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WO1992013810A1 - Composition de ceramique dielectrique - Google Patents

Composition de ceramique dielectrique Download PDF

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Publication number
WO1992013810A1
WO1992013810A1 PCT/JP1992/000085 JP9200085W WO9213810A1 WO 1992013810 A1 WO1992013810 A1 WO 1992013810A1 JP 9200085 W JP9200085 W JP 9200085W WO 9213810 A1 WO9213810 A1 WO 9213810A1
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WO
WIPO (PCT)
Prior art keywords
composition
lead
dielectric
temperature
dielectric constant
Prior art date
Application number
PCT/JP1992/000085
Other languages
English (en)
Japanese (ja)
Inventor
Shinji Abe
Tetsuo Yoshimoto
Original Assignee
Nippon Soda Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Publication of WO1992013810A1 publication Critical patent/WO1992013810A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
    • H01G4/1263—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates containing also zirconium oxides or zirconates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C04B35/497—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides

Definitions

  • the present invention provides a dielectric porcelain composition, in particular, which can be sintered at a low temperature of around 1000 ° G, has a high dielectric constant, a small temperature change rate of the dielectric constant, a high insulation resistance at room and high temperatures, and a mechanical strength.
  • TECHNICAL FIELD The present invention relates to a dielectric ceramic composition for a ceramic capacitor having a high sintering temperature, a low dependence of electrical characteristics on a sintering temperature, and a small sintered body particle size.
  • a dielectric ceramic composition for a ceramic capacitor but porcelain composed mainly of titanate Barium (BaT i 0 3) has been widely put into practical use, as a main component barium titanate, usually 1
  • the sintering temperature is as high as 1300-1400 ° C.
  • materials that can withstand this sintering temperature such as platinum and palladium, are used as internal electrodes. They had to be used and had the disadvantage of high manufacturing costs.
  • porcelain In order to make multilayer ceramic capacitors cheap, it is necessary to use porcelain that can be sintered at the lowest possible temperature, especially at 1000 ° C or lower, so that inexpensive metals, mainly silver and nickel, can be used for internal electrodes.
  • the electrical properties of the dielectric ceramic composition are basically required to have a high dielectric constant, a small dielectric loss, and a high insulation resistance.
  • dielectric ceramics that can be sintered at 1000 ° C or less and have high mechanical strength are required.
  • multilayer ceramic capacitors have been required to have a small capacity change rate with respect to the operating temperature and to be small and large in order to use electronic components at high temperatures and stabilize circuit characteristics.
  • rate of change in capacitance for example, there have been known some that satisfy the Y5U characteristic and Y5T characteristic of the EIA standard in a temperature range of -30 to 85, but all have a dielectric constant of It is as low as 8000-12000 for Y5U characteristics and 6000-8000 for Y5T characteristics. Therefore, in order to reduce the size and capacitance of the ferroelectric capacitor and improve its temperature characteristics, it is necessary to find a dielectric ceramic composition with a high dielectric constant and a small rate of change in capacitance with respect to the measurement temperature.
  • Pb (g, / 2 W, / 2) 03-Pb for (g l / 3Nb 2/3 ) 03 -PfaTi0 3 system are disclosed in such as JP 55- 1 No. 16662, magnesium tungstate It is known that a dielectric porcelain composition containing a large amount of lead has excellent characteristics in which the temperature change of the child is small. However, on the other hand, it is also known that there is a problem that the electrical characteristics are highly dependent on the sintering temperature and it is difficult to obtain a sintered body having stable electrical characteristics. In addition, since the sintered ceramics had a large particle size and low mechanical strength, it was difficult to manufacture a multilayer chip capacitor having a thinner film thickness. In order to improve this, various methods of synthesizing the powder of the raw material powder have been studied, but all have the disadvantage of increasing the production cost.
  • the present invention solves the above-mentioned problems, and at a low temperature range of 1000 ° G or less. Sinterable, high dielectric constant, low rate of temperature change of dielectric constant, low dielectric loss, high insulation resistance at room temperature and high temperature, high dielectric breakdown voltage, high mechanical strength, sintering temperature of electrical characteristics It is an object of the present invention to provide a dielectric ceramic composition having a low dependency and a small sintered body particle diameter.
  • dielectric ceramic composition containing 4 mol% or less of manganese or a composite oxide containing manganese with respect to this composition.
  • the dielectric porcelain composition of the present invention uses, as a starting material, a starting compound such as an oxide, a hydroxide, or a carbonate, which becomes an oxide at a temperature of 600 ° C. or higher.
  • a starting compound such as an oxide, a hydroxide, or a carbonate
  • a weighed starting compound is subjected to ball milling or the like.
  • calcining is performed to obtain a raw material powder for the porcelain composition.
  • the obtained raw material powder is molded, and then sintered at about 1000 ° C in the air. It can be manufactured.
  • magnesium, nickel, tungsten, niobium, and other compounds are mixed and calcined to obtain magnesium niobate, nickel niobate, magnesium tungstate, etc.
  • Complex oxides, mixtures thereof, and solid solutions of these complex oxides can also be used as starting materials.
  • the calcining step is required twice or more, which increases the raw material cost, but increases the dielectric constant depending on the composition. It is advantageous as a material for high-performance ceramic capacitors.
  • the dielectric constant is small, the electrical characteristics are highly dependent on the sintering temperature, and the particle size of the sintered porcelain composition is large. It is not practical because it has disadvantages such as reduced strength.
  • a composition having a content of less than 0.05 has a drawback that the temperature change of the dielectric constant is large and the temperature characteristic of the dielectric constant is unsuitable as a material for a ceramic capacitor having a flat temperature characteristic.
