CN107304130B - Dielectric composition, dielectric ceramic, and capacitor - Google Patents

Dielectric composition, dielectric ceramic, and capacitor Download PDF

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Publication number
CN107304130B
CN107304130B CN201610244671.1A CN201610244671A CN107304130B CN 107304130 B CN107304130 B CN 107304130B CN 201610244671 A CN201610244671 A CN 201610244671A CN 107304130 B CN107304130 B CN 107304130B
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dielectric composition
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dielectric
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CN107304130A (en
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张帆
葛桂宾
张瑞伦
庄剑勇
黄***
武藤和也
渡边翔
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TDK Xiamen Corp
TDK Corp
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TDK Corp
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    • 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
    • C04B35/16—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 silicates other than clay
    • C04B35/22—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 silicates other than clay rich in calcium oxide, e.g. wollastonite
    • 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
    • C04B35/46—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 titanium oxides or titanates
    • C04B35/462—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 titanium oxides or titanates based on titanates
    • C04B35/465—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/61—Mechanical properties, e.g. fracture toughness, hardness, Young's modulus or strength

Abstract

The dielectric composition according to the present invention is a dielectric composition containing calcium titanium silicate, calcium titanate, and a manganese-containing compound or a vanadium-containing compound. In the case of containing a compound containing manganese, the content of calcium titanium silicate is set to CaSiTiO5Converted to a mol%; the content of calcium titanate was set to CaTiO3Conversion into b mol%; setting the content of the manganese-containing compound to MnO2When the conversion is carried out in terms of c mol%, a is not less than 23.4 and not more than 75.0, b is not less than 21.0 and not more than 76.4, c is not less than 0.21, and a + b + c is 100. In the case of containing a vanadium-containing compound, the content of calcium titanium silicate is set to CaSiTiO5Converted to d mol%; the content of calcium titanate was set to CaTiO3Converted to e mol%; the content of the vanadium-containing compound is set to V2O5When the conversion is f mol%, d is not less than 23.0 and not more than 61.7, e is not less than 37.9 and not more than 76.8, f is not less than 0.16, and d + e + f is 100.

Description

Dielectric composition, dielectric ceramic, and capacitor
Technical Field
The invention relates to a dielectric composition, a dielectric ceramic and a capacitor.
Background
In recent years, with the rapid development of electronic parts, the demand for electronic parts and materials constituting the electronic parts has become increasingly high. For example, a dielectric composition used as a material of a capacitor is required to have not only a high relative permittivity and excellent temperature characteristics but also improved reliability. Accordingly, it is required to improve the reliability of the dielectric composition and to improve the life of the capacitor.
Further, in order to reduce the cost, it is also required to miniaturize the dielectric ceramic and not to use an expensive rare earth element, harmful substance Pb, or the like.
With respect to a conventional dielectric composition, patent document 1 describes that a predetermined range of CaTiO is contained3And CaTiSiO5As a basic component and contains B in a predetermined range2O3、SiO2And a dielectric ceramic composition containing at least 1 or more metal oxides as an additive component.
Patent document 2 describes that the content of CaTiO is in a predetermined range3And CaTiSiO5As a basic component and contains Li in a predetermined range2O、SiO2And a dielectric ceramic composition containing at least 1 or more metal oxides as an additive component.
Further, patent document 3 describes that the compound is represented by { (Sr)1-xCax)O}k{(Ti1-yZry)O2Main component represented by (9) adding Li2SiO3And at least 1 or more alkaline earth metal fluorides.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 62-222513
Patent document 2: japanese laid-open patent publication No. 62-222514
Patent document 3: japanese patent laid-open No. H11-340075
Disclosure of Invention
The present invention aims to provide a dielectric composition having a desired relative permittivity, good temperature characteristics of electrostatic capacity, excellent voltage resistance against high alternating voltage, small variation in electrostatic capacity, and high reliability, and a dielectric ceramic comprising the dielectric composition, and a capacitor comprising the dielectric ceramic.
