said first subsidiary component being glass mainly comprising SiO 2 , and said second subsidiary component being at least one selected from the group consisting of oxides of Cr, Mn, Fe, Co, and Ni.

Inventors: HAMAJI YUKIO, IWAMOTO SAKIKO, SHIBATA MASAMITSU, HAMAJI, YUKIO, IWAMOTO, SAKIKO, SHIBATA, MASAMITSU, HAMAJI, YUKIO, MURATA MANUFACTURING CO., LTD., IWAMOTO, SAKIKO, MURATA MANUFACTURING CO., LTD., SHIBATA, MASAMITSU, MURATA MANUFACTURING CO., LTD.
Applicants: MURATA MANUFACTURING CO, MURATA MANUFACTURING CO., LTD.
Application year: 1995
Main classification: C04B35
IPC codes: H01B3, H01G4, C04B35