  • the porcelain composition of the present invention containing five components including lead zirconate as a main component, it is possible to suppress the temperature change of the dielectric constant, to reduce the sintering temperature dependence of the electrical characteristics, and to suppress the grain growth. It becomes possible to sinter.
  • a composition containing more lead zirconate than the range of the present invention is not practical because the dielectric constant is small and the induced loss at room temperature is large.
  • a composition having a small content of 0.05 has a drawback that the temperature change of the dielectric constant is large, grain growth cannot be suppressed, and the transverse rupture strength is low.
  • Nickel 'lead niobate, magnesium' lead niobate, and a composition with a low lead titanate content of 0.05 are not practical because the dielectric constant is small.
  • a composition in which the content of these components is larger than the range of the present invention has a disadvantage that the change in the dielectric constant with the measurement temperature is large.
  • the temperature characteristics of the dielectric constant are suitable for practical ceramic capacitor materials. In order to achieve this, the content of lead zirconate must be increased, and the dielectric constant is greatly reduced, which is not preferable.
  • a disk with a diameter of 10 mm and a thickness of 3 It was placed in a sheer sagger and fired in the atmosphere at 1000 ° C for 1 hour.
  • the silver electrode was baked on the upper and lower surfaces of the sintered disk with a 600, and a 50V DC voltage was applied for 1 minute at room temperature with a super insulation resistance meter to measure the insulation resistance and calculate the specific resistance.
  • the sample was placed in a thermostat and the capacitance and dielectric loss at 25 at a frequency of 1 kHz and a voltage of 1 Vrms were measured with a digital LCR meter to calculate the dielectric constant. The average value of the four samples was used as the representative value.
  • the capacitance and the dielectric loss were measured in a temperature range of ⁇ 55 to +125, and the capacitance change rate based on the capacitance at 20 ° C. was calculated.
  • Table 1 shows the compounding ratio of each main component, the type and amount of additives, the dielectric constant and dielectric loss at 25 ° C, the specific resistance at room temperature, and the values at ⁇ 30 and 85 with reference to 20 °. The values of Yongman change rate are shown.
  • the main component, magnesium ⁇ Lead tungstate is denoted by P
  • nickel 'lead niobate is denoted by PNN
  • magnesium' lead niobate is denoted by PMN
  • lead titanate is denoted by PT
  • lead zirconate is denoted by ⁇ . ⁇ ', ⁇ ', ⁇ '
  • Example 1 In the same manner as in Example 1, raw material powders of the ifi combination shown in Table 1 were prepared, and a sintered body was prepared at a sintering temperature of 1000, and the gas characteristics were measured. Table 1 summarizes the measured results. In addition, as a result of observing the fracture surface of the sintered body of Example 11 with a scanning electron microscope, the average particle size was 2 #m, which was a small and uniform microstructure.
  • Raw material powders having the composition shown in Table 1 were prepared in the same manner as in Example 1, and sintered bodies were prepared by changing the sintering temperature to 950, 1000, and 1050 ° G, and the electrical characteristics were measured. Even when the sintering temperature was changed at 100, almost no change was observed in the electrical characteristics. Table 1 summarizes the measured results.
  • Raw material powders having the composition shown in Table 1 were prepared in the same manner as in Example I, and sintered bodies were prepared at sintering temperatures of 1000 ° C and 1050 ° C, and the electrical characteristics were measured. The results of the measurement are summarized in Table 1.
  • Powders having the main component mixing ratios shown in Table 2 were prepared in the same manner as in Example 1, and a sintered body of the porcelain composition was prepared at a sintering temperature of 1050, and the electrical characteristics were measured. The results shown in Table 2 were obtained. . Comparative examples 3 to 5
  • Raw material powders having the main component mixing ratios shown in Table 2 were prepared in the same manner as in Example 1, and sintered bodies were prepared at sintering temperatures of 1050 and 1100, and the electrical characteristics were measured. Table 2 summarizes the measured results. Further, as a result of observing the fracture surface of the sintered body of Comparative Example 4 with a scanning electron microscope, the average particle size was as large as 5 to ⁇ / zm, and the particle size distribution was not uniform.
  • a dielectric constant of 16000 is obtained with a dielectric constant of 6000 and a dielectric constant of 5 with characteristics of 5. Therefore, the porcelain composition of the present invention provides a small, large-sized ferromagnetic cell with a flat temperature characteristic of the dielectric constant. It can be said that it is extremely excellent as a material for lamic capacitors.
  • the porcelain in the composition region according to the present invention has an extremely fine and uniform microstructure, so that the thickness of the ceramic layer is thinner. It can be said that it is suitable for manufacturing a capacitor.
  • the grain size is large and the grain size distribution is not uniform. Therefore, when a ridged ceramic capacitor having a small thickness is manufactured, the dielectric breakdown voltage is reduced. Therefore, it was unsuitable as a practical material because its properties deteriorated.
  • the porcelain composition of the present invention has a low sintering temperature, the price of the internal electrode of the multilayer capacitor can be reduced by using an inexpensive metal, and the obtained porcelain can be made electrically. Since it has excellent characteristics and can cope with thinning of the dielectric layer, it is possible to manufacture a small and large-capacity multilayer ceramic capacitor.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Une composition de céramique diélectrique de solution solide comprend du manganotungstate de plomb [Pb(Mg1/2W1/2)O3], du nickeloniobate de plomb [Pb(Ni1/3Nb2/3)O3], du manganoniobate de plomb [Pb(Mg1/3Nb2/3)O3], du titanate de plomb [PbTiO3], ainsi que du zirconate de plomb [PbZrO3]. Ce matériau composite est exprimé par la formule [Pb(Mg1/2W1/2)O3]X - [Pb(Ni1/3Nb2/3)O3]Y - [Pb(Mg1/3Nb2/3)O3]Z - [PbTiO3]U - [PbZrO3]W, dans laquelle X + Y + Z + U + W = 1, et 0,05 « X « 0,3, 0,05 « Y « 0,5, 0,05 « Z « 0,75, 0,05 « U « 0,35, et 0,05 « W « 0,3. Ce matériau composite de céramique diélectrique présente d'excellentes caractéristiques comme matériau diélectrique pour un condensateur céramique monolithique.
PCT/JP1992/000085 1991-01-31 1992-01-29 Composition de ceramique dielectrique WO1992013810A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3/29204 1991-01-31
JP2920491 1991-01-31