Means for solving the problems
In order to achieve the above object, a dielectric composition according to claim 1 of the present application is characterized in that: contains calcium titanium silicate (calcium titanate), calcium titanate and manganese-containing compound, wherein the content of calcium titanium silicate is set to CaSiTiO5Converted to a mol%; the content of calcium titanate was set to CaTiO3Conversion into b mol%; setting the content of the manganese-containing compound to MnO2When the conversion is carried out in terms of c mol%, a is not less than 23.4 and not more than 75.0, b is not less than 21.0 and not more than 76.4, c is not less than 0.21, and a + b + c is 100.
The dielectric composition according to claim 1 of the present application preferably has 0.21. ltoreq. c.ltoreq.4.0.
The dielectric composition according to claim 1 of the present application preferably has 0.50. ltoreq. c.ltoreq.4.0.
The dielectric composition according to claim 1 of the present application preferably has 1.00. ltoreq. c.ltoreq.4.0.
In order to achieve the above object, a dielectric composition according to claim 2 of the present application is characterized in that: containing calcium titanium silicate, calcium titanate and vanadium-containing compound, wherein the content of calcium titanium silicate is set to CaSiTiO5Converted to d mol%; the content of calcium titanate was set to CaTiO3Converted to e mol%; the content of the vanadium-containing compound is set to V2O5When the conversion is f mol%, d is not less than 23.0 and not more than 61.7, e is not less than 37.9 and not more than 76.8, f is not less than 0.16, and d + e + f is 100.
The dielectric composition according to claim 2 of the present application is preferably 0.16. ltoreq. f.ltoreq.0.57.
The dielectric composition according to the invention of the present application has a structure containing both calcium titanium silicate and calcium titanate and further containing manganese or vanadium within a predetermined range, and therefore, has a desired relative permittivity and good temperature characteristics of electrostatic capacity, is excellent in voltage resistance against high ac voltage, does not crack a blank even if a high-temperature load is applied, and has a small change in electrostatic capacity and high reliability.
Further, the dielectric composition of the present invention has a characteristic that the quality factor (Q) is improved by 0.21. ltoreq. c.ltoreq.4.0 or 0.16. ltoreq. f.ltoreq.0.57.
In the dielectric composition according to the invention of the present application, the content of magnesium oxide may be 0 to 18.1 wt% (including 0 wt%) in terms of MgO, and the content of silicon dioxide may be SiO2Converted to 0 to 12.9 wt% (including 0 wt%).
The content of magnesium oxide is expressed as x (wt%) in terms of MgO, and the content of silicon dioxide is expressed as SiO2The dielectric composition according to the present invention satisfies the following formulae (1) to (5) in terms of y (wt%):
y is less than or equal to-11.28 x +204.27 … … formula (1);
y is less than or equal to-0.40 x +14.90 … … formula (2);
y is less than or equal to 0.62x +9.80 … … formula (3);
x is more than or equal to 0 … … formula (4);
y is not less than 0 … … formula (5).
The content of magnesium oxide in the dielectric composition according to the invention of the present application is 0 to 18.1 wt% (including 0 wt%) in terms of MgO; may be substantially free of silicon dioxide.
The content of silicon dioxide in the dielectric composition related to the invention of the application is 0-10 wt% (including 0 wt%); magnesium oxide may be substantially absent.
The dielectric ceramic according to the present invention is composed of the dielectric composition.
Further, the capacitor according to the present invention includes the dielectric ceramic and a pair of electrodes.
Detailed Description
The present invention will be described below based on specific embodiments.
The dielectric composition according to embodiment 1 contains calcium titanium silicate, calcium titanate, and a manganese-containing compound in specific ranges.
Specifically, the content of calcium titanium silicate is set to CaSiTiO5Converted to a (mol%); the content of calcium titanate was set to CaTiO3Conversion to b (mol%); setting the content of the manganese-containing compound to MnO2When c (mol%) is converted, the following formula is satisfied.
23.4≤a≤75.0；
21.0≤b≤76.4；
c≥0.21；
a+b+c＝100。
The dielectric composition according to the present embodiment contains the respective components so as to satisfy the above formula, and thus has a desired relative permittivity and SL characteristics in which the temperature characteristics of the electrostatic capacity satisfy JIS standards, is excellent in voltage resistance against a high ac voltage, and has a small change in electrostatic capacity and high reliability without breaking a green body even if a high-temperature load is applied.