Publications (1)

Publication Number Publication Date
WO1992013810A1 true WO1992013810A1 (fr) 1992-08-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100434418B1 (ko) * 2000-08-18 2004-06-04 가부시키가이샤 무라타 세이사쿠쇼 압전 세라믹재, 소결 압전 세라믹 컴팩트 및 압전 세라믹 소자

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5850727A (ja) * 1981-07-03 1983-03-25 アイ・テイ・テイ・インダストリ−ズ 誘電体組成物及びセラミツクコンデンサ−の製造方法
JPS6049502A (ja) * 1983-08-30 1985-03-18 日本電気株式会社 磁器組成物
JPS6214490B2 (fr) * 1984-08-18 1987-04-02 Kagaku Gijutsucho Mukizaishitsu Kenkyushocho
JPS6291420A (ja) * 1985-10-18 1987-04-25 Ube Ind Ltd 多段湿式法による易焼結性の複合ペロブスカイトの原料粉末の製造方法
JPS62100907A (ja) * 1985-10-24 1987-05-11 エステイ−シ−　ピ−エルシ− 誘電体組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5850727A (ja) * 1981-07-03 1983-03-25 アイ・テイ・テイ・インダストリ−ズ 誘電体組成物及びセラミツクコンデンサ−の製造方法
JPS6049502A (ja) * 1983-08-30 1985-03-18 日本電気株式会社 磁器組成物
JPS6214490B2 (fr) * 1984-08-18 1987-04-02 Kagaku Gijutsucho Mukizaishitsu Kenkyushocho
JPS6291420A (ja) * 1985-10-18 1987-04-25 Ube Ind Ltd 多段湿式法による易焼結性の複合ペロブスカイトの原料粉末の製造方法
JPS62100907A (ja) * 1985-10-24 1987-05-11 エステイ−シ−　ピ−エルシ− 誘電体組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100434418B1 (ko) * 2000-08-18 2004-06-04 가부시키가이샤 무라타 세이사쿠쇼 압전 세라믹재, 소결 압전 세라믹 컴팩트 및 압전 세라믹 소자

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