When a, b, or c does not satisfy the above formula, one or more of the above-described various characteristics may be deteriorated.
For example, if a is too low, the temperature characteristic of the capacitance does not satisfy the SL characteristic of JIS standard. If a is too high, not only may the temperature characteristic of the capacitance not satisfy the SL characteristic of JIS standard, but also the change in capacitance due to the high-temperature load may become large.
When b is too low, not only may the temperature characteristic of the capacitance not satisfy the SL characteristic of JIS standard, but also the change in capacitance due to a high-temperature load may become large. If b is too high, the temperature characteristic of the capacitance may not satisfy the SL characteristic of JIS standard.
When c is too low, the change in capacitance due to the high-temperature load becomes large. C is preferably 0.50 or more, and more preferably 1.00 or more.
There is no upper limit to c in the present embodiment, and c is usually not more than 12.0. Furthermore, the quality factor (Q) can be improved by controlling c to be less than or equal to 4.0.
The dielectric composition according to the present embodiment contains calcium titanium silicate (CaSiTiO)5) And calcium titanate (CaTiO)3) The crystallization of (4). This can be confirmed by XRD Rietveld analysis (X-Ray Diffraction Rietveld analysis). Further, the values of a, b and c can be confirmed by XRD Rietveld analysis. a. The values of b and c do not substantially change before and after firing.
The dielectric composition according to embodiment 2 contains calcium titanium silicate, calcium titanate, and a compound containing vanadium in specific ranges.
Specifically, the content of calcium titanium silicate is set to CaSiTiO5Converted to d (mol%); the content of calcium titanate was set to CaTiO3Conversion to e (mol%); the content of the vanadium-containing compound is set to V2O5When converted to f (mol%), the following formula is satisfied:
23.0≤d≤61.7；
37.9≤e≤76.8；
f≥0.16；
d+e+f＝100。
the dielectric composition according to the present embodiment contains the respective components so as to satisfy the above formula, and thus has a desired relative permittivity and SL characteristics in which the temperature characteristics of the electrostatic capacity satisfy JIS standards, is excellent in voltage resistance against a high ac voltage, and has a small change in electrostatic capacity and high reliability without breaking a green body even if a high-temperature load is applied.
When d, e, and f do not satisfy the above formula, one or more of the various characteristics may be deteriorated.
When d and e are too low or too high, the temperature characteristics of the electrostatic capacity do not satisfy the SL characteristics of JIS standard.
If f is too low, the change in capacitance due to the high-temperature load becomes large.
In addition, there is no upper limit on the amount of vanadium-containing compound (i.e., f), but typically f.ltoreq.2.0. Further, the quality factor (Q) can be improved by controlling f to be 0.57 or less.
The dielectric composition according to the present embodiment contains calcium titanium silicate (CaSiTiO)5) And calcium titanate (CaTiO)3) The crystallization of (4). This can be confirmed by XRD Rietveld analysis (X-Ray Diffraction Rietveld analysis). Further, the values of d, e, f can also be analyzed by XRD Rietveld analysis. In general, the values of d, e, and f do not substantially change before and after firing.
The dielectric composition according to embodiment 1 and the dielectric composition according to embodiment 2 may contain both a compound containing manganese and a compound containing vanadium.
Hereinafter, the description will be given of the embodiment 1 and the embodiment 2 only, respectively.
The perovskite in the present embodiment may be represented by CaSiTiO5And CaTiSiO5And the like, and the ratio of atoms of Ca to Si to Ti to O is 1:1:1: 5. In addition, the perovskite silicate in the present embodiment may be referred to by various names. For example, calcium silicotitanate, calcium silicate titanate, titanite (titanite), Sphene (Sphene), and the like may be referred to by their names. In addition, any compound other than the above-described compounds represented by the above-described names and chemical formulae is included in the perovskite silicate of the present embodiment as long as the atomic ratio of Ca to Si to Ti to O is 1:1:1: 5.
The calcium titanate in the present embodiment may be CaTiO3The compound represented by (1) and (3) wherein the atomic ratio is Ca, Ti and O is 1:1: 3. In addition, any compound other than the above-described compounds represented by the above-described names and chemical formulae is included in the calcium titanate as long as the atomic ratio is Ca to Ti to O is 1 to 3.
The dielectric composition according to the present embodiment may further contain a compound other than a calcium titanium silicate, calcium titanate, a manganese-containing compound, and/or a vanadium-containing compound, depending on the purpose of use. For example, magnesium oxide, titanium oxide (TiO) may be contained2) Silicon dioxide (SiO)2) And the like. As the magnesium oxide, a composite oxide containing magnesium (e.g., MgTi) is included in addition to magnesium oxide (MgO)2O5、Mg2SiO4、MgTiO3Etc.). The content of these compounds is not particularly limited, but when the total amount of the dielectric composition is set to 100 wt%, the total amount is preferably 30.0 wt% or less. The content of the magnesium oxide is a content in terms of MgO.
In particular, when the magnesium oxide is contained, the change in the electrostatic capacity due to the high-temperature load can be further reduced. When titanium oxide is contained, IR can be improved. When silica is contained, the temperature change in electrostatic capacity can be further reduced. Further, the voltage resistance to a high ac voltage can be improved.
The content of the magnesium oxide is preferably 18.1 wt% or less (including 0 wt%), and particularly preferably 6.0 to 18.1 wt%, in terms of MgO. When the content of the magnesium oxide is 18.1 wt% or less, silica may be substantially not contained.
The content of silicon dioxide is SiO2The content is preferably 10 wt% or less (including 0 wt%), and particularly preferably 6.0 to 10.0 wt%. When the content of silica is 10.0 wt% or less, magnesium oxide may not be substantially contained.
The content of magnesium oxide is represented by x (wt%) in terms of MgO, and the content of silicon dioxide is represented by SiO2When the conversion is performed as y (wt%), it is preferable that the following formulae (1) to (5) are completely satisfied:
y is less than or equal to-11.28 x +204.27 … … formula (1);
y is less than or equal to-0.40 x +14.90 … … formula (2);
y is less than or equal to 0.62x +9.80 … … formula (3);
x is more than or equal to 0 … … formula (4);
y is not less than 0 … … formula (5).
By satisfying the above equations (1) to (5), it is possible to easily obtain a dielectric composition having a relative permittivity, a temperature characteristic of a capacitance, a rate of change in capacitance after a high-temperature load, a voltage resistance to a high ac voltage, and an insulation resistance that are all excellent.
In particular, when the formula (2) is satisfied, it is easy to appropriately control the relative permittivity.
In particular, when the formula (1) and the formula (2) are satisfied, it is easy to appropriately control the temperature characteristics of the relative permittivity and the electrostatic capacity.
In particular, when the formula (3) is satisfied, it is easy to appropriately control the rate of change in capacitance after a high-temperature load.
However, lithium and boron are not suitable for positive addition. When the total amount of the dielectric composition is set to 100 wt%, the contents of lithium and boron are represented by Li2O、B2O3The content is preferably 0.4 wt% or less in terms of conversion. When lithium and boron are contained in a large amount, reliability tends to be lowered. In addition, the voltage resistance to the ac voltage tends to be poor and the insulation resistance also tends to be low.
In addition, when lithium is added, the change in capacitance tends to increase when a high-temperature load is applied. Further, the Q value also tends to decrease.
In addition, when boron is added, the temperature characteristics of the capacitance tend to be deteriorated. When a high-temperature load is applied, the change in capacitance tends to increase. Further, the Q value also tends to decrease.
Further, the dielectric composition according to the present embodiment has good characteristics even if it does not substantially contain a rare earth element such as lanthanum and a harmful substance such as lead. The term "substantially not contained" means that the content is 0.01 wt% or less when the total amount of the dielectric composition is set to 100 wt%.
The shape of the dielectric composition is not particularly limited, and can be freely set according to the purpose of use.
The following describes a method for producing the dielectric composition, the dielectric ceramic, and the capacitor according to the present embodiment, but the method for producing the dielectric composition, the dielectric ceramic, and the capacitor is not limited to the following method.
First, a raw material powder of the dielectric composition according to the present embodiment is prepared. As the raw material powder, a compound of each component or a powder of a compound that becomes each component by firing is prepared. In each component, calcium titanium silicate (CaSiTiO)5) And calcium titanate (CaTiO)3) Preferably, the calcium titanosilicate powder and the calcium titanate powder are prepared at the time of preparing the raw material. As for other components, for example, a compound containing manganese, a compound containing vanadium, and the like, in addition to the oxide of each element, a compound which can be an oxide of each element after firing, for example, a carbonate, a nitrate, a sulfate, and the like can be prepared.
Next, the raw material powders of the respective components are mixed to obtain a mixed powder. The mixing method is not particularly limited, and a commonly used method such as dry mixing or wet mixing can be used.
Then, the mixed powder is granulated to obtain a granulated powder. The granulation method is not particularly limited. For example, there is a method of adding an aqueous PVA (polyvinyl alcohol) solution to the mixed powder and granulating the mixture. Further, the granulated powder may be sieved to remove coarse granulated powder after granulation.
Next, the granulated powder is molded to obtain a molded body composed of the dielectric composition. The molding method is not particularly limited, and a commonly used method can be used. For example, a press molding method can be used. The pressure at the time of pressurization is not particularly limited, and for example, a pressure of 250 to 550MPa may be applied.
Next, the obtained molded body is fired to obtain a sintered body (dielectric ceramic) made of the dielectric composition. The firing conditions are not particularly limited. The firing temperature may be set to 1150 to 1300 ℃. The firing atmosphere is not particularly limited. For example, the atmosphere may be air, a nitrogen atmosphere, a reducing atmosphere using nitrogen and hydrogen, or another atmosphere.
Further, a capacitor can be obtained by joining a pair of electrodes to the obtained sintered body. A pair of electrodes is bonded to, for example, 2 opposite surfaces of the obtained sintered body.
The method for joining the electrode to the obtained sintered body is not particularly limited, and for example, the electrode can be joined to the obtained sintered body by applying an electrode paste to the obtained sintered body and firing the paste under high temperature conditions.
The application of the dielectric composition and the dielectric ceramic according to the present embodiment is not limited to capacitors.
In the above description, the method of manufacturing the capacitor according to the present embodiment as a single plate capacitor has been described, but the capacitor of the present invention is not limited to the single plate capacitor, and may be a capacitor other than the single plate capacitor such as a multilayer capacitor. The method for producing the multilayer capacitor or the like is not particularly limited, and a known production method can be used.
Examples
The present invention will be further described below based on specific examples, but the present invention is not limited to these examples.
(example 1)
Preparation of CaSiTiO as raw Material powder5Powder, CaTiO3Powder, MnO2The powders were weighed so as to obtain sintered bodies having the compositions of examples and comparative examples shown in table 1. For a, b, and c in Table 1, the 2 nd digit after the decimal point is rounded off. However, in order to clarify whether c is 0.21 or more, the 3 rd digit after the decimal point is rounded when c is less than or equal to 0.24. Thus, there are samples where a + b + c is not 100.00.
Subsequently, the respective raw material powders are wet-mixed. For the wet mixing, a ball mill using zirconia balls was used. The solvent used for wet mixing is ion exchange water. Then, the wet-mixed raw materials are dried to obtain a dielectric composition powder.
Then, 100 parts by weight of the dielectric composition powder was granulated by adding 10 parts by weight of an aqueous PVA (polyvinyl alcohol) solution to the dielectric composition powder, thereby obtaining a granulated powder. The granulated powder was sieved to remove coarse granulated powder. The granulated powder after sieving was subjected to a pressure of 396MPa to produce a disk-shaped compact having a diameter of 7.5mm and a thickness of 0.7 to 0.8 mm.
The molded body is fired in air at 1175 to 1250 ℃ for 2 hours to obtain a disk-shaped sintered body having a thickness of about 0.5 mm. The presence of CaSiTiO in the sintered body obtained was confirmed by XRD Rietveld analysis5And CaTiO3The crystallization of (4). Further, it was confirmed by XRD Rietveld analysis that the composition of the obtained sintered body became the composition shown in table 1. Next, a Cu electrode paste was applied to both surfaces of the sintered body and fired at 800 ℃ for 15 minutes in a nitrogen atmosphere to obtain a capacitor sample having an electrode diameter of 5 mm. Capacitor samples were prepared in the number required for complete evaluation as described below.
Then, the obtained capacitor samples were evaluated for AC breakdown electric field, relative permittivity, quality factor, capacitance-temperature characteristics, and reliability (rate of change in capacitance after high-temperature load). The evaluation method will be described below.
The AC breakdown electric field Eb (kV/mm) was measured by the following method. An alternating electric field is applied to both ends of the obtained capacitor sample. The magnitude of the AC electric field was increased at 184V/s, and the change in the leakage current was observed with an AC withstand voltage tester. The electric field when the leakage current became 5mA was taken as the AC breakdown electric field Eb. The higher Eb is, the more excellent voltage resistance to a high ac voltage can be said to be. Eb > 10kV/mm is good in this example.
The relative dielectric constant (. epsilon.) was calculated from the electrostatic capacity measured on a disc-shaped capacitor sample at a temperature of 20 ℃ under the conditions of a frequency of 1MHz and an input signal level (measurement voltage) of 1.0Vrms using an LCR tester. In this embodiment,. epsilon.gtoreq.75 is preferable.
The capacitance temperature characteristic ā (ppm/. degree. C.) was measured in the following manner. First, the temperature was varied within a range of +20 ℃ to +85 ℃ to measure the capacitance at each temperature. The capacitance was measured using an LCR tester at a frequency of 1MHz and an input signal level of 1 Vrms. Then, the electrostatic capacity at +20 ℃ was set to C20And the electrostatic capacity at T (. degree. C.) is set to CTIn the case of (3), the capacitance-temperature characteristic ā was measured according to the following equation.
ā(ppm/℃)＝{(CT-C20)/[C20×(T-20)]}×106
In the present example, it is preferable that the temperature is always-1000. ltoreq. ā. ltoreq.350 in the range of +20 ℃ to +85 ℃. In this example, the capacitor sample satisfying-1000. ltoreq. ā. ltoreq.350 at +85 ℃ also satisfies-1000. ltoreq. ā. ltoreq.350 at other temperatures within the range of +20 ℃ to +85 ℃. Accordingly, ā at +85 ℃ is described in Table 1.
The quality factor (Q) was measured using an LCR tester at a temperature of 20 ℃ and a frequency of 1MHz on the above capacitor sample. In this example, Q > 2000 is preferable. However, the above object of the present invention can be achieved even if Q is 2000 or less.
The measurement of the rate of change in capacitance (Δ C) after a high-temperature load and the evaluation of reliability were carried out by the following methods.
First, the electrostatic capacity before high-temperature load was measured by using an LCR tester under the conditions of a temperature of 20 ℃, a measurement frequency of 1MHz, and a measurement voltage of 1.0 Vrms.
Next, a high-temperature load test was performed. The high temperature load test was carried out by immersing the above capacitor sample in silicone oil at 150 ℃ and continuously applying 7kV AC voltage for 8 hours.
In the high-temperature load test, a capacitor sample having a leakage current of 5mA was judged to be cracked. The reliability was evaluated by conducting the high-temperature load test on 5 capacitor samples and counting the number of cracks in the green tire. The condition that none of the plain tires had broken was regarded as good.
After the high-temperature load test, the capacitance after the high-temperature load was measured on the capacitor sample in which the green body was not broken under the same conditions as the measurement of the capacitance before the high-temperature load. The electrostatic capacity before high-temperature load is set to C1And the electrostatic capacity after high-temperature load is set to C2In the case of (2), Δ C (%) is obtained according to the following formula. In the present embodiment, the case where Δ C is less than or equal to 5.0 is regarded as having good reliability.
ΔC(％)＝[︱C2-C1︱/C1]×100
Figure BDA0000968086760000121
As is clear from Table 1, examples (sample Nos. 1 to 9) having compositions within the scope of the present invention are excellent in AC breakdown electric field Eb, electrostatic capacity temperature characteristics ā and reliability.
In contrast, sample number 18 of the comparative example with a low and b high had ā at 85 ℃ of less than-1000. Sample No. 19 of the comparative example, which is high in a and low in b, exceeds 350 in ā at 85 ℃ and also decreases in reliability.
The comparative examples having c less than 0.21 have reduced reliability for sample numbers 20 to 22.
In addition, the examples (sample Nos. 1 to 13) in which c is 0.21. ltoreq. c.ltoreq.4.0 are superior in quality factor (Q) to the examples (sample Nos. 14 to 17) in which c > 4.0, and Q exceeds 2000.
(example 2)
MnO preparation of sample No. 12 of example 12Change to Li of prescribed amount2O and SiO2Capacitor samples of comparative examples (sample No. 23 to 25) and B obtained by changing the capacitor samples to a predetermined amount2O3And SiO2The capacitor samples of comparative examples (sample No. 26 to 28). In addition to the characteristics measured in example 1, Insulation Resistance (IR) and dielectric loss were measured. Will measure the knotThe results are shown in table 2. In addition, for a and b in table 2, the 2 nd bit after each decimal point is rounded, and for c, the 3 rd bit after the decimal point is rounded.
For the Insulation Resistance (IR), a direct voltage of 500V was applied to a capacitor sample at a temperature of 20 ℃ and the resistance value (in Ω) after 60 seconds from the application of the voltage was measured. In this example, 1.0E +12 Ω or more is preferable. However, the above object of the present invention can be achieved even if the IR is less than 1.0E + 12. omega. In addition, 1.0E + 12. omega. means 1.0X 1012。
The dielectric loss (tan. delta.) was measured at a reference temperature of 20 ℃ using an LCR tester under conditions of a frequency of 1MHz and an input signal level (measurement voltage) of 1.0Vrms for a capacitor sample. In this example, 0.05% or less is preferable. However, the above object of the present invention can be achieved even if the tan δ exceeds 0.05%.
Figure BDA0000968086760000141
As is clear from Table 2, the composition contains MnO2Sample No. 12 of (a) is excellent in insulation resistance and dielectric loss. In contrast, no MnO is contained2And contains Li2The Q value, AC breakdown field Eb and reliability results of samples No. 23-25 of O are inferior to those of sample No. 12. In addition, does not contain MnO2And contains B2O3The results of the Q values, the AC breakdown electric field Eb and the electrostatic capacity temperature characteristic ā of samples 26 to 28 are inferior to those of sample 12. In samples 23 to 28, the green tires of all the capacitor samples were cracked by the high-temperature load.
(example 3)
As the raw material powder, except CaSiTiO5Powder, CaTiO3Powder, MnO2MgO powder and SiO powder were prepared in addition to the powder2The powders were weighed to finally obtain sintered bodies having the compositions shown in Table 3. Then, capacitor samples were produced in the same manner as in examples 1 and 2, and the AC breakdown electric field, the relative permittivity, and the electrostatic capacity temperature were evaluatedDegree characteristic, reliability (rate of change in capacitance after high-temperature load), and insulation resistance. The results are shown in table 3. In addition, the magnesium oxide acts as MgTi in addition to MgO in the sintered body2O5、Mg2SiO4、MgTiO3And the like. In table 3, the values of the content of magnesium oxide converted to MgO are shown in the MgO column. All samples in table 3 satisfy the above formulas (1) to (5).
[ Table 3]
Figure BDA0000968086760000151
As is clear from table 3, sample number 29B containing magnesium oxide has a lower Δ C and improved reliability than sample number 29A containing no magnesium oxide. In addition, contains SiO2Sample Nos. 29D and 29E of (1) and SiO-free2Compared with sample No. 29A, the AC breakdown electric field is improved and the temperature characteristic of the electrostatic capacity is also improved.
Further, contains magnesium oxide and SiO2Both of them were also satisfactory in all of sample numbers 29F to 29M satisfying the above-mentioned formulas (1) to (5).
Further, contains magnesium oxide and does not contain SiO2Sample No. 29L, 29M of (1) and sample No. 29L, 29M containing no magnesium oxide and no SiO2Sample number 29K of (1) is reduced compared to Δ C and reliability is improved.
(example 4)
Preparation of CaSiTiO as raw Material powder5Powder, CaTiO3Powder, V2O5The powders were weighed so as to obtain sintered bodies having the compositions of examples and comparative examples shown in table 4. In table 4, for d and e, the 2 nd bit after each decimal point is rounded, and for f, the 3 rd bit after each decimal point is rounded. Therefore, there are samples in which d + e + f does not become 100.00. Capacitor samples were produced and evaluated in the same manner as in example 1.
[ Table 4]
Figure BDA0000968086760000161
Is a comparative example
As is clear from Table 4, examples (sample Nos. 31 to 39) having compositions within the scope of the present invention have good AC breakdown electric field Eb, electrostatic capacity temperature characteristics ā, and reliability.
In contrast, sample number 40 of the comparative example with d lower and e higher had ā at 85 ℃ of less than-1000. Sample No. 41 of comparative example with d high and e low had ā exceeding 350 at 85 ℃.
The samples 42 and 43 of the comparative example in which F is less than 0.16 have reduced reliability.
In addition, the examples (sample Nos. 31 to 37) in which f is 0.16. ltoreq.f.ltoreq.0.57 are superior in quality factor (Q) to the examples (sample Nos. 38 to 39) in which f > 0.57, and Q exceeds 2000.

Claims (12)

1. A dielectric composition characterized by:
containing a calcium titanium silicate, calcium titanate and a compound containing manganese,
the content of calcium titanium silicate is set to CaSiTiO5Converted to a mol%; the content of calcium titanate was set to CaTiO3Conversion into b mol%; setting the content of the manganese-containing compound to MnO2When c mol% is converted, a is not less than 23.4 and not more than 75.0, b is not less than 21.0 and not more than 76.4, c is not less than 0.21, a + b + c is 100,
when the total dielectric composition is set to 100 wt%, the content of the magnesium oxide is 6.0-18.1 wt% in terms of MgO.
2. The dielectric composition of claim 1, wherein:
0.21≤c≤4.0。
3. the dielectric composition of claim 1 or 2, wherein:
0.50≤c≤4.0。
4. the dielectric composition of claim 1 or 2, wherein:
1.00≤c≤4.0。
5. a dielectric composition characterized by:
containing a calcium titanium silicate, calcium titanate and a compound comprising vanadium,
the content of calcium titanium silicate is set to CaSiTiO5Converted to d mol%; the content of calcium titanate was set to CaTiO3Converted to e mol%; the content of the vanadium-containing compound is set to V2O5When converted to f mol%, d is not less than 23.0 and not more than 61.7, e is not less than 37.9 and not more than 76.8, f is not less than 0.16, d + e + f is 100,
when the total dielectric composition is set to 100 wt%, the content of the magnesium oxide is 6.0-18.1 wt% in terms of MgO.
6. The dielectric composition of claim 5, wherein:
0.16≤f≤0.57。
7. the dielectric composition of claim 1 or 5, wherein:
the content of silicon dioxide is SiO2Converted to 0 to 12.9 wt%, including 0 wt%.
8. The dielectric composition of claim 1 or 5, wherein:
the content of the magnesium oxide is expressed as x in terms of MgO, and the unit is wt%; the content of silicon dioxide is set to SiO2When the unit is wt% in terms of y, the following formulae (1) to (5) are satisfied:
y is less than or equal to-11.28 x +204.27 … … formula (1);
y is less than or equal to-0.40 x +14.90 … … formula (2);
y is less than or equal to 0.62x +9.80 … … formula (3);
x is more than or equal to 6.0 … … formula (4);
y is not less than 0 … … formula (5).
9. The dielectric composition of claim 1 or 5, wherein:
substantially free of silicon dioxide.
10. The dielectric composition of claim 1 or 5, wherein:
the content of the silicon dioxide is 0-10 wt%, including 0 wt%.
11. A dielectric ceramic, characterized in that:
is composed of the dielectric composition according to any one of claims 1 to 10.
12. A capacitor, characterized by:
having a dielectric ceramic as claimed in claim 11 and a pair of electrodes.